JPH0424372B2 - - Google Patents
Info
- Publication number
- JPH0424372B2 JPH0424372B2 JP12865788A JP12865788A JPH0424372B2 JP H0424372 B2 JPH0424372 B2 JP H0424372B2 JP 12865788 A JP12865788 A JP 12865788A JP 12865788 A JP12865788 A JP 12865788A JP H0424372 B2 JPH0424372 B2 JP H0424372B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- flame retardant
- prepreg
- varnish
- polyaromatic cyanate
- 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.)
- Expired
Links
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims description 28
- 239000003063 flame retardant Substances 0.000 claims description 28
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 25
- 239000002966 varnish Substances 0.000 claims description 16
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 125000003367 polycyclic group Chemical group 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 238000000465 moulding Methods 0.000 description 15
- 239000011347 resin Substances 0.000 description 11
- 229920005989 resin Polymers 0.000 description 11
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 239000002184 metal Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000011889 copper foil Substances 0.000 description 5
- 239000004744 fabric Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 150000001868 cobalt Chemical class 0.000 description 3
- 229910001429 cobalt ion Inorganic materials 0.000 description 3
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 3
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920006380 polyphenylene oxide Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- KDVYCTOWXSLNNI-UHFFFAOYSA-N 4-t-Butylbenzoic acid Chemical compound CC(C)(C)C1=CC=C(C(O)=O)C=C1 KDVYCTOWXSLNNI-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- ZDZHCHYQNPQSGG-UHFFFAOYSA-N binaphthyl group Chemical group C1(=CC=CC2=CC=CC=C12)C1=CC=CC2=CC=CC=C12 ZDZHCHYQNPQSGG-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- LJDZFAPLPVPTBD-UHFFFAOYSA-N nitroformic acid Chemical compound OC(=O)[N+]([O-])=O LJDZFAPLPVPTBD-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Chemical group 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Chemical group 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
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
- H05K1/0346—Organic insulating material consisting of one material containing N
-
- 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
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
Landscapes
- Reinforced Plastic Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
Description
本発明は、プリント配線板として用いられる積
層板の製造方法に関するものである。
The present invention relates to a method for manufacturing a laminate used as a printed wiring board.
近年、電子工業や通信、コンピユータなどの分
野において使用される周波数がMHzやGHzのよう
に高周波の領域にシフトしている。そしてこのよ
うな高周波領域で用いられるプリント配線板の絶
縁層においては、信号の伝播遅延を短くするうえ
で誘電率がより小さいことが、また電力ロスを小
さくするうえで誘電正接がより小さいことがそれ
ぞれ望まれる。
このために誘電率や誘電正接が小さい四フツ化
エチレン樹脂(テフロン)やポリフエニレンオキ
サイド(PPO)などの樹脂を用いて絶縁層を形
成することが試みられるに至つている。
In recent years, frequencies used in fields such as the electronic industry, communications, and computers have shifted to high frequency regions such as MHz and GHz. In the insulating layers of printed wiring boards used in such high frequency ranges, it is necessary to have a smaller dielectric constant in order to shorten signal propagation delay, and a smaller dielectric loss tangent in order to reduce power loss. Each is desired. For this reason, attempts have been made to form an insulating layer using resins such as tetrafluoroethylene resin (Teflon) and polyphenylene oxide (PPO), which have small dielectric constants and dielectric loss tangents.
【発明が解決しようとする課題】
しかしこれらの樹脂を用して絶縁層を形成する
場合、ガラス転移温度(Tg)が180〜200℃程度
と低く耐熱性が不十分で、スルーホール加工時の
スミアの発生などスルーホールの信頼性を高く得
られないために多層のプリント配線板に形成する
ことができないなどの問題があつた。
本発明は上記の点に鑑みて為されたものであ
り、低い誘電率や誘電正接、高い耐熱性を保持す
ることができ、加えて難燃性を高めることができ
る積層板の製造方法を提供することを目的とする
ものである。[Problems to be Solved by the Invention] However, when forming an insulating layer using these resins, the glass transition temperature (Tg) is low at about 180 to 200°C, and the heat resistance is insufficient, making it difficult to process through-holes. There were problems such as the occurrence of smear and the inability to obtain high reliability through the through holes, making it impossible to form them in multilayer printed wiring boards. The present invention has been made in view of the above points, and provides a method for manufacturing a laminate that can maintain low dielectric constant, dielectric loss tangent, and high heat resistance, and can also improve flame retardancy. The purpose is to
本発明は、次式()に示されるポリ芳香族シ
アネートに、
(式中Arは芳香族。BはC7〜20の多環式脂肪族
基。Dは各々独立に活性水素を含まない置換基。
q,r,sは各々独立に0,1,2又は3の整数
であり、ただしq,r,sの合計は2より大きい
か又は2に等しい。tは各々独立に0から4まで
の整数。xは0〜5までの数)
次式()に示される難燃剤と、
(式中R及びR′は活性水素を含まない芳香族
又は臭素化芳香族の置換基。nは正数)
次式()に示される難燃剤と、
(式中nは0,1又は2の整数)
ポリ芳香族シアネートの反応触媒とを配合して
ワニスを調製すると共にこのワニスを基材に含浸
してプリプレグを作成し、このプリプレグを積層
成形することを特徴とする積層板の製造方法に係
るものである。
以下本発明を詳細に説明する。
式()で示すポリ芳香族シアネートとして
は、特許出願公表昭61−500434号広報によつて開
示されているものを用いることができる。すなわ
ち、このポリ芳香族シアネートは、従来のポリト
リアジンよりも加水分解作用に対して著しく安定
で熱安定性に優れた芳香族ポリトリアジン(ポリ
芳香族シアネート樹脂)を与えるものである。
本発明において用いる式()のポリ芳香族シ
アネートにおいて、芳香族基Arは芳香族基を含
む総ての基を意味するものであり、例えばベンゼ
ン、ナフタリン、フエナントラセン、アントラセ
ン、またはビ芳香族基、アルキレン部分によつて
架橋された2個以上の芳香族基である。好適には
ベンゼン、ナフタリン、ビフエニル、ビナフチ
ル、ジフエニルアルキレン基であり、特にベンゼ
ン基であることが望ましい。C7〜20の多環式脂肪
族基Bとは、2個以上の環を含む脂肪族基を意味
するものであり、多環式脂肪族基には1つ以上の
二重結合または三重結合が含まれていてもよい。
好適な多環式脂肪族基を列挙すれば次のものがあ
る。
(式中Yは−CH2−,−S−,
The present invention provides a polyaromatic cyanate represented by the following formula (), (In the formula, Ar is aromatic. B is a C7-20 polycyclic aliphatic group. D is each independently a substituent containing no active hydrogen.
q, r, and s are each independently an integer of 0, 1, 2, or 3, provided that the sum of q, r, and s is greater than or equal to 2. t is an integer from 0 to 4, each independently. x is a number from 0 to 5) A flame retardant represented by the following formula (), (In the formula, R and R' are aromatic or brominated aromatic substituents that do not contain active hydrogen. n is a positive number) A flame retardant represented by the following formula (), (In the formula, n is an integer of 0, 1 or 2) A varnish is prepared by blending with a polyaromatic cyanate reaction catalyst, and a base material is impregnated with this varnish to create a prepreg, and this prepreg is laminated and molded. The present invention relates to a method for manufacturing a laminate, which is characterized by the following. The present invention will be explained in detail below. As the polyaromatic cyanate represented by the formula (), those disclosed in Patent Application Publication No. 1988-500434 can be used. That is, this polyaromatic cyanate provides an aromatic polytriazine (polyaromatic cyanate resin) that is significantly more stable against hydrolysis and has superior thermal stability than conventional polytriazine. In the polyaromatic cyanate of formula () used in the present invention, the aromatic group Ar means any group containing an aromatic group, such as benzene, naphthalene, phenanthracene, anthracene, or biaromatic group. group, two or more aromatic groups bridged by alkylene moieties. Suitable examples include benzene, naphthalene, biphenyl, binaphthyl, and diphenylalkylene groups, with benzene groups being particularly preferred. The C 7-20 polycyclic aliphatic group B means an aliphatic group containing two or more rings, and the polycyclic aliphatic group has one or more double bonds or triple bonds. may be included.
Suitable polycyclic aliphatic groups include the following. (In the formula, Y is -CH 2 -, -S-,
【式】【formula】
【式】であり、D1はC1〜5のアルキル基である。)
なかでも(a)(b)(c)(d)(e)(f)(g)又は(l)のものが好適で
あ
り、より好適には(a)(b)(c)(d)(l)で、特に(a)のものが
好ましい。
式()中のDは有機炭化水素基上に置換され
得る総ての置換基を意味するものであるが、活性
水素原子を含む置換基は除外される。活性水素原
子とは酸素、硫黄、窒素原子に結合した水素原子
を意味する。式()中の各Dはそれぞれ独立し
て規定されるものであり、例えば、アルキル、ア
ルケニル、アルキニル、アリール、アルカリー
ル、アルアルキル、ハロ、アルコキシ、ニトロ、
カルボキシレート、スルホン、スルフイド、カー
ボネートなどであり、好適にはC1〜10のアルキル、
C1〜10のアルケニル、ニトロ、ハロであり、C1〜3
のアルキル、C1〜3のアルキニル、ブロモ、クロロ
が最も好ましい。
また式()中のtは0から4までの整数であ
り、なかでも0,1又は2の整数が好ましく、よ
り好適には0又は1で、最適には0である。式
()中の各tはそれぞれ独立して規定される。
q,r,sは0,1,2又は3の整数であり、最
適には1である。q,r,sはそれぞれ独立して
規定されるが、これらの合計は2以上になるよう
に設定される。さらにxは0から5までの正数で
ある。式()のポリ芳香族シアネートはxが0
〜5までの化合物類の混合物として見出だされる
ものであり、xはこの混合物の平均の数として規
定されるものである。
式()のポリ芳香族シアネートの好ましい実
施態様は次の式で表される。
しかして、式()のポリ芳香族シアネートか
ら得られる芳香族ポリトリアジン(ポリ芳香族シ
アネート樹脂)は、低い誘電率(ε2.78前後)、低
い誘電正接(tanδ0.003前後)及び高い耐熱性
(ガラス転移温度Tg250以上、オーブン耐熱性300
℃程度)を有するという、プリント配線板の絶縁
基板を構成する樹脂として優れた特性を有する。
そこで本発明ではさらに式()で表される難燃
剤と式()で表される難燃剤とを配合して、プ
リント配線板において要求される難燃特性を付与
するようにしたものである。
式()のフエノキシ ターミネーテツド テ
トラブロモビスフエノールA カーボネーテツド
オリゴマーにおいて、R及びR′は活性水素を
含まない芳香族又は臭素化芳香族の置換基であ
り、例えば[Formula], and D 1 is a C 1-5 alkyl group. ) Among these, (a)(b)(c)(d)(e)(f)(g) or (l) are preferable, and (a)(b)(c)(d )(l), and (a) is particularly preferred. D in formula () means all substituents that can be substituted on the organic hydrocarbon group, but substituents containing active hydrogen atoms are excluded. Active hydrogen atom means a hydrogen atom bonded to an oxygen, sulfur, or nitrogen atom. Each D in formula () is defined independently, and includes, for example, alkyl, alkenyl, alkynyl, aryl, alkaryl, aralkyl, halo, alkoxy, nitro,
carboxylate, sulfone, sulfide, carbonate, etc., preferably C1-10 alkyl,
C 1-10 alkenyl, nitro, halo, C 1-3
most preferred are alkyl, C1-3 alkynyl, bromo, chloro. Further, t in formula () is an integer from 0 to 4, preferably an integer of 0, 1 or 2, more preferably 0 or 1, and most preferably 0. Each t in formula () is defined independently.
q, r, s are integers of 0, 1, 2, or 3, and optimally 1. Although q, r, and s are each defined independently, their total is set to be 2 or more. Furthermore, x is a positive number from 0 to 5. The polyaromatic cyanate of formula () has x of 0
It is found as a mixture of up to 5 compounds, where x is defined as the average number of this mixture. A preferred embodiment of the polyaromatic cyanate of formula () is represented by the following formula. Therefore, the aromatic polytriazine (polyaromatic cyanate resin) obtained from the polyaromatic cyanate of formula () has a low dielectric constant (ε2.78 or so), a low dielectric loss tangent (tan δ0.003 or so), and high heat resistance. (Glass transition temperature Tg250 or higher, oven heat resistance 300
It has excellent properties as a resin constituting the insulating substrate of a printed wiring board.
Therefore, in the present invention, a flame retardant represented by the formula () and a flame retardant represented by the formula () are further blended to impart flame retardant properties required for printed wiring boards. In the phenoxy-terminated tetrabromobisphenol A carbonated oligomer of formula (), R and R' are aromatic or brominated aromatic substituents containing no active hydrogen, e.g.
【式】【formula】
【式】
(R1はBrやCH3,C2H5などやこれらが組み合
わされたものであり、mは1,2又は3の整数)
などである。また式()においてnは限定され
ない正数であるが、現在入手することができるも
のはn=10〜20の混合物のものである。nがこれ
以外のものでも使用することができる。
式()や式()の難燃剤の配合による難燃
効果はBr量に応じて決定するものであり、UL規
格の94V−0のレベルの難燃性を得るためには、
式()のポリ芳香族シアネートと式()及び
式()の難燃剤の合計量に対してBrの含有率
が5〜10重量%になるように式()の難燃剤
を、Brの含有率が5〜10重量%になるように式
()の難燃剤をそれぞれ配合するようにするの
がよい。式()の難燃剤をBr含有率が5〜10
重量%になるように配合するには化合物としての
配合量は10〜20重量%に、また式()の難燃剤
をBr含有率が5〜10重量%になるように配合す
るには化合物としての配合量は10〜20重量%にそ
れぞれ設定するのが一般的である。難燃剤の配合
量が多すぎると耐熱性に問題が生じるおそれがあ
るので、上限は上記の数値に設定するのがよい。
式()のポリ芳香族シアネートを重合させる
反応触媒としては、イミダゾール類、第三級アミ
ン、ナフテン酸コバルトやオクチル酸コバルトな
ど有機コバルト塩類等の有機金属塩類を用いるこ
とができるものであり、特に有機コバルト塩類が
好ましい。反応触媒の配合量は特に限定されない
が、例えば有機コバルト塩類を反応触媒として用
いる場合には、ワニス(後述)の所望するゲルタ
イムに応じて、式()のポリ芳香族シアネート
の重量に対するコバルトイオンの重量比で10〜
700ppm程度の範囲で配合される。
そして上記式()のポリ芳香族シアネート、
式()及び式()の難燃剤、及び反応触媒等
を有機溶剤に溶解することによつて、ワニスの調
製する。有機溶剤としては式()のポリ芳香族
シアネートや式()及び式()の難燃剤を溶
解し反応に悪い影響を与えないものであれば芳香
族炭化水素、アルコール、ケトンなど特に限定さ
れない。例えばトルエン、アセトン、メチルエチ
ルケトン、ジメチルホルムアミド、メチルセロソ
ルブなどを一種もしくは二種以上を混合して用い
ることができる。ワニスの濃度は固形分が50〜70
重量%になるように調整するのが一般的である。
しかしてプリプレグを調製するにあたつては、
基材としては特に限定されるものではないが、ガ
ラス繊維の織布あるいは不織布を使用するのが一
般的であり、この基材にワニスを含浸させて加熱
乾燥する。基材へのワニスの含浸量は、基材に対
する固形分(式()の化合物と式()、式
()の化合物)の比率が45重量%以上になるよ
うに設定するのが好ましい。樹脂分の含有量によ
つて誘電率の水準に影響が出るものであり、基材
をEガラスの布で形成した場合は45重量%以上の
含浸で誘電率4.0以下を達成することができ、ま
た基材をDガラスの布で形成した場合は45重量%
以上の含浸で誘電率3.5以下を達成することがで
きる。プリプレグを調製する際の加熱乾燥条件
は、反応触媒の配合量などによつて影響される
が、例えば加熱温度が160℃の場合は加熱時間を
3〜10分間程度に設定することによつて、所望の
プリプレグのストロークゲルタイムを得るように
することができる。プリプレグのストロークゲル
タイムは成形条件等によつて異なるが、170℃で
2〜10分程度が一般的である。
そしてこのように調製したプリプレグを複数枚
重ね、さらに上下の両面もしくは片面に銅箔など
の金属箔を重ね、これを加熱加圧成形することに
よつて、プリプレグ中のポリ芳香族シアネートが
重合硬化して構成される絶縁基板の両面又は片面
に金属箔を積層接着した両面金属箔張り若しくは
片面金属箔張り積層板を作成することができる。
この積層板の金属箔をエツチング加工等して回路
形成することによつて内層プリント配線板を作成
することができ、この内層プリント配線板を複数
枚の上記プリプレグを介して複数枚重ねると共に
最外層に金属箔を重ね、これを加熱加圧成形する
ことによつて、多層のプリント配線板を作成する
ことができる。成形条件は、加熱温度を170℃〜
230℃、圧力を最高圧力で30〜40Kg/cm2程度、時
間を90〜120分程度に設定するのが一般的である。
成形後に220〜230℃程度の温度でアフターキユア
ーする場合には成形温度は170〜180℃程度で十分
である。[Formula] (R 1 is Br, CH 3 , C 2 H 5 , etc., or a combination thereof, m is an integer of 1, 2, or 3)
etc. Further, in the formula (), n is a positive number without limitation, but those currently available are mixtures where n=10 to 20. Other values of n can also be used. The flame retardant effect of formula () or formula () combination of flame retardants is determined according to the amount of Br, and in order to obtain flame retardancy at the level of UL standard 94V-0,
The flame retardant of the formula () is added so that the Br content is 5 to 10% by weight based on the total amount of the polyaromatic cyanate of the formula (), the flame retardant of the formula (), and the flame retardant of the formula (). It is preferable to mix the flame retardants of formula () so that the ratio is 5 to 10% by weight. The flame retardant of formula () has a Br content of 5 to 10
In order to blend the flame retardant of formula () so that the Br content is 5 to 10% by weight, the compound should be blended in an amount of 10 to 20% by weight. The blending amount of each is generally set at 10 to 20% by weight. If the amount of flame retardant is too large, problems may arise in heat resistance, so the upper limit is preferably set to the above value. As the reaction catalyst for polymerizing the polyaromatic cyanate of formula (), organic metal salts such as imidazoles, tertiary amines, organic cobalt salts such as cobalt naphthenate and cobalt octylate can be used, and in particular Organic cobalt salts are preferred. Although the amount of the reaction catalyst is not particularly limited, for example, when organic cobalt salts are used as the reaction catalyst, the amount of cobalt ions relative to the weight of the polyaromatic cyanate of formula () may be adjusted depending on the desired gel time of the varnish (described later). Weight ratio: 10~
It is blended in a range of about 700ppm. and polyaromatic cyanate of the above formula (),
A varnish is prepared by dissolving formula (), a flame retardant of formula (), a reaction catalyst, etc. in an organic solvent. The organic solvent is not particularly limited as long as it dissolves the polyaromatic cyanate of formula () and the flame retardant of formula () and formula () and does not adversely affect the reaction, such as aromatic hydrocarbons, alcohols, and ketones. For example, toluene, acetone, methyl ethyl ketone, dimethyl formamide, methyl cellosolve, etc. can be used alone or in combination of two or more. The concentration of varnish is 50 to 70 solids.
It is common to adjust it so that it is % by weight. However, when preparing prepreg,
The base material is not particularly limited, but woven or nonwoven glass fiber fabric is generally used, and this base material is impregnated with varnish and dried by heating. The amount of varnish impregnated into the base material is preferably set so that the ratio of solid content (compound of formula () to compound of formula (), formula ()) to the base material is 45% by weight or more. The dielectric constant level is affected by the resin content, and when the base material is made of E glass cloth, a dielectric constant of 4.0 or less can be achieved with impregnation of 45% by weight or more. In addition, when the base material is made of D glass cloth, it is 45% by weight.
With the above impregnation, a dielectric constant of 3.5 or less can be achieved. The heating drying conditions when preparing prepreg are influenced by the amount of reaction catalyst blended, etc., but for example, if the heating temperature is 160 ° C., by setting the heating time to about 3 to 10 minutes, It is possible to obtain a desired prepreg stroke gel time. The stroke gel time of prepreg varies depending on molding conditions, etc., but is generally about 2 to 10 minutes at 170°C. Then, the polyaromatic cyanate in the prepreg is polymerized and hardened by layering multiple sheets of prepreg prepared in this way, then layering metal foil such as copper foil on both or one side of the top and bottom, and molding this under heat and pressure. A double-sided metal foil-clad laminate or a single-sided metal foil-clad laminate can be produced by laminating and bonding metal foil on both sides or one side of an insulating substrate configured by the above method.
An inner layer printed wiring board can be created by etching the metal foil of this laminate to form a circuit, and by stacking a plurality of inner layer printed wiring boards via a plurality of the above prepregs, the outermost layer A multilayer printed wiring board can be created by overlaying metal foil on the substrate and molding it under heat and pressure. Molding conditions include heating temperature of 170℃~
Generally, the temperature is set at 230°C, the maximum pressure is about 30 to 40 kg/cm 2 , and the time is about 90 to 120 minutes.
When after-curing at a temperature of about 220 to 230°C after molding, a molding temperature of about 170 to 180°C is sufficient.
以下本発明を実施例によつて詳述する。
実施例 1
次式に示されるポリ芳香族シアネート(ダウケ
ミカル社製XU−71787)を75重量部、
式()においてR及びR′が(b)式で、nが10
〜20の混合体の難燃剤(臭素化カーボネートオリ
ゴマー;グレートレーク社製BC−58)を12.5重
量部、式()においてn=0の難燃剤(テトラ
ブロモビスフエノールA:TBBA)を12.5重量部
それぞれ採り(全Br含有率は13重量%になる)、
これらをメチルエチルケトンとジメチルホルムア
ミドの1:1混合溶媒に固形分が60重量%になる
ように攪拌溶解し、これに反応触媒としてナフテ
ン酸コバルトをポリ芳香族シアネートに対するコ
バルトイオンの重量比で150ppm添加して、ワニ
スを調製した。
このワニスを2116タイプEガラス布基材(日東
紡績社製116E)に固形分含量(ポリ芳香族シア
ネートと難燃剤)が45重量%になるように含浸
し、150℃、4分間の条件で加熱乾燥することに
よつてプリプレグを調製した。
次にこのプリプレグを4枚重ねると共にその上
下両側に70μ厚の両面粗面化銅箔を重ね、成形温
度170℃、成形圧力40Kg/cm2、成形時間90分の条
件で積層成形をおこない、さらに成形後に電気オ
ーブンにて230℃、2時間の条件でアフターキユ
アーして、厚み0.4mmの内層プリント配線板用の
両面銅張り積層板を得た。
実施例 2
式()の難燃剤としてn=1のもの(テトラ
ブロモビスフエノールAビス(2−ハイドロキシ
ルエーテル);グレートレイク社製)を用いるよ
うにした他は、実施例1と同様にしてワニスを調
製すると共にプリプレグを作成し、さらに実施例
1と同様にして積層成形及びアフターキユアーを
おこなつて、厚み0.4mmの内層プリント配線板用
の両面銅張り積層板を得た。
実施例 3
式()の難燃剤としてn=2のもの(第一工
業製薬社製GX−6107)を用いるようにした他
は、実施例1と同様にしてワニスを調製すると共
にプリプレグを作成し、さらに実施例1と同様に
して積層成形及びアフターキユアーをおこなつ
て、厚み0.4mmの内層プリント配線板用の両面銅
張り積層板を得た。
比較例 1
ポリアミノビスマレイミド樹脂(日本ポリイミ
ド社製ケルイミド601)を固形分が60重量%にな
るようにN−メチル−2−ピロリドンに溶解して
ポリイミド樹脂ワニスを調製した。このワニスを
実施例と同様のEガラス布基材に樹脂含量が45重
量%になるように含浸し、実施例と同様に乾燥し
てプリプレグを作成した。次にこのプリプレグを
4枚重ねると共にその上下両側に70μ厚の両面粗
面化銅箔を重ね、実施例1と同じ条件で積層成形
をおこない、さらに電気オーブンにて200℃、2
時間の条件でアフターキユアーして、厚み0.4mm
の内層プリント配線板用の両面銅張り積層板を得
た。このようにして得た両面銅張り積層板の銅箔
をエツチング処理して回路形成することによつて
内層プリント配線板を作成し、3枚の内層プリン
ト配線板をそれぞれの間に上記と同じ3枚のプリ
プレグを介して重ねると共にその上下にさらに3
枚のプリプレグを介して18μ厚の銅箔を重ね、こ
れを上記と同じ条件で積層成形し、さらに200℃、
2時間の条件でアフターキユアーすることによつ
て、厚み2.4mmの8層の回路構成を多層プリント
配線板を得た。
比較例 2
実施例で用いたポリ芳香族シアネート(ダウケ
ミカル社製XU−71787)のみを使用し(難燃剤
は使用せず)、これをメチルエチルケトンとジメ
チルホルムアミドの1:1混合溶媒に固形分が60
重量%になるように攪拌溶解し、これに反応触媒
としてナフテン酸コバルトをポリ芳香族シアネー
ト樹脂に対するコバルトイオンの重量比で
200ppm添加して、ワニスを調製した。後は実施
例と同様にしてプリプレグを作成すると共に実施
例と同様にして積層成形及びアフターキユアーを
おこなつて、厚み0.4mmの内層プリント配線板用
の両面銅張り積層板を得た。
上記のようにして得た実施例1乃至3及び比較
例1,2の積層板について、その電気的特性や熱
的特性などを測定し、その結果を次表に示す。次
表において、誘電率、誘電正接、耐熱性、オーブ
ン耐熱性はJIS C 6481に基づいて測定をおこな
つた。またガラス転移温度は粘弾性スペクトルの
チヤートから計測した。
The present invention will be explained in detail below using examples. Example 1 75 parts by weight of polyaromatic cyanate (XU-71787 manufactured by Dow Chemical Company) represented by the following formula, In formula (), R and R' are formula (b), and n is 10
12.5 parts by weight of a flame retardant mixture of ~20 (brominated carbonate oligomer; BC-58 manufactured by Great Lakes), and 12.5 parts by weight of a flame retardant (tetrabromobisphenol A: TBBA) with n = 0 in formula () (total Br content is 13% by weight),
These were stirred and dissolved in a 1:1 mixed solvent of methyl ethyl ketone and dimethyl formamide so that the solid content was 60% by weight, and to this was added cobalt naphthenate as a reaction catalyst at a weight ratio of 150 ppm of cobalt ions to polyaromatic cyanate. A varnish was prepared. This varnish was impregnated into a 2116 type E glass cloth substrate (116E manufactured by Nittobo Co., Ltd.) to a solid content (polyaromatic cyanate and flame retardant) of 45% by weight, and heated at 150°C for 4 minutes. A prepreg was prepared by drying. Next, four sheets of this prepreg were stacked together, and 70 μ thick double-sided roughened copper foil was stacked on both sides of the top and bottom, and laminated molding was performed at a molding temperature of 170°C, a molding pressure of 40 Kg/cm 2 , and a molding time of 90 minutes. After molding, the product was after-cured in an electric oven at 230° C. for 2 hours to obtain a double-sided copper-clad laminate with a thickness of 0.4 mm for inner layer printed wiring boards. Example 2 Varnish was prepared in the same manner as in Example 1, except that n=1 (tetrabromobisphenol A bis(2-hydroxyl ether); manufactured by Great Lake) was used as the flame retardant of formula (). A prepreg was prepared, and laminated molding and after-curing were performed in the same manner as in Example 1 to obtain a double-sided copper-clad laminate with a thickness of 0.4 mm for an inner layer printed wiring board. Example 3 A varnish was prepared and a prepreg was prepared in the same manner as in Example 1, except that n = 2 (GX-6107 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was used as the flame retardant of formula (). Further, lamination molding and after-curing were performed in the same manner as in Example 1 to obtain a double-sided copper-clad laminate for an inner layer printed wiring board having a thickness of 0.4 mm. Comparative Example 1 A polyimide resin varnish was prepared by dissolving polyamino bismaleimide resin (Kelimide 601 manufactured by Nippon Polyimide Co., Ltd.) in N-methyl-2-pyrrolidone so that the solid content was 60% by weight. This varnish was impregnated into the same E glass cloth base material as in the example so that the resin content was 45% by weight, and dried in the same manner as in the example to prepare a prepreg. Next, four sheets of this prepreg were stacked together, and double-sided roughened copper foil with a thickness of 70μ was stacked on both the top and bottom sides, and laminated molding was performed under the same conditions as in Example 1, and then in an electric oven at 200℃,
After curing under certain conditions, the thickness is 0.4mm.
A double-sided copper-clad laminate for inner-layer printed wiring boards was obtained. An inner layer printed wiring board was created by etching the copper foil of the double-sided copper-clad laminate thus obtained to form a circuit. It is layered with two sheets of prepreg, and three more layers are placed above and below it.
A layer of 18μ thick copper foil was layered through two sheets of prepreg, and this was laminated and molded under the same conditions as above, and further heated at 200℃.
By performing after-curing for 2 hours, a multilayer printed wiring board having an 8-layer circuit structure with a thickness of 2.4 mm was obtained. Comparative Example 2 Only the polyaromatic cyanate (XU-71787 manufactured by Dow Chemical Company) used in the example was used (no flame retardant was used), and the solid content was dissolved in a 1:1 mixed solvent of methyl ethyl ketone and dimethyl formamide. 60
% by weight, and add cobalt naphthenate as a reaction catalyst to this by weight ratio of cobalt ion to polyaromatic cyanate resin.
A varnish was prepared by adding 200 ppm. Thereafter, a prepreg was prepared in the same manner as in the example, and lamination molding and after-curing were performed in the same manner as in the example to obtain a double-sided copper-clad laminate for an inner layer printed wiring board having a thickness of 0.4 mm. The electrical properties, thermal properties, etc. of the laminates of Examples 1 to 3 and Comparative Examples 1 and 2 obtained as described above were measured, and the results are shown in the following table. In the following table, dielectric constant, dielectric loss tangent, heat resistance, and oven heat resistance were measured based on JIS C 6481. Moreover, the glass transition temperature was measured from the chart of the viscoelastic spectrum.
【表】
表の結果にみられるように、ポリ芳香族シアネ
ートを重合させた芳香族ポリトリアジン(ポリ芳
香族シアネート樹脂)で絶縁基板を形成するよう
にした各実施例のものは、ポリイミド樹脂で絶縁
基板を形成するようにした比較例1のものよりも
誘電率や誘電正接が低いことが確認されるもので
あり、またポリ芳香族シアネートに難燃剤を配合
した各実施例のものでは、難燃剤を配合しない比
較例2のHBレベルから94V−0のレベルに難燃
性が高まることが確認されると共に、しかもガラ
ス転移温度や耐熱温度のレベルも劣化されず高く
保持されていることが確認される。[Table] As seen in the results in the table, each example in which the insulating substrate was formed using aromatic polytriazine (polyaromatic cyanate resin) obtained by polymerizing polyaromatic cyanate was formed using polyimide resin. It is confirmed that the dielectric constant and dielectric loss tangent are lower than those of Comparative Example 1 in which an insulating substrate was formed, and each of the examples in which a flame retardant was blended with polyaromatic cyanate had a lower dielectric constant and dielectric loss tangent. It was confirmed that the flame retardancy increased from the HB level of Comparative Example 2, which did not contain a flame agent, to the level of 94V-0, and it was also confirmed that the glass transition temperature and heat resistance temperature levels remained high without deterioration. be done.
上述のように本発明にあつては、式()のポ
リ芳香族シアネートに式()及び式()の難
燃剤を併用して配合することによつて積層板を製
造するようにしたので、ポリ芳香族シアネートの
重合体の低い誘電率や誘電正接によつて積層板の
高周波特性を高く確保することができるものであ
り、しかも難燃剤の配合によつて積層板の難燃グ
レードを高めることができると共に、また耐熱性
のレベルを高く保持することができるものであ
る。
As mentioned above, in the present invention, the laminate is manufactured by blending the polyaromatic cyanate of the formula () with the flame retardants of the formula () and the formula (). Due to the low dielectric constant and dielectric loss tangent of the polyaromatic cyanate polymer, the high frequency characteristics of the laminate can be ensured, and the flame retardant grade of the laminate can be improved by adding a flame retardant. It is possible to maintain a high level of heat resistance.
Claims (1)
に、 (式中Arは芳香族。BはC7〜20の多環式脂肪族
基。Dは各々独立に活性水素を含まない置換基。
q,r,sは各々独立に0,1,2又は3の整数
であり、ただしq,r,sの合計は2より大きい
か又は2に等しい。tは各々独立に0から4まで
の整数。xは0〜5までの数) 次式()に示される難燃剤と、 (式中R及びR′は活性水素を含まない芳香族
又は臭素化芳香族の置換基。nは正数) 次式()に示される難燃剤と、 (式中nは0,1又は2の整数) ポリ芳香族シアネートの反応触媒とを配合して
ワニスを調製すると共にこのワニスを基材に含浸
してプリプレグを作成し、このプリプレグを積層
成形することを特徴とする積層板の製造方法。[Claims] A polyaromatic cyanate represented by the primary formula (), (In the formula, Ar is aromatic. B is a C7-20 polycyclic aliphatic group. D is each independently a substituent containing no active hydrogen.
q, r, and s are each independently an integer of 0, 1, 2, or 3, provided that the sum of q, r, and s is greater than or equal to 2. t is an integer from 0 to 4, each independently. x is a number from 0 to 5) A flame retardant represented by the following formula (), (In the formula, R and R' are aromatic or brominated aromatic substituents that do not contain active hydrogen. n is a positive number) A flame retardant represented by the following formula (), (In the formula, n is an integer of 0, 1 or 2) A varnish is prepared by blending with a polyaromatic cyanate reaction catalyst, and a base material is impregnated with this varnish to create a prepreg, and this prepreg is laminated and molded. A method for manufacturing a laminate, characterized by:
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP12865788A JPH01299836A (en) | 1988-05-26 | 1988-05-26 | Production of laminate |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP12865788A JPH01299836A (en) | 1988-05-26 | 1988-05-26 | Production of laminate |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH01299836A JPH01299836A (en) | 1989-12-04 |
JPH0424372B2 true JPH0424372B2 (en) | 1992-04-24 |
Family
ID=14990228
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP12865788A Granted JPH01299836A (en) | 1988-05-26 | 1988-05-26 | Production of laminate |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH01299836A (en) |
-
1988
- 1988-05-26 JP JP12865788A patent/JPH01299836A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPH01299836A (en) | 1989-12-04 |
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