JP2000133900A - Pre-preg for printed wiring board - Google Patents
Pre-preg for printed wiring boardInfo
- Publication number
- JP2000133900A JP2000133900A JP30694698A JP30694698A JP2000133900A JP 2000133900 A JP2000133900 A JP 2000133900A JP 30694698 A JP30694698 A JP 30694698A JP 30694698 A JP30694698 A JP 30694698A JP 2000133900 A JP2000133900 A JP 2000133900A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- prepreg
- printed wiring
- wiring board
- weight
- 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
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、成形性、耐熱性な
どに優れた、印刷配線板用のプリプレグに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a prepreg for a printed wiring board which is excellent in moldability, heat resistance and the like.
【０００２】[0002]
【従来の技術】従来、電子機器に使用される積層板は、
ガラス布などの基材をエポキシ樹脂組成物からなるワニ
スに含浸し、次いで乾燥して得られるプリプレグを複数
枚積層し、さらにその上下に銅箔を配置し、次いで成形
して製造されている。この用途に使用されるエポキシ樹
脂は数平均分子量が１０００以下の低分子量エポキシ樹
脂が使用されている。しかし数平均分子量が１０００以
下の低分子量エポキシ樹脂を用いた場合には、樹脂の最
低溶融粘度が低いため、Ｂステージ化時の加熱温度、加
熱時間などの条件を特定範囲内に厳密に制御する必要が
あり、また、Ｂステージ化後の樹脂の溶融粘度も低いた
め、良好に成形できる範囲が限定され積層板や多層板を
製造する際の成形時の圧力及び昇温速度などを厳密に設
定する必要があった。また、この問題を解決するために
市販のフェノキシ樹脂に代表されるような高分子量エポ
キシ樹脂を配合し、樹脂の最低溶融粘度を高くすること
により成形時の圧力、昇温速度などの条件を緩やかに設
定することも可能になるが、この場合には、配合する高
分子量エポキシ樹脂の反応性は通常用いられている低分
子量エポキシ樹脂と比較して、著しく低いため、このプ
リプレグを用いて成形した積層板は、耐熱性に劣るもの
であった。2. Description of the Related Art Conventionally, laminated boards used in electronic equipment are:
It is manufactured by impregnating a base material such as a glass cloth with a varnish made of an epoxy resin composition, then laminating a plurality of prepregs obtained by drying, further arranging copper foil above and below, and then molding. As the epoxy resin used for this purpose, a low molecular weight epoxy resin having a number average molecular weight of 1,000 or less is used. However, when a low molecular weight epoxy resin having a number average molecular weight of 1000 or less is used, since the minimum melt viscosity of the resin is low, conditions such as a heating temperature and a heating time at the time of the B stage are strictly controlled within a specific range. In addition, since the melt viscosity of the resin after B-stage conversion is low, the range in which molding can be performed well is limited, and the pressure and temperature rise rate during molding when manufacturing laminated boards and multilayer boards are strictly set. I needed to. Also, in order to solve this problem, a high-molecular-weight epoxy resin typified by a commercially available phenoxy resin is blended, and by increasing the minimum melt viscosity of the resin, the conditions such as pressure during molding and a rate of temperature rise are moderated. However, in this case, the reactivity of the high-molecular-weight epoxy resin to be compounded is significantly lower than that of a low-molecular-weight epoxy resin that is usually used, and thus, molding is performed using this prepreg. The laminate had poor heat resistance.
【０００３】[0003]
【発明が解決しようとする課題】本発明は印刷配線板の
高密度化、高性能化を進めるのに際して必要とされる成
形性、耐熱性、電気特性などに優れ、積層板や多層板の
板厚の均一化に優れた印刷配線板用プリプレグを提供す
ることを目的とする。DISCLOSURE OF THE INVENTION The present invention has excellent moldability, heat resistance, electrical characteristics, etc. required for increasing the density and performance of a printed wiring board, and is a sheet of a laminated board or a multilayer board. An object of the present invention is to provide a prepreg for a printed wiring board excellent in uniformity of thickness.
【０００４】[0004]
【課題を解決するための手段】本発明は、エポキシ樹脂
を用いる印刷配線板用プリプレグにおいて、数平均分子
量が１０００以上３０００未満の多官能エポキシ樹脂を
用いたワニスを厚さ０．０２〜０．４０ｍｍのガラス基
材に含浸し、乾燥温度６０〜２００℃で１〜３０分間乾
燥することを特徴とする印刷配線板用プリプレグであ
る。本発明者らは、前記課題を解決するために鋭意検討
を行った結果、印刷配線板用プリプレグに用いるエポキ
シ樹脂として、数平均分子量が１０００以上の多官能エ
ポキシ樹脂を用い、成形時における樹脂の流動性の最適
化を図り、成形時の昇温速度、成形圧力の設定範囲幅を
広げることを試みた。すなわち、従来の低分子量エポキ
シ樹脂から製造するプリプレグはＢステージ状態におけ
る樹脂の最低溶融粘度が著しく低くなる傾向があり、こ
の最低溶触粘度から、内層板の導体回路をボイド等が無
く埋めることができる回路充填性が良好で、積層板や多
層板の周辺部の板厚が薄くなることもないような成形幅
を有するプリプレグを得るためには、Ｂステージ化にお
ける加熱乾燥温度、加熱乾燥時間などを厳密に設定し、
一定の成形条件で成形できるようにする必要がある。こ
の加熱乾燥温度、加熱乾燥時間が設定範囲から若干異な
った場合には、Ｂステージ状態での最低溶融粘度及びそ
の後の加熱加圧による多層板成形時の硬化性が異なり、
良好な回路充填性、板厚精度を有する多層板を得ること
は困難である。一方、前述したように、ワニスに用いる
エポキシ樹脂組成物中に、市販のフェノキシ樹脂に代表
されるような高分子量エポキシ樹脂を配合した場合に
は、その配合量により樹脂の最低溶融粘度の制御が容易
になるが、配合する高分子量エポキシ樹脂の反応性は通
常用いられている低分子量エポキシ樹脂と比較して、著
しく低いため、このプリプレグを用いて成形した積層板
の耐熱性は低下することがあった。そこで本発明では、
エポキシ樹脂組成物に適用するエポキシ樹脂について鋭
意検討した結果、数平均分子量が１０００以上３０００
未満の多官能エポキシ樹脂を主成分とし、このエポキシ
樹脂を多官能のフェノールノボラック類またはジシアン
ジアミドに代表されるようなアミン類で硬化するのが有
効であることを見出した。さらに、本発明における印刷
配線板用プリプレグの樹脂組成物としては、必要に応じ
て、難燃剤、硬化促進剤、溶剤、その他添加剤などを配
合することができる。なお、エポキシ樹脂に対する硬化
剤の配合量は、フェノールノボラック類を硬化剤として
用いる場合には、エポキシ基の数に対するフェノール性
水酸基の当量として、０．５当量から２．０当量が好ま
しく、０．７当量から１．５当量が特に好ましい。また
硬化剤の一例としてジシアンジアミドを用いる場合に
は、エポキシ樹脂１００重量部に対するジシアンジアミ
ドの配合量として、１重量部から１０重量部が好まし
く、２重量部から５重量部がさらに好ましい。また、エ
ポキシ樹脂組成物中に難燃成分を配合する方法として
は、難燃成分としてハロゲン化エポキシ樹脂を配合する
方法、ハロゲン化フェノールノボラック類を配合する方
法などが挙げられる。すなわち、本発明における多官能
エポキシ樹脂と、従来から用いられている臭素化エポキ
シ樹脂を併用する方法、また、難燃剤としてテトラブロ
モビスフェノールＡを配合する方法などが挙げられる。
さらに本発明において用いるエポキシ樹脂組成物は必要
に応じて溶剤類を添加することにより、任意の固形分濃
度およびワニス粘度に調整することができる。According to the present invention, there is provided a prepreg for a printed wiring board using an epoxy resin, wherein a varnish using a polyfunctional epoxy resin having a number-average molecular weight of 1,000 or more and less than 3,000 has a thickness of 0.02-0. A prepreg for a printed wiring board, wherein a prepreg for a printed wiring board is impregnated into a 40 mm glass substrate and dried at a drying temperature of 60 to 200 ° C. for 1 to 30 minutes. The present inventors have conducted intensive studies to solve the above-described problems, and as a result, using a polyfunctional epoxy resin having a number average molecular weight of 1,000 or more as an epoxy resin used for a prepreg for a printed wiring board, We tried to optimize the fluidity and widen the setting range of the heating rate and molding pressure during molding. That is, the prepreg produced from the conventional low-molecular-weight epoxy resin has a tendency that the minimum melt viscosity of the resin in the B-stage state tends to be extremely low. From this minimum contact viscosity, the conductor circuit of the inner layer plate can be filled without voids or the like. In order to obtain a prepreg having a good circuit filling property and a molding width such that the thickness of the peripheral portion of the laminated board or the multilayer board does not become thin, the heating drying temperature, the heating drying time, etc. in the B stage are required. Strictly set,
It is necessary to be able to mold under certain molding conditions. When the heating and drying temperature and the heating and drying time are slightly different from the set ranges, the minimum melt viscosity in the B stage state and the curability at the time of forming a multilayer board by subsequent heating and pressing are different,
It is difficult to obtain a multilayer board having good circuit filling properties and board thickness accuracy. On the other hand, as described above, when a high molecular weight epoxy resin represented by a commercially available phenoxy resin is blended in the epoxy resin composition used for the varnish, control of the minimum melt viscosity of the resin is controlled by the blending amount. Although it becomes easier, the reactivity of the high-molecular-weight epoxy resin to be compounded is significantly lower than that of the low-molecular-weight epoxy resin that is commonly used, so that the heat resistance of the laminate molded using this prepreg may decrease. there were. Therefore, in the present invention,
As a result of intensive studies on the epoxy resin applied to the epoxy resin composition, the number average molecular weight was 1000 or more and 3000 or more.
It has been found that it is effective to cure this epoxy resin with a polyfunctional phenol novolak or an amine represented by dicyandiamide as a main component. Further, the resin composition of the prepreg for a printed wiring board according to the present invention may optionally contain a flame retardant, a curing accelerator, a solvent, and other additives. When a phenol novolak is used as a curing agent, the amount of the curing agent relative to the epoxy resin is preferably from 0.5 to 2.0 equivalents, more preferably from 0.5 to 2.0 equivalents, as the equivalent of the phenolic hydroxyl group to the number of epoxy groups. 7 to 1.5 equivalents are particularly preferred. When dicyandiamide is used as an example of the curing agent, the amount of dicyandiamide relative to 100 parts by weight of the epoxy resin is preferably 1 to 10 parts by weight, more preferably 2 to 5 parts by weight. Examples of the method of blending the flame retardant component into the epoxy resin composition include a method of blending a halogenated epoxy resin as the flame retardant component, a method of blending a halogenated phenol novolak, and the like. That is, a method in which the polyfunctional epoxy resin of the present invention is used in combination with a conventionally used brominated epoxy resin, a method in which tetrabromobisphenol A is blended as a flame retardant, and the like are exemplified.
Further, the epoxy resin composition used in the present invention can be adjusted to an arbitrary solid content concentration and varnish viscosity by adding a solvent as required.
【０００５】[0005]
【発明の実施の形態】本発明では、数平均分子量が１０
００以上３０００未満の多官能エポキシ樹脂、硬化剤、
必要に応じて、難燃剤、硬化促進剤、溶剤、その他添加
剤などを配合したエポキシ樹脂組成物ワニスを厚さ０．
０２〜０．４０ｍｍのガラス基材であるガラス織布また
はガラス不織布に含浸させて、乾燥することにより印刷
配線板用プリプレグを得ることができる。本発明で用い
る数平均分子量が１０００以上３０００未満の多官能エ
ポキシ樹脂は、ビスフェノールＡノボラック型エポキシ
樹脂、クレゾールノボラック型エポキシ樹脂、フェノー
ルノボラック型エポキシ樹脂が、例示され、数平均分子
量が１０００未満では、乾燥条件によるタックが生じや
すくＢステージ化したプリプレグの成形性や取扱性が低
く、数平均分子量が３０００を超えるとＢステージ化し
たプリプレグの樹脂の最低溶融粘度が高くなる傾向にあ
り好ましくない。これらから、より好ましくは、数平均
分子量が２０００以上３０００未満の多官能エポキシ樹
脂を用いるのが良い。DETAILED DESCRIPTION OF THE INVENTION In the present invention, the number average molecular weight is 10
A polyfunctional epoxy resin of at least 00 and less than 3000, a curing agent,
If necessary, an epoxy resin composition varnish containing a flame retardant, a curing accelerator, a solvent, other additives, and the like is added to a thickness of 0.
A prepreg for a printed wiring board can be obtained by impregnating a glass woven fabric or a glass nonwoven fabric, which is a glass base material having a thickness of 02 to 0.40 mm, and drying. The polyfunctional epoxy resin having a number average molecular weight of 1,000 or more and less than 3000 used in the present invention is exemplified by bisphenol A novolak type epoxy resin, cresol novolak type epoxy resin, and phenol novolak type epoxy resin. When the number average molecular weight is less than 1,000, Tack is likely to occur due to drying conditions, and the moldability and handleability of the B-staged prepreg are low. If the number average molecular weight exceeds 3000, the minimum melt viscosity of the B-staged prepreg resin tends to increase, which is not preferable. From these, it is more preferable to use a polyfunctional epoxy resin having a number average molecular weight of 2000 or more and less than 3000.
【０００６】本発明で用いるガラス織布またはガラス不
織布の種類は特に制限はなく、厚さ０．０２ｍｍ〜０．
４０ｍｍまでの任意のものを用いる。ガラス基材の厚み
が０．０２ｍｍ未満であると、ガラス基材の強度（引張
り強さ）が著しく弱いため塗工作業が極めて困難であ
り、ガラス基材の厚みが０．４ｍｍを超えるとワニスの
含浸性が著しく低下しボイドの発生につながるため好ま
しくない。乾燥条件としては、乾燥温度６０〜２００
℃、乾燥時間１〜３０分間の任意の条件で乾燥を行う。
乾燥温度、乾燥時間が上記範囲外では、溶剤性分が多く
残存したり、硬化が進みすぎて良好なＢステージ状態に
ならないためである。得られた印刷配線板用プリプレグ
を複数枚重ね、その両面に銅箔を配し、加熱加圧成形す
ることにより、ガラス基材エポキシ樹脂積層板を得るこ
とができる。また、本発明におけるエポキシ樹脂組成物
ワニスをガラス織布に含浸し、加熱乾燥することによ
り、多層板用の印刷配線板用プリプレグを得ることがで
きる。この場合、ガラス織布の厚さは、０．１０ｍｍ程
度のものが多く用いられる。すなわち、この多層化用の
印刷配線板用プリプレグを用いると、内層板の表面に厚
さ３５μｍの導体回路が存在する場合にも良好な回路充
填性を示し、さらに、プリプレグの樹脂の流動性が良好
であるにもかかわらず、成形後の内層導体から外層銅箔
までの距離も、一定以上保たれて、良好な絶縁信頼性を
保っことができる。The type of glass woven fabric or glass nonwoven fabric used in the present invention is not particularly limited, and has a thickness of 0.02 mm to 0.2 mm.
Use any one up to 40 mm. When the thickness of the glass substrate is less than 0.02 mm, the strength (tensile strength) of the glass substrate is extremely weak, so that the coating operation is extremely difficult. When the thickness of the glass substrate exceeds 0.4 mm, the varnish is used. Is not preferred because the impregnating property of the styrene significantly decreases and leads to the generation of voids. As drying conditions, a drying temperature of 60 to 200
Drying is carried out under an optional condition of 1 ° C. and a drying time of 1 to 30 minutes.
If the drying temperature and the drying time are outside the above ranges, a large amount of the solvent component remains, or the curing proceeds excessively, so that a good B-stage state is not obtained. By stacking a plurality of the obtained prepregs for a printed wiring board, arranging copper foil on both surfaces thereof, and performing heating and press molding, a glass base epoxy resin laminate can be obtained. Further, a prepreg for a printed wiring board for a multilayer board can be obtained by impregnating a glass woven fabric with the epoxy resin composition varnish of the present invention and drying by heating. In this case, a glass woven fabric having a thickness of about 0.10 mm is often used. In other words, when the prepreg for a printed wiring board for multilayering is used, good circuit filling properties are exhibited even when a conductor circuit having a thickness of 35 μm is present on the surface of the inner layer board. Despite being good, the distance from the inner layer conductor to the outer layer copper foil after molding is maintained at a certain level or more, and good insulation reliability can be maintained.
【０００７】[0007]
【実施例】以下本発明を実施例に基づいて詳細に説明す
るが、本発明はこれに限定されるものではない。 （実施例１）数平均分子量が２４００の多官能エポキシ
樹脂（テトラブロムビスフェノールＡとビスフェノール
Ａ混合型エポキシ樹脂、エポキシ当量４２５）１００重
量部、硬化剤としてフェノールノボラック樹脂３０重量
部、硬化促進剤として２−エチル−４−メチルイミダゾ
ール０．５重量部、溶剤としてメチルエチルケトン５０
重量部を混合攪拌してエポキシ樹脂ワニスとした。この
ワニスを厚さ０．２ｍｍのガラスクロス（坪量２１０ｇ
／ｍ2）に含浸し、１６０℃の乾燥機中で、５分間乾燥
してＢステージ状態のエポキシ樹脂プリプレグとした。
この得られたエポキシ樹脂プリプレグをもみほぐして得
られた樹脂粉の溶融粘度を高化式フローテスタを用いて
１３０℃の一定条件で測定したところ、１２０Ｐａ・ｓ
であった。またこの樹脂粉の硬化時間を１７０℃の熱盤
上で測定したところ１２０秒であった。上記で得られた
エポキシ樹脂プリプレグ（印刷配線板用プリプレグ）を
５枚重ね、その両面に３５μｍの銅箔を配し、成形温度
１７０℃、成形圧力２ＭＰａで６０分間加熱加圧成形す
ることにより、銅箔付きガラスエポキシ積層板を得た。
得られたエポキシ樹脂積層板は、その積層板の板厚が均
一であり、成形時の端部からの樹脂のしみ出しも少な
く、良好に成形できることが確かめられた。銅箔の引き
剥がし強さは、常温下で、１．８ＫＮ／ｍであった。得
られたエポキシ樹脂積層板を全面エッチングしたもの
を、１２１℃、０．２ＭＰａのＰＣＴ（プレッシャーク
ッカーテスト）で４時間処理した後、２６０℃の溶融は
んだ槽に２０秒間浸漬したが、積層板のふくれなどの異
常は見られなかった。The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples. Example 1 100 parts by weight of a polyfunctional epoxy resin having a number average molecular weight of 2,400 (tetrabromobisphenol A and bisphenol A mixed epoxy resin, epoxy equivalent: 425), 30 parts by weight of a phenol novolak resin as a curing agent, and a curing accelerator 0.5 parts by weight of 2-ethyl-4-methylimidazole, methyl ethyl ketone 50 as a solvent
The parts by weight were mixed and stirred to obtain an epoxy resin varnish. This varnish was applied to a 0.2 mm thick glass cloth (basis weight 210 g).
/ M 2 ) and dried in a dryer at 160 ° C. for 5 minutes to obtain a B-stage epoxy resin prepreg.
The melt viscosity of the resin powder obtained by unraveling the obtained epoxy resin prepreg was measured under a constant condition of 130 ° C. using a Koka type flow tester.
Met. The curing time of the resin powder measured on a hot plate at 170 ° C. was 120 seconds. By stacking five epoxy resin prepregs (prepregs for printed wiring boards) obtained above, arranging 35 μm copper foil on both surfaces thereof, and molding by heating and pressing at a molding temperature of 170 ° C. and a molding pressure of 2 MPa for 60 minutes, A glass epoxy laminate with a copper foil was obtained.
It was confirmed that the obtained epoxy resin laminate had a uniform thickness, had less resin exudation from the end portion during molding, and could be molded favorably. The peel strength of the copper foil was 1.8 KN / m at room temperature. The resulting epoxy resin laminate was etched on the entire surface, treated with 121 ° C., 0.2 MPa PCT (pressure cooker test) for 4 hours, and then immersed in a 260 ° C. molten solder bath for 20 seconds. No abnormalities such as blisters were observed.
【０００８】（実施例２）数平均分子量が２４００の多
官能エポキシ樹脂（テトラブロムビスフェノールＡとビ
スフェノールＡ混合型エポキシ樹脂、エポキシ当量４２
５）１００重量部、硬化剤としてジシアンジアミドを３
重量部、硬化促進剤として２−エチル−４−メチルイミ
ダゾール０．５重量部、溶剤としてメチルエチルケトン
と３０重量部と２−メトキシエタノール３０重量部を混
合攪拌してエポキシ樹脂ワニスとした。このワニスを厚
さ０．１ｍｍのガラスクロス（坪量１０４ｇ／ｍ2）に
含浸し、１６０℃の乾燥機中で、３分間乾燥してＢステ
ージ状態のエポキシ樹脂プリプレグとした。この得られ
たエポキシ樹脂プリプレグをもみほぐして得られた樹脂
粉の溶融粘度を高化式フローテスタを用いて１３０℃の
一定条件で測定したところ、７０Ｐａ・ｓであった。ま
たこの樹脂粉の硬化時間を１７０℃の熱盤上で測定した
ところ１６０秒であった。厚さ０．４ｍｍでその両面に
３５μｍの銅箔を有する銅張積層板に回路加工を施した
内層板の両面に、得られたエポキシ樹脂プリプレグを１
枚づつ重ね、その両面に３５μｍの銅箔を配し、成形温
度１７０℃、成形圧力２ＭＰａで６０分間加熱加圧成形
することにより、ガラスエポキシ４層板を得た。得られ
たガラスエポキシ４層板は、板厚が均一であり、成形時
の端部からの樹脂のしみ出しも少なく、良好に成形でき
ることが確かめられた。外層銅箔の引き剥がし強さは、
常温下で、１．８ＫＮ／ｍであった。得られたガラスエ
ポキシ４層板の内層回路と外層回路との間の距離は、４
層板の端部及び中心部でいずれも９０μｍの厚みを示
し、絶縁性は良好であった。また、得られたガラスエポ
キシ４層板を全面エッチングしたものを、沸騰水中で４
時間処理した後、２６０℃の溶融はんだ槽に２０秒間浸
漬したが、基板のふくれなどの異常は見られなかった。(Example 2) A polyfunctional epoxy resin having a number average molecular weight of 2400 (an epoxy resin mixed with tetrabromobisphenol A and bisphenol A, epoxy equivalent of 42)
5) 100 parts by weight, 3 parts of dicyandiamide as a curing agent
Parts by weight, 0.5 parts by weight of 2-ethyl-4-methylimidazole as a curing accelerator, 30 parts by weight of methyl ethyl ketone as a solvent, and 30 parts by weight of 2-methoxyethanol were mixed and stirred to obtain an epoxy resin varnish. This varnish was impregnated into a glass cloth (basis weight: 104 g / m 2 ) having a thickness of 0.1 mm, and dried in a dryer at 160 ° C. for 3 minutes to obtain a B-stage epoxy resin prepreg. The melt viscosity of the resin powder obtained by unraveling the obtained epoxy resin prepreg was measured under a constant condition of 130 ° C. using a Koka type flow tester and found to be 70 Pa · s. The curing time of the resin powder measured on a hot plate at 170 ° C. was 160 seconds. The obtained epoxy resin prepreg was placed on both sides of an inner layer board obtained by performing circuit processing on a copper-clad laminate having a thickness of 0.4 mm and a copper foil of 35 μm on both sides thereof.
The sheets were stacked one by one, and a copper foil of 35 μm was placed on both sides thereof, and heated and pressed at a molding temperature of 170 ° C. and a molding pressure of 2 MPa for 60 minutes to obtain a glass epoxy four-layer plate. It was confirmed that the obtained glass epoxy four-layer plate had a uniform plate thickness, had less resin exudation from the end portion during molding, and could be molded favorably. The peel strength of the outer copper foil is
At room temperature, it was 1.8 KN / m. The distance between the inner layer circuit and the outer layer circuit of the obtained glass epoxy four-layer board is 4
Both the edge and the center of the layer plate showed a thickness of 90 μm, and the insulation was good. Further, the obtained glass epoxy four-layer plate was etched on the entire surface, and was then dried in boiling water.
After the time treatment, the substrate was immersed in a molten solder bath at 260 ° C. for 20 seconds, but no abnormality such as blistering of the substrate was observed.
【０００９】（実施例３）数平均分子量が２２００の多
官能エポキシ樹脂（３官能型エポキシ樹脂、ＶＧ３１０
１（三井化学株式会社商品名）にテトラブロムビスフェ
ノールＡとビスフェノールＡ型エポキシ樹脂共重合体付
加物、エポキシ当量４７５）１００重量部、硬化剤とし
てジシアンジアミドを３重量部、硬化促進剤として２−
エチル−４−メチルイミダゾール０．５重量部、溶剤と
してメチルエチルケトン３０重量部と２−メトキシエタ
ノール３０重量部を混合攪拌してエポキシ樹脂ワニスと
した。このエポキシ樹脂ワニスを厚さ０．１ｍｍのガラ
スクロス（坪量１０４ｇ／ｍ2）に含浸し、１６０℃の
乾燥機中で、５分間乾燥してＢステージ状態のエポキシ
樹脂プリプレグとした。得られたエポキシ樹脂プリプレ
グをもみほぐして得られた樹脂粉の溶融粘度を高化式フ
ローテスタで１３０℃の一定条件で測定したところ１０
０Ｐａ・ｓであった。またこの樹脂粉の硬化時間を１７
０℃の熱盤上で測定したところ、１５０秒であった。厚
さ０．４ｍｍでその両面に３５μｍの銅箔を有する銅張
積層板に回路加工を施した内層板の両面に、得られたエ
ポキシ樹脂プリプレグを１枚づつ重ね、その両面に３５
μｍの銅箔を配し、成形時のプレス機の熱盤の昇温速度
を３℃／分に設定して１７０℃まで加熱し、その後、成
形温度１７０℃、成形圧力２ＭＰａで６０分間加熱加圧
成形することにより、ガラスエポキシ4層板を得た。得
られたエポキシ樹脂４層板は、その板厚が均一であり、
成形時の端部からの樹脂のしみだしも少なく、良好に成
形できることが確かめられた。外層銅箔引き剥がし強さ
は、常温下で、１．７ＫＮ／ｍであった。得られたガラ
スエポキシ４層板の内層回路と外層銅箔との間の距離は
４層板の端部および中心部でいずれも９０μｍの厚さを
示し、絶縁性は良好であった。また、得られたガラスエ
ポキシ樹脂４層板を全面エッチングしたものを、沸騰水
中で４時間処理した後、２６０℃の溶融はんだ槽に２０
秒間浸漬したが、基板のふくれなどの異常は見られなか
った。(Example 3) A polyfunctional epoxy resin having a number average molecular weight of 2200 (trifunctional epoxy resin, VG310
1 (trade name of Mitsui Chemicals, Inc.), 100 parts by weight of an adduct of tetrabromobisphenol A and a bisphenol A-type epoxy resin copolymer, epoxy equivalent 475), 3 parts by weight of dicyandiamide as a curing agent, and 2-parts as a curing accelerator
0.5 parts by weight of ethyl-4-methylimidazole, 30 parts by weight of methyl ethyl ketone and 30 parts by weight of 2-methoxyethanol as a solvent were mixed and stirred to obtain an epoxy resin varnish. This epoxy resin varnish was impregnated into a glass cloth (basis weight: 104 g / m 2 ) having a thickness of 0.1 mm, and dried in a dryer at 160 ° C. for 5 minutes to obtain a B-stage epoxy resin prepreg. The melt viscosity of the resin powder obtained by unraveling the obtained epoxy resin prepreg was measured under a constant condition of 130 ° C. with a Koka type flow tester.
It was 0 Pa · s. Also, the curing time of this resin powder is 17
It was 150 seconds when measured on a hot plate at 0 ° C. The obtained epoxy resin prepregs are laminated one by one on both sides of an inner layer board obtained by performing circuit processing on a copper-clad laminate having a thickness of 0.4 mm and a copper foil of 35 μm on both sides thereof.
A copper foil of μm is arranged, and the heating rate of the hot platen of the pressing machine at the time of molding is set to 3 ° C./min and heated to 170 ° C., and then heated at a molding temperature of 170 ° C. and a molding pressure of 2 MPa for 60 minutes. By pressing, a glass epoxy four-layer plate was obtained. The resulting epoxy resin four-layer plate has a uniform plate thickness,
It was confirmed that the resin did not exude from the end portion during molding, and that molding was possible. The peel strength of the outer layer copper foil was 1.7 KN / m at room temperature. The distance between the inner layer circuit and the outer layer copper foil of the obtained glass epoxy four-layer plate was 90 μm at both the end and the center of the four-layer plate, and the insulation was good. Further, the obtained glass epoxy resin four-layer plate was entirely etched and treated in boiling water for 4 hours, and then placed in a 260 ° C. molten solder bath.
After immersion for 2 seconds, no abnormality such as blistering of the substrate was observed.
【００１０】（実施例４）実施例３におけるガラスエポ
キシ４層板成形時のプレス機の熱盤昇温速度を１０℃／
分に設定した以外は実施例３と同様な方法でガラスエポ
キシ４層板の成形を行った。その結果、得られたガラス
エポキシ４層板は、その板厚が均一であり、成形時の端
部からの樹脂のしみだしも少なく、良好に成形できるこ
とが確かめられた。外層銅箔引き剥がし強さは、常温下
で、１．７ＫＮ／ｍであった。得られたガラスエポキシ
４層板の内層回路と外層銅箔との間の距離は４層板の端
部および中心部でいずれも９０μｍの厚さを示し、絶縁
性は良好であった。得られたガラスエポキシ４層板を全
面エッチングしたものを、沸騰水中で４時間処理した
後、２６０℃の溶融はんだ槽に２０秒間浸漬したが、基
板のふくれなどの異常は見られなかった。(Embodiment 4) The temperature rise rate of the hot plate of the press machine at the time of forming the glass epoxy four-layer plate in the embodiment 3 was 10 ° C. /
A four-layer glass epoxy plate was formed in the same manner as in Example 3 except that the time was set to minutes. As a result, it was confirmed that the obtained four-layer glass epoxy plate had a uniform thickness, had little resin exudation from the end portion during molding, and could be molded favorably. The peel strength of the outer layer copper foil was 1.7 KN / m at room temperature. The distance between the inner layer circuit and the outer layer copper foil of the obtained glass epoxy four-layer plate was 90 μm at both the end and the center of the four-layer plate, and the insulation was good. After the obtained glass epoxy four-layer plate was entirely etched and treated in boiling water for 4 hours, it was immersed in a molten solder bath at 260 ° C. for 20 seconds, but no abnormality such as blistering of the substrate was observed.
【００１１】以上の実施例に示したように、本発明によ
り得られた印刷配線板用プリプレグは、良好な耐熱性、
銅箔接着性、絶縁性を示し、また、多層板成形時に内層
導体と外層銅箔との距離を均一に保つことにより、絶縁
信頼性の向上につながる。さらに、実施例中に示したよ
うに、多層板成形時のプレス機の熱盤の昇温速度によら
ず、広い成形幅を示しているということは、生産性の向
上にもつながり、非常に有用である。次に、上記実施例
に対する比較例を示す。As shown in the above examples, the prepreg for a printed wiring board obtained by the present invention has good heat resistance,
By exhibiting copper foil adhesion and insulation properties, and maintaining uniform distance between the inner layer conductor and the outer layer copper foil at the time of forming a multilayer board, insulation reliability is improved. Further, as shown in the examples, regardless of the heating rate of the hot plate of the press machine during the formation of the multilayer board, showing a wide forming width leads to an improvement in productivity, and very Useful. Next, a comparative example with respect to the above embodiment will be described.
【００１２】（比較例１）数平均分子量が３４０の二官
能エポキシ樹脂（ビスフェノールＡ型エポキシ樹脂、エ
ポキシ当量１７０）１００重量部、硬化剤としてフェノ
ールノボラック３０重量部、硬化促進剤として２−エチ
ル−４−メチルイミダゾール０．５重量部、溶剤として
メチルエチルケトン５０重量部を混合攪拌してエポキシ
樹脂ワニスとした。このワニスを厚さ０．２ｍｍのガラ
スクロス（坪量２１０ｇ／ｍ2）に含浸し、１６０℃の
乾燥機中で、５分間乾燥してＢステージ状態のエポキシ
樹脂プリプレグとした。得られたエポキシ樹脂プリプレ
グから樹脂粉の溶融粘度を、高化式フローテスタで１３
０℃一定の条件で測定したところ、２０Ｐａ・ｓであっ
た。またこの樹脂粉の硬化時間を１７０℃の熱盤上で測
定したところ、１００秒であった。得られたエポキシ樹
脂プリプレグを５枚重ねその両面に３５μｍの銅箔を配
し、成形温度１７０℃、成形圧力２ＭＰａで６０分間加
熱加圧成形することにより、銅箔付きガラスエポキシ積
層板を得ることを試みた。しかし、成形時の樹脂の流動
が非常に大きく、厚さが均一な積層板は得られなかっ
た。Comparative Example 1 100 parts by weight of a bifunctional epoxy resin having a number average molecular weight of 340 (bisphenol A type epoxy resin, epoxy equivalent 170), 30 parts by weight of phenol novolak as a curing agent, and 2-ethyl- as a curing accelerator 0.5 parts by weight of 4-methylimidazole and 50 parts by weight of methyl ethyl ketone as a solvent were mixed and stirred to obtain an epoxy resin varnish. This varnish was impregnated into a glass cloth (basis weight 210 g / m 2 ) having a thickness of 0.2 mm, and dried in a dryer at 160 ° C. for 5 minutes to obtain a B-stage epoxy resin prepreg. The melt viscosity of the resin powder from the obtained epoxy resin prepreg was measured using a Koka type flow tester.
It was 20 Pa · s when measured under a constant condition of 0 ° C. When the curing time of the resin powder was measured on a hot plate at 170 ° C., it was 100 seconds. Five pieces of the obtained epoxy resin prepregs are stacked, 35 μm copper foil is arranged on both sides thereof, and a glass epoxy laminate with a copper foil is obtained by heating and pressing at a molding temperature of 170 ° C. and a molding pressure of 2 MPa for 60 minutes. Tried. However, the flow of the resin at the time of molding was very large, and a laminate having a uniform thickness could not be obtained.
【００１３】（比較例２）数平均分子量が３４０の二官
能エポキシ樹脂（ビスフェノールＡ型エポキシ樹脂、エ
ポキシ当量１７０）重量部、硬化剤としてジシアンジア
ミドを３重量部、硬化促進剤として２−エチル−４−メ
チルイミダゾール０．５重量部、溶剤としてメチルエチ
ルケトン３０重量部と２−メトキシエタノ−ル３０重量
部を混合攪拌してエポキシ樹脂ワニスとした。このワニ
スを厚さ０．１ｍｍのガラスクロスに含浸し、１６０℃
の乾燥機中で、３分間乾燥してＢステージ状態のエポキ
シ樹脂プリプレグとした。得られたエポキシ樹脂プリプ
レグから樹脂粉の溶融粘度を、高化式フローテスタで１
３０℃一定の条件で測定したところ、１０Ｐａ・ｓであ
った。またこの樹脂粉の硬化時間を１７０℃の熱盤上で
測定したところ、１４０秒であった。厚さ０．４ｍｍで
その両面に３５μｍの銅箔を有する銅張積層板に回路加
工を施した内層板の両面に、得られたエポキシ樹脂プリ
プレグを１枚づつ重ね、その両面に３５μｍの銅箔を配
し、成形温度１７０℃、成形圧力２ＭＰａで６０分加熱
加圧成形したが、樹脂の流動性が大きく良好な４層板は
成形できなかった。Comparative Example 2 A bifunctional epoxy resin having a number average molecular weight of 340 (bisphenol A type epoxy resin, epoxy equivalent 170) parts by weight, dicyandiamide 3 parts by weight as a curing agent, and 2-ethyl-4 as a curing accelerator 0.5 parts by weight of methyl imidazole, 30 parts by weight of methyl ethyl ketone and 30 parts by weight of 2-methoxyethanol as a solvent were mixed and stirred to obtain an epoxy resin varnish. This varnish is impregnated into a glass cloth having a thickness of 0.1 mm,
Was dried in a dryer for 3 minutes to obtain a B-stage epoxy resin prepreg. From the obtained epoxy resin prepreg, measure the melt viscosity of the resin powder with a Koka type flow tester.
It was 10 Pa · s when measured under a constant condition of 30 ° C. When the curing time of the resin powder was measured on a hot plate at 170 ° C., it was 140 seconds. The obtained epoxy resin prepreg is laminated one by one on both sides of an inner layer board obtained by performing circuit processing on a copper-clad laminate having a thickness of 0.4 mm and having 35 μm of copper foil on both sides thereof, and a 35 μm copper foil on both sides thereof Was heated and pressed at a molding temperature of 170 ° C. and a molding pressure of 2 MPa for 60 minutes, but a good four-layer plate with a large flowability of the resin could not be formed.
【００１４】（比較例３）数平均分子量が３４０の多官
能エポキシ樹脂（ビスフェノールＡ型エポキシ樹脂、エ
ポキシ当量１７０）１００重量部、硬化剤としてジシア
ンジアミド３重量部、硬化促進剤として２−エチル−４
−メチルイミダゾール０．５重量部、溶剤としてメチル
エチルケトン３０重量部と２−メトキシエタノ−ル３０
重量部を混合攪拌してエポキシ樹脂ワニスとした。この
ワニスを厚さ０．１ｍｍのガラスクロス（坪量１０４ｇ
／ｍ2）に含浸し、１６０℃の乾燥機中で、５分間乾燥
してＢステージ状態のエポキシ樹脂プリプレグとした。
得られたエポキシ樹脂プリプレグから得られる樹脂粉の
溶融粘度を、高化式フローテスタで１３０℃一定の条件
で測定したところ１０Ｐａ・ｓであった。またこの樹脂
粉の硬化時間を１７０℃の熱盤上で測定したところ、１
００秒であった。厚さ０．４ｍｍでその両面に３５μｍ
の銅箔を有する銅張積層板に回路加工を施した内層板の
両面に、得られたエポキシ樹脂プリプレグを１枚づつ重
ね、その両面に３５μｍの銅箔を配し、成形時のプレス
機の熱盤の昇温速度を３℃／分に設定して１７０℃まで
加熱し、その後、成形温度１７０℃、成形圧力２ＭＰａ
で６０分間加熱加圧成形することにより、ガラスエポキ
シ４層板を得ることができた。しかし、４層板成形時の
プレス機の熱盤昇温速度を５℃／分にした場合には、樹
脂の流動が大きすぎて板厚精度の良好な４層板は得られ
なかった。Comparative Example 3 100 parts by weight of a polyfunctional epoxy resin having a number average molecular weight of 340 (bisphenol A type epoxy resin, epoxy equivalent 170), 3 parts by weight of dicyandiamide as a curing agent, and 2-ethyl-4 as a curing accelerator
0.5 parts by weight of methyl imidazole, 30 parts by weight of methyl ethyl ketone as a solvent and 30 parts of 2-methoxyethanol 30
The parts by weight were mixed and stirred to obtain an epoxy resin varnish. This varnish is applied to a glass cloth (basis weight 104 g) having a thickness of 0.1 mm.
/ M 2 ) and dried in a dryer at 160 ° C. for 5 minutes to obtain a B-stage epoxy resin prepreg.
The melt viscosity of the resin powder obtained from the obtained epoxy resin prepreg was measured with a Koka type flow tester at a constant temperature of 130 ° C. and found to be 10 Pa · s. The curing time of this resin powder was measured on a hot plate at 170 ° C.
00 seconds. 0.4mm thick and 35μm on both sides
The obtained epoxy resin prepreg is laminated one by one on both sides of the inner layer board obtained by performing circuit processing on the copper-clad laminate having the copper foil, and 35 μm copper foil is arranged on both sides thereof. The heating rate of the hot platen was set at 3 ° C./min and heated to 170 ° C., after which the molding temperature was 170 ° C. and the molding pressure was 2 MPa.
By heating and pressing for 60 minutes, a glass epoxy four-layer plate could be obtained. However, when the heating plate heating rate of the press at the time of forming the four-layer plate was set to 5 ° C./min, the flow of the resin was too large to obtain a four-layer plate with good plate thickness accuracy.
【００１５】以上の実施例、比較例における実験方法の
詳細を以下に示す。銅箔引き剥がし強さは、オリエンテ
ック製テンシロンを用い、１０ｍｍ幅、引っ張り速度５
０ｍｍ／分で９０度方向の引き剥し強さを測定した。高
化式フローテスタは、ノズル径を０．７ｍｍとして、荷
重５ｋｇ、１３０℃一定で測定した。プリプレグ樹脂粉
の硬化時間は、１７０℃の熱盤上での樹脂の硬化時間を
測定した。各実施例に示したように、本発明における数
平均分子量が１０００から３０００の多官能エポキシ樹
脂を用いることにより、成形性が良好であり、さらに成
形幅が広いことにより生産性も良好になり、得られる多
層板の特性も良好となる印刷配線板用プリプレグを得る
ことができる。The details of the experimental methods in the above Examples and Comparative Examples are shown below. Copper foil peel strength is 10mm width, tensile speed 5 using Orientec Tensilon.
The peel strength in the 90-degree direction was measured at 0 mm / min. The Koka type flow tester was measured with a nozzle diameter of 0.7 mm and a load of 5 kg at a constant temperature of 130 ° C. The curing time of the prepreg resin powder was determined by measuring the curing time of the resin on a hot plate at 170 ° C. As shown in each example, by using a polyfunctional epoxy resin having a number average molecular weight of 1,000 to 3,000 in the present invention, the moldability is good, and the productivity is also good due to the wide mold width, It is possible to obtain a prepreg for a printed wiring board in which the properties of the obtained multilayer board are good.
【００１６】[0016]
【発明の効果】数平均分子量が１０００から３０００の
多官能エポキシ樹脂を用い、フェノールノボラック類ま
たはジシアンジアミドで硬化するエポキシ樹脂組成物を
用いたガラス基材印刷配線板用プリプレグは、多層板成
形時の溶融粘度が５０Ｐａ・ｓ〜２００Ｐａ・ｓの範囲
に制御しやすく、多層板成形時の樹脂の溶融による内層
板の回路充填性が良好であるばかりでなく、成形時の樹
脂の流動性が多すぎることに起因する絶縁層厚さの低下
による絶縁信頼性の低下や板厚精度の低下を防止するこ
とができる。According to the present invention, a prepreg for a glass substrate printed wiring board using a polyfunctional epoxy resin having a number average molecular weight of 1,000 to 3,000 and an epoxy resin composition curable with phenol novolaks or dicyandiamide is used for forming a multilayer board. The melt viscosity is easy to control in the range of 50 Pa · s to 200 Pa · s, and not only is the circuit filling property of the inner layer board good due to the melting of the resin at the time of molding the multilayer board, but also the fluidity of the resin at the time of molding is too large. As a result, it is possible to prevent a decrease in insulation reliability and a decrease in plate thickness accuracy due to a decrease in the thickness of the insulating layer.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｈ０５Ｋ 3/46 Ｈ０５Ｋ 3/46 Ｔ (72)発明者 高野 希 茨城県下館市大字小川1500番地 日立化成 工業株式会社下館研究所内 Ｆターム(参考） 4F072 AA02 AB09 AB28 AD15 AD24 AD54 AE01 AF28 AG03 AL13 4F100 AB17 AB33 AG00A AH03A AH03H AK33A AK33H AK53A BA01 BA05 BA06 CA02A DG11 DH01A EJ82A EJ86A GB43 JA07A JJ03 JL01 YY00A 4J002 CD001 DL006 FA046 GQ00 5E346 AA02 AA06 AA12 AA15 BB01 CC04 CC09 CC32 DD02 EE02 EE06 EE09 EE20 GG02 HH08 HH11 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) H05K 3/46 H05K 3/46 T (72) Inventor Nozomi Takano 1500 Oji Ogawa, Shimodate City, Ibaraki Prefecture Hitachi Chemical Co., Ltd. F-term in Shimodate Research Laboratories Co., Ltd. (reference) 4F072 AA02 AB09 AB28 AD15 AD24 AD54 AE01 AF28 AG03 AL13 4F100 AB17 AB33 AG00A AH03A AH03H AK33A AK33H AK53A BA01 BA05 BA06 CA02A DG11 DH01A EJ82A EJ86A03J00A04J07A00 AA06 AA12 AA15 BB01 CC04 CC09 CC32 DD02 EE02 EE06 EE09 EE20 GG02 HH08 HH11
Claims (5)
プレグにおいて、数平均分子量が１０００以上３０００
未満の多官能エポキシ樹脂を用いたワニスを厚さ０．０
２〜０．４０ｍｍのガラス基材に含浸し、乾燥温度６０
〜２００℃で１〜３０分間乾燥することを特徴とする印
刷配線板用プリプレグ。1. A prepreg for a printed wiring board using an epoxy resin, having a number average molecular weight of 1,000 or more and 3,000.
A varnish using a polyfunctional epoxy resin having a thickness of less than 0.0
Impregnated in a glass substrate of 2 to 0.40 mm, and dried at a drying temperature of 60
A prepreg for a printed wiring board, wherein the prepreg is dried at a temperature of 200C for 1 to 30 minutes.
０００以上３０００未満である請求項１に記載の印刷配
線板用プリプレグ。2. The polyfunctional epoxy resin having a number average molecular weight of 2
The prepreg for a printed wiring board according to claim 1, wherein the prepreg is not less than 000 and less than 3000.
００〜５００である請求項１または請求項２に記載の印
刷配線板用プリプレグ。3. The epoxy equivalent of the polyfunctional epoxy resin is 3
3. The prepreg for a printed wiring board according to claim 1, wherein the prepreg is from 00 to 500. 4.
ノールノボラック類を用いる請求項１ないし請求項３の
いずれかに記載の印刷配線板用プリプレグ。4. The prepreg for a printed wiring board according to claim 1, wherein a phenol novolak is used as a curing agent for the polyfunctional epoxy resin.
ン類を用いる請求項１ないし請求項３のいずれかに記載
の印刷配線板用プリプレグ。5. The prepreg for a printed wiring board according to claim 1, wherein an amine is used as a curing agent for the polyfunctional epoxy resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30694698A JP4341086B2 (en) | 1998-10-28 | 1998-10-28 | Prepreg for printed wiring board |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30694698A JP4341086B2 (en) | 1998-10-28 | 1998-10-28 | Prepreg for printed wiring board |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000133900A true JP2000133900A (en) | 2000-05-12 |
| JP4341086B2 JP4341086B2 (en) | 2009-10-07 |
Family
ID=17963187
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30694698A Expired - Lifetime JP4341086B2 (en) | 1998-10-28 | 1998-10-28 | Prepreg for printed wiring board |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4341086B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001329080A (en) * | 2000-05-23 | 2001-11-27 | Mitsubishi Gas Chem Co Inc | Prepreg, metal clad laminate and use thereof |
| JP2002254543A (en) * | 2000-12-28 | 2002-09-11 | Shin Kobe Electric Mach Co Ltd | Composite laminated sheet and method for manufacturing the same |
| JP2004103617A (en) * | 2002-07-18 | 2004-04-02 | Hitachi Chem Co Ltd | Multilayer wiring board, its manufacturing method, semiconductor device, and radio electronic equipment |
| JP2005268543A (en) * | 2004-03-18 | 2005-09-29 | Hitachi Chem Co Ltd | Insulating layer and material for forming the same |
| US7239013B2 (en) | 2002-07-18 | 2007-07-03 | Hitachi Chemical Co., Ltd. | Multilayer wiring board, method for producing the same, semiconductor device and radio electronic device |
-
1998
- 1998-10-28 JP JP30694698A patent/JP4341086B2/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001329080A (en) * | 2000-05-23 | 2001-11-27 | Mitsubishi Gas Chem Co Inc | Prepreg, metal clad laminate and use thereof |
| JP2002254543A (en) * | 2000-12-28 | 2002-09-11 | Shin Kobe Electric Mach Co Ltd | Composite laminated sheet and method for manufacturing the same |
| JP2004103617A (en) * | 2002-07-18 | 2004-04-02 | Hitachi Chem Co Ltd | Multilayer wiring board, its manufacturing method, semiconductor device, and radio electronic equipment |
| US7239013B2 (en) | 2002-07-18 | 2007-07-03 | Hitachi Chemical Co., Ltd. | Multilayer wiring board, method for producing the same, semiconductor device and radio electronic device |
| CN100413383C (en) * | 2002-07-18 | 2008-08-20 | 日立化成工业株式会社 | Multilayer wiring board, method for producing the same, semiconductor device and radio electronic device |
| US7592250B2 (en) | 2002-07-18 | 2009-09-22 | Hitachi Chemical Company, Ltd. | Multilayer wiring board, manufacturing method thereof, semiconductor device, and wireless electronic device |
| JP2005268543A (en) * | 2004-03-18 | 2005-09-29 | Hitachi Chem Co Ltd | Insulating layer and material for forming the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4341086B2 (en) | 2009-10-07 |
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