JPH04222840A - Production of laminated board - Google Patents
Production of laminated boardInfo
- Publication number
- JPH04222840A JPH04222840A JP2418177A JP41817790A JPH04222840A JP H04222840 A JPH04222840 A JP H04222840A JP 2418177 A JP2418177 A JP 2418177A JP 41817790 A JP41817790 A JP 41817790A JP H04222840 A JPH04222840 A JP H04222840A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- bisphenol
- dicyandiamide
- weight
- parts
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000003822 epoxy resin Substances 0.000 claims abstract description 57
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 57
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 30
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims abstract description 14
- 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 claims abstract description 12
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 10
- 239000002966 varnish Substances 0.000 claims abstract description 9
- 150000004984 aromatic diamines Chemical class 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 238000000465 moulding Methods 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000010030 laminating Methods 0.000 claims description 2
- 239000002075 main ingredient Substances 0.000 claims description 2
- 238000005476 soldering Methods 0.000 abstract description 14
- 239000000758 substrate Substances 0.000 abstract description 6
- 150000002460 imidazoles Chemical class 0.000 abstract description 3
- WECDUOXQLAIPQW-UHFFFAOYSA-N 4,4'-Methylene bis(2-methylaniline) Chemical compound C1=C(N)C(C)=CC(CC=2C=C(C)C(N)=CC=2)=C1 WECDUOXQLAIPQW-UHFFFAOYSA-N 0.000 abstract description 2
- 125000000217 alkyl group Chemical group 0.000 abstract description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 12
- 239000004593 Epoxy Substances 0.000 description 10
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- QJENIOQDYXRGLF-UHFFFAOYSA-N 4-[(4-amino-3-ethyl-5-methylphenyl)methyl]-2-ethyl-6-methylaniline Chemical compound CC1=C(N)C(CC)=CC(CC=2C=C(CC)C(N)=C(C)C=2)=C1 QJENIOQDYXRGLF-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- CQOZJDNCADWEKH-UHFFFAOYSA-N 2-[3,3-bis(2-hydroxyphenyl)propyl]phenol Chemical compound OC1=CC=CC=C1CCC(C=1C(=CC=CC=1)O)C1=CC=CC=C1O CQOZJDNCADWEKH-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229920001187 thermosetting polymer Polymers 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
- H05K1/0326—Organic insulating material consisting of one material containing O
Landscapes
- Epoxy Resins (AREA)
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
- Moulding By Coating Moulds (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、従来のものに比べて耐
湿性、リフロー半田付け加工時の耐熱性に優れたエポキ
シ樹脂銅張積層板の製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an epoxy resin copper-clad laminate which has superior moisture resistance and heat resistance during reflow soldering compared to conventional laminates.
【０００２】0002
【従来の技術】エポキシ樹脂銅張積層板は主に産業用エ
レクトロニクス機器やＯＡ機器等のプリント配線板用材
料として用いられているが、プリント配線板を構成する
積層板に対する要求特性も益々多岐にわたっている。近
年電気・電子分野における小型化、精密化に伴い、プリ
ント配線板の高密度化の要求も高まってきており、実装
形態も表面実装型となり、その半田付け方法としてリフ
ローソルダリング法が多く用いられる様になってきてい
る。[Prior Art] Epoxy resin copper-clad laminates are mainly used as materials for printed wiring boards in industrial electronics equipment, OA equipment, etc., but the characteristics required of the laminates that make up printed wiring boards are becoming increasingly diverse. There is. In recent years, with the miniaturization and precision in the electrical and electronic fields, the demand for higher density printed wiring boards has increased, and the mounting form has also become surface-mounted, and reflow soldering is often used as the soldering method. It's starting to look like this.
【０００３】しかしながら、リフロー半田付け時に積層
板の基材に剥離或いはミーズリングなどの問題が発生し
ている。これは基板内に吸湿した水分が爆発的に膨張す
ることが原因であり、基板が銅箔回路よりも２０〜３０
℃高い温度になるためである。また板厚が薄くなる程、
基板の耐熱性が低下し、剥離が発生しやすくなる。However, problems such as peeling or measling occur in the base material of the laminate during reflow soldering. This is caused by the explosive expansion of moisture absorbed into the board, and the board is 20 to 30 times smaller than a copper foil circuit.
This is because the temperature is ℃ higher. Also, as the plate thickness becomes thinner,
The heat resistance of the substrate decreases, making peeling more likely.
【０００４】この問題を解決する手段として耐熱性の向
上があり、フェノールノボラック型エポキシ樹脂などの
多官能性エポキシ樹脂が使用されているが、粘度が高い
ので基材の含浸性が劣るといった欠点があった。そのた
めテトラブロモビスフェノールＡ型エポキシ樹脂を添加
して低粘度化する方法が知られているが、多く添加する
と逆に耐熱性が低下するという欠点があった。One way to solve this problem is to improve heat resistance, and polyfunctional epoxy resins such as phenol novolac type epoxy resins are used, but they have the disadvantage that their high viscosity makes it difficult to impregnate the base material. there were. Therefore, a method of lowering the viscosity by adding a tetrabromobisphenol A type epoxy resin is known, but it has the drawback that adding a large amount conversely reduces heat resistance.
【０００５】また、リフロー半田付け時における剥離、
ミーズリングなどの問題に対する手段としては、他にリ
フロー半田付け時の温度を見直すとか、リフロー半田付
け前に基板を乾燥するとか、ガラスクロスを開繊してそ
の通気度を５ｃｃ／ｃｍ２／ｓｅｃ以下するといった手
段しか取られていない。[0005] Also, peeling during reflow soldering,
Other measures to deal with problems such as measling include reconsidering the temperature during reflow soldering, drying the board before reflow soldering, and opening glass cloth to reduce its air permeability to 5cc/cm2/sec or less. The only thing that has been taken is to do so.
【０００６】[0006]
【発明が解決しようとする課題】この発明の目的とすと
ころは、電気的、機械的特性を劣化させることなく、耐
湿性及びリフロー半田付け加工時の耐熱性に優れたエポ
キシ樹脂銅張積層板を提供することにある。[Problems to be Solved by the Invention] An object of the present invention is to provide an epoxy resin copper-clad laminate that has excellent moisture resistance and heat resistance during reflow soldering without deteriorating electrical or mechanical properties. Our goal is to provide the following.
【０００７】[0007]
【課題を解決するための手段】上記目的を達成するため
に本発明は、
（Ａ）１分子中に少なくとも２個以上のエポキシ基を含
むエポキシ樹脂
（Ｂ）ジシアンジアミド
（Ｃ）下記式［Ｉ］で示される構造の芳香族ジアミン[Means for Solving the Problems] In order to achieve the above object, the present invention provides: (A) an epoxy resin containing at least two or more epoxy groups in one molecule (B) dicyandiamide (C) the following formula [I] Aromatic diamine with the structure shown in
【
０００８】[
0008
【化２】
及び（Ｄ）硬化促進剤及び溶剤から成るワニスを基材に
含浸乾燥して得たプリプレグを所定数積層成形して得ら
れた積層板にリフロー半田付け加工を行うことを特徴と
する熱硬化性樹脂積層板の製造方法である。[Chemical formula 2] and (D) A laminate plate obtained by laminating and molding a predetermined number of prepregs obtained by impregnating and drying a base material with a varnish consisting of a curing accelerator and a solvent, and performing reflow soldering processing on the laminate plate obtained. This is a method for manufacturing a thermosetting resin laminate.
【０００９】主剤であるエポキシ樹脂は、ビスフェノー
ルＡ型エポキシ樹脂、３官能以上の多官能性エポキシ樹
脂、テトラブロモビスフェノールＡ型エポキシ樹脂及び
ビスフェノールＡ又はテトラブロモビスフェノールＡを
触媒の存在下で反応させたエポキシ樹脂が好ましく、更
に、硬化剤であるジシアンジアミドの割合は０．３〜０
．７当量であることが好ましい。[0009] The epoxy resin that is the main ingredient is made by reacting bisphenol A type epoxy resin, trifunctional or higher polyfunctional epoxy resin, tetrabromobisphenol A type epoxy resin, and bisphenol A or tetrabromobisphenol A in the presence of a catalyst. Epoxy resin is preferable, and the ratio of dicyandiamide as a curing agent is 0.3 to 0.
．． Preferably it is 7 equivalents.
【００１０】0010
【作用】本発明は、１分子中に２個以上のエポキシ基を
含み、かつ含浸性に優れたエポキシ樹脂と、硬化剤とし
てジシアンジアミド及び特性構造の芳香族ジアミンを併
用することにより、耐湿性及びリフロー半田付け加工時
の耐熱性に優れたエポキシ樹脂銅張積層板を提供するこ
とにある。[Function] The present invention uses an epoxy resin that contains two or more epoxy groups in one molecule and has excellent impregnating properties, and dicyandiamide and an aromatic diamine with a special structure as a curing agent. An object of the present invention is to provide an epoxy resin copper-clad laminate having excellent heat resistance during reflow soldering.
【００１１】本発明で用いられるエポキシ樹脂としては
、通常１分子中に２個以上のエポキシ基を有するもので
あればいかなるものでもよく、例えばビスフェノールＡ
型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、臭
素化ビスフェノールＡ型エポキシ樹脂、トリフェノール
類のグリシジルエーテル、フェノールノボラックエポキ
シ樹脂などが挙げられる。これらのエポキシ樹脂は１種
あるいは２種以上併用してもよい。しかしながら、耐熱
性向上の点からトリフェノール類のグリシジルエーテル
やフェノールノボラックエポキシ樹脂などの３個以上の
エポキシ基をもったエポキシ樹脂を使用する場合、高粘
度になり、ガラス基材への含浸性が低下してくるので、
それを補うために３個以上のエポキシ基を含むエポキシ
樹脂と低粘度である２官能のエポキシ樹脂を触媒の存在
下でビスフェノールＡ及びテトラブロモビスフェノール
Ａとともに反応させたエポキシ樹脂を用いた方がよい。
特にその中でも含浸性、耐熱性更に高温時の臭素化エポ
キシ樹脂の臭素原子の脱離り、変色といった点を考えれ
ば、３個以上のエポキシ基をもったエポキシ樹脂、ビス
フェノールＡ型エポキシ樹脂、臭素化ビスフェノールＡ
型エポキシ樹脂及びビスフェノールＡ又はテトラブロモ
ビスフェノールＡを触媒の存在下で反応させたエポキシ
樹脂が最も好ましい。この時の反応に使用される触媒と
しては第３級アミン、４級アンモニウム塩やイミダゾー
ル類などがある。本発明に用いるジシアンジアミドはエ
ポキシ樹脂に対する潜在性硬化剤として知られており、
所定温度以上で優れた硬化作用を与える硬化剤である。
しかし、エポキシ樹脂に対する配合比率を上げるに従っ
て成形性、耐湿性に劣るといった欠点がある。本発明で
併用する下記式［Ｉ］で示される構造の芳香族ジアミン
は硬化速度がおそいが、硬化物の耐湿性は優れている。The epoxy resin used in the present invention may be any resin as long as it has two or more epoxy groups in one molecule, such as bisphenol A.
Type epoxy resins, bisphenol F type epoxy resins, brominated bisphenol A type epoxy resins, glycidyl ethers of triphenols, phenol novolac epoxy resins, and the like. These epoxy resins may be used alone or in combination of two or more. However, when using epoxy resins with three or more epoxy groups, such as glycidyl ether of triphenols or phenol novolak epoxy resin, from the viewpoint of improving heat resistance, the viscosity becomes high and impregnating into glass substrates becomes difficult. As it decreases,
To compensate for this, it is better to use an epoxy resin made by reacting an epoxy resin containing three or more epoxy groups with a low-viscosity bifunctional epoxy resin together with bisphenol A and tetrabromobisphenol A in the presence of a catalyst. . Especially considering the impregnating properties, heat resistance, detachment of bromine atoms of brominated epoxy resins at high temperatures, and discoloration, epoxy resins with three or more epoxy groups, bisphenol A type epoxy resins, brominated epoxy resins, etc. bisphenol A
Most preferred is an epoxy resin prepared by reacting a type epoxy resin and bisphenol A or tetrabromobisphenol A in the presence of a catalyst. Catalysts used in this reaction include tertiary amines, quaternary ammonium salts, and imidazoles. Dicyandiamide used in the present invention is known as a latent curing agent for epoxy resins,
It is a curing agent that provides excellent curing action at a predetermined temperature or higher. However, as the blending ratio with respect to the epoxy resin increases, there are drawbacks such as poor moldability and moisture resistance. Although the aromatic diamine having the structure represented by the following formula [I] used in combination in the present invention has a slow curing speed, the cured product has excellent moisture resistance.
【００１２】0012
【化３】
式［Ｉ］のアルキル基としては、メチル基、エチル基、
ブチル基などがあるが、特にメチル基、エチル基が好ま
しい。具体的には例えば４，４′−ジアミノ−３，３′
−ジエチル−５，５′ジメチルジフェニルメタン、４，
４′−ジアミノ−３，３′，５，５′−テトラメチルジ
フェニルメタン、４，４′−ジアミノ−３，３′−ジメ
チルジフェニルメタンなどがある。ジシアンジアミドと
芳香族ジアミンを併用する場合のエポキシ樹脂に対する
配合量は、エポキシ基１当量に対して、ジシアンジアミ
ドと前記芳香族ジアミンの合計の活性水素基が０．３〜
１．１当量である。好ましくは０．５〜１．０当量であ
る。その中でジシアンジアミドは耐湿性の面からエポキ
シ基１当量に対して０．３〜０．７当量が好ましい。そ
の他必要により、２−メチルイミダゾール、２−エチル
−４−メチルイミダゾールなどのイミダゾール類、エチ
ルアミン、トリエチルアミンなどのアミン類、トリフェ
ニルホスフィン、４級アンモニウム塩などの硬化促進剤
、更にアセトン、メチルエチルケトン、ジメチルホルム
アミドなどの溶剤を適宜添加配合することができる。[I] The alkyl group of formula [I] includes a methyl group, an ethyl group,
Although there are butyl groups, methyl groups and ethyl groups are particularly preferred. Specifically, for example, 4,4'-diamino-3,3'
-diethyl-5,5'dimethyldiphenylmethane, 4,
Examples include 4'-diamino-3,3',5,5'-tetramethyldiphenylmethane and 4,4'-diamino-3,3'-dimethyldiphenylmethane. When dicyandiamide and aromatic diamine are used together, the amount to be added to the epoxy resin is such that the total active hydrogen group of dicyandiamide and the aromatic diamine is 0.3 to 1 equivalent of epoxy group.
It is 1.1 equivalent. Preferably it is 0.5 to 1.0 equivalent. Among these, dicyandiamide is preferably used in an amount of 0.3 to 0.7 equivalents per equivalent of epoxy group from the viewpoint of moisture resistance. If necessary, other imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole, amines such as ethylamine and triethylamine, curing accelerators such as triphenylphosphine and quaternary ammonium salts, and further acetone, methyl ethyl ketone, dimethyl A solvent such as formamide can be appropriately added and blended.
【００１３】[0013]
【実施例】実施例１
臭素化ビスフェノールＡ型エポキシ樹脂（エポキシ当量
７７０） ９０重量部ｏ−クレゾールノボラック
型エポキシ樹脂（エポキシ当量２１５） １０重量部
ジシアンジアミド
１．７重量部４，４′−ジアミノ−３，３′−ジエ
チル−５，５′−ジメチルジフェニルメタン
２．８重量部２−エチル
−４−メチルイミダゾール
０．１５重量部及び溶剤を常温
で均一に混合溶解し、ワニスを得た。得られたワニスを
厚さ０．１８ｍｍのガラス基材に含浸し乾燥させプリプ
レグを得た。このプリプレグ３枚積層し、その上下に厚
さ１８μｍの銅箔を入れ、加熱加圧して０．６ｍｍ厚の
積層板を得た。その特性を表１に示す。[Example] Example 1 Brominated bisphenol A type epoxy resin (epoxy equivalent: 770) 90 parts by weight o-cresol novolac type epoxy resin (epoxy equivalent: 215) 10 parts by weight dicyandiamide
1.7 parts by weight 4,4'-diamino-3,3'-diethyl-5,5'-dimethyldiphenylmethane
2.8 parts by weight 2-ethyl-4-methylimidazole
A varnish was obtained by uniformly mixing and dissolving 0.15 parts by weight and a solvent at room temperature. A glass substrate having a thickness of 0.18 mm was impregnated with the obtained varnish and dried to obtain a prepreg. Three sheets of this prepreg were laminated, copper foils with a thickness of 18 μm were placed above and below the prepreg, and a laminate with a thickness of 0.6 mm was obtained by heating and pressing. Its characteristics are shown in Table 1.
【００１４】実施例２
表１に示した配合割合でワニスを作成し、実施例１と同
様にして積層板を得た。その特性を表１に示す。Example 2 A varnish was prepared in the proportions shown in Table 1, and a laminate was obtained in the same manner as in Example 1. Its characteristics are shown in Table 1.
【００１５】比較例１
表１に示した配合割合でワニスを作成し、実施例１と同
様にして積層板を得た。その特性を表２に示す。Comparative Example 1 A varnish was prepared with the blending ratio shown in Table 1, and a laminate was obtained in the same manner as in Example 1. Its characteristics are shown in Table 2.
【００１６】実施例３
トリフェノール型３官能エポキシ樹脂（エポキシ当量２
１０）４０重量部、ビスフェノールＡ型エポキシ樹脂（
エポキシ当量１９０）２３重量部、テトラブロモビスフ
ェノールＡ型エポキシ樹脂（エポキシ当量４４０）１４
重量部、テトラブロモビスフェノールＡ２０重量部、ビ
スフェノールＡ３重量部、２−エチル−４−メチルイミ
ダゾール０．０３重量部を反応温度１６０℃、反応時間
２時間で反応させてエポキシ当量３９０の多官能エポキ
シ樹脂（Ａ）を得た。この樹脂（Ａ）１００重量部とジ
シアンジアミド１．７重量部、４，４′−ジアミノ−３
，３′ジエチル−５，５′−ジメチルジフェニルメタン
２．８重量部、２−エチル−４−メチルイミダゾールの
０．１５重量部及び溶剤からワニスを作り、以下実施例
１と同様にして積層板を得た。その特性を表１に示す。Example 3 Triphenol type trifunctional epoxy resin (epoxy equivalent: 2
10) 40 parts by weight, bisphenol A type epoxy resin (
Epoxy equivalent: 190) 23 parts by weight, tetrabromobisphenol A type epoxy resin (epoxy equivalent: 440) 14
parts by weight, 20 parts by weight of tetrabromobisphenol A, 3 parts by weight of bisphenol A, and 0.03 parts by weight of 2-ethyl-4-methylimidazole were reacted at a reaction temperature of 160°C for a reaction time of 2 hours to obtain a polyfunctional epoxy resin with an epoxy equivalent of 390. (A) was obtained. 100 parts by weight of this resin (A), 1.7 parts by weight of dicyandiamide, 4,4'-diamino-3
, 2.8 parts by weight of 3'diethyl-5,5'-dimethyldiphenylmethane, 0.15 parts by weight of 2-ethyl-4-methylimidazole and a solvent, and a laminate was prepared in the same manner as in Example 1. Obtained. Its characteristics are shown in Table 1.
【００１７】比較例２
トリフェノール型３官能性エポキシ樹脂（エポキシ当量
２１０）４０重量部、ビスフェノールＡ型エポキシ樹脂
（エポキシ当量１９０）２４重量部、テトラブロモビス
フェノールＡ１９重量部、ビスフェノールＡ３重量部、
２−エチル−４−メチルイミダゾール０．０３重量部を
反応温度１６０℃、反応時間２時間で反応させてエポキ
シ当量３８６の多官能エポキシ樹脂（Ｂ）を得た。その
樹脂（Ｂ）８６重量部とテトラブロモビスフェノールＡ
型エポキシ樹脂（エポキシ当量４００）１４重量部、ジ
シアンジアミド２．７重量部、２−エチル−４−メチル
イミダゾール０．１５重量部及び溶剤からワニスを作り
、以下実施例１と同様にして積層板を得た。その特性を
表２に示す。Comparative Example 2 40 parts by weight of triphenol-type trifunctional epoxy resin (epoxy equivalent: 210), 24 parts by weight of bisphenol A-type epoxy resin (epoxy equivalent: 190), 19 parts by weight of tetrabromobisphenol A, 3 parts by weight of bisphenol A,
A polyfunctional epoxy resin (B) having an epoxy equivalent of 386 was obtained by reacting 0.03 parts by weight of 2-ethyl-4-methylimidazole at a reaction temperature of 160° C. for a reaction time of 2 hours. 86 parts by weight of the resin (B) and tetrabromobisphenol A
A varnish was made from 14 parts by weight of mold epoxy resin (epoxy equivalent: 400), 2.7 parts by weight of dicyandiamide, 0.15 parts by weight of 2-ethyl-4-methylimidazole, and a solvent, and a laminate was prepared in the same manner as in Example 1. Obtained. Its characteristics are shown in Table 2.
【００１８】実施例と比較例で得られた各積層板に銅メ
ッキ２５μｍを施し、サイズ１５０×９０ｍｍの表面実
装用パターンを作成した。前処理としてプレッシャーク
ッカー処理（１２５℃、蒸気圧２．３ｋｇｆ／ｃｍ２）
３０分間を行った。ランド上の温度を２６０，２８０，
３００℃になるように設定し、評価用基板を遠赤外リフ
ロー炉に２回通した後、基板のふくれ、剥離の有無を調
べた。Each of the laminates obtained in Examples and Comparative Examples was plated with copper to a thickness of 25 μm to form a pattern for surface mounting with a size of 150×90 mm. Pressure cooker treatment (125℃, vapor pressure 2.3kgf/cm2) as pretreatment
This was carried out for 30 minutes. The temperature on the land is 260, 280,
After passing the evaluation substrate through a far-infrared reflow oven twice at a temperature of 300° C., the presence or absence of blistering and peeling of the substrate was examined.
【００１９】[0019]
【表１】[Table 1]
【００２０】[0020]
【表２】[Table 2]
【００２１】[0021]
【発明の効果】本発明に従うことによって耐湿性、リフ
ロー半田付け加工時の耐熱性に優れたエポキシ樹脂銅張
積層板を得ることができる。これは、リフロー半田付け
前の再加熱などをしなくても良く、リフローソルダー時
の温度の高い分野にも利用できることから、表面実装の
面で工業的価値は非常に大きなものである。According to the present invention, an epoxy resin copper-clad laminate having excellent moisture resistance and heat resistance during reflow soldering can be obtained. This has great industrial value in terms of surface mounting because it does not require reheating before reflow soldering and can be used in fields where the temperature is high during reflow soldering.
Claims (3)
のエポキシ基を含むエポキシ樹脂 （Ｂ）ジシアンジアミド （Ｃ）下記式［Ｉ］で示される構造の芳香族ジアミン【
化１】 及び、 （Ｄ）硬化促進剤及び溶剤からなるワニスを基材に含浸
乾燥して得たプリプレグを所定数積層成形することを特
徴とするエポキシ樹脂銅張積層板の製造方法。Claim 1: (A) an epoxy resin containing at least two epoxy groups in one molecule; (B) dicyandiamide; (C) an aromatic diamine having a structure represented by the following formula [I]:
(D) A method for producing an epoxy resin copper-clad laminate, which comprises laminating and molding a predetermined number of prepregs obtained by impregnating and drying a base material with a varnish consisting of a curing accelerator and a solvent.
ノールＡ型エポキシ樹脂、３官能以上の多官能性エポキ
シ樹脂、テトラブロモビスフェノールＡ型エポキシ樹脂
及びビスフェノールＡ又はテトラブロモビスフェノール
Ａを触媒の存在下で反応させたエポキシ樹脂である請求
項１記載の積層板の製造方法。[Claim 2] The epoxy resin as the main ingredient is produced by reacting bisphenol A type epoxy resin, trifunctional or higher polyfunctional epoxy resin, tetrabromobisphenol A type epoxy resin, and bisphenol A or tetrabromobisphenol A in the presence of a catalyst. 2. The method for producing a laminate according to claim 1, wherein the epoxy resin is a laminate made of epoxy resin.
．７当量である請求項１記載の積層板の製造方法。[Claim 3] The proportion of dicyandiamide is 0.3 to 0.
．． The method for manufacturing a laminate according to claim 1, wherein the amount is 7 equivalents.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP41817790A JP3159390B2 (en) | 1990-12-25 | 1990-12-25 | Manufacturing method of laminated board |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP41817790A JP3159390B2 (en) | 1990-12-25 | 1990-12-25 | Manufacturing method of laminated board |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04222840A true JPH04222840A (en) | 1992-08-12 |
| JP3159390B2 JP3159390B2 (en) | 2001-04-23 |
Family
ID=18526098
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP41817790A Expired - Fee Related JP3159390B2 (en) | 1990-12-25 | 1990-12-25 | Manufacturing method of laminated board |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3159390B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5859155A (en) * | 1994-05-24 | 1999-01-12 | Mitsui Chemicals, Inc. | Adhesive of epoxy resin, carboxylated rubber aromatic amine and dicyandiamide |
-
1990
- 1990-12-25 JP JP41817790A patent/JP3159390B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5859155A (en) * | 1994-05-24 | 1999-01-12 | Mitsui Chemicals, Inc. | Adhesive of epoxy resin, carboxylated rubber aromatic amine and dicyandiamide |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3159390B2 (en) | 2001-04-23 |
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