JPH0987367A - Epoxy resin composition for laminate and its production - Google Patents
Epoxy resin composition for laminate and its productionInfo
- Publication number
- JPH0987367A JPH0987367A JP24293295A JP24293295A JPH0987367A JP H0987367 A JPH0987367 A JP H0987367A JP 24293295 A JP24293295 A JP 24293295A JP 24293295 A JP24293295 A JP 24293295A JP H0987367 A JPH0987367 A JP H0987367A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- resin composition
- phosphorus
- based curing
- curing accelerator
- 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.)
- Withdrawn
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 81
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 81
- 239000000203 mixture Substances 0.000 title claims abstract description 63
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 46
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 44
- 239000011574 phosphorus Substances 0.000 claims abstract description 44
- 239000002245 particle Substances 0.000 claims abstract description 36
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- 239000003960 organic solvent Substances 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 10
- -1 tetraphenylphosphonium tetraphenylborate Chemical group 0.000 claims description 7
- QLAGHGSFXJZWKY-UHFFFAOYSA-N triphenylborane;triphenylphosphane Chemical group C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QLAGHGSFXJZWKY-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 abstract description 7
- 239000000470 constituent Substances 0.000 abstract description 3
- 239000004570 mortar (masonry) Substances 0.000 abstract description 2
- 239000011342 resin composition Substances 0.000 abstract 1
- 238000001723 curing Methods 0.000 description 56
- 229910000679 solder Inorganic materials 0.000 description 17
- 239000002966 varnish Substances 0.000 description 17
- 238000009835 boiling Methods 0.000 description 15
- 230000009477 glass transition Effects 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- 229920003986 novolac Polymers 0.000 description 8
- 238000013329 compounding Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 239000004594 Masterbatch (MB) Substances 0.000 description 5
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 229930003836 cresol Natural products 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- LHENQXAPVKABON-UHFFFAOYSA-N 1-methoxypropan-1-ol Chemical compound CCC(O)OC LHENQXAPVKABON-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Epoxy Resins (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、プリント配線板等
の材料として使用される積層板を製造するための積層板
用エポキシ樹脂組成物及びその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy resin composition for laminates for producing laminates used as materials for printed wiring boards and the like and a method for producing the same.
【０００２】[0002]
【従来の技術】近年、エポキシ樹脂、フェノール系硬化
剤、リン系硬化促進剤及び有機溶媒を含む積層板用エポ
キシ樹脂組成物が耐熱性に優れることから検討されてお
り、さらにリン系硬化促進剤としてテトラフェニルホス
ホニウムテトラフェニルボレートやトリフェニルホスフ
ィントリフェニルボラン等の有機溶媒に非相溶性のもの
を使用することがプリプレグの保存安定性改善の観点か
ら検討されている。このような有機溶媒に非相溶性のリ
ン系硬化促進剤をエポキシ樹脂組成物中に粒子として分
散させたものを、プリプレグを製造するためのワニスと
して使用すると、プリプレグの保存安定性の改善は達成
されるが、プリプレグを硬化させた積層板の耐熱特性
（ガラス転移温度、煮沸後の半田耐熱性等）が不十分で
あるという問題が生じることがあった。これは、非相溶
性のリン系硬化促進剤のエポキシ樹脂組成物中への分散
が不十分なため、積層板中での硬化促進剤の濃度分布に
バラツキが生じ、そのため硬化状態が不均一な積層板と
なっているためではないかと考えられる。従来、非相溶
性のリン系硬化促進剤をエポキシ樹脂組成物中へ分散さ
せる方法としては、低粘度のエポキシ樹脂組成物中に、
ディスパーと呼ばれる攪拌装置を用いて分散させてお
り、この場合の分散された硬化促進剤の最大粒子径は５
０μｍ以上である場合が一般的であり、この最大粒子径
をさらに小さくすることは困難であった。2. Description of the Related Art In recent years, epoxy resin compositions for laminates containing an epoxy resin, a phenol-based curing agent, a phosphorus-based curing accelerator and an organic solvent have been studied because of their excellent heat resistance. The use of an incompatible organic solvent such as tetraphenylphosphonium tetraphenylborate or triphenylphosphinetriphenylborane has been studied as a method for improving the storage stability of the prepreg. When the phosphorus-based curing accelerator, which is incompatible with such an organic solvent, is dispersed as particles in an epoxy resin composition and used as a varnish for producing a prepreg, improvement in storage stability of the prepreg is achieved. However, there has been a problem in that the heat resistance characteristics (glass transition temperature, solder heat resistance after boiling, etc.) of the laminate obtained by curing the prepreg are insufficient. This is because the incompatible phosphorus-based curing accelerator is insufficiently dispersed in the epoxy resin composition, so that the concentration distribution of the curing accelerator in the laminate varies, and the cured state becomes uneven. Probably because it is a laminated plate. Conventionally, as a method of dispersing an incompatible phosphorus-based curing accelerator into an epoxy resin composition, in a low-viscosity epoxy resin composition,
Dispersion is carried out using a stirring device called Disper, and the maximum particle size of the dispersed curing accelerator in this case is 5
It is generally 0 μm or more, and it was difficult to further reduce the maximum particle size.
【０００３】[0003]
【発明が解決しようとする課題】本発明は上記のような
事情に鑑みてなされたものであって、その目的とすると
ころは、エポキシ樹脂、フェノール系硬化剤、リン系硬
化促進剤及び有機溶媒を含む積層板用エポキシ樹脂組成
物であって、リン系硬化促進剤がエポキシ樹脂組成物中
に粒子として分散していて、かつ、耐熱特性（ガラス転
移温度、煮沸後の半田耐熱性等）の優れる積層板を得る
ことが可能な積層板用エポキシ樹脂組成物を提供するこ
と及びそのような積層板用エポキシ樹脂組成物を製造で
きる製造方法を提供することである。SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object thereof is to provide an epoxy resin, a phenol type curing agent, a phosphorus type curing accelerator and an organic solvent. An epoxy resin composition for laminates containing, wherein the phosphorus-based curing accelerator is dispersed as particles in the epoxy resin composition, and having heat resistance characteristics (glass transition temperature, solder heat resistance after boiling, etc.) An object of the present invention is to provide an epoxy resin composition for a laminate capable of obtaining an excellent laminate and a method for producing such an epoxy resin composition for a laminate.
【０００４】[0004]
【課題を解決するための手段】請求項１に係る発明の積
層板用エポキシ樹脂組成物は、エポキシ樹脂、フェノー
ル系硬化剤、リン系硬化促進剤及び有機溶媒を含む積層
板用エポキシ樹脂組成物において、リン系硬化促進剤が
エポキシ樹脂組成物中に粒子として分散していて、か
つ、その粒子の最大粒子径が０．１〜２０μｍであるこ
とを特徴とする。The epoxy resin composition for a laminated board of the invention according to claim 1 is an epoxy resin composition for a laminated board containing an epoxy resin, a phenol-based curing agent, a phosphorus-based curing accelerator and an organic solvent. In the above, the phosphorus-based curing accelerator is dispersed as particles in the epoxy resin composition, and the maximum particle size of the particles is 0.1 to 20 μm.
【０００５】請求項２に係る発明の積層板用エポキシ樹
脂組成物は、請求項１記載の積層板用エポキシ樹脂組成
物において、リン系硬化促進剤が、テトラフェニルホス
ホニウムテトラフェニルボレートであることを特徴とす
る。According to a second aspect of the present invention, there is provided an epoxy resin composition for laminates according to the first aspect, wherein the phosphorus-based curing accelerator is tetraphenylphosphonium tetraphenylborate. Characterize.
【０００６】請求項３に係る発明の積層板用エポキシ樹
脂組成物は、請求項１記載の積層板用エポキシ樹脂組成
物において、リン系硬化促進剤が、トリフェニルホスフ
ィントリフェニルボランであることを特徴とする。According to a third aspect of the present invention, there is provided an epoxy resin composition for laminates according to the first aspect, wherein the phosphorus-based curing accelerator is triphenylphosphinetriphenylborane. Characterize.
【０００７】請求項４に係る発明の積層板用エポキシ樹
脂組成物の製造方法は、請求項１から請求項３までのい
ずれかに記載の積層板用エポキシ樹脂組成物を得るにあ
たり、３本ロールを用いてリン系硬化促進剤をエポキシ
樹脂組成物中に分散させることを特徴とする。The method for producing an epoxy resin composition for a laminated board according to a fourth aspect of the present invention is a three-roll roll for obtaining the epoxy resin composition for a laminated sheet according to any one of the first to third aspects. Is used to disperse the phosphorus-based curing accelerator in the epoxy resin composition.
【０００８】請求項５に係る発明の積層板用エポキシ樹
脂組成物の製造方法は、請求項１から請求項３までのい
ずれかに記載の積層板用エポキシ樹脂組成物を得るにあ
たり、らいかい機を用いてリン系硬化促進剤をエポキシ
樹脂組成物中に分散させることを特徴とする。The method for producing an epoxy resin composition for a laminated board according to a fifth aspect of the present invention is a raider machine for obtaining the epoxy resin composition for a laminated sheet according to any one of the first to third aspects. Is used to disperse the phosphorus-based curing accelerator in the epoxy resin composition.
【０００９】請求項６に係る発明の積層板用エポキシ樹
脂組成物の製造方法は、請求項１から請求項３までのい
ずれかに記載の積層板用エポキシ樹脂組成物を得るにあ
たり、リン系硬化促進剤をエポキシ樹脂及び／又はフェ
ノール系硬化剤と予備混合してリン系硬化促進剤を予め
分散させた後、残りの構成成分を添加して混合すること
を特徴とする。The method for producing an epoxy resin composition for a laminated board according to a sixth aspect of the present invention is a phosphorus-based curing method for obtaining the epoxy resin composition for a laminated sheet according to any one of the first to third aspects. It is characterized in that the accelerator is premixed with the epoxy resin and / or the phenol-based curing agent to disperse the phosphorus-based curing accelerator in advance, and then the remaining components are added and mixed.
【００１０】[0010]
【発明の実施の形態】本発明で使用するエポキシ樹脂
は、１分子中に２個以上のエポキシ基を有する化合物で
あればよく、例えばビスフェノールＡジグリシジルエー
テル、ブロム化ビスフェノールＡジグリシジルエーテ
ル、クレゾールノボラックのグリシジルエーテル等があ
げられ、これらを単独または２種以上併用して用いられ
る。BEST MODE FOR CARRYING OUT THE INVENTION The epoxy resin used in the present invention may be a compound having two or more epoxy groups in one molecule, for example, bisphenol A diglycidyl ether, brominated bisphenol A diglycidyl ether, cresol. Examples thereof include glycidyl ether of novolac, and these may be used alone or in combination of two or more kinds.
【００１１】本発明で使用するフェノール系硬化剤は、
分子中に２個以上のフェノール性水酸基を有する化合物
であればよく、例えばフェノール、クレゾール、ビスフ
ェノールＡ、レゾルシノール等のフェノール系化合物と
ホルムアルデヒド等とを触媒下で縮合して得られる各種
のノボラック型フェノール樹脂を使用することができ
る。また、フェノール系硬化剤と併せて、アミン系硬化
剤を使用することも可能である。硬化剤の配合量は、特
に限定するものではないが、１エポキシ基当量のエポキ
シ樹脂に対して０．８〜１．２反応基当量の硬化剤を配
合することが、良好な性能の積層板を得るためには望ま
しい。０．８当量未満では耐熱性が低下する傾向があ
り、また１．２当量を越えると耐湿特性が低下する傾向
がある。また、全硬化剤中のフェノール系硬化剤の割合
は、全硬化剤の反応基当量を１当量としたときに、フェ
ノール系硬化剤を０．５〜１当量含むことが望ましく、
０．５当量未満では耐湿特性が低下する傾向がある。The phenolic curing agent used in the present invention is
Any compound having two or more phenolic hydroxyl groups in the molecule may be used, and for example, various novolac type phenols obtained by condensing a phenol compound such as phenol, cresol, bisphenol A, resorcinol and formaldehyde with a catalyst. Resins can be used. Further, it is also possible to use an amine-based curing agent in combination with the phenol-based curing agent. The compounding amount of the curing agent is not particularly limited, but it is preferable to compound 0.8 to 1.2 reactive group equivalent of the curing agent with respect to one epoxy group equivalent of the epoxy resin, which is a laminate having good performance. Desirable to get. If it is less than 0.8 equivalent, the heat resistance tends to decrease, and if it exceeds 1.2 equivalent, the moisture resistance tends to decrease. Further, the ratio of the phenolic curing agent in the total curing agent is preferably 0.5 to 1 equivalent of the phenolic curing agent when the reactive group equivalent of the total curing agent is 1 equivalent.
If it is less than 0.5 equivalent, the moisture resistance tends to be deteriorated.
【００１２】また、従来技術の欄で記載したように、リ
ン系硬化促進剤がエポキシ樹脂組成物中に粒子として分
散しているエポキシ樹脂組成物によれば、保存安定性の
優れたプリプレグを得ることができる。そこで、本発明
で使用するリン系硬化促進剤は、エポキシ樹脂、フェノ
ール系硬化剤、リン系硬化促進剤及び有機溶媒を含む積
層板用エポキシ樹脂組成物中に粒子として分散できるも
のに限定される。有機溶媒に対し非相溶性であるリン系
硬化促進剤としては、特に限定するものではないが、例
えばテトラフェニルホスホニウムテトラフェニルボレー
ト、トリフェニルホスフィントリフェニルボラン等を挙
げることができる。リン系硬化促進剤の添加量について
は、特に限定するものではないが、有機溶媒を除いた積
層板用エポキシ樹脂組成物全体量の０．１〜１．０重量
％程度の添加量とすることが好ましい。０．１重量％未
満では得られるプリプレグの反応速度が遅くなる恐れが
あり、１．０重量％を越えると逆にプリプレグの反応速
度が早くなり過ぎる恐れがある。Further, as described in the section of the prior art, an epoxy resin composition in which a phosphorus-based curing accelerator is dispersed as particles in the epoxy resin composition gives a prepreg excellent in storage stability. be able to. Therefore, the phosphorus-based curing accelerator used in the present invention is limited to those that can be dispersed as particles in the epoxy resin composition for a laminate containing an epoxy resin, a phenol-based curing agent, a phosphorus-based curing accelerator and an organic solvent. . The phosphorus-based curing accelerator that is incompatible with the organic solvent is not particularly limited, and examples thereof include tetraphenylphosphonium tetraphenylborate and triphenylphosphine triphenylborane. The addition amount of the phosphorus-based curing accelerator is not particularly limited, but the addition amount should be about 0.1 to 1.0% by weight of the total amount of the epoxy resin composition for laminates excluding the organic solvent. Is preferred. If it is less than 0.1% by weight, the reaction rate of the prepreg obtained may be slow, and if it exceeds 1.0% by weight, the reaction rate of the prepreg may be too fast.
【００１３】本発明で使用する有機溶媒としては、特に
限定するものではないが、例えばメチルエチルケトン、
メトキシプロパノール等があげられ、これらを単独また
は２種以上併用して用いられる。本発明における、積層
板用エポキシ樹脂組成物中の有機溶媒の含有量は３０〜
５０重量％程度が一般的であるが、使用状況に応じて適
宜決定すればよく、特に限定はない。The organic solvent used in the present invention is not particularly limited, but for example, methyl ethyl ketone,
Methoxypropanol and the like can be mentioned, and these can be used alone or in combination of two or more kinds. In the present invention, the content of the organic solvent in the epoxy resin composition for laminated boards is 30 to
Although it is generally about 50% by weight, it may be appropriately determined according to the use situation and is not particularly limited.
【００１４】そして、本発明ではエポキシ樹脂組成物中
に粒子として分散しているリン系硬化促進剤の粒子の最
大粒子径が０．１〜２０μｍであることが重要である。
２０μｍを越えている場合は、エポキシ樹脂組成物中で
のリン系硬化促進剤の分散が不十分であり、そのため硬
化状態が不均一となり、耐熱特性（ガラス転移温度、煮
沸後の半田耐熱性等）が不十分な積層板しか得られない
という問題が生じる。一方、長時間かけて分散させても
最大粒子径を０．１μｍ未満とすることは困難であり、
０．１μｍ未満としたとしても格別の効果を期待できな
いと考えられるので、本発明では最大粒子径は０．１μ
ｍ以上と限定している。In the present invention, it is important that the maximum particle size of the particles of the phosphorus-based curing accelerator dispersed as particles in the epoxy resin composition is 0.1 to 20 μm.
When it exceeds 20 μm, the dispersion of the phosphorus-based curing accelerator in the epoxy resin composition is insufficient, so that the cured state becomes uneven, and the heat resistance characteristics (glass transition temperature, solder heat resistance after boiling, etc.) The problem arises that only a laminate having insufficient) can be obtained. On the other hand, even if dispersed over a long time, it is difficult to make the maximum particle size less than 0.1 μm,
Even if it is less than 0.1 μm, it is considered that no particular effect can be expected. Therefore, in the present invention, the maximum particle size is 0.1 μm.
It is limited to m or more.
【００１５】本発明では、エポキシ樹脂組成物中に粒子
として分散しているリン系硬化促進剤の粒子の最大粒子
径を２０μｍ以下とするための手段として、請求項４〜
請求項６に記載している方法で行うことが好ましい。す
なわち、３本ロール又はらいかい機を用いてリン系硬化
促進剤をエポキシ樹脂組成物中に分散させると、エポキ
シ樹脂組成物中のリン系硬化促進剤の粒子の最大粒子径
を２０μｍ以下とすることが容易に可能となる。また、
リン系硬化促進剤をエポキシ樹脂及び／又はフェノール
系硬化剤と予備混合してリン系硬化促進剤を予め分散さ
せた後、残りの構成成分を添加して混合すると、やはり
容易に粒子の最大粒子径を２０μｍ以下とすることがで
きる。なお、フェノール系硬化剤のみではリン系硬化促
進剤によって反応が進行することが少ないので、フェノ
ール系硬化剤と予備混合する方が、エポキシ樹脂と予備
混合するよりも、混合条件の自由度が広い点で好まし
い。また、この予備混合は、エポキシ樹脂やフェノール
系硬化剤が固形又は高粘度の場合には加温して適当な粘
度にして行うのが好ましく、具体的にはエポキシ樹脂又
はフェノール系硬化剤の粘度を１００〜１５００ポイズ
に調整して予備混合を行うのが好ましい。In the present invention, the means for controlling the maximum particle diameter of the particles of the phosphorus-based curing accelerator dispersed in the epoxy resin composition as particles to be 20 μm or less is defined in claims 4 to 5.
The method described in claim 6 is preferable. That is, when the phosphorus-based curing accelerator is dispersed in the epoxy resin composition by using a three-roll or ladle machine, the maximum particle diameter of the particles of the phosphorus-based curing accelerator in the epoxy resin composition becomes 20 μm or less. It becomes possible easily. Also,
If the phosphorus-based curing accelerator is premixed with the epoxy resin and / or the phenol-based curing agent to disperse the phosphorus-based curing accelerator in advance, and then the remaining constituents are added and mixed, the maximum particle size of the particles can be easily increased. The diameter can be 20 μm or less. Since the reaction is less likely to be promoted by the phosphorus-based curing accelerator with only the phenol-based curing agent, premixing with the phenolic curing agent has a wider degree of freedom in mixing conditions than premixing with the epoxy resin. It is preferable in terms. Further, this premixing is preferably carried out by heating to a suitable viscosity when the epoxy resin or the phenol-based curing agent is solid or has a high viscosity, and specifically, the viscosity of the epoxy resin or the phenol-based curing agent. Is preferably adjusted to 100 to 1500 poise and premixed.
【００１６】[0016]
【実施例】以下、本発明を実施例及び比較例に基づいて
説明する。The present invention will be described below based on examples and comparative examples.
【００１７】まず、下記の実施例及び比較例で使用した
原材料について説明する。エポキシ樹脂としては、エポ
キシ当量５００のブロム化ビスフェノールＡ型エポキシ
樹脂（ダウケミカル社製、品番ＤＥＲ５１１）とエポキ
シ当量２２０のクレゾールノボラック型エポキシ樹脂
（東都化成社製、品番ＹＤＣＮ７０２Ｐ）を表１に示す
配合量で使用した。First, raw materials used in the following examples and comparative examples will be described. As the epoxy resin, a brominated bisphenol A type epoxy resin having an epoxy equivalent of 500 (manufactured by Dow Chemical Co., product number DER511) and a cresol novolac type epoxy resin having an epoxy equivalent of 220 (manufactured by Toto Kasei Co., product number YDCN702P) are shown in Table 1. Used in quantity.
【００１８】フェノール系硬化剤としては、水酸基当量
１０５のフェノールノボラック（荒川化学工業社製、商
品名タマノール７５２）を表１に示す配合量で使用し
た。リン系硬化促進剤としては、テトラフェニルホスホ
ニウムテトラフェニルボレート（北興化学工業社製、商
品名ＴＰＰ−Ｋ）又はトリフェニルホスフィントリフェ
ニルボラン（北興化学工業社製、商品名ＴＰＰ−Ｓ）を
表１に示す配合量で使用した。As the phenol-based curing agent, phenol novolac having a hydroxyl equivalent of 105 (trade name: Tamanol 752, manufactured by Arakawa Chemical Industry Co., Ltd.) was used in a compounding amount shown in Table 1. As the phosphorus-based curing accelerator, tetraphenylphosphonium tetraphenylborate (manufactured by Hokuko Chemical Industry Co., Ltd., trade name TPP-K) or triphenylphosphine triphenylborane (manufactured by Kitako Chemical Industry Co., Ltd., trade name TPP-S) is shown in Table 1. The compounding amount shown in was used.
【００１９】有機溶媒としては、メチルエチルケトンを
表１に示す配合量で使用した。As the organic solvent, methyl ethyl ketone was used in the blending amount shown in Table 1.
【００２０】（実施例１）表１の配合量に従って各原材
料は配合する。まず、フェノールノボラックを、１５０
℃に加温して溶融したものにテトラフェニルホスホニウ
ムテトラフェニルボレート（以下ＴＰＰ−Ｋと呼ぶ）を
添加しながらディスパー（特殊機化工業社製）で１５分
間混合分散を行い、冷却、固化した後、細かく粉砕す
る。得られた粉砕物を、以後ＴＰＰ−Ｋマスターバッチ
と呼ぶ。次にこのＴＰＰ−Ｋマスターバッチに残りの構
成成分（エポキシ樹脂及び有機溶剤）を添加し、さらに
ディスパーで６０分間混合して、積層板用エポキシ樹脂
組成物（ワニス）を作製した。このワニスから０．０５
ｇの試料を採取し、光学顕微鏡で観察して分散している
ＴＰＰ−Ｋの最大粒子径を測定したところ表１に示すよ
うに１０μｍであった。その後、ワニスを０．１ｍｍ厚
のガラスクロスに含浸し、１５０℃で乾燥、反応させ、
樹脂含有率５５重量％のプリプレグを作製した。(Example 1) Each raw material is blended according to the blending amount shown in Table 1. First, add phenol novolac to 150
After adding tetraphenylphosphonium tetraphenylborate (hereinafter referred to as TPP-K) to the melted material heated to 0 ° C, mixing and dispersing with Disper (manufactured by Tokushu Kika Kogyo Co., Ltd.) for 15 minutes, cooling and solidifying , Finely crush. The obtained pulverized product is hereinafter referred to as TPP-K masterbatch. Next, the remaining constituents (epoxy resin and organic solvent) were added to this TPP-K masterbatch, and the mixture was further mixed with a disper for 60 minutes to prepare an epoxy resin composition (varnish) for laminated board. 0.05 from this varnish
A sample of g was sampled and observed with an optical microscope to measure the maximum particle size of the dispersed TPP-K, which was 10 μm as shown in Table 1. Then, the varnish is impregnated into a glass cloth having a thickness of 0.1 mm, dried at 150 ° C. and reacted,
A prepreg having a resin content of 55% by weight was produced.
【００２１】次いで、厚み０．８ｍｍの両面銅張り積層
板（銅箔の厚みは３５μｍ）の表面の銅箔に黒化処理
（表面処理の１種）を施したものをコア材とし、その上
下に上記で得られたプリプレグを各３枚重ね、さらにそ
の両外側に厚み１８μｍの銅箔を配して積層したもの
を、１７０℃、６０分間成形して４層の導体層を有する
多層板を得た。得られた多層板を用いて、プリプレグが
硬化した層の性能（ガラス転移温度、煮沸後の半田耐熱
性）の評価を行い、その結果を表１に示す。なお、ガラ
ス転移温度及び煮沸後の半田耐熱性の評価は下記に示す
方法で行った。Next, a 0.8 mm-thick double-sided copper-clad laminate (copper foil having a thickness of 35 μm) that has been subjected to blackening treatment (one type of surface treatment) on the surface is used as the core material The above-prepared three prepregs are laminated on each other, and a copper foil having a thickness of 18 μm is further laminated on both outer sides of the prepreg and laminated to form a multilayer board having four conductor layers at 170 ° C. for 60 minutes. Obtained. The obtained multilayer board was used to evaluate the performance (glass transition temperature, solder heat resistance after boiling) of the layer in which the prepreg was cured, and the results are shown in Table 1. The glass transition temperature and solder heat resistance after boiling were evaluated by the following methods.
【００２２】（ガラス転移温度の評価方法）得られた多
層板からプリプレグが硬化した層のみをはぎ取り、この
はぎ取った部分について、粘弾性測定装置（セイコー電
子工業社製）を用いて、５℃／分で昇温させて、ｔａｎ
δの温度分散を測定し、ｔａｎδのピークが生じた温度
をガラス転移温度として測定する。(Evaluation Method of Glass Transition Temperature) Only the layer in which the prepreg was cured was peeled off from the obtained multilayer plate, and the peeled portion was measured at 5 ° C. / Raise the temperature in minutes, then tan
The temperature dispersion of δ is measured, and the temperature at which the tan δ peak occurs is measured as the glass transition temperature.
【００２３】（煮沸後の半田耐熱性の評価方法）得られ
た多層板の外層の厚み１８μｍの銅箔をエッチングで除
去したものを、５ｃｍ角に切断して試験片とする。この
試験片の端面を研磨した後、煮沸したイオン水（イオン
交換膜を用いて精製した水）中に、所定時間浸漬した
後、表面の水分を拭き取り、２６０℃の半田浴に３０秒
間浸漬する。半田浸漬後の試験片の表面を目視で観察
し、ミーズリング現象（樹脂とガラス布とが剥離して生
じる現象）の発生の有無を評価する。ｎ数４で試験し
て、４個共にミーズリング現象が発生していない最長の
煮沸したイオン水への浸漬時間を、煮沸後の半田耐熱性
の指標とする。(Evaluation method of solder heat resistance after boiling) A copper foil having a thickness of 18 μm, which is an outer layer of the obtained multilayer board, was removed by etching and cut into a 5 cm square to obtain a test piece. After polishing the end face of this test piece, it was immersed in boiled ionic water (water purified using an ion exchange membrane) for a predetermined time, and then the surface water was wiped off and immersed in a solder bath at 260 ° C for 30 seconds. . The surface of the test piece after the solder immersion is visually observed to evaluate whether or not a measling phenomenon (a phenomenon caused by peeling between the resin and the glass cloth) occurs. Tested with n of 4, the longest immersion time in boiled ionic water in which no measling phenomenon occurred was used as an index of solder heat resistance after boiling.
【００２４】（実施例２）ＴＰＰ−Ｋマスターバッチ作
製時のディスパーによる混合時間を５分間とした以外
は、実施例１と同様にして、ワニス、プリプレグ及び多
層板を作製すると共に、分散しているＴＰＰ−Ｋの最大
粒子径、ガラス転移温度及び煮沸後の半田耐熱性の評価
を行った。得られた結果を表１に示す。(Example 2) A varnish, a prepreg and a multilayer board were prepared and dispersed in the same manner as in Example 1 except that the mixing time with the disperser at the time of preparing the TPP-K masterbatch was 5 minutes. The maximum particle size, glass transition temperature, and solder heat resistance after boiling of TPP-K were evaluated. The results obtained are shown in Table 1.
【００２５】（実施例３）ＴＰＰ−Ｋに代えてＴＰＰ−
Ｓを使用した以外は実施例２と同様にして、ワニス、プ
リプレグ及び多層板を作製すると共に、分散しているＴ
ＰＰ−Ｓの最大粒子径、ガラス転移温度及び煮沸後の半
田耐熱性の評価を行った。得られた結果を表１に示す。(Embodiment 3) Instead of TPP-K, TPP-
A varnish, a prepreg and a multilayer board were prepared and dispersed in the same manner as in Example 2 except that S was used.
The maximum particle size of PP-S, the glass transition temperature, and the solder heat resistance after boiling were evaluated. The results obtained are shown in Table 1.
【００２６】（実施例４）エポキシ樹脂、フェノールノ
ボラック及びＴＰＰ−Ｋについては表１に示す配合量、
そして有機溶剤については表１に示す配合量の１／２量
を配合、混合し、次いで常温の３本ロールで５分間混練
した後、残りの有機溶剤を加え、ディスパー（特殊機化
工業社製）で１５分間混合分散を行い、積層板用エポキ
シ樹脂組成物（ワニス）を作製した。(Example 4) For epoxy resin, phenol novolac and TPP-K, the compounding amounts shown in Table 1,
Regarding the organic solvent, 1/2 of the compounding amount shown in Table 1 was mixed and mixed, and then the mixture was kneaded with a three-roll roller at room temperature for 5 minutes, and then the remaining organic solvent was added to disperse ) Was mixed and dispersed for 15 minutes to prepare an epoxy resin composition (varnish) for laminated board.
【００２７】ワニス作製以降については実施例１と同様
の操作を行い、プリプレグ及び多層板を作製すると共
に、ワニス中に分散しているＴＰＰ−Ｋの最大粒子径、
ガラス転移温度及び煮沸後の半田耐熱性の評価を行っ
た。得られた結果を表１に示す。After the production of the varnish, the same operation as in Example 1 was carried out to produce the prepreg and the multilayer board, and the maximum particle size of TPP-K dispersed in the varnish,
The glass transition temperature and solder heat resistance after boiling were evaluated. The results obtained are shown in Table 1.
【００２８】（実施例５）エポキシ樹脂、フェノールノ
ボラック及びＴＰＰ−Ｋについては表１に示す配合量、
そして有機溶剤については表１に示す配合量の１／２量
を配合、混合し、次いでらいかい機（日陶科学社製の自
動乳鉢、型式：ＡＴＭ１０００型）を用いて、常温で２
０分間混練した後、残りの有機溶剤を加え、ディスパー
（特殊機化工業社製）で６０分間混合分散を行い、積層
板用エポキシ樹脂組成物（ワニス）を作製した。(Example 5) For epoxy resin, phenol novolac and TPP-K, the compounding amounts shown in Table 1,
Regarding the organic solvent, 1/2 of the compounding amount shown in Table 1 is blended and mixed, and then 2 at room temperature using a Raikarai machine (automatic mortar manufactured by Nitto Kagaku Co., model: ATM1000).
After kneading for 0 minutes, the remaining organic solvent was added and mixed and dispersed for 60 minutes with Disper (manufactured by Tokushu Kika Kogyo Co., Ltd.) to prepare an epoxy resin composition (varnish) for laminated board.
【００２９】ワニス作製以降については実施例１と同様
の操作を行い、プリプレグ及び多層板を作製すると共
に、ワニス中に分散しているＴＰＰ−Ｋの最大粒子径、
ガラス転移温度及び煮沸後の半田耐熱性の評価を行っ
た。得られた結果を表１に示す。After the production of the varnish, the same operation as in Example 1 was carried out to produce the prepreg and the multilayer board, and the maximum particle size of TPP-K dispersed in the varnish,
The glass transition temperature and solder heat resistance after boiling were evaluated. The results obtained are shown in Table 1.
【００３０】（実施例６）ＴＰＰ−Ｋマスターバッチ作
製時の混合装置としてディスパーの代わりに３本ロール
を使用し、３本ロールによる混練時間を５分間とした以
外は、実施例１と同様にして、ワニス、プリプレグ及び
多層板を作製すると共に、分散しているＴＰＰ−Ｋの最
大粒子径、ガラス転移温度及び煮沸後の半田耐熱性の評
価を行った。得られた結果を表１に示す。(Example 6) The same as Example 1 except that three rolls were used in place of the disperser as the mixing apparatus for preparing the TPP-K masterbatch, and the kneading time by the three rolls was 5 minutes. Then, a varnish, a prepreg, and a multilayer board were produced, and the maximum particle size of the dispersed TPP-K, the glass transition temperature, and the solder heat resistance after boiling were evaluated. The results obtained are shown in Table 1.
【００３１】（比較例１）表２に示す配合量の、エポキ
シ樹脂、フェノールノボラック、ＴＰＰ−Ｋ及び有機溶
剤を配合し、次いでディスパー（特殊機化工業社製）で
６０分間混合分散を行い、積層板用エポキシ樹脂組成物
（ワニス）を作製した。(Comparative Example 1) Epoxy resin, phenol novolac, TPP-K and organic solvent in the amounts shown in Table 2 were mixed, and then mixed and dispersed with Disper (manufactured by Tokushu Kika Kogyo Co., Ltd.) for 60 minutes, An epoxy resin composition (varnish) for laminated board was produced.
【００３２】ワニス作製以降については実施例１と同様
の操作を行い、プリプレグ及び多層板を作製すると共
に、ワニス中に分散しているＴＰＰ−Ｋの最大粒子径、
ガラス転移温度及び煮沸後の半田耐熱性の評価を行っ
た。得られた結果を表２に示す。After the production of the varnish, the same operation as in Example 1 was carried out to produce the prepreg and the multilayer board, and the maximum particle size of TPP-K dispersed in the varnish,
The glass transition temperature and solder heat resistance after boiling were evaluated. Table 2 shows the obtained results.
【００３３】（比較例２）ＴＰＰ−Ｋに代えてＴＰＰ−
Ｓを使用した以外は比較例１と同様にして、ワニス、プ
リプレグ及び多層板を作製すると共に、分散しているＴ
ＰＰ−Ｓの最大粒子径、ガラス転移温度及び煮沸後の半
田耐熱性の評価を行った。得られた結果を表２に示す。(Comparative Example 2) Instead of TPP-K, TPP-
A varnish, a prepreg, and a multilayer board were prepared and dispersed in the same manner as in Comparative Example 1 except that S was used.
The maximum particle size of PP-S, the glass transition temperature, and the solder heat resistance after boiling were evaluated. Table 2 shows the obtained results.
【００３４】[0034]
【表１】 [Table 1]
【００３５】[0035]
【表２】 [Table 2]
【００３６】表１及び表２の結果から、実施例１〜実施
例６では分散しているリン系硬化促進剤の最大粒子系は
２０μｍ以下であり、比較例に比べ、細かい粒子となっ
て分散していることが確認できる。そして、実施例１〜
実施例６で得られたプリプレグの硬化物の耐熱特性（ガ
ラス転移温度及び煮沸後の半田耐熱性）は比較例に比べ
良好であることも確認できる。From the results shown in Tables 1 and 2, the maximum particle size of the phosphorus-based curing accelerator dispersed in Examples 1 to 6 is 20 μm or less, which is smaller than the comparative example and dispersed. You can confirm that you are doing. And Example 1-
It can also be confirmed that the heat resistance characteristics (glass transition temperature and solder heat resistance after boiling) of the cured product of the prepreg obtained in Example 6 are better than those of Comparative Example.
【００３７】また、実施例１と比較例１の比較、実施例
２と比較例１の比較及び実施例３と比較例２の比較か
ら、混合装置としてディスパーを用いてもマスターバッ
チ工法を採用すれば、リン系硬化促進剤を細かい粒子と
して分散させることが可能であることが確認できる。そ
して、実施例４と比較例１及び実施例５と比較例１の比
較から、混合装置としてらいかい機又は３本ロールを使
用すると、リン系硬化促進剤を細かい粒子として分散さ
せることが可能であることが確認できる。Further, from the comparison between Example 1 and Comparative Example 1, the comparison between Example 2 and Comparative Example 1 and the comparison between Example 3 and Comparative Example 2, even if a disper is used as the mixing device, the masterbatch method should be adopted. For example, it can be confirmed that the phosphorus-based curing accelerator can be dispersed as fine particles. From the comparison between Example 4 and Comparative Example 1 and Example 5 and Comparative Example 1, it is possible to disperse the phosphorus-based curing accelerator in the form of fine particles by using a ladle machine or a triple roll as a mixing device. It can be confirmed that there is.
【００３８】[0038]
【発明の効果】請求項１〜請求項３に係る発明の積層板
用エポキシ樹脂組成物は、エポキシ樹脂、フェノール系
硬化剤、リン系硬化促進剤及び有機溶媒を含み、リン系
硬化促進剤が粒子として分散しているエポキシ樹脂組成
物であって、耐熱特性の優れる積層板を得ることが可能
なエポキシ樹脂組成物となるので、積層板を製造するた
めの材料として有用である。The epoxy resin composition for laminated boards of the invention according to claims 1 to 3 contains an epoxy resin, a phenol-based curing agent, a phosphorus-based curing accelerator and an organic solvent. It is an epoxy resin composition dispersed as particles, and is an epoxy resin composition capable of obtaining a laminate having excellent heat resistance characteristics, and thus is useful as a material for producing a laminate.
【００３９】請求項４〜請求項６に係る発明の積層板用
エポキシ樹脂組成物の製造方法によれば、上記の効果を
奏する積層板用エポキシ樹脂組成物を容易に製造するこ
とができる。According to the method for producing an epoxy resin composition for a laminated board of the present invention according to claims 4 to 6, an epoxy resin composition for a laminated board having the above effects can be easily produced.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 元部 英次 大阪府門真市大字門真1048番地松下電工株 式会社内 (72)発明者 八田 行大 大阪府門真市大字門真1048番地松下電工株 式会社内 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Eiji Motobu 1048, Kadoma, Kadoma, Osaka Prefecture Matsushita Electric Works Co., Ltd. (72) Inventor, Yukihiro Hatta, 1048, Kadoma, Kadoma, Osaka Prefecture Matsushita Electric Works Co., Ltd. In the company
Claims (6)
ン系硬化促進剤及び有機溶媒を含む積層板用エポキシ樹
脂組成物において、リン系硬化促進剤がエポキシ樹脂組
成物中に粒子として分散していて、かつ、その粒子の最
大粒子径が０．１〜２０μｍであることを特徴とする積
層板用エポキシ樹脂組成物。1. An epoxy resin composition for a laminate comprising an epoxy resin, a phenol-based curing agent, a phosphorus-based curing accelerator and an organic solvent, wherein the phosphorus-based curing accelerator is dispersed as particles in the epoxy resin composition. And an epoxy resin composition for laminated boards, wherein the maximum particle diameter of the particles is 0.1 to 20 μm.
スホニウムテトラフェニルボレートであることを特徴と
する請求項１記載の積層板用エポキシ樹脂組成物。2. The epoxy resin composition for a laminate according to claim 1, wherein the phosphorus-based curing accelerator is tetraphenylphosphonium tetraphenylborate.
フィントリフェニルボランであることを特徴とする請求
項１記載の積層板用エポキシ樹脂組成物。3. The epoxy resin composition for a laminate according to claim 1, wherein the phosphorus-based curing accelerator is triphenylphosphine triphenylborane.
記載の積層板用エポキシ樹脂組成物を得るにあたり、３
本ロールを用いてリン系硬化促進剤をエポキシ樹脂組成
物中に分散させることを特徴とする積層板用エポキシ樹
脂組成物の製造方法。4. In obtaining the epoxy resin composition for laminated board according to any one of claims 1 to 3, 3
A method for producing an epoxy resin composition for a laminate, which comprises using the present roll to disperse a phosphorus-based curing accelerator in the epoxy resin composition.
記載の積層板用エポキシ樹脂組成物を得るにあたり、ら
いかい機を用いてリン系硬化促進剤をエポキシ樹脂組成
物中に分散させることを特徴とする積層板用エポキシ樹
脂組成物の製造方法。5. When obtaining the epoxy resin composition for a laminate according to any one of claims 1 to 3, a phosphorus-based curing accelerator is dispersed in the epoxy resin composition by using a ladle machine. A method for producing an epoxy resin composition for a laminated board, comprising:
記載の積層板用エポキシ樹脂組成物を得るにあたり、リ
ン系硬化促進剤をエポキシ樹脂及び／又はフェノール系
硬化剤と予備混合してリン系硬化促進剤を予め分散させ
た後、残りの構成成分を添加して混合することを特徴と
する積層板用エポキシ樹脂組成物の製造方法。6. In obtaining the epoxy resin composition for a laminate according to any one of claims 1 to 3, a phosphorus-based curing accelerator is premixed with an epoxy resin and / or a phenol-based curing agent. A method for producing an epoxy resin composition for a laminate, which comprises dispersing a phosphorus-based curing accelerator in advance and then adding and mixing the remaining components.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24293295A JPH0987367A (en) | 1995-09-21 | 1995-09-21 | Epoxy resin composition for laminate and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24293295A JPH0987367A (en) | 1995-09-21 | 1995-09-21 | Epoxy resin composition for laminate and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0987367A true JPH0987367A (en) | 1997-03-31 |
Family
ID=17096368
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24293295A Withdrawn JPH0987367A (en) | 1995-09-21 | 1995-09-21 | Epoxy resin composition for laminate and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0987367A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008201998A (en) * | 2007-02-22 | 2008-09-04 | Shin Etsu Chem Co Ltd | Epoxy resin adhesive composition |
-
1995
- 1995-09-21 JP JP24293295A patent/JPH0987367A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008201998A (en) * | 2007-02-22 | 2008-09-04 | Shin Etsu Chem Co Ltd | Epoxy resin adhesive composition |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1170908C (en) | Interlamellar insulation adhesive using for multilayer printed circuit board | |
| JP5260400B2 (en) | Multilayer board for producing multilayer printed wiring boards | |
| EP0610075A1 (en) | Polyphenylene oxide epoxy prepegs | |
| JP5549183B2 (en) | Method for producing epoxy resin composition, method for producing prepreg, method for producing laminated board and wiring board | |
| WO2015001764A1 (en) | Resin composition, prepreg and laminate board | |
| TWI502013B (en) | Resin composition, prepreg, and paste metal sheet laminate | |
| JP2687805B2 (en) | Resin composition, prepreg and laminated board | |
| JPH10158472A (en) | Epoxy resin composition, epoxy resin varnish, epoxy resin prepreg and multilayer printed wiring board made by using this epoxy resin prepreg as prepreg for bonding | |
| JPH0987367A (en) | Epoxy resin composition for laminate and its production | |
| JP3339815B2 (en) | Epoxy resin composition for producing laminate for electrical insulating material and method for producing prepreg | |
| TWI221477B (en) | Thermosetting resin compositions for build-up method | |
| JP2003160726A (en) | Polyphenylene oxide resin composition, its production method, prepreg, laminated board, printed wiring board and multi-layered printed wiring board | |
| WO2016031228A1 (en) | Resin composition, prepreg, metal foil with resin, metal-clad laminate, printed wiring board | |
| JP3363388B2 (en) | Epoxy resin composition, prepreg and metal foil-clad laminate | |
| JP3243027B2 (en) | Copper clad laminate | |
| JP2848241B2 (en) | Epoxy resin composition for laminate and method for producing the same | |
| JPH09316219A (en) | Prepreg, manufacturing method thereof, and laminated plate | |
| JP3265871B2 (en) | Epoxy resin composition for laminated board | |
| JP2015013941A (en) | Resin composition, prepreg and laminate | |
| JP3770989B2 (en) | Manufacturing method of prepreg | |
| JP3288819B2 (en) | Copper clad laminate | |
| JPH08269173A (en) | Epoxy resin composition | |
| JPH0726122A (en) | Epoxy resin composition for printed-wiring board | |
| JPH0745716B2 (en) | Resist ink for electroless plating | |
| JP4301009B2 (en) | Prepreg and laminate manufacturing method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Withdrawal of application because of no request for examination |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 20021203 |