JPH09207271A - Glass epoxy copper-plated laminated board - Google Patents
Glass epoxy copper-plated laminated boardInfo
- Publication number
- JPH09207271A JPH09207271A JP4426096A JP4426096A JPH09207271A JP H09207271 A JPH09207271 A JP H09207271A JP 4426096 A JP4426096 A JP 4426096A JP 4426096 A JP4426096 A JP 4426096A JP H09207271 A JPH09207271 A JP H09207271A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- weight
- glass
- epoxy
- copper
- 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
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
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ハロゲンフリー
で、燃焼時有毒ガスを発生することなく、耐熱性、耐湿
性、耐トラッキング性、難燃性等に優れたガラスエポキ
シ銅張積層板に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a glass-epoxy copper-clad laminate which is halogen-free, does not generate toxic gas upon combustion, and is excellent in heat resistance, moisture resistance, tracking resistance, flame retardancy and the like.
【０００２】[0002]
【従来の技術】近年、地球環境保全の見地から、オゾン
層破壊物質への規制が高まり、特定フロン、トリクロロ
エタン等は、１９９５年末全廃が確定している。一方、
難燃剤としてプリント基板に使用されているハロゲン物
質は、ガラスエポキシ銅張積層板の場合、大半が臭素系
で、テトラブロモビスフェノールＡを中心とする誘導体
が広く使用されており、燃焼の際に有毒ガスであるハロ
ゲン化水素を発生するという欠点があり、脱ハロゲン化
への要求が高まっている。また、１９９５年７月からＰ
Ｌ法が施行された背景から、安全性向上を目的とした耐
トラッキング性（ＣＴＩ 600Ｖ）が要求されつつある。2. Description of the Related Art In recent years, regulations on ozone layer depleting substances have been increasing from the viewpoint of global environmental protection, and specific fluorocarbons, trichloroethane and the like have been completely abolished at the end of 1995. on the other hand,
In the case of glass epoxy copper-clad laminates, most of the halogen substances used in printed circuit boards as flame retardants are bromine-based, and derivatives mainly based on tetrabromobisphenol A are widely used. It has the disadvantage of generating poisonous gas, hydrogen halide, and the demand for dehalogenation is increasing. Also, since July 1995, P
Under the background of the enforcement of the L law, tracking resistance (CTI 600 V) for the purpose of improving safety is being demanded.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、上記の事情
に鑑みてなされたもので、難燃化の手法としてハロゲン
を用いないハロゲンフリーで、このため燃焼の際に有毒
ガスの発生がなく、耐熱性、耐湿性、耐トラッキング
性、難燃性等に優れたガラスエポキシ銅張積層板を提供
するものである。DISCLOSURE OF THE INVENTION The present invention has been made in view of the above circumstances, and is a halogen-free method that does not use halogen as a flame-retarding method, so that no toxic gas is generated during combustion. Another object of the present invention is to provide a glass epoxy copper clad laminate excellent in heat resistance, moisture resistance, tracking resistance, flame retardancy and the like.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、上記の目
的を達成しようと鋭意研究を重ねた結果、難燃剤として
ハロゲンを使用することなく、エポキシ樹脂組成物に窒
素変性フェノール樹脂硬化剤と赤リンを配合することに
よって、上記目的が達成できることを見いだし、本発明
を完成したものである。Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, a nitrogen-modified phenolic resin curing agent was added to an epoxy resin composition without using a halogen as a flame retardant. It has been found that the above object can be achieved by blending red phosphorus with red phosphorus, and the present invention has been completed.
【０００５】即ち、本発明は、ガラス基材にエポキシ樹
脂組成物を含浸・乾燥させたプリプレグを複数枚積層
し、その少なくとも片面に銅箔を重ね合わせて一体に成
形するガラスエポキシ銅張積層板において、前記エポキ
シ樹脂組成物として（Ａ）ビスフェノールＡ型エポキシ
樹脂、（Ｂ）ノボラック型エポキシ樹脂、（Ｃ）窒素変
性フェノール樹脂、（Ｄ）赤リン、（Ｅ）硬化促進剤お
よび（Ｆ）無機充填剤を必須成分とし、全体の樹脂組成
物に対して、（Ｃ）の窒素変性フェノール樹脂を 5〜50
重量％、また（Ｄ）の赤リンを 1〜10重量％の割合でそ
れぞれ含有するエポキシ樹脂組成物を用いてなることを
特徴とするガラスエポキシ銅張積層板である。That is, the present invention relates to a glass epoxy copper clad laminate in which a plurality of prepregs, each impregnated with an epoxy resin composition and dried on a glass substrate, are laminated, and a copper foil is laminated on at least one side thereof and integrally molded. In the above, as the epoxy resin composition, (A) bisphenol A type epoxy resin, (B) novolak type epoxy resin, (C) nitrogen-modified phenol resin, (D) red phosphorus, (E) curing accelerator and (F) inorganic A filler is an essential component, and the nitrogen-modified phenolic resin (C) is added to the entire resin composition in an amount of 5 to 50%.
A glass epoxy copper clad laminate characterized by using an epoxy resin composition containing 1% by weight and 1 to 10% by weight of red phosphorus of (D).
【０００６】以下、本発明を詳細に説明する。Hereinafter, the present invention will be described in detail.
【０００７】本発明に用いるエポキシ樹脂組成物は
（Ａ）ビスフェノールＡ型エポキシ樹脂、（Ｂ）ノボラ
ック型エポキシ樹脂、（Ｃ）窒素変性フェノール樹脂、
（Ｄ）赤リン、（Ｅ）硬化促進剤及び（Ｆ）無機充填剤
を必須成分とするものである。これらの各成分について
説明する。The epoxy resin composition used in the present invention comprises (A) a bisphenol A epoxy resin, (B) a novolak epoxy resin, (C) a nitrogen-modified phenol resin,
(D) Red phosphorus, (E) a curing accelerator, and (F) an inorganic filler are essential components. Each of these components will be described.
【０００８】エポキシ樹脂組成物の成分である（Ａ）ビ
スフェノールＡ型エポキシ樹脂としては、エポキシ当量
が 170〜1000であればよく、特に制限はなく広く使用す
ることができる。そしてこれらのビスフェノールＡ型エ
ポキシ樹脂は、単独または 2種以上混合して使用するこ
とができる。ビスフェノールＡ型エポキシ樹脂は一般に
エポキシ当量が 170以上であり、また1000を超えると含
浸性が低下し好ましくない。The bisphenol A type epoxy resin (A), which is a component of the epoxy resin composition, may have an epoxy equivalent of from 170 to 1000, and is not particularly limited and can be widely used. These bisphenol A type epoxy resins can be used alone or in combination of two or more. The bisphenol A type epoxy resin generally has an epoxy equivalent of 170 or more, and if it exceeds 1,000, the impregnation property is undesirably reduced.
【０００９】エポキシ樹脂組成物の成分である（Ｂ）ノ
ボラック型エポキシ樹脂としては、フェノール型、クレ
ゾール型、ビスフェノールＡ型等が挙げられ、これらは
単独または 2種以上混合して使用することができる。The novolak type epoxy resin (B) which is a component of the epoxy resin composition includes phenol type, cresol type, bisphenol A type and the like, and these can be used alone or in combination of two or more. .
【００１０】エポキシ樹脂組成物の成分である（Ｃ）窒
素変性フェノール樹脂としては、前記（Ａ）および
（Ｂ）のエポキシ樹脂の硬化剤として使用するもので、
窒素変性にはアニリン変性、メラミン変性、グアニジン
変性、ジシアンアミド変性、グアナミン変性、ユリア変
性、脂肪酸アミド変性、ポリアミド変性、トルジン変
性、シアヌール酸変性およびこれらの誘導体変性があ
る。窒素変性フェノール樹脂はその水酸基当量、窒素変
性量に特に制限されるものではなく使用することができ
るが、窒素変性量が少ないと良好な難燃性及び耐トラッ
キング性が得られない。窒素変性フェノール樹脂の配合
割合は、全体の樹脂組成物に対して10〜50重量％配合す
ることが望ましい。配合割合が10重量％未満では窒素含
有量が不足し、十分な難燃性が得られず、また、50重量
％を超えると硬化剤過多となり、十分な耐熱性が得られ
ず好ましくない。The (C) nitrogen-modified phenolic resin, which is a component of the epoxy resin composition, is used as a curing agent for the epoxy resins of (A) and (B) above.
Nitrogen modification includes aniline modification, melamine modification, guanidine modification, dicyanamide modification, guanamine modification, urea modification, fatty acid amide modification, polyamide modification, tolzine modification, cyanuric acid modification and derivatives thereof. The nitrogen-modified phenolic resin can be used without any particular limitation on its hydroxyl group equivalent and nitrogen modification amount, but if the nitrogen modification amount is small, good flame retardancy and tracking resistance cannot be obtained. The compounding ratio of the nitrogen-modified phenol resin is desirably 10 to 50% by weight based on the entire resin composition. If the compounding ratio is less than 10% by weight, the nitrogen content is insufficient and sufficient flame retardancy cannot be obtained, and if it exceeds 50% by weight, the curing agent becomes excessive and sufficient heat resistance cannot be obtained, which is not preferable.
【００１１】エポキシ樹脂組成物の成分である（Ｄ）赤
リンとしては、表面未処理の赤リン、表面樹脂コートし
た赤リン、無機フィラーでコートした赤リン等が挙げら
れ、特に制限されるものではない。赤リンの配合割合
は、 1〜20重量％であることが望ましい。その配合割合
が1 重量％未満では十分な難燃性が得られず、また、20
重量％を超えると十分な耐熱性、耐湿性が得られず好ま
しくない。The (D) red phosphorus which is a component of the epoxy resin composition includes, for example, red phosphorus having no surface treatment, red phosphorus coated with a surface resin, red phosphorus coated with an inorganic filler, and the like. is not. The mixing ratio of red phosphorus is preferably 1 to 20% by weight. If the compounding ratio is less than 1% by weight, sufficient flame retardancy cannot be obtained.
If the content exceeds 10% by weight, sufficient heat resistance and moisture resistance cannot be obtained, which is not preferable.
【００１２】またエポキシ樹脂組成物の成分である
（Ｅ）の硬化促進剤については特に制限はなく、通常エ
ポキシ樹脂の硬化に使用されている化合物でよく、アミ
ン硬化系としては、ジシアンジアミド、芳香族アミン等
が挙げられ、フェノール硬化系としては、フェノールノ
ボラック樹脂、クレゾールノボラック樹脂、ビスフェノ
ールＡ型ノボラック樹脂等が挙げられ、これらは単独ま
たは 2種以上混合して使用することができる。The curing accelerator (E), which is a component of the epoxy resin composition, is not particularly limited, and may be a compound usually used for curing an epoxy resin. Examples of amine curing systems include dicyandiamide and aromatic compounds. Examples include amines. Examples of the phenol curing system include phenol novolak resins, cresol novolak resins, and bisphenol A-type novolak resins. These can be used alone or as a mixture of two or more.
【００１３】エポキシ樹脂組成物の成分である（Ｆ）無
機充填剤としては、タルク、シリカ、アルミナ、水酸化
アルミニウム、水酸化マグネシウム、酸化チタン等が挙
げられ、これらは単独はまたは 2種以上混合して使用す
ることができる。無機充填剤の配合割合は、樹脂組成物
全体に対して、10〜50重量％の割合で、配合することが
望ましい。配合量が10重量％未満では、十分な難燃性、
耐熱性、耐湿性が得られず、また50重量％を超えると粘
度が増加し、基材に塗布ムラが発生しボイドや板厚不良
となり好ましくない。Examples of the (F) inorganic filler which is a component of the epoxy resin composition include talc, silica, alumina, aluminum hydroxide, magnesium hydroxide, and titanium oxide. These may be used alone or in combination of two or more. Can be used. It is desirable to mix the inorganic filler at a ratio of 10 to 50% by weight based on the entire resin composition. If the amount is less than 10% by weight, sufficient flame retardancy,
Heat resistance and moisture resistance cannot be obtained, and if it exceeds 50% by weight, the viscosity increases and coating unevenness occurs on the base material, resulting in voids and poor plate thickness, which is not preferable.
【００１４】上述した（Ａ）ビスフェノールＡ型エポキ
シ樹脂、（Ｂ）ノボラック型エポキシ樹脂、（Ｃ）窒素
変性フェノール樹脂、（Ｄ）赤リン、（Ｅ）硬化促進剤
および（Ｆ）無機充填剤を配合混合して容易にエポキシ
樹脂組成物を製造することができる。このエポキシ樹脂
組成物を常法のとおりガラス基材に塗布・含浸・乾燥し
てプリプレグをつくることができる。The above-mentioned (A) bisphenol A type epoxy resin, (B) novolak type epoxy resin, (C) nitrogen-modified phenol resin, (D) red phosphorus, (E) curing accelerator and (F) inorganic filler. The epoxy resin composition can be easily produced by mixing and mixing. The prepreg can be prepared by applying, impregnating and drying the epoxy resin composition on a glass substrate in a conventional manner.
【００１５】本発明に用いるガラス基材および銅箔は、
ともに、通常ガラスエポキシ銅張積層板に使用されるも
のであれば特に制限はなく使用することができる。ガラ
ス基材としてガラス織布、ガラス不織布、ガラスマット
等が挙げられる。また、銅箔としては通常ガラスエポキ
シ銅張積層板に使用されている圧延銅箔、電解銅箔等が
使用することができる。The glass substrate and the copper foil used in the present invention are:
Both can be used without particular limitation as long as they are usually used for a glass epoxy copper clad laminate. Examples of the glass substrate include a glass woven fabric, a glass nonwoven fabric, and a glass mat. Further, as the copper foil, a rolled copper foil, an electrolytic copper foil or the like which is usually used for a glass epoxy copper clad laminate can be used.
【００１６】本発明のガラスエポキシ銅張積層板の製造
方法は、上述のようにして作ったプリプレグの複数枚
と、銅箔を重ねて加熱加圧一体に成形して製造すること
ができる。The method for producing a glass-epoxy copper-clad laminate of the present invention can be produced by laminating a plurality of prepregs produced as described above and a copper foil, and integrally molding them by heating and pressing.
【００１７】本発明は、ガラスエポキシ銅張積層板の難
燃化手法としてエポキシ樹脂組成物に窒素変性フェノー
ル樹脂硬化剤と赤リンを配合することによって、燃焼時
の有毒ガスを発生させることなく、難燃性、耐熱性、耐
湿性、耐トラッキング性を付与させることができたもの
である。The present invention provides a method of making a glass epoxy copper-clad laminate flame-retardant by blending a nitrogen-modified phenolic resin curing agent and red phosphorus into an epoxy resin composition without generating toxic gas during combustion. Flame resistance, heat resistance, moisture resistance, and tracking resistance can be imparted.
【００１８】[0018]
【発明の実施形態】次に本発明を実施例によって説明す
る。本発明はこれらの実施例よって限定されるものでは
ない。以下の実施例および比較例において「部」とは
「重量部」を意味する。Next, the present invention will be described with reference to examples. The present invention is not limited by these examples. In the following Examples and Comparative Examples, “parts” means “parts by weight”.
【００１９】実施例１ ビスフェノールＡ型エポキシ樹脂（エポキシ当量 456、
固形分70重量％）260部、クレゾールノボラックエポキ
シ樹脂（エポキシ当量 210、固形分70重量％）65部、窒
素変性フェノール樹脂［水酸基価 118、固形分70重量％
（窒素8 重量％）］ 104部、水酸化アルミニウム150
部、赤リン10部、2-エチル−4-メチルイミダゾール 0.1
部よびプロピレングリコールモノメチルエーテルを加え
て樹脂固形分65重量％のエポキシ樹脂ワニスを調製し
た。このエポキシ樹脂ワニスを用いてガラス不織布に連
続的に塗布・含浸させ、160 ℃の温度に乾燥させてプリ
プレグを得た。このプリプレグを 8枚重ね合わせ、その
両面に厚さ18μｍの銅箔を重ね、温度170 ℃，圧力40ｋ
ｇ／ｃｍで90分間、加熱加圧一体に成形して厚さ 1.6ｍ
ｍのガラスエポキシ銅張積層板を製造した。Example 1 Bisphenol A type epoxy resin (epoxy equivalent: 456,
260 parts, solid content 70% by weight, cresol novolak epoxy resin (epoxy equivalent 210, solid content 70% by weight) 65 parts, nitrogen-modified phenol resin [hydroxyl value 118, solid content 70% by weight
(Nitrogen 8% by weight)] 104 parts, aluminum hydroxide 150
Parts, red phosphorus 10 parts, 2-ethyl-4-methylimidazole 0.1
And propylene glycol monomethyl ether were added to prepare an epoxy resin varnish having a resin solid content of 65% by weight. Using this epoxy resin varnish, the glass nonwoven fabric was continuously applied and impregnated, and dried at a temperature of 160 ° C. to obtain a prepreg. Eight sheets of this prepreg are stacked, and copper foil with a thickness of 18 μm is stacked on both sides thereof, at a temperature of 170 ° C. and a pressure of 40 k.
Formed by heating / pressurizing for 90 minutes at g / cm for a thickness of 1.6m
m glass epoxy copper clad laminates were produced.
【００２０】実施例２ ビスフェノールＡ型エポキシ樹脂（エポキシ当量 456、
固形分70重量％）260部、クレゾールノボラックエポキ
シ樹脂（エポキシ当量 210、固形分70重量％）65部、窒
素変性フェノール樹脂［水酸基価 118、固形分70重量％
（窒素 8重量％）］104 部、水酸化アルミニウム100
部、赤リン10部、2-エチル−4-メチルイミダゾール 0.1
部およびプロピレングリコールモノメチルエーテルを加
えて樹脂固形分65重量％のエポキシ樹脂ワニスを調製し
た。このエポキシ樹脂ワニスを用いてガラス不織布に連
続的に塗布・含浸させ、160 ℃の温度に乾燥させてプリ
プレグを得た。このプリプレグを 8枚重ね合わせ、その
両面に厚さ18μｍの銅箔を重ね、温度170 ℃，圧力40ｋ
ｇ／ｃｍで90分間、加熱加圧一体に成形して厚さ 1.6ｍ
ｍのガラスエポキシ銅張積層板を製造した。Example 2 Bisphenol A type epoxy resin (epoxy equivalent: 456,
260 parts, solid content 70% by weight, cresol novolak epoxy resin (epoxy equivalent 210, solid content 70% by weight) 65 parts, nitrogen-modified phenol resin [hydroxyl value 118, solid content 70% by weight
(Nitrogen 8% by weight)] 104 parts, aluminum hydroxide 100
Parts, red phosphorus 10 parts, 2-ethyl-4-methylimidazole 0.1
And propylene glycol monomethyl ether were added to prepare an epoxy resin varnish having a resin solid content of 65% by weight. Using this epoxy resin varnish, the glass nonwoven fabric was continuously applied and impregnated, and dried at a temperature of 160 ° C. to obtain a prepreg. Eight sheets of this prepreg are stacked, and copper foil with a thickness of 18 μm is stacked on both sides thereof, at a temperature of 170 ° C. and a pressure of 40 k.
Formed by heating / pressurizing for 90 minutes at g / cm for a thickness of 1.6m
m glass epoxy copper clad laminates were produced.
【００２１】実施例３ ビスフェノールＡ型エポキシ樹脂（エポキシ当量 456、
固形分70重量％）260部、クレゾールノボラックエポキ
シ樹脂（エポキシ当量 210、固形分70重量％）65部、窒
素変性フェノール樹脂［水酸基価 118、固形分70重量％
（窒素16重量％）］104 部、水酸化アルミニウム100
部、赤リン10部、2-エチル−4-メチルイミダゾール 0.1
部およびプロピレングリコールモノメチルエーテルを加
えて樹脂固形分65重量％のエポキシ樹脂ワニスを調製し
た。このエポキシ樹脂ワニスを用いてガラス不織布に連
続的に塗布・含浸させ、160 ℃の温度に乾燥させてプリ
プレグを得た。このプリプレグを 8枚重ね合わせ、その
両面に厚さ18μｍの銅箔を重ね、温度170 ℃．圧力40ｋ
ｇ／ｃｍで90分間、加熱加圧一体に成形して厚さ 1.6ｍ
ｍのガラスエポキシ銅張積層板を製造した。Example 3 Bisphenol A type epoxy resin (epoxy equivalent: 456,
260 parts, solid content 70% by weight, cresol novolak epoxy resin (epoxy equivalent 210, solid content 70% by weight) 65 parts, nitrogen-modified phenol resin [hydroxyl value 118, solid content 70% by weight
(Nitrogen 16% by weight)] 104 parts, aluminum hydroxide 100
Parts, red phosphorus 10 parts, 2-ethyl-4-methylimidazole 0.1
And propylene glycol monomethyl ether were added to prepare an epoxy resin varnish having a resin solid content of 65% by weight. Using this epoxy resin varnish, the glass nonwoven fabric was continuously applied and impregnated, and dried at a temperature of 160 ° C. to obtain a prepreg. Eight sheets of this prepreg were laminated, and copper foil having a thickness of 18 μm was laminated on both sides thereof at a temperature of 170 ° C. Pressure 40k
Formed by heating / pressurizing for 90 minutes at g / cm for a thickness of 1.6m
m glass epoxy copper clad laminates were produced.
【００２２】比較例１ 臭素化エポキシ樹脂（エポキシ当量 490、固形分75重量
％）283 部、クレゾールノボラックエポキシ樹脂（エポ
キシ当量 210、固形分70重量％）34部、ビスフェノール
Ａ型ノボラック樹脂（水酸基価 118、固形分70重量％）
92部、水酸化アルミニウム 200部、2-エチル−4-メチル
イミダゾール 0.1部およびプロピレングリコールモノメ
チルエーテルを加えて樹脂固形分65重量％のエポキシ樹
脂ワニスを調製した。このエポキシ樹脂ワニスを用いて
ガラス不織布に連続的に塗布・含浸させ、160 ℃の温度
に乾燥させてプリプレグを得た。このプリプレグを 8枚
重ね合わせ、その両面に厚さ18μｍの銅箔を重ね、温度
170 ℃，圧力40ｋｇ／ｃｍで90分間、加熱加圧一体に成
形して厚さ 1.6ｍｍのガラスエポキシ銅張積層板を製造
した。Comparative Example 1 283 parts of a brominated epoxy resin (epoxy equivalent: 490, solid content: 75% by weight), 34 parts of cresol novolak epoxy resin (epoxy equivalent: 210, solid content: 70% by weight), bisphenol A type novolak resin (hydroxyl value) 118, solid content 70% by weight)
92 parts, 200 parts of aluminum hydroxide, 0.1 part of 2-ethyl-4-methylimidazole and propylene glycol monomethyl ether were added to prepare an epoxy resin varnish having a resin solid content of 65% by weight. Using this epoxy resin varnish, the glass nonwoven fabric was continuously applied and impregnated, and dried at a temperature of 160 ° C. to obtain a prepreg. Eight sheets of this prepreg are stacked, copper foil of 18 μm thickness is stacked on both sides,
The glass-epoxy-clad laminate having a thickness of 1.6 mm was manufactured by integrally heating and pressing at 170 ° C. and a pressure of 40 kg / cm for 90 minutes.
【００２３】比較例２ 臭素化エポキシ樹脂（エポキシ当量 490、固形分75重量
％）360 部、クレゾールノボラックエポキシ樹脂（エポ
キシ当量 210、固形分70重量％）43部、ジシアンジアミ
ド 7.5部、水酸化アルミニウム200 部、2-エチル−4-メ
チルイミダゾール 0.1部およびプロピレングリコールモ
ノメチルエーテルを加えて樹脂固形分65重量％のエポキ
シ樹脂ワニスを調製した。このエポキシ樹脂ワニスを用
いてガラス不織布に連続的に塗布・含浸させ、160 ℃の
温度に乾燥させてプリプレグを得た。このプリプレグを
8枚重ね合わせ、その両面に厚さ18μｍの銅箔を重ね、
温度170 ℃，圧力40ｋｇ／ｃｍで90分間、加熱加圧一体
に成形して厚さ 1.6ｍｍのガラスエポキシ銅張積層板を
製造した。Comparative Example 2 360 parts of brominated epoxy resin (epoxy equivalent: 490, solid content: 75% by weight), 360 parts, cresol novolak epoxy resin (epoxy equivalent: 210, solid content: 70% by weight): 43 parts, dicyandiamide: 7.5 parts, aluminum hydroxide: 200 Then, 0.1 parts of 2-ethyl-4-methylimidazole and propylene glycol monomethyl ether were added to prepare an epoxy resin varnish having a resin solid content of 65% by weight. Using this epoxy resin varnish, the glass nonwoven fabric was continuously applied and impregnated, and dried at a temperature of 160 ° C. to obtain a prepreg. This prepreg
Eight sheets are stacked, and copper foil with a thickness of 18 μm is stacked on both sides,
The glass epoxy copper clad laminate having a thickness of 1.6 mm was manufactured by integrally forming the body at a temperature of 170 ° C. under a pressure of 40 kg / cm for 90 minutes under heating and pressure.
【００２４】実施例１〜３および比較例１〜２で製造し
たガラスエポキシ銅張積層板を用いて、難燃性、耐トラ
ッキング性、絶縁抵抗、引剥がし強さ、耐熱性、耐湿性
を試験したのでその結果を表１に示した。本発明はいず
れの特性においても優れており、本発明の効果を確認す
ることができた。Using the glass epoxy copper-clad laminates produced in Examples 1 to 3 and Comparative Examples 1 and 2, the flame retardancy, tracking resistance, insulation resistance, peeling strength, heat resistance and moisture resistance were tested. The results are shown in Table 1. The present invention was excellent in any of the characteristics, and the effect of the present invention could be confirmed.
【００２５】[0025]
【表１】 ＊1 ：ＵＬ９４難燃性試験法に基づき試験した。 ＊2 ：ＩＥＣ−ＰＢ１１２に基づき試験した。 ＊3 ：ＪＩＳ−Ｃ−６４８１に基づき試験した。 ＊4 ：ＪＩＳ−Ｃ−６４８１に基づき試験した。 ＊5 ：ガラスエポキシ銅張積層板25ｍｍ×25ｍｍの試験片を260 ℃の半田浴に 5 〜20分間浮かべ、フクレの有無を試験した。 ◎印…全くなし、○印…一部有り、△…大部分有り、×印…全部有り。 ＊6 ：Ａ及びＢの条件で処理後、120 ℃の半田浴中に10秒間浸漬し、フクレの有 無を試験した。 Ａ 煮沸 4時間 Ｂ 120 ℃，2 気圧の水蒸気中 ◎印…全くなし、○印…一部有り、△…大部分有り、×印…全部有り。[Table 1] * 1: Tested based on UL94 flame retardancy test method. * 2: Tested based on IEC-PB112. * 3: Tested based on JIS-C-6481. * 4: Tested based on JIS-C-6481. * 5: A glass epoxy copper-clad laminate of 25 mm x 25 mm was floated in a 260 ° C solder bath for 5 to 20 minutes to test for blisters. ◎: none, ○: some, △: most, ×: all. * 6: After treatment under the conditions A and B, it was immersed in a solder bath at 120 ° C. for 10 seconds to test for blisters. A Boiling for 4 hours B In steam at 120 ° C and 2 atm ◎ mark: none, ○ mark: some, △: most, x: all.
【００２６】[0026]
【発明の効果】以上の説明および表１から明らかなよう
に、本発明のガラスエポキシ銅張積層板は、ハロゲンフ
リーで有毒ガス発生がなく、難燃性、耐熱性、耐湿性、
耐トラッキング性等に優れたもので電子機器等に好適な
ものである。As is clear from the above description and Table 1, the glass epoxy copper-clad laminate of the present invention is halogen-free, does not generate toxic gas, has flame retardancy, heat resistance, moisture resistance, etc.
It has excellent tracking resistance and is suitable for electronic equipment and the like.
フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０８Ｌ 63/00 ＮＪＵ Ｃ０８Ｌ 63/00 ＮＪＵ // Ｃ０９Ｋ 21/14 Ｃ０９Ｋ 21/14 Ｃ０８Ｋ 3:22 Continuation of the front page (51) Int.Cl. 6 Identification code Office reference number FI Technical display location C08L 63/00 NJU C08L 63/00 NJU // C09K 21/14 C09K 21/14 C08K 3:22
Claims (1)
・乾燥させたプリプレグを複数枚積層し、その少なくと
も片面に銅箔を重ね合わせて一体に成形するガラスエポ
キシ銅張積層板において、前記エポキシ樹脂組成物とし
て（Ａ）ビスフェノールＡ型エポキシ樹脂、（Ｂ）ノボ
ラック型エポキシ樹脂、（Ｃ）窒素変性フェノール樹
脂、（Ｄ）赤リン （Ｅ）硬化促進剤および（Ｆ）無機充填剤を必須成分と
し、全体の樹脂組成物に対して、（Ｃ）の窒素変性フェ
ノール樹脂を 5〜50重量％、また（Ｄ）の赤リンを 1〜
10重量％の割合でそれぞれ含有するエポキシ樹脂組成物
を用いてなることを特徴とするガラスエポキシ銅張積層
板。1. A glass-epoxy copper-clad laminate obtained by laminating a plurality of prepregs obtained by impregnating and drying an epoxy resin composition on a glass base material and laminating a copper foil on at least one surface thereof and integrally forming the same. Essential components of the resin composition are (A) bisphenol A type epoxy resin, (B) novolak type epoxy resin, (C) nitrogen-modified phenolic resin, (D) red phosphorus (E) curing accelerator and (F) inorganic filler. Based on the total resin composition, the nitrogen-modified phenol resin of (C) is 5 to 50% by weight, and the red phosphorus of (D) is 1 to 50% by weight.
A glass-epoxy copper-clad laminate characterized by using an epoxy resin composition which is contained at a ratio of 10% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4426096A JP2794681B2 (en) | 1996-02-06 | 1996-02-06 | Glass epoxy copper clad laminate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4426096A JP2794681B2 (en) | 1996-02-06 | 1996-02-06 | Glass epoxy copper clad laminate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09207271A true JPH09207271A (en) | 1997-08-12 |
| JP2794681B2 JP2794681B2 (en) | 1998-09-10 |
Family
ID=12686553
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4426096A Expired - Fee Related JP2794681B2 (en) | 1996-02-06 | 1996-02-06 | Glass epoxy copper clad laminate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2794681B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100610709B1 (en) * | 1998-09-07 | 2006-08-09 | 소니 가부시끼 가이샤 | Printed Circuit Board |
| JP2008007575A (en) * | 2006-06-27 | 2008-01-17 | Matsushita Electric Works Ltd | Epoxy resin composition, resin film, prepreg and multilayer printed wiring board |
| US7723407B2 (en) | 2004-08-06 | 2010-05-25 | Nippon Shokubai Co., Ltd. | Resin composition, method of its composition, and cured formulation |
-
1996
- 1996-02-06 JP JP4426096A patent/JP2794681B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100610709B1 (en) * | 1998-09-07 | 2006-08-09 | 소니 가부시끼 가이샤 | Printed Circuit Board |
| US7723407B2 (en) | 2004-08-06 | 2010-05-25 | Nippon Shokubai Co., Ltd. | Resin composition, method of its composition, and cured formulation |
| JP2008007575A (en) * | 2006-06-27 | 2008-01-17 | Matsushita Electric Works Ltd | Epoxy resin composition, resin film, prepreg and multilayer printed wiring board |
| JP4600359B2 (en) * | 2006-06-27 | 2010-12-15 | パナソニック電工株式会社 | Epoxy resin composition, resin film, prepreg, and multilayer printed wiring board |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2794681B2 (en) | 1998-09-10 |
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