JP2594323B2 - Adhesive composition - Google Patents
Adhesive compositionInfo
- Publication number
- JP2594323B2 JP2594323B2 JP63154240A JP15424088A JP2594323B2 JP 2594323 B2 JP2594323 B2 JP 2594323B2 JP 63154240 A JP63154240 A JP 63154240A JP 15424088 A JP15424088 A JP 15424088A JP 2594323 B2 JP2594323 B2 JP 2594323B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- adhesive composition
- heat resistance
- adhesive
- bonding
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/386—Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive
Landscapes
- Laminated Bodies (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） この発明は、接着剤組成物に関するものである。さら
に詳しくは、この発明は耐熱性に優れているとともに、
高温時の接着力をも向上させることのできる積層板金属
箔接着用の接着剤組成物に関するものである。Description: TECHNICAL FIELD The present invention relates to an adhesive composition. More specifically, this invention has excellent heat resistance,
The present invention relates to an adhesive composition for bonding a laminated metal foil, which can also improve the adhesive strength at high temperatures.
（従来の技術） 近年、プリント配線版に用いる金属箔積層板につい
て、金属箔の高温接着性能の向上が要請されており、こ
の接着のための接着剤の耐熱性の向上のために、エポキ
シ樹脂を主剤としたものが広く用いられてきている。(Prior Art) In recent years, with respect to a metal foil laminate used for a printed wiring board, improvement in high-temperature bonding performance of metal foil has been demanded. In order to improve heat resistance of an adhesive for this bonding, an epoxy resin has been used. The main ingredient has been widely used.
このような接着剤として、たとえば、エポキシ樹脂
に、芳香族アミンまたはジアミン等の硬化剤や硬化助剤
を配合したものが知られている。As such an adhesive, for example, an epoxy resin mixed with a curing agent such as an aromatic amine or a diamine or a curing assistant is known.
（発明が解決しようとする課題） しかしながら、これらの従来のエポキシ樹脂を主剤と
する金属箔接着用の接着剤の場合には、一般に耐熱性の
向上の効果は不充分であり、高温時の金属箔接着力をピ
ール強度（150℃）でたかだか0.3〜0.4kg/cm程度と満足
できるものではなかった。しかもこれまでのものは室温
（常態）での接着力も充分ではないという欠点があっ
た。(Problems to be Solved by the Invention) However, in the case of these conventional adhesives for bonding metal foils mainly composed of an epoxy resin, the effect of improving the heat resistance is generally insufficient, and the metal at high temperatures is not sufficiently effective. The foil adhesion was not satisfactory at a peel strength (150 ° C.) of only about 0.3 to 0.4 kg / cm. Moreover, the conventional one has a disadvantage that the adhesive strength at room temperature (normal state) is not sufficient.
このため、このような欠点を早急に解決することが望
まれていた。Therefore, it has been desired to solve such a shortcoming as soon as possible.
この発明は、以上の通りの事情に鑑みてなされたもの
であり、従来の金属箔接着用の接着剤の欠点を解消し、
耐熱性に優れるとともに、高温時の金属箔の接着力をも
向上させることのできる新しい積層板金属箔接着用の接
着剤組成物を提供することを目的としている。The present invention has been made in view of the above circumstances, and eliminates the disadvantages of the conventional adhesive for metal foil bonding,
An object of the present invention is to provide a new adhesive composition for bonding a metal foil to a laminate, which has excellent heat resistance and can also improve the adhesive strength of the metal foil at a high temperature.
（課題を解決するための手段） この発明は、上記の課題を解決するために、ブチラー
ル樹脂とエポキシ樹脂を含有する樹脂組成物に、フェノ
ールノボラック樹脂オリゴマーおよびジシアンジアミド
を配合してなることを特徴とする積層板金属箔接着用の
接着剤組成物を提供するものである。(Means for Solving the Problems) In order to solve the above problems, the present invention is characterized in that a resin composition containing a butyral resin and an epoxy resin is blended with a phenol novolak resin oligomer and dicyandiamide. The present invention provides an adhesive composition for bonding a laminate metal foil.
ブチラール樹脂およびエポキシ樹脂については、その
種類に格別の限定はなく、従来公知のものをはじめとし
て任意のものを使用することができる。たとえばエポキ
シ樹脂としては、フェノール、クレゾール、ビスフェノ
ールＡ等のフェノール類のノボラック型のもの、特にク
レゾールノボラック型のものを好適なものとして例示す
ることができる。The butyral resin and the epoxy resin are not particularly limited in their types, and any ones including conventionally known ones can be used. For example, as the epoxy resin, a novolak type of phenols such as phenol, cresol and bisphenol A, particularly a cresol novolak type can be exemplified as a preferable one.
ブチラール樹脂とエポキシ樹脂との配合割合は、広い
範囲のものとすることができるが、一般的には、エポキ
シ樹脂100重量部に対して20〜60、特に30〜50部用いる
のが好ましい。あまり多すぎると高温時の接着力は低下
し、また少なすぎると常態での接着力が低下するので好
ましくない。The mixing ratio of the butyral resin and the epoxy resin can be in a wide range, but it is generally preferable to use 20 to 60, particularly 30 to 50 parts by weight per 100 parts by weight of the epoxy resin. If the amount is too large, the adhesive strength at a high temperature decreases, and if the amount is too small, the adhesive force in a normal state decreases, which is not preferable.
硬化剤成分として配合するフェノールノボラック樹脂
オリゴマーとしては、その分子量（Mn）が1000〜3000、
より好ましくは1500〜2500程度のものを用いる。The phenol novolak resin oligomer to be blended as a curing agent component has a molecular weight (Mn) of 1,000 to 3,000,
More preferably, about 1500 to 2500 are used.
これらのフェノールノボラック樹脂オリゴマーとジジ
アンジアミドの水酸基当量と活性水素当量との比は1/1
〜4/1、より好ましくは2/1〜3/1の範囲とし、また、こ
れらの全当量はエポキシ当量に内して1/0.8〜1/1とする
こと好ましい。もちろん、これらは特に限定的なもので
はなく、使用するオリゴマーの種類やエポキシ樹脂等に
よって適宜に変更することができる。The ratio of the hydroxyl group equivalent to the active hydrogen equivalent of these phenol novolak resin oligomers and didiandiamide is 1/1.
44/1, more preferably in the range of 2/1 to 3/1, and the total equivalent of these is preferably 1 / 0.8 to 1/1 within the epoxy equivalent. Of course, these are not particularly limited, and can be appropriately changed depending on the type of oligomer used, epoxy resin, and the like.
以上の成分を配合する接着剤組成物は、溶剤として所
定量のメチルエチルケトン、トルエン、メタノール等を
用いて樹脂液とする。この場合の樹脂液の粘度は、通常
は500〜1500cps（25℃）程度とするのが好ましい。The adhesive composition containing the above components is made into a resin liquid by using a predetermined amount of methyl ethyl ketone, toluene, methanol or the like as a solvent. In this case, the viscosity of the resin liquid is usually preferably about 500 to 1500 cps (25 ° C.).
積層板への金属箔の接着は、この樹脂液を、たとえば
15〜45μｍ程度の厚さで銅、アルミニウム、鉄等の金属
箔に塗布し、140〜160℃の温度で２〜６分程度乾燥させ
た後に行う。塗布樹脂量は、一般に銅箔の場合には20〜
50g/m2、より好ましくは30〜40g/m2となるように調整す
る。Adhesion of the metal foil to the laminate is performed by using this resin liquid, for example.
It is applied after being coated on a metal foil of copper, aluminum, iron or the like with a thickness of about 15 to 45 μm and dried at a temperature of 140 to 160 ° C. for about 2 to 6 minutes. The amount of applied resin is generally 20 to
50 g / m 2, and more preferably adjusted to a 30 to 40 g / m 2.
これを通常の方法で、ガラスクロス、ガラスマット、
紙等の基材にフェノール樹脂、エポキシ樹脂、ポリアミ
ド樹脂、不飽和ポリエステル樹脂等の樹脂を含浸させた
樹脂含浸基材積層板に載せて加熱、加圧して接着する。
通常は150〜180℃程度の温度において、20〜80kg/cm2の
圧力で加圧する。This is done in the usual way using a glass cloth, glass mat,
The resin is impregnated with a resin such as a phenolic resin, an epoxy resin, a polyamide resin, or an unsaturated polyester resin on a base material such as paper, and is then bonded by heating and pressing.
Usually, pressure is applied at a temperature of about 150 to 180 ° C. and a pressure of 20 to 80 kg / cm 2 .
（作 用） この発明の接着剤組成物においては、ブチラール樹
脂、ウェノールノボラック樹脂オリゴマーおよびジシア
ンジアミドを配合することにより、耐熱性（ハンダ耐熱
性）を、従来品の25〜35secを40sec以上にまで向上さ
せ、またTgも大幅に向上させる。(Action) In the adhesive composition of the present invention, the heat resistance (solder heat resistance) can be increased from 25 to 35 sec of the conventional product to 40 sec or more by blending the butyral resin, the wenol novolak resin oligomer and dicyandiamide. And also significantly increase the T g .
高温時の接着力も従来品の２倍以上に向上させ、しか
も常態での接着力も良好なものとする。The adhesive strength at high temperature is improved to more than twice that of the conventional product, and the adhesive strength under normal conditions is also good.
（実施例） 次に実施例を示し、さらに詳しくこの発明の接着剤組
成物について説明する。(Example) Next, an example is shown and the adhesive composition of this invention is demonstrated in more detail.
実施例 １ 次の配合からなる接着剤組成物を作製した。Example 1 An adhesive composition having the following composition was prepared.
（１）ブチラール樹脂（電気化学工業社製:6000C）40
（ｇ） （２）エポキシ樹脂（クレゾールノボラック型：京都化
成社製:YDCN−704） 100 （３）フェノールノボラック樹脂オリゴマー（三菱油化
社製:Resin−Ｘ） 37.8 （４）ジシアンジアミド 2.2 溶剤を加えて粘度700cps（25℃）とした樹脂液を銅箔
に塗布し、150℃で３分間乾燥させた。塗布樹脂量30g/c
m2で紙フェノールレジンペーパーに載せて加熱、加圧し
て銅張積層板を得た。(1) Butyral resin (6000C, manufactured by Denki Kagaku Kogyo Co., Ltd.) 40
(G) (2) Epoxy resin (cresol novolak type: YDCN-704 manufactured by Kyoto Kasei Co., Ltd.) 100 (3) Phenol novolak resin oligomer (Resin-X manufactured by Mitsubishi Yuka Co., Ltd.) 37.8 (4) Dicyandiamide 2.2 Solvent was added. A resin liquid having a viscosity of 700 cps (25 ° C.) was applied to a copper foil and dried at 150 ° C. for 3 minutes. 30g / c coating resin
It was placed on paper phenolic resin paper at m 2 and heated and pressed to obtain a copper-clad laminate.
この積層板について耐熱性、接着力を評価した。その
結果を表１に示した。ハンダ耐熱性は45〜48secと従来
品（25〜35sec）を大きく上まわり、高温（150℃）時の
接着力も0.53〜0.64kg/cmと従来の約２倍に向上してい
る。Tgも119℃と、従来の75〜95℃を大きく上まわって
いる。また、常態でも接着力も良好である。This laminate was evaluated for heat resistance and adhesive strength. The results are shown in Table 1. Solder heat resistance is 45-48 sec, much higher than conventional products (25-35 sec), and adhesive strength at high temperatures (150 ° C) is 0.53-0.64 kg / cm, which is about twice as high as that of conventional products. T g and even 119 ° C., and around the upper larger conventional 75 to 95 ° C.. Also, the adhesive strength is good even under normal conditions.
実施例 ２ ブチラール樹脂の配合量を50gとした以外は実施例１
と同様にして接着剤樹脂組成物を作製し、銅箔の接着に
使用した。Example 2 Example 1 except that the amount of butyral resin was changed to 50 g.
An adhesive resin composition was prepared in the same manner as described above, and used for bonding a copper foil.
表１に示した通り、高温（150℃）時の接着力は0.42
〜0.46kg/cmとなり、耐熱性は47〜52sec、Tgは110℃で
あった。As shown in Table 1, the adhesive strength at high temperature (150 ° C) is 0.42
~0.46kg / cm, and the heat resistance 47~52sec, T g was 110 ° C..
実施例 ３ フェノールノボラック樹脂オリゴマーの配合量を33.6
gとした以外は実施例１と同様にして銅箔の接着を行っ
た。Example 3 The compounding amount of the phenol novolak resin oligomer was 33.6
Bonding of the copper foil was carried out in the same manner as in Example 1 except that g was used.
表１に示した通り高温（150℃）時の接着力は、0.49
〜0.55kg/cmであった。耐熱性は40〜46sec、Tgは112℃
であった。As shown in Table 1, the adhesive strength at high temperature (150 ° C) is 0.49
It was ~ 0.55 kg / cm. Heat resistance 40~46sec, T g is 112 ° C.
Met.
実施例 ４ ブチラール樹脂配合量を20gとした以外は実施例１と
同様にして銅箔の接着を行った。この場合の性能につい
ても評価した。高温（150℃）時の接着力は0.55〜0.67k
g/cmであり、耐熱性も良好であった。ただし、常態での
接着力のわずかの低下が認められた。Example 4 A copper foil was adhered in the same manner as in Example 1 except that the amount of butyral resin was changed to 20 g. The performance in this case was also evaluated. Adhesive strength at high temperature (150 ℃) is 0.55 ~ 0.67k
g / cm, and heat resistance was also good. However, a slight decrease in adhesive strength under normal conditions was observed.
比較例 １ ジシアンジアミドを配合しないで実施例２と同様にし
て銅箔の接着を行った。この場合、高温（150℃）時の
接着力は0.25〜0.35kg/cmと実施例のものをはるかに下
まわり、耐熱性も30〜34secと不充分なものであった。Comparative Example 1 A copper foil was bonded in the same manner as in Example 2 without blending dicyandiamide. In this case, the adhesive strength at a high temperature (150 ° C.) was 0.25 to 0.35 kg / cm, which was much lower than that of the example, and the heat resistance was insufficient, being 30 to 34 seconds.
比較例 ２ フェノールノボラック樹脂オリゴマーを配合しないで
実施例２と同様にして銅箔の接着を行った。耐熱性は34
〜40secであったが、高温時（150℃）の接着力は0.22〜
0.32kg/cmにしかすぎなかった。 Comparative Example 2 A copper foil was bonded in the same manner as in Example 2 without blending a phenol novolak resin oligomer. Heat resistance is 34
~ 40sec, but the adhesive strength at high temperature (150 ℃) is 0.22 ~
It was only 0.32 kg / cm.
比較例 ３ ジシアンジアミドを添加せずに5.2gのジアミノジフェ
ニルメタンを配合し、実施例２と同様にして銅箔の接着
を行ったところ、高温（150℃）時の接着力は、0.21〜
0.26kg/cmにしかすぎなかった。またハンダ耐熱性（260
℃）は30〜38secであり、Tgは87℃であった。Comparative Example 3 When adding 5.2 g of diaminodiphenylmethane without adding dicyandiamide and bonding a copper foil in the same manner as in Example 2, the adhesive force at a high temperature (150 ° C.) was 0.21 to
It was only 0.26 kg / cm. Solder heat resistance (260
℃) is a 30~38sec, T g was 87 ℃.
（発明の効果） この発明により、耐熱性が40〜50sec（ハンダ耐熱性;
260℃）と優れ、Tgは従来の75〜95℃を上まわり、かつ
高温時の接着力が、たとえば0.6〜0.8kg/cm（150℃；銅
箔ピール強度）と従来品の２倍以上に向上する金属箔接
着用の接着剤組成物が得られる。また、この組成物は、
室温（常態）での接着力も良好である。(Effect of the Invention) According to the present invention, the heat resistance is 40 to 50 sec (solder heat resistance;
260 ° C.) and excellent, T g around on the conventional 75 to 95 ° C., and the adhesive force at high temperature, for example 0.6~0.8kg / cm (150 ℃; copper foil peel strength) at least twice the conventional Thus, an adhesive composition for bonding a metal foil, which is improved to a high degree, can be obtained. Also, this composition
The adhesive strength at room temperature (normal state) is also good.
Claims (4)
樹脂組成物にフェノールノボラック樹脂オリゴマーおよ
びジシアンジアミドを配合してなることを特徴とする積
層板金属箔接着用の接着剤組成物。An adhesive composition for bonding a metal foil on a laminate, characterized in that a resin composition containing a butyral resin and an epoxy resin is compounded with a phenol novolak resin oligomer and dicyandiamide.
ル樹脂30〜50部を含有する請求項（１）記載の接着剤組
成物。2. The adhesive composition according to claim 1, which contains 30 to 50 parts of butyral resin per 100 parts by weight of epoxy resin.
シアンジアミドを、水酸基当量と活性水素当量の比が2/
1〜3/1で配合する請求項（１）記載の接着剤組成物。3. A phenol novolak resin oligomer and dicyandiamide having a ratio of hydroxyl equivalent to active hydrogen equivalent of 2 /
The adhesive composition according to claim 1, which is blended in an amount of 1 to 3/1.
量に対して1/0.8〜1/1で配合する請求項（１）記載の接
着剤組成物。4. The adhesive composition according to claim 1, wherein the hydroxyl equivalent and the active hydrogen equivalent are blended in a ratio of 1 / 0.8 to 1/1 with respect to the epoxy equivalent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63154240A JP2594323B2 (en) | 1988-06-22 | 1988-06-22 | Adhesive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63154240A JP2594323B2 (en) | 1988-06-22 | 1988-06-22 | Adhesive composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH024887A JPH024887A (en) | 1990-01-09 |
| JP2594323B2 true JP2594323B2 (en) | 1997-03-26 |
Family
ID=15579904
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63154240A Expired - Lifetime JP2594323B2 (en) | 1988-06-22 | 1988-06-22 | Adhesive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2594323B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5173596A (en) * | 1991-03-07 | 1992-12-22 | General Instrument Corporation | Paper card reader/validator |
-
1988
- 1988-06-22 JP JP63154240A patent/JP2594323B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH024887A (en) | 1990-01-09 |
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