JPH0471408B2 - - Google Patents

Info

Publication number
JPH0471408B2
JPH0471408B2 JP12522085A JP12522085A JPH0471408B2 JP H0471408 B2 JPH0471408 B2 JP H0471408B2 JP 12522085 A JP12522085 A JP 12522085A JP 12522085 A JP12522085 A JP 12522085A JP H0471408 B2 JPH0471408 B2 JP H0471408B2
Authority
JP
Japan
Prior art keywords
epoxy resin
paper
copper
silver
resin composition
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
Application number
JP12522085A
Other languages
Japanese (ja)
Other versions
JPS61283650A (en
Inventor
Toshuki Seki
Kazuo Ishigami
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sumitomo Bakelite Co Ltd
Original Assignee
Sumitomo Bakelite Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Sumitomo Bakelite Co Ltd filed Critical Sumitomo Bakelite Co Ltd
Priority to JP12522085A priority Critical patent/JPS61283650A/en
Publication of JPS61283650A publication Critical patent/JPS61283650A/en
Publication of JPH0471408B2 publication Critical patent/JPH0471408B2/ja
Granted legal-status Critical Current

Links

Classifications

    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00Printed circuits
    • H05K1/02Details
    • H05K1/03Use of materials for the substrate
    • H05K1/0313Organic insulating material
    • H05K1/032Organic insulating material consisting of one material
    • H05K1/0326Organic insulating material consisting of one material containing O

Description

【発明の詳細な説明】[Detailed description of the invention]

〔産業上の利用分野〕 本発明は、銀の移行現象の発生しにくい(以
下、“耐銀移行性に優れた”と称する)印刷回路
配線板用紙基材エポキシ樹脂銅張積層板の製造に
用いられる積層板用熱硬化性樹脂組成物に関する
ものである。 〔従来技術〕 従来、印刷回路配線板用紙基材エポキシ樹脂銅
張積層板は、エポキシ樹脂配合物ワニスをクラフ
ト紙またはリンター紙等に含浸乾燥させ、該含浸
紙を複数枚積層し、用途に応じてこの片面又は両
面に接着剤付銅箔を加えた後、加熱加圧成形され
製造されている。 しかるに、このようにして得られた紙基材エポ
キシ樹脂銅張板は、温湿度条件下において積層板
表面上に形成された銀電極間に電界を加えると、
所定時間の経過後、銀の移行現象が発生すること
は、良く知られている。 この銀の移行現象を電気化学的に解析する試み
は、数多く行なわれており、絶縁材料による銀の
移行現象の差異についても指摘されているが、紙
基材エポキシ樹脂銅張積層板は、紙基材フエノー
ル樹脂銅張積層板とともに、極めて銀の移行現象
が発生し易いものとして位置づけられている。 しかるに近年の印刷回路配線板の高密度化に伴
い信頼性の確保は重要な課題であるが、この銀の
移行現象は印刷回路配線板にとつて致命的欠陥と
なり得る要素をもつているため、印刷回路配線板
の生産段階において、銀の移行現象を抑制し得る
各種の処理が試みられ、また現実に実施されてい
るが、積層板の本質的特性に依存する部分が強
く、耐銀移行性に優れた紙基材エポキシ樹脂銅張
積層板が必要とされるものである。 本発明者らは、紙基材エポキシ樹脂銅張積層板
表面の銀の移行について詳細な検討を加えた結
果、エポキシ樹脂組成物の紙基材への含浸性が大
きな要因を有していることを見い出している。 このような紙への含浸性を向上させる手段とし
ては2回塗りが良く知られているところである
が、作業能率の低下、使用原材料の増加等のほ
か、得られた銅張積層板特性の点でも、機械特性
等の低下が見られ好ましくない。 〔発明の目的〕 本発明は、以上のような問題点を改善し、耐銀
移行性に有れた紙基材エポキシ樹脂銅張積層板を
1回塗りによつて得ることのできる積層板用熱硬
化性樹脂を提供することを目的とする。 〔発明の構成〕 本発明は、紙基材エポキシ樹脂銅張積層板に用
いられるエポキシ樹脂配合物に、 一般式 (但し、n=5〜20、m=2n+1又はm=2n−
1) なる化合物()を添加することを特徴とする積
層板用熱硬化性樹脂組成物である。 本発明の熱硬化性樹脂組成物に用いられるエポ
キシ樹脂配合物は、エポキシ樹脂(a)と硬化剤(b)を
所定の割合で配合したものであり、必要に応じて
これに硬化促進剤(c)を加えたものを使用すること
も可能である。 エポキシ樹脂(a)、硬化剤(b)、硬化促進剤(c)の種
類及び使用量は、目的によつて種々変えることが
でき、これらを限定することに格別の意義はな
い。 また、化合物()としては、ラウリン酸ジメ
チルアミド、オレイン酸ジメチルアミド等の飽和
脂肪酸、又は不飽和脂肪酸のジメチルアミドが用
いられる。 これらの脂肪酸ジメチルアミドは、エポキシ樹
脂配合物との親和性が良く、またエポキシ樹脂配
合物ワニスに添加することにより、エポキシ樹脂
配合物ワニスの粘度を大幅に下げる効果を有して
いる。 また脂肪酸ジメチルアミドは極性が強く、銅張
積層板の基材に用いられるリンター紙やクラフト
紙等の繊維質基材とも親和性が良いため、脂肪酸
ジメチルアミドをエポキシ樹脂配合物に添加した
場合、脂肪酸ジメチルアミドを添加していないエ
ポキシ樹脂配合物に比べ格段に高度の含浸性を賦
与することができるものである。 エポキシ樹脂配合物ワニスに対する化合物
()の添加量は、固型分換算にてエポキシ樹脂
(a)100重量部に対し、0.1乃至10重量部、好ましく
は、0.3乃至6重量部である。 化合物()の添加量が0.1重量部に満たない
場合所望の含浸効果をあげることができず、また
10重量部を越えると含浸効果は一定限度以上はあ
がらず、一方積層板にした場合の特性低下が見ら
れ好ましくない。 〔発明の効果〕 上述のように、本発明の積層板用樹脂組成物は
紙基材への含浸性を従来のエポキシ樹脂配合物に
比べ著しく向上させることができる。従つて該樹
脂組成物の含浸紙を積層し、加熱加圧成形した紙
基材エポキシ樹脂銅張積層板に高度の耐銀移行性
を賦与することができるものである。 実施例 本発明の実施例を次に示す。「部」は「重量部」
を示す。 実施例 1 市販のエポキシ樹脂エピコート1045(シエル化
学製)100部をメチルエチルケトン25部に溶解し
て樹脂液(A)を得た。 また、ジシアンジアミド4.5部をメチルセロソ
ルブ40部に溶解して溶液(B)を得た。更に2−エチ
ル−4−メチルイミゾール0.1部をメチルセロソ
ルブ1部に溶解して溶液(C)を得た。この樹脂液
(A)、溶液(B)、溶液(C)を混合撹拌することにより、
エポキシ樹脂配合物ワニス(D)170.6部を得た。 次いでこのエポキシ樹脂配合物ワニス(D)170.6
部にラウリン酸ジメチルアミドを1部添加して撹
拌、混合し、所望のエポキシ樹脂組成物(E)を得
た。 このエポキシ樹脂組成物(E)を厚さ0.2mmの混抄
紙に含浸・乾燥して、樹脂付着率45%の含浸紙を
得た。 次いで、この含浸紙を8枚積層した後、厚さ
0.035mmの接着剤付銅箔を接着剤面を含浸紙と対
向させて後、圧力100Kg/cm2、温度170℃で120分
間加熱加圧して厚さ1.6mmの片面銅張積層板(e)を
得た。 実施例 2 実施例1と同様にしてエポキシ樹脂配合物ワニ
ス(D)170.6部を得た後、これにラウリン酸ジメチ
ルアミドを6部添加して撹拌・混合し所望のエポ
キシ樹脂組成物(F)を得た。 このエポキシ樹脂組成物(F)を用いて、以下実施
例1と同様にして厚さ1.6mmの片面銅張板(f)を得
た。 比較例 1 実施例1と同様にしてエポキシ樹脂配合物ワニ
ス(D)170.6部を得た後、これにラウリン酸ジメチ
ルアミドを0.08部添加してエポキシ樹脂組成物(G)
を得た。 このエポキシ樹脂組成物(G)を用いて、以下実施
例1と同様にして、厚さ1.6mmの片面銅張板(g)を
得た。 比較例 2 実施例1と同様にして、エポキシ樹脂配合物ワ
ニス(D)170.6部を得た後、これを用いて以下実施
例と同様にして厚さ1.6mmの片面銅張板(d)を得た。 これらの実施例・比較例で得られた銅張積層板
(e)、(f)、(g)、(d)の銅箔をエツチング除去した後、
基板面に導電性銀ペイントを図1に示すような回
路パターンを用いてスクリーン印刷したものを試
料とした。図1において、1,2は銀回路を示
す。なお対向する銀回路の間隔は1.0mmである。 この試料は温度40℃湿度93%の恒温恒湿槽中に
入れ、対向する回路間に直流50Vの電圧を印加し
て1000時間放置した。次いで各試料について回路
間の絶縁抵抗を測定すると共に、外観を変化を判
定した結果を表1に示す。 また、該積層板の性能をJIS C 6481にもとづ
いて測定した。結果を表2に示す。 これらの結果から実施例1、2で得られた銅張
積層板は、比較例1、2で得られた銅張積層板に
比べ耐銀移行性が著しく向上していると共に、他
の諸特性の低下はほとんどないことがわかつた。
[Industrial Application Field] The present invention is applicable to the production of paper-based epoxy resin copper-clad laminates for printed circuit wiring boards that are less susceptible to silver migration (hereinafter referred to as "excellent silver migration resistance"). The present invention relates to a thermosetting resin composition for use in laminates. [Prior art] Conventionally, paper-based epoxy resin copper-clad laminates for printed circuit wiring boards have been produced by impregnating and drying kraft paper or linter paper with an epoxy resin compound varnish, then laminating a plurality of sheets of the impregnated paper, and fabricating paper-based epoxy resin copper-clad laminates according to the application. After adding adhesive-coated copper foil to one or both sides of the lever, it is manufactured by heating and press forming. However, when an electric field is applied between the silver electrodes formed on the surface of the laminate under temperature and humidity conditions, the paper-based epoxy resin copper-clad board obtained in this manner
It is well known that a silver migration phenomenon occurs after a certain period of time. Many attempts have been made to electrochemically analyze this silver migration phenomenon, and differences in the silver migration phenomenon depending on the insulating material have been pointed out. Along with the base material phenolic resin copper-clad laminate, it is positioned as a material that is extremely susceptible to the silver migration phenomenon. However, as the density of printed circuit wiring boards has increased in recent years, ensuring reliability has become an important issue, but since this silver migration phenomenon has the potential to become a fatal defect for printed circuit wiring boards, At the production stage of printed circuit wiring boards, various treatments that can suppress the silver migration phenomenon have been tried and actually implemented, but they largely depend on the essential characteristics of the laminate, and the silver migration resistance is A paper-based epoxy resin copper-clad laminate with excellent properties is needed. The present inventors conducted a detailed study on the migration of silver on the surface of paper-based epoxy resin copper-clad laminates, and found that the impregnation of the epoxy resin composition into the paper base material is a major factor. is being discovered. Two coats is a well-known method for improving the impregnating properties of paper, but this method reduces work efficiency, increases the amount of raw materials used, and causes problems with the properties of the resulting copper-clad laminate. However, it is not preferable because it causes a decrease in mechanical properties and the like. [Object of the Invention] The present invention improves the above-mentioned problems and provides a paper-based epoxy resin copper-clad laminate with excellent silver migration resistance that can be obtained by one coating. The purpose is to provide thermosetting resins. [Structure of the Invention] The present invention provides an epoxy resin compound used for a paper-based epoxy resin copper-clad laminate having the general formula (However, n = 5 to 20, m = 2n + 1 or m = 2n -
1) A thermosetting resin composition for a laminate, which is characterized by adding the following compound (). The epoxy resin compound used in the thermosetting resin composition of the present invention is a mixture of epoxy resin (a) and curing agent (b) in a predetermined ratio, and if necessary, a curing accelerator ( It is also possible to use a combination of c). The types and amounts of the epoxy resin (a), curing agent (b), and curing accelerator (c) can be varied depending on the purpose, and there is no particular significance in limiting them. Further, as the compound (), saturated fatty acids such as lauric acid dimethylamide and oleic acid dimethylamide, or dimethylamide of unsaturated fatty acids are used. These fatty acid dimethylamides have good affinity with epoxy resin blends, and when added to epoxy resin blend varnishes, they have the effect of significantly lowering the viscosity of the epoxy resin blend varnishes. In addition, fatty acid dimethylamide is highly polar and has good affinity with fibrous base materials such as linter paper and kraft paper used as base materials for copper-clad laminates, so when fatty acid dimethylamide is added to an epoxy resin formulation, Compared to epoxy resin formulations to which fatty acid dimethylamide is not added, it is possible to impart significantly higher impregnating properties. The amount of compound () added to the epoxy resin compound varnish is calculated based on the solid content of the epoxy resin.
The amount is 0.1 to 10 parts by weight, preferably 0.3 to 6 parts by weight, per 100 parts by weight of (a). If the amount of compound () added is less than 0.1 part by weight, the desired impregnation effect may not be achieved;
If the amount exceeds 10 parts by weight, the impregnating effect will not increase beyond a certain limit, and on the other hand, properties will deteriorate when formed into a laminate, which is not preferable. [Effects of the Invention] As described above, the resin composition for laminates of the present invention can significantly improve the impregnation properties into paper base materials compared to conventional epoxy resin formulations. Therefore, a high degree of silver migration resistance can be imparted to a paper-based epoxy resin copper-clad laminate formed by laminating papers impregnated with the resin composition and molding them under heat and pressure. Examples Examples of the present invention are shown below. "Part" means "part by weight"
shows. Example 1 A resin liquid (A) was obtained by dissolving 100 parts of a commercially available epoxy resin Epicoat 1045 (manufactured by Ciel Chemical Co., Ltd.) in 25 parts of methyl ethyl ketone. Further, 4.5 parts of dicyandiamide was dissolved in 40 parts of methyl cellosolve to obtain a solution (B). Further, 0.1 part of 2-ethyl-4-methylimizole was dissolved in 1 part of methyl cellosolve to obtain a solution (C). This resin liquid
By mixing and stirring (A), solution (B), and solution (C),
170.6 parts of epoxy resin blend varnish (D) was obtained. Then this epoxy resin compound varnish (D) 170.6
1 part of lauric acid dimethylamide was added thereto, and the mixture was stirred and mixed to obtain a desired epoxy resin composition (E). This epoxy resin composition (E) was impregnated into mixed paper having a thickness of 0.2 mm and dried to obtain impregnated paper with a resin adhesion rate of 45%. Next, after laminating 8 sheets of this impregnated paper, the thickness
A 0.035 mm adhesive-coated copper foil was placed with the adhesive side facing the impregnated paper, and then heated and pressed at a pressure of 100 Kg/cm 2 and a temperature of 170°C for 120 minutes to produce a 1.6 mm thick single-sided copper-clad laminate (e). I got it. Example 2 After obtaining 170.6 parts of epoxy resin compound varnish (D) in the same manner as in Example 1, 6 parts of lauric acid dimethylamide was added thereto and stirred and mixed to obtain the desired epoxy resin composition (F). I got it. Using this epoxy resin composition (F), a single-sided copper-clad board (f) with a thickness of 1.6 mm was obtained in the same manner as in Example 1. Comparative Example 1 After obtaining 170.6 parts of epoxy resin compound varnish (D) in the same manner as in Example 1, 0.08 part of lauric acid dimethylamide was added thereto to prepare an epoxy resin composition (G).
I got it. Using this epoxy resin composition (G), a single-sided copper-clad board (g) with a thickness of 1.6 mm was obtained in the same manner as in Example 1. Comparative Example 2 After obtaining 170.6 parts of epoxy resin compound varnish (D) in the same manner as in Example 1, a single-sided copper-clad board (d) with a thickness of 1.6 mm was made using this in the same manner as in the Example. Obtained. Copper-clad laminates obtained in these Examples and Comparative Examples
After removing the copper foils in (e), (f), (g), and (d) by etching,
A sample was prepared by screen printing conductive silver paint on a substrate surface using a circuit pattern as shown in FIG. In FIG. 1, 1 and 2 indicate silver circuits. Note that the distance between the opposing silver circuits is 1.0 mm. This sample was placed in a constant temperature and humidity chamber at a temperature of 40° C. and a humidity of 93%, and a DC voltage of 50 V was applied between the opposing circuits for 1000 hours. Next, the insulation resistance between the circuits was measured for each sample, and the changes in appearance were determined. The results are shown in Table 1. Furthermore, the performance of the laminate was measured based on JIS C 6481. The results are shown in Table 2. From these results, the copper-clad laminates obtained in Examples 1 and 2 have markedly improved silver migration resistance compared to the copper-clad laminates obtained in Comparative Examples 1 and 2, and have other properties as well. It was found that there was almost no decrease in

【表】【table】

【表】【table】 【図面の簡単な説明】[Brief explanation of the drawing]

第1図は銀移行性試験に用いられる銀回路パタ
ーンの図である。 1,2は銀回路である。
FIG. 1 is a diagram of the silver circuit pattern used in the silver migration test. 1 and 2 are silver circuits.

Claims (1)

【特許請求の範囲】 1 エポキシ樹脂(a)及び硬化剤(b)を含有するエポ
キシ樹脂配合物に、 一般式 (但し、n=5〜20、m=2n+1又はm=2n−
1) なる化合物()を添加することを特徴とする積
層板用熱硬化性樹脂組成物。 2 化合物()の添加量がエポキシ樹脂(a)に対
し0.1〜10重量%である特許請求の範囲第1項記
載の積層板用熱硬化性樹脂組成物。
[Scope of Claims] 1. An epoxy resin compound containing an epoxy resin (a) and a curing agent (b) has the general formula (However, n = 5 to 20, m = 2n + 1 or m = 2n -
1) A thermosetting resin composition for a laminate, characterized in that the compound () is added thereto. 2. The thermosetting resin composition for a laminate according to claim 1, wherein the amount of compound () added is 0.1 to 10% by weight based on the epoxy resin (a).
JP12522085A 1985-06-11 1985-06-11 Thermosetting resin composition for laminated sheet Granted JPS61283650A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP12522085A JPS61283650A (en) 1985-06-11 1985-06-11 Thermosetting resin composition for laminated sheet

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP12522085A JPS61283650A (en) 1985-06-11 1985-06-11 Thermosetting resin composition for laminated sheet

Publications (2)

Publication Number Publication Date
JPS61283650A JPS61283650A (en) 1986-12-13
JPH0471408B2 true JPH0471408B2 (en) 1992-11-13

Family

ID=14904819

Family Applications (1)

Application Number Title Priority Date Filing Date
JP12522085A Granted JPS61283650A (en) 1985-06-11 1985-06-11 Thermosetting resin composition for laminated sheet

Country Status (1)

Country Link
JP (1) JPS61283650A (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0622060D0 (en) 2006-11-06 2006-12-13 Hexcel Composites Ltd Improved composite materials

Also Published As

Publication number Publication date
JPS61283650A (en) 1986-12-13

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