JPH0662734B2 - Epoxy resin composition for laminated board - Google Patents
Epoxy resin composition for laminated boardInfo
- Publication number
- JPH0662734B2 JPH0662734B2 JP63224691A JP22469188A JPH0662734B2 JP H0662734 B2 JPH0662734 B2 JP H0662734B2 JP 63224691 A JP63224691 A JP 63224691A JP 22469188 A JP22469188 A JP 22469188A JP H0662734 B2 JPH0662734 B2 JP H0662734B2
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- resin composition
- novolac type
- resin
- weight
- 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
- 239000003822 epoxy resin Substances 0.000 title claims description 51
- 229920000647 polyepoxide Polymers 0.000 title claims description 51
- 239000000203 mixture Substances 0.000 title claims description 30
- 229920003986 novolac Polymers 0.000 claims description 36
- 239000005011 phenolic resin Substances 0.000 claims description 25
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 239000010680 novolac-type phenolic resin Substances 0.000 claims description 13
- 229920001568 phenolic resin Polymers 0.000 claims description 8
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 7
- 150000002989 phenols Chemical class 0.000 claims description 3
- 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 claims description 2
- 229930003836 cresol Natural products 0.000 claims description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- 239000000306 component Substances 0.000 description 18
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 15
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 10
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000006297 dehydration reaction Methods 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 238000006482 condensation reaction Methods 0.000 description 5
- 235000006408 oxalic acid Nutrition 0.000 description 5
- 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 4
- 238000006243 chemical reaction Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000007664 blowing Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 229920001342 Bakelite® Polymers 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Landscapes
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は主として電気用積層板に使用されるエポキシ樹
脂組成物に関する。The present invention relates to an epoxy resin composition mainly used for electrical laminates.
従来から電気用多層プリント配線基材などの積層板には
主としてエポキシ樹脂組成物が使用されているが、この
エポキシ樹脂組成物に原料として用いるエポキシ樹脂に
は、ビスフェノールＡ型エポキシ樹脂、オルソクレゾー
ルノボラック型エポキシ樹脂、フェノールノボラック型
エポキシ樹脂が主として使用されている。またエポキシ
樹脂の硬化剤としてはジシアンジアミド、芳香族アミ
ン、または酸無水物などに加えてノボラック型フェノー
ル樹脂も使われている。しかし配線パターンの多層化や
高密度が進むと共にエポキシ樹脂組成物への耐熱性向上
の要求が強くなっている。エポキシ樹脂組成物の耐熱性
を向上させるための方法として、エポキシ樹脂として前
記のノボラック型エポキシ樹脂、あるいはエポキシ樹脂
の硬化剤として前記ノボラック型フェノール樹脂が使用
されることもあるが、これらを使用しても耐熱性は不十
分となっている。ノボラック型エポキシ樹脂の使用につ
いては特開昭62−64821号において核体数３〜８のエポ
キシ樹脂を使用する例もあるが、このような９核体以上
の成分を全く含有しないような平均分子量の小さいノボ
ラック型エポキシ樹脂を使用すると基材への含浸性は良
好となるが、耐熱性の向上については全く不満足であ
る。また、硬化剤のノボラック型フェノール樹脂につい
ては特開昭56−98227号や特開昭56−112924号において
２核体を含まないｎが1000〜3000のノボラックの使用
からなるエポキシ樹脂組成物が紹介されているが、ｎ
が1000〜3000のように大きなノボラック型フェノール樹
脂を硬化剤として使用すると、硬化性が悪くなるため耐
熱性や耐湿性が不十分である。Conventionally, an epoxy resin composition has been mainly used for a laminated board such as a multilayer printed wiring board for electrical use. The epoxy resin used as a raw material for this epoxy resin composition includes bisphenol A type epoxy resin and orthocresol novolac. Type epoxy resin and phenol novolac type epoxy resin are mainly used. In addition to dicyandiamide, aromatic amines, acid anhydrides and the like, novolac type phenolic resins are also used as curing agents for epoxy resins. However, as the wiring pattern becomes multi-layered and the density becomes higher, the demand for improving the heat resistance of the epoxy resin composition is increasing. As a method for improving the heat resistance of the epoxy resin composition, the novolac type epoxy resin as an epoxy resin, or the novolac type phenol resin as a curing agent for the epoxy resin may be used, but these are used. However, the heat resistance is insufficient. Regarding the use of a novolac type epoxy resin, there is an example of using an epoxy resin having 3 to 8 nuclides in JP-A-62-64821, but an average molecular weight not containing such a component having 9 or more nuclides at all. When a novolac type epoxy resin having a small value is used, the impregnation property into the base material becomes good, but the improvement in heat resistance is completely unsatisfactory. As for the novolac type phenolic resin as a curing agent, an epoxy resin composition containing a novolac containing no binuclear body and having n of 1000 to 3000 is introduced in JP-A-56-98227 and JP-A-56-112924. Has been done, but n
If a large novolac type phenolic resin such as 1000 to 3000 is used as a curing agent, the curability deteriorates and the heat resistance and moisture resistance are insufficient.
本発明者はエポキシ樹脂組成物の耐熱性の向上について
鋭意研究を行なった結果、エポキシ樹脂組成物中の硬化
剤であるフェノール樹脂に２核体成分が少なく、かつ数
平均分子量が限定された範囲にあるノボラック型フェノ
ール樹脂を使用すると、きわめて有効であるとの知見を
得、さらにこの知見に基づいて種々研究を重ねて本発明
を完成するに至ったものである。As a result of earnest studies on the improvement of heat resistance of the epoxy resin composition, the present inventor has found that the phenol resin, which is a curing agent in the epoxy resin composition, has a small number of binuclear components and a number average molecular weight limited. It was found that the use of the novolac type phenolic resin in 1) is extremely effective, and based on this finding, various studies have been repeated to complete the present invention.
本発明の目的とするところはエポキシ樹脂組成物の本質
的な特性を決して損うことなく、３次元架橋性に富み、
耐熱性や耐湿性にすぐれたエポキシ樹脂組成物を提供す
ることにある。The object of the present invention is that the epoxy resin composition is rich in three-dimensional crosslinkability without impairing the essential properties of the epoxy resin composition,
An object is to provide an epoxy resin composition having excellent heat resistance and moisture resistance.
本発明の積層板用エポキシ樹脂組成物の利用分野は、近
年ますます多層化されている電気用プリント配線基材な
どの積層板であり、３次元架橋密度の高い硬化物を形成
するため、耐熱性や耐湿性にすぐれた効果を発揮する。The field of application of the epoxy resin composition for a laminated plate of the present invention is a laminated plate such as a printed wiring board for electrical use which is becoming more and more multilayered in recent years. Exhibits excellent properties and moisture resistance.
ここで、本発明者らは以前から積層板用エポキシ樹脂組
成物の耐湿性の向上について研究を行ない、先に特願昭
62−285192号において、２核体成分の少ないノボラック
型のフェノール系樹脂をグリシジルエーテル化してなる
ノボラック型エポキシ樹脂を含有することを特徴とする
積層板用エポキシ樹脂組成物、さらに特願昭62−288395
号において、上記の２核体成分の少ないノボラック型フ
ェノール系樹脂をグリシジルエーテル化してなるノボラ
ック型エポキシ樹脂に加えて、硬化剤用のフェノール樹
脂として２核体成分の少ないノボラック樹脂を併含する
ことを特徴とする積層板用エポキシ樹脂組成物の２件の
発明を行なった。Here, the inventors of the present invention have previously conducted research on improving the moisture resistance of an epoxy resin composition for laminated boards, and previously reported that
No. 62-285192, an epoxy resin composition for a laminate, characterized by containing a novolac type epoxy resin obtained by converting a novolac type phenolic resin having a small amount of binuclear component into a glycidyl ether, and Japanese Patent Application No. 62-285192. 288395
In addition to a novolak type epoxy resin obtained by glycidyl etherification of the above-mentioned novolak type phenolic resin having a small amount of binuclear component, a novolak resin having a small amount of binuclear component is also included as a phenol resin for a curing agent. Two inventions of the epoxy resin composition for laminated board characterized by the above were carried out.
しかしその後研究を重ねた結果、積層板用エポキシ樹脂
組成物に含有される硬化剤用フェノール樹脂は２核体成
分が少なく、かつ硬化点と数平均分子量が限定された範
囲内にあるノボラック樹脂であるならば、エポキシ樹脂
は汎用の多官能性エポキシ樹脂であっても耐熱性と耐湿
性の向上にきわめて有効であるとの知見を得たことによ
り本発明を完成するに至った。However, as a result of repeated research after that, the phenolic resin for the curing agent contained in the epoxy resin composition for laminated board is a novolac resin which has few binuclear components and has a curing point and a number average molecular weight within a limited range. If so, the present invention has been completed by the finding that the epoxy resin is extremely effective in improving heat resistance and moisture resistance even if it is a general-purpose polyfunctional epoxy resin.
〔課題を解決するための手段〕 本発明は、ノボラック型フェノール樹脂を硬化剤とする
積層板用エポキシ樹脂組成物において、エポキシ樹脂
が、２核体含有率５重量パーセント以下のノボラック型
エポキシ樹脂を除くエポキシ樹脂であり、ノボラック型
フェノール樹脂がフェノールまたは／およびクレゾール
からなるフェノール類とアルデヒドを反応させて得られ
るノボラック樹脂であって、ノボラック樹脂に含まれる
２核体成分(X)が5.0重量パーセント以下であり、かつ数
平均分子量(M)が300≦Ｍ≦900であることを特徴とする
積層板用エポキシ樹脂組成物である。[Means for Solving the Problems] The present invention relates to an epoxy resin composition for a laminate using a novolac type phenolic resin as a curing agent, wherein the epoxy resin is a novolac type epoxy resin having a binuclear content of 5% by weight or less. Epoxy resin to be removed, which is a novolak type phenolic resin obtained by reacting phenols and / or cresol-containing phenols with aldehydes, and the binuclear component (X) contained in the novolac resin is 5.0% by weight. The epoxy resin composition for laminates is characterized by the following and a number average molecular weight (M) of 300 ≦ M ≦ 900.
ここで、前記ノボラック型フェノール樹脂に含有される
２核体成分(X)は5.0重量パーセント以下であるが、好ま
しくは0.5≦Ｘ≦3.0重量パーセントであり、さらに好ま
しくは1.0≦Ｘ≦2.0重量パーセントである。従来からの
ノボラック型フェノール樹脂の２核体成分の含有率は、
例えば軟化点が95℃のフェノール樹脂では13〜16重量パ
ーセント、また軟化点が110℃のフェノール樹脂では８
〜11重量パーセントであったのと比べて非常に少ない。
また前記ノボラック型フェノール樹脂の数平均分子量
（Ｍ）は300≦Ｍ≦900重量パーセントであり、好ましく
は400≦Ｍ≦800重量パーセントであり、さらに好ましく
は450≦Ｍ≦700である。Here, the content of the binuclear component (X) contained in the novolac type phenol resin is 5.0% by weight or less, preferably 0.5 ≦ X ≦ 3.0% by weight, more preferably 1.0 ≦ X ≦ 2.0% by weight. Is. The content ratio of the binuclear component of the conventional novolac type phenolic resin is
For example, 13 to 16 weight percent for a phenolic resin with a softening point of 95 ° C and 8 for a phenolic resin with a softening point of 110 ° C.
Very low compared to ~ 11 weight percent.
The number average molecular weight (M) of the novolac type phenolic resin is 300 ≦ M ≦ 900 weight percent, preferably 400 ≦ M ≦ 800 weight percent, and more preferably 450 ≦ M ≦ 700.
前記ノボラック型フェノール樹脂の２核体成分が5.0重
量パーセントを上回る場合は、従来からのノボラック型
フェノール樹脂に比べて３次元架橋性が目立って大きく
ならないので、エポキシ樹脂組成物の硬化物特性である
耐熱性や耐湿性に顕著な特長が発現しにくい。なお、２
核体成分(X)は少量である程好ましいが、0.1重量パーセ
ントを下回る場合については、ノボラック型フェノール
樹脂が0.1重量パーセントを下回るように工業的に製造
するには工数がかかり、0.1重量パーセントを下回る量
が存在したとしても微量であるので0.1重量程度存在す
る場合と比較して品質に及ぼす影響に殆ど差がない。When the content of the binuclear component of the novolac type phenolic resin exceeds 5.0% by weight, the three-dimensional crosslinkability does not significantly increase as compared with the conventional novolac type phenolic resin, which is a characteristic of the cured product of the epoxy resin composition. Difficult to develop remarkable features in heat resistance and moisture resistance. 2
A small amount of the core component (X) is preferable, but in the case of less than 0.1% by weight, it takes man-hours to industrially manufacture the novolac type phenolic resin so as to be less than 0.1% by weight. Even if a lower amount is present, it is a very small amount, so there is almost no difference in the effect on the quality as compared with the case where the amount is about 0.1 weight.
ノボラック型フェノール樹脂の数平均分子量(M)が900を
上回る場合は硬化性が悪くなり、300を下回る場合は耐
熱性が悪くなるので不適である。If the number average molecular weight (M) of the novolac type phenol resin is more than 900, the curability will be poor, and if it is less than 300, the heat resistance will be poor, which is not suitable.
本発明において、２核体成分(X)が5.0重量パーセント以
下であり、かつ数平均分子量(X)が300≦Ｍ≦900である
ノボラック型フェノール樹脂は、本発明者らの出願によ
る特願昭61−95900号、特願昭61−110878号、特願昭61
−110879号、特願昭61−117412号、特願昭61−117413
号、特願昭61−119369号および特願昭61−119370号によ
るノボラック型フェノール樹脂が該当する。すなわち本
発明の積層板用エポキシ樹脂組成物に使用するノボラッ
ク型フェノール樹脂は、このような本発明者らによるノ
ボラック型フェノール樹脂を使用することが可能であ
る。In the present invention, the novolac type phenolic resin in which the binuclear component (X) is 5.0% by weight or less and the number average molecular weight (X) is 300 ≦ M ≦ 900 is a patent application filed by the present inventors. 61-95900, Japanese Patent Application No. 61-110878, Japanese Patent Application No. 61
-110879, Japanese Patent Application No. 61-117412, Japanese Patent Application No. 61-117413
Novolak type phenolic resins according to Japanese Patent Application No. 61-119369 and Japanese Patent Application No. 61-119370 are applicable. That is, as the novolac type phenol resin used in the epoxy resin composition for a laminated plate of the present invention, it is possible to use the novolac type phenol resin by the present inventors.
次に、ノボラック型フェノール樹脂の２核体成分(X)の
含有率と数平均分子量（Ｍ）は分子量既知の標準物質に
より検量した東洋曹達工業(株)の高速液体クロマトグラ
フ型式HLC−802Aと分析カラムTSK−GELG1000H８×１
本、TSK−GELG2000H８×２本、TSK−GELG3000H８×１本
の組合せにより測定した。Next, the content and number average molecular weight (M) of the binuclear component (X) of the novolac type phenol resin were calibrated with a high-performance liquid chromatograph model HLC-802A of Toyo Soda Kogyo Co., Ltd. Analytical column TSK-GELG1000H 8 x 1
Book, TSK-GELG2000H 8 x 2, and TSK-GELG3000H 8 x 1 in combination.
本発明の積層板用エポキシ樹脂組成物を得るためには、
エポキシ樹脂のエポキシ基とノボラック型フェノール樹
脂の水酸基との当量比は1.0対0.7〜1.3の範囲となるの
が望ましい。To obtain the epoxy resin composition for laminated boards of the present invention,
The equivalent ratio of the epoxy group of the epoxy resin to the hydroxyl group of the novolac type phenol resin is preferably in the range of 1.0 to 0.7 to 1.3.
本発明においては、エポキシ樹脂はビスフェノールＡ
型、ノボラック型（但し、２核体含有率5.0重量パーセ
ント以下のものを除く）、脂環型等特に限定されない
が、エポキシ当量180〜1000のビスフェノール型、平均
分子量500〜2000のノボラック型、あるいはそれらの臭
素化物が好ましい。In the present invention, the epoxy resin is bisphenol A.
Type, novolac type (excluding those having a binuclear content of 5.0% by weight or less), alicyclic type, etc., but not particularly limited, bisphenol type having an epoxy equivalent of 180 to 1000, novolac type having an average molecular weight of 500 to 2000, or Those bromides are preferred.
硬化促進剤としては各種イミダゾール類や、ベンジルジ
メチルアミンなどの第三級アミン類などが有効である。
ハロゲン化合物などの難燃剤、あるいは充填剤などを適
宜配合して用いることができる。As the curing accelerator, various imidazoles and tertiary amines such as benzyldimethylamine are effective.
A flame retardant such as a halogen compound or a filler can be appropriately mixed and used.
本発明の積層板用エポキシ樹脂組成物はこれらの各種原
料を通常溶剤に溶解させた後、基材に含浸させてプリプ
レグを作製して用いるが、このプリプレグは必要枚数を
積重ね、必要に応じて金属箔や金属板を重ねて積層成形
することによって耐熱性にすぐれた積層板が得られる。
なお、基材にはガラス、無機繊維、有機繊維の織布や不
織布、紙などが使用できる。The epoxy resin composition for a laminated board of the present invention is usually prepared by dissolving these various raw materials in a solvent and then impregnating the base material to prepare a prepreg. A laminated plate having excellent heat resistance can be obtained by stacking and laminating metal foils and metal plates.
As the substrate, glass, inorganic fiber, woven or non-woven fabric of organic fiber, paper or the like can be used.
以下本発明を実施例によって詳細に説明するが、本発明
は実施例によって限定されるものではない。なお、この
実施例および比較例に記載されている「部」および
「％」は「重量部」および「重量パーセント」を示す。Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the examples. In addition, "part" and "%" described in this Example and a comparative example show a "weight part" and "weight percentage."
(1)硬化剤用ノボラック型フェノール樹脂の合成 製造例１ 撹拌機、熱交換器、温度計の付いた反応装置にフェノー
ル10モル、37％ホルマリン5.0モル、蓚酸0.1モルを仕込
み、常圧で90分間還流反応を行ない、続いて150℃にな
るまで脱水反応を行なって初期総合反応を終了した。(1) Synthesis of novolak type phenolic resin for curing agent Production Example 1 A reactor equipped with a stirrer, heat exchanger, and thermometer was charged with 10 mol of phenol, 5.0 mol of 37% formalin, and 0.1 mol of oxalic acid at atmospheric pressure. A reflux reaction was performed for a minute, and then a dehydration reaction was performed until the temperature reached 150 ° C. to complete the initial overall reaction.
その後第１図に示すように固定式羽根(5)を管内に有す
る配管(4)を第２図のように接続し、供給ポンプ(2)を用
いて配管(4)内に初期縮合反応液を0.1kg／分で定量圧送
供給した。配管(4)内温度を170℃に保ちながら、水蒸気
供給口(3)から水蒸気を0.05Nm３／分で供給混合して、
混合物を反応装置(1)に戻すことからなる循環処理を80T
orrの減圧下で５時間行なった。続いて60Torrの減圧下
で１時間脱水縮合反応を行なってノボラック型フェノー
ル樹脂を得た。After that, as shown in FIG. 1, the pipe (4) having fixed blades (5) in the pipe is connected as shown in FIG. Was fed at a constant pressure of 0.1 kg / min. While maintaining the temperature in the pipe (4) at 170 ° C, water vapor was supplied and mixed from the water vapor supply port (3) at 0.05 Nm 3 / min,
80T circulation process consisting of returning the mixture to the reactor (1)
It was carried out under reduced pressure of orr for 5 hours. Subsequently, a dehydration condensation reaction was carried out for 1 hour under a reduced pressure of 60 Torr to obtain a novolac type phenol resin.
この樹脂の軟化点は100℃、２核体成分の含有率は0.3
％、水酸基当量は104、数平均分子量ｎは540であっ
た。The softening point of this resin is 100 ° C and the content of dinuclear component is 0.3.
%, The hydroxyl group equivalent was 104, and the number average molecular weight n was 540.
製造例２ フェノール10モル、37％ホルマリン4.3モル、蓚酸0.1モ
ルを仕込む以外は実施例１の硬化剤用ノボラック型フェ
ノール樹脂の合成の場合と同じ条件で反応を行ない、ノ
ボラック型フェノール樹脂を得た。この樹脂の硬化点は
91℃、２核体成分の含有率は2.8％、水酸基当量は104、
数平均分子量は390であった。Production Example 2 A novolak type phenol resin was obtained by carrying out the reaction under the same conditions as in the synthesis of the novolak type phenol resin for a curing agent of Example 1 except that 10 mol of phenol, 4.3 mol of 37% formalin and 0.1 mol of oxalic acid were charged. . The cure point of this resin is
91 ℃, content of dinuclear component is 2.8%, hydroxyl equivalent is 104,
The number average molecular weight was 390.
製造例３ フェノール10モル、37％ホルマリン7.0モル、蓚酸0.1モ
ルを仕込む以外は実施例１の硬化剤用ノボラック型フェ
ノール樹脂の合成の場合と同じ条件反応を行ない、ノボ
ラック型フェノール樹脂を得た。この樹脂の軟化点は11
5℃、２核体成分の含有率は3.5％、水酸基当量は104、
数平均分子量は810であった。Production Example 3 A novolak type phenol resin was obtained by performing the same reaction conditions as in the synthesis of the novolak type phenol resin for a curing agent of Example 1 except that 10 mol of phenol, 7.0 mol of 37% formalin and 0.1 mol of oxalic acid were charged. The softening point of this resin is 11
5 ° C, content of binuclear component is 3.5%, hydroxyl equivalent is 104,
The number average molecular weight was 810.
製造例４ 撹拌機、熱交換器、温度計の付いた反応装置にフェノー
ル10モル、37％ホルマリン5.7モル、蓚酸0.1モルを仕込
み、常圧で90分間の還流反応を行なった後、反応液の温
度が150℃になるまで脱水反応を行なって初期縮合反応
を終了した。その後175℃に昇温した反応液に0.02Nm3/
分の水蒸気を吹込むことからなる蒸留処理を70Torrの減
圧下で５時間行なった。続いて70Torrの減圧にして160
℃で１時間の脱水縮合反応を行ない、ノボラック型フェ
ノール樹脂を得た。得られた樹脂は軟化点が95℃、数平
均分子量が512、２核体成分の含有率が9.0％、水酸基当
量が104であった。Production Example 4 A reactor equipped with a stirrer, a heat exchanger, and a thermometer was charged with 10 mol of phenol, 5.7 mol of 37% formalin, and 0.1 mol of oxalic acid, and the mixture was refluxed for 90 minutes at normal pressure. The initial condensation reaction was completed by performing a dehydration reaction until the temperature reached 150 ° C. After that, 0.02 Nm 3 /
A distillation treatment consisting of blowing in a minute of steam was carried out under a reduced pressure of 70 Torr for 5 hours. Then decompress to 70 Torr and 160
A dehydration condensation reaction was carried out at 1 ° C. for 1 hour to obtain a novolac type phenol resin. The obtained resin had a softening point of 95 ° C., a number average molecular weight of 512, a content of dinuclear component of 9.0%, and a hydroxyl equivalent of 104.
製造例５ 撹拌機、熱交換器、温度計の付いた反応装置にフェノー
ル10モル、37％ホルマリン7.7モル、蓚酸0.1モルを仕込
み、常圧で90分間の還流反応を行なった後、反応液の温
度が150℃になるまで脱水反応を行なって初期縮合反応
を終了した。その後175℃に昇温した反応液に0.02Nm3/
分の水蒸気を吹込むことからなる蒸留処理を60Torrの減
圧下で３時間行なった。続いて60Torrの減圧にして160
℃で１時間の脱水縮合反応を行ない、ノボラック型フェ
ノール樹脂を得た。得られた樹脂は軟化点が125℃、数
平均分子量1025、２核体成分の含有率が3.5％、水酸基
当量が104であった。Production Example 5 A reactor equipped with a stirrer, a heat exchanger, and a thermometer was charged with 10 mol of phenol, 7.7 mol of 37% formalin, and 0.1 mol of oxalic acid, and the mixture was refluxed for 90 minutes at atmospheric pressure. The initial condensation reaction was completed by performing a dehydration reaction until the temperature reached 150 ° C. After that, 0.02 Nm 3 /
A distillation process consisting of blowing in a minute of steam was carried out for 3 hours under a reduced pressure of 60 Torr. Then reduce the pressure to 60 Torr and 160
A dehydration condensation reaction was carried out at 1 ° C. for 1 hour to obtain a novolac type phenol resin. The obtained resin had a softening point of 125 ° C., a number average molecular weight of 1025, a content of dinuclear component of 3.5%, and a hydroxyl group equivalent of 104.
(2)積層板の製造及び特性評価結果 第１表に示した実施例、比較例の樹脂処方のエポキシ樹
脂ワニス（溶媒メチルエチルケトン）をガラス織布に含
浸し、乾燥して樹脂分46％のプリプレグを得た。このプ
リプレグ８枚及び銅箔を重ね、温度170℃圧力40kg/cm2
で120分間加熱加圧成形して、厚さ1.6mmのエポキシ樹脂
積層板を得た。得られた積層板を特性評価結果を第１表
に示す。(2) Manufacture of laminated plate and characteristic evaluation results A glass woven cloth was impregnated with an epoxy resin varnish (solvent methyl ethyl ketone) having a resin formulation of Examples and Comparative Examples shown in Table 1, and dried to obtain a prepreg having a resin content of 46%. Got Eight pieces of this prepreg and copper foil are piled up, and temperature is 170 ℃ and pressure is 40kg / cm 2.
Was heated and pressed for 120 minutes to obtain an epoxy resin laminate having a thickness of 1.6 mm. Table 1 shows the results of the characteristic evaluation of the obtained laminate.
（特性の測定方法） (1)成形性 前記条件により成形して成形性を判定 ◎：非常に良好、〇：良好、△：一部に不良発生 (2)ガラス転移温度 粘弾性法によりtanδのピーク値の温度を求める。 (Measurement method of characteristics) (1) Moldability Moldability is determined by molding under the above conditions ◎: Very good, ◯: Good, △: Partly defective (2) Glass transition temperature of tan δ by viscoelastic method Calculate the peak temperature.
(3)吸湿率 JIS Ｃ 6481による。(3) Moisture absorption rate According to JIS C 6481.
Ｅ−１／105＋Ｄ−４／100処理後測定 (4)半田耐熱性 JIS Ｃ 6481による。E-1 / 105 + D-4 / 100 Measurement after treatment (4) Soldering heat resistance According to JIS C 6481.
Ｄ−４／100処理後、260℃で測定 〔発明の効果〕 本発明による積層板用エポキシ樹脂組成物は、硬化剤と
して使用するノボラック型フェノール樹脂が従来からの
汎用樹脂に比べて２核体成分が少なく、かつ数平均分子
量が限定された範囲にあるため、極めて３次元架橋性が
富み硬化性がすぐれており、従って耐熱性や耐湿性が飛
躍的に向上するので、電気・電子用多層プリント配線基
板などの積層板に極めて有用である。Measured at 260 ° C. after D-4 / 100 treatment [Effect of the invention] In the epoxy resin composition for laminates according to the present invention, the novolac type phenol resin used as the curing agent is a binuclear compound as compared with conventional general-purpose resins. Since it contains few components and the number average molecular weight is in a limited range, it is extremely rich in three-dimensional crosslinkability and has excellent curability. Therefore, heat resistance and moisture resistance are dramatically improved. It is extremely useful for laminated boards such as printed wiring boards.
第１図はスパイラル式固定式羽根を有する配管の部分断
面正面図である。 第２図は固定式羽根を有する配管を用いた場合の設備概
要図である。FIG. 1 is a partially sectional front view of a pipe having a spiral fixed blade. FIG. 2 is a schematic view of equipment when a pipe having fixed blades is used.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 大鳥 利行 東京都港区三田３丁目11番36号 住友ベー クライト株式会社内 審査官 冨士 良宏 (56)参考文献 特開 昭56−112924（ＪＰ，Ａ) 特開 昭63−254123（ＪＰ，Ａ) 特開 昭63−225621（ＪＰ，Ａ) 特開 平１−131273（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toshiyuki Otori 3-11-36 Mita, Minato-ku, Tokyo Sumitomo Bakelite Co., Ltd. Yoshihiro Fuji (56) Reference JP-A-56-112924 (JP, A) ) JP-A-63-254123 (JP, A) JP-A-63-225621 (JP, A) JP-A-1-131273 (JP, A)
Claims (1)
る積層板用エポキシ樹脂組成物において、エポキシ樹脂
が、２核体含有率５重量パーセント以下のノボラック型
エポキシ樹脂を除くエポキシ樹脂であり、ノボラック型
フェノール樹脂がフェノールまたは／およびクレゾール
からなるフェノール類とアルデヒドを反応させて得られ
るノボラック樹脂であって、ノボラック樹脂に含まれる
２核体成分（Ｘ）が5.0重量パーセント以下であり、か
つ数平均分子量（Ｍ）が300≦Ｍ≦900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, which comprises a novolac type phenolic resin as a curing agent, wherein the epoxy resin is an epoxy resin excluding a novolac type epoxy resin having a binuclear content of 5% by weight or less. Phenolic resin is a novolac resin obtained by reacting phenols consisting of phenol and / or cresol with an aldehyde, wherein the binuclear component (X) contained in the novolac resin is 5.0% by weight or less, and the number average molecular weight is (M) is 300 ≦ M ≦ 900, an epoxy resin composition for laminated boards, characterized in that
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63224691A JPH0662734B2 (en) | 1988-09-09 | 1988-09-09 | Epoxy resin composition for laminated board |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63224691A JPH0662734B2 (en) | 1988-09-09 | 1988-09-09 | Epoxy resin composition for laminated board |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0273824A JPH0273824A (en) | 1990-03-13 |
| JPH0662734B2 true JPH0662734B2 (en) | 1994-08-17 |
Family
ID=16817727
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63224691A Expired - Lifetime JPH0662734B2 (en) | 1988-09-09 | 1988-09-09 | Epoxy resin composition for laminated board |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0662734B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5614600A (en) * | 1994-06-03 | 1997-03-25 | Kashima Oil Co., Ltd. | Fiber-reinforced resin plate and process for producing the same |
| JP4658070B2 (en) | 2004-12-21 | 2011-03-23 | 三井化学株式会社 | Modified phenolic resin, epoxy resin composition containing the same, and prepreg using the same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01131273A (en) * | 1987-11-17 | 1989-05-24 | Sumitomo Deyurezu Kk | Epoxy resin composition for laminated board |
-
1988
- 1988-09-09 JP JP63224691A patent/JPH0662734B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0273824A (en) | 1990-03-13 |
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