JPS63199725A - Epoxy resin composition - Google Patents
Epoxy resin compositionInfo
- Publication number
- JPS63199725A JPS63199725A JP3231187A JP3231187A JPS63199725A JP S63199725 A JPS63199725 A JP S63199725A JP 3231187 A JP3231187 A JP 3231187A JP 3231187 A JP3231187 A JP 3231187A JP S63199725 A JPS63199725 A JP S63199725A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- bisphenol
- polycondensate
- curing agent
- formaldehyde
- 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
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 86
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 86
- 239000000203 mixture Substances 0.000 title claims abstract description 23
- 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 claims abstract description 57
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 35
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims abstract description 12
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims abstract description 6
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 claims description 6
- 210000000988 bone and bone Anatomy 0.000 claims description 4
- 229930185605 Bisphenol Natural products 0.000 claims description 3
- 230000001588 bifunctional effect Effects 0.000 claims description 2
- 229920005989 resin Polymers 0.000 abstract description 9
- 239000011347 resin Substances 0.000 abstract description 9
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 150000002739 metals Chemical class 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- 239000011342 resin composition Substances 0.000 abstract description 3
- 239000004593 Epoxy Substances 0.000 description 12
- 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 12
- 239000002966 varnish Substances 0.000 description 12
- 239000011521 glass Substances 0.000 description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 239000011889 copper foil Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- -1 formaldehyde, halogenated bisphenol A Chemical class 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- CMQUQOHNANGDOR-UHFFFAOYSA-N 2,3-dibromo-4-(2,4-dibromo-5-hydroxyphenyl)phenol Chemical compound BrC1=C(Br)C(O)=CC=C1C1=CC(O)=C(Br)C=C1Br CMQUQOHNANGDOR-UHFFFAOYSA-N 0.000 description 1
- 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 1
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 241001585714 Nola Species 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 239000004844 aliphatic epoxy resin Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- FDPIMTJIUBPUKL-UHFFFAOYSA-N dimethylacetone Natural products CCC(=O)CC FDPIMTJIUBPUKL-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
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 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
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 150000003003 phosphines Chemical group 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0326—Organic insulating material consisting of one material containing O
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
Description
【発明の詳細な説明】
(a) 発明の目的
(産業上の利用分野)
本発明は、エポキシ樹脂組成物、特に耐熱性及び金属と
の密着性に優れた硬化物を与えることができ、したがっ
てプリント配線板用の銅張エポキシ樹脂積層板等の製造
に有利に使用されるエポキシ樹脂組成物に関する。DETAILED DESCRIPTION OF THE INVENTION (a) Object of the invention (industrial application field) The present invention is capable of providing an epoxy resin composition, particularly a cured product having excellent heat resistance and adhesion to metals. The present invention relates to an epoxy resin composition that is advantageously used for manufacturing copper-clad epoxy resin laminates for printed wiring boards.
(従来の技術)
近年、電子機器の小型化に伴ない、プリント配線板の高
密度化が進んでいる。そのために、その基材の耐熱性、
耐ミーズリング性などの向上が望まれている。(Prior Art) In recent years, with the miniaturization of electronic devices, the density of printed wiring boards has been increasing. Therefore, the heat resistance of the base material,
Improvements in measling resistance, etc. are desired.
また、エポキシ樹脂の硬化剤としては、従来、芳香族ア
ミン、ジシアンジアミド、酸無水物、BF、錯体などが
使用されているが、硬化物の耐熱性が不充分であった。Furthermore, aromatic amines, dicyandiamide, acid anhydrides, BF, complexes, and the like have been conventionally used as curing agents for epoxy resins, but the heat resistance of the cured products has been insufficient.
エポキシ樹脂硬化物の耐熱性向上のために、使用するエ
ポキシ樹脂にフェノールノ?う、り型エポキシ樹脂、ク
レゾールノゲラ、り型エイキシ樹脂、ノ母うアミノフェ
ノールのトリグリシジルエーテルなどの多官能エポキシ
樹脂を添加することが行なわれるが、これらの多官能エ
ポキシ樹脂を添加しても硬化物の耐熱性はなお充分とい
えなかった。また、積層板用の工lキシ樹脂の耐熱性向
上手段として、フェノールノゴラ、り型樹脂を硬化性な
どに問題があった。Is phenol added to the epoxy resin used to improve the heat resistance of cured epoxy resin products? Polyfunctional epoxy resins such as polyurethane-type epoxy resin, cresol nogera, polyurethane-type epoxy resin, and triglycidyl ether of triglycidyl phenol are often added. However, the heat resistance of the cured product was still not sufficient. In addition, as a means for improving the heat resistance of synthetic resins for laminates, phenolic resins and resins have had problems in their curability.
(発明が解決しようとする問題点)
本発明は、グリント配線基板等に使用される銅張エポキ
シ樹脂積層板などの製造に適する耐熱性に優れ、しかも
鋼箔等との密着性に優れた硬化物を与えることのできる
エポキシ樹脂組成物を提供硬化促進剤及び溶剤を含有し
てなるエポキシ樹脂組成物において、該エポキシ樹脂が
下記のエポキシ樹脂aを主成分とするエポキシ樹脂から
なり、該硬化剤が下記の硬化剤すを主成分とする硬化剤
からなることを特徴とするエポキシ樹脂組成物である。(Problems to be Solved by the Invention) The present invention provides a cured resin with excellent heat resistance suitable for manufacturing copper-clad epoxy resin laminates used for glint wiring boards, etc., and excellent adhesion to steel foils, etc. An epoxy resin composition containing a curing accelerator and a solvent, in which the epoxy resin is composed of an epoxy resin having the following epoxy resin a as a main component, and the curing agent is an epoxy resin composition characterized in that it consists of a curing agent having the following curing agent as a main component.
エポキシ樹脂a:
(I)ビスフェノールAとホルムアルデヒドとの重縮合
物のグリシジルエーテル化物、及びハロゲン化ビスフェ
ノールAとホルムアルデヒドとの重縮合物のグリシジル
エーテル化物よりなる群から選ばれた少なくとも1種の
グリシジルエーテル化物と、(■)ピスフ、ノールA、
ビスフェノールF及びテトラブロモビスフェノールAよ
シなる群から選ばれた少な、くとも1種の化合物骨核の
みを骨核とする二官能エポキシ樹脂ト、cm)ビスフェ
ノ−/l/ A 、ビスフェノールF及びテトラツロモ
ビスフェノールAよシなる群から選ばれた少なくとも1
種のびスフ、ノールとを反応させて得られたエポキシ樹
脂。Epoxy resin a: (I) At least one glycidyl ether selected from the group consisting of a glycidyl ether of a polycondensate of bisphenol A and formaldehyde, and a glycidyl ether of a polycondensate of halogenated bisphenol A and formaldehyde. A compound, (■) Pisfu, Nord A,
At least one compound selected from the group consisting of bisphenol F and tetrabromobisphenol A. Bifunctional epoxy resin having only a bone core as a bone core, cm) bispheno-/l/A, bisphenol F and tetrabromobisphenol. At least one selected from the group consisting of Tulomobisphenol A
Epoxy resin obtained by reacting seeds, bisulfur, and nol.
硬化剤b=
ビスフェノールAとホルムアルデヒドとの重縮合物及ヒ
バロダン化ビスフェノールAとホルムアルデヒドとの重
縮合物より選ばれた少なくとも1種の重縮合物からなる
硬化剤。Curing agent b = A curing agent comprising at least one polycondensate selected from a polycondensate of bisphenol A and formaldehyde and a polycondensate of hybarodanated bisphenol A and formaldehyde.
このように、本発明のエポキシ樹脂組成物は、そのエポ
キシ樹脂として特定のエポキシ樹脂aを主成分とするエ
ポキシ樹脂を使用し、かつ七の硬化剤として特定の硬化
剤bを主成分とする硬化剤を使用する点に特徴がある。As described above, the epoxy resin composition of the present invention uses an epoxy resin containing a specific epoxy resin a as its main component, and a curing agent containing a specific curing agent b as its curing agent. It is characterized by the use of agents.
ビスフェノールAとホルムアルデヒドとの重縮合物のグ
リシジルエーテル化物や、ハロゲン化ビスフェノールA
とホルムアルデヒドとの重縮合物のグリシジルエーテル
化物を単独で用いた工lキシ樹脂、或いはこれらを主成
分として使用し、これに比較的少量の他のエポキシ樹脂
を配合したエポキシ樹脂は、これらをジンアンジアミド
やフェノールノがう、り型硬化剤で硬化させれば耐熱性
の非常に良好なエポキシ樹脂積層板を与えることができ
るが、銅箔密着性等の接着特性が充分でない欠点があり
た(比較例1〜6参照]。Glycidyl etherified polycondensate of bisphenol A and formaldehyde, halogenated bisphenol A
An epoxy resin that uses glycidyl ether, a polycondensate of formaldehyde, and a polycondensate of formaldehyde, or an epoxy resin that uses these as the main component and blends a relatively small amount of other epoxy resins. If cured with andiamide or phenolic adhesive type curing agent, an epoxy resin laminate with very good heat resistance can be obtained, but it has the disadvantage that adhesive properties such as copper foil adhesion are not sufficient. (See Comparative Examples 1 to 6).
これに対し、本発明のエポキシ樹脂組成物は、そのエポ
キシ樹脂として特定のエポキシ樹脂aを用い、このエポ
キシ樹脂?:4IP定の硬化剤すを用いて硬化させるの
で、耐熱性に著しく優れ、しかも銅箔等の金属などとの
接着性にも優れた硬化物を与えることができるのである
。On the other hand, the epoxy resin composition of the present invention uses a specific epoxy resin a as the epoxy resin, and this epoxy resin ? Since it is cured using a curing agent with a constant IP rating of 4, it is possible to provide a cured product that has excellent heat resistance and also has excellent adhesion to metals such as copper foil.
本発明のエポキシ樹脂組成物は、特定のエポキシ樹脂a
が使用されるが、このエポキシ樹脂aはこれを単独使用
してもよいし、これに1分子中に2個以上のニブキシ基
を有する他のエポキシ樹脂を併用することも可能である
。その併用できる他のエポキシ樹脂としては、たとえば
ビスフェノールA型二−ギシ樹脂、フェノールノゲラ、
り型エポキシ樹脂、クレゾールツカラック型工fキシ樹
脂などのグリシジルエーテル型エポキシ樹脂、グリシジ
ルエステル型工゛lキシ樹脂、クリシジルアミン型工f
キシ樹脂、線状脂肪族エポキシ樹脂、脂環式エポキシ樹
脂、複素環式エポキシ樹脂、ハロゲン化エポキシ樹脂な
どの種々のエポキシ樹脂があげられる。これらの他のエ
ポキシ樹脂の併用量は、エポキシ樹脂全景、すなわちエ
ポキシ樹脂a及び併用する他のエポキシ樹脂の合計量1
00重量部に対して50重量部よシも少ない量にすべき
である。その併用する他のエポキシ樹脂量が多くなると
、硬化物の架橋密度が低下し、耐熱性が悪くなる。The epoxy resin composition of the present invention has a specific epoxy resin a.
This epoxy resin a may be used alone, or may be used in combination with another epoxy resin having two or more niboxy groups in one molecule. Other epoxy resins that can be used in combination include, for example, bisphenol A type 2-gish resin, phenol nogela,
Glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, etc.
Examples include various epoxy resins such as epoxy resins, linear aliphatic epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, and halogenated epoxy resins. The amount of these other epoxy resins used in combination is the total amount of epoxy resin, that is, the total amount of epoxy resin a and other epoxy resins used in combination 1
The amount should be as much as 50 parts by weight compared to 00 parts by weight. When the amount of other epoxy resins used in combination increases, the crosslinking density of the cured product decreases and heat resistance deteriorates.
本発明のエポキシ樹脂組成物においては、その硬化剤と
して特定の硬化剤bを主成分とする硬化剤が使用される
。このような特定の硬化剤すを用いることにより耐熱性
の良好な硬化物を与えることができるが、その理由は、
この硬化剤すがエポキシ樹脂aの骨核に類似する分子骨
核をもつ化合物であるので、両者の相溶性が良くなり、
架橋密度を高めることができるため、と考えられる。In the epoxy resin composition of the present invention, a curing agent containing a specific curing agent b as a main component is used as the curing agent. By using such a specific curing agent, a cured product with good heat resistance can be obtained, and the reason is that
Since this curing agent is a compound with a molecular core similar to that of epoxy resin A, the compatibility between the two is improved.
This is thought to be because the crosslinking density can be increased.
本発明のエポキシ樹脂組成物は、硬化剤b′@:単独使
用してもよいし、これに他の硬化剤を比較的少量なれば
併用してもよい。その併用できる他の硬化剤としては、
たとえば芳香族ポリアミン、ジシアンジアミF、酸無水
物、各種のフェノール型ノーラ、り樹脂などがあげられ
る。In the epoxy resin composition of the present invention, the curing agent b'@ may be used alone, or in combination with other curing agents in relatively small amounts. Other curing agents that can be used in combination include:
Examples include aromatic polyamines, dicyandiamide F, acid anhydrides, various phenol-type nolas, and resins.
本発明におけるエポキシ樹脂と硬化剤の配合割合は、工
lキシ樹脂全量1001ifi部に対して硬化剤が全量
で10〜100重責部になる範囲内である。硬化剤量が
この範囲よシ多くても、或いは少なくても硬化物性が悪
くなる。The blending ratio of the epoxy resin and the curing agent in the present invention is within a range where the total amount of the curing agent is 10 to 100 parts by weight per 1001 parts of the total amount of the epoxy resin. Even if the amount of the curing agent is greater or less than this range, the cured physical properties will deteriorate.
本発明のニーキシ樹脂組成物における硬化促進剤として
は種々のものが使用できる。たとえばベンジルジメチル
アミン、各種のイミダゾール系化合物などのアミン類、
トリフェニルホスフィンなどの三級ホスフィン類等があ
げられる。Various types of curing accelerators can be used in the NIXY resin composition of the present invention. For example, amines such as benzyldimethylamine and various imidazole compounds,
Examples include tertiary phosphines such as triphenylphosphine.
本発明のエポキシ樹脂組μ物における溶剤としては、種
々のものが使用できる。たとえば、アセトン、メチルエ
チルケトン、トルエン、キシレン、メチルイソブチルケ
トン、酢酸エチル、エチレングリ;−ルモノメチルエー
テル、 N、N−ジメチルホルムアミド、 N、N−ジ
メチルアセトアミド、メタノール、エタノールなどがあ
げられ、これらの溶剤は適宜に2種又はそれ以上の混合
溶剤として使用することも可能である。Various solvents can be used in the epoxy resin composition of the present invention. Examples of these solvents include acetone, methyl ethyl ketone, toluene, xylene, methyl isobutyl ketone, ethyl acetate, ethylene glycol monomethyl ether, N,N-dimethylformamide, N,N-dimethylacetamide, methanol, and ethanol. It is also possible to use a mixed solvent of two or more kinds as appropriate.
本発明のニーキシ樹脂組成物には、さらに必要に応じて
種々の他の添加剤、たとえけ難燃剤や充填剤等を適宜に
配合することができる。If necessary, various other additives, such as flame retardants, fillers, etc., may be appropriately blended into the NIXY resin composition of the present invention.
本発明のエポキシ樹脂組成物を用いて、たとえば銅張エ
ポキシ樹脂積層板を製造するには、常法にしたがって行
なうことができる。たとえば、ガラスクロス等圧とのエ
ポキシ樹脂組成物を含浸・塗布してから加熱乾燥して溶
剤を除去してプリプレグとし、このプリプレグの1枚若
しくは複数枚重ねたものの片面若しくは両面に銅箔を重
ね、次いで常法にしたがって加熱加圧して積層成形する
。For example, a copper-clad epoxy resin laminate can be produced using the epoxy resin composition of the present invention according to a conventional method. For example, a prepreg is obtained by impregnating and applying an epoxy resin composition with glass cloth and then heating and drying it to remove the solvent, and then layering copper foil on one or both sides of one or more layers of this prepreg. Then, according to a conventional method, the material is heated and pressurized to form a laminate.
(実施例等)
以下に、実施例及び比較例をあけてさらに詳述するが、
本発明はこれらの実施例によって限定されるものではな
い。実施例及び比較例に記載の1部」及び「憾」は、そ
れぞれ「重量部」及び「重量%」を意味する。(Examples, etc.) Below, Examples and Comparative Examples will be explained in more detail.
The present invention is not limited to these examples. "1 part" and "regret" described in Examples and Comparative Examples mean "part by weight" and "% by weight", respectively.
実施例1
Vスフ1ノールAとホルムアルデヒドとの重縮合物のグ
リシジルエーテル化物(油化シ、ルエポキシ株式会社商
品名 工♂コート 157、エポ1/当8208)80
部と、ビスフェノールAMエポキシ樹脂(油化シェルエ
4キシ株式会社商品名 工ぜコート 828、エポキシ
当量187)20部と、ビスフェノールA40部とを、
触媒(ジメチルイミダゾール)0.03部の存在下で反
応させてエポキシ当量57°0のエポキシ樹脂を得た。Example 1 Glycidyl etherified product of the polycondensate of V-Sufu 1 Nor A and formaldehyde (Yuka Shi, Ruepoxy Co., Ltd. trade name Ko♂ Coat 157, Epo 1/To 8208) 80
1 part, 20 parts of bisphenol AM epoxy resin (trade name: Kozekoat 828, epoxy equivalent: 187, manufactured by Yuka Shell E4-Ki Co., Ltd.), and 40 parts of bisphenol A.
The reaction was carried out in the presence of 0.03 part of a catalyst (dimethylimidazole) to obtain an epoxy resin having an epoxy equivalent of 57°0.
このエポキシ樹脂を「エポキシ樹脂、Jという。This epoxy resin is called "epoxy resin, J.
次いで、このエポキシ樹脂&’100部、硬化剤として
ビスフェノールAとホルムアルデヒドとの重縮合物 2
0部、硬化促進剤として2−エチル−4−メチルイミダ
ゾール0.2部を混合し、これ忙メチルエチルケトン/
エチレングリコールモノメチルエーテル混合溶剤(混合
重量比1/l)を加えて、不揮発分が55俤のワニスを
調製した。Next, 100 parts of this epoxy resin, a polycondensate of bisphenol A and formaldehyde as a curing agent 2
0 parts, 0.2 parts of 2-ethyl-4-methylimidazole as a curing accelerator were mixed, and this mixture was mixed with methyl ethyl ketone/
Ethylene glycol monomethyl ether mixed solvent (mixed weight ratio 1/l) was added to prepare a varnish with a nonvolatile content of 55 liters.
このワニスをガラスクロスに含浸・塗布し、130℃で
5分間乾燥し、エポキシ樹脂組成物含有量が451のプ
リプレグを得た。このプリプレグを8枚重ね、その両面
に0.35μm厚さの銅箔を重ね、温度170℃、圧力
40 kg/cm”で1時間積層成形して、厚さ1.6
−の銅張ガラスエイキシ積層板を製造した。この積層板
の特性は表1に示すとおりであった。A glass cloth was impregnated and applied with this varnish, and dried at 130° C. for 5 minutes to obtain a prepreg having an epoxy resin composition content of 451. 8 sheets of this prepreg were stacked, copper foil with a thickness of 0.35 μm was layered on both sides, and lamination molding was performed at a temperature of 170°C and a pressure of 40 kg/cm for 1 hour to obtain a thickness of 1.6
- A copper-clad glass Eixyx laminate was manufactured. The properties of this laminate were as shown in Table 1.
実施例2
ビスフェノールAとホルムアルデヒドとの重縮合物のグ
リシジルエーテル化物(実施例1で用いたエビコー)1
57)8部部、ビスフェノールA型エポキシ樹脂(実施
例1で用いたエピコート828 )20部、及びテトラ
ブロモビスフェノールA30部を、実施例IKおけると
同様の方法で反応させ、エポキシ当量342のエポキシ
樹脂を得た。このエポキシ樹脂を「工Iキシ樹脂12」
という。Example 2 Glycidyl etherified product of polycondensate of bisphenol A and formaldehyde (Ebicor used in Example 1) 1
57) 8 parts of bisphenol A type epoxy resin (Epicote 828 used in Example 1), and 30 parts of tetrabromobisphenol A were reacted in the same manner as in Example IK to form an epoxy resin with an epoxy equivalent of 342. I got it. This epoxy resin is called "Ko I-Kyoshi Resin 12".
That's what it means.
実施例Iにおいて用いた工Iキシ樹脂a1の代5に工I
キシ樹脂a を使用し、かつ硬化剤のビスフェノール・
Aとホルムアルデヒドの重縮合物の配合量を39部に変
更し、そのほかは実施例1と同様にしてワニスを調製し
、とのワニスを用いて実施例IKThけると同様にして
銅張ガラスエポキシ積層板を製造した。この積層板の特
性は表1に示すとおりであった。5 of the resin a1 used in Example I.
xy resin a and the curing agent bisphenol.
A varnish was prepared in the same manner as in Example 1 except that the blending amount of the polycondensate of A and formaldehyde was changed to 39 parts, and a copper-clad glass epoxy laminate was prepared in the same manner as in Example IKTh using the varnish. The board was manufactured. The properties of this laminate were as shown in Table 1.
実施例3
実施例2において製造したエポキシ樹脂a を60部、
ブロム化ビスフェノールA型エポキシ樹脂(油化シェル
エポキシ株式会社商品名 ニーコート 5049、エポ
キシ当t748、臭素含有量26チ)を40部、ビスフ
ェノールAとホルムアルデヒドの重縮合物t30部使用
し、そのほかは実施例1と同様にしてワニスを調製した
。とのワニスを使用して実施例1におけると同様の方法
で銅張ガラスエポキシ積層板を製造した。この積層板の
特性は表1に示すとおシであった。Example 3 60 parts of the epoxy resin a produced in Example 2,
40 parts of brominated bisphenol A type epoxy resin (product name of Yuka Shell Epoxy Co., Ltd., Nicoat 5049, t748 per epoxy, bromine content 26%) and 30 parts of a polycondensate of bisphenol A and formaldehyde were used, and the rest were as in the example. A varnish was prepared in the same manner as in Example 1. A copper-clad glass epoxy laminate was produced in the same manner as in Example 1 using the varnish of The properties of this laminate were as shown in Table 1.
実施例4
プロふ化ビスフェノールAとホルムアルデヒドとの重縮
合物のグリシジルエーテル化物(エポキシ当量420)
80部、ビスフェノールA型エポキシ樹脂(実施例1で
用いたエピコート 828)20部、及びテトラブロモ
ビスフェノールA30部を用い、実施例IKおけると同
様にして反応させ、エポキシ当量700のエポキシ樹脂
を製造した。このニーキシ樹脂を「工lキシ樹脂a 」
という。Example 4 Glycidyl etherified product of polycondensate of pro-phthalated bisphenol A and formaldehyde (epoxy equivalent: 420)
80 parts of bisphenol A type epoxy resin (Epicote 828 used in Example 1), and 30 parts of tetrabromobisphenol A were reacted in the same manner as in Example IK to produce an epoxy resin with an epoxy equivalent of 700. . This Nixi resin is called "Ki Kishi Resin A".
That's what it means.
このエポキシ樹脂1 を100部、ビスフェノールAと
ホルムアルデヒドとの重縮合物を17部用い、そのほか
は実施例1と同様にしてワニスを調製し、このワーニス
を用いて実施例IKおけると同様圧して銅張ガラスエポ
キシ積層板を製造した。A varnish was prepared in the same manner as in Example 1 except for using 100 parts of this epoxy resin 1 and 17 parts of a polycondensate of bisphenol A and formaldehyde. A clad glass epoxy laminate was manufactured.
この積層板の特性は表IK示すとおりであった。The properties of this laminate were as shown in Table IK.
実施例5
ニーキシ樹脂a を100部、ビスフェノールAとホル
ムアルデヒドとの重縮合物30部、及びオルトクレゾー
ルとホルムアルデヒドとの重縮合物10部を使用し、そ
のほかは実施例1の方法に準じてワニスを調製し、この
ワニスを用いて実施例1の方法に準じて銅張ガラスニブ
キシ積層板を製造した。この積層板の特性は表1に示す
とおシであった。Example 5 A varnish was prepared according to the method of Example 1 except that 100 parts of Nixy resin a, 30 parts of a polycondensate of bisphenol A and formaldehyde, and 10 parts of a polycondensate of orthocresol and formaldehyde were used. A copper-clad glass niboxy laminate was manufactured using this varnish according to the method of Example 1. The properties of this laminate were as shown in Table 1.
実施例6
実施例2における硬化剤を、プロふ化ビスフェノールA
とホルムアルデヒドとの重縮合物42部に変更し、その
ほかは実施例2と同様にしてワニスを調製し、このワニ
スを用いて実施例2と同様にして銅張ガラスニブキシ積
層板を製造した。この積層板の特性は表IK示すとおり
であった。Example 6 The curing agent in Example 2 was replaced with prophylated bisphenol A.
A varnish was prepared in the same manner as in Example 2 except that 42 parts of a polycondensate of The properties of this laminate were as shown in Table IK.
比較例1
ビスフェノールAとホルムアルデヒドとの重縮合物のグ
リシジルエーテル化物(実施例1で用い−たエピコート
157)60部、ビスフェノールA型エポキシ樹脂(
油化シ、ルエ一キシ株式会社商品名 エピコート 10
01、ニーキシ当量478)40部、硬化剤としてVス
フ1ノールAとホルムアルデヒドとの重縮合物47部、
及び硬化促進剤として2−エチル−4−メチルイミダゾ
ール0.2部を混合した。この混合物に実施例1で用い
たと同ジメチルエチルケトン/エチレングリコールモノ
メチルエーテル混合溶剤を加え、不揮発分が55俤にな
るようにワニスを調製した。Comparative Example 1 60 parts of glycidyl etherified polycondensate of bisphenol A and formaldehyde (Epicote 157 used in Example 1), bisphenol A type epoxy resin (
Yuka Shi, Rue Ikkishi Co., Ltd. Product name Epicote 10
01, Niexy equivalent 478) 40 parts, 47 parts of a polycondensate of V-sulfinol A and formaldehyde as a curing agent,
and 0.2 part of 2-ethyl-4-methylimidazole as a curing accelerator. The same dimethyl ethyl ketone/ethylene glycol monomethyl ether mixed solvent used in Example 1 was added to this mixture to prepare a varnish with a nonvolatile content of 55 ml.
このワニスを用いtそのほかは実施例IKおける方法に
準じて銅張ガラスエポキシ積層板を製造した。この積層
板の特性は表IK示すとおシであったO
比較例2〜7
表1に示す各配合を用い、そのほかは比較例IK準じて
それぞれワニスを調製し、得られた各ワニスを用いて実
施例1の方法に準じて各銅張ガラスエポキシ積層板を製
造した。それらの各積層板の特性は表1にそれぞれ示す
とおシであった。Using this varnish, a copper-clad glass epoxy laminate was manufactured in accordance with the method in Example IK except for the above. The properties of this laminate were as shown in Table IK. Each copper-clad glass epoxy laminate was manufactured according to the method of Example 1. The characteristics of each of these laminates are shown in Table 1.
以下余白
表1の注:
*1・・・l−1001、E−5049、E−5050
、E−157、及びE−180865は、それぞれエビ
コー) −1001、エピコート−5049、エピコー
ト−5050,エピコー) −157、エピコー) −
180865(以上いずれも油化シェルエポキシ株式会
社の商品名)!略称したものである。Notes for Margin Table 1 below: *1...l-1001, E-5049, E-5050
, E-157, and E-180865 are respectively Epicor)-1001, Epicor-5049, Epicor-5050, Epicor)-157, Epicor)-
180865 (all of the above are product names of Yuka Shell Epoxy Co., Ltd.)! It is an abbreviation.
*2・・・動的粘弾性(−δ〕で測定。*2: Measured by dynamic viscoelasticity (-δ).
*3・・・沸とう水に4時間浸漬(ハンダ温度260℃
)による。その評価結果は下記の略号で示した。*3...Immersed in boiling water for 4 hours (soldering temperature 260℃)
)by. The evaluation results are indicated by the following abbreviations.
O板のふくれ、はがれが全くな゛い。There is no bulging or peeling of the O plate.
Δ 板のふくれ、はがれが僅かにある。Δ There is slight swelling and peeling of the board.
X 板のふくれ、はがれがある。X There is swelling and peeling of the board.
表1に示された結果から明らかなように、各実施例のエ
ポキシ樹脂組成物は、比較例の組成物に較べて、耐熱性
、銅箔の密着性及び耐ミーズリング性がバランスよく優
れている。As is clear from the results shown in Table 1, the epoxy resin compositions of each example had better heat resistance, copper foil adhesion, and measling resistance in a well-balanced manner than the composition of the comparative example. There is.
(e) 発明の効果
本発明のエポキシ樹脂組成物は、プリント配線用銅張エ
ポキシ積層板の製造に使用した場合に、耐熱性、銅箔密
着性及び耐ミーズリング性等に優れた積層板が得られる
。(e) Effects of the Invention When the epoxy resin composition of the present invention is used in the production of copper-clad epoxy laminates for printed wiring, it produces laminates with excellent heat resistance, copper foil adhesion, measling resistance, etc. can get.
Claims (1)
してなるエポキシ樹脂組成物において、該エポキシ樹脂
が下記のエポキシ樹脂aを主成分とするエポキシ樹脂か
らなり、該硬化剤が下記の硬化剤bを主成分とする硬化
剤からなることを特徴とするエポキシ樹脂組成物。 エポキシ樹脂a: ( I )ビスフェノールAとホルムアルデヒドとの重縮
合物のグリシジルエーテル化物、及びハロゲン化ビスフ
ェノールAとホルムアルデヒドとの重縮合物のグリシジ
ルエーテル化物よりなる群から選ばれた少なくとも1種
のグリシジルエーテル化物と、(II)ビスフェノールA
、ビスフェノールF及びテトラブロモビスフェノールA
よりなる群から選ばれた少なくとも1種の化合物骨核の
みを骨核とする二官能エポキシ樹脂と、(III)ビスフ
ェノールA、ビスフェノールF及びテトラブロモビスフ
ェノールAよりなる群から選ばれた少なくとも1種のビ
スフェノールとを反応させて得られたエポキシ樹脂。 硬化剤b: ビスフェノールAとホルムアルデヒドとの重縮合物及び
ハロゲン化ビスフェノールAとホルムアルデヒドとの重
縮合物より選ばれた少なくとも1種の重縮合物からなる
硬化剤。[Scope of Claims] 1) An epoxy resin composition containing an epoxy resin, a curing agent, a curing accelerator, and a solvent, wherein the epoxy resin is composed of an epoxy resin whose main component is the following epoxy resin a; An epoxy resin composition characterized in that the curing agent consists of a curing agent whose main component is the following curing agent b. Epoxy resin a: (I) At least one glycidyl ether selected from the group consisting of a glycidyl ether of a polycondensate of bisphenol A and formaldehyde, and a glycidyl ether of a polycondensate of halogenated bisphenol A and formaldehyde. (II) Bisphenol A
, bisphenol F and tetrabromobisphenol A
(III) At least one compound selected from the group consisting of a bifunctional epoxy resin whose bone core is only a bone core, and (III) at least one compound selected from the group consisting of bisphenol A, bisphenol F, and tetrabromobisphenol A. Epoxy resin obtained by reacting with bisphenol. Curing agent b: A curing agent comprising at least one polycondensate selected from a polycondensate of bisphenol A and formaldehyde and a polycondensate of halogenated bisphenol A and formaldehyde.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62032311A JPH0717736B2 (en) | 1987-02-17 | 1987-02-17 | Epoxy resin composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62032311A JPH0717736B2 (en) | 1987-02-17 | 1987-02-17 | Epoxy resin composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS63199725A true JPS63199725A (en) | 1988-08-18 |
JPH0717736B2 JPH0717736B2 (en) | 1995-03-01 |
Family
ID=12355394
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP62032311A Expired - Fee Related JPH0717736B2 (en) | 1987-02-17 | 1987-02-17 | Epoxy resin composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0717736B2 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03145143A (en) * | 1989-10-31 | 1991-06-20 | Sumitomo Bakelite Co Ltd | Conductive resin paste for semiconductor |
EP0498505A2 (en) * | 1991-02-06 | 1992-08-12 | Shell Internationale Researchmaatschappij B.V. | Epoxy resin composition for use in electrical laminates |
JPH11209456A (en) * | 1998-01-29 | 1999-08-03 | Hitachi Chem Co Ltd | Flame-retardant epoxy resin composition for printed circuit board, and prepreg and metal-clad laminate prepared therefrom |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61148226A (en) * | 1984-12-21 | 1986-07-05 | Toto Kasei Kk | Solid epoxy resin for paint and laminated board |
JPS61246228A (en) * | 1985-04-24 | 1986-11-01 | Shin Kobe Electric Mach Co Ltd | Resin composition for laminate |
JPS6215221A (en) * | 1985-07-12 | 1987-01-23 | Hitachi Chem Co Ltd | Epoxy resin composition |
JPS6348324A (en) * | 1986-08-18 | 1988-03-01 | Dainippon Ink & Chem Inc | Epoxy resin composition |
-
1987
- 1987-02-17 JP JP62032311A patent/JPH0717736B2/en not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61148226A (en) * | 1984-12-21 | 1986-07-05 | Toto Kasei Kk | Solid epoxy resin for paint and laminated board |
JPS61246228A (en) * | 1985-04-24 | 1986-11-01 | Shin Kobe Electric Mach Co Ltd | Resin composition for laminate |
JPS6215221A (en) * | 1985-07-12 | 1987-01-23 | Hitachi Chem Co Ltd | Epoxy resin composition |
JPS6348324A (en) * | 1986-08-18 | 1988-03-01 | Dainippon Ink & Chem Inc | Epoxy resin composition |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03145143A (en) * | 1989-10-31 | 1991-06-20 | Sumitomo Bakelite Co Ltd | Conductive resin paste for semiconductor |
EP0498505A2 (en) * | 1991-02-06 | 1992-08-12 | Shell Internationale Researchmaatschappij B.V. | Epoxy resin composition for use in electrical laminates |
JPH11209456A (en) * | 1998-01-29 | 1999-08-03 | Hitachi Chem Co Ltd | Flame-retardant epoxy resin composition for printed circuit board, and prepreg and metal-clad laminate prepared therefrom |
Also Published As
Publication number | Publication date |
---|---|
JPH0717736B2 (en) | 1995-03-01 |
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