JPH0476021A - Epoxy resin varnish and its cured product - Google Patents
Epoxy resin varnish and its cured productInfo
- Publication number
- JPH0476021A JPH0476021A JP18804390A JP18804390A JPH0476021A JP H0476021 A JPH0476021 A JP H0476021A JP 18804390 A JP18804390 A JP 18804390A JP 18804390 A JP18804390 A JP 18804390A JP H0476021 A JPH0476021 A JP H0476021A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- epoxy
- resin
- varnish
- resin varnish
- 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.)
- Pending
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 52
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 52
- 239000002966 varnish Substances 0.000 title claims abstract description 26
- 239000004593 Epoxy Substances 0.000 claims abstract description 27
- 229920003986 novolac Polymers 0.000 claims abstract description 22
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 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 description 14
- 239000011248 coating agent Substances 0.000 abstract description 17
- 238000000576 coating method Methods 0.000 abstract description 17
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 abstract description 4
- 239000004841 bisphenol A epoxy resin Substances 0.000 abstract description 3
- ZJRAAAWYHORFHN-UHFFFAOYSA-N 2-[[2,6-dibromo-4-[2-[3,5-dibromo-4-(oxiran-2-ylmethoxy)phenyl]propan-2-yl]phenoxy]methyl]oxirane Chemical compound C=1C(Br)=C(OCC2OC2)C(Br)=CC=1C(C)(C)C(C=C1Br)=CC(Br)=C1OCC1CO1 ZJRAAAWYHORFHN-UHFFFAOYSA-N 0.000 abstract description 2
- 230000001351 cycling effect Effects 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 13
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 239000003348 petrochemical agent Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 239000003973 paint Substances 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- 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
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- VKEQBMCRQDSRET-UHFFFAOYSA-N Methylone Chemical compound CNC(C)C(=O)C1=CC=C2OCOC2=C1 VKEQBMCRQDSRET-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、エポキシ樹脂ワニスに関する。さらに詳しく
は、ハイブリッドＩＣ等の電子材料の外装用エポキシ樹
脂ワニス及びその硬化物に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an epoxy resin varnish. More specifically, the present invention relates to an epoxy resin varnish for the exterior of electronic materials such as hybrid ICs and a cured product thereof.
（従来の技術）
ハイブリッドＩＣ等の電子材料は耐湿性の向−にと外力
からの保護を目的に、外装用樹脂で被覆する方法かとら
れている。この外装用樹脂としては、エポキシ系粉体塗
料、フェノール樹脂（ワニス）、エポキシ樹脂（ワニス
）かある。(Prior Art) Electronic materials such as hybrid ICs are coated with an exterior resin for the purpose of moisture resistance and protection from external forces. Examples of this exterior resin include epoxy powder paint, phenol resin (varnish), and epoxy resin (varnish).
このうぢエポキシ系粉体塗料は流動浸漬法により塗装す
るか、固形の粉末を用いるため、ピンホールや基板との
密着性に問題かあり耐湿性か劣る欠点かある。またフェ
ノール樹脂はエツジ部や金属部分の被覆性能には優れる
ものの、硬化時の脱水（レゾール系）、発ガス（ノボラ
ック系）かあるためやはりピンホールか発生しやすく、
耐水性に問題かある。また塗膜か硬くて脆いためし−ト
ザイクル（熱衝撃）によりクラックか発生しやすい。Since this epoxy powder coating is applied by a fluidized dipping method or uses solid powder, there are problems with pinholes and adhesion to the substrate, and there are disadvantages such as poor moisture resistance. In addition, although phenolic resin has excellent coating performance for edges and metal parts, it is prone to pinholes due to dehydration (resol type) and gas generation (novolac type) during curing.
There is a problem with water resistance. Also, since the paint film is hard and brittle, cracks are likely to occur due to thermal shock.
このため無機フィラーを多量に添加して耐ヒー１へザイ
クル性を向−１ニさせているか、そのため塗膜を薄くす
ることか困難である。For this reason, it is difficult to either add a large amount of inorganic filler to increase the heat resistance to 1 or -1, or to make the coating film thinner.
またエポキシ樹脂（ワニス）は耐湿性に優れるものの、
やはり塗膜が硬くて脆いため、ヒートサイクルによりク
ラックを発生しやすい。このためフェノール樹脂の場合
と同様に多量の無機フィラーを添加して改良しているか
、やはり薄い塗膜を得ることが困難で膜厚は１０００〜
２０００μｍとなり５０〜３００μｍの膜厚は得られな
い。Also, although epoxy resin (varnish) has excellent moisture resistance,
As the paint film is hard and brittle, it is prone to cracking due to heat cycles. For this reason, it is either improved by adding a large amount of inorganic filler as in the case of phenolic resin, or it is difficult to obtain a thin coating film, and the film thickness is 1000~
The thickness is 2000 μm, and a film thickness of 50 to 300 μm cannot be obtained.
（発明が解決しようとする課題）
塗膜の薄膜化か可能で、耐湿性、耐ヒートサイクル性に
優れる外装用樹脂の開発が望まれている。(Problems to be Solved by the Invention) It is desired to develop a resin for exterior use that allows for thinning of the coating film and has excellent moisture resistance and heat cycle resistance.
（課題を解決するための手段）
本発明者等は前記した問題点を解決すべく鋭意研究を重
ねた結果本発明をなしたものである。即ち本発明は
ａ、エポキシ当量が８００〜２５００であり、かつエポ
キシ当量か１８００〜２５００である成分を３０〜１０
０重量％含有する、ビスフェノールＡ型エポキシ樹脂。(Means for Solving the Problems) The present inventors have made the present invention as a result of extensive research in order to solve the above-mentioned problems. That is, in the present invention, a component having an epoxy equivalent of 800 to 2,500 and a component having an epoxy equivalent of 1,800 to 2,500 is mixed with 30 to 10
Bisphenol A type epoxy resin containing 0% by weight.
ｂ、臭素化エポキシ樹脂
Ｃ６軟化点か７５°Ｃ以下であるフェノールノボラック
樹脂
ｄ、有機溶媒
らなるエポキシ樹脂ワニス及びその硬化物を提供す・る
。b. A phenol novolac resin having a softening point of brominated epoxy resin C6 of 75° C. or lower; d. An epoxy resin varnish consisting of an organic solvent and a cured product thereof.
本発明で使用するエポキシ樹脂は、エポキシ当量が８０
０〜２５００の範囲のビスフェノールＡ型エポキシ樹脂
で、さらにエポキシ当量が１８００〜２５００である成
分を３０〜１００重量％含有することを必須とする。The epoxy resin used in the present invention has an epoxy equivalent of 80
It is essential that the bisphenol A type epoxy resin has an epoxy equivalent weight of 0 to 2,500, and further contains 30 to 100% by weight of a component having an epoxy equivalent of 1,800 to 2,500.
エポキシ当量が８００より小さい値を有するエポキシ樹
脂を用いた場合、エツジ部の塗膜か極めて薄くなり好ま
しくなく、また基板とのはじきが起り均一な塗膜を得る
ことかできない。またエポキシ当量か２５００以上であ
るエポキシ樹脂を用いた場合、塗膜にしわか生じ、やは
り均一な塗膜を得ることができない。また耐熱性か低下
し、半田耐熱に耐えられない。When an epoxy resin having an epoxy equivalent of less than 800 is used, the coating film at the edge portion becomes extremely thin, which is undesirable, and also repelling occurs from the substrate, making it impossible to obtain a uniform coating film. Furthermore, when an epoxy resin having an epoxy equivalent of 2,500 or more is used, wrinkles occur in the coating film, making it impossible to obtain a uniform coating film. Also, the heat resistance decreases and it cannot withstand soldering heat.
エポキシ当量が１８００〜２５００である成分は基板と
のはじきを防止し均一な塗膜を得る硬化か大きく、さら
に耐ヒートサイクル性を向上させる効果かある。この成
分が３０重量％より少ない場合、エポキシ当量が前記し
た範囲にあってもヒートサイクルによるクラックの発生
を防止することができない。A component having an epoxy equivalent of 1,800 to 2,500 has the effect of preventing repulsion with the substrate, increasing the curing rate to obtain a uniform coating film, and further improving heat cycle resistance. If this component is less than 30% by weight, it is not possible to prevent the occurrence of cracks due to heat cycles even if the epoxy equivalent is within the above range.
本発明で使用するエポキシ樹脂は例えば、以下のように
して得られるものである。すなわちエポキシ当量４００
〜１０００のビスフェノールＡ型エポキシ樹脂、例えば
、エポミックＲ−３０１’（エポキシ当量４５０、三井
石油化学社製）、エポミックＲ−３０２（エポキシ当量
６５０、同上）エポミックＲ３０４（エポキシ当量９５
０、同上）などと、エポキシ当量１８００〜２５００の
ビスフェノールＡ型エポキシ樹脂、例えばＹＤ９２９
（エポキシ当量２５００、東都化成社製）エポミック
Ｒ−３０７（エポキシ当量１９００、同上）などを前記
した比率の範囲で配合することにより得られる。The epoxy resin used in the present invention can be obtained, for example, as follows. That is, the epoxy equivalent is 400
-1000 bisphenol A type epoxy resins, such as Epomic R-301' (epoxy equivalent: 450, manufactured by Mitsui Petrochemicals), Epomic R-302 (epoxy equivalent: 650, same as above), Epomic R304 (epoxy equivalent: 95)
0, same as above), and a bisphenol A type epoxy resin having an epoxy equivalent of 1800 to 2500, such as YD929.
(Epoxy equivalent: 2500, manufactured by Toto Kasei Co., Ltd.) Epomic R-307 (Epoxy equivalent: 1900, same as above) etc. are blended in the above ratio range.
本発明のワニスにおいてエポキシ樹脂の使用量は通常、
有機溶媒を除く固形分の５０〜９０重量％好ましくは６
０〜８０重量％使用する。In the varnish of the present invention, the amount of epoxy resin used is usually:
50 to 90% by weight of solids excluding organic solvents, preferably 6
Use from 0 to 80% by weight.
次に本発明で使用する臭素化エポキシ樹脂は例えば、テ
トラブロムビスフェノールＡジグリシジルエーテル例え
ばＥＴＢＡ （日本化薬社製）または臭素化フェノール
ノボラックエポキシ樹脂例えばＢＲＥＮＳ（日本化薬社
製）の一種、又はこれらを任意の比率で混合して用いる
ことができ、その使用量は有機溶媒を除く固形分の１５
〜３０重量％、好ましくは１８〜２５重量％である。該
臭素化エポキシ樹脂は塗膜の難燃性を付与するた゛めに
用いる。Next, the brominated epoxy resin used in the present invention is, for example, a type of tetrabromo bisphenol A diglycidyl ether such as ETBA (manufactured by Nippon Kayaku Co., Ltd.) or a brominated phenol novolak epoxy resin such as BRENS (manufactured by Nippon Kayaku Co., Ltd.); These can be mixed and used in any ratio, and the amount used is 15% of the solid content excluding organic solvents.
-30% by weight, preferably 18-25% by weight. The brominated epoxy resin is used to impart flame retardancy to the coating film.
次に硬化剤として使用するフェノールノボラック樹脂に
ついて説明する。Next, the phenol novolak resin used as a curing agent will be explained.
本発明で使用するフェノールノボラック樹脂の軟化点は
７５°Ｃ以下好ましくは５０°Ｃ以下の物性を有するも
のである。フェノールノボラック樹脂は従来ＩＣチップ
の封止用エポキシ樹脂の硬化剤等に利用され公知である
。しかしながら、これ等に使用される通常のフェノール
ノボラック樹脂は軟化点８０〜１００°Ｃの物性を有す
るもので、その硬化物は硬くて脆い性質を有しており、
外装用に用いた場合、その塗膜はヒートサイクルにより
クラックを生じやすく使用に耐えないものである。そこ
で本発明者は、外装用に使用が可能な硬化剤としてのフ
ェノールノボラック樹脂について種々検討した結果、軟
化点か７５°Ｃ以下好ましくは５０’Ｃ以ｔ′のフェノ
ールノボラック樹脂を硬化剤として用いるとヒートザイ
クルによるクラックの発生のない外装用エポキシ樹脂ワ
ニスか得られることを見い出した。 本発明で使用す
るフェノールノボラック樹脂は例えば以Ｆのよ一′）に
して得ることかできる。すなわちしゅう酸等の酸触媒の
存在下過剰のフェノールとホルマリンを反応させた後、
未反応のフェノ
ルを回収することにより得られ、下記−能代（式中Ｒは
水素、低級アルギル、低級アルコキシ又はハロゲンを示
し、ｍは１〜３の整数を示しｍか２又は３のときＲは異
なった種類であってもよい。ｎは正の整数）
においてｎ＝１及び２て示される成分か好ましくは３５
〜８０９６含有されるフェノールノボラック樹脂である
。通常使用されているフ毛ノール、ノボラック樹脂は、
ｎ＝］及び２て示される成分はぜいぜい２５％以下であ
る。The phenol novolak resin used in the present invention has physical properties of a softening point of 75°C or lower, preferably 50°C or lower. Phenol novolac resins are conventionally known and used as curing agents for epoxy resins for sealing IC chips. However, the normal phenol novolak resin used for these products has a softening point of 80 to 100°C, and its cured product is hard and brittle.
When used for exterior purposes, the coating film tends to crack due to heat cycling and is unusable. Therefore, as a result of various studies on phenol novolac resins as curing agents that can be used for exterior applications, the present inventor used phenol novolac resins with a softening point of 75°C or lower, preferably 50°C or higher, as a curing agent. It has been found that it is possible to obtain an epoxy resin varnish for exterior use that does not generate cracks due to heat cycles. The phenol novolak resin used in the present invention can be obtained, for example, by the following method. That is, after reacting excess phenol with formalin in the presence of an acid catalyst such as oxalic acid,
Obtained by recovering unreacted phenol, the following - Noshiro (in the formula, R represents hydrogen, lower argyl, lower alkoxy, or halogen, m represents an integer of 1 to 3, and when m, 2, or 3, R is (n is a positive integer) where n=1 and 2 or preferably 35
It is a phenolic novolac resin containing ~8096. The commonly used fluorol and novolak resins are
The components indicated by n=] and 2 are at most 25% or less.
本発明で使用するフェノ−・ルノボラ・リフ樹脂の使用
量は有機溶媒を除く固形分の通常５〜２５重量％好まし
くは５〜１５重量％である。The amount of pheno-lunovora rif resin used in the present invention is usually 5 to 25% by weight of solids excluding organic solvents, preferably 5 to 15% by weight.
式（１）における置換基Ｒとしては例えは水素、メチル
基、エチル基、メＩ・キシ基、エトキシ基、塩素原子、
フッ素原子か挙げられ、又（Ｒ）。とじてはこれらの同
種又は異種か１〜３ゲベンセン環に結合したものか挙げ
られる。Examples of the substituent R in formula (1) include hydrogen, methyl group, ethyl group, methoxy group, ethoxy group, chlorine atom,
A fluorine atom is mentioned, and (R). Examples include those of the same type or different types, or those bonded to 1 to 3 gevensen rings.
本発明で使用する有機溶媒としては例えはトルエン、キ
シレン等の芳香族炭化水素、メタノール、エタノール、
メチルセロソルブ、エチルセロソルブ等のアルコール類
、アセトン、メチルエチルケトン、メチルイソブヂルケ
トン等のケトン類が挙げられ、これらの一種又はそれ以
上を任意の比率で用いることかできる。Examples of organic solvents used in the present invention include aromatic hydrocarbons such as toluene and xylene, methanol, ethanol,
Examples include alcohols such as methyl cellosolve and ethyl cellosolve, and ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, and one or more of these can be used in any ratio.
有機溶媒の使用量は塗膜の厚さの調整に必要な任意の量
用いることができ、通常、有機溶媒を除く固形分の濃度
か１０重量％〜６ｏ重量％好ましくは、３０〜５０重量
％になる量使用非る。The amount of organic solvent used can be any amount necessary to adjust the thickness of the coating film, and is usually 10 to 6% by weight, preferably 30 to 50% by weight, based on the solid content excluding the organic solvent. The amount used will be different.
本発明のエポキシ樹脂ワニスは、前記したエポキシ樹脂
１、交素化エボギシ樹脂、フェノールノボラック樹脂の
所定量を前記しッた所定量の有機溶媒中に加え必要であ
れは加熱溶解した後、必要であれば顔料、分散剤、フィ
ラー等を加えさらに硬化促進剤を加え均一に攪拌するこ
とにより得られる。The epoxy resin varnish of the present invention can be prepared by adding predetermined amounts of the above-mentioned epoxy resin 1, crossinated epoxy resin, and phenol novolak resin to the above-mentioned predetermined amount of organic solvent, heating and dissolving if necessary, It can be obtained by adding pigments, dispersants, fillers, etc., if any, and further adding a curing accelerator and stirring uniformly.
本発明で使用することのできる硬化促進剤は通常エポキ
シ樹脂の硬化に使用されるいかなる促進剤も使用するこ
とかでき、その使用量は任意であるか、通常は、ｒノニ
ス固形分に対し０．１〜５重量９６、好よｌ、７＜は０
．５〜２重量９ｏである。促進剤の例としては、イミダ
ゾール類、Ｉ・リスジアミノメチルフェノール、ｌ・リ
フェニルフォスフィン、１．８−ジアザ−ビシクロ（５
，４，０）ウンデセン−７等かあげられる。The curing accelerator that can be used in the present invention can be any accelerator that is normally used for curing epoxy resins, and the amount used is arbitrary, or is usually 0% relative to the solid content of r-nonis. .1-5 weight 96, good l, 7< is 0
．． 5-2 weight 9o. Examples of accelerators include imidazoles, l.lisdiaminomethylphenol, l.liphenylphosphine, 1,8-diaza-bicyclo(5
, 4, 0) undecene-7, etc.
本発明のエポキシ樹脂ワニスは例えばハイブリッドＩＣ
等をディップイング方法で外装被覆し、８０°Ｃ〜１５
０°Ｃの温度で硬化することかできる。通常基板とチッ
プの間にある気泡を除去するため、低温から高温に徐々
に昇温しで硬化するか、２〜３段階の温度を設定してス
テップギュアを行う方法が一般的である。硬化時間は硬
化温度にもよるか、３〜１０時間か適当である。The epoxy resin varnish of the present invention can be applied to, for example, a hybrid IC.
etc. by dipping method and heat at 80°C to 15°C.
It can be cured at a temperature of 0°C. In order to remove air bubbles between the substrate and the chip, it is common to cure the material by gradually increasing the temperature from a low temperature to a high temperature, or to perform step cure by setting two to three temperature levels. The curing time depends on the curing temperature and is suitably 3 to 10 hours.
（実施例） 以下に実施例で本発明をさらに詳しく説明する。(Example) The present invention will be explained in more detail with reference to Examples below.
実施例１
エポキシ当量９５０のビスフェノールＡ型エポキシ樹脂
（エボミックＲ−３０４、三井石油化学社製）とエポキ
シ当量１９００のビスフェノールＡ型エポキシ樹脂（エ
ポミックＲ，−３０７、三井石油化学社製）を重量比で
７：３に配合して得られた。Example 1 Weight ratio of bisphenol A epoxy resin (Evomic R-304, manufactured by Mitsui Petrochemicals) with an epoxy equivalent of 950 and bisphenol A epoxy resin (Epomic R, -307, manufactured by Mitsui Petrochemicals) with an epoxy equivalent of 1900 It was obtained by blending in a ratio of 7:3.
エポキシ当量１１２０のエポキシ樹脂８０ｇ、テトラプ
ロ１＼ビスフェノールＡジグリシジルエーテル（ＥＴＢ
Ａ、日本化薬社製） ２０ｇ 、前記−能代（１）にお
いてＲか水素原子でｎ＝１及び２て示される成分の含有
率が７５％である。軟化点２３°Ｃのフェノールノボラ
ック樹脂（ＰＮ１５２）日本化薬社製） ］、４ｇ 、
２エチル−４−メチルイミダゾール１ｇをエチルセロソ
ルブ１４０ｇに溶解して２５°Ｃ帖度４５０ＣＰＳのエ
ポキシ樹脂ワニスを得た。80 g of epoxy resin with an epoxy equivalent of 1120, tetrapro 1\bisphenol A diglycidyl ether (ETB
A, manufactured by Nippon Kayaku Co., Ltd.) 20g, the content of the components represented by R or hydrogen atoms with n=1 and 2 in Noshiro (1) above is 75%. Phenol novolac resin (PN152) manufactured by Nippon Kayaku Co., Ltd. with a softening point of 23°C], 4g,
1 g of 2-ethyl-4-methylimidazole was dissolved in 140 g of ethyl cellosolve to obtain an epoxy resin varnish having a thickness of 450 CPS at 25°C.
このエポキシ樹脂ワニスを用いて、ハイブリッドＩＣを
デイツプ方式で外装被覆し、１００°Ｃで２時間ついで
１５０℃で３時間加熱硬化した。得られた硬化物を下記
条件で耐湿試験及びヒートサイクルテストの試験を行っ
た。その結果を表−１に示す。Using this epoxy resin varnish, a hybrid IC was coated with a dip method, and then heated and cured at 100°C for 2 hours and then at 150°C for 3 hours. The obtained cured product was subjected to a moisture resistance test and a heat cycle test under the following conditions. The results are shown in Table-1.
耐湿試験（プレッシャークツカー試験）＝１２１°Ｃ１
２気圧、湿度１００％の条件下に硬化物をさらし、表−
１に示した各時間における印刷抵抗値を測定し、初期値
が３％以上変化した物を不良発生物とした。測定資料数
を１０個について測定したヒートサイクルテスト：
硬化物に一５５°Ｃ×３０分ついで１５０°Ｃ３０分を
１サイクルとする熱衝撃を加え各サイクルにおける印刷
抵抗値を測定し、初期値か３％以上変化した物を不良発
生物とした。測定資料数は１０個について測定した。Moisture resistance test (pressure test) = 121°C1
The cured product was exposed to conditions of 2 atm and 100% humidity, and the table
The printing resistance value at each time shown in 1 was measured, and those whose initial value changed by 3% or more were considered to be defective. Heat cycle test with 10 measurement samples: A thermal shock was applied to the cured product at 155°C for 30 minutes, then 150°C for 30 minutes, and the printing resistance value in each cycle was measured, and the initial value was measured. Items with a change of 3% or more were considered defective. The number of measurement samples was 10.
膜厚：
外装被覆前後のハイブリッドＩＣの基板平坦部の厚さの
差を測定し、２等分した値を片面の膜厚とした。Film thickness: The difference in the thickness of the flat part of the hybrid IC substrate before and after the outer coating was measured, and the value divided into two was taken as the film thickness on one side.
実施例２
実施例１で使用したフェノールノボラック樹脂１４ｇの
代りに前記一般式（１）においてＲか水素原子でｎ＝１
及び２で示される成分の含有率か４５％である軟化点５
０°Ｃのフェノールノボラックの樹脂（ＰＮ１５２）日
本化薬社製）１４ｇを用いた他は実施例１と全く同様に
して２５°Ｃの粘度４７０ＣＰＳのエポキシ樹脂ワニス
を得た。得られたエポキシ樹脂ワニスを用いて実施例１
と同様にしてハイブリットＩＣの外装被覆を行い、耐湿
テスト試験及びヒートサイクルテストを行った。その結
果を表−１に示す。Example 2 Instead of 14 g of phenol novolac resin used in Example 1, R or hydrogen atom in the general formula (1) was used, and n=1
Softening point 5 where the content of the components shown in and 2 is 45%
An epoxy resin varnish with a viscosity of 470 CPS at 25°C was obtained in exactly the same manner as in Example 1, except that 14 g of phenol novolac resin (PN152, manufactured by Nippon Kayaku Co., Ltd.) at 0°C was used. Example 1 using the obtained epoxy resin varnish
The exterior coating of the hybrid IC was performed in the same manner as above, and a moisture resistance test and a heat cycle test were performed. The results are shown in Table-1.
実施例３
実施例１で使用したエポキシ樹脂の代りに、エポキシ当
量１９００のビスフェノールＡ型エポキシ樹脂（エポミ
ックＲ−３０７、三井石油化学社製）８０ｇを用いた他
は実施例１と同様にして、エポキシ樹脂ワニスを得た。Example 3 In place of the epoxy resin used in Example 1, 80 g of bisphenol A type epoxy resin (Epomic R-307, manufactured by Mitsui Petrochemical Co., Ltd.) having an epoxy equivalent of 1900 was used, but in the same manner as in Example 1, An epoxy resin varnish was obtained.
（２５°Ｃ粘度６００ＣＰＳ）の得られたエポキシ樹脂
ワニスを用いて実施例１と同様にしてハイブリッドＩＣ
の外装被覆を行い、耐湿テスト試験及びヒートサイクル
テストを行った。その結果を表−１に示す。A hybrid IC was prepared in the same manner as in Example 1 using the obtained epoxy resin varnish (viscosity 600 CPS at 25°C).
A moisture resistance test and a heat cycle test were conducted. The results are shown in Table-1.
実施例４
実施例１て使用した、テトラブロムビスフェノールＡジ
ク゛リシジルエーテル２０ｇの代りに臭素化フェノール
ノボラックエポキシ樹脂（ＢＲＥＮ−３、日本化薬社製
）２０ｇを用い、エチルセロソルブ１４０ｇの代りに、
メチルエチルケトン２０重量％、トルエン２０重量％、
メチルイソブチルケトン６０重量％からなる混合溶媒１
４０ｇを用いた他は、実施例１と同様にしてエポキシ樹
脂ワニスを得た（２５℃の粘度４９０ＣＰＳ） 。Example 4 20 g of brominated phenol novolak epoxy resin (BREN-3, manufactured by Nippon Kayaku Co., Ltd.) was used instead of 20 g of tetrabromobisphenol A dicyclocidyl ether used in Example 1, and 140 g of ethyl cellosolve was replaced with:
Methyl ethyl ketone 20% by weight, toluene 20% by weight,
Mixed solvent 1 consisting of 60% by weight of methyl isobutyl ketone
An epoxy resin varnish was obtained in the same manner as in Example 1, except that 40 g was used (viscosity at 25°C: 490 CPS).
得られたエポキシ樹脂ワニスを用いて実施例１と同様に
してハイブリッドＩＣの外装被覆を行い、耐湿テスト試
験及びヒートサイクルテストを行った。The resulting epoxy resin varnish was used to cover the exterior of a hybrid IC in the same manner as in Example 1, and a moisture resistance test and a heat cycle test were performed.
その結果を表−１に示す。The results are shown in Table-1.
比較例１
実施例１で使用したエポキシ樹脂８０ｇの代りに、エポ
キシ当量９５０のビスフェノールＡ型エポキシ樹脂（エ
ポミックＲ−３０４、三井石油化学社製）８０ｇ、軟化
点２３°Ｃのフェノールノボラック樹脂１４ｇの代りに
、軟化点８０°Ｃのフェノールノボラック樹脂（前記一
般式においてｎ＝１及び２で示される成分の含有率が２
５％、ＰＮ−８０、昭和化成社製）１５ｇを用いた他は
実施例と同様にして、２５°Ｃの粘度４９０ＣＰＳのエ
ポキシ樹脂ワニスを得た。Comparative Example 1 Instead of 80 g of epoxy resin used in Example 1, 80 g of bisphenol A type epoxy resin (Epomic R-304, manufactured by Mitsui Petrochemicals) with an epoxy equivalent of 950 and 14 g of a phenol novolac resin with a softening point of 23°C were used. Instead, a phenol novolac resin with a softening point of 80°C (the content of the components represented by n=1 and 2 in the general formula above is 2
An epoxy resin varnish having a viscosity of 490 CPS at 25° C. was obtained in the same manner as in the example except that 15 g of 5% PN-80 (manufactured by Showa Kasei Co., Ltd.) was used.
このエポキシ樹脂ワニスを用いて実施例１と同様にして
ハイブリッドＩＣを外装被覆を行い、耐湿テスト試験及
びヒートサイクルテストを行った。その結果を表−１に
示す。Using this epoxy resin varnish, a hybrid IC was externally coated in the same manner as in Example 1, and a moisture resistance test and a heat cycle test were conducted. The results are shown in Table-1.
（発明の効果）
表−１で明らかなようにエポキシ樹脂の優れた耐湿性を
低下さすことなく耐ヒートザイクル性に優イユたエポキ
シ樹脂ワニスの開発により膜厚の薄い外装被覆が可能に
なった。(Effects of the invention) As is clear from Table 1, the development of an epoxy resin varnish with excellent heat cycle resistance without reducing the excellent moisture resistance of epoxy resin has made it possible to provide a thin exterior coating. .
特許出願人 ｌ］本化薬株式会社 ■Patent applicant l] Honkayaku Co., Ltd. ■
Claims (2)
つエポキシ当量が１８００〜２５００である成分を３０
〜１００重量％含有するビスフェノールＡ型のエポキシ
樹脂 ｂ、臭素化エポキシ樹脂 ｃ、軟化点が７５℃以下であるフェノールノボラック樹
脂 ｄ、有機溶媒 からなることを特徴とするエポキシ樹脂ワニス。(1)a, the epoxy equivalent is 800-2500, and the epoxy equivalent is 1800-2500.
An epoxy resin varnish comprising a bisphenol A type epoxy resin b containing ~100% by weight, a brominated epoxy resin c, a phenol novolac resin d having a softening point of 75°C or less, and an organic solvent.
化物(2) Cured product of epoxy resin varnish according to claim 1
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18804390A JPH0476021A (en) | 1990-07-18 | 1990-07-18 | Epoxy resin varnish and its cured product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18804390A JPH0476021A (en) | 1990-07-18 | 1990-07-18 | Epoxy resin varnish and its cured product |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0476021A true JPH0476021A (en) | 1992-03-10 |
Family
ID=16216684
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18804390A Pending JPH0476021A (en) | 1990-07-18 | 1990-07-18 | Epoxy resin varnish and its cured product |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0476021A (en) |
-
1990
- 1990-07-18 JP JP18804390A patent/JPH0476021A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI496803B (en) | Hardener composition for epoxy resins | |
| US4876324A (en) | High molecular weight ortho cresol-novolak resins and process for the preparation thereof using alcoholic or acidic organic solvents | |
| TW455613B (en) | Copolymer of styrene and maleic anhydride comprising an epoxy resin composition and a co-cross linking agent | |
| KR100632169B1 (en) | Interlayer Insulation Adhesive For Multilayer Printed Circuit Board | |
| JP6428082B2 (en) | Thermosetting resin composition, prepreg, laminate and printed wiring board | |
| JP2017531059A (en) | Low thermal expansion halogen-free flame retardant composition for high density printed circuit boards | |
| CN101896529B (en) | Solid power formulations for the preparation of resin-coated foils and their use in the manufacture of printed circuit boards | |
| TWI274771B (en) | Resin composition, prepreg and laminate using the same | |
| TW201823336A (en) | Maleimide resin composition, prepreg, laminated board and printed circuit board for obtaining a metal foil-clad laminated board with excellent flame retarding capability, low water absorption rate, high glass transition temperature and excellent stripping temperature | |
| Binyamin et al. | 3D Printing Thermally Stable High‐Performance Polymers Based on a Dual Curing Mechanism | |
| TW574313B (en) | Resin composition for circuit boards | |
| JPH0476021A (en) | Epoxy resin varnish and its cured product | |
| JP2017101197A (en) | Polyamide-imide resin composition and paint | |
| JP2006089595A (en) | Build-up resin composition and its application | |
| TW513465B (en) | Flame retardant epoxy resin composition for printed board, and prepreg and metal foil clad laminate using the same | |
| US20040214005A1 (en) | Resin film and multilayer printed wiring board using thereof | |
| TWI221477B (en) | Thermosetting resin compositions for build-up method | |
| JP3861552B2 (en) | Epoxy resin composition and electrical laminate | |
| JP2005154739A (en) | Resin composition, and prepreg and laminate using the composition | |
| JP6472408B2 (en) | Polyphenylene ether-modified phenolbenzaldehyde polyfunctional epoxy resin and use thereof | |
| JPH07268277A (en) | Coating resin composition | |
| JPH04351654A (en) | Epoxy resin varnish and its cured product | |
| JP4509539B2 (en) | Epoxy resin composition sheet | |
| JPH02158619A (en) | Storage-stable, rapidly curing | |
| JP2016060840A (en) | Thermosetting resin composition, prepreg, laminate and printed wiring board |