JP3579800B2 - Low dielectric epoxy resin composition - Google Patents
Low dielectric epoxy resin composition Download PDFInfo
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Description
【0001】
【産業上の利用分野】
本発明は、電子回路基板に用いられる銅張り積層板や電子部品に用いられる電気絶縁塗料・封止材・成形材・接着剤・注型材などに適した低誘電性エポキシ樹脂組成物に関する。
【0002】
【従来の技術】
エポキシ樹脂は接着性、耐熱性、成形性に優れていることから電子部品、電気機器、自動車部品、FRP、スポーツ用品など広範囲に使用されている。特に電子部品、電気機器に使用される銅張り積層板は、近年大量情報を高速処理するため、多層化、薄板化、回路のファインピッチ化等が行われてきた。
しかし、更なる高速処理を実現するため、誘電率の低い積層板が求められるようになってきた。また、移動体通信等に用いられる高周波用積層板では信号の損失を防ぐため低誘電正接のものが求められている。
このような要求に対して、フッ素樹脂やポリフェニレンオキサイド樹脂など低誘電率・低誘電正接の樹脂が提案されている。しかし、これらの樹脂は成形性・接着性等に問題があるため限られた用途でしか使用されていない。このような状況下成形性・接着性等の良好なエポキシ樹脂の誘電特性を改良することが望まれていた。
本発明者らは、先に電気・電子産業における好適なエポキシ樹脂組成物としてスチレン化フェノールノボラック樹脂のポリグリシジルエーテルを見出した。そして、このエポキシ樹脂組成物の硬化物は低吸水性、低応力性を有する点からこの樹脂組成物は封止用成形物や印刷回路用積層材料として好適であることが知られている(特開平5−140265号参照)。
【0003】
【発明が解決しようとする課題】
本発明者は、このスチレン化フェノールノボラック樹脂のポリグリシジルエーテル樹脂組成物について種々検討した結果、特定の硬化剤を使用することによって低誘電率を付与することができることを見出し、本発明を完成したもので、本発明は、エポキシ樹脂の欠点であった誘電特性を改良し、従来のエポキシ樹脂と同様な作業性で、電子回路基板に用いられる銅張り積層板や電子部品に用いられる電気絶縁塗料・封止材・成形材・接着剤などに適し、且つ、低誘電性を付与したエポキシ樹脂組成物を提供することを目的とするものである。
【0004】
【課題を解決するための手段】
本発明は、一般式(1)で示されるスチレン化フェノールノボラック型エポキシ樹脂(a)を含有するエポキシ樹脂類(A)と硬化剤類(B)とからなる低誘電性エポキシ樹脂組成物において、前記硬化剤類(B)のうち少なくとも一部は一般式(2)で示されるスチレン化ノボラック型フェノール樹脂(b)よりなる硬化剤を使用することを特徴とする、周波数1MHzで測定した硬化物の誘電率が3.23以下で且つ誘電正接が0.012以下である低誘電性エポキシ樹脂組成物である。
【0005】
【化3】
【0006】
【化4】
【0007】
即ち、本発明においては、前記スチレン化ノボラック型フェノール結合を含有するエポキシ樹脂類(A)に対して、同様のスチレン化ノボラック型フェノール結合を含有する硬化剤(b)を用いてエポキシ樹脂類(A)を硬化するのであって、得られたエポキシ樹脂は低誘電率、低誘電正接を有し、好適な電子回路基板の銅張り積層板や電子部品を提供することができる。特に、硬化したエポキシ樹脂類(A)中にスチレン化ノボラック型フェノール結合がエポキシ樹脂類(A)と硬化剤類(B)の合計量に対して10重量%以上存在することが好ましく、かかる量存在することによって低誘電率、低誘電正接が著しく改良されるのである。
【0008】
本発明で使用する一般式(1)で示されるエポキシ樹脂(a)は、一般式(2)で示されるフェノール樹脂(b)にエピハロヒドリンを反応させることによって得られる。この反応は従来公知のフェノール樹脂とエピハロヒドリンからポリグリシジルエーテルを得る方法に従って行われる。たとえば、フェノールノボラック樹脂のフェノール性水酸基に対して過剰モルのエピクロルヒドリンの混合物に、苛性ソーダ等のアルカリ金属水酸化物を固形または濃厚水溶液として加え、30〜120℃の温度で0.5〜10時間反応させるか、あるいはフェノールノボラック樹脂と過剰のエピクロルヒドリンにテトラエチルアンモニウムクロライド等の第4級アンモニウム塩を触媒として加え、50〜150℃の温度で1〜5時間反応させて得られるポリクロルヒドリンエーテルに苛性ソーダ等のアルカリ金属酸化物を固形または濃厚水溶液として加え30〜120℃の温度で1〜10時間反応させてポリグリシジルエーテルを得る方法がある。
【0009】
また、エポキシ樹脂として一般式(1)のエポキシ樹脂と2官能以上のフェノール樹脂類とを反応させることにより高分子量化したエポキシ樹脂を配合しても良い。2官能以上のフェノール樹脂類としてはビスフェノールA、ビスフェノールF、テトラブロムビスフェノールA、9,9−ビス(4−ヒドロキシフェニル)フルオレン、テトラフェニロールエタン、ジナフトール、各種フェノール類のノボラック樹脂、各種フェノール類とジシクロペンタジエンの縮合物等が挙げられる。
【0010】
更に、本発明で使用されるエポキシ樹脂類(A)は上記のエポキシ樹脂(a)にその他のエポキシ樹脂を添加、混合しても良く、その他のエポキシ樹脂としては、例えば、エポトートYD−128、YD−900等を代表とするビスフェノールA型エポキシ樹脂やエポトートYDF−170、YDF−2001等を代表とするビスフェノールF型エポキシ樹脂、エポトートYDCN−701、YDCN−702、YDPN−638を代表とする各種フェノール類のノボラックエポキシ樹脂等のエポキシ樹脂、或いはエポトートYDB−400、YDB−500を代表とする臭素化エポキシ樹脂、エポトートYH−434といったアミン型エポキシ樹脂、サントートST−3000、ST−5080を代表とする水添ビスフェノールA型エポキシ樹脂等を挙げることができる。
【0011】
一般式(2)で示されるフェノール樹脂(b)はスチレン化フェノールとアルデヒド類を酸性触媒の存在下に縮合して合成する。スチレン化フェノールとしてはp−スチレン化フェノール、o−スチレン化フェノール、m−スチレン化フェノール、α−メチルスチレン化フェノールあるいはアルキル置換モノスチレン化フェノール類、ハロゲン置換モノスチレン化フェノール類等が挙げられ、これらのスチレン化フェノール類は1種類用いても2種類以上の混合物を用いても良い。アルデヒド成分としてはホルムアルデヒド、パラホルムアルデヒド、アセトアルデヒド、プロピルアルデヒド、ブチルアルデヒド、ベンズアルデヒド、p−ヒドロキシベンズアルデヒド等が挙げられ、これらアルデヒド類も1種類あるいは2種類以上の混合物であっても良い。酸性触媒としては、塩酸、リン酸、硫酸、硝酸、トルエンスルホン酸等のプロトン酸、三弗化ホウ素、塩化アルミニウム、塩化錫、塩化亜鉛、塩化鉄などのルイス酸、シュウ酸、モノクロル酢酸等が挙げられる。
【0012】
上記の硬化剤の外、公知の硬化剤を併用することができるが、本発明においては硬化したエポキシ樹脂100重量部に対し、スチレン化ノボラック型フェノール結合を少なくとも10重量部含有せしめることが好ましい。
【0013】
反応方法としてはスチレン化フェノールと酸性触媒を反応容器に仕込み、アルデヒド類を1〜3時間かけて滴下していく方法と、スチレン化フェノールとアルデヒド類を反応容器に仕込み、触媒を1〜3時間かけて滴下していく方法があるが、いずれの方法によっても目的とするスチレン化フェノールノボラック樹脂を得ることができる。
【0014】
そして、本発明にかかる一般式(1)で示されるエポキシ樹脂(a)を含有するエポキシ樹脂類(A)と、一般式(2)で示されるフェノール樹脂(b)よりなる硬化剤類(B)からなるエポキシ樹脂組成物100重量部に対し、スチレン化ノボラック型フェノール結合を少なくとも10重量部含有せしめることによって低誘電率、低誘電正接であるエポキシ樹脂組成物を得ることができ、電子回路基板に用いられる銅張り積層板や電子部品に用いられる電気絶縁塗料・封止材・成形材・接着剤・注型材などに好適に用いられるのである。 本発明のエポキシ組成物には必要に応じて第3級アミン、第4級アンモニウム塩、ホスフィン類、イミダゾール類等の硬化促進剤を配合することができる。また、必要に応じて無機充填剤やガラスクロスなどの補強材、充填材、顔料等を用いられる。
【0015】
【実施例及び比較例】
次に実施例及び比較例をあげて本発明を具体的に説明する。なお、硬化物の誘電特性はJIS K 6911に準じて測定を行った。
【0016】
合成例1
スチレン化フェノール(モノスチレン化フェノール含有量96.5重量% フェノール性水酸基当量200.0g/eq)400部、92重量%パラホルムアルデヒド58.7部、及び蒸留水12部をガラス製セパラブルフラスコに仕込み、撹拌しながら80℃まで加温した。同温度で維持しながら10重量%パラトルエンスルホン酸水溶液13.7部を30分間で滴下した。更に95〜100℃の温度で4時間反応し、10重量%苛性ソーダ3.0部を加えた。さらに10重量%のシュウ酸1.8部を添加した。次にメチルイソブチルケトンを1400部添加し、溶解した。純水2500部を3回に分けて添加し、水洗分液を行った。その後、溶剤を回収し、最終的に170℃で5mmHgの減圧下で乾固した。得られたスチレン化フェノールノボラック樹脂は420部であり、淡黄色透明の固体でフェノール性水酸基当量213.0g/eq、軟化点80℃であった。
【0017】
合成例2
ガラス製セパラブルフラスコに合成例1のスチレン化フェノールノボラック樹脂150部とエピクロルヒドリン423部、ベンジルトリエチルアンモニウムクロライド1.5部及び、ジエチレングリコールジメチルエーテル85部を加え、100〜110℃にて3時間撹拌して反応を行った。その後、150mmHgの減圧下65〜70℃の温度に保ちながら、49重量%苛性ソーダ50.1部を4時間で滴下した。この間エピクロルヒドリンは水と共沸させて留出してくる水は系外へ除去した。反応終了後、水115部を加えて副生した食塩を溶解し、静置して下層の食塩水を除去した。未反応のエピクロルヒドリンを減圧下に蒸発回収し、メチルイソブチルケトン430部を加え、生成したエポキシ樹脂を溶解した。その後、10重量%の苛性ソーダ20部を加えて、85℃にて2時間反応させ、リン酸水溶液にて中和した後、水洗液が中性になるまで樹脂溶液を水洗した。5mmHgの減圧下、190℃に加熱してメチルイソブチルケトンを留去し、目的とするポリグリシジルエーテル185部を得た。得られエポキシ樹脂は淡黄色透明の固体でエポキシ当量333.0g/eq、全塩素含有量700ppm、軟化点71.5℃であった。
【0018】
実施例1
合成例2で得られたモノスチレン化フェノールノボラック型エポキシ樹脂に合成例1で得られたモノスチレン化フェノールノボラック樹脂硬化剤を64部配合し、硬化促進剤として2E4MZ(四国化成株式会社製 2エチル4メチルイミダゾール)0.1部を配合した。150℃で2時間加熱を行い、更に180℃で3時間硬化を行った。得られた硬化物の誘電率と誘電正接を測定した。測定結果を表1に示す。
【0019】
実施例2
エポキシ樹脂類として合成例2で得られたモノスチレン化フェノールノボラック型エポキシ樹脂5.0部、エポトートYDB−400(東都化成株式会社製 臭素化エポキシ樹脂 エポキシ当量396.2g/eq 臭素含有率49.0%)を70.0部、エポトートYD−8125(東都化成株式会社製 高純度ビスフェノールA型エポキシ樹脂 エポキシ当量172.6g/eq)を25.0部配合した。更に合成例1で得られたモノスチレン化フェノールノボラック樹脂硬化剤を71.7部配合し、硬化促進剤として2E4MZ 0.1部を配合した。実施例1と同様な硬化条件で硬化物を作成した。得られた硬化物の誘電率と誘電正接を測定した。測定結果を表1に示す。
【0020】
実施例3
エポキシ樹脂類として合成例2で得られたモノスチレン化フェノールノボラック型エポキシ樹脂5.0部、エポトートYD−8125を95.0部配合し、合成例1で得られたモノスチレン化フェノールノボラック樹脂硬化剤を120.4部配合し、硬化促進剤として2E4MZ 0.1部を配合した。実施例1と同様な硬化条件で硬化物を作成した。得られた硬化物の誘電率と誘電正接を測定した。測定結果を表1に示す。
【0023】
比較例1
エポトートYD−8125 100.0部に硬化剤としてBRG−555(昭和電工株式会社製 フェノールノボラック樹脂 フェノール性水酸基当量105g/eq)60.8部を配合し、硬化促進剤として2E4MZ 0.1部を配合した。実施例1と同様な硬化条件で硬化物を作成した。測定結果を表1に示す。
【0024】
【表1】
【0025】
比較例2
エポトートYDB−400 100.0部にカヤボンドC−190 16.2部を配合した。実施例1と同様な硬化条件で硬化物を作成した。測定結果を表2に示す。
【0026】
比較例3
エポトートYD−8125 100.0部にカヤボンドC−190 37.1部を配合した。実施例1と同様な硬化条件で硬化物を作成した。測定結果を表2に示す。
【0027】
【表2】
【0028】
【発明の効果】
以上のように、本発明のエポキシ樹脂組成物は低誘電率・低誘電正接であり、電子回路基板に用いられる銅張り積層板や電子部品に用いられる電気絶縁塗料・封止材・成形材・接着剤・注型材などに好適に用いることができる。[0001]
[Industrial applications]
TECHNICAL FIELD The present invention relates to a low dielectric epoxy resin composition suitable for an electrically insulating paint, a sealing material, a molding material, an adhesive, a casting material, and the like used for a copper-clad laminate used for an electronic circuit board and an electronic component.
[0002]
[Prior art]
Epoxy resins are widely used in electronic parts, electric equipment, automobile parts, FRP, sports equipment, etc. because of their excellent adhesiveness, heat resistance, and moldability. In particular, in recent years, copper-clad laminates used for electronic components and electric devices have been multi-layered, thinned, and fine-pitched circuits in order to process a large amount of information at high speed.
However, in order to realize higher-speed processing, a laminate having a low dielectric constant has been required. In addition, a high-frequency laminate used for mobile communication and the like is required to have a low dielectric loss tangent in order to prevent signal loss.
In response to such demands, resins having a low dielectric constant and a low dielectric loss tangent such as a fluororesin and a polyphenylene oxide resin have been proposed. However, these resins are used only in limited applications because of their problems in moldability and adhesiveness. Under such circumstances, it has been desired to improve the dielectric properties of an epoxy resin having good moldability and adhesiveness.
The present inventors have previously found polyglycidyl ether of a styrenated phenol novolak resin as a suitable epoxy resin composition in the electric and electronic industries. It is known that the cured product of this epoxy resin composition is suitable as a molded article for sealing or a laminated material for printed circuits because it has low water absorption and low stress. No. 5-140265).
[0003]
[Problems to be solved by the invention]
The present inventor has conducted various studies on the polyglycidyl ether resin composition of the styrenated phenol novolak resin, and as a result, found that a low dielectric constant can be imparted by using a specific curing agent, and completed the present invention. The present invention improves the dielectric properties, which was a drawback of epoxy resins, and has the same workability as conventional epoxy resins, and is an electrically insulating paint used for copper-clad laminates used for electronic circuit boards and electronic components. An object of the present invention is to provide an epoxy resin composition that is suitable for a sealing material, a molding material, an adhesive, and has a low dielectric property.
[0004]
[Means for Solving the Problems]
The present invention provides a low dielectric epoxy resin composition comprising an epoxy resin (A) containing a styrenated phenol novolak type epoxy resin (a) represented by the general formula (1) and a curing agent (B), characterized by using a curing agent consisting of styrenated phenolic novolak resin (b) represented by at least some general formula (2) of the curing agents (B), the cured product was measured at a frequency 1MHz Is a low dielectric epoxy resin composition having a dielectric constant of 3.23 or less and a dielectric loss tangent of 0.012 or less .
[0005]
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[0006]
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[0007]
That is, in the present invention, the epoxy resin (A) containing the styrenated novolak type phenol bond is used for the epoxy resin (B ) containing the same styrenated novolak type phenol bond. A) is cured, and the obtained epoxy resin has a low dielectric constant and a low dielectric loss tangent, and can provide a copper-clad laminate or an electronic component of a suitable electronic circuit board. In particular, it is preferable that the styrenated novolak type phenol bond is present in the cured epoxy resin (A) in an amount of 10% by weight or more based on the total amount of the epoxy resin (A) and the curing agent (B). Their presence significantly improves low dielectric constant and low dielectric loss tangent.
[0008]
The epoxy resin (a) represented by the general formula (1) used in the present invention is obtained by reacting epihalohydrin with the phenol resin (b) represented by the general formula (2). This reaction is carried out according to a conventionally known method for obtaining a polyglycidyl ether from a phenol resin and epihalohydrin. For example, an alkali metal hydroxide such as caustic soda or the like is added as a solid or concentrated aqueous solution to a mixture of epichlorohydrin in a molar excess relative to the phenolic hydroxyl group of the phenol novolak resin, and the mixture is reacted at a temperature of 30 to 120 ° C. for 0.5 to 10 hours. Alternatively, a quaternary ammonium salt such as tetraethylammonium chloride is added as a catalyst to the phenol novolak resin and excess epichlorohydrin, and the mixture is reacted at a temperature of 50 to 150 ° C. for 1 to 5 hours. There is a method in which a polyglycidyl ether is obtained by adding an alkali metal oxide as a solid or concentrated aqueous solution and reacting at a temperature of 30 to 120 ° C. for 1 to 10 hours.
[0009]
Further, as the epoxy resin, an epoxy resin having a high molecular weight by reacting the epoxy resin of the general formula (1) with a phenol resin having two or more functionalities may be blended. Bifunctional or higher functional phenol resins include bisphenol A, bisphenol F, tetrabromobisphenol A, 9,9-bis (4-hydroxyphenyl) fluorene, tetraphenylolethane, dinaphthol, novolak resins of various phenols, various phenols And dicyclopentadiene.
[0010]
Further, the epoxy resins (A) used in the present invention may be mixed with the above-mentioned epoxy resin (a) by adding other epoxy resins. Examples of other epoxy resins include Epototo YD-128, Bisphenol A type epoxy resin represented by YD-900 and the like, bisphenol F type epoxy resin represented by Epototo YDF-170 and YDF-2001, and various types represented by Epototo YDCN-701, YDCN-702 and YDPN-638 Epoxy resins such as phenolic novolak epoxy resin, or brominated epoxy resins such as Epotote YDB-400 and YDB-500, amine type epoxy resins such as Epotote YH-434, and Santoto ST-3000 and ST-5080 as representatives. Hydrogenated bisphenol A type epoxy Mention may be made of a resin or the like.
[0011]
The phenolic resin (b) represented by the general formula (2) is synthesized by condensing a styrenated phenol and an aldehyde in the presence of an acidic catalyst. Examples of the styrenated phenol include p-styrenated phenol, o-styrenated phenol, m-styrenated phenol, α-methylstyrenated phenol or alkyl-substituted monostyrenated phenols, and halogen-substituted monostyrenated phenols. One of these styrenated phenols may be used, or a mixture of two or more thereof may be used. Examples of the aldehyde component include formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, butyraldehyde, benzaldehyde, and p-hydroxybenzaldehyde. These aldehydes may be used alone or as a mixture of two or more. Examples of the acidic catalyst include protonic acids such as hydrochloric acid, phosphoric acid, sulfuric acid, nitric acid, and toluenesulfonic acid, Lewis acids such as boron trifluoride, aluminum chloride, tin chloride, zinc chloride, and iron chloride, oxalic acid, and monochloroacetic acid. No.
[0012]
Outside of the upper Symbol curing agent, can be used together known curing agent, relative to the epoxy resin 100 parts by weight of the curing in the present invention, it is preferable that allowed to at least containing 10 parts by weight of styrenated phenolic novolak bond .
[0013]
As a reaction method, a method in which a styrenated phenol and an acidic catalyst are charged into a reaction vessel and aldehydes are added dropwise over 1 to 3 hours, and a method in which the styrenated phenol and an aldehyde are charged into the reaction vessel and the catalyst is 1 to 3 hours There is a method in which the mixture is added dropwise, and the desired styrenated phenol novolak resin can be obtained by any method.
[0014]
The epoxy resins containing an epoxy resin (a) represented by the general formula (1) according to the present invention and (A), a phenol resin (b) good Li Cheng curatives represented by the general formula (2) ( An epoxy resin composition having a low dielectric constant and a low dielectric loss tangent can be obtained by incorporating at least 10 parts by weight of a styrenated novolak type phenol bond with respect to 100 parts by weight of the epoxy resin composition comprising B). It is suitable for use as an electrically insulating paint, a sealing material, a molding material, an adhesive, a casting material, and the like used for a copper-clad laminate used for a substrate and an electronic component. The epoxy composition of the present invention may optionally contain a curing accelerator such as a tertiary amine, a quaternary ammonium salt, a phosphine, or an imidazole. Further, a reinforcing material such as an inorganic filler or glass cloth, a filler, a pigment, and the like are used as needed.
[0015]
[Examples and Comparative Examples]
Next, the present invention will be specifically described with reference to Examples and Comparative Examples. The dielectric properties of the cured product were measured according to JIS K 6911.
[0016]
Synthesis Example 1
400 parts of styrenated phenol (monostyrenated phenol content: 96.5% by weight, phenolic hydroxyl equivalent: 200.0 g / eq), 92 parts by weight of paraformaldehyde, 58.7 parts, and 12 parts of distilled water were placed in a glass separable flask. It was charged and heated to 80 ° C. with stirring. While maintaining the same temperature, 13.7 parts of a 10% by weight aqueous solution of p-toluenesulfonic acid was added dropwise over 30 minutes. The mixture was further reacted at a temperature of 95 to 100 ° C. for 4 hours, and 3.0 parts of 10% by weight sodium hydroxide was added. Further, 1.8 parts of oxalic acid of 10% by weight was added. Next, 1400 parts of methyl isobutyl ketone was added and dissolved. 2500 parts of pure water were added in three portions, and the mixture was washed with water and separated. Thereafter, the solvent was recovered and finally dried at 170 ° C. under a reduced pressure of 5 mmHg. The obtained styrenated phenol novolak resin was 420 parts, and was a pale yellow transparent solid having a phenolic hydroxyl equivalent of 213.0 g / eq and a softening point of 80 ° C.
[0017]
Synthesis Example 2
To a glass separable flask were added 150 parts of the styrenated phenol novolak resin of Synthesis Example 1, 423 parts of epichlorohydrin, 1.5 parts of benzyltriethylammonium chloride, and 85 parts of diethylene glycol dimethyl ether, and the mixture was stirred at 100 to 110 ° C. for 3 hours. The reaction was performed. Thereafter, while maintaining the temperature at 65 to 70 ° C. under a reduced pressure of 150 mmHg, 50.1 parts of 49% by weight caustic soda was added dropwise over 4 hours. During this time, epichlorohydrin was azeotropically distilled with water, and water distilled out was removed from the system. After completion of the reaction, 115 parts of water was added to dissolve the salt produced as a by-product, and the mixture was allowed to stand to remove the lower layer of salt solution. Unreacted epichlorohydrin was recovered by evaporation under reduced pressure, and 430 parts of methyl isobutyl ketone was added to dissolve the generated epoxy resin. Thereafter, 20 parts of 10% by weight caustic soda was added, reacted at 85 ° C. for 2 hours, neutralized with a phosphoric acid aqueous solution, and then the resin solution was washed with water until the washing solution became neutral. The mixture was heated to 190 ° C. under a reduced pressure of 5 mmHg to distill off methyl isobutyl ketone to obtain 185 parts of a target polyglycidyl ether. The obtained epoxy resin was a pale yellow transparent solid, having an epoxy equivalent of 333.0 g / eq, a total chlorine content of 700 ppm, and a softening point of 71.5 ° C.
[0018]
Example 1
64 parts of the monostyrenated phenol novolak resin curing agent obtained in Synthesis Example 1 was blended with 64 parts of the monostyrenated phenol novolak resin obtained in Synthesis Example 2 and 2E4MZ (Shikoku Chemicals Co., Ltd. 0.1 part of (4-methylimidazole). Heating was performed at 150 ° C. for 2 hours, and further curing was performed at 180 ° C. for 3 hours. The dielectric constant and the dielectric loss tangent of the obtained cured product were measured. Table 1 shows the measurement results.
[0019]
Example 2
As epoxy resins, 5.0 parts of the monostyrenated phenol novolak type epoxy resin obtained in Synthesis Example 2 and Epotote YDB-400 (a brominated epoxy resin manufactured by Toto Kasei Co., Ltd., epoxy equivalent 396.2 g / eq, bromine content 49. (0%) and 25.0 parts of Epototo YD-8125 (high purity bisphenol A type epoxy resin, epoxy equivalent: 172.6 g / eq, manufactured by Toto Kasei Co., Ltd.). Further, 71.7 parts of the monostyrenated phenol novolak resin curing agent obtained in Synthesis Example 1 was blended, and 0.1 parts of 2E4MZ was blended as a curing accelerator. A cured product was prepared under the same curing conditions as in Example 1. The dielectric constant and the dielectric loss tangent of the obtained cured product were measured. Table 1 shows the measurement results.
[0020]
Example 3
As the epoxy resins, 5.0 parts of the monostyrenated phenol novolak type epoxy resin obtained in Synthesis Example 2 and 95.0 parts of Epotote YD-8125 were blended, and the monostyrenated phenol novolak resin obtained in Synthesis Example 1 was cured. 120.4 parts of an agent was added, and 0.1 part of 2E4MZ was added as a curing accelerator. A cured product was prepared under the same curing conditions as in Example 1. The dielectric constant and the dielectric loss tangent of the obtained cured product were measured. Table 1 shows the measurement results.
[0023]
Comparative Example 1
100.8 parts of Epotote YD-8125 was mixed with 60.8 parts of BRG-555 (phenol novolak resin manufactured by Showa Denko KK, phenolic hydroxyl equivalent: 105 g / eq) as a curing agent, and 0.1 part of 2E4MZ was used as a curing accelerator. Was blended. A cured product was prepared under the same curing conditions as in Example 1. Table 1 shows the measurement results.
[0024]
[Table 1]
[0025]
Comparative Example 2
10.02 parts of Epotote YDB-400 was mixed with 16.2 parts of Kayabond C-190. A cured product was prepared under the same curing conditions as in Example 1. Table 2 shows the measurement results.
[0026]
Comparative Example 3
37.1 parts of Kayabond C-190 were mixed with 100.0 parts of Epotote YD-8125. A cured product was prepared under the same curing conditions as in Example 1. Table 2 shows the measurement results.
[0027]
[Table 2]
[0028]
【The invention's effect】
As described above, the epoxy resin composition of the present invention has a low dielectric constant and a low dielectric loss tangent, and is used for an electrically insulating paint, a sealing material, a molding material, and a copper-clad laminate used for an electronic circuit board and an electronic component. It can be suitably used for adhesives, casting materials, and the like.
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JP31078794A JP3579800B2 (en) | 1994-12-14 | 1994-12-14 | Low dielectric epoxy resin composition |
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JP31078794A JP3579800B2 (en) | 1994-12-14 | 1994-12-14 | Low dielectric epoxy resin composition |
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KR100995678B1 (en) * | 2008-09-01 | 2010-11-22 | 주식회사 코오롱 | Phenol novolak resin, phenol novolak epoxy resin and epoxy resin composition |
TWI521009B (en) * | 2010-09-27 | 2016-02-11 | Nippon Steel & Sumikin Chem Co | The epoxy resin composition and cured |
MY157418A (en) * | 2010-09-27 | 2016-06-15 | Nippon Steel & Sumikin Chem Co | Polyhydric hydroxy resin, epoxy resin, production method thereof, epoxy resin composition, and cured product thereof |
JP5914027B2 (en) * | 2012-02-16 | 2016-05-11 | 新日鉄住金化学株式会社 | Epoxy resin composition and cured product |
JP6124865B2 (en) * | 2012-02-23 | 2017-05-10 | 新日鉄住金化学株式会社 | Polyvalent hydroxy resin, epoxy resin, production method thereof, epoxy resin composition and cured product thereof |
KR20150008108A (en) * | 2012-04-16 | 2015-01-21 | 신닛테츠 수미킨 가가쿠 가부시키가이샤 | Epoxy resin composition and cured product |
TWI631173B (en) * | 2012-10-11 | 2018-08-01 | 新日鐵住金化學股份有限公司 | Epoxy resin composition and hardened material |
JP6113454B2 (en) * | 2012-10-11 | 2017-04-12 | 新日鉄住金化学株式会社 | Epoxy resin composition and cured product |
JP6073720B2 (en) * | 2013-03-21 | 2017-02-01 | 新日鉄住金化学株式会社 | Alkali development type photosensitive resin composition and cured product thereof |
TW201520245A (en) * | 2013-11-22 | 2015-06-01 | Kolon Inc | Novolac resin, hardener comprising the same and epoxy resin composition, and novolak epoxy resin, method for preparing the same and epoxy resin composition containing the novolak epoxy resin |
KR101472222B1 (en) * | 2013-11-22 | 2014-12-11 | 코오롱인더스트리 주식회사 | Epoxy Resin Having Excellent Curing and Chemical Resistance and Method for Preparing the Same |
JP6758087B2 (en) * | 2016-05-19 | 2020-09-23 | 日鉄ケミカル&マテリアル株式会社 | Epoxy resin curing agent composition, epoxy resin composition and cured product |
JP6924000B2 (en) * | 2016-05-20 | 2021-08-25 | 日鉄ケミカル&マテリアル株式会社 | Epoxy resin composition and its cured product |
JP7193337B2 (en) * | 2018-12-27 | 2022-12-20 | 日鉄ケミカル&マテリアル株式会社 | Polyvalent hydroxy resin, epoxy resin, epoxy resin composition and cured product thereof |
TWI751064B (en) * | 2021-03-29 | 2021-12-21 | 長春人造樹脂廠股份有限公司 | Polyhydric phenol resin, glycidyl ether of polyhydric phenol resin, and uses thereof |
WO2023171572A1 (en) * | 2022-03-09 | 2023-09-14 | 株式会社Adeka | One-pack type epoxy resin composition |
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