JP2017110183A - Conductive resin composition, conductive adhesive sheet and laminate - Google Patents
Conductive resin composition, conductive adhesive sheet and laminate Download PDFInfo
- Publication number
- JP2017110183A JP2017110183A JP2016215135A JP2016215135A JP2017110183A JP 2017110183 A JP2017110183 A JP 2017110183A JP 2016215135 A JP2016215135 A JP 2016215135A JP 2016215135 A JP2016215135 A JP 2016215135A JP 2017110183 A JP2017110183 A JP 2017110183A
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- Prior art keywords
- conductive
- mass
- parts
- resin composition
- adhesive sheet
- 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
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- 239000000853 adhesive Substances 0.000 title claims abstract description 70
- 239000011342 resin composition Substances 0.000 title claims abstract description 69
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- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 11
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- 229920005989 resin Polymers 0.000 claims description 27
- 239000011347 resin Substances 0.000 claims description 27
- 239000004593 Epoxy Substances 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 20
- 239000000945 filler Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 3
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- 238000004519 manufacturing process Methods 0.000 abstract description 5
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- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
本発明は、例えばフレキシブルプリント配線板に実装された部品の脱落等を防止するために設けられる補強部等の形成に使用可能な導電性樹脂組成物及び導電性接着シートに関する。 The present invention relates to a conductive resin composition and a conductive adhesive sheet that can be used for forming a reinforcing portion or the like provided to prevent a component mounted on a flexible printed wiring board from falling off, for example.
携帯電子端末等の小型化及び薄型化に伴って、それらに搭載される配線板としては、薄型で屈曲可能なフレキシブルプリント配線板が広く使用されている。 With the downsizing and thinning of portable electronic terminals and the like, thin and bendable flexible printed wiring boards are widely used as wiring boards mounted on them.
前記フレキシブルプリント配線板としては、一般に、ポリイミドフィルム等の表面に銅等によって形成されたグラウンド回路と、前記回路の一部にコネクター等の部品が実装された構成を有するものが知られている。 As the flexible printed wiring board, one having a configuration in which a ground circuit formed of copper or the like on the surface of a polyimide film or the like and a component such as a connector is mounted on a part of the circuit is generally known.
前記フレキシブルプリント配線板としては、電磁波の影響によるノイズの発生を防止するうえで、前記グラウンド回路と他の部材とを、導電性接着テープを用いて電気的に接続させたものが知られている（例えば特許文献１参照。）。 As the flexible printed wiring board, in order to prevent the generation of noise due to the influence of electromagnetic waves, the ground circuit and other members are electrically connected using a conductive adhesive tape. (For example, refer to Patent Document 1).
しかし、前記接着テープの導電性を高めるべく、導電性フィラーの使用量を増加させると、前記接着テープの接着性が著しく低下する場合があった。 However, if the amount of conductive filler used is increased in order to increase the conductivity of the adhesive tape, the adhesive property of the adhesive tape may be significantly reduced.
また、電子機器の薄型化等が求められるなかで、前記導電性フィラーを多く含有する導電性接着テープの厚さを薄型化すると、フレキシブルプリント配線板が有する段差部に対する前記導電性接着テープの接着性が著しく低下し、それらの界面に気泡が残存しやすくなり、その結果、部品の脱落や電磁波シールド特性の低下を引き起こす場合があった。 In addition, when the thickness of the conductive adhesive tape containing a large amount of the conductive filler is reduced while the electronic device is required to be thinned, the conductive adhesive tape is bonded to the step portion of the flexible printed wiring board. As a result, the air bubbles are likely to remain at the interface between them, and as a result, parts may fall off and the electromagnetic shielding characteristics may be deteriorated.
本発明が解決しようとする課題は、優れた導電性と優れた接着性とを両立した導電性接着テープ及びその製造に使用できる導電性樹脂組成物を提供することである。 The problem to be solved by the present invention is to provide a conductive adhesive tape having both excellent conductivity and excellent adhesiveness, and a conductive resin composition that can be used in the production thereof.
本発明者は、２個以上のエポキシ基を有する化合物（Ａ）と、針状または鱗片状の導電性フィラー（ｂ１）及び略球状の導電性フィラー（ｂ２）を含む導電性フィラー（Ｂ）とを含有することを特徴とする導電性樹脂組成物によって上記課題を解決した。 The inventor has a compound (A) having two or more epoxy groups, a conductive filler (B) containing a needle-like or scaly conductive filler (b1) and a substantially spherical conductive filler (b2); The above-mentioned problems have been solved by a conductive resin composition characterized by comprising
本発明の導電性樹脂組成物及び導電性接着シートは、優れた導電性と優れた接着性とを備えることから、例えば電子機器を構成する部品の固定等に好適に使用することができる。また、本発明の導電性樹脂組成物及び導電性接着シートは、フレキシブルプリント配線板への電磁波シールド特性の付与や、補強（補強層の形成）等に好適に使用することができる。 Since the conductive resin composition and the conductive adhesive sheet of the present invention have excellent conductivity and excellent adhesiveness, they can be suitably used, for example, for fixing components constituting electronic equipment. Moreover, the conductive resin composition and the conductive adhesive sheet of the present invention can be suitably used for imparting electromagnetic wave shielding characteristics to a flexible printed wiring board, reinforcing (forming a reinforcing layer), and the like.
本発明の導電性樹脂組成物は、２個以上のエポキシ基を有する化合物（Ａ）と、針状または鱗片状の導電性フィラー（ｂ１）及び略球状の導電性フィラー（ｂ２）を含む導電性フィラー（Ｂ）とを含有する導電性樹脂組成物であって、前記針状または鱗片状の導電性フィラー（ｂ１）と、略球状の導電性フィラー（ｂ２）との体積割合［（ｂ１）／（ｂ２）］が、１／１〜３／１であることを特徴とする。 The conductive resin composition of the present invention comprises a compound (A) having two or more epoxy groups, a needle-like or scale-like conductive filler (b1), and a substantially spherical conductive filler (b2). A conductive resin composition containing a filler (B), the volume ratio of the needle-like or scale-like conductive filler (b1) and the substantially spherical conductive filler (b2) [(b1) / (B2)] is 1/1 to 3/1.
前記化合物（Ａ）としては、エポキシ基を２個以上有するエポキシ樹脂が優れた接着性を示し、１分子あたり平均２〜３個エポキシ基を有するエポキシ樹脂が銅などの金属やＰＥＴ、ポリイミドなどのプラスチックフィルムに対する優れた接着性に加えて、硬化前後における寸法安定性に優れ、更に、例えばフレキシブルプリント配線板等の被着体をより強固に補強可能なレベルの剛性を備えた補強層を形成可能とする剛性を硬化物に付与できることが出来ることから好ましい。 As the compound (A), an epoxy resin having two or more epoxy groups exhibits excellent adhesion, and an epoxy resin having an average of 2-3 epoxy groups per molecule is a metal such as copper, PET, polyimide or the like. In addition to excellent adhesion to plastic film, it has excellent dimensional stability before and after curing, and can form a reinforcing layer with a level of rigidity that can reinforce adherends such as flexible printed wiring boards more firmly. It is preferable because the rigidity can be imparted to the cured product.
前記エポキシ樹脂としては、具体的には、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂等のビスフェノール型エポキシ樹脂、ジシクロペンタジエン−フェノール付加反応型エポキシ樹脂等のジシクロペンタジエン型エポキシ樹脂、ビフェニル型エポキシ樹脂、テトラメチルビフェニル型エポキシ樹脂、ポリヒドロキシナフタレン型エポキシ樹脂、イソシアネート変性エポキシ樹脂、１０−（２，５−ジヒドロキシフェニル）−９，１０−ジヒドロ９−オキサ−１０−フォスファフェナントレン−１０−オキサイド変性エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、トリフェニルメタン型エポキシ樹脂、テトラフェニルエタン型エポキシ樹脂、フェノールアラルキル型エポキシ樹脂、ナフトールノボラック型エポキシ樹脂、ナフトールアラルキル型エポキシ樹脂、ナフトール−フェノール共縮ノボラック型エポキシ樹脂、ナフトール−クレゾール共縮ノボラック型エポキシ樹脂、芳香族炭化水素ホルムアルデヒド樹脂変性フェノール樹脂型エポキシ樹脂、ビフェニル変性ノボラック型エポキシ樹脂等を使用することができる。 Specific examples of the epoxy resin include bisphenol type epoxy resins such as bisphenol A type epoxy resins and bisphenol F type epoxy resins, dicyclopentadiene type epoxy resins such as dicyclopentadiene-phenol addition reaction type epoxy resins, and biphenyl types. Epoxy resin, tetramethylbiphenyl type epoxy resin, polyhydroxynaphthalene type epoxy resin, isocyanate-modified epoxy resin, 10- (2,5-dihydroxyphenyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10- Oxide-modified epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, phenol aralkyl type epoxy resin Xyoxy resin, naphthol novolak type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenolic resin type epoxy resin, biphenyl modified A novolac type epoxy resin or the like can be used.
なかでも、前記エポキシ樹脂としては、２３℃で液状のエポキシ当量１００〜３５０ｇ／ｅｑ．であるエポキシ樹脂（ａ１）、２３℃で固体のエポキシ当量２００〜２，０００ｇ／ｅｑ．であるエポキシ樹脂（ａ２）を使用することが好ましく、それらを組み合わせ使用することが、優れた剛性と接着性とを両立するうえでより好ましい。 Especially, as said epoxy resin, liquid epoxy equivalent 100-350 g / eq. Epoxy resin (a1), which is a solid epoxy equivalent of 200 to 2,000 g / eq. It is preferable to use the epoxy resin (a2), and it is more preferable to use them in combination in order to achieve both excellent rigidity and adhesiveness.
前記エポキシ樹脂（ａ１）としては、例えばビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂等のビスフェノール型エポキシ樹脂、１，６−ジヒドロキシナフタレン型エポキシ樹脂、ｔ−ブチルカテコール型エポキシ樹脂、４，４‘−ジフェニルジアミノメタン型エポキシ樹脂、ｐ−又はｍ−アミノフェノール型エポキシ樹脂などが挙げられる。 Examples of the epoxy resin (a1) include bisphenol type epoxy resins such as bisphenol A type epoxy resins and bisphenol F type epoxy resins, 1,6-dihydroxynaphthalene type epoxy resins, t-butylcatechol type epoxy resins, and 4,4 ′. -Diphenyl diaminomethane type epoxy resin, p- or m-aminophenol type epoxy resin, etc. are mentioned.
また、前記エポキシ樹脂（ａ２）としては、例えばビスフェノール型エポキシ樹脂とビスフェノール化合物を反応させたエポキシ樹脂やジシクロペンタジエン−フェノール付加反応型エポキシ樹脂等のジシクロペンタジエン型エポキシ樹脂、ポリヒドロキシナフタレン型エポキシ樹脂、イソシアネート変性ビスフェノール型エポキシ樹脂、１０−（２，５−ジヒドロキシフェニル）−９，１０−ジヒドロ ９−オキサ−１０−フォスファフェナントレン−１０−オキサイド変性エポキシ樹脂、２−メトキシナフタレンとオルソクレゾールノボラック型エポキシ樹脂の共重合物、ビフェニレン型フェノールアラルキル樹脂、フェノールアラルキル樹脂などが挙げられ、中でもジシクロペンタジエン−フェノール付加反応型エポキシ樹脂等のジシクロペンタジエン型エポキシ樹脂、イソシアネート変性ビスフェノール型エポキシ樹脂、１０−（２，５−ジヒドロキシフェニル）−９，１０−ジヒドロ ９−オキサ−１０−フォスファフェナントレン−１０−オキサイド変性エポキシ樹脂を使用することが剛性と接着性とを両立するうえで好ましい。 Examples of the epoxy resin (a2) include dicyclopentadiene type epoxy resins such as epoxy resins obtained by reacting bisphenol type epoxy resins and bisphenol compounds, dicyclopentadiene-phenol addition type epoxy resins, and polyhydroxynaphthalene type epoxies. Resin, isocyanate-modified bisphenol-type epoxy resin, 10- (2,5-dihydroxyphenyl) -9,10-dihydro 9-oxa-10-phosphophenanthrene-10-oxide-modified epoxy resin, 2-methoxynaphthalene and orthocresol novolak Type epoxy resin copolymer, biphenylene type phenol aralkyl resin, phenol aralkyl resin, etc., among them dicyclopentadiene-phenol addition reaction type epoxy resin etc. It is possible to use lopentadiene type epoxy resin, isocyanate modified bisphenol type epoxy resin, 10- (2,5-dihydroxyphenyl) -9,10-dihydro 9-oxa-10-phosphaphenanthrene-10-oxide modified epoxy resin It is preferable for achieving both rigidity and adhesiveness.
また、前記エポキシ樹脂としては、上記エポキシ樹脂（ａ１）及びエポキシ樹脂（ａ２）とともに、好ましくはエポキシ当量が２０００ｇ／ｅｑ．以上、好ましくは２０００ｇ／ｅｑ．を超え１００００ｇ／ｅｑ．以下のエポキシ樹脂を組み合わせ使用することができる。 In addition to the epoxy resin (a1) and the epoxy resin (a2), the epoxy resin preferably has an epoxy equivalent of 2000 g / eq. Or more, preferably 2000 g / eq. Exceeding 10,000 g / eq. The following epoxy resins can be used in combination.
また、本発明の導電性樹脂組成物に使用する導電性フィラー（Ｂ）としては、針状または鱗片状の導電性フィラー（ｂ１）及び略球状の導電性フィラー（ｂ２）を組み合わせ使用する。 Moreover, as a conductive filler (B) used for the conductive resin composition of the present invention, a needle-like or scaly conductive filler (b1) and a substantially spherical conductive filler (b2) are used in combination.
前記針状または鱗片状の導電性フィラー（ｂ１）と、略球状の導電性フィラー（ｂ２）とは、それらの体積割合［（ｂ１）／（ｂ２）］が、１／１〜４／１となる範囲で使用することが好ましく、１．５／１〜３／１となる範囲で使用することが、優れた導電性と接着性とを両立した導電性樹脂組成物を得るうえで好ましい。前記導電性樹脂組成物を使用することによって得られた導電性接着シートは、導電性接着シートを熱硬化させる際に、前記２個以上のエポキシ基を有する化合物（Ａ）等の接着剤成分の流動を抑制できるため、取り扱い性や加工適性に優れる。 The acicular or scaly conductive filler (b1) and the substantially spherical conductive filler (b2) have a volume ratio [(b1) / (b2)] of 1/1 to 4/1. It is preferable to use in the range which becomes, and it is preferable to use in the range which becomes 1.5 / 1-3 / 1, when obtaining the conductive resin composition which made the outstanding electroconductivity and adhesiveness compatible. When the conductive adhesive sheet obtained by using the conductive resin composition is thermally cured, the adhesive component such as the compound (A) having two or more epoxy groups is used. Since flow can be suppressed, it is excellent in handleability and processability.
前記針状または鱗片状の導電性フィラー（ｂ１）としては、例えば金、銀、銅、ニッケル、ステンレス、アルミニウム等の金属の粒子状物、カーボン、グラファイトをはじめ、針状または鱗片状の樹脂やガラスフレーク等の表面が金属被覆されたもの等を使用することができ、なかでも、ニッケルや銅を使用することが好ましく、特にカーボニル法で製造した針状ニッケルを使用することが、より一層優れた導電性を発現させるうえでより好ましい。具体的には、前記導電性フィラーとしては、カーボニル法で製造されたニッケル粉ＮＩ２５５、ＮＩ２８７（インコリミテッド社製）等を好適に使用することができる。 Examples of the needle-like or scale-like conductive filler (b1) include metal particles such as gold, silver, copper, nickel, stainless steel, and aluminum, carbon, graphite, needle-like or scale-like resins, The surface of the glass flake or the like coated with metal can be used, and among these, nickel and copper are preferably used, and it is even more excellent to use acicular nickel produced by the carbonyl method. It is more preferable in terms of developing electrical conductivity. Specifically, as the conductive filler, nickel powder NI255, NI287 (manufactured by Incori Ltd.) manufactured by a carbonyl method can be preferably used.
前記導電性フィラー（ｂ１）は、平均で３を超える範囲のアスペクト比を有する程度の針状または鱗片形状を有するものであることが好ましい。 The conductive filler (b1) preferably has a needle shape or scale shape having an aspect ratio in a range exceeding 3 on average.
前記導電性フィラー（ｂ１）としては、その５０％平均体積粒子径が０．１〜２００μｍであるものを使用することが好ましく、１〜１００μｍであるものを使用することがより好ましく、１５〜５０μｍであるものを使用することがさらに好ましく、１５〜４０μｍであるものを使用することが、導電性樹脂組成物中における導電性フィラーの良好な分散性と、塗工のしやすさとを両立するうえで特に好ましい。なお、前記導電性フィラーの５０％体積粒子径は、株式会社島津製作所製レーザー回折式粒度分布測定器ＳＡＬＤ−３０００を用い、分散媒にイソプロパノールを使用して測定された値である。 The conductive filler (b1) preferably has a 50% average volume particle diameter of 0.1 to 200 μm, more preferably 1 to 100 μm, and more preferably 15 to 50 μm. It is more preferable to use a material having a thickness of 15 to 40 μm to achieve both good dispersibility of the conductive filler in the conductive resin composition and ease of coating. Is particularly preferable. The 50% volume particle diameter of the conductive filler is a value measured using a laser diffraction particle size distribution analyzer SALD-3000 manufactured by Shimadzu Corporation and isopropanol as a dispersion medium.
また、前記アスペクト比（Ｌ／ｔ）の算出に使用する導電性フィラーの「長軸平均長さＬ」、「短軸平均長さｄ」及び「平均厚みＴ」は、走査型電子顕微鏡（ＳＥＭ）を用いて撮影したＳＥＭ写真を観察することにより測定した。「長軸平均長さＬ」及び「短軸平均長さｄ」は、最長の長さの直線を長軸とし、その長さを「長軸長さ」Ｌとして測定し、その長軸を有し矩形で近似できる部分を主幹部とした。粒子の長軸に対して垂直な方向の最長長さｄを「短軸長さ」として測定し、その比率によりアスペクト比を算出した。主幹部から主幹部の方向とは異なる方向に突出している部分（分岐）がある場合、最も長い長軸の部分をＬ、長軸の幅に相当する部分を短軸ｄとした。 Further, the “major axis average length L”, “minor axis average length d”, and “average thickness T” of the conductive filler used for calculating the aspect ratio (L / t) are measured with a scanning electron microscope (SEM). ) Was observed by observing SEM photographs taken using The “major axis average length L” and “minor axis average length d” are measured with the longest straight line as the major axis and the length as the “major axis length” L, and the major axis is present. The portion that can be approximated by a rectangle is defined as the main trunk. The longest length d in the direction perpendicular to the long axis of the particles was measured as the “short axis length”, and the aspect ratio was calculated from the ratio. In the case where there is a portion (branch) protruding in a direction different from the direction of the main trunk from the main trunk, the longest major axis portion is L, and the portion corresponding to the major axis width is the minor axis d.
また、前記略球状の導電性フィラー（ｂ２）としては、熱の影響で導電性フィラーの表面に酸化皮膜が形成されることによって前記導電性が低下することを効果的に抑制でき、かつ、熱硬化性材料の生産コストを低減するうえで、ステンレスの粒子状物、ニッケルの粒子状物等を使用することが好ましい。 Moreover, as said substantially spherical conductive filler (b2), it can suppress effectively that the said electroconductivity falls by forming an oxide film on the surface of a conductive filler by the influence of heat, and heat In order to reduce the production cost of the curable material, it is preferable to use stainless particles, nickel particles, and the like.
なお、前記導電性フィラー（ｂ２）は、真球形状、だ円形状を有するものを使用することができ、アスペクト比でいえば平均で２未満の範囲のものを使用することが好ましい。 As the conductive filler (b2), those having a true sphere shape or an ellipse shape can be used, and those having an average ratio of less than 2 are preferably used in terms of aspect ratio.
前記導電性フィラー（ｂ２）としては、その５０％平均体積粒子径が０．１〜２００μｍであるものを使用することが好ましく、１〜１００μｍであるものを使用することがより好ましく、１５〜５０μｍであるものを使用することがさらに好ましく、１５〜４０μｍであるものを使用することが、導電性樹脂組成物中における導電性フィラーの良好な分散性と、塗工のしやすさとを両立するうえで特に好ましい。なお、前記導電性フィラーの５０％体積粒子径は、株式会社島津製作所製レーザー回折式粒度分布測定器ＳＡＬＤ−３０００を用い、分散媒にイソプロパノールを使用して測定された値である。 As the conductive filler (b2), those having a 50% average volume particle diameter of 0.1 to 200 μm are preferable, those having 1 to 100 μm are more preferable, and 15 to 50 μm are more preferable. It is more preferable to use a material having a thickness of 15 to 40 μm to achieve both good dispersibility of the conductive filler in the conductive resin composition and ease of coating. Is particularly preferable. The 50% volume particle diameter of the conductive filler is a value measured using a laser diffraction particle size distribution analyzer SALD-3000 manufactured by Shimadzu Corporation and isopropanol as a dispersion medium.
また、前記導電性フィラー（Ｂ）としては、導電性樹脂組成物中で導電性フィラー（Ｂ）が沈降しにくく、数時間にわたり比較的均一な分散状態を維持できるため、５．０ｇ／ｃｍ３以下の見かけ密度を有するものを使用することが好ましく、４．５ｇ／ｃｍ３以下の見かけ密度を有するものを使用することがより好ましく、４．０ｇ／ｃｍ３以下であることが特に好ましい。なお、前記導電性フィラー（Ｂ）の見かけ密度は、ＪＩＳＺ２５０４−２０００「金属粉の見かけ密度の測定方法」に準じて測定された値である。 Further, as the conductive filler (B), the conductive filler (B) hardly settles in the conductive resin composition and can maintain a relatively uniform dispersion state for several hours, so that 5.0 g / cm 3 it is preferable to use one having an apparent density of less, and particularly preferably it is more preferable to use those having a 4.5 g / cm 3 or less of the apparent density is 4.0 g / cm 3 or less. In addition, the apparent density of the said conductive filler (B) is the value measured according to JISZ2504-2000 "The measuring method of the apparent density of a metal powder".
また、前記導電性フィラー（Ｂ）としては、前記導電性樹脂組成物中における分散性をより一層向上でき、優れた導電性の点でばらつきが少ない補強部を得るうえで、チタネートカップリング剤やアルミネートカップリング剤等によって表面処理された導電性フィラーを使用しても良い。 Further, as the conductive filler (B), the dispersibility in the conductive resin composition can be further improved, and a titanate coupling agent, A conductive filler surface-treated with an aluminate coupling agent or the like may be used.
前記導電性フィラー（Ｂ）は、前記化合物（Ａ）及び前記導電性フィラー（Ｂ）の合計体積に対する体積割合が１０体積％〜５０体積％の範囲で使用することが好ましく、１０体積％〜３０体積％の範囲で使用することがより好ましく、２０〜３０体積％の範囲で使用することが更に好ましい。導電性フィラーの使用量が増加すると、通常、優れた導電性を発現する一方で、接着性の著しい低下を引き起こす場合がある。しかし、本発明の導電性樹脂組成物であれば、導電性フィラー（Ｂ）の使用量を増加させた場合であっても優れた接着性を保持可能で、前記導電性樹脂組成物を使用することによって得られた導電性接着シートは、導電性接着シートを熱硬化させる際に、前記２個以上のエポキシ基を有する化合物（Ａ）等の接着剤成分の流動を抑制できるため、取り扱い性や加工適性に優れる。 The conductive filler (B) is preferably used in a range of 10% by volume to 50% by volume with respect to the total volume of the compound (A) and the conductive filler (B). It is more preferable to use in the range of volume%, and it is still more preferable to use in the range of 20-30 volume%. When the amount of the conductive filler used is increased, it usually exhibits excellent conductivity, but may cause a significant decrease in adhesion. However, with the conductive resin composition of the present invention, excellent adhesiveness can be maintained even when the amount of the conductive filler (B) used is increased, and the conductive resin composition is used. Since the conductive adhesive sheet obtained by this can suppress the flow of the adhesive component such as the compound (A) having two or more epoxy groups when the conductive adhesive sheet is thermally cured, Excellent processability.
本発明の導電性樹脂組成物としては、前記化合物（Ａ）及び導電性フィラー（Ｂ）のほかに必要に応じてその他の成分を含有するものを使用することができる。 As the conductive resin composition of the present invention, those containing other components as required in addition to the compound (A) and the conductive filler (B) can be used.
また、前記その他の成分としては、前記導電性フィラー（Ｂ）以外のフィラーである水酸化アルミニウム、酸化アルミニウム、窒化アルミニウム、水酸化マグネシウム、酸化マグネシウム、マイカ、タルク、窒化ホウ素、ガラスフレーク等の電気絶縁性フィラー等を使用することができる。 Moreover, as said other component, electricity other than the said conductive filler (B), such as aluminum hydroxide, aluminum oxide, aluminum nitride, magnesium hydroxide, magnesium oxide, mica, talc, boron nitride, glass flakes, etc. An insulating filler or the like can be used.
また、前記その他の成分としては、前記化合物（Ａ）として前記エポキシ樹脂等の熱硬化性樹脂を使用する場合であれば、それと反応しうる硬化剤を使用することが好ましい。 Moreover, as said other component, when using thermosetting resins, such as said epoxy resin, as said compound (A), it is preferable to use the hardening | curing agent which can react with it.
前記硬化剤としては、例えば前記化合物（Ａ）としてエポキシ基を有するエポキシ樹脂やアクリル樹脂を使用する場合であれば、そのエポキシ基と反応しうる官能基を有するものを使用することが好ましい。 As the curing agent, for example, when an epoxy resin or acrylic resin having an epoxy group is used as the compound (A), it is preferable to use a compound having a functional group capable of reacting with the epoxy group.
前記硬化剤としては、アミン系化合物、アミド系化合物、酸無水物系化合物、フェノール系化合物などが挙げられる。例えば、アミン系化合物としてはジアミノジフェニルメタン、ジエチレントリアミン、トリエチレンテトラミン、ジアミノジフェニルスルホン、イソホロンジアミン、イミダゾール誘導体、ＢＦ３−アミン錯体、グアニジン誘導体等を使用することができる。 Examples of the curing agent include amine compounds, amide compounds, acid anhydride compounds, and phenol compounds. For example, diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole derivatives, BF3-amine complexes, guanidine derivatives and the like can be used as the amine compounds.
前記アミド系化合物としては、例えばジシアンジアミド、リノレン酸の２量体とエチレンジアミンとより合成されるポリアミド樹脂等が挙げられ、前記酸無水物系化合物としては、例えば無水フタル酸、無水トリメリット酸、無水ピロメリット酸、無水マレイン酸、テトラヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、無水メチルナジック酸、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸等が挙げられ、前記フェノール系化合物としては、例えばフェノールノボラック樹脂、クレゾールノボラック樹脂、芳香族炭化水素ホルムアルデヒド樹脂変性フェノール樹脂、ジシクロペンタジエンフェノール付加型樹脂、フェノールアラルキル樹脂（ザイロック樹脂）、ナフトールアラルキル樹脂、トリメチロールメタン樹脂、テトラフェニロールエタン樹脂、ナフトールノボラック樹脂、ナフトール−フェノール共縮ノボラック樹脂、ナフトール−クレゾール共縮ノボラック樹脂、ビフェニル変性フェノール樹脂（ビスメチレン基でフェノール核が連結された多価フェノール化合物）、ビフェニル変性ナフトール樹脂（ビスメチレン基でフェノール核が連結された多価ナフトール化合物）、アミノトリアジン変性フェノール樹脂（フェノール骨格、トリアジン環及び１級アミノ基を分子構造中に有する化合物）やアルコキシ基含有芳香環変性ノボラック樹脂（ホルムアルデヒドでフェノール核及びアルコキシ基含有芳香環が連結された多価フェノール化合物）等の多価フェノール化合物が挙げられる。 Examples of the amide compounds include polyamide resins synthesized from dicyandiamide, a dimer of linolenic acid and ethylenediamine, and examples of the acid anhydride compounds include phthalic anhydride, trimellitic anhydride, anhydrous anhydride, and the like. Examples include pyromellitic acid, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride. Examples of the phenol compound include phenol novolac. Resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin (Zylok resin), naphthol aralkyl resin, trimethylol methane tree , Tetraphenylolethane resin, naphthol novolak resin, naphthol-phenol co-condensed novolak resin, naphthol-cresol co-condensed novolak resin, biphenyl-modified phenol resin (polyhydric phenol compound in which phenol nucleus is linked by bismethylene group), biphenyl-modified naphthol Resin (polyvalent naphthol compound with phenol nucleus linked by bismethylene group), aminotriazine modified phenolic resin (compound having phenol skeleton, triazine ring and primary amino group in molecular structure) and alkoxy group-containing aromatic ring modified novolak resin Examples thereof include polyhydric phenol compounds such as (polyhydric phenol compounds in which a phenol nucleus and an alkoxy group-containing aromatic ring are linked with formaldehyde).
前記硬化剤としては、前記エポキシ樹脂等の化合物（Ａ）の合計１００質量部に対し、１質量部〜６０質量部の範囲で使用することが好ましく、５質量部〜３０質量部の範囲で使用することが好ましい。 As said hardening | curing agent, it is preferable to use in the range of 1 mass part-60 mass parts with respect to a total of 100 mass parts of compounds (A), such as the said epoxy resin, and it is used in the range of 5 mass parts-30 mass parts. It is preferable to do.
また、前記その他の成分としては、硬化促進剤を使用することができる。前記硬化促進剤としては、リン系化合物、アミン化合物、イミダゾール誘導体等を使用することができる。前記硬化促進剤を使用する場合の使用量は、前記エポキシ樹脂等の化合物（Ａ）の合計１００質量部に対し、０．１質量部〜５質量部であることが好ましく、０．５質量部〜３質量部の範囲であることがより好ましい。 Moreover, a hardening accelerator can be used as said other component. As the curing accelerator, phosphorus compounds, amine compounds, imidazole derivatives and the like can be used. When the curing accelerator is used, the amount used is preferably 0.1 parts by mass to 5 parts by mass with respect to 100 parts by mass in total of the compound (A) such as the epoxy resin, and 0.5 parts by mass. More preferably, it is in the range of ˜3 parts by mass.
前記硬化剤及び硬化促進剤としては、粉体状、且つ常温において樹脂組成物に溶解しないものを用いることが好ましい。前記粉体状の硬化促進剤は、液状の硬化促進剤と比較して低温下での熱硬化反応が抑制されるため、熱硬化前の熱硬化性材料の常温下における保存安定性をより一層向上させることができる。 As the curing agent and the curing accelerator, it is preferable to use a powder that does not dissolve in the resin composition at room temperature. The powdery curing accelerator suppresses the thermosetting reaction at a low temperature as compared with the liquid curing accelerator, so that the storage stability of the thermosetting material before thermosetting at room temperature is further increased. Can be improved.
また、前記導電性樹脂組成物としては、その熱硬化物が、温度変化の大きい環境下で使用された場合であっても、熱硬化物の欠損等を引き起こしにくい靭性を確保するうえで、熱可塑性樹脂を含有するものを使用することができる。 In addition, as the conductive resin composition, even when the thermoset is used in an environment where the temperature change is large, in order to ensure toughness that does not easily cause loss of the thermoset, What contains a plastic resin can be used.
前記熱可塑性樹脂としては、例えば熱可塑性ポリエステル樹脂、熱可塑性ウレタン樹脂等を使用することができ、なかでも、熱可塑性ポリエステル樹脂を使用することが好ましく、ポリエーテルエステルアミド樹脂、ポリビニルアセトアセタール樹脂を使用することが、本発明の導電性樹脂組成物及び導電性接着シートを熱硬化させる際に、前記導電性樹脂組成物及び導電性接着シートの流動を抑制でき、また前記したレベルの良好な脆性と、フレキシブルプリント配線板等の被着体を十分に補強可能なレベルの剛性とを両立することができる。 As the thermoplastic resin, for example, a thermoplastic polyester resin, a thermoplastic urethane resin, and the like can be used. Among them, a thermoplastic polyester resin is preferably used, and a polyetheresteramide resin and a polyvinyl acetoacetal resin are used. When the conductive resin composition and the conductive adhesive sheet of the present invention are thermally cured, the flow of the conductive resin composition and the conductive adhesive sheet can be suppressed, and the above-described level of good brittleness And a level of rigidity capable of sufficiently reinforcing an adherend such as a flexible printed wiring board.
前記熱可塑性樹脂は、上記理由から、前記化合物（Ａ）１００質量部に対して１〜１００質量部の範囲で使用することが好ましく、５質量部〜４０質量部の範囲で使用することがより好ましい。 From the above reason, the thermoplastic resin is preferably used in the range of 1 to 100 parts by mass, more preferably in the range of 5 to 40 parts by mass with respect to 100 parts by mass of the compound (A). preferable.
前記導電性樹脂組成物としては、前記したとおり予めシート状等の任意の形状に成形された導電性接着シートとして使用することができる。前記導電性樹脂組成物は、それを用い導電性接着シートを製造する際の作業効率を向上させるうえで、前記化合物（Ａ）や導電性フィラー（Ｂ）や硬化剤等の他に溶媒を含有するものを使用することが好ましい。 As said conductive resin composition, as above-mentioned, it can use as a conductive adhesive sheet previously shape | molded by arbitrary shapes, such as a sheet form. The conductive resin composition contains a solvent in addition to the compound (A), the conductive filler (B), a curing agent, and the like in order to improve work efficiency when producing a conductive adhesive sheet using the conductive resin composition. It is preferable to use what to do.
前記溶媒としては、例えば酢酸メチル、酢酸エチル、酢酸プロピル、酢酸ブチル等のエステル系溶剤；アセトン、メチルケチルケトン、メチルイソブチルケトン、ジイソブチルケトン、シクロヘキサノン等のケトン系溶剤；トルエン、キシレン等の芳香族炭化水素類等を使用することができる。 Examples of the solvent include ester solvents such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate; ketone solvents such as acetone, methyl ketyl ketone, methyl isobutyl ketone, diisobutyl ketone, and cyclohexanone; aromatics such as toluene and xylene. Hydrocarbons and the like can be used.
また、前記導電性樹脂組成物としては、前記したものの他に、本発明の効果を損なわない範囲で、例えば充填剤、軟化剤、安定剤、接着促進剤、レベリング剤、消泡剤、可塑剤、粘着付与樹脂、繊維類、酸化防止剤、紫外線吸収剤、加水分解防止剤、増粘剤、顔料などの着色剤、充填剤などの添加剤を含有するものを使用することができる。 In addition to the above-described conductive resin composition, the conductive resin composition is, for example, a filler, a softener, a stabilizer, an adhesion promoter, a leveling agent, an antifoaming agent, and a plasticizer, as long as the effects of the present invention are not impaired. , Tackifying resins, fibers, antioxidants, ultraviolet absorbers, hydrolysis inhibitors, thickeners, pigments and other additives, and additives such as fillers can be used.
本発明の導電性樹脂組成物は、前記化合物（Ａ）と前記導電性フィラー（Ｂ）と、硬化剤や溶媒等の任意の成分とを混合することによって製造することができる。 The conductive resin composition of the present invention can be produced by mixing the compound (A), the conductive filler (B), and optional components such as a curing agent and a solvent.
前記した成分を混合し導電性樹脂組成物を製造する際には、必要に応じてディゾルバー、バタフライミキサー、ＢＤＭ２軸ミキサー、プラネタリーミキサー等を使用することができ、ディゾルバー、バタフライミキサーを使用することが好ましく、前記導電性フィラーを使用する場合には、それらの分散性を向上させるうえでプラネタリーミキサーを使用することが好ましい。 When mixing the above-mentioned components to produce a conductive resin composition, a dissolver, a butterfly mixer, a BDM biaxial mixer, a planetary mixer, etc. can be used as necessary, and a dissolver and a butterfly mixer should be used. In the case of using the conductive filler, it is preferable to use a planetary mixer in order to improve the dispersibility thereof.
なお、前記硬化剤及び硬化促進剤は、導電性樹脂組成物を熱硬化させる前、または、シート状等に成形し導電性接着シートを製造する前に、使用することが好ましい。 In addition, it is preferable to use the said hardening | curing agent and hardening accelerator before thermosetting a conductive resin composition, or before shape | molding in a sheet form etc. and manufacturing a conductive adhesive sheet.
また、導電性接着シートは、例えば前記化合物（Ａ）と、前記導電性フィラー（Ｂ）と、前記任意成分とを混合し導電性樹脂組成物を製造した後、それを、例えば剥離ライナーの表面に塗工し乾燥等させることによって製造することができる。 In addition, the conductive adhesive sheet is prepared by mixing the compound (A), the conductive filler (B), and the optional component to produce a conductive resin composition, for example, and then applying it to the surface of the release liner, for example. It can be manufactured by coating and drying.
前記乾燥は、好ましくは５０℃〜１２０℃、より好ましくは５０℃〜９０℃程度の温度で行うことが、熱硬化性材料の熱硬化反応を進行させることを抑制するうえで好適である。 The drying is preferably performed at a temperature of about 50 ° C. to 120 ° C., more preferably about 50 ° C. to 90 ° C., in order to prevent the thermosetting reaction of the thermosetting material from proceeding.
前記導電性接着シートは、例えばフレキシブルプリント配線板等の被着体に貼付される前まで、前記剥離ライナーによって挟持されていてもよい。 The conductive adhesive sheet may be sandwiched between the release liners before being attached to an adherend such as a flexible printed wiring board.
前記剥離ライナーとしては、例えばクラフト紙、グラシン紙、上質紙等の紙；ポリエチレン、ポリプロピレン（ＯＰＰ、ＣＰＰ）、ポリエチレンテレフタレート等の樹脂フィルム；前記紙と樹脂フィルムとを積層したラミネート紙、前記紙にクレーやポリビニルアルコールなどで目止め処理を施したものの片面もしくは両面に、シリコーン系樹脂等の剥離処理を施したもの等を用いることができる。 Examples of the release liner include paper such as kraft paper, glassine paper, and high-quality paper; resin films such as polyethylene, polypropylene (OPP, CPP), and polyethylene terephthalate; laminated paper in which the paper and the resin film are laminated, and the paper A material obtained by applying a release treatment such as a silicone-based resin to one or both surfaces of a material subjected to a sealing treatment with clay or polyvinyl alcohol can be used.
前記導電性接着シートとしては、熱硬化前の厚さが５０〜３５０μｍの範囲のものを使用することが好ましく、１００〜３５０μｍのものを使用することがより好ましく、１１５〜３００μｍのものを使用することが、それをロールに巻き取った際に割れ等を引き起こしにくいため好ましい。 As the conductive adhesive sheet, it is preferable to use a sheet having a thickness in the range of 50 to 350 μm, more preferably 100 to 350 μm, and more preferably 115 to 300 μm before thermosetting. It is preferable because it is difficult to cause cracking when it is wound on a roll.
前記導電性接着シートとしては、熱硬化後の厚さが５０〜３５０μｍの範囲のものを使用することが好ましく、８０〜３００μｍであることがより好ましく、１００〜３５０μｍのものを使用することが、熱硬化前後での寸法安定性に優れ、取り扱いしやすく、かつ、電子機器等の厚膜化の要因とされる金属補強板を使用せずとも、実装部品の脱落等を防止可能なレベルにまでフレキシブルプリント配線板を強固に補強可能なレベルの剛性を発現できるためより好ましい。 As the conductive adhesive sheet, it is preferable to use a sheet having a thickness after thermosetting of 50 to 350 μm, more preferably 80 to 300 μm, and a sheet having a thickness of 100 to 350 μm. Excellent dimensional stability before and after thermosetting, easy to handle, and to a level where mounting components can be prevented from falling off without using a metal reinforcing plate, which is the cause of thick film in electronic devices. It is more preferable because it can exhibit a level of rigidity that can reinforce the flexible printed wiring board.
前記導電性接着シートとしては、常温下においてはタック感がほとんどないシート状物であってもよく、およそ１００℃以上の温度に加熱された場合に溶融し、２以上の被着体を接着（接合）可能なものであることが好ましい。 The conductive adhesive sheet may be a sheet having almost no tackiness at room temperature, and melts when heated to a temperature of about 100 ° C. or higher to bond two or more adherends ( It is preferable that it can be joined).
前記導電性接着シートは、熱硬化前の２５℃における引っ張り弾性率（ｘ１）が５〜２，５００ＭＰａの範囲であることが、打ち抜き加工法によって精度よく任意の形状に成形しやすいため、フレキシブルプリント配線板の補強が必要な箇所の形状に応じた任意の形状に加工しやすく、また、例えばフレキシブルプリント配線板等の被着体が有する段差部等への追従性に優れ、その結果、優れた接着性と導電性とを発現するうえで好ましい。 Since the conductive adhesive sheet has a tensile elastic modulus (x1) at 25 ° C. before thermosetting in the range of 5 to 2500 MPa, it can be easily formed into an arbitrary shape with a punching process. It is easy to process into an arbitrary shape according to the shape of the place where the reinforcement of the wiring board is necessary, and also excellent in the followability to the stepped part etc. of the adherend such as a flexible printed wiring board, and as a result, excellent It is preferable when expressing adhesiveness and conductivity.
前記導電性接着シートとしては、その２５℃における引っ張り弾性率（ｘ１）が５〜１，０００ＭＰａの範囲であるものを使用することが、前記したとおり打ち抜き加工しやすく、かつ、それをロールに巻き取った際に割れ等を引き起こしにくいため好ましい。 As the conductive adhesive sheet, the one having a tensile elastic modulus (x1) in the range of 5 to 1,000 MPa at 25 ° C. is easy to punch as described above, and is wound around a roll. It is preferable because it is difficult to cause cracking when taken.
また、前記導電性接着シートとしては、その熱硬化後の２５℃における引っ張り弾性率（ｘ２）が４，０００ＭＰａ以上の範囲であるものを使用することが、フレキシブルプリント配線板等の被着体の実用上十分なレベルに補強するうえでより好ましい。また、前記引っ張り弾性率（ｘ２）の上限は、特に制限はないが、１０，０００ＭＰａ以下であることが好ましく、７，０００ＭＰａ以下であることがより好ましい。 Moreover, as said electroconductive adhesive sheet, it is possible to use what has a tensile elastic modulus (x2) in the range of 4,000 Mpa or more in 25 degreeC after the thermosetting of adherends, such as a flexible printed wiring board. It is more preferable to reinforce to a practically sufficient level. The upper limit of the tensile elastic modulus (x2) is not particularly limited, but is preferably 10,000 MPa or less, and more preferably 7,000 MPa or less.
ここで、前記引っ張り弾性率（ｘ２）は、前記熱硬化性材料を２００℃で１２０分加熱して得られた熱硬化物の２５℃における引っ張り弾性率を指す。 Here, the tensile elastic modulus (x2) refers to the tensile elastic modulus at 25 ° C. of a thermoset obtained by heating the thermosetting material at 200 ° C. for 120 minutes.
また、本発明の導電性樹脂組成物及び導電性接着シートとしては、その体積抵抗値が０．１〜５０ｍΩ・ｃｍの範囲の導電性を有するものを使用することが好ましく、０．１〜２０ｍΩ・ｃｍの範囲であるものを使用することが、後述する補強部付フレキシブルプリント配線板を電子機器へ搭載する際、その補強板付フレキシブルプリント配線板を構成するグラウンド配線に、導電性スポンジ等のクッション材を介して金属パネルを電気的に接続させることができ、その結果、電子機器から発せられるノイズを効果的に抑制できるためより好ましい。また、前記導電性樹脂組成物及び導電性接着シートの熱硬化物の体積抵抗値は、前記熱硬化前のそれと同一または異なる値であってよいが、熱硬化物の体積抵抗値もまた上記好ましい範囲内であることが、補強部付フレキシブルプリント配線板を電子機器へ搭載する際に、その補強板付フレキシブルプリント配線板を構成するグラウンド配線に、導電性スポンジ等のクッション材を介して金属パネルを電気的に接続させることができ、その結果、電子機器から発せられるノイズを効果的に抑制できるためより好ましい。 In addition, as the conductive resin composition and the conductive adhesive sheet of the present invention, it is preferable to use those having a volume resistance of 0.1 to 50 mΩ · cm, and 0.1 to 20 mΩ.・ When a flexible printed wiring board with a reinforcing portion, which will be described later, is mounted on an electronic device, it is necessary to use a material having a cm range, and a cushion such as a conductive sponge is formed on the ground wiring constituting the flexible printed wiring board with the reinforcing plate. The metal panel can be electrically connected through the material, and as a result, noise generated from the electronic device can be effectively suppressed, which is more preferable. Further, the volume resistance value of the thermosetting product of the conductive resin composition and the conductive adhesive sheet may be the same as or different from that before the thermosetting, but the volume resistance value of the thermosetting product is also preferable. When mounting a flexible printed wiring board with a reinforcing part on an electronic device, a metal panel is placed on the ground wiring constituting the flexible printed wiring board with the reinforcing plate via a cushioning material such as a conductive sponge. Since it can electrically connect and, as a result, the noise emitted from an electronic device can be suppressed effectively, it is more preferable.
なお、前記体積抵抗値は、抵抗率計Ｌｏｒｅｓｔａ−ＧＰ ＭＣＰ−Ｔ６００（三菱化学株式会社製）によって測定した値を指す。 In addition, the said volume resistance value points out the value measured with the resistivity meter Loresta-GP MCP-T600 (made by Mitsubishi Chemical Corporation).
上記方法で得られた本発明の導電性樹脂組成物及び導電性接着シートは、硬化前においては比較的柔軟であるため被着体に対する段差追従性に優れ、かつ、熱硬化後においては、非常に硬くなるため被着体を十分に補強できることから、もっぱらフレキシブルプリント配線板の補強部を形成する材料に使用することができる。 The conductive resin composition and conductive adhesive sheet of the present invention obtained by the above method are relatively flexible before curing, and thus have excellent step followability to the adherend, and are extremely Since the adherend can be sufficiently reinforced because it becomes hard, it can be used exclusively as a material for forming the reinforcing portion of the flexible printed wiring board.
フレキシブルプリント配線板としては、フレキシブルプリント配線板と補強部とが積層された構成を有する補強部付フレキシブルプリント配線板として使用される場合が多い。前記補強部としては、従来、ステンレス板が使用されていたが、本発明においては、前記導電性樹脂組成物及び導電性接着シートの熱硬化物を単独で、前記補強部として使用することができる。そのため、フレキシブルプリント配線板の薄型化と、例えばフレキシブルプリント配線板が有する開口部等に起因した段差部に対する優れた段差追従性とを両立することができる。 In many cases, the flexible printed wiring board is used as a flexible printed wiring board with a reinforcing portion having a configuration in which a flexible printed wiring board and a reinforcing portion are laminated. Conventionally, a stainless steel plate has been used as the reinforcing portion. However, in the present invention, the conductive resin composition and the thermosetting product of the conductive adhesive sheet can be used alone as the reinforcing portion. . Therefore, it is possible to achieve both a reduction in thickness of the flexible printed wiring board and excellent step following performance with respect to a stepped portion caused by, for example, an opening portion of the flexible printed wiring board.
前記補強部は、その２５℃における引っ張り弾性率（ｘ３）が２，５００ＭＰａ以上であることが好ましく、３，０００ＭＰａ以上であることがより好ましく、４，０００〜２０，０００ＭＰａであることが、前記ステンレス板等を使用しなくてもフレキシブルプリント配線板を強固に補強できるためさらに好ましい。 The reinforcing part preferably has a tensile modulus (x3) at 25 ° C. of 2,500 MPa or more, more preferably 3,000 MPa or more, and 4,000 to 20,000 MPa. It is more preferable because the flexible printed wiring board can be reinforced strongly without using a stainless steel plate or the like.
前記補強部は、例えば前記導電性樹脂組成物及び導電性接着シートを好ましくは１２０℃以上、より好ましくは１２０〜２００℃の温度条件で、５分〜１２０分間加熱し硬化させることによって得ることができる。 The reinforcing part can be obtained, for example, by heating and curing the conductive resin composition and the conductive adhesive sheet at a temperature of preferably 120 ° C. or higher, more preferably 120 to 200 ° C. for 5 to 120 minutes. it can.
前記補強部を有するフレキシブルプリント配線板は、一般に、補強部付フレキシブルプリント配線板といわれ、電子機器に搭載される。 The flexible printed wiring board having the reinforcing portion is generally called a flexible printed wiring board with a reinforcing portion, and is mounted on an electronic device.
前記補強部付フレキシブルプリント配線板は、例えばフレキシブルプリント配線板の実装面に対する裏面に、前記導電性樹脂組成物及び導電性接着シートを貼付または塗布する工程［１］、及び、前記導電性樹脂組成物及び導電性接着シートを１２０℃以上に加熱し熱硬化させることによって補強部を形成する工程［２］を経ることによって製造することができる。 The step of applying or applying the conductive resin composition and the conductive adhesive sheet to the back surface of the flexible printed wiring board with respect to the mounting surface of the flexible printed wiring board [1] and the conductive resin composition, for example, It can manufacture by passing through the process [2] which forms a reinforcement part by heating an object and an electroconductive adhesive sheet to 120 degreeC or more, and thermosetting.
前記フレキシブルプリント配線板への部品の実装は、前記工程［１］の前にあらかじめ行われていてもよいが、前記工程［１］及び工程［２］を経た後に、行われることが、実装工程における前記部品の接続不良を効果的に防止するうえで好ましい。 The mounting of the component on the flexible printed wiring board may be performed in advance before the step [1], but is performed after the step [1] and the step [2]. This is preferable in effectively preventing the connection failure of the components.
前記補強部付フレキシブルプリント配線板は、もっぱらスマートフォン等の携帯型電子機器やパソコン等の電子機器に搭載される。その際、フレキシブルプリント配線板及び前記補強部付フレキシブルプリント配線板の前記補強部の表面には、直接または他の層を介して、クッション材が積層された状態で、前記電子機器に搭載されることが好ましい。 The flexible printed wiring board with a reinforcing portion is exclusively mounted on a portable electronic device such as a smartphone or an electronic device such as a personal computer. At that time, the cushioning material is mounted on the surface of the reinforcing part of the flexible printed wiring board and the flexible printed wiring board with the reinforcing part, directly or via another layer, and is mounted on the electronic device. It is preferable.
前記クッション材との積層は、接着成分等で接着された状態であってもよく、単に接している状態であってもよい。 The lamination with the cushion material may be in a state of being bonded with an adhesive component or the like, or may be in a state of being simply in contact therewith.
前記クッション材としては、例えばウレタンフォームや、ポリエチレンフォーム、シリコンスポンジ等が挙げられ、導電性ウレタンフォームを使用することが好ましい。 Examples of the cushion material include urethane foam, polyethylene foam, silicon sponge, and the like, and it is preferable to use conductive urethane foam.
前記クッション材としては、０．１〜５．０ｍｍ程度の厚さを有するものを使用することが好ましい。 As the cushion material, it is preferable to use a material having a thickness of about 0.1 to 5.0 mm.
前記クッション材の積層された構成を備えた電子機器は、ノイズを原因とする誤作動を効果的に抑制する。 An electronic device having a configuration in which the cushion material is laminated effectively suppresses malfunction caused by noise.
以下に実施例及び比較例について具体的に説明をする。 Examples and comparative examples will be specifically described below.
（実施例１）
ＪＥＲ−１２５６（三菱化学株式会社製、ビスフェノールＡ型エポキシ樹脂、エポキシ当量８，０００ｇ／ｅｑ．）のメチルエチルケトン溶液（固形分３０質量％）２００質量部、８５０−Ｓ（ＤＩＣ株式会社製、ビスフェノールＡ型エポキシ樹脂、エポキシ当量１８８ｇ／ｅｑ．）を１０質量部、ＨＰ−７２００（ＤＩＣ株式会社製、ジシクロペンタジエン型エポキシ樹脂、エポキシ当量２８５ｇ／ｅｑ．）のメチルエチルケトン溶液（固形分７０質量％）４２．９質量部、ＤＩＣＹ−７（三菱化学株式会社製、ジシアンジアミド）２．０質量部を混合することによって熱硬化性樹脂組成物（Ｘ−１）を調製した。
Example 1
200 parts by mass of a methyl ethyl ketone solution (solid content 30% by mass) of JER-1256 (Mitsubishi Chemical Corporation, bisphenol A type epoxy resin, epoxy equivalent 8,000 g / eq.), 850-S (DIC Corporation, bisphenol A) Type epoxy resin, epoxy equivalent 188 g / eq.) 10 parts by mass, HP-7200 (manufactured by DIC Corporation, dicyclopentadiene type epoxy resin, epoxy equivalent 285 g / eq.) Methyl ethyl ketone solution (solid content 70% by mass) 42 A thermosetting resin composition (X-1) was prepared by mixing .9 parts by mass and 2.0 parts by mass of DICY-7 (manufactured by Mitsubishi Chemical Corporation, dicyandiamide).
次に、針状の導電性フィラーとしてＮＩ−２５５（インコリミテッド社製のニッケル粉、平均のアスペクト比３超え、５０％平均粒子径：２１μｍ、見かけ密度：０．６ｇ／ｃｍ３、針状）を前記熱硬化性樹脂組成物（Ｘ−１）の固形分１００質量部に対し２１７．３質量部、略球形状の導電性フィラーとしてＤＡＰ−３１６Ｌ−ＨＴＤ（大同特殊鋼株式会社製、ステンレス粉、平均のアスペクト比２未満、５０％平均粒子径：１０．７μｍ、タップ密度：４．１ｇ／ｃｍ３、丸み状）９６．８質量部を入れ、分散撹拌機を用いて１０分間撹拌することによって導電性熱硬化性樹脂組成物（Ｙ−１）を得た。 Next, NI-255 (Nickel powder manufactured by Incori Ltd., average aspect ratio exceeding 3, 50% average particle size: 21 μm, apparent density: 0.6 g / cm 3 , needle shape) as a needle-like conductive filler 217.3 parts by mass relative to 100 parts by mass of the solid content of the thermosetting resin composition (X-1), DAP-316L-HTD (manufactured by Daido Steel Co., Ltd., stainless steel powder as a substantially spherical conductive filler) Average aspect ratio of less than 2, 50% average particle diameter: 10.7 μm, tap density: 4.1 g / cm 3 , rounded) 96.8 parts by mass are added and stirred for 10 minutes using a dispersion stirrer. As a result, a conductive thermosetting resin composition (Y-1) was obtained.
次に、離型ライナー（厚さ５０μｍのポリエチレンテレフタレートフィルムの片面がシリコーン化合物によって剥離処理されたもの）の表面に、前記導電性熱硬化性樹脂組成物（Ｙ−１）を、棒状の金属アプリケータを用いて、乾燥後の厚さが１４０μｍになるように塗工した。 Next, the conductive thermosetting resin composition (Y-1) is applied to the surface of a release liner (one surface of a polyethylene terephthalate film having a thickness of 50 μm is peeled with a silicone compound). Using a coater, coating was performed so that the thickness after drying was 140 μm.
次に、前記塗工物を８５℃の乾燥機に５分間投入し乾燥することによって、厚さ１４０μｍの導電性接着シート（Ｚ−１）を得た。 Next, the coated product was put into a dryer at 85 ° C. for 5 minutes and dried to obtain a conductive adhesive sheet (Z-1) having a thickness of 140 μm.
（実施例２）
ＤＩＣＹ−７（三菱化学株式会社製、ジシアンジアミド）２．０質量部の代わりに２ＭＡ−ＯＫ（四国化成工業株式会社製、２，４−ジアミノ−６−［２’−メチルイミダゾリル−（１’）］−エチル−ｓ−トリアジンイソシアヌル酸付加物）２質量部を使用すること以外は実施例１と同様の方法で、導電性熱硬化性樹脂組成物（Ｙ−２）及び厚さ１４０μｍの導電性接着シート（Ｚ−２）を得た。
(Example 2)
Instead of 2.0 parts by mass of DICY-7 (Mitsubishi Chemical Corporation, dicyandiamide), 2MA-OK (Shikoku Kasei Kogyo Co., Ltd., 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)] ] -Ethyl-s-triazine isocyanuric acid adduct) A conductive thermosetting resin composition (Y-2) and a 140 μm thick conductive material in the same manner as in Example 1 except that 2 parts by mass are used. An adhesive sheet (Z-2) was obtained.
（実施例３）
ＪＥＲ−１２５６（三菱化学株式会社製、ビスフェノールＡ型エポキシ樹脂）のメチルエチルケトン溶液（固形分３０質量％）の使用量を２００質量部から１３３．３質量部に変更し、８５０−Ｓ（ＤＩＣ株式会社製、ビスフェノールＡ型エポキシ樹脂、エポキシ当量１８８ｇ／ｅｑ．）の代わりに８３０−Ｓ（ビスフェノールＦ型エポキシ樹脂、エポキシ当量１７０ｇ／ｅｑ．）を１０質量部使用し、かつ、ＥＸＡ−９７２６（ＤＩＣ株式会社製、リン変性エポキシ樹脂、エポキシ当量４７５ｇ／ｅｑ．）のメチルエチルケトン溶液（固形分７０質量％）を２８．６質量部使用すること以外は、実施例１と同様の方法で、導電性熱硬化性樹脂組成物（Ｙ−３）及び厚さ１４０μｍの導電性接着シート（Ｚ−３）を得た。
(Example 3)
The amount of methyl ethyl ketone solution (solid content 30% by mass) of JER-1256 (Mitsubishi Chemical Corporation, bisphenol A type epoxy resin) was changed from 200 parts by mass to 133.3 parts by mass, and 850-S (DIC Corporation). 10 parts by mass of 830-S (bisphenol F type epoxy resin, epoxy equivalent 170 g / eq.) Instead of bisphenol A type epoxy resin, epoxy equivalent 188 g / eq., And EXA-9726 (DIC stock) Conductive thermosetting in the same manner as in Example 1 except that 28.6 parts by mass of a methyl ethyl ketone solution (solid content: 70% by mass) of phosphor modified epoxy resin, epoxy equivalent of 475 g / eq. Conductive resin composition (Y-3) and a conductive adhesive sheet (Z-3) having a thickness of 140 μm were obtained.
（実施例４）
ＪＥＲ−１２５６（三菱化学株式会社製、ビスフェノールＡ型エポキシ樹脂）のメチルエチルケトン溶液（固形分３０質量％）の使用量を１３３．３質量部から１６６．７質量部に変更し、ＥＸＡ−９７２６（ＤＩＣ株式会社製、リン変性エポキシ樹脂、エポキシ当量４７５ｇ／ｅｑ．）のメチルエチルケトン溶液（固形分７０質量％）の代わりにＴＳＲ−４００（ＤＩＣ株式会社製、イソシアネート変性ビスフェノールＡ型エポキシ樹脂、エポキシ当量３４３ｇ／ｅｑ．）のメチルエチルケトン溶液（固形分８０質量％）を５０質量部使用し、ＨＰ−７２００（ＤＩＣ株式会社製、ジシクロペンタジエン型エポキシ樹脂、エポキシ当量２８５ｇ／ｅｑ．）のメチルエチルケトン溶液（固形分７０質量％）の使用量を４２．９質量部から０質量部に変更し、かつ、ＤＩＣＹ−７（三菱化学株式会社製、ジシアンジアミド）２．０質量部の代わりに２ＭＡ−ＯＫ（四国化成工業株式会社製、２，４−ジアミノ−６−［２’−メチルイミダゾリル−（１’）］−エチル−ｓ−トリアジンイソシアヌル酸付加物）１質量部使用すること以外は、実施例３と同様の方法で導電性熱硬化性樹脂組成物（Ｙ−４）及び厚さ１４０μｍの導電性接着シート（Ｚ−４）を得た。
Example 4
The amount of methyl ethyl ketone solution (solid content 30% by mass) of JER-1256 (Mitsubishi Chemical Corporation, bisphenol A epoxy resin) was changed from 133.3 parts by mass to 166.7 parts by mass, and EXA-9726 (DIC TSR-400 (manufactured by DIC Corporation, isocyanate-modified bisphenol A type epoxy resin, epoxy equivalent 343 g / in place of a methyl ethyl ketone solution (solid content 70% by mass) of phosphor modified epoxy resin, epoxy equivalent 475 g / eq.) eq.) methyl ethyl ketone solution (solid content 80 mass%) 50 parts by mass, HP-7200 (DIC Corporation, dicyclopentadiene type epoxy resin, epoxy equivalent 285 g / eq.) methyl ethyl ketone solution (solid content 70) Mass) is reduced from 42.9 parts by mass. And 2MA-OK (Shikoku Kasei Kogyo Co., Ltd., 2,4-diamino-6- [2'-) instead of 2.0 parts by mass of DICY-7 (Mitsubishi Chemical Corporation, dicyandiamide) Methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct) Except for using 1 part by mass, in the same manner as in Example 3, the conductive thermosetting resin composition (Y-4) and A conductive adhesive sheet (Z-4) having a thickness of 140 μm was obtained.
（実施例５）
２ＭＡ−ＯＫ（四国化成工業株式会社製、２，４−ジアミノ−６−［２’−メチルイミダゾリル−（１’）］−エチル−ｓ−トリアジンイソシアヌル酸付加物）の使用量を１質量部から０．９質量部に変更し、さらにＤＩＣＹ−７（三菱化学株式会社製、ジシアンジアミド）１．５質量部と４，４’−ジアミノジフェニルスルホン５．４質量部とを使用すること以外は、実施例４と同様の方法で導電性熱硬化性樹脂組成物（Ｙ−５）及び厚さ１４０μｍの導電性接着シート（Ｚ−５）を得た。
(Example 5)
The amount of 2MA-OK (manufactured by Shikoku Kasei Kogyo Co., Ltd., 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct) from 1 part by mass The procedure was changed to 0.9 parts by mass, except that 1.5 parts by mass of DICY-7 (Mitsubishi Chemical Corporation, dicyandiamide) and 5.4 parts by mass of 4,4′-diaminodiphenylsulfone were used. In the same manner as in Example 4, a conductive thermosetting resin composition (Y-5) and a conductive adhesive sheet (Z-5) having a thickness of 140 μm were obtained.
（実施例６）
前記ＮＩ−２５５（インコリミテッド社製のニッケル粉、５０％平均粒子径：２１μｍ、見かけ密度：０．６ｇ／ｃｍ３、針状）の使用量を２１７．３質量部から１６２質量部に変更し、かつ、ＤＡＰ−３１６Ｌ−ＨＴＤ（大同特殊鋼株式会社製、ステンレス粉、５０％平均粒子径：１０．７μｍ、タップ密度：４．１ｇ／ｃｍ３、丸み状）の使用量を９６．８質量部から１４５質量部に変更したこと以外は、実施例４と同様の方法で、導電性熱硬化性樹脂組成物（Ｙ−６）及び厚さ１４０μｍの導電性接着シート（Ｚ−６）を得た。
(Example 6)
The amount of NI-255 (nickel powder manufactured by Incori Ltd., 50% average particle size: 21 μm, apparent density: 0.6 g / cm 3 , needle shape) was changed from 217.3 parts by mass to 162 parts by mass. In addition, the amount of DAP-316L-HTD (manufactured by Daido Steel Co., Ltd., stainless powder, 50% average particle size: 10.7 μm, tap density: 4.1 g / cm 3 , rounded) is used as 96.8 mass. A conductive thermosetting resin composition (Y-6) and a conductive adhesive sheet (Z-6) having a thickness of 140 μm were obtained in the same manner as in Example 4 except that the amount was changed from 145 parts to 145 parts by weight. It was.
（実施例７）
８３０−Ｓ（ＤＩＣ株式会社製、ビスフェノールＦ型エポキシ樹脂、エポキシ当量１７０ｇ／ｅｑ．）の使用量を１０質量部から２０質量部に変更し、ＴＳＲ−４０（ＤＩＣ株式会社製、イソシアネート変性ビスフェノールＡ型エポキシ樹脂、エポキシ当量３４３ｇ／ｅｑ．）の代わりに１０５５（ＤＩＣ株式会社製、ビスフェノールＡ型エポキシ樹脂、エポキシ当量４７５ｇ／ｅｑ．）を３０質量部使用し、ＪＥＲ−１２５６（三菱化学株式会社製、ビスフェノールＡ型エポキシ樹脂）の使用量を１６６．７質量部から１５０質量部に変更し、エスレックＫＳ−１（積水化学工業株式会社製、ポリビニルアセタール樹脂）を５質量部使用し、かつ、ＤＮ−９８０（ＤＩＣ株式会社製、ポリイソシアネート硬化剤）を１．５質量部使用すること以外は、実施例４と同様の方法で、導電性熱硬化性樹脂組成物（Ｙ−７）及び厚さ１４０μｍの導電性接着シート（Ｚ−７）を得た。
(Example 7)
830-S (made by DIC Corporation, bisphenol F type epoxy resin, epoxy equivalent 170 g / eq.) Was changed from 10 parts by mass to 20 parts by mass, and TSR-40 (made by DIC Corporation, isocyanate-modified bisphenol A) Type epoxy resin, epoxy equivalent of 343 g / eq.) 1055 (DIC Corporation, bisphenol A type epoxy resin, epoxy equivalent of 475 g / eq.) Is used in an amount of 30 parts by mass, and JER-1256 (Mitsubishi Chemical Corporation) , Bisphenol A type epoxy resin) is changed from 166.7 parts by mass to 150 parts by mass, and 5 parts by mass of ESREC KS-1 (Sekisui Chemical Co., Ltd., polyvinyl acetal resin) is used. -980 (made by DIC Corporation, polyisocyanate curing agent) Otherwise, in the same manner as in Example 4 to obtain conductive thermosetting resin composition (Y-7) and having a thickness of 140μm conductive adhesive sheet (Z-7).
（実施例８）
ＮＩ−２５５（インコリミテッド社製のニッケル粉、５０％平均粒子径：２１μｍ、見かけ密度：０．６ｇ／ｃｍ３、針状）の使用量を２１７．３質量部から１６８質量部に変更し、かつ、ＤＡＰ−３１６Ｌ−ＨＴＤ（大同特殊鋼株式会社製、ステンレス粉、５０％平均粒子径：１０．７μｍ、タップ密度：４．１ｇ／ｃｍ３、丸み状）の使用量を９６．８質量部から７５．２質量部に変更すること以外は、実施例７と同様の方法で、導電性熱硬化性樹脂組成物（Ｙ−８）及び厚さ１４０μｍの導電性接着シート（Ｚ−８）を得た。
(Example 8)
The usage amount of NI-255 (nickel powder manufactured by Incori Ltd., 50% average particle size: 21 μm, apparent density: 0.6 g / cm 3 , needle shape) was changed from 217.3 parts by mass to 168 parts by mass, And the usage-amount of DAP-316L-HTD (The Daido Special Steel Co., Ltd. make, stainless steel powder, 50% average particle diameter: 10.7 micrometer, tap density: 4.1 g / cm < 3 >, round shape) is 96.8 mass parts. Except for changing to 75.2 parts by mass, a conductive thermosetting resin composition (Y-8) and a 140 μm thick conductive adhesive sheet (Z-8) were prepared in the same manner as in Example 7. Obtained.
（実施例９）
ＮＩ−２５５（インコリミテッド社製のニッケル粉、５０％平均粒子径：２１μｍ、見かけ密度：０．６ｇ／ｃｍ３、針状）の使用量を２１７．３質量部から２７１．３質量部に変更し、かつ、ＤＡＰ−３１６Ｌ−ＨＴＤ（大同特殊鋼株式会社製、ステンレス粉、５０％平均粒子径：１０．７μｍ、タップ密度：４．１ｇ／ｃｍ３、丸み状）の使用量を９６．８質量部から１２１．５質量部に変更すること以外は、実施例７と同様の方法で、導電性熱硬化性樹脂組成物（Ｙ−９）及び厚さ１４０μｍの導電性接着シート（Ｚ−９）を得た。
Example 9
The usage amount of NI-255 (Nickel powder manufactured by Incori Ltd., 50% average particle size: 21 μm, apparent density: 0.6 g / cm 3 , needle shape) was changed from 217.3 parts by mass to 271.3 parts by mass In addition, the amount used of DAP-316L-HTD (manufactured by Daido Steel Co., Ltd., stainless powder, 50% average particle size: 10.7 μm, tap density: 4.1 g / cm 3 , round shape) is 96.8. A conductive thermosetting resin composition (Y-9) and a 140 μm thick conductive adhesive sheet (Z-9) were prepared in the same manner as in Example 7 except that the amount was changed from 12 parts by mass to 121.5 parts by mass. )
（実施例１０）
ＮＩ−２５５（インコリミテッド社製のニッケル粉、５０％平均粒子径：２１μｍ、見かけ密度：０．６ｇ／ｃｍ３、針状）の使用量を２１７．３質量部から１６２質量部に変更し、かつ、ＤＡＰ−３１６Ｌ−ＨＴＤ（大同特殊鋼株式会社製、ステンレス粉、５０％平均粒子径：１０．７μｍ、タップ密度：４．１ｇ／ｃｍ３、丸み状）の使用量を９６．８質量部から１４５．１質量部に変更すること以外は、実施例７と同様の方法で、導電性熱硬化性樹脂組成物（Ｙ−１０）及び厚さ１４０μｍの導電性接着シート（Ｚ−１０）を得た。
(Example 10)
The usage amount of NI-255 (nickel powder manufactured by Incori Ltd., 50% average particle size: 21 μm, apparent density: 0.6 g / cm 3 , needle shape) was changed from 217.3 parts by mass to 162 parts by mass, And the usage-amount of DAP-316L-HTD (The Daido Special Steel Co., Ltd. make, stainless steel powder, 50% average particle diameter: 10.7 micrometer, tap density: 4.1 g / cm < 3 >, round shape) is 96.8 mass parts. Except for changing to 145.1 parts by mass, a conductive thermosetting resin composition (Y-10) and a conductive adhesive sheet (Z-10) having a thickness of 140 μm were prepared in the same manner as in Example 7. Obtained.
（実施例１１）
ＮＩ−２５５（インコリミテッド社製のニッケル粉、５０％平均粒子径：２１μｍ、見かけ密度：０．６ｇ／ｃｍ３、針状）の使用量を２１７．３質量部から２４３質量部に変更し、かつ、ＤＡＰ−３１６Ｌ−ＨＴＤ（大同特殊鋼株式会社製、ステンレス粉、５０％平均粒子径：１０．７μｍ、タップ密度：４．１ｇ／ｃｍ３、丸み状）の使用量を９６．８質量部から７２．５質量部に変更すること以外は、実施例７と同様の方法で、導電性熱硬化性樹脂組成物（Ｙ−１１）及び厚さ１４０μｍの導電性接着シート（Ｚ−１１）を得た。
(Example 11)
The usage amount of NI-255 (nickel powder manufactured by Incori Ltd., 50% average particle size: 21 μm, apparent density: 0.6 g / cm 3 , needle shape) was changed from 217.3 parts by mass to 243 parts by mass, And the usage-amount of DAP-316L-HTD (The Daido Special Steel Co., Ltd. make, stainless steel powder, 50% average particle diameter: 10.7 micrometer, tap density: 4.1 g / cm < 3 >, round shape) is 96.8 mass parts. Except for changing to 72.5 parts by mass, a conductive thermosetting resin composition (Y-11) and a conductive adhesive sheet (Z-11) having a thickness of 140 μm were prepared in the same manner as in Example 7. Obtained.
（実施例１２）
ＤＡＰ−３１６Ｌ−ＨＴＤ（大同特殊鋼株式会社製、ステンレス粉、５０％平均粒子径：１０．７μｍ、タップ密度：４．１ｇ／ｃｍ３、丸み状）の代わりにＮＩ―１２３（インコリミテッド社製のニッケル粉、５０％平均粒子径：１１．７μｍ、見かけ密度：２．５ｇ／ｃｍ３、丸み状）を８１質量部使用すること以外は、実施例１１と同様の方法で、導電性熱硬化性樹脂組成物（Ｙ−１２）及び厚さ１４０μｍの導電性接着シート（Ｚ−１２）を得た。
(Example 12)
Instead of DAP-316L-HTD (Daido Special Steel Co., Ltd., stainless powder, 50% average particle size: 10.7 μm, tap density: 4.1 g / cm 3 , round shape), NI-123 (manufactured by Incori Ltd.) Of nickel powder, 50% average particle diameter: 11.7 μm, apparent density: 2.5 g / cm 3 , round shape) is used in the same manner as in Example 11, except that 81 parts by mass is used. Conductive resin composition (Y-12) and a conductive adhesive sheet (Z-12) having a thickness of 140 μm were obtained.
（実施例１３）
ＤＡＰ−３１６Ｌ−ＨＴＤ（大同特殊鋼株式会社製、ステンレス粉、５０％平均粒子径：１０．７μｍ、タップ密度：４．１ｇ／ｃｍ３、丸み状）の代わりにＮＩ―１２３（インコリミテッド社製のニッケル粉、５０％平均粒子径：１１．７μｍ、見かけ密度：２．５ｇ／ｃｍ３、丸み状）を１０８質量部使用すること以外は、実施例７と同様の方法で、導電性熱硬化性樹脂組成物（Ｙ−１３）及び厚さ１４０μｍの導電性接着シート（Ｚ−１３）を得た。
(Example 13)
Instead of DAP-316L-HTD (Daido Special Steel Co., Ltd., stainless powder, 50% average particle size: 10.7 μm, tap density: 4.1 g / cm 3 , round shape), NI-123 (manufactured by Incori Ltd.) Of nickel powder, 50% average particle size: 11.7 μm, apparent density: 2.5 g / cm 3 , round shape) is used in the same manner as in Example 7, except that 108 parts by mass is used. Conductive resin composition (Y-13) and a conductive adhesive sheet (Z-13) having a thickness of 140 μm were obtained.
（実施例１４）
導電性接着シートの厚さを１４０μｍから１６０μｍに変更すること以外は、実施例７と同様の方法で、導電性接着シート（Ｚ−１４）を得た。
(Example 14)
A conductive adhesive sheet (Z-14) was obtained in the same manner as in Example 7 except that the thickness of the conductive adhesive sheet was changed from 140 μm to 160 μm.
（実施例１５）
導電性接着シートの厚さを１４０μｍから１１０μｍに変更すること以外は、実施例７と同様の方法で、導電性接着シート（Ｚ−１５）を得た。
(Example 15)
A conductive adhesive sheet (Z-15) was obtained in the same manner as in Example 7 except that the thickness of the conductive adhesive sheet was changed from 140 μm to 110 μm.
（実施例１６）
導電性接着シートの厚さを１４０μｍから９０μｍに変更すること以外は、実施例７と同様の方法で、導電性接着シート（Ｚ−１６）を得た。
(Example 16)
A conductive adhesive sheet (Z-16) was obtained in the same manner as in Example 7 except that the thickness of the conductive adhesive sheet was changed from 140 μm to 90 μm.
（実施例１７）
ＮＩ−２５５（インコリミテッド社製のニッケル粉、５０％平均粒子径：２１μｍ、見かけ密度：０．６ｇ／ｃｍ３、針状）の使用量を２１７．３質量部から２５９質量部に変更し、かつ、ＤＡＰ−３１６Ｌ−ＨＴＤ（大同特殊鋼株式会社製、ステンレス粉、５０％平均粒子径：１０．７μｍ、タップ密度：４．１ｇ／ｃｍ３、丸み状）の使用量を９６．８質量部から５８質量部に変更すること以外は、実施例７と同様の方法で、導電性熱硬化性樹脂組成物（Ｚ−１７）及び厚さ１４０μｍの導電性接着シート（Ｚ−１７）を得た。
(Example 17)
The amount of NI-255 (Nickel powder manufactured by Incori Ltd., 50% average particle size: 21 μm, apparent density: 0.6 g / cm 3 , needle shape) was changed from 217.3 parts by mass to 259 parts by mass, And the usage-amount of DAP-316L-HTD (The Daido Special Steel Co., Ltd. make, stainless steel powder, 50% average particle diameter: 10.7 micrometer, tap density: 4.1 g / cm < 3 >, round shape) is 96.8 mass parts. A conductive thermosetting resin composition (Z-17) and a conductive adhesive sheet (Z-17) having a thickness of 140 μm were obtained in the same manner as in Example 7 except that the content was changed from 58 to 58 parts by mass. .
（比較例１）
前記ＮＩ−２５５（インコリミテッド社製のニッケル粉）の使用量を２１７．３質量部から３２４質量部に変更し、ＤＡＰ−３１６Ｌ−ＨＴＤ（大同特殊鋼株式会社製、ステンレス粉）の使用量を９６．８質量部から０質量部に変更し、かつ、８５０−Ｓ（ＤＩＣ株式会社製、ビスフェノールＡ型エポキシ樹脂、エポキシ当量１８８ｇ／ｅｑ．）の代わりに８３０−Ｓ（ＤＩＣ株式会社製、ビスフェノールＦ型エポキシ樹脂、エポキシ当量１７０ｇ／ｅｑ．）を１０質量部使用したこと以外は、実施例１と同様の方法で、導電性熱硬化性樹脂組成物（Ｙ’−１）及び厚さ１４０μｍの導電性接着シート（Ｚ’−１）を得た。
(Comparative Example 1)
The amount of NI-255 (nickel powder manufactured by Incori Ltd.) was changed from 217.3 parts by mass to 324 parts by mass, and the amount of DAP-316L-HTD (manufactured by Daido Special Steel Co., Ltd., stainless powder) was changed. It is changed from 96.8 parts by mass to 0 parts by mass, and 830-S (manufactured by DIC Corporation, bisphenol instead of 850-S (DIC Corporation, bisphenol A type epoxy resin, epoxy equivalent 188 g / eq.) F-type epoxy resin, epoxy equivalent 170 g / eq.) 10 mass parts was used in the same manner as in Example 1, except that the conductive thermosetting resin composition (Y′-1) and the thickness of 140 μm were A conductive adhesive sheet (Z′-1) was obtained.
（比較例２）
前記ＮＩ−２５５（インコリミテッド社製のニッケル粉）の使用量を２１７．３質量部から０質量部に変更し、ＤＡＰ−３１６Ｌ−ＨＴＤ（大同特殊鋼株式会社製、ステンレス粉）の使用量を９６．８質量部から２９０．３質量部に変更し、かつ、８５０−Ｓ（ＤＩＣ株式会社製、ビスフェノールＡ型エポキシ樹脂、エポキシ当量１８８ｇ／ｅｑ．）の代わりに８３０−Ｓ（ＤＩＣ株式会社製、ビスフェノールＦ型エポキシ樹脂、エポキシ当量１７０ｇ／ｅｑ．）を１０質量部使用したこと以外は、実施例１と同様の方法で、導電性熱硬化性樹脂組成物（Ｙ’−２）及び厚さ１４０μｍの導電性接着シート（Ｚ’−２）を得た。
(Comparative Example 2)
The amount of NI-255 (nickel powder manufactured by Incori Ltd.) was changed from 217.3 parts by mass to 0 parts by mass, and the amount of DAP-316L-HTD (manufactured by Daido Special Steel Co., Ltd., stainless powder) was changed. It changed from 96.8 mass parts to 290.3 mass parts, and 830-S (made by DIC Corporation) instead of 850-S (DIC Corporation make, bisphenol A type epoxy resin, epoxy equivalent 188 g / eq.) , Bisphenol F type epoxy resin, epoxy equivalent 170 g / eq.), Except that 10 parts by mass was used, and the same method as in Example 1, conductive thermosetting resin composition (Y′-2) and thickness A 140 μm conductive adhesive sheet (Z′-2) was obtained.
（比較例３）
前記ＮＩ−２５５（インコリミテッド社製のニッケル粉）の使用量を１６２質量部から１９０質量部に変更し、ＤＡＰ−３１６Ｌ−ＨＴＤ（大同特殊鋼株式会社製、ステンレス粉）の使用量を１４５質量部から０質量部に変更し、かつ、ＪＥＲ−１２５６（三菱化学株式会社製、ビスフェノールＡ型エポキシ樹脂）のメチルエチルケトン溶液（固形分３０質量％）の使用量を１６６．７質量部から２００質量部に変更し、ＴＳＲ−４００（ＤＩＣ株式会社製、イソシアネート変性ビスフェノールＡ型エポキシ樹脂、エポキシ当量３４３ｇ／ｅｑ．）のメチルエチルケトン溶液（固形分８０質量％）を５０質量部から３７．５質量部に変更したこと以外は、実施例６と同様の方法で、導電性熱硬化性樹脂組成物（Ｙ’−３）及び厚さ１４０μｍの導電性接着シート（Ｚ’−３）を得た。
(Comparative Example 3)
The amount of NI-255 (nickel powder manufactured by Incori Ltd.) was changed from 162 parts by mass to 190 parts by mass, and the amount of DAP-316L-HTD (Daido Special Steel Co., Ltd., stainless powder) was changed to 145 masses. The amount of the methyl ethyl ketone solution (solid content 30% by mass) of JER-1256 (Mitsubishi Chemical Co., Ltd., bisphenol A type epoxy resin) is changed from 166.7 parts by mass to 200 parts by mass. The methyl ethyl ketone solution (solid content 80% by mass) of TSR-400 (manufactured by DIC Corporation, manufactured by DIC Corporation, isocyanate-modified bisphenol A type epoxy resin, epoxy equivalent 343 g / eq.) Was changed from 50 parts by mass to 37.5 parts by mass. Except for the above, in the same manner as in Example 6, the conductive thermosetting resin composition (Y′-3) and the thickness of 140 μm It was obtained conductive adhesive sheet (Z'-3).
（比較例４）
前記ＮＩ−２５５（インコリミテッド社製のニッケル粉）の使用量を１６２質量部から１０８質量部に変更し、ＤＡＰ−３１６Ｌ−ＨＴＤ（大同特殊鋼株式会社製、ステンレス粉）の使用量を１４５質量部から１９３．５質量部に変更したこと以外は、実施例６と同様の方法で、導電性熱硬化性樹脂組成物（Ｙ’−４）及び厚さ１４０μｍの導電性接着シート（Ｚ’−４）を得た。
(Comparative Example 4)
The amount of NI-255 (nickel powder manufactured by Incori Ltd.) was changed from 162 parts by mass to 108 parts by mass, and the amount of DAP-316L-HTD (Daido Special Steel Co., Ltd., stainless powder) was changed to 145 masses. The conductive thermosetting resin composition (Y′-4) and the conductive adhesive sheet (Z′−) having a thickness of 140 μm were the same as in Example 6 except that the amount was changed from 19 parts to 193.5 parts by mass. 4) was obtained.
（比較例５）
ＮＩ−２５５（インコリミテッド社製のニッケル粉、５０％平均粒子径：２１μｍ、見かけ密度：０．６ｇ／ｃｍ３、針状）の代わりにＮＩ―１２３（インコリミテッド社製のニッケル粉、５０％平均粒子径：１１．７μｍ、見かけ密度：２．５ｇ／ｃｍ３、丸み状）を２１７．３質量部使用すること以外は、実施例７と同様の方法で、導電性熱硬化性樹脂組成物（Ｙ’−５）及び厚さ１４０μｍの導電性接着シート（Ｚ’−５）を得た。
(Comparative Example 5)
Instead of NI-255 (Nickel powder manufactured by Incori Ltd., 50% average particle size: 21 μm, apparent density: 0.6 g / cm 3 , needle shape), NI-123 (Nickel powder manufactured by Incori Ltd., 50%) The conductive thermosetting resin composition was the same as in Example 7 except that 217.3 parts by mass of average particle diameter: 11.7 μm, apparent density: 2.5 g / cm 3 , rounded) was used. A conductive adhesive sheet (Z′-5) having a thickness of (Y′-5) and 140 μm was obtained.
（比較例６）
ＮＩ―１２３（大同特殊鋼株式会社製、ステンレス粉、５０％平均粒子径：１０．７μｍ、タップ密度：４．１ｇ／ｃｍ３、丸み状）の使用量を２１７．３質量部から３３７質量部に変更し、ＤＡＰ−３１６Ｌ−ＨＴＤ（大同特殊鋼株式会社製、ステンレス粉、５０％平均粒子径：１０．７μｍ、タップ密度：４．１ｇ／ｃｍ３、丸み状）の使用量を９６．８質量部から１４９質量部に変更すること以外は、比較例５と同様の方法で、導電性熱硬化性樹脂組成物（Ｙ’−６）及び厚さ１４０μｍの導電性接着シート（Ｚ’−６）を得た。
(Comparative Example 6)
The amount of NI-123 (manufactured by Daido Steel Co., Ltd., stainless powder, 50% average particle size: 10.7 μm, tap density: 4.1 g / cm 3 , rounded) is used from 217.3 parts by mass to 337 parts by mass. The amount of DAP-316L-HTD (manufactured by Daido Steel Co., Ltd., stainless powder, 50% average particle size: 10.7 μm, tap density: 4.1 g / cm 3 , rounded) is used as 96.8. A conductive thermosetting resin composition (Y′-6) and a conductive adhesive sheet having a thickness of 140 μm (Z′-6) are the same as in Comparative Example 5 except that the weight is changed to 149 parts by mass. )
（比較例７）
ＮＩ―１２３（インコリミテッド社製のニッケル粉、５０％平均粒子径：１１．７μｍ、見かけ密度：２．５ｇ／ｃｍ３、丸み状）の使用量を２１７．３質量部から５０６質量部に変更し、ＤＡＰ−３１６Ｌ−ＨＴＤ（大同特殊鋼株式会社製、ステンレス粉、５０％平均粒子径：１０．７μｍ、タップ密度：４．１ｇ／ｃｍ３、丸み状）の使用量を９６．８質量部から２２３質量部に変更すること以外は、比較例５と同様の方法で、導電性熱硬化性樹脂組成物（Ｙ’−７）及び厚さ１４０μｍの導電性接着シート（Ｚ’−７）を得た。
(Comparative Example 7)
Changed the amount of NI-123 (nickel powder manufactured by Incori Ltd., 50% average particle size: 11.7 μm, apparent density: 2.5 g / cm 3 , rounded) from 217.3 parts by mass to 506 parts by mass And 96.8 parts by mass of DAP-316L-HTD (manufactured by Daido Steel Co., Ltd., stainless powder, 50% average particle size: 10.7 μm, tap density: 4.1 g / cm 3 , round shape). Except for changing to 223 parts by mass, the conductive thermosetting resin composition (Y′-7) and the conductive adhesive sheet (Z′-7) having a thickness of 140 μm were prepared in the same manner as in Comparative Example 5. Obtained.
（比較例８）
ＮＩ−２５５（インコリミテッド社製のニッケル粉、５０％平均粒子径：２１μｍ、見かけ密度：０．６ｇ／ｃｍ３、針状）の使用量を２１７．３質量部から１０８．７質量部に変更し、かつ、ＮＩ―１２３（インコリミテッド社製のニッケル粉、５０％平均粒子径：１１．７μｍ、見かけ密度：２．５ｇ／ｃｍ３、丸み状）を１０８．７質量部使用すること以外は、実施例７と同様の方法で、導電性熱硬化性樹脂組成物（Ｙ’−８）及び厚さ１４０μｍの導電性接着シート（Ｚ’−８）を得た。
(Comparative Example 8)
The amount of NI-255 (Nickel powder manufactured by Incori Ltd., 50% average particle size: 21 μm, apparent density: 0.6 g / cm 3 , needle shape) was changed from 217.3 parts by mass to 108.7 parts by mass And NI-123 (nickel powder manufactured by Incori Ltd., 50% average particle size: 11.7 μm, apparent density: 2.5 g / cm 3 , round shape) is used except 108.7 parts by mass. In the same manner as in Example 7, a conductive thermosetting resin composition (Y′-8) and a conductive adhesive sheet (Z′-8) having a thickness of 140 μm were obtained.
［導電性接着シートの熱硬化後の厚さの測定方法］
離型ライナーを除去した導電性接着シートを、幅１０ｍｍ×長さ１００ｍｍの大きさに裁断したものを試験片１とした。
[Measurement method of thickness after heat curing of conductive adhesive sheet]
The test piece 1 was obtained by cutting the conductive adhesive sheet from which the release liner had been removed into a size of 10 mm width × 100 mm length.
次に、前記試験片１を厚さ０．１ｍｍの２枚のＮＩＴＦＬＯＮ（日東電工株式会社製、ＰＴＦＥフィルム）の間に挟み、熱プレス装置を用い２ＭＰａで加圧した状態で、１６５℃で６０分加熱硬化させることによって試験片２（熱硬化後）を得た。 Next, the test piece 1 was sandwiched between two NITFLONs (manufactured by Nitto Denko Corporation, PTFE film) having a thickness of 0.1 mm, and was pressed at 165 ° C. with a pressure of 2 MPa using a hot press device. Test piece 2 (after thermosetting) was obtained by heat-curing for minutes.
前記試験片２（熱硬化後）の厚さをテスター産業株式会社製厚さ計「ＴＨ−１０２」を用いて測定した。 The thickness of the test piece 2 (after thermosetting) was measured using a thickness meter “TH-102” manufactured by Tester Sangyo Co., Ltd.
［２５℃における引っ張り弾性率（ｘ１）及び引っ張り弾性率（ｘ２）の測定方法］
前記試験片１（硬化前）の２５℃における引っ張り弾性率（ｘ１）を、テンシロン引張り試験機を用いて引張り速度２０mm／分の条件の下測定した。
[Measurement Method of Tensile Elastic Modulus (x1) and Tensile Elastic Modulus (x2) at 25 ° C.]
The tensile modulus (x1) at 25 ° C. of the test piece 1 (before curing) was measured using a Tensilon tensile tester under the condition of a tensile speed of 20 mm / min.
前記試験片２（熱硬化後）の２５℃における引っ張り弾性率（ｘ２）を、テンシロン引張り試験機を用いて引張り速度２０mm／分の条件の下測定した。 The tensile modulus (x2) at 25 ° C. of the test piece 2 (after thermosetting) was measured using a Tensilon tensile tester under the condition of a tensile speed of 20 mm / min.
［接着剤フロー量］
厚さ２５μｍのポリイミドフィルム（東レ・デュポン株式会社製、商品名：カプトン１００Ｈ）と、厚さ３５μｍの銅箔（艶面）の間に、直径６ｍｍのパンチ穴を３箇所空けた前記導電性接着シートを挟みこんだものを、温度１６５℃及び圧力２ＭＰａで６０分間プレスした。
[Adhesive flow rate]
Conductive adhesion in which 3 punch holes with a diameter of 6 mm are formed between a polyimide film with a thickness of 25 μm (manufactured by Toray DuPont, trade name: Kapton 100H) and a copper foil with a thickness of 35 μm (glossy surface). The sandwiched sheet was pressed at a temperature of 165 ° C. and a pressure of 2 MPa for 60 minutes.
前記プレス後、光学顕微鏡を用いて、前記パンチ穴の内部への接着剤の最大浸出距離をパンチ穴毎に測定し、その平均距離を「接着剤フロー量[ｍｍ]」とした。 After the pressing, the maximum leaching distance of the adhesive into the punch hole was measured for each punch hole using an optical microscope, and the average distance was defined as “adhesive flow amount [mm]”.
［体積抵抗率の測定方法］
上記試験片２（熱硬化後）と同一のものを用意し、それを５０×８０ｍｍの大きさに裁断して得た試験片３の体積抵抗率を、抵抗率計（三菱化学株式会社製「Ｌｏｒｅｓｔａ−ＧＰ ＭＣＰ−Ｔ６００」）を用い四探針法で測定した。
[Measurement method of volume resistivity]
Prepare the same test piece 2 (after thermosetting), and cut the volume resistivity of the test piece 3 into a size of 50 × 80 mm. Loresta-GP MCP-T600 ") and measured by the four-probe method.
［接着性の評価方法］
実施例及び比較例で得た導電性接着シートを幅２０ｍｍ×長さ１００ｍｍの大きさに裁断したものを試験片３とした。
[Adhesion evaluation method]
A test piece 3 was obtained by cutting the conductive adhesive sheets obtained in Examples and Comparative Examples into a size of 20 mm wide × 100 mm long.
厚さ１．５ｍｍのアルミニウム板と、厚み３５μｍの電解銅箔との間に前記試験片３を挟み、熱プレス機で１ＭＰａの圧力を維持しながら１８０℃で１０分熱接着し、その後１８０℃環境下に５０分静置し試験片３を熱硬化することで、前記試験片３によってアルミニウム板と電解銅箔とが接着された銅箔貼り積層体を作製した。 The test piece 3 was sandwiched between an aluminum plate having a thickness of 1.5 mm and an electrolytic copper foil having a thickness of 35 μm, and thermally bonded at 180 ° C. for 10 minutes while maintaining a pressure of 1 MPa with a hot press machine, and then 180 ° C. The test piece 3 was allowed to stand in the environment for 50 minutes and the test piece 3 was heat-cured, whereby a copper foil-clad laminate in which the aluminum plate and the electrolytic copper foil were bonded by the test piece 3 was produced.
前記銅箔貼り積層板を２３℃×５０％ＲＨ雰囲気下に１時間静置後、同環境下で、その１８０°方向へ剥離した際の接着強度（剥離速度５０ｍｍ／分）を測定した。 The copper foil-clad laminate was allowed to stand in a 23 ° C. × 50% RH atmosphere for 1 hour, and the adhesive strength (peeling speed 50 mm / min) when peeled in the 180 ° direction was measured in the same environment.
ここで、前記引っ張り弾性率（ｘ２）は、前記熱硬化性材料を１６５℃で１２０分加熱して得られた熱硬化物の２５℃における引っ張り弾性率を指す。
Here, the tensile elastic modulus (x2) refers to the tensile elastic modulus at 25 ° C. of a thermoset obtained by heating the thermosetting material at 165 ° C. for 120 minutes.
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