JP6451451B2 - Manufacturing method of conductive sheet - Google Patents
Manufacturing method of conductive sheet Download PDFInfo
- Publication number
- JP6451451B2 JP6451451B2 JP2015069225A JP2015069225A JP6451451B2 JP 6451451 B2 JP6451451 B2 JP 6451451B2 JP 2015069225 A JP2015069225 A JP 2015069225A JP 2015069225 A JP2015069225 A JP 2015069225A JP 6451451 B2 JP6451451 B2 JP 6451451B2
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- JP
- Japan
- Prior art keywords
- conductive
- sheet
- conductive sheet
- resin
- manufacturing
- 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.)
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- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- Manufacture Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Cooling Or The Like Of Electrical Apparatus (AREA)
- Cooling Or The Like Of Semiconductors Or Solid State Devices (AREA)
Description
本発明は、電子機器の熱や帯電した静電気を逃がすためなどの伝導性シートとその製造方法、伝導性接着シート及び発熱部材と伝導性シートの積層体に関する。 The present invention relates to a conductive sheet for releasing heat and charged static electricity of an electronic device, a manufacturing method thereof, a conductive adhesive sheet, and a laminate of a heat generating member and a conductive sheet.
近年、エレクトロニクス分野の発展が目覚しく、特に電子機器の小型化、軽量化、高密度化、高出力化が進み、これらの性能に対する要求がますます高度なものとなっている。電子回路の小型化、高密度化のために高絶縁性や信頼性が求められるほか、特に、電子機器の高出力化に伴う発熱による電子機器の劣化防止のための放熱性向上が強く求められている。 In recent years, the development of the electronics field has been remarkable, and in particular, electronic devices have become smaller, lighter, higher density, and higher in output, and demands for these performances have become increasingly sophisticated. High insulation and reliability are required to reduce the size and density of electronic circuits, and in particular, there is a strong need to improve heat dissipation to prevent deterioration of electronic devices due to heat generated by higher output of electronic devices. ing.
エレクトロニクス分野では絶縁材として高分子材料が好適に用いられており、放熱性を向上させるため、高分子材料の熱伝導性の向上が望まれるようになった。しかし、高分子材料の熱伝導性向上には限界があったため、熱伝導性粒子を高分子材料に混合し、放熱性を向上させる方法が開発された。また、近年は、熱伝導性部材として、それらをシート状に成形した熱伝導性を有する接着シートや、粘着シートとしての利用も検討されている。 In the electronics field, a polymer material is suitably used as an insulating material, and in order to improve heat dissipation, it has been desired to improve the thermal conductivity of the polymer material. However, since there is a limit to improving the thermal conductivity of the polymer material, a method has been developed to improve heat dissipation by mixing thermally conductive particles with the polymer material. In recent years, the use as a heat conductive adhesive sheet obtained by molding them into a sheet shape or a pressure sensitive adhesive sheet has been studied.
熱伝導性粒子を使用した熱伝導性部材として、例えば、特許文献１や２には無機粒子を使用した熱伝導性接着シートが開示されている。これら熱伝導性部材の熱伝導性を高めるためには、粒子の充填率を上げることが効果的であるが、粒子量の増加に伴い、高分子材料成分が減少するため、成膜性、基材追従性の低下が起こってしまう。また、特に接着シート用途においては、充填率を高めることにより接着成分が減少し、接着性が失われてしまうといった課題があった。 As a heat conductive member using heat conductive particles, for example, Patent Documents 1 and 2 disclose heat conductive adhesive sheets using inorganic particles. In order to increase the thermal conductivity of these thermally conductive members, it is effective to increase the packing rate of the particles. However, as the amount of particles increases, the polymer material component decreases. Decrease in material followability occurs. Moreover, especially in the adhesive sheet use, there existed a subject that an adhesive component will reduce by raising a filling rate, and adhesiveness will be lost.
そこで、特許文献３や４のように、粒子の充填率が低い状態で粒子の接触（熱伝パス）を形成させるため、熱伝導性部材に磁場や電場をかけて粒子の配向制御する方法が報告されている。しかし、これらの手法は、工業化を考えたときに実用的なものではない。 Therefore, as in Patent Documents 3 and 4, there is a method for controlling the orientation of particles by applying a magnetic field or an electric field to a heat conductive member in order to form contact (heat transfer path) of particles with a low particle filling rate. It has been reported. However, these methods are not practical when considering industrialization.
また、特許文献５や６では、シート厚み方向の熱伝導性を向上させた熱伝導性シートとして、マトリックス樹脂中に鱗片状窒化ホウ素の二次凝集粒子を含む熱伝導性シートが提案されている。しかしこれらの手法は、熱伝導性シート中の鱗片状窒化ホウ素をランダムに配向させているに過ぎず、熱伝導物質の長径方向がシート厚み方向へ十分に配向できていない。 Patent Documents 5 and 6 propose a thermally conductive sheet containing secondary aggregated particles of flaky boron nitride in a matrix resin as a thermally conductive sheet with improved thermal conductivity in the sheet thickness direction. . However, these methods merely align the scaly boron nitride in the heat conductive sheet at random, and the major axis direction of the heat conductive material cannot be sufficiently aligned in the sheet thickness direction.
すなわち、凝集粒子の配向度が熱伝導シート中における配向度の限界となっており、シート厚み方向の熱伝導性が十分に向上しないため、放熱特性に優れた熱伝導シートが得られないという問題がある。
また、特許文献５及び６に記載の熱伝導性シートを得るための二次凝集窒化ホウ素粒子を得るためには、噴霧乾燥、撹拌乾燥、静置乾燥等の公知の方法によって製造する必要があり、生産工程が増加するという問題がある。
That is, the degree of orientation of the aggregated particles is the limit of the degree of orientation in the heat conductive sheet, and the heat conductivity in the sheet thickness direction is not sufficiently improved, so that a heat conductive sheet with excellent heat dissipation characteristics cannot be obtained. There is.
Moreover, in order to obtain the secondary agglomerated boron nitride particles for obtaining the thermally conductive sheet described in Patent Documents 5 and 6, it is necessary to produce the particles by a known method such as spray drying, stirring drying, or stationary drying. There is a problem that the production process increases.
また、特許文献７では、パワーデバイスにおいて、熱伝導性シートと接する面に所定の大きさの凹凸を設けることで、熱伝導シートをパワーモジュールに組み込んだ際に、部材との界面付近において熱伝導性シート中の鱗片状窒化ホウ素を厚み方向に配向させたパワーモジュールが提案されている。しかしこの手法では、パワーモジュールの熱伝導性シートに接する部材に凹凸面を設ける必要があり、シートとしての汎用性が不足しているという問題がある。 Also, in Patent Document 7, in a power device, by providing irregularities of a predetermined size on the surface in contact with the heat conductive sheet, heat conduction is performed near the interface with the member when the heat conductive sheet is incorporated into the power module. A power module in which scaly boron nitride in a conductive sheet is oriented in the thickness direction has been proposed. However, in this method, it is necessary to provide an uneven surface on the member that contacts the heat conductive sheet of the power module, and there is a problem that versatility as a sheet is insufficient.
このように、従来の手法では、高い熱伝導性を有する熱伝導性樹脂組成物や熱伝導性シートを作製することが困難であった。 As described above, it has been difficult to produce a thermally conductive resin composition or a thermally conductive sheet having high thermal conductivity by the conventional technique.
本発明の目的は、所定のアスペクト比を有する伝導性物質を含む伝導性シート表面に、凸部を有する部材を接触させることで伝導性シート表面に凹凸を形成させ、シート厚み方向の熱伝導性を向上させた伝導性シートの製造方法を提案することである。
An object of the present invention is to form irregularities on the surface of a conductive sheet by bringing a member having a convex portion into contact with the surface of the conductive sheet containing a conductive material having a predetermined aspect ratio, and thereby conducting thermal conductivity in the sheet thickness direction. It is to propose a method for producing a conductive sheet with improved resistance.
すなわち、本発明は、バインダーと、平均アスペクト比が１０〜１０００の伝導性物質とを含んでなる凹部を有する伝導性シートの製造方法であって、
前記凹部の十点平均粗さＲｚＪＩＳが、前記伝導性物質の平均長径の１／３以上且つ前記伝導性シートの厚みの１／２以下である伝導性シートの製造方法であって、
バインダーと、平均アスペクト比が１０〜１０００の伝導性物質とを含んでなる伝導性シート原反の片面もしくは両面を、凸部を有する部材に接触させる接触工程と、
前記凸部を有する部材と前記伝導性シート原反と剥離させる剥離工程を含むことを特徴とする伝導性シートの製造方法に関する。
That is, the present invention is a method for producing a conductive sheet having a concave portion comprising a binder and a conductive material having an average aspect ratio of 10 to 1000,
The ten-point average roughness RzJIS of the concave portion is a method for producing a conductive sheet that is 1/3 or more of the average major axis of the conductive material and 1/2 or less of the thickness of the conductive sheet,
A contact step in which one side or both sides of a conductive sheet original fabric comprising a binder and a conductive material having an average aspect ratio of 10 to 1000 are brought into contact with a member having a convex portion;
It is related with the manufacturing method of the conductive sheet characterized by including the peeling process made to peel from the member which has the said convex part, and the said conductive sheet original fabric.
また、本発明は、伝導性物質が、熱伝導性物質である上記伝導性シートの製造方法に関する。 Moreover, this invention relates to the manufacturing method of the said conductive sheet whose conductive substance is a heat conductive substance.
また、本発明は、さらに、剥離工程に、伝導性シートの凹部を充填材料で充填すること充填工程を含む、上記伝導性シートの製造方法に関する。 Moreover, this invention relates to the manufacturing method of the said conductive sheet further including the filling process which fills the recessed part of a conductive sheet with a filling material in a peeling process.
また、本発明は、請上記伝導性シートを加圧加熱してなる、伝導性接着シートに関する。 The present invention also relates to a conductive adhesive sheet obtained by pressurizing and heating the conductive sheet.
また、本発明は、伝導性物質が、窒化ホウ素であり、
伝導性接着シートの厚み方向にＸ線を照射して得られるＸ線回折図において、窒化ホウ素の配向度（＜１００＞面と＜００２＞面の回折ピークの強度比（Ｉ＜１００＞／Ｉ＜００２＞）が０．０１５以上であることを特徴とする上記伝導性接着シートに関する。
In the present invention, the conductive substance is boron nitride,
In the X-ray diffraction diagram obtained by irradiating X-rays in the thickness direction of the conductive adhesive sheet, the degree of orientation of boron nitride (ratio of diffraction peaks between <100> plane and <002> plane (I <100> / I <002>) is 0.015 or more.
また、本発明は、伝導性物質が、アルミナであり、
伝導性接着シートの厚み方向にＸ線を照射して得られるＸ線回折図において、アルミナの配向度（＜１１０＞面と＜００６＞面の回折ピーク強度比（Ｉ＜１１０＞／Ｉ＜００６＞）が５以上であることを特徴とする上記伝導性接着シートに関する。
In the present invention, the conductive substance is alumina.
In the X-ray diffraction diagram obtained by irradiating X-rays in the thickness direction of the conductive adhesive sheet, the degree of orientation of alumina (diffraction peak intensity ratio between <110> plane and <006> plane (I <110> / I <006) >) Is 5 or more. The present invention relates to the above conductive adhesive sheet.
また、本発明は、上記伝導性シートと、発熱部材と積層してなる積層体に関する。 Moreover, this invention relates to the laminated body formed by laminating | stacking the said electroconductive sheet and a heat generating member.
また、本発明は、発熱部材が、電子部品である上記積層体に関する。 Moreover, this invention relates to the said laminated body whose heat generating member is an electronic component.
本発明の凹部を有する伝導性シートは、あらかじめ伝導性シートの表面に凹凸を形成することにより、所定のアスペクト比を有する伝導性物質を、シート厚み方向に配向させることで、伝導性を向上させることができ、加圧加熱して積層体を得る際にもその配向が低下しない放熱特性に優れた伝導性シートの製造方法及び伝導性接着シートを提供することができる。
The conductive sheet having a recess according to the present invention improves conductivity by orienting a conductive material having a predetermined aspect ratio in the sheet thickness direction by forming irregularities on the surface of the conductive sheet in advance. It is possible to provide a method for producing a conductive sheet and a conductive adhesive sheet excellent in heat dissipation characteristics that do not decrease the orientation even when a laminate is obtained by heating under pressure.
＜実施の工程１(接触工程）、２（剥離工程）＞
＜凸部を有する部材に接触させる接触工程と、前記凸部を有する部材と前記伝導性シート原反と剥離させる剥離工程を含むことを特徴とする伝導性シートの製造方法＞
本発明に用いられる凹部を有する伝導性シートの製造方法について説明する。前記伝導性物質の平均長径の１／３以上且つ前記伝導シートの厚みの１／２以下の十点平均粗さＲｚＪＩＳを有する凹部が前記伝導シート片面もしくは両面に形成されればよく、凹部を形成させる方法については限定しない。
<Implementation process 1 (contact process), 2 (peeling process)>
<The manufacturing method of the conductive sheet characterized by including the contact process made to contact the member which has a convex part, and the peeling process made to peel the member which has the said convex part, and the said conductive sheet original fabric>
The manufacturing method of the conductive sheet which has a recessed part used for this invention is demonstrated. A recess having a ten-point average roughness RzJIS that is not less than 1/3 of the average major axis of the conductive material and not more than 1/2 of the thickness of the conductive sheet may be formed on one or both sides of the conductive sheet. There is no limitation on the method.
凹部を形成させる方法として、例えば、伝導シートの片面もしくは両面に、凸部を有するシート状の部材を貼り合せ、プレス機により圧力をかけ、その後、シート状部材を剥離する方法が挙げられる。
また、プレス機は、２つのロールで圧力をかけるものであってもよく、この場合、凸部を有するシート状の部材の代わりに、凸部を有するロールを用いても良い。
凸部を有するロールを用いた場合、もう一方のロールが、平滑な面を有するロール（例えば、金属ロール）である場合は、表面は凹部を有し、裏面は平滑な伝導シートを得ることができる。また、もう一方のロール面が、変形可能なロール（例えば、ゴムロール）である場合、表面に凹部が形成されると同時に裏面に凸部を有する伝導シートを得ることもできる。
２つのロールがそれぞれ、凸部を有するロールであってもよい。より好ましいのは、表面と裏面の凹部の位置を合わせた加工であり、同じ賦型の２つのロールの位置を合わすことで、そのロール間にある伝導シートの両面の凹部の位置を合わせた加工が可能である。
また、片面に凹部を形成させた伝導シートを、凹部が表面にくるように、２枚以上積層させる方法によって作製してもよい。
As a method for forming the concave portion, for example, there is a method in which a sheet-like member having a convex portion is bonded to one side or both sides of a conductive sheet, pressure is applied by a press, and then the sheet-like member is peeled off.
Moreover, a press machine may apply a pressure with two rolls, In this case, you may use the roll which has a convex part instead of the sheet-like member which has a convex part.
When a roll having a convex portion is used, when the other roll is a roll having a smooth surface (for example, a metal roll), the surface has a concave portion and the back surface can obtain a smooth conductive sheet. it can. Moreover, when the other roll surface is a deformable roll (for example, rubber roll), a conductive sheet having a convex portion on the back surface can be obtained at the same time as a concave portion is formed on the front surface.
Each of the two rolls may be a roll having a convex portion. More preferably, processing is performed by aligning the positions of the concave portions on the front surface and the back surface, and by aligning the positions of two rolls of the same shaping, the processing is performed by aligning the concave portions on both sides of the conductive sheet between the rolls. Is possible.
Moreover, you may produce the conductive sheet which formed the recessed part in one side by the method of laminating | stacking 2 or more sheets so that a recessed part may come to the surface.
本発明における「十点平均粗さＲｚＪＩＳ」とは、ＪＩＳ表面粗さ（Ｂ０６０１：２０１３）により定義される。
この十点平均粗さＲｚＪＩＳは、断面曲線から基準長さだけ抜き取った部分において、最高から５番目までの山頂の標高の平均値と、最深から５番目までの谷底の標高の平均値との差であり、以下の式によって表される。
Ｒｚ＝（（Ｒ１＋Ｒ３＋Ｒ５＋Ｒ７＋Ｒ９）−（Ｒ２＋Ｒ４＋Ｒ６＋Ｒ８＋Ｒ１０）／５
上記式中、Ｒ１＋Ｒ３＋Ｒ５＋Ｒ７＋Ｒ９は、最高から５番目までの山頂の標高を意味し、Ｒ２＋Ｒ４＋Ｒ６＋Ｒ８＋Ｒ１０は、最深から５番目までの谷底の標高を意味する。
凹部の十点平均粗さＲｚＪＩＳが、前記伝導性物質の平均長径の１／３未満であると、伝導性シートと発熱部材とを積層してなる積層体を形成した際に、伝導性物質の配向制御効果が十分に得られない。
The “ten-point average roughness RzJIS” in the present invention is defined by JIS surface roughness (B0601: 2013).
This 10-point average roughness RzJIS is the difference between the average value of the highest altitude at the top of the peak from the fifth to the average value of the altitude at the bottom of the valley from the deepest to the fifth in the part extracted by the reference length from the cross-sectional curve. And is represented by the following equation.
Rz = ((R1 + R3 + R5 + R7 + R9) − (R2 + R4 + R6 + R8 + R10) / 5
In the above formula, R1 + R3 + R5 + R7 + R9 means the altitude of the top from the highest to the fifth, and R2 + R4 + R6 + R8 + R10 means the altitude of the bottom from the deepest to the fifth.
When the ten-point average roughness RzJIS of the concave portion is less than 1/3 of the average major axis of the conductive material, the conductive material and the heat-generating member are laminated to form a laminate. A sufficient orientation control effect cannot be obtained.
また、凹部の十点平均粗さＲｚＪＩＳが、伝導性シートの厚みの１／２を超えると、伝導性シートの電気絶縁性が低下してしまう。 On the other hand, if the ten-point average roughness RzJIS of the recess exceeds 1/2 of the thickness of the conductive sheet, the electrical insulation of the conductive sheet will be reduced.
＜伝導性シートの製造方法＞
伝導性シートは、基材上に溶剤を含有する伝導性樹脂組成物を塗工・乾燥し、形成できる。なお、伝導性シートは伝導性フィルムと称されることもある。
塗工方法としては、特に限定されず、公知の手法を用いることができ、例えば、ナイフコート、ダイコート、リップコート、ロールコート、カーテンコート、バーコート、グラビアコート、フレキソコート、ディップコート、スプレーコート、スピンコート等が挙げられる。
<Method for producing conductive sheet>
The conductive sheet can be formed by coating and drying a conductive resin composition containing a solvent on a substrate. In addition, a conductive sheet may be called a conductive film.
The coating method is not particularly limited, and a known method can be used. For example, knife coating, die coating, lip coating, roll coating, curtain coating, bar coating, gravure coating, flexo coating, dip coating, spray coating , Spin coating and the like.
基材は、例えば、ポリエステルフィルム、ポリエチレンフィルム、ポリプロピレンフィルム、ポリイミドフィルム等のプラスチックフィルムに離型処理したフィルム（以下、剥離フィルムという）等を使用することができる。 As the substrate, for example, a film obtained by releasing a plastic film such as a polyester film, a polyethylene film, a polypropylene film, or a polyimide film (hereinafter referred to as a release film) can be used.
シートの厚さは、用途に応じて適宜決定しうるが、接着シートや粘着シート等のように、発熱部材と放熱部材の間に存在し、熱を逃がすために用いられるような場合には、熱伝導性や種々の物性の観点より、通常１０〜２００μｍ、好ましくは３０〜１５０μｍとするのが良い。また、筺体のように発熱部材からの熱がこもらないようなパッケージとして用いられるような場合には、強度等を鑑みて２００μｍ以上、場合によっては１ｍｍ程度の厚さとすることもできる。 The thickness of the sheet can be appropriately determined according to the use, but it exists between the heat generating member and the heat radiating member, such as an adhesive sheet or an adhesive sheet, and is used to release heat, From the viewpoint of thermal conductivity and various physical properties, the thickness is usually 10 to 200 μm, preferably 30 to 150 μm. Further, when used as a package that does not collect heat from the heat generating member, such as a housing, the thickness may be about 200 μm or more, and in some cases about 1 mm in view of strength and the like.
＜伝導性樹脂組成物の製造方法＞
伝導性樹脂組成物は、伝導性物質と、バインダー樹脂と、必要に応じて溶剤とを撹拌混合することで製造することが好ましい。撹拌混合には一般的な撹拌方法を用いることができ、例えば、ディスパー、スキャンデックス、ペイントコンディショナー、サンドミル、らいかい機、メディアレス分散機、三本ロール、ビーズミル等が挙げられ、これらを組み合わせて行うことができる。
撹拌混合後は、伝導性樹脂組成物から気泡を除去するために、脱泡工程を経ることが好ましい。脱泡の方法については特に限定されず、一般的な手法を用いて行うことができるが、例えば、真空脱泡、超音波脱泡等が挙げられる。
<Method for producing conductive resin composition>
The conductive resin composition is preferably produced by stirring and mixing a conductive substance, a binder resin, and, if necessary, a solvent. Common stirring methods can be used for stirring and mixing, for example, disperse, scandex, paint conditioner, sand mill, rake machine, medialess disperser, three rolls, bead mill, etc. It can be carried out.
After stirring and mixing, it is preferable to go through a defoaming step in order to remove bubbles from the conductive resin composition. The method of defoaming is not particularly limited and can be performed using a general method, and examples thereof include vacuum defoaming and ultrasonic defoaming.
＜伝導性物質＞
平均アスペクト比が１０〜１０００の伝導性物質がアルミナ、窒化ホウ素、カーボンブラック、グラフェン、カーボンナノチューブ、炭素繊維等の炭素化合物、及び鱗片状又は板状に加工した金、銀、アルミニウム等の金属粉末等が挙げられる。これらは、１種を単独で用いても良く、２種以上を併用することもできる。絶縁且つ熱伝導性が求められる場合は、アルミナ及び窒化ホウ素が良い。
<Conductive material>
Conductive materials with an average aspect ratio of 10 to 1000 are carbon compounds such as alumina, boron nitride, carbon black, graphene, carbon nanotubes, and carbon fibers, and metal powders such as gold, silver, and aluminum processed into scales or plates Etc. These may be used alone or in combination of two or more. When insulation and thermal conductivity are required, alumina and boron nitride are preferable.
伝導性物質の平均長径は、３μｍ以上５０μｍ以下が好ましい。
伝導性物質の平均長径が３μｍ未満であると、伝導性物質の平均アスペクト比が小さくなり、凹部を有する伝導性シートの凹凸によって、伝導性物質の長径方向をシート厚み方向に配向させることが難しくなる。
また、伝導性物質とバインダー樹脂との界面が増大するため、界面抵抗によって所望の熱伝導性が得られない。
The average major axis of the conductive material is preferably 3 μm or more and 50 μm or less.
If the average major axis of the conductive material is less than 3 μm, the average aspect ratio of the conductive material becomes small, and it is difficult to orient the major axis direction of the conductive material in the sheet thickness direction due to the irregularities of the conductive sheet having a recess. Become.
In addition, since the interface between the conductive substance and the binder resin increases, desired thermal conductivity cannot be obtained due to the interface resistance.
逆に、伝導性物質 の平均長径が５０μｍを超えると、シート厚み方向に加わる圧力によって伝導性物質がシート面方向に配向する割合が大きくなり、所望の熱伝導性が得られない。
伝導性シートにおける伝導性物質の含有量は、２０体積％以上９０体積％以下であることが好ましい。
さらに好ましくは３０〜８０体積％の範囲であることが好ましい。
特に、伝導性シートは、伝導性物質の配向制御によってシート厚み方向の熱伝導性を高めることができるため、伝導性物質の含有量を増大させなくても、所望の熱伝導性が得られる。
On the other hand, when the average major axis of the conductive material exceeds 50 μm, the ratio of the conductive material oriented in the sheet surface direction is increased by the pressure applied in the sheet thickness direction, and the desired thermal conductivity cannot be obtained.
The content of the conductive substance in the conductive sheet is preferably 20% by volume or more and 90% by volume or less.
More preferably, it is in the range of 30 to 80% by volume.
In particular, since the conductive sheet can increase the thermal conductivity in the sheet thickness direction by controlling the orientation of the conductive material, the desired thermal conductivity can be obtained without increasing the content of the conductive material.
２０体積％未満の含有量だと、伝導性物質の添加効果が薄く十分な熱伝導性が得られない。
一方、９０体積％を越えると相対的にバインダー樹脂の含有量が少なくなり、形成される伝導性シートが脆く、伝導性シート内に空隙が出来るおそれがあり、伝導性シートを使用している間に熱伝導性が徐々に低下する可能性がある。
ここでいう体積％とは、伝導性樹脂組成物中の固形分に対する伝導性物質、バインダー樹脂の重量比と比重をもとに計算した理論値を示す。
If the content is less than 20% by volume, the effect of adding a conductive substance is so thin that sufficient thermal conductivity cannot be obtained.
On the other hand, when the volume exceeds 90% by volume, the content of the binder resin is relatively reduced, the formed conductive sheet is fragile, and there is a possibility that voids are formed in the conductive sheet. There is a possibility that the thermal conductivity gradually decreases.
The volume% here indicates a theoretical value calculated based on the weight ratio and specific gravity of the conductive material and the binder resin with respect to the solid content in the conductive resin composition.
伝導性シートは、伝導性を向上させる観点から、伝導性物質の一次粒子を凝集させた二次凝集体をさらに含有することができる。
この二次凝集体を構成する一次粒子の平均長径は、好ましくは１５μｍ以下、より好ましくは１μｍ以上１０μｍ以下である。
The conductive sheet can further contain a secondary aggregate obtained by aggregating the primary particles of the conductive substance from the viewpoint of improving the conductivity.
The average major axis of the primary particles constituting the secondary aggregate is preferably 15 μm or less, more preferably 1 μm or more and 10 μm or less.
大きさの異なる複数の種類の伝導性物質を用いることもでき、その場合には、比較的小さなものと比較的大きなものを組み合わせて用いることが、凝集体内の空隙率を減らすという点で好ましい。 A plurality of types of conductive materials having different sizes can be used. In that case, it is preferable to use a combination of a relatively small material and a relatively large material in terms of reducing the porosity in the aggregate.
一次粒子の平均長径が小さ過ぎると、凝集体内における一次粒子同士の接点が多くなり、接触抵抗が大きくなるため熱伝導性が低下する傾向にある。
一方、一次粒子の平均長径が大き過ぎると、一次粒子の凝集密度が低く、空隙が多くなりすぎてしまうため、二次凝集体自体の熱伝導性が低下すると共に、伝導性シートを作製する際に二次凝集体が崩れ易くなる。その結果、所望の伝導性の向上効果が得られない。
なお、本発明における伝導性物質の平均一次粒子径は、粒度分布計（例えば、Ｍａｌｖｅｒｎ Ｉｎｓｔｒｕｍｅｎｔｓ社製、マスターサイザー２０００）で測定したときの値である。
If the average major axis of the primary particles is too small, the number of contacts between the primary particles in the aggregate increases, and the contact resistance increases, so the thermal conductivity tends to decrease.
On the other hand, if the average major axis of the primary particles is too large, the aggregation density of the primary particles is low and the number of voids is excessive, so that the thermal conductivity of the secondary aggregate itself is lowered and the conductive sheet is produced. In addition, the secondary aggregate tends to collapse. As a result, the desired conductivity improvement effect cannot be obtained.
In addition, the average primary particle diameter of the conductive material in the present invention is a value when measured with a particle size distribution meter (for example, Mastersizer 2000 manufactured by Malvern Instruments).
二次凝集体の平均粒径は、好ましくは１０μｍ以上１００μｍ以下、より好ましくは２０μｍ以上８０μｍ以下である。二次凝集体の平均粒径が１０μｍ未満であると、所望の伝導性が得られないことがある。一方、二次凝集体の平均粒径が１００μｍを超えると、伝導性シート を与える樹脂組成物に二次凝集体を混練分散させることが難しくなり、作業性や成形性に支障を生じることがある。
なお、二次凝集体の形状は、球状に限定されることはなく、鱗片状等の他の形状であってもよい。ただし、球状以外の他の形状の場合、平均粒径は当該形状における長辺の長さを意味する。
The average particle size of the secondary aggregate is preferably 10 μm or more and 100 μm or less, more preferably 20 μm or more and 80 μm or less. When the average particle size of the secondary aggregate is less than 10 μm, desired conductivity may not be obtained. On the other hand, when the average particle size of the secondary aggregates exceeds 100 μm, it becomes difficult to knead and disperse the secondary aggregates in the resin composition that gives the conductive sheet, which may hinder workability and moldability. .
The shape of the secondary aggregate is not limited to a spherical shape, and may be another shape such as a scale shape. However, in the case of a shape other than the spherical shape, the average particle diameter means the length of the long side in the shape.
二次凝集体は、所定の伝導性物質の一次粒子を用いて、公知の方法に従って製造することができる。具体的には、所定の伝導性物質の一次粒子を噴霧乾燥、撹拌乾燥、静置乾燥等の公知の方法によって得ることができる。 The secondary aggregate can be produced according to a known method using primary particles of a predetermined conductive substance. Specifically, primary particles of a predetermined conductive substance can be obtained by a known method such as spray drying, stirring drying, or stationary drying.
＜バインダー＞
本発明に用いられるバインダー樹脂について説明する。
バインダー樹脂は、伝導性シートを形成しうるものであれば特に限定されないが、例えば、ポリウレタン樹脂、ポリエステル樹脂、ポリエステルウレタン樹脂、アルキッド樹脂、ブチラール樹脂、アセタール樹脂、ポリアミド樹脂、アクリル樹脂、スチレン−アクリル樹脂、スチレン樹脂、ニトロセルロース、ベンジルセルロース、セルロース（トリ）アセテート、カゼイン、シェラック、ギルソナイト、ゼラチン、スチレン−無水マレイン酸樹脂、ポリブタジエン樹脂、ポリ塩化ビニル樹脂、ポリ塩化ビニリデン樹脂、ポリフッ化ビニリデン樹脂、ポリ酢酸ビニル樹脂、エチレン酢酸ビニル樹脂、塩化ビニル／酢酸ビニル共重合体樹脂、塩化ビニル／酢酸ビニル／マレイン酸共重合体樹脂、フッ素樹脂、シリコン樹脂、エポキシ樹脂、フェノキシ樹脂、フェノール樹脂、マレイン酸樹脂、尿素樹脂、メラミン樹脂、ベンゾグアナミン樹脂、ケトン樹脂、石油樹脂、ロジン、ロジンエステル、ポリビニルアルコール、ポリビニルピロリドン、ポリアクリルアミド、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、メチルセルロース、エチルセルロース、ヒドロキシエチルメチルセルロース、ヒドロキシプロピルメチルセルロース、カルボキシメチルセルロース、カルボキシメチルエチルセルロース、カルボキシメチルニトロセルロース、エチレン／ビニルアルコール樹脂、ポリオレフィン樹脂、塩素化ポリオレフィン樹脂、変性塩素化ポリオレフィン樹脂および塩素化ポリウレタン樹脂からなる郡より用途に応じて選ばれる１種または２種以上を適宜使用することができる。
中でも柔軟性の観点からウレタン系樹脂、電子部品として用いる際の絶縁性、耐熱性等の観点からエポキシ系樹脂が好適に用いられる。
バインダー樹脂自体硬化するか、もしくは適当な硬化剤との反応により硬化するものを用いることができる。
<Binder>
The binder resin used in the present invention will be described.
The binder resin is not particularly limited as long as it can form a conductive sheet. For example, polyurethane resin, polyester resin, polyester urethane resin, alkyd resin, butyral resin, acetal resin, polyamide resin, acrylic resin, styrene-acrylic can be used. Resin, styrene resin, nitrocellulose, benzylcellulose, cellulose (tri) acetate, casein, shellac, gilsonite, gelatin, styrene-maleic anhydride resin, polybutadiene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinylidene fluoride resin, Polyvinyl acetate resin, ethylene vinyl acetate resin, vinyl chloride / vinyl acetate copolymer resin, vinyl chloride / vinyl acetate / maleic acid copolymer resin, fluorine resin, silicon resin, epoxy resin, Xy resin, phenol resin, maleic resin, urea resin, melamine resin, benzoguanamine resin, ketone resin, petroleum resin, rosin, rosin ester, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, ethyl cellulose, For applications from the county consisting of hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, carboxymethylethylcellulose, carboxymethylnitrocellulose, ethylene / vinyl alcohol resin, polyolefin resin, chlorinated polyolefin resin, modified chlorinated polyolefin resin and chlorinated polyurethane resin The use of one or more selected as appropriate is appropriate Kill.
Among these, from the viewpoint of flexibility, an epoxy resin is preferably used from the viewpoints of urethane resin and insulation and heat resistance when used as an electronic component.
The binder resin itself can be cured, or can be cured by reaction with an appropriate curing agent.
＜添加剤＞
伝導性樹脂組成物には、必要に応じて各種添加剤を加えることができる。各種添加剤としては、例えば、基材密着性を高めるためのカップリング剤、吸湿時の絶縁信頼性を高めるためのイオン捕捉剤、レベリング剤、難燃剤等、その他充填剤等が挙げられる。難燃剤としては、特に限定されないが、例えば、水酸化アルミニウム、水酸化マグネシウム等が挙げられる。これらは１種を用いてもよいし、複数種を併用することもできる。
<Additives>
Various additives can be added to the conductive resin composition as necessary. Examples of the various additives include a coupling agent for improving the adhesion to the substrate, an ion scavenger for enhancing the insulation reliability at the time of moisture absorption, a leveling agent, a flame retardant, and other fillers. Although it does not specifically limit as a flame retardant, For example, aluminum hydroxide, magnesium hydroxide, etc. are mentioned. These may use 1 type and can also use multiple types together.
＜実施の工程３(充填工程）＞
＜剥離工程に、伝導性シートの凹部を充填材料で充填する充填工程を含む伝導性シートの製造方法＞
本発明に用いられる伝導性シートの凹部を充填材料で充填する充填工程について説明する。
熱伝導性にくわえ、シートとしては、接着性が求められており、凹部に充填材料を充填することで、樹脂層が厚くなるために、被着体との接着性が向上し、凸部は、樹脂層が薄いために熱伝導性が維持する。
その結果、得られる伝導性シートは、熱伝導性と接着性に優れたものとなる。
充填方法としては、特に限定されず、公知の手法を用いることができ、例えば、予め種々の方法により作製された充填材料のシートと伝導性シートをラミネートもしくは加圧プレスする方法、伝導性シート上へ種々の方法で塗布する方法などが挙げられる。
充填材料は、樹脂のみでもよく、場合によっては、上記伝導性物質が含まれていてもよい。
<Implementation process 3 (filling process)>
<The manufacturing method of the conductive sheet which includes the filling process which fills the recessed part of a conductive sheet with a filling material in a peeling process>
A filling process for filling the concave portions of the conductive sheet used in the present invention with a filling material will be described.
In addition to thermal conductivity, the sheet is required to have adhesiveness, and by filling the concave portion with a filling material, the resin layer becomes thicker, so the adhesiveness with the adherend is improved, and the convex portion is The heat conductivity is maintained because the resin layer is thin.
As a result, the obtained conductive sheet is excellent in thermal conductivity and adhesiveness.
The filling method is not particularly limited, and a known method can be used. For example, a method of laminating or press-pressing a sheet of a filling material prepared in advance by various methods and a conductive sheet, on a conductive sheet The method of apply | coating by various methods etc. is mentioned.
The filling material may be a resin alone, and may contain the conductive material in some cases.
＜積層体＞
本発明の伝導性シート（凹部を有する伝導性シートあるいは凹部を充填した伝導性シート）と発熱部材とを積層してなる積層体は、伝導性シートを発熱部材と放熱部材との間に介在させ、伝導性シートをこれら被着体に接着させることで得られる。
発熱部材としては、集積回路、ＩＣチップ、ハイブリッドパッケージ、マルチモジュール、パワートランジスタやＬＥＤ用基板等の種々の電子部品が挙げられる他、建材、車両、航空機、船舶等に用いられる物品であって、熱を帯び易く、耐久性、性能劣化を防ぐためにその熱を外部に逃がす必要がある物品があげられる。
放熱部材としては、例えば、アルミニウムや銅のフィンや板等を利用したヒートスプレッダ又はヒートシンク、ヒートパイプに接続されているアルミニウムや銅のブロック、内部に冷却液体をポンプで循環させているアルミニウムや銅のブロック、又はペルチェ素子及びこれを備えたアルミニウムや銅のブロック等が挙げられる。
本発明の積層体は、本発明の製造方法により得られた伝導性シートを介して、発熱部材と放熱部材とを接着させることで成立する。
例えば、半導体チップとヒートシンクとを接着させてなる半導体装置が挙げられる。
接着させる方法に特に制限はないが、１５０〜２００℃に加熱して接着させる方法が簡便であり、一般的である。
また、十分に密着させた状態で接着させるため、低圧力をかけた状態で加熱する方法が好ましい。
<Laminate>
The laminate formed by laminating the conductive sheet of the present invention (the conductive sheet having a concave portion or the conductive sheet filled with the concave portion) and the heat generating member has the conductive sheet interposed between the heat generating member and the heat radiating member. It is obtained by adhering a conductive sheet to these adherends.
Examples of the heat generating member include various electronic components such as an integrated circuit, an IC chip, a hybrid package, a multi-module, a power transistor and an LED substrate, and articles used for building materials, vehicles, aircraft, ships, etc. Examples include articles that are easily heated and require the heat to be released to the outside in order to prevent durability and performance deterioration.
Examples of the heat radiating member include a heat spreader or a heat sink using aluminum or copper fins or plates, an aluminum or copper block connected to a heat pipe, and an aluminum or copper circulated cooling liquid by a pump inside. Examples of the block include a Peltier element and an aluminum or copper block including the same.
The laminated body of this invention is materialized by adhere | attaching a heat generating member and a heat radiating member through the conductive sheet obtained by the manufacturing method of this invention.
For example, a semiconductor device in which a semiconductor chip and a heat sink are bonded is given.
Although there is no restriction | limiting in particular in the method to adhere | attach, The method of heating and adhering to 150-200 degreeC is simple, and is common.
Moreover, in order to make it adhere | attach in the state contact | adhered enough, the method of heating in the state which applied the low pressure is preferable.
伝導性シートと、発熱部材と積層してなる積層体を作製する方法は、発熱部材と放熱部材との間に、前記凹部を有する伝導性シートを挟み、加熱下で加圧プレスすることによって、積層体を得ることができ、発熱部材の熱を効率良く放熱部材に伝えることができる。
加圧プレス処理は、特に限定されず、公知のプレス処理機を使用することができる。また、プレス時の温度は適宜選択することが出来るが、熱硬化性接着シートとして使用するのであれば、バインダー樹脂の熱硬化が起こる温度以上で加熱することが望ましい。必要に応じて真空下にてプレスすることができる。
A method of producing a laminate formed by laminating a conductive sheet and a heat generating member sandwiches the conductive sheet having the concave portion between the heat generating member and the heat radiating member, and presses and presses under heating. A laminated body can be obtained and the heat of the heat generating member can be efficiently transmitted to the heat radiating member.
The pressure press treatment is not particularly limited, and a known press processor can be used. The temperature at the time of pressing can be appropriately selected. However, when used as a thermosetting adhesive sheet, it is desirable to heat at a temperature higher than the temperature at which thermosetting of the binder resin occurs. If necessary, it can be pressed under vacuum.
プレス時の圧力は、適宜選択することができるが、１ＭＰａ以上であることが好ましい。
本発明の凹部を有する伝導性シートは、あらかじめ伝導性シートの表面に凹凸を形成することにより、所定のアスペクト比を有する伝導性物質を、シート厚み方向に配向させることで伝導性が向上することを特徴としており、積層体を得た際にも、発熱部材の熱を、凹部を有する伝導性シートを介して効率良く放熱部材に伝えることが可能となる。
Although the pressure at the time of pressing can be selected suitably, it is preferable that it is 1 Mpa or more.
The conductive sheet having a concave portion of the present invention is improved in conductivity by orienting a conductive material having a predetermined aspect ratio in the sheet thickness direction by forming irregularities on the surface of the conductive sheet in advance. Even when a laminate is obtained, the heat of the heat generating member can be efficiently transmitted to the heat radiating member through the conductive sheet having the recess.
本発明の伝導性シートの凹部を充填材料で充填する充填工程を含む伝導性シートは、凹部を充填材料で充填することにより、積層体を得る際に、伝導性物質のシート厚み方向への配向がより低下しないものとなる。しかし、内部に凹部の形状をそのまま保持しているため、伝導性シートとしての性能は維持されている。 The conductive sheet including the filling step of filling the concave portion of the conductive sheet of the present invention with the filling material is oriented in the sheet thickness direction of the conductive substance when the laminate is obtained by filling the concave portion with the filling material. Will not decrease further. However, since the shape of the recess is held as it is inside, the performance as a conductive sheet is maintained.
また、本発明の凹部を有する伝導性シートは、あらかじめ伝導性シートの表面または内部に凹凸を形成させていることから、積層体において、伝導性シートに接する部材(発熱部材及び放熱部材)に凹凸面を設ける必要がなく、シートとしての汎用性が高い。
In addition, since the conductive sheet having a concave portion of the present invention has irregularities formed on the surface or inside of the conductive sheet in advance, the laminated body has irregularities on the members (heat generating member and heat radiating member) in contact with the conductive sheet. There is no need to provide a surface, and versatility as a sheet is high.
以下、実施例により本発明をさらに具体的に説明するが、以下の実施例は本発明の権利範囲を何ら制限するものではない。なお、実施例における、「部」、「％」、及び「ｖｏｌ％」は、それぞれ「重量部」、「重量％」、及び「体積％」を表し、Ｍｗは重量平均分子量を意味する。
なお、平均一次粒子径、平均粒子径、配向度、熱伝導率については以下のようにして求めた。
EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, a following example does not restrict | limit the right range of this invention at all. In the examples, “parts”, “%”, and “vol%” represent “parts by weight”, “wt%”, and “volume%”, respectively, and Mw represents a weight average molecular weight.
The average primary particle diameter, average particle diameter, orientation degree, and thermal conductivity were determined as follows.
＜平均一次粒子径＞
Ｍａｌｖｅｒｎ Ｉｎｓｔｒｕｍｅｎｔｓ社製粒度分布計マスターサイザー２０００を用いて測定した。測定条件は乾式ユニットを用いて空気圧２．５バール、また、フィード速度はサンプルにより最適化を行った。
<Average primary particle size>
It measured using the particle size distribution meter master sizer 2000 by Malvern Instruments. The measurement conditions were a dry unit and an air pressure of 2.5 bar, and the feed rate was optimized by the sample.
＜平均粒子径＞
Ｍａｌｖｅｒｎ Ｉｎｓｔｒｕｍｅｎｔｓ社製粒度分布計マスターサイザー２０００を用いて測定した。測定条件は乾式ユニットを用いて空気圧２．５バール、また、フィード速度はサンプルにより最適化を行った。
<Average particle size>
It measured using the particle size distribution meter master sizer 2000 by Malvern Instruments. The measurement conditions were a dry unit and an air pressure of 2.5 bar, and the feed rate was optimized by the sample.
＜配向度の測定方法＞
伝導性接着シートにおける鱗片状窒化ホウ素の配向度については、Ｘ線回折装置を用い、ＣｕＫα線で４５ＫＶ、４０ｍＡの条件で２θ＝３〜９０°をスキャニングし、４１．６°＜１００＞面と２６．９°＜００２＞面の回折ピークを求め、回折ピークの強度比（Ｉ＜１００＞／Ｉ＜００２＞）より求めた。
伝導性接着シートにおける鱗片状アルミナの配向度については、Ｘ線回折装置を用い、ＣｕＫα線で４５ＫＶ、４０ｍＡの条件で２θ＝３〜９０°をスキャニングし、３７．８°＜１１０＞面と４１．７°＜００６＞面の回折ピークを求め、回折ピークの強度比（Ｉ＜１１０＞／Ｉ＜００６＞）より求めた。
<Measurement method of orientation degree>
Regarding the orientation degree of the flaky boron nitride in the conductive adhesive sheet, using an X-ray diffractometer, scanning was performed at 2θ = 3 to 90 ° under the conditions of 45 KV and 40 mA with CuKα ray, and 41.6 ° <100> plane. The diffraction peak of the 26.9 ° <002> plane was obtained, and the diffraction peak intensity ratio (I <100> / I <002>) was obtained.
Regarding the degree of orientation of the scaly alumina in the conductive adhesive sheet, using an X-ray diffractometer, 2θ = 3-90 ° was scanned with CuKα ray at 45 KV and 40 mA, and 37.8 ° <110> plane and 41 The diffraction peak of .7 ° <006> plane was determined and determined from the intensity ratio of diffraction peaks (I <110> / I <006>).
＜熱伝導率＞
サンプル試料を１５ｍｍ角に切り出し、サンプル表面に金を蒸着し、カーボンスプレーによりカーボンを被覆した後、キセノンフラッシュアナライザーＬＦ４４７ＮａｎｏＦｌａｓｈ（ＮＥＴＺＳＣＨ社製）にて、試料環境２５℃での熱拡散率を測定した。比熱容量はエスアイアイ・ナノテクノロジー株式会社製の高感度型示差走査熱量計ＤＳＣ２２０Ｃを用いて測定した。密度は水中置換法を用いて算出した。これらパラメータから、熱伝導率を求めた。
表中の略語について以下に示す。
Ｔｏｌ：トルエン、
ＩＰＡ：２−プロパノール
<Thermal conductivity>
A sample sample was cut into a 15 mm square, gold was vapor-deposited on the sample surface and coated with carbon by carbon spray, and then the thermal diffusivity in a sample environment at 25 ° C. was measured with a xenon flash analyzer LF447 NanoFlash (manufactured by NETZSCH). The specific heat capacity was measured using a high-sensitivity differential scanning calorimeter DSC220C manufactured by SII Nano Technology. The density was calculated using an underwater substitution method. From these parameters, the thermal conductivity was determined.
Abbreviations in the table are shown below.
Tol: Toluene,
IPA: 2-propanol
＜樹脂合成例１＞
攪拌機、温度計、還流冷却器、滴下装置、窒素導入管を備えた反応容器に、テレフタル酸とアジピン酸と３−メチル−１，５−ペンタンジオールから得られるポリエステルポリオール（（株）クラレ製「クラレポリオールＰ−１０１１」、Ｍｎ＝１００６）４０１．９重量部、ジメチロールブタン酸１２．７重量部、イソホロンジイソシアネート１５１．０重量部、トルエン４０.０重量部を仕込み、窒素雰囲気下９０℃、３時間反応させ、これ
にトルエン３００．０重量部を加えてイソシアネート基を有するウレタンプレポリマー溶液を得た。
次に、イソホロンジアミン２７．８重量部、ジ−ｎ−ブチルアミン３．２重量部、２−プロパノール３４２．０重量部、トルエン３９６．０重量部を混合したものに、得られたイソシアネート基を有するウレタンプレポリマー溶液８１５．１重量部を添加し、７０℃、３時間反応させ、トルエン１４４．０重量部、２−プロパノール７２．０重量部で希釈し、Ｍｗ＝５４，０００、酸価＝８ｍｇＫＯＨ／ｇのポリウレタンポリウレア樹脂（樹脂合成例１）溶液を得た。
<Resin synthesis example 1>
Polyester polyol (made by Kuraray Co., Ltd.) obtained from terephthalic acid, adipic acid and 3-methyl-1,5-pentanediol in a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introduction tube. Kuraray polyol P-1011 ", Mn = 1006) 401.9 parts by weight, 12.7 parts by weight of dimethylolbutanoic acid, 151.0 parts by weight of isophorone diisocyanate, 40.0 parts by weight of toluene, 90 ° C under nitrogen atmosphere, It was made to react for 3 hours, 300.0 weight part of toluene was added to this, and the urethane prepolymer solution which has an isocyanate group was obtained.
Next, 27.8 parts by weight of isophorone diamine, 3.2 parts by weight of di-n-butylamine, 342.0 parts by weight of 2-propanol, and 396.0 parts by weight of toluene have the obtained isocyanate group. Add 815.1 parts by weight of urethane prepolymer solution, react at 70 ° C. for 3 hours, dilute with 144.0 parts by weight of toluene and 72.0 parts by weight of 2-propanol, Mw = 54,000, acid value = 8 mgKOH / G polyurethane polyurea resin (resin synthesis example 1) solution was obtained.
＜樹脂合成例２＞
攪拌機、温度計、還流冷却器、滴下装置、導入管、窒素導入管を備えた４口フラスコに、ポリカーボネートジオール（クラレポリオール Ｃ−２０９０：株式会社クラレ製）２９２．１重量部、テトラヒドロ無水フタル酸（リカシッドＴＨ：新日本理化株式会社製）４４．９重量部、溶剤としてトルエン３５０．０重量部を仕込み、窒素気流下、攪拌しながら６０℃まで昇温し、均一に溶解させた。続いてこのフラスコを１１０℃に昇温し、３時間反応させた。その後、４０℃に冷却後、ビスフェノールＡ型エポキシ樹脂（ＹＤ−８１２５：東都化成株式会社製）６２．９重量部、触媒としてトリフェニルホスフィン４．０重量部を添加して１１０℃に昇温し、８時間反応させた。室温まで冷却後、トルエンで固形分が３５％になるように調整し、Ｍｗ＝２５０００のカルボキシル基含有変性エステル樹脂（樹脂合成例２）溶液を得た。
<Resin synthesis example 2>
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser, dropping device, introduction tube, and nitrogen introduction tube, 292.1 parts by weight of polycarbonate diol (Kuraray polyol C-2090: manufactured by Kuraray Co., Ltd.), tetrahydrophthalic anhydride (Licacid TH: manufactured by Shin Nippon Rika Co., Ltd.) 44.9 parts by weight and 350.0 parts by weight of toluene as a solvent were charged, and the mixture was heated to 60 ° C. with stirring in a nitrogen stream, and dissolved uniformly. Subsequently, the flask was heated to 110 ° C. and reacted for 3 hours. Then, after cooling to 40 ° C., 62.9 parts by weight of bisphenol A type epoxy resin (YD-8125: manufactured by Tohto Kasei Co., Ltd.) and 4.0 parts by weight of triphenylphosphine as a catalyst were added, and the temperature was raised to 110 ° C. , Reacted for 8 hours. After cooling to room temperature, the solid content was adjusted to 35% with toluene to obtain a carboxyl group-containing modified ester resin (resin synthesis example 2) solution having Mw = 25000.
＜樹脂合成例３＞
攪拌機、還流冷却管、窒素導入管、温度計、滴下ロートを備えた４口フラスコに、ブチルアクリレート９８．５重量部、アクリル酸１．５重量部、酢酸エチル１５０．０重量部を仕込み、窒素置換下で７０℃まで加熱し、アゾビスイソブチロニトリル０．１５重量部を添加し重合を開始した。重合開始後３時間後から1時間おきに５時間後までそれぞれアゾビスイソブチロニトリル０．１５重量部を添加し更に２時間重合を行った。その後、酢酸エチル１５０．０重量部を追加して重合を終了させ、固形分２５％、Ｍｗ＝８４０００のアクリル樹脂（樹脂合成例３）を得た。
<Resin synthesis example 3>
A four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel was charged with 98.5 parts by weight of butyl acrylate, 1.5 parts by weight of acrylic acid, and 150.0 parts by weight of ethyl acetate. The mixture was heated to 70 ° C. under substitution, and 0.15 parts by weight of azobisisobutyronitrile was added to initiate polymerization. 0.13 parts by weight of azobisisobutyronitrile was added for another 2 hours from 3 hours after the start of polymerization until 5 hours after every other hour. Thereafter, 150.0 parts by weight of ethyl acetate was added to terminate the polymerization, and an acrylic resin (resin synthesis example 3) having a solid content of 25% and Mw = 84000 was obtained.
＜実施例１＞
＜伝導性樹脂組成物＞
伝導性物質として窒化ホウ素粒子（モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製「ＰＴ１６０」、平均一次粒子径：８μｍ）２７．６９質量部と、シランカップリング剤（信越化学工業株式会社製「ＫＢＭ-５１０３」）０．２８質量部と、バインダー樹脂として、樹脂合成例１で得られたポリウレタンポリウレア樹脂の２５％ＭＥＫ（メチルエチルケトン）溶液４８．１３質量部と、ビスフェノールＡ型エポキシ樹脂（ジャパンエポキシレジン（株）製「エピコート１００１）の５０％ＭＥＫ溶液４．８１質量部とをディスパー攪拌により混合し、溶剤としてイソプロピルアルコール４．７８質量部およびトルエン１９．１２質量部で固形分が４０重量％となるように調整した後、真空脱泡して伝導性物質の含有率が４５ｖｏｌ％の伝導性樹脂組成物を得た。
<Example 1>
<Conductive resin composition>
Boron nitride particles as conductive materials (“PT160” manufactured by Momentive Performance Materials Japan GK, average primary particle size: 8 μm) 27.69 parts by mass and silane coupling agent (“KBM manufactured by Shin-Etsu Chemical Co., Ltd.) -5103 ") 0.28 parts by mass, 48.13 parts by mass of 25% MEK (methyl ethyl ketone) solution of polyurethane polyurea resin obtained in Resin Synthesis Example 1 as binder resin, and bisphenol A type epoxy resin (Japan Epoxy Resin) 4.81 parts by mass of 50% MEK solution of “Epicoat 1001” manufactured by Co., Ltd. was mixed by disper stirring, and 4.78 parts by mass of isopropyl alcohol and 19.12 parts by mass of toluene as a solvent had a solid content of 40% by weight. After adjusting so that the content of conductive material is vacuum degassed It was obtained 5 vol% of the conductive resin composition.
＜伝導性シート＞
得られた伝導性樹脂組成物を、ナイフコーターを用いて剥離処理シート（厚さ７５μｍの離型処理ポリエチレンテレフタレートフィルム）に塗工し、１００℃で２分加熱乾燥し、伝導性シート原反を得た。
<Conductive sheet>
The obtained conductive resin composition was applied to a release-treated sheet (a release-treated polyethylene terephthalate film having a thickness of 75 μm) using a knife coater, and dried by heating at 100 ° C. for 2 minutes. Obtained.
＜両面に凹部を有する伝導性シート＞
得られた伝導性シート原反を、凸部を有するエンボスロール（凸部が、四角錐台形状で上辺３０μm, 底辺２５０μm, 高さ１１０μm）に接触させ、凸部を有するエンボスロールと伝導性シートと剥離させ、凹部を有する伝導性シートを得た。得られた凹部を有する伝導性シートの剥離処理シートを剥離し、剥離面同士を、ラミネーターを用いて、温度８０℃、圧力０．６ＭＰａ、０．５ｍ／ｓの条件で、加熱加圧処理し、貼り合せ、十点平均粗さＲｚＪＩＳ＝１６．８である凹部を有する伝導性シートを得た。
<Conductive sheet having recesses on both sides>
The obtained conductive sheet original fabric is brought into contact with an embossing roll having a convex part (the convex part is a quadrangular pyramid shape with an upper side of 30 μm, a base side of 250 μm, a height of 110 μm), and the embossing roll having the convex part and the conductive sheet And a conductive sheet having a recess was obtained. The obtained release treatment sheet of the conductive sheet having the recesses is peeled off, and the peeled surfaces are subjected to heat and pressure treatment using a laminator at a temperature of 80 ° C., a pressure of 0.6 MPa, and 0.5 m / s. Then, a conductive sheet having a concave portion having a ten-point average roughness RzJIS = 16.8 was obtained.
＜伝導性接着シート＞
この凹部を有する伝導性シートを、１５０℃、２ＭＰａで１時間プレスすることにより、厚みが１３８μｍ、配向度０．０１８、熱伝導率３．５（Ｗ／ｍ・Ｋ）の伝導性接着シートを得た。
<Conductive adhesive sheet>
A conductive adhesive sheet having a thickness of 138 μm, an orientation degree of 0.018, and a thermal conductivity of 3.5 (W / m · K) is obtained by pressing the conductive sheet having the recesses at 150 ° C. and 2 MPa for 1 hour. Obtained.
＜実施例２＞
伝導性物質として窒化ホウ素粒子を含有率５５ｖｏｌ％となるように添加したこと以外は、実施例１と同様にしての凹部を有する伝導性シート及び伝導性接着シートを得た。
<Example 2>
A conductive sheet having a recess and a conductive adhesive sheet were obtained in the same manner as in Example 1 except that boron nitride particles were added as a conductive substance so that the content was 55 vol%.
＜実施例３＞
伝導性物質として窒化ホウ素粒子を含有率６５ｖｏｌ％となるように添加したこと以外は、実施例１と同様にしての凹部を有する伝導性シート及び伝導性接着シートを得た。
<Example 3>
A conductive sheet and a conductive adhesive sheet having recesses were obtained in the same manner as in Example 1 except that boron nitride particles were added as a conductive substance so as to have a content of 65 vol%.
＜実施例４＞
伝導性物質として窒化ホウ素粒子（モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製「ＰＴ１２０」、平均一次粒子径：１３μｍ）を用いたこと以外は、実施例１と同様にしての凹部を有する伝導性シート及び伝導性接着シートを得た。
<Example 4>
Conductivity having recesses as in Example 1 except that boron nitride particles (“PT120” manufactured by Momentive Performance Materials Japan GK, average primary particle size: 13 μm) were used as the conductive material. A sheet and a conductive adhesive sheet were obtained.
＜実施例５＞
伝導性物質として窒化ホウ素粒子（モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製「ＰＴ１１０」、平均一次粒子径：４５μｍ）を用いたこと以外は、実施例１と同様にしての凹部を有する伝導性シート及び伝導性接着シートを得た。
<Example 5>
Conductivity having concave portions as in Example 1 except that boron nitride particles (“PT110” manufactured by Momentive Performance Materials Japan GK, average primary particle size: 45 μm) were used as the conductive material. A sheet and a conductive adhesive sheet were obtained.
＜実施例６＞
バインダー樹脂として、樹脂合成例２で得られたカルボキシル基含有変性エステル樹脂の３５％ＭＥＫ溶液を用いたこと以外は、実施例２と同様にしての凹部を有する伝導性シートを及び伝導性接着シート得た。
<Example 6>
As the binder resin, a conductive sheet having a recess and a conductive adhesive sheet as in Example 2 except that the 35% MEK solution of the carboxyl group-containing modified ester resin obtained in Resin Synthesis Example 2 was used. Obtained.
＜実施例７＞
伝導性物質として窒化ホウ素粒子（スリーエム・ジャパン株式会社製「Ｐｌｅｔｅｌｅｔ００９」、平均一次粒子径：９μｍ）を用いたこと以外は、実施例２と同様にしての凹部を有する伝導性シート及び伝導性接着シートを得た。
<Example 7>
A conductive sheet and conductive adhesive having recesses as in Example 2 except that boron nitride particles ("Pletelet 009" manufactured by 3M Japan Co., Ltd., average primary particle size: 9 μm) were used as the conductive material. A sheet was obtained.
＜実施例８＞
伝導性物質としてアルミナ（キンセイマテックス株式会社製「０２０２５」、平均一次粒子径：２μｍ）を用い、含有率６０ｖｏｌ％となるように添加したこと以外は、実施例１と同様にしての凹部を有する伝導性シート及び伝導性接着シートを得た。
<Example 8>
Alumina (“02025” manufactured by Kinsei Matex Co., Ltd., average primary particle size: 2 μm) was used as the conductive material, and the concave portions were the same as in Example 1 except that the content was 60 vol%. A conductive sheet and a conductive adhesive sheet were obtained.
＜実施例９＞
伝導性物質としてアルミナ（キンセイマテックス株式会社製「０２０５０」、平均一次粒子径：５μｍ）を用いたこと以外は、実施例８と同様にしての凹部を有する伝導性シート及び伝導性接着シートを得た。
<Example 9>
A conductive sheet and a conductive adhesive sheet having recesses are obtained in the same manner as in Example 8 except that alumina (“02050” manufactured by Kinsei Matex Co., Ltd., average primary particle size: 5 μm) is used as the conductive material. It was.
＜実施例１０＞
伝導性物質としてＸＧＳｃｉｅｎｃｅｓ社（鱗片状グラフェン粉末Ｍグレード、平均アスペクト比３０００、平均厚み３ｎｍ）を用いたこと以外は、実施例１と同様にしての凹部を有する伝導性シート及び伝導性接着シートを得た。
<Example 10>
A conductive sheet and a conductive adhesive sheet having recesses in the same manner as in Example 1 except that XGSciences (scale-like graphene powder M grade, average aspect ratio 3000, average thickness 3 nm) was used as the conductive substance. Obtained.
＜実施例１１＞
＜充填材料＞
バインダー樹脂として、樹脂合成例１で得られたポリウレタンポリウレア樹脂の２５％ＭＥＫ溶液１００質量部と、ビスフェノールＡ型エポキシ樹脂（ジャパンエポキシレジン（株）製「エピコート１００１）の５０％ＭＥＫ溶液１０質量部とをディスパー攪拌により混合し、真空脱泡して樹脂組成物を得た。
得られた樹脂組成物を、ナイフコーターを用いて剥離処理シート（厚さ２５μｍの離型処理ポリエチレンテレフタレートフィルム）に塗工し、１００℃で２分加熱乾燥し、厚さ１０μｍの充填材料を得た。
<Example 11>
<Filling material>
As binder resin, 100 parts by mass of 25% MEK solution of polyurethane polyurea resin obtained in Resin Synthesis Example 1 and 10 parts by mass of 50% MEK solution of bisphenol A type epoxy resin (“Epicoat 1001” manufactured by Japan Epoxy Resin Co., Ltd.) Were mixed by disper stirring and vacuum degassed to obtain a resin composition.
The obtained resin composition was applied to a release-treated sheet (release-treated polyethylene terephthalate film having a thickness of 25 μm) using a knife coater and dried by heating at 100 ° C. for 2 minutes to obtain a filling material having a thickness of 10 μm. It was.
＜伝導性シートの凹部を充填材料で充填する充填工程を含む伝導性シート＞
得られた充填材料を実施例１で得られた凹部を有する伝導性シートの凹部を充填するように、ラミネーターを用いて、温度８０℃、圧力０．６ＭＰａ、０．５ｍ／ｓの条件で、加熱加圧処理し、貼り合せ、厚みが１５９μｍの凹部を充填材料で充填する充填工程を含む伝導性シートを得た。
<Conductive sheet including a filling step of filling the concave portion of the conductive sheet with a filling material>
Using a laminator, the obtained filling material was filled with the concave portion of the conductive sheet having the concave portion obtained in Example 1, under the conditions of a temperature of 80 ° C., a pressure of 0.6 MPa, and 0.5 m / s. A conductive sheet including a filling step in which a heat-pressing treatment was performed and bonding and a concave portion having a thickness of 159 μm was filled with a filling material was obtained.
＜伝導性接着シート＞
この凹部を充填材料で充填する充填工程を含む伝導性シートを、１５０℃、２ＭＰａで１時間プレスすることにより、伝導性接着シートを得た。
<Conductive adhesive sheet>
A conductive adhesive sheet was obtained by pressing a conductive sheet including a filling step of filling the concave portion with a filling material at 150 ° C. and 2 MPa for 1 hour.
＜実施例１２＞
伝導性物質として窒化ホウ素粒子を含有率５５ｖｏｌ％となるように添加したこと以外は、実施例１１と同様にしての凹部を充填材料で充填する充填工程を含む伝導性シート及び伝導性接着シートを得た。
<Example 12>
A conductive sheet and a conductive adhesive sheet including a filling step of filling a concave portion with a filling material in the same manner as in Example 11 except that boron nitride particles are added as a conductive substance so as to have a content of 55 vol%. Obtained.
＜実施例１３＞
伝導性物として窒化ホウ素粒子を含有率６５ｖｏｌ％となるように添加したこと以外は、実施例１１と同様にしての凹部を充填材料で充填する充填工程を含む伝導性シート及び伝導性接着シートを得た。
<Example 13>
A conductive sheet and a conductive adhesive sheet including a filling step of filling a concave portion with a filling material in the same manner as in Example 11 except that boron nitride particles are added as a conductive material so as to have a content of 65 vol%. Obtained.
＜実施例１４＞
伝導性物質として窒化ホウ素粒子（モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製「ＰＴ１２０」、平均一次粒子径：１３μｍ）を用いたこと以外は、実施例１１と同様にしての凹部を充填材料で充填する充填工程を含む伝導性シート及び伝導性接着シートを得た。
<Example 14>
Except that boron nitride particles (“PT120” manufactured by Momentive Performance Materials Japan GK, average primary particle size: 13 μm) were used as the conductive material, the concave portions in the same manner as in Example 11 were filled with the filling material. A conductive sheet and a conductive adhesive sheet including a filling step for filling were obtained.
＜実施例１５＞
＜片面に凹部を有する伝導性シート＞
実施例７で得られた伝導性シートを、凸部を有するエンボスロール（凸部が、四角錐台形状で上辺３０μm, 底辺２５０μm, 高さ１１０μm）に接触させ、凸部を有するエンボスロールと伝導性シートと剥離させ、凹部を有する伝導性シートを得た。得られた凹部を有する伝導性シートと実施例１１の充填材料を、凹部を充填するように、ラミネーターを用いて、温度８０℃、圧力０．６ＭＰａ、０．５ｍ／ｓの条件で、加熱加圧処理し、貼り合せ、厚みが８５μｍの伝導性シート凹部を充填材料で充填する充填工程を含む伝導性シートを得た。
<Example 15>
<Conductive sheet having a recess on one side>
The conductive sheet obtained in Example 7 is brought into contact with an embossing roll having a convex portion (the convex portion has a quadrangular pyramid shape and has an upper side of 30 μm, a bottom side of 250 μm, and a height of 110 μm). The conductive sheet was peeled off to obtain a conductive sheet having a recess. The obtained conductive sheet having recesses and the filling material of Example 11 were heated under the conditions of a temperature of 80 ° C., a pressure of 0.6 MPa, and 0.5 m / s using a laminator so as to fill the recesses. A conductive sheet including a filling step of filling the concave portion of the conductive sheet having a thickness of 85 μm with a filling material by pressure treatment and bonding was obtained.
＜伝導性接着シート＞
この凹部を充填材料で充填する充填工程を含む伝導性シートを、１５０℃、２ＭＰａで１時間プレスすることにより、伝導性接着シートを得た。
<Conductive adhesive sheet>
A conductive adhesive sheet was obtained by pressing a conductive sheet including a filling step of filling the concave portion with a filling material at 150 ° C. and 2 MPa for 1 hour.
＜実施例１６＞
伝導性物質として窒化ホウ素粒子（スリーエム・ジャパン株式会社製「Ｐｌｅｔｅｌｅｔ００９」、平均一次粒子径：９μｍ）を用い、含有率５５ｖｏｌ％となるように添加したこと以外は、実施例１１と同様にしての凹部を有する凹部を充填材料で充填する充填工程を含む伝導性シート及び伝導性接着シートを得た。
<Example 16>
Boron nitride particles (“Pletelet 009” manufactured by 3M Japan Co., Ltd., average primary particle size: 9 μm) were used as the conductive material and were added in the same manner as in Example 11 except that the content was 55 vol%. A conductive sheet and a conductive adhesive sheet including a filling step of filling a concave portion having a concave portion with a filling material were obtained.
＜実施例１７＞
＜伝導性樹脂組成物＞
伝導性物質として窒化ホウ素粒子（モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製「ＰＴ１６０」、平均一次粒子径：８μｍ）１４．２８質量部と、シランカップリング剤（信越化学工業株式会社製「ＫＢＭ-５１０３」）０．１４質量部と、バインダー樹脂として、樹脂合成例１で得られたポリウレタンポリウレア樹脂の２５％ＭＥＫ溶液８２．３０質量部と、ビスフェノールＡ型エポキシ樹脂（ジャパンエポキシレジン（株）製「エピコート１００１）の５０％ＭＥＫ溶液８．２３質量部とをディスパー攪拌により混合し、溶剤としてイソプロピルアルコール０．６５質量部およびトルエン２．６２質量部で固形分が３５重量％となるように調整した後、真空脱泡して伝導性物質の含有率が２０ｖｏｌ％の伝導性樹脂組成物を得た。
<Example 17>
<Conductive resin composition>
Boron nitride particles as conductive materials (“PT160” manufactured by Momentive Performance Materials Japan GK, average primary particle size: 8 μm) 14.28 parts by mass and silane coupling agent (“KBM manufactured by Shin-Etsu Chemical Co., Ltd.) -5103 ") 0.14 parts by mass, as binder resin, 82.30 parts by mass of 25% MEK solution of polyurethane polyurea resin obtained in Resin Synthesis Example 1, and bisphenol A type epoxy resin (Japan Epoxy Resin Co., Ltd.) Combining 8.23 parts by mass of 50% MEK solution of “Epicoat 1001” manufactured by Disper Stirring so that the solid content is 35% by weight with 0.65 parts by mass of isopropyl alcohol and 2.62 parts by mass of toluene as a solvent. After adjustment, the resin is vacuum degassed and the conductive resin content is 20 vol%. It was obtained Narubutsu.
＜フィラー入り充填材料＞
得られた伝導性樹脂組成物を、ナイフコーターを用いて剥離処理シート（厚さ３８μｍの離型処理ポリエチレンテレフタレートフィルム）に塗工し、１００℃で２分加熱乾燥し、厚さ１０μｍのフィラー入り充填材料を得た。
<Filling material with filler>
The obtained conductive resin composition was applied to a release-treated sheet (a release-treated polyethylene terephthalate film having a thickness of 38 μm) using a knife coater, dried by heating at 100 ° C. for 2 minutes, and filled with a filler having a thickness of 10 μm. A filling material was obtained.
＜伝導性シート凹部を充填材料で充填する充填工程を含む伝導性シート＞
得られたフィラー入り充填材料を実施例３で得られた凹部を有する伝導性シートの凹部を充填するように、ラミネーターを用いて、温度８０℃、圧力０．６ＭＰａ、０．５ｍ／ｓの条件で処理し、貼り合せ、厚みが１５４μｍの凹部をフィラー入り充填材料で充填する充填工程を含む伝導性シートを得た。
<Conductive sheet including filling step of filling conductive sheet recess with filling material>
Using a laminator, the filler-filled material thus obtained was filled with the concave portions of the conductive sheet having the concave portions obtained in Example 3, and conditions of a temperature of 80 ° C., a pressure of 0.6 MPa, and 0.5 m / s. Then, a conductive sheet including a filling step in which a concave portion having a thickness of 154 μm was filled with a filler-containing filling material was obtained.
＜伝導性接着シート＞
この凹部をフィラー入り充填材料で充填する充填工程を含む伝導性シートを、１５０℃、２ＭＰａで１時間プレスすることにより、伝導性接着シートを得た。
<Conductive adhesive sheet>
A conductive adhesive sheet was obtained by pressing a conductive sheet including a filling step for filling the concave portion with a filler-containing filling material at 150 ° C. and 2 MPa for 1 hour.
＜実施例１８＞
伝導性物質として窒化ホウ素粒子（スリーエム・ジャパン株式会社製「Ｐｌｅｔｅｌｅｔ００９」、平均一次粒子径：９μｍ）を用いたこと以外は、実施例１７と同様にして、凹部をフィラー入り充填材料で充填する充填工程を含む伝導性シート及び伝導性接着シートを得た。
<Example 18>
Filling in which concave portions are filled with a filler-filled material in the same manner as in Example 17 except that boron nitride particles ("Pletelet 009" manufactured by 3M Japan Co., Ltd., average primary particle size: 9 μm) are used as the conductive substance. A conductive sheet and a conductive adhesive sheet including the steps were obtained.
＜実施例１９＞
＜伝導性樹脂組成物＞
伝導性物質として窒化ホウ素粒子（モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製「ＰＴ１６０」、平均一次粒子径：８μｍ）１０．２８質量部及び窒化ホウ素の二次凝集体（モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製「ＰＴＸ６０」、平均粒子径：６０μｍ）２３．１３質量部と、シランカップリング剤（信越化学工業株式会社製「ＫＢＭ-５１０３」）０．３３質量部と、バインダー樹脂として、樹脂合成例１で得られたポリウレタンポリウレア樹脂の２５％ＭＥＫ溶液２４．９７質量部と、ビスフェノールＡ型エポキシ樹脂（ジャパンエポキシレジン（株）製「エピコート１００１）の５０％ＭＥＫ溶液２．５０質量部とをディスパー攪拌により混合し、溶剤としてイソプロピルアルコール８．２５質量部およびトルエン３３．０２質量部で固形分が４０重量％となるように調整した後、真空脱泡して伝導性物質の含有率が４５ｖｏｌ％の伝導性樹脂組成物を得た。
<Example 19>
<Conductive resin composition>
Boron nitride particles as conductive materials (Momentive Performance Materials Japan “PT160”, average primary particle size: 8 μm) 10.28 parts by mass and secondary aggregate of boron nitride (Momentive Performance Materials) -Japan GK “PTX60”, average particle size: 60 μm) 23.13 parts by mass, silane coupling agent (“KBM-5103” manufactured by Shin-Etsu Chemical Co., Ltd.) 0.33 parts by mass, and as binder resin 24.97 parts by mass of 25% MEK solution of polyurethane polyurea resin obtained in Resin Synthesis Example 1 and 2.50 parts by mass of 50% MEK solution of bisphenol A type epoxy resin (“Epicoat 1001” manufactured by Japan Epoxy Resin Co., Ltd.) And isopropyl alcohol as a solvent. 8.25 parts by weight and 33.02 parts by weight of toluene were adjusted so that the solid content was 40% by weight, and then vacuum degassed to obtain a conductive resin composition having a conductive material content of 45 vol%. .
＜伝導性シートの凹部を充填材料で充填する充填工程を含む伝導性シート及び伝導性接着シート＞
得られた伝導性樹脂組成物から、実施例１同様に伝導性シート及び凹部を有する伝導性シートを得、更に実施例１１同様に伝導性シート凹部を充填材料で充填する充填工程を含む伝導性シート及び伝導性接着シートを得た。
<Conductive sheet and conductive adhesive sheet including a filling step of filling the concave portion of the conductive sheet with a filling material>
From the obtained conductive resin composition, a conductive sheet having a conductive sheet and a concave portion is obtained in the same manner as in Example 1, and a conductive step including a filling step of filling the concave portion of the conductive sheet with a filling material as in Example 11 A sheet and a conductive adhesive sheet were obtained.
＜実施例２０＞
窒化ホウ素粒子（モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製「ＰＴ１６０」、平均一次粒子径：８μｍ）の代わりに、窒化ホウ素粒子（スリーエム・ジャパン株式会社製「Ｐｌｅｔｅｌｅｔ００９」、平均一次粒子径：９μｍ）を用い、バインダー樹脂として、樹脂合成例３で得られたアクリル樹脂の２５％ＭＥＫ溶液を用いたこと以外は、実施例１９と同様に伝導性シート凹部を充填材料で充填する充填工程を含む伝導性シート及び伝導性接着シートを得た。
<Example 20>
Instead of boron nitride particles (“PT160” manufactured by Momentive Performance Materials Japan LLC, average primary particle size: 8 μm), boron nitride particles (“Pletelet 009” manufactured by 3M Japan Co., Ltd., average primary particle size: 9 μm) And a filling step of filling the conductive sheet recess with a filling material in the same manner as in Example 19 except that the 25% MEK solution of the acrylic resin obtained in Resin Synthesis Example 3 was used as the binder resin. A conductive sheet and a conductive adhesive sheet were obtained.
＜比較例１＞
＜伝導性樹脂組成物＞
伝導性物質として窒化ホウ素粒子（モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製「ＰＴ１６０」、平均一次粒子径：８μｍ）２７．６９質量部と、シランカップリング剤（信越化学工業株式会社製「ＫＢＭ-５１０３」）０．２８質量部と、バインダー樹脂として、樹脂合成例１で得られたポリウレタンポリウレア樹脂の２５％ＭＥＫ溶液４８．１３質量部と、ビスフェノールＡ型エポキシ樹脂（ジャパンエポキシレジン（株）製「エピコート１００１）の５０％ＭＥＫ溶液４．８１質量部とをディスパー攪拌により混合し、溶剤としてイソプロピルアルコール４．７８質量部およびトルエン１９．１２質量部で固形分が４０重量％となるように調整した後、真空脱泡して伝導性物質の含有率が４５ｖｏｌ％の伝導性樹脂組成物を得た。
<Comparative Example 1>
<Conductive resin composition>
Boron nitride particles as conductive materials (“PT160” manufactured by Momentive Performance Materials Japan GK, average primary particle size: 8 μm) 27.69 parts by mass and silane coupling agent (“KBM manufactured by Shin-Etsu Chemical Co., Ltd.) -5103 ") 0.28 parts by mass, 48.13 parts by mass of 25% MEK solution of polyurethane polyurea resin obtained in Resin Synthesis Example 1 as binder resin, and bisphenol A type epoxy resin (Japan Epoxy Resin Co., Ltd.) 4.81 parts by mass of “Epicoat 1001” 50% MEK solution was mixed by disper stirring so that 4.78 parts by mass of isopropyl alcohol and 19.12 parts by mass of toluene were 40% by weight as a solvent. After the adjustment, vacuum defoaming and conductive material with a conductive material content of 45 vol% To obtain a composition.
＜伝導性シート＞
得られた伝導性樹脂組成物を、ナイフコーターを用いて剥離処理シート（厚さ７５μｍの離型処理ポリエチレンテレフタレートフィルム）に塗工し、１００℃で２分加熱乾燥し、伝導性シートを得た。
<Conductive sheet>
The obtained conductive resin composition was applied to a release-treated sheet (a release-treated polyethylene terephthalate film having a thickness of 75 μm) using a knife coater and dried by heating at 100 ° C. for 2 minutes to obtain a conductive sheet. .
＜伝導性接着シート＞
得られた伝導性シートの剥離処理シートを剥離し、剥離面同士を，ラミネーターを用いて、温度８０℃、圧力０．６ＭＰａ、０．５ｍ／ｓの条件で、加熱加圧処理し、貼り合せ、１５０℃、２ＭＰａで１時間プレスすることにより、厚みが１４６μｍの伝導性接着シートを得た。このシートの配向度は０．０１２と低く、熱伝導率も２．７（Ｗ／ｍ・Ｋ）と低いものであった。
<Conductive adhesive sheet>
The obtained release sheet of the conductive sheet is peeled off, and the peeled surfaces are heat-pressed under the conditions of a temperature of 80 ° C., a pressure of 0.6 MPa, and 0.5 m / s using a laminator, and bonded together. The conductive adhesive sheet having a thickness of 146 μm was obtained by pressing at 150 ° C. and 2 MPa for 1 hour. The degree of orientation of this sheet was as low as 0.012, and the thermal conductivity was as low as 2.7 (W / m · K).
＜比較例２＞
伝導性物質として窒化ホウ素粒子を含有率５５ｖｏｌ％となるように添加したこと以外は、比較例１と同様にして伝導性シート及び伝導性接着シートを得た。
<Comparative Example 2>
A conductive sheet and a conductive adhesive sheet were obtained in the same manner as in Comparative Example 1 except that boron nitride particles were added as a conductive substance so that the content was 55 vol%.
＜比較例３＞
伝導性物質として窒化ホウ素粒子を含有率６５ｖｏｌ％となるように添加したこと以外は、比較例１と同様にして伝導性シート及び伝導性接着シートを得た。
<Comparative Example 3>
A conductive sheet and a conductive adhesive sheet were obtained in the same manner as in Comparative Example 1 except that boron nitride particles were added as a conductive substance so that the content was 65 vol%.
＜比較例４＞
伝導性物質として窒化ホウ素粒子（モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製「ＰＴ１２０」、平均一次粒子径：１３μｍ）を用いたこと以外は、比較例１と同様にして伝導性シート及び伝導性接着シートを得た。
<Comparative example 4>
A conductive sheet and a conductive material in the same manner as in Comparative Example 1 except that boron nitride particles (“PT120” manufactured by Momentive Performance Materials Japan GK, average primary particle size: 13 μm) were used as the conductive material. An adhesive sheet was obtained.
＜比較例５＞
伝導性物質として窒化ホウ素粒子（モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製「ＰＴ１１０」、平均一次粒子径：４５μｍ）を用いたこと以外は、比較例１と同様にして伝導性シート及び伝導性接着シートを得た。
<Comparative Example 5>
The conductive sheet and the conductive material were the same as in Comparative Example 1 except that boron nitride particles (“PT110” manufactured by Momentive Performance Materials Japan GK, average primary particle size: 45 μm) were used as the conductive material. An adhesive sheet was obtained.
＜比較例６＞
バインダー樹脂として、樹脂合成例２で得られたカルボキシル基含有変性エステル樹脂の３５％ＭＥＫ溶液を用いたこと以外は、比較例２と同様にして伝導性シート及び伝導性接着シートを得た。
<Comparative Example 6>
A conductive sheet and a conductive adhesive sheet were obtained in the same manner as in Comparative Example 2 except that the 35% MEK solution of the carboxyl group-containing modified ester resin obtained in Resin Synthesis Example 2 was used as the binder resin.
＜比較例７＞
伝導性物質として窒化ホウ素粒子（スリーエム・ジャパン株式会社製「Ｐｌｅｔｅｌｅｔ００９」、平均一次粒子径：９μｍ）を用いたこと以外は、比較例２と同様にして伝導性シート及び伝導性接着シートを得た。
<Comparative Example 7>
A conductive sheet and a conductive adhesive sheet were obtained in the same manner as in Comparative Example 2 except that boron nitride particles (“Pletelet 009” manufactured by 3M Japan Co., Ltd., average primary particle size: 9 μm) were used as the conductive substance. .
＜比較例８＞
伝導性物質としてアルミナ（キンセイマテックス株式会社製「０２０２５」、平均一次粒子径：２μｍ）を用い、含有率６０ｖｏｌ％となるように添加したこと以外は、比較例１と同様にして伝導性シート及び伝導性接着シートを得た。
<Comparative Example 8>
A conductive sheet and a conductive sheet were formed in the same manner as in Comparative Example 1 except that alumina (“02025” manufactured by Kinsei Matex Co., Ltd., average primary particle size: 2 μm) was used as the conductive material, and was added so that the content was 60 vol%. A conductive adhesive sheet was obtained.
＜比較例９＞
伝導性物質としてアルミナ（キンセイマテックス株式会社製「０２０５０」、平均一次粒子径：５μｍ）を用いたこと以外は、比較例８と同様にして伝導性シート及び伝導性接着シートを得た。
<Comparative Example 9>
A conductive sheet and a conductive adhesive sheet were obtained in the same manner as in Comparative Example 8, except that alumina (“02050” manufactured by Kinsei Matex Co., Ltd., average primary particle size: 5 μm) was used as the conductive substance.
＜比較例１０＞
伝導性物質としてＸＧＳｃｉｅｎｃｅｓ社（鱗片状グラフェン粉末Ｍグレード、平均アスペクト比３０００、平均厚み３ｎｍ）を用いたこと以外は、比較例１と同様にして伝導性シート及び伝導性接着シートを得た。
<Comparative Example 10>
A conductive sheet and a conductive adhesive sheet were obtained in the same manner as in Comparative Example 1, except that XGSciences (scale-like graphene powder M grade, average aspect ratio 3000, average thickness 3 nm) was used as the conductive substance.
＜比較例１１＞
＜伝導性樹脂組成物＞
バインダー樹脂として、樹脂合成例１で得られたポリウレタンポリウレア樹脂の２５％ＭＥＫ溶液１００質量部と、ビスフェノールＡ型エポキシ樹脂（ジャパンエポキシレジン（株）製「エピコート１００１）の５０％ＭＥＫ溶液１０質量部とをディスパー攪拌により混合し、真空脱泡して樹脂組成物を得た。
<Comparative Example 11>
<Conductive resin composition>
As binder resin, 100 parts by mass of 25% MEK solution of polyurethane polyurea resin obtained in Resin Synthesis Example 1 and 10 parts by mass of 50% MEK solution of bisphenol A type epoxy resin (“Epicoat 1001” manufactured by Japan Epoxy Resin Co., Ltd.) Were mixed by disper stirring and vacuum degassed to obtain a resin composition.
＜接着材料＞
得られた樹脂組成物を、ナイフコーターを用いて剥離処理シート（厚さ２５μｍの離型処理ポリエチレンテレフタレートフィルム）に塗工し、１００℃で２分加熱乾燥し、厚さ１０μｍの接着材料を得た。
<Adhesive material>
The obtained resin composition was applied to a release treatment sheet (release treatment polyethylene terephthalate film having a thickness of 25 μm) using a knife coater and dried by heating at 100 ° C. for 2 minutes to obtain an adhesive material having a thickness of 10 μm. It was.
＜伝導性シート及び伝導性接着シート＞
得られた接着材料と比較例１で得られた伝導性シートを、ラミネーターを用いて、温度８０℃、圧力０．６ＭＰａ、０．５ｍ／ｓの条件で、加熱加圧処理し、貼り合せ、１５０℃、２ＭＰａで１時間プレスすることにより、伝導性接着シートを得た。
<Conductive sheet and conductive adhesive sheet>
The obtained adhesive material and the conductive sheet obtained in Comparative Example 1 were heated and pressurized using a laminator under the conditions of a temperature of 80 ° C., a pressure of 0.6 MPa, and 0.5 m / s, and bonded together. A conductive adhesive sheet was obtained by pressing at 150 ° C. and 2 MPa for 1 hour.
＜比較例１２＞
伝導性物質として窒化ホウ素粒子を含有率５５ｖｏｌ％となるように添加したこと以外は、比較例１１と同様にして伝導性シート及び伝導性接着シートを得た。
<Comparative Example 12>
A conductive sheet and a conductive adhesive sheet were obtained in the same manner as in Comparative Example 11 except that boron nitride particles were added as a conductive substance so that the content was 55 vol%.
＜比較例１３＞
伝導性物として窒化ホウ素粒子を含有率６５ｖｏｌ％となるように添加したこと以外は、比較例１１と同様にして伝導性シート及び伝導性接着シートを得た。
<Comparative Example 13>
A conductive sheet and a conductive adhesive sheet were obtained in the same manner as in Comparative Example 11 except that boron nitride particles were added as a conductive material so that the content was 65 vol%.
＜比較例１４＞
伝導性物質として窒化ホウ素粒子（モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製「ＰＴ１２０」、平均一次粒子径：１３μｍ）を用いたこと以外は、比較例１１と同様にして伝導性シート及び伝導性接着シートを得た。
<Comparative example 14>
The conductive sheet and the conductive material were the same as Comparative Example 11 except that boron nitride particles (“PT120” manufactured by Momentive Performance Materials Japan GK, average primary particle size: 13 μm) were used as the conductive material. An adhesive sheet was obtained.
＜比較例１５＞
＜伝導性樹脂組成物＞
伝導性物質として窒化ホウ素粒子（モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製「ＰＴ１６０」、平均一次粒子径：８μｍ）１０．２８質量部及び窒化ホウ素の二次凝集体（モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製「ＰＴX６０」、平均粒子径：６０μｍ）２３．１３質量部と、シランカップリング剤（信越化学工業株式会社製「ＫＢＭ-５１０３」）０．３３質量部と、バインダー樹脂として、樹脂合成例１で得られたポリウレタンポリウレア樹脂の２５％ＭＥＫ溶液２４．９７質量部と、ビスフェノールＡ型エポキシ樹脂（ジャパンエポキシレジン（株）製「エピコート１００１）の５０％ＭＥＫ溶液２．５０質量部とをディスパー攪拌により混合し、溶剤としてイソプロピルアルコール８．２５質量部およびトルエン３３．０２質量部で固形分が４０重量％となるように調整した後、真空脱泡して伝導性物質の含有率が４５ｖｏｌ％の伝導性樹脂組成物を得た。
<Comparative Example 15>
<Conductive resin composition>
Boron nitride particles as conductive materials (Momentive Performance Materials Japan “PT160”, average primary particle size: 8 μm) 10.28 parts by mass and secondary aggregate of boron nitride (Momentive Performance Materials) -Japan Pty Ltd. "PTX60", average particle diameter: 60 micrometers) 23.13 mass parts, silane coupling agent (Shin-Etsu Chemical Co., Ltd. "KBM-5103") 0.33 mass part, and binder resin, 24.97 parts by mass of 25% MEK solution of polyurethane polyurea resin obtained in Resin Synthesis Example 1 and 2.50 parts by mass of 50% MEK solution of bisphenol A type epoxy resin (“Epicoat 1001” manufactured by Japan Epoxy Resin Co., Ltd.) And isopropyl alcohol as a solvent. After the solid content was adjusted to 40% by weight .25 parts by weight and toluene 33.02 parts by weight, the content of the conductive material to obtain a 45 vol% of the conductive resin composition was vacuum defoamed.
＜伝導性シート及び伝導性接着シート＞
得られた伝導性樹脂組成物から、比較例１同様に伝導性シートを得、更に実施例１１同様に伝導性接着シートを得た。
<Conductive sheet and conductive adhesive sheet>
From the obtained conductive resin composition, a conductive sheet was obtained in the same manner as in Comparative Example 1, and a conductive adhesive sheet was obtained in the same manner as in Example 11.
＜比較例１６＞
窒化ホウ素粒子（モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製「ＰＴ１６０」、平均一次粒子径：８μｍ）の代わりに、窒化ホウ素粒子（スリーエム・ジャパン株式会社製「Ｐｌｅｔｅｌｅｔ００９」、平均一次粒子径：９μｍ）を用い、バインダー樹脂として、樹脂合成例３で得られたアクリル樹脂の２５％ＭＥＫ溶液を用いたこと以外は、比較例１５と同様に伝導性シート及び伝導性接着シートを得た。
<Comparative Example 16>
Instead of boron nitride particles (“PT160” manufactured by Momentive Performance Materials Japan LLC, average primary particle size: 8 μm), boron nitride particles (“Pletelet 009” manufactured by 3M Japan Co., Ltd., average primary particle size: 9 μm) The conductive sheet and the conductive adhesive sheet were obtained in the same manner as in Comparative Example 15 except that the 25% MEK solution of the acrylic resin obtained in Resin Synthesis Example 3 was used as the binder resin.
＜熱伝導率の測定方法＞
サンプル試料を１５ｍｍ角に切り出し、サンプル表面を金蒸着しカーボンスプレーでカーボン被覆した後、キセノンフラッシュアナライザーＬＦＡ４４７ ＮａｎｏＦｌａｓｈ（ＮＥＴＺＳＣＨ社製)にて、試料環境２５℃での熱拡散率を測定した。また、比熱容量はエスアイアイ・ナノテクノロジー株式会社製の高感度型示差走査熱量計ＤＳＣ２２０Ｃを用いて測定した。さらに、密度は水中置換法を用いて算出した。
上記実施例１〜２０及び比較例１〜１６の伝導性接着シートの熱伝導性について、レーザーフラッシュ法を用いて測定したシート厚み方向の熱伝導率により評価した。この熱伝導率の結果を、表１に示した。
<Measurement method of thermal conductivity>
A sample sample was cut into a 15 mm square, and the sample surface was gold-deposited and carbon-coated with carbon spray, and then the thermal diffusivity in a sample environment at 25 ° C. was measured with a xenon flash analyzer LFA447 NanoFlash (manufactured by NETZSCH). The specific heat capacity was measured using a high-sensitivity differential scanning calorimeter DSC220C manufactured by SII Nano Technology. Furthermore, the density was calculated using an underwater substitution method.
About the heat conductivity of the conductive adhesive sheet of the said Examples 1-20 and Comparative Examples 1-16, it evaluated by the heat conductivity of the sheet | seat thickness direction measured using the laser flash method. The results of this thermal conductivity are shown in Table 1.
＜十点平均粗さＲｚＪＩＳの測定方法＞
図１に示すような凹部を有する伝導性シートの「十点平均粗さＲｚＪＩＳ」をレーザー顕微鏡（株式会社キーエンス製：ＶＫ−１００）にて、以下の方法にて算出した。
「十点平均粗さＲｚＪＩＳ」とは、ＪＩＳ表面粗さ（Ｂ０６０１：２０１３）により定義される。
この十点平均粗さＲｚＪＩＳは、断面曲線から基準長さだけ抜き取った部分において、最高から５番目までの山頂の標高の平均値と、最深から５番目までの谷底の標高の平均値との差であり、以下の式によって表される。
Ｒｚ＝（（Ｒ１＋Ｒ３＋Ｒ５＋Ｒ７＋Ｒ９）−（Ｒ２＋Ｒ４＋Ｒ６＋Ｒ８＋Ｒ１０）／５
上記式中、Ｒ１＋Ｒ３＋Ｒ５＋Ｒ７＋Ｒ９は、最高から５番目までの山頂の標高を意味し、Ｒ２＋Ｒ４＋Ｒ６＋Ｒ８＋Ｒ１０は、最深から５番目までの谷底の標高を意味する。
<Measuring method of ten-point average roughness RzJIS>
The “ten-point average roughness RzJIS” of the conductive sheet having recesses as shown in FIG. 1 was calculated by the following method using a laser microscope (manufactured by Keyence Corporation: VK-100).
“10-point average roughness RzJIS” is defined by JIS surface roughness (B0601: 2013).
This 10-point average roughness RzJIS is the difference between the average value of the highest altitude at the top of the peak from the fifth to the average value of the altitude at the bottom of the valley from the deepest to the fifth in the part extracted by the reference length from the cross-sectional curve. And is represented by the following equation.
Rz = ((R1 + R3 + R5 + R7 + R9) − (R2 + R4 + R6 + R8 + R10) / 5
In the above formula, R1 + R3 + R5 + R7 + R9 means the altitude of the top from the highest to the fifth, and R2 + R4 + R6 + R8 + R10 means the altitude of the bottom from the deepest to the fifth.
＜配向度の測定方法＞
伝導性接着シートにおける鱗片状窒化ホウ素の配向度については、Ｘ線回折装置を用い、ＣｕＫα線で４５ＫＶ、４０ｍＡの条件で２θ＝３〜９０°をスキャニングし、４１．６°＜１００＞面と２６．９°＜００２＞面の回折ピークを求め、回折ピークの強度比（Ｉ＜１００＞／Ｉ＜００２＞）として表１に示した。
<Measurement method of orientation degree>
Regarding the orientation degree of the flaky boron nitride in the conductive adhesive sheet, using an X-ray diffractometer, scanning was performed at 2θ = 3 to 90 ° under the conditions of 45 KV and 40 mA with CuKα ray, and 41.6 ° <100> plane. The diffraction peak of the 26.9 ° <002> plane was determined and shown in Table 1 as the diffraction peak intensity ratio (I <100> / I <002>).
伝導性接着シートにおける鱗片状アルミナの配向度については、Ｘ線回折装置を用い、ＣｕＫα線で４５ＫＶ、４０ｍＡの条件で２θ＝３〜９０°をスキャニングし、３７．８°＜１１０＞面と４１．７°＜００６＞面の回折ピークを求め、回折ピークの強度比（Ｉ＜１１０＞／Ｉ＜００６＞）として表１に示した。 Regarding the degree of orientation of the scaly alumina in the conductive adhesive sheet, using an X-ray diffractometer, 2θ = 3-90 ° was scanned with CuKα ray at 45 KV and 40 mA, and 37.8 ° <110> plane and 41 The diffraction peak of .7 ° <006> plane was determined and shown in Table 1 as the intensity ratio of diffraction peaks (I <110> / I <006>).
実施例１〜１４は、それぞれ同じ数字の比較例と対比すると、実施例のシートは、本発明の製造方法で製造されているのに対し、比較例のシートは、凸部を有する部材と接触する工程がない製法で製造されている。
また、実施例１９は比較例１５に、実施例２０は比較例１６と対比される。
表１の結果に示されているように、実施例１〜２０の伝導性接着シートは、比較例１〜１６の伝導性接着シートに比べて、凸部を有する部材と接触することによって、配向度及び熱伝導率が高く、熱伝導性に優れていることがわかった。
特に図２からもわかるように、加熱加圧処理し、伝導性接着シート作製後も、伝導性シートの凹部形状を維持できており、伝導性物質のシート厚み方向の配向により、熱伝導性が向上できている。
In Examples 1 to 14, when compared with Comparative Examples having the same numbers, the sheets of Examples are manufactured by the manufacturing method of the present invention, whereas the sheets of Comparative Examples are in contact with members having convex portions. It is manufactured by a manufacturing method that does not have a process to do.
In addition, Example 19 is compared with Comparative Example 15 and Example 20 is compared with Comparative Example 16.
As shown in the results of Table 1, the conductive adhesive sheets of Examples 1 to 20 are aligned by contacting a member having a convex portion as compared with the conductive adhesive sheets of Comparative Examples 1 to 16. It was found that the temperature and the thermal conductivity were high and the thermal conductivity was excellent.
In particular, as can be seen from FIG. 2, the concave shape of the conductive sheet can be maintained after the heat and pressure treatment and the conductive adhesive sheet is produced, and the thermal conductivity is improved by the orientation of the conductive material in the sheet thickness direction. It has improved.
以上の結果から、本発明の凹部を有する伝導性シートは、あらかじめ伝導性シートの表面に凹凸を形成することにより、所定のアスペクト比を有する伝導性物質を、シート厚み方向に配向させることで伝導性を向上させることができ、加圧加熱して積層体を得る際にもその配向が低下しない放熱特性に優れた伝導性シートの製造方法及び伝導性接着シートを提供することができる。 From the above results, the conductive sheet having a recess according to the present invention is conductive by orienting a conductive material having a predetermined aspect ratio in the sheet thickness direction by forming irregularities on the surface of the conductive sheet in advance. Thus, it is possible to provide a method for producing a conductive sheet and a conductive adhesive sheet excellent in heat dissipation characteristics in which the orientation does not decrease even when a laminate is obtained by pressurization and heating.
Claims (8)
前記凹部の十点平均粗さＲｚＪＩＳが、前記伝導性物質の平均長径の１／３以上且つ前記伝導性シートの厚みの１／２以下である伝導性シートの製造方法であって、
バインダーと、平均アスペクト比が１０〜３０００の伝導性物質とを含んでなる伝導性シート原反の片面もしくは両面を、凸部を有する部材に接触させる接触工程と、
前記凸部を有する部材と前記伝導性シート原反と剥離させる剥離工程を含むことを特徴とする伝導性シートの製造方法。 A method for producing a conductive sheet having a concave portion comprising a binder and a conductive material having an average aspect ratio of 10 to 3000,
The ten-point average roughness RzJIS of the concave portion is a method for producing a conductive sheet that is 1/3 or more of the average major axis of the conductive material and 1/2 or less of the thickness of the conductive sheet,
A contact step in which one side or both sides of a conductive sheet original fabric comprising a binder and a conductive material having an average aspect ratio of 10 to 3000 are brought into contact with a member having a convex portion;
The manufacturing method of the conductive sheet characterized by including the peeling process made to peel from the member which has the said convex part, and the said conductive sheet original fabric.
前記伝導性シートを加圧する工程を備える、伝導性接着シートの製造方法。The manufacturing method of a conductive adhesive sheet provided with the process of pressing the said conductive sheet.
伝導性接着シートの厚み方向にＸ線を照射して得られるＸ線回折図において、窒化ホウ素の配向度（＜１００＞面と＜００２＞面の回折ピークの強度比（Ｉ＜１００＞／Ｉ＜００２＞）が０．０１５以上であることを特徴とする請求項４記載の伝導性接着シートの製造方法。In the X-ray diffraction diagram obtained by irradiating X-rays in the thickness direction of the conductive adhesive sheet, the degree of orientation of boron nitride (ratio of diffraction peaks between <100> plane and <002> plane (I <100> / I <002>) is 0.015 or more, The manufacturing method of the conductive adhesive sheet of Claim 4 characterized by the above-mentioned.
伝導性接着シートの厚み方向にＸ線を照射して得られるＸ線回折図において、アルミナの配向度（＜１１０＞面と＜００６＞面の回折ピーク強度比（Ｉ＜１１０＞／Ｉ＜００６＞）が５以上であることを特徴とする請求項４記載の伝導性接着シートの製造方法。In the X-ray diffraction diagram obtained by irradiating X-rays in the thickness direction of the conductive adhesive sheet, the degree of orientation of alumina (diffraction peak intensity ratio between <110> plane and <006> plane (I <110> / I <006) >) Is 5 or more, The manufacturing method of the conductive adhesive sheet of Claim 4 characterized by the above-mentioned.
前記伝導性シートおよび発熱部材を積層する工程と、Laminating the conductive sheet and the heating member;
を備える積層体の製造方法。The manufacturing method of a laminated body provided with.
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