JP2008195850A - Method for producing resin molded article - Google Patents
Method for producing resin molded article Download PDFInfo
- Publication number
- JP2008195850A JP2008195850A JP2007033353A JP2007033353A JP2008195850A JP 2008195850 A JP2008195850 A JP 2008195850A JP 2007033353 A JP2007033353 A JP 2007033353A JP 2007033353 A JP2007033353 A JP 2007033353A JP 2008195850 A JP2008195850 A JP 2008195850A
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- resin
- heat conductive
- resin molded
- molded product
- 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
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、熱伝導性フィラーと熱硬化性樹脂とを含有する熱伝導性樹脂組成物により形成されてなる樹脂成形品の製造方法に関する。 The present invention relates to a method for producing a resin molded product formed from a heat conductive resin composition containing a heat conductive filler and a thermosetting resin.
従来、金属粒子、無機酸化物粒子、無機窒化物粒子やこれらの複合粒子、さらには、それらに表面処理が施された粒子が熱伝導性フィラーとして広く用いられている。
これらの熱伝導性フィラーを含有する樹脂組成物（以下「熱伝導性樹脂組成物」ともいう）は、熱伝導性が求められる樹脂成形品の形成に用いられており、特に電子部品用途において広く用いられている。
例えば、エポキシ樹脂などの熱硬化性のベース樹脂と、熱伝導性フィラーを含有する熱伝導性樹脂組成物が、チップ部品の封止や、発熱部品の搭載された回路と放熱板との間の絶縁層の形成などといった用途に用いられたりもしている。
また、特許文献１には、ベース樹脂とフィラーとを含む熱伝導性樹脂組成物によりシート状に形成された高熱伝導性樹脂層が、金属箔を用いた金属箔層上に積層されて形成された金属箔付高熱伝導接着シートが記載されており、この金属箔付高熱伝導接着シートが半導体チップの接着に用いられることが記載されている。
Conventionally, metal particles, inorganic oxide particles, inorganic nitride particles and composite particles thereof, and particles obtained by subjecting them to surface treatment have been widely used as heat conductive fillers.
Resin compositions containing these thermally conductive fillers (hereinafter also referred to as “thermally conductive resin compositions”) are used for the formation of resin molded products that are required to have thermal conductivity. It is used.
For example, a thermosetting base resin such as an epoxy resin and a heat conductive resin composition containing a heat conductive filler can be used to seal chip parts or between a circuit on which a heat generating part is mounted and a heat sink. It is also used for applications such as the formation of insulating layers.
In Patent Document 1, a high thermal conductive resin layer formed in a sheet shape from a thermal conductive resin composition containing a base resin and a filler is laminated on a metal foil layer using a metal foil. In addition, a high heat conductive adhesive sheet with metal foil is described, and it is described that this high heat conductive adhesive sheet with metal foil is used for bonding semiconductor chips.
この金属箔付高熱伝導接着シートのような高い熱伝導性が求められる樹脂成形品（以下「熱伝導性樹脂成形品」ともいう）には、通常、熱伝導率をより向上させることが求められている。
このことから、熱伝導性樹脂成形品の形成には、窒化ホウ素や窒化アルミニウムなどといった高い熱伝導率を有する無機窒化物が用いられたりしており、しかも、このような熱伝導性フィラーを高充填させることが検討されている。
例えば、特許文献２には、エポキシ樹脂中に熱伝導性フィラーを８０〜９５質量％もの高充填させた樹脂組成物を用いることにより、樹脂成形品の熱伝導率を３〜１０Ｗ／ｍＫとさせ得ることが記載されている。
Resin molded products that require high thermal conductivity such as this highly heat conductive adhesive sheet with metal foil (hereinafter also referred to as “thermal conductive resin molded products”) are usually required to further improve thermal conductivity. ing.
For this reason, inorganic nitrides having high thermal conductivity such as boron nitride and aluminum nitride are used to form thermally conductive resin molded products. Filling is being considered.
For example, in Patent Document 2, by using a resin composition in which 80 to 95% by mass of a thermally conductive filler is filled in an epoxy resin, the thermal conductivity of the resin molded product is set to 3 to 10 W / mK. It is described to obtain.
エポキシ樹脂などの熱硬化性樹脂に熱伝導性フィラーが高充填された熱伝導性シートのような樹脂成形品を作製する場合には、通常、熱硬化性樹脂を有機溶剤に溶解させた溶液中に熱伝導性フィラーを混合して粘稠な液体状の樹脂組成物を一旦作製し、この樹脂組成物を基材などに塗工・乾燥させてシート化した後に熱プレスで熱硬化を実施する成形加工方法が採用されたりしている。 When producing a resin molded product such as a heat conductive sheet in which a heat conductive filler is highly filled in a thermosetting resin such as an epoxy resin, it is usually in a solution in which the thermosetting resin is dissolved in an organic solvent. A viscous liquid resin composition is once prepared by mixing with a heat conductive filler, and this resin composition is coated on a substrate and dried to form a sheet, followed by thermosetting with a hot press. A molding method is adopted.
しかし、熱伝導性樹脂組成物中に熱伝導性フィラーを高充填させると有機溶剤が残留しやすくなり、熱伝導性樹脂組成物から有機溶剤を十分に除去させ得る工程を設けずに樹脂成形品の成型加工を実施すると樹脂成形品中に残留有機溶剤に起因する発泡が生じて空気層を形成させるおそれを有する。
このように、樹脂成形品中に空気層が形成されると熱伝導率などの特性を低下させてしまうこととなるため、従来、熱伝導性フィラーが分散されてなる樹脂成形品の製造方法においては、工程を簡略化させつつ得られる熱伝導率の低下を抑制させることが困難であるという問題を有している。
However, if the thermally conductive filler is highly filled in the thermally conductive resin composition, the organic solvent tends to remain, and the resin molded product is not provided with a process that can sufficiently remove the organic solvent from the thermally conductive resin composition. When the molding process is carried out, foaming due to the residual organic solvent is generated in the resin molded product, and an air layer may be formed.
As described above, when an air layer is formed in a resin molded product, characteristics such as thermal conductivity are deteriorated. Therefore, conventionally, in a method of manufacturing a resin molded product in which a thermally conductive filler is dispersed, Has a problem that it is difficult to suppress a decrease in thermal conductivity obtained while simplifying the process.
本発明は、上記問題に鑑みてなされたものであり、工程を簡略化しつつ得られる樹脂成形品の熱伝導率の低下を抑制させ得る樹脂成形品製造方法の提供を課題としている。 This invention is made | formed in view of the said problem, and makes the subject the provision of the resin molded product manufacturing method which can suppress the fall of the heat conductivity of the resin molded product obtained while simplifying a process.
本発明は、前記課題を解決すべく、熱伝導性フィラーと熱硬化性樹脂とが含有され、該熱硬化性樹脂が未硬化状態で含有されている熱伝導性樹脂組成物を作製する樹脂組成物作製工程と、前記樹脂組成物作製工程で作製された熱伝導性樹脂組成物を成形加工する成形加工工程とを実施し、しかも、前記樹脂組成物作製工程ならびに前記成形加工工程を有機溶剤を用いることなく実施して前記熱伝導性フィラーが分散されてなる樹脂成形品を形成することを特徴とする樹脂成形品製造方法を提供する。 In order to solve the above problems, the present invention provides a resin composition for producing a thermally conductive resin composition containing a thermally conductive filler and a thermosetting resin, and containing the thermosetting resin in an uncured state. And a molding process for molding the thermally conductive resin composition produced in the resin composition production process, and the organic resin is used for the resin composition production process and the molding process. The present invention provides a method for producing a resin molded product, characterized in that it is carried out without use to form a resin molded product in which the thermally conductive filler is dispersed.
本発明によれば、熱伝導性フィラーと熱硬化性樹脂とが含有されており、前記熱硬化性樹脂が未硬化状態で含有されている熱伝導性樹脂組成物を作製する樹脂組成物作製工程と、前記樹脂組成物作製工程で作製された熱伝導性樹脂組成物を成形加工する成形加工工程とを実施し、しかも、前記樹脂組成物作製工程ならびに前記成形加工工程を、有機溶剤を用いることなく実施して前記熱伝導性フィラーが分散されてなる樹脂成形品を形成することから、有機溶剤の除去に要する工程を省略させ得るとともに、樹脂成形品中に残留有機溶剤による気泡の発生を防止でき、空気層の形成を抑制させ得る。
すなわち、工程を簡略化しつつ得られる樹脂成形品の熱伝導率の低下を抑制させ得る樹脂成形品製造方法を提供し得る。
According to the present invention, a resin composition preparation step for preparing a heat conductive resin composition containing a heat conductive filler and a thermosetting resin and containing the thermosetting resin in an uncured state. And a molding process for molding the thermally conductive resin composition produced in the resin composition production process, and the organic resin is used for the resin composition production process and the molding process. Since the resin molded product in which the thermally conductive filler is dispersed is formed, the process required for removing the organic solvent can be omitted and the generation of bubbles due to the residual organic solvent in the resin molded product can be prevented. It is possible to suppress the formation of the air layer.
That is, it is possible to provide a resin molded product manufacturing method capable of suppressing a decrease in thermal conductivity of a resin molded product obtained while simplifying the process.
しかも、樹脂組成物作製工程ならびに成形加工工程を、有機溶剤を用いることなく実施することから、樹脂成形品の製造作業環境を良好なものとさせ得るとともに環境にやさしい製品を提供することができる。 Moreover, since the resin composition preparation process and the molding process are carried out without using an organic solvent, it is possible to improve the manufacturing work environment of the resin molded product and provide an environment-friendly product.
以下に、無機物粒子が分散されている樹脂成形品として、全体がシート状に形成されている熱伝導性シートを例に、該熱伝導性シートを製造する製造方法について説明する。 Below, the manufacturing method which manufactures this heat conductive sheet as an example of the heat conductive sheet currently formed in the sheet form as a resin molded product in which the inorganic particle is disperse | distributed is demonstrated.
まず、本実施形態の樹脂成形品（熱伝導性シート）の製造方法に用いる材料について説明する。
本実施形態の熱伝導性シートには、熱伝導性フィラーが含有された樹脂組成物が用いられている。
First, the material used for the manufacturing method of the resin molded product (heat conductive sheet) of this embodiment is demonstrated.
A resin composition containing a heat conductive filler is used for the heat conductive sheet of the present embodiment.
前記樹脂組成物は、熱伝導性フィラー、マトリックス成分を含有しており、この熱伝導性フィラーには、酸化アルミニウム、酸化マグネシウム、窒化ホウ素、窒化アルミニウム、窒化ケイ素、窒化ガリウム、二酸化ケイ素、炭化ケイ素あるいはダイヤモンドなどを主成分とする無機物粒子を用いることができる。
これらの中でも、比較的安価で良好なる熱伝導性を有する点において窒化ホウ素を主成分とする無機物粒子（以下「窒化ホウ素フィラー」ともいう）が好適である。
The resin composition contains a thermally conductive filler and a matrix component. The thermally conductive filler includes aluminum oxide, magnesium oxide, boron nitride, aluminum nitride, silicon nitride, gallium nitride, silicon dioxide, silicon carbide. Alternatively, inorganic particles containing diamond as a main component can be used.
Among these, inorganic particles containing boron nitride as a main component (hereinafter also referred to as “boron nitride filler”) are preferable in that they are relatively inexpensive and have good thermal conductivity.
この無機物粒子は、その大きさや形状に特に限定されるものではないが、通常、平均粒径が数μｍから数十μｍの大きさで、球状、棒状、鱗片状、破砕状、丸味状のものなどが用いられる。
なお、窒化ホウ素の粒子形状は、通常、鱗片状であり、この鱗片状の粒子や、この鱗片状粒子が凝集されてなる凝集粒子のいずれものも窒化ホウ素フィラーとして用いることができる。
The inorganic particles are not particularly limited in size or shape, but usually have an average particle size of several μm to several tens of μm, and are spherical, rod-like, scale-like, crushed, or roundish Etc. are used.
The particle shape of boron nitride is usually scaly, and any of the scaly particles and agglomerated particles obtained by agglomerating the scaly particles can be used as the boron nitride filler.
前記マトリックス成分には、熱硬化性樹脂を含むポリマー成分と添加剤成分とを含有するものを用いることができ、前記ポリマー成分における熱硬化性樹脂としては、エポキシ樹脂、フェノール樹脂などが挙げられる。 As the matrix component, one containing a polymer component containing a thermosetting resin and an additive component can be used. Examples of the thermosetting resin in the polymer component include an epoxy resin and a phenol resin.
なかでも、優れた接着性を示すと共に耐熱性にも優れていることからエポキシ樹脂を用いることが好適である。
しかも、常温固体のエポキシ樹脂が好ましい。
この常温固体のエポキシが好ましいのは、常温液体状のエポキシ樹脂を用いた場合には、熱伝導性シートを被着体に接着すべく加熱条件下において被着体に当接させた場合に、エポキシ樹脂の粘度が低下しすぎて、熱伝導性シートの端縁部から外にエポキシ樹脂が大きく滲み出してしまうおそれがあるためである。
このエポキシ樹脂の滲み出しが激しい場合には、熱伝導性シートの周囲で、例えは、放熱器取り付け箇所や接点箇所などの本来金属部分が露出しているべき個所にエポキシ樹脂被膜を形成させて、熱伝達に問題が生じたり、あるいは、導通不良などといった問題を生じさせたりするおそれがある。
Among them, it is preferable to use an epoxy resin because it exhibits excellent adhesiveness and excellent heat resistance.
Moreover, a room temperature solid epoxy resin is preferred.
This room temperature solid epoxy is preferable, when a room temperature liquid epoxy resin is used, when the heat conductive sheet is brought into contact with the adherend under heating conditions to adhere to the adherend, This is because the viscosity of the epoxy resin is too low and the epoxy resin may ooze out from the edge of the heat conductive sheet.
If this epoxy resin bleeds heavily, an epoxy resin film is formed around the heat conductive sheet, for example, where the metal parts should be exposed, such as where the radiator is attached or where the contacts are located. There is a risk of problems in heat transfer, or problems such as poor conduction.
一方で、被着体への接着時にある程度の粘度低下が生じないと被着体と熱伝導性シートとの間に空隙などが生じやすく被着体側からの熱伝導性を低下させるおそれがある。
これらの問題をより確実に抑制させ得る点において、このエポキシ樹脂としては、エポキシ当量４５０〜２０００ｇ／ｅｑの常温固体のビスフェノールＡ型エポキシ樹脂と、エポキシ当量１６０〜２２０ｇ／ｅｑの多官能の常温固体で８７℃から９３℃の間に軟化点を有するノボラック型エポキシ樹脂とが（ビスフェノールＡ型エポキシ樹脂／ノボラック型エポキシ樹脂）＝４０／６０〜６０／４０となる質量比率で混合されているものを用いることが好ましい。
なお、このエポキシ当量は、ＪＩＳ Ｋ ７２３６により求めることができる。
On the other hand, if a certain degree of viscosity reduction does not occur at the time of adhesion to the adherend, a gap or the like is likely to be generated between the adherend and the thermal conductive sheet, and the thermal conductivity from the adherend side may be reduced.
In the point which can suppress these problems more reliably, as this epoxy resin, the epoxy equivalent 450-2000 g / eq of normal temperature solid bisphenol A type epoxy resin and the epoxy equivalent 160-220 g / eq of polyfunctional normal temperature solid And a novolac type epoxy resin having a softening point between 87 ° C. and 93 ° C. (bisphenol A type epoxy resin / novolak type epoxy resin) = 40/60 to 60/40 It is preferable to use it.
In addition, this epoxy equivalent can be calculated | required by JISK7236.
また、前記熱伝導性樹脂組成物には、本発明の効果を損ねない範囲において、各種の熱可塑性樹脂成分、ならびに、ゴム成分を前記ポリマー成分として含有させることも可能である。
前記熱伝導性樹脂組成物に含有される熱可塑性樹脂としては、ポリエチレン樹脂、ポリプロピレン樹脂、エチレン−酢酸ビニル共重合体樹脂などのポリオレフィン樹脂、ポリ塩化ビニル樹脂、ポリエステル樹脂、フェノキシ樹脂、アクリル樹脂、ポリアミド樹脂、ポリアミドイミド樹脂、ポリイミド樹脂、ポリエーテルアミドイミド樹脂、ポリエーテルアミド樹脂、ポリエーテルイミド樹脂などが挙げられる。
Further, the thermoplastic resin composition may contain various thermoplastic resin components and rubber components as the polymer component as long as the effects of the present invention are not impaired.
Examples of the thermoplastic resin contained in the thermally conductive resin composition include polyethylene resins, polypropylene resins, polyolefin resins such as ethylene-vinyl acetate copolymer resins, polyvinyl chloride resins, polyester resins, phenoxy resins, acrylic resins, Examples thereof include a polyamide resin, a polyamideimide resin, a polyimide resin, a polyetheramideimide resin, a polyetheramide resin, and a polyetherimide resin.
また、前記熱伝導性樹脂組成物に含有されるゴム成分としては、天然ゴム、ポリイソプレンゴム、スチレン−ブタジエン共重合体ゴム、ポリブタジエンゴム、エチレン−プロピレン共重合体ゴム、エチレン−プロピレン−ジエン共重合体ゴム、ブタジエン−アクリロニトリル共重合体ゴム、イソブチレン−イソプレン共重合体ゴム、クロロプレンゴム、シリコーンゴム、フッ素ゴム、クロロ・スルホン化ポリエチレン、ポリウレタンゴムなどが挙げられる。 The rubber component contained in the thermally conductive resin composition includes natural rubber, polyisoprene rubber, styrene-butadiene copolymer rubber, polybutadiene rubber, ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer. Examples thereof include polymer rubber, butadiene-acrylonitrile copolymer rubber, isobutylene-isoprene copolymer rubber, chloroprene rubber, silicone rubber, fluororubber, chlorosulfonated polyethylene, and polyurethane rubber.
前記マトリックス成分に前記ポリマー成分とともに含有される添加剤としては、特に限定されず、例えば、カップリング剤、分散剤、硬化剤、硬化促進剤、老化防止剤、酸化防止剤、安定剤、消泡剤、難燃剤、増粘剤、顔料などといったものを用いることができる。 The additive contained in the matrix component together with the polymer component is not particularly limited. For example, a coupling agent, a dispersant, a curing agent, a curing accelerator, an anti-aging agent, an antioxidant, a stabilizer, an antifoaming agent. Agents, flame retardants, thickeners, pigments and the like can be used.
前記マトリックス成分にエポキシ樹脂が含まれる場合においては、前記添加剤にエポキシ樹脂の硬化剤、硬化促進剤を含有させて熱伝導性樹脂組成物に熱硬化性を付与することができる。
この硬化剤としては、特に限定されるものではないが、例えば、ジアミノジフェニルスルホン、ジシアンジアミド、ジアミノジフェニルメタン、トリエチレンテトラミンなどのアミン系硬化剤、フェノールノボラック樹脂、アラルキル型フェノール樹脂、ジシクロペンタジエン変性フェノール樹脂、ナフタレン型フェノール樹脂、ビスフェノール系フェノール樹脂などのフェノール系硬化剤、酸無水物などを用いることができる。
中でも、ジアミノジフェニルスルホンが好適である。
前記硬化促進剤としては、特に限定されるものではないが、三フッ化ホウ素モノエチルアミンなどのアミン系硬化促進剤が好適である。
When the matrix component contains an epoxy resin, the additive can contain an epoxy resin curing agent and a curing accelerator to impart thermosetting properties to the thermally conductive resin composition.
The curing agent is not particularly limited, and examples thereof include amine curing agents such as diaminodiphenyl sulfone, dicyandiamide, diaminodiphenylmethane, and triethylenetetramine, phenol novolac resins, aralkyl type phenol resins, and dicyclopentadiene modified phenols. Resin, phenolic curing agents such as naphthalene type phenolic resin and bisphenolic phenolic resin, acid anhydrides and the like can be used.
Of these, diaminodiphenylsulfone is preferred.
The curing accelerator is not particularly limited, but an amine curing accelerator such as boron trifluoride monoethylamine is suitable.
このような熱伝導性フィラーとマトリックス成分との使用割合は特に限定されるものではないが、作製される熱伝導性シートに優れた熱伝導性を付与させ得る点からは、前記熱伝導性フィラーに窒化ホウ素フィラーを採用し、しかも、該窒化ホウ素フィラーがマトリックス成分１００質量部に対して２００〜６００質量部となる割合で用いることが好ましく、２５０〜５５０質量部となる割合で用いることがさらに好ましい。
熱伝導性シートの形成に窒化ホウ素フィラーをマトリックス成分に対してこのような割合で用いることが好ましいのは、マトリックス成分１００質量部に対する窒化ホウ素フィラーの量が２００質量部未満の場合には、得られる熱伝導性シートに十分な熱伝導性を付与することが困難となるためである。
また、６００質量部を超えて使用すると樹脂組成物作製工程にて作製される樹脂組成物の粘度が高くなりすぎて、均質な樹脂組成物を作製することが困難となり、成形加工工程における作業性を低下させるおそれがあるためである。
The use ratio of such a thermally conductive filler and a matrix component is not particularly limited. However, from the viewpoint of imparting excellent thermal conductivity to the produced thermally conductive sheet, the thermally conductive filler is used. In addition, it is preferable to use a boron nitride filler at a ratio of 200 to 600 parts by mass, and a ratio of 250 to 550 parts by mass with respect to 100 parts by mass of the matrix component. preferable.
It is preferable to use the boron nitride filler in such a ratio with respect to the matrix component for forming the thermally conductive sheet when the amount of the boron nitride filler with respect to 100 parts by mass of the matrix component is less than 200 parts by mass. This is because it becomes difficult to impart sufficient heat conductivity to the heat conductive sheet to be obtained.
Moreover, when it exceeds 600 mass parts, the viscosity of the resin composition produced in the resin composition production process becomes too high, making it difficult to produce a homogeneous resin composition, and workability in the molding process. It is because there is a possibility of lowering.
なお、窒化ホウ素フィラーは、通常、その粒子形状が鱗片状であり、粒子形状が球状の熱伝導性フィラーが用いられる場合に比べて熱伝導性樹脂組成物中における有機溶剤の拡散速度を低下させやすく有機溶剤の残留を発生させやすい。
このような点から、窒化ホウ素フィラーが樹脂成形品中に高充填されるような場合には、工程の簡略化ならびに熱伝導率の低下抑制といった本発明の効果を顕著に発揮させることができ、特に、窒化ホウ素フィラーが６５体積％以上の割合で含有されている熱伝導性樹脂組成物で樹脂成形品を形成させる場合においては、本発明の効果をより顕著に発揮させ得る。
The boron nitride filler usually has a scaly particle shape, and reduces the diffusion rate of the organic solvent in the heat conductive resin composition as compared with the case where a heat conductive filler having a spherical particle shape is used. It is easy to generate organic solvent residue.
From such a point, when the boron nitride filler is highly filled in the resin molded product, the effects of the present invention such as simplification of the process and suppression of decrease in thermal conductivity can be remarkably exhibited. In particular, in the case where a resin molded product is formed with a heat conductive resin composition containing a boron nitride filler in a proportion of 65% by volume or more, the effects of the present invention can be exhibited more remarkably.
次いで、前記のような材料を用いて熱伝導性シートを製造する方法について説明する。
本実施形態の樹脂成形品製造方法においては、まず、前記熱伝導性フィラーと、前記マトリックス成分とを用いて熱伝導性樹脂組成物を作製する樹脂組成物作製工程を実施し、前記樹脂組成物作製工程で作製された熱伝導性樹脂組成物を成形加工する成形加工工程を実施する。
Next, a method for producing a heat conductive sheet using the above materials will be described.
In the resin molded product production method of the present embodiment, first, a resin composition production step of producing a heat conductive resin composition using the heat conductive filler and the matrix component is performed, and the resin composition A molding process for molding the thermally conductive resin composition produced in the production process is performed.
前記樹脂組成物作製工程においては、次段の成形加工工程における成型加工を容易とさせるべくマトリックス成分に含有されている熱硬化性樹脂を未硬化状態となるように熱伝導性樹脂組成物を作製する。
なお、この樹脂組成物作製工程においては、有機溶剤を使用することなくマトリックス成分と熱伝導性フィラーとの混合を実施して熱伝導性樹脂組成物を作製する。
この樹脂組成物作製工程は、通常、ミキサーなどの一般的な混合攪拌手段を用いて実施することができ、有機溶剤を用いる場合のように防爆構造や排気機構などを有する特別な混合攪拌手段を必ずしも要さない。
In the resin composition preparation step, a heat conductive resin composition is prepared so that the thermosetting resin contained in the matrix component is in an uncured state in order to facilitate the forming process in the next forming step. To do.
In this resin composition preparation step, the heat conductive resin composition is prepared by mixing the matrix component and the heat conductive filler without using an organic solvent.
This resin composition preparation step can usually be carried out using a general mixing and stirring means such as a mixer, and a special mixing and stirring means having an explosion-proof structure and an exhaust mechanism as in the case of using an organic solvent. Not necessarily required.
この樹脂組成物作製工程においては、例えば、ポリマー成分が常温で液体状のものであれば、予めポリマー成分と添加剤とを混合してマトリックス成分を作製し、該マトリックス成分と熱伝導性フィラーとをミキサーで混合攪拌して熱伝導性樹脂組成物を作製することができる。
このとき、マトリックス成分と熱伝導性フィラー成分との比率によりマトリックス成分を比較的多く含む液状またはペースト状の熱伝導性樹脂組成物を作製したり、熱伝導性フィラー成分を比較的多く含む粉末状の熱伝導性樹脂組成物を作製したりすることができる。
In this resin composition preparation step, for example, if the polymer component is liquid at room temperature, a matrix component is prepared by previously mixing the polymer component and an additive, and the matrix component and the thermally conductive filler Can be mixed and stirred with a mixer to prepare a thermally conductive resin composition.
At this time, a liquid or paste-like heat conductive resin composition containing a relatively large amount of the matrix component is produced depending on the ratio of the matrix component and the heat conductive filler component, or a powdery state containing a relatively large amount of the heat conductive filler component. The heat conductive resin composition can be produced.
また、例えば、ポリマー成分が常温で固体状のものであれば、予めポリマー成分を粉砕するなどして粉末化して、この粉末と、添加剤と、熱伝導性フィラーとをミキサーで混合攪拌して粉末状の熱伝導性樹脂組成物を作製することができる。
あるいは、加熱手段の備えられたミキサーを用いて、軟化温度以上にポリマー成分を加熱して、この軟化状態のポリマー成分と、添加剤ならびに熱伝導性フィラーを混練した後にこの混練物の温度をポリマー成分の軟化温度以上に維持したまま次段の成形加工工程に供することもできる。
また、この加熱状態の混練物を造粒機などに投じて粒状の熱伝導性樹脂組成物を作製することもでき、さらには、この粒状の熱伝導性樹脂組成物を粉砕して粉末状の熱伝導性樹脂組成物を作製することもできる。
また、シランカップリング剤や分散剤など熱伝導性フィラー表面に担持させることが好適な添加剤を用いる場合には、予めシランカップリング剤や分散剤などと熱伝導性フィラーとを混合攪拌した後に、この熱伝導性フィラーとポリマー成分とを混合攪拌させて熱伝導性樹脂組成物を作製する二段階の樹脂組成物作製工程を採用することも可能である。
For example, if the polymer component is solid at room temperature, the polymer component is pulverized in advance, and the powder, additive, and heat conductive filler are mixed and stirred with a mixer. A powdery heat conductive resin composition can be produced.
Alternatively, using a mixer equipped with a heating means, the polymer component is heated to a temperature above the softening temperature, and the softened polymer component, the additive, and the thermally conductive filler are kneaded, and then the temperature of the kneaded product is changed to the polymer. It can also be used for the next molding step while maintaining the temperature above the softening temperature of the components.
Further, the heated kneaded product can be poured into a granulator or the like to produce a granular heat conductive resin composition. Furthermore, the granular heat conductive resin composition is pulverized to form a powder. A heat conductive resin composition can also be produced.
In addition, when using an additive suitable to be carried on the surface of the heat conductive filler such as a silane coupling agent or a dispersant, the silane coupling agent or the dispersant and the heat conductive filler are mixed and stirred in advance. It is also possible to employ a two-step resin composition preparation process in which the heat conductive filler and polymer component are mixed and stirred to prepare a heat conductive resin composition.
次いで、樹脂組成物作製工程で作製された熱伝導性樹脂組成物を用いてシート状に成形加工する成形加工工程を実施して熱伝導性シートを製造する。
この成形加工工程においても、有機溶剤を使用することなく成型加工を実施する。
この成形加工方法については、例えば、金型を用いたプレス成形、押出し成形、射出成形、カレンダー成形など広く一般に用いられている樹脂成形品の成型加工方法を本実施形態の樹脂成形品製造方法においても採用することができる。
なお、要すれば、真空プレスやベント機構付の押出し機を用いることにより、熱伝導性シート内に空気層が形成されるおそれを低減させ得る。
また、前記添加剤として硬化剤を熱伝導性樹脂組成物に含有させておいて、この成形加工工程において樹脂成形品の成型加工方法を実施するとともに、熱硬化性樹脂の熱硬化を同時に実施させることも可能である。
Next, a heat conductive sheet is manufactured by carrying out a molding process in which the heat conductive resin composition produced in the resin composition production process is molded into a sheet.
In this molding process, the molding process is performed without using an organic solvent.
With respect to this molding method, for example, a widely used resin molding product molding method such as press molding using a mold, extrusion molding, injection molding, calender molding, etc. in the resin molded product manufacturing method of the present embodiment Can also be adopted.
In addition, if needed, a possibility that an air layer may be formed in a heat conductive sheet can be reduced by using an extruder with a vacuum press or a vent mechanism.
In addition, a curing agent is included in the thermally conductive resin composition as the additive, and in this molding process, the molding method of the resin molded product is performed, and the thermosetting of the thermosetting resin is simultaneously performed. It is also possible.
この樹脂組成物作製工程、成形加工工程のいずれにおいても有機溶剤が用いられないことから、有機溶剤を除去するための乾燥工程などを省略させ得るとともに乾燥工程で排出される有機溶剤を含む排ガスなどを処理するための工程も省略させ得る。
しかも、残留有機溶剤の起因する発泡が熱伝導性シート内に発生することを防止し得ることから、樹脂成形品の熱伝導率の低下を抑制させ得る。
Since neither an organic solvent is used in any of the resin composition preparation process and the molding process, an exhaust gas containing an organic solvent discharged in the drying process can be omitted and the drying process for removing the organic solvent can be omitted. The process for processing can also be omitted.
And since it can prevent that the foaming resulting from a residual organic solvent generate | occur | produces in a heat conductive sheet, the fall of the heat conductivity of a resin molded product can be suppressed.
なお、本実施形態においては、熱伝導性シートを例に説明したが、本発明の樹脂成形品製造方法によって製造される樹脂成形品を熱伝導性シートに限定するものではない。
また、熱硬化性樹脂として、主として、エポキシ樹脂を用いる場合を例示したが、本発明においては熱硬化性樹脂をエポキシ樹脂に限定するものではない。
In the present embodiment, the heat conductive sheet has been described as an example. However, the resin molded product manufactured by the resin molded product manufacturing method of the present invention is not limited to the heat conductive sheet.
Moreover, although the case where an epoxy resin is mainly used as a thermosetting resin was illustrated, in this invention, a thermosetting resin is not limited to an epoxy resin.
次に実施例を挙げて本発明をさらに詳しく説明するが、本発明はこれらに限定されるものではない。 EXAMPLES Next, although an Example is given and this invention is demonstrated in more detail, this invention is not limited to these.
（実施例１）
（樹脂組成物作製工程）
ビフェニルタイプのエポキシ樹脂（ジャパンエポキシレジン社製、商品名「ＹＸ−４０００Ｈ」）５５０ｇと、フェノール樹脂（明和化成社製、商品名「ＭＥＨ−７８５１ＳＳ」）５５０ｇと、硬化剤である４，４’−ジアミノジフェニルスルホン（和歌山精化社製、商品名「セイカキュアーＳ」）１５ｇ、窒化ホウ素フィラー（昭和電工社製。商品名「ＵＨＰ−１」）１０ｋｇ、シランカップリング剤（３−グリシドキシプロピルトリメトキシシラン）（信越化学工業社製、商品名「ＫＢＭ−４０３」）１０ｇをヘンシェルミキサーで混合攪拌して一次分散体を作製し、該一次分散体を５ｋｇ／ｈの供給スピードで二軸混練機（栗本鐵工社製）に供給して混練を行いエポキシ樹脂が未硬化状態で含有されている熱伝導性樹脂組成物を作製した。
なお、この樹脂組成物作製工程において作製された熱伝導性樹脂組成物に占める窒化ホウ素フィラーの割合は、体積で６０％であった。
(Example 1)
(Resin composition preparation process)
550 g of biphenyl type epoxy resin (trade name “YX-4000H” manufactured by Japan Epoxy Resin Co., Ltd.), 550 g of phenol resin (trade name “MEH-7851SS” manufactured by Meiwa Kasei Co., Ltd.), and 4,4 ′ as a curing agent -Diaminodiphenyl sulfone (Wakayama Seika Co., Ltd., trade name “Seika Cure S”) 15 g, Boron nitride filler (Showa Denko Co., Ltd., trade name “UHP-1”) 10 kg, Silane coupling agent (3-glycidoxy Propyltrimethoxysilane) (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBM-403”) was mixed and stirred with a Henschel mixer to prepare a primary dispersion, and the primary dispersion was biaxially fed at a supply speed of 5 kg / h. The mixture was supplied to a kneader (manufactured by Kurimoto Seiko Co., Ltd.) and kneaded to prepare a thermally conductive resin composition containing an epoxy resin in an uncured state. .
In addition, the ratio of the boron nitride filler to the heat conductive resin composition produced in this resin composition production process was 60% by volume.
（成形加工工程）
樹脂組成物作製工程において作製された熱伝導性樹脂組成物を熱プレスによるプレス成形を実施して０．２ｍｍ厚さのシート状に加工するとともにエポキシ樹脂の硬化反応を実施させて熱伝導性シートを製造した。
(Molding process)
The thermally conductive resin composition produced in the resin composition production process is subjected to press molding by hot pressing to be processed into a sheet having a thickness of 0.2 mm, and a curing reaction of the epoxy resin is carried out to produce a thermally conductive sheet. Manufactured.
（実施例２）
樹脂組成物作製工程における窒化ホウ素フィラーの使用量を増大させて、窒化ホウ素フィラーの割合が、体積で６５％となるように熱伝導性樹脂組成物を作製した以外は、実施例１と同様に樹脂組成物作製工程および成形加工工程を実施して熱伝導性シートを製造した。
(Example 2)
As in Example 1, except that the amount of boron nitride filler used in the resin composition preparation step was increased and the heat conductive resin composition was prepared such that the proportion of boron nitride filler was 65% by volume. The heat conductive sheet was manufactured by implementing the resin composition preparation process and the molding process.
（実施例３）
樹脂組成物作製工程における窒化ホウ素フィラーの使用量を増大させて、窒化ホウ素フィラーの割合が、体積で７０％となるように熱伝導性樹脂組成物を作製した以外は、実施例１と同様に樹脂組成物作製工程および成形加工工程を実施して熱伝導性シートを製造した。
(Example 3)
As in Example 1, except that the amount of boron nitride filler used in the resin composition preparation step was increased and the heat conductive resin composition was prepared such that the proportion of boron nitride filler was 70% by volume. The heat conductive sheet was manufactured by implementing the resin composition preparation process and the molding process.
（比較例１）
（樹脂組成物作製工程）
ビフェニルタイプのエポキシ樹脂（ジャパンエポキシレジン社製、商品名「ＹＸ−４０００Ｈ」）５５０ｇと、フェノール樹脂（明和化成社製、商品名「ＭＥＨ−７８５１ＳＳ」）５５０ｇと、硬化剤である４，４’−ジアミノジフェニルスルホン（和歌山精化社製、商品名「セイカキュアーＳ」）１５ｇを２−ブタノンに溶解させて固形分濃度６０質量％の樹脂溶液を作製した。
窒化ホウ素フィラー（昭和電工社製。商品名「ＵＨＰ−１」）１００ｇを、減圧装置を備えた攪拌釜に投入し、前記樹脂溶液１７ｇ（を加え、ゆっくりと攪拌しながら攪拌釜内部を減圧状態にして２０分間攪拌を実施した後に常圧に戻し、さらに、残留する２−ブタノンを除去すべく常温・常圧で一昼夜乾燥させてエポキシ樹脂が未硬化状態で含有されている熱伝導性樹脂組成物を作製した。
なお、この粉末状の熱伝導性樹脂組成物に占める窒化ホウ素フィラーの割合は、体積で６０％であった。
(Comparative Example 1)
(Resin composition preparation process)
550 g of biphenyl type epoxy resin (trade name “YX-4000H” manufactured by Japan Epoxy Resin Co., Ltd.), 550 g of phenol resin (trade name “MEH-7851SS” manufactured by Meiwa Kasei Co., Ltd.), and 4,4 ′ as a curing agent -Diaminodiphenyl sulfone (trade name “Seika Cure S” manufactured by Wakayama Seika Co., Ltd.) 15 g was dissolved in 2-butanone to prepare a resin solution having a solid content of 60% by mass.
100 g of boron nitride filler (made by Showa Denko Co., Ltd., trade name “UHP-1”) was put into a stirring vessel equipped with a decompression device, and 17 g of the resin solution (added) was stirred and the inside of the stirring vessel was in a reduced pressure state. The composition is then returned to normal pressure after stirring for 20 minutes, and further dried at room temperature and pressure for 24 hours to remove residual 2-butanone, and the epoxy resin is contained in an uncured state. A product was made.
In addition, the ratio of the boron nitride filler to this powdery heat conductive resin composition was 60% by volume.
（成形加工工程）
樹脂組成物作製工程において作製された粉末状の熱伝導性樹脂組成物を熱プレスによるプレス成形を実施して０．２ｍｍ厚さのシート状に加工するとともにエポキシ樹脂の硬化反応を実施させて熱伝導性シートを製造した。
(Molding process)
The powdered thermally conductive resin composition produced in the resin composition production step is subjected to press molding by hot pressing to be processed into a sheet having a thickness of 0.2 mm, and a curing reaction of the epoxy resin is carried out to produce heat. A conductive sheet was produced.
（比較例２）
樹脂組成物作製工程における窒化ホウ素フィラーの使用量を増大させて、窒化ホウ素フィラーの割合が、体積で６５％となるように熱伝導性樹脂組成物を作製した以外は、比較例１と同様に樹脂組成物作製工程および成形加工工程を実施して熱伝導性シートを製造した。
(Comparative Example 2)
As in Comparative Example 1, except that the amount of boron nitride filler used in the resin composition preparation step was increased and the heat conductive resin composition was prepared so that the proportion of boron nitride filler was 65% by volume. The heat conductive sheet was manufactured by implementing the resin composition preparation process and the molding process.
（比較例３）
樹脂組成物作製工程における窒化ホウ素フィラーの使用量を増大させて、窒化ホウ素フィラーの割合が、体積で７０％となるように熱伝導性樹脂組成物を作製した以外は、比較例１と同様に樹脂組成物作製工程および成形加工工程を実施して熱伝導性シートを製造した。
(Comparative Example 3)
As in Comparative Example 1, except that the amount of boron nitride filler used in the resin composition preparation step was increased and the heat conductive resin composition was prepared so that the proportion of boron nitride filler was 70% by volume. The heat conductive sheet was manufactured by implementing the resin composition preparation process and the molding process.
（評価）
各実施例、比較例で作製した熱伝導性シートを用いて熱伝導率の測定を実施した。
熱伝導率は、アイフェイズ社製、商品名「ａｉ−ｐｈａｓｅ ｍｏｂｉｌｅ」により熱拡散率を求め、さらに、示差走査熱量計（ＤＳＣ）を用いた測定により熱伝導性シートの単位体積あたりの熱容量を測定し、先の熱拡散率に乗じることにより算出した。
また、硬化された熱伝導性シートの脆さを指触にて判定し、取り扱いが良好で成形時における支障が生じないと見られるものを「○」、やや脆い感じがあるものの実用上問題ない普通レベルと感じられるものを「△」、もろく、成形時に慎重な取り扱いを要するものを「×」として判定した。
結果を表１に示す。
(Evaluation)
The thermal conductivity was measured using the thermal conductive sheet produced in each example and comparative example.
The thermal conductivity is obtained by the product name “ai-phase mobile” manufactured by Eye Phase Co., Ltd., and the heat capacity per unit volume of the thermal conductive sheet is determined by measurement using a differential scanning calorimeter (DSC). Measured and calculated by multiplying the previous thermal diffusivity.
Also, the brittleness of the cured thermal conductive sheet is judged by touch, and “○” indicates that the handling is good and does not cause trouble during molding, but there is no problem in practical use although there is a slight brittle feeling. A material that was felt to be a normal level was evaluated as “Δ”, and a material that was fragile and required careful handling at the time of molding was determined as “×”.
The results are shown in Table 1.
この表１の結果からも、本発明によれば有機溶剤の除去に要する手間を省略させて樹脂成形品製造方法を簡略化しつつ得られる樹脂成形品の熱伝導率の低下を抑制させ得ることがわかる。
また、窒化ホウ素フィラーが６５体積％以上含有されている熱伝導性樹脂組成物を用いた実施例２、３においては、同じ窒化ホウ素フィラー含有率である比較例２、３に対して優れた熱伝導性を示す樹脂成形品が製造されていることもこの表１からわかる。
Also from the results of Table 1, according to the present invention, it is possible to suppress the decrease in the thermal conductivity of the resin molded product obtained while simplifying the resin molded product manufacturing method by omitting the labor required for removing the organic solvent. Recognize.
Further, in Examples 2 and 3 using the thermally conductive resin composition containing 65% by volume or more of the boron nitride filler, heat superior to Comparative Examples 2 and 3 having the same boron nitride filler content. It can also be seen from Table 1 that a resin molded product exhibiting conductivity is manufactured.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007033353A JP5002280B2 (en) | 2007-02-14 | 2007-02-14 | Resin molded product manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007033353A JP5002280B2 (en) | 2007-02-14 | 2007-02-14 | Resin molded product manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2008195850A true JP2008195850A (en) | 2008-08-28 |
| JP5002280B2 JP5002280B2 (en) | 2012-08-15 |
Family
ID=39755096
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2007033353A Expired - Fee Related JP5002280B2 (en) | 2007-02-14 | 2007-02-14 | Resin molded product manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5002280B2 (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012031242A (en) * | 2010-07-29 | 2012-02-16 | Nitto Denko Corp | Heat-conductive sheet |
| JP2012039066A (en) * | 2010-01-29 | 2012-02-23 | Nitto Denko Corp | Heat-conductive sheet |
| JP2012039061A (en) * | 2010-01-29 | 2012-02-23 | Nitto Denko Corp | Heat-conductive sheet |
| JP2012039060A (en) * | 2010-01-29 | 2012-02-23 | Nitto Denko Corp | Heat-conductive sheet |
| JP2012036364A (en) * | 2010-01-29 | 2012-02-23 | Nitto Denko Corp | Heat-conductive sheet |
| JP2012036365A (en) * | 2010-01-29 | 2012-02-23 | Nitto Denko Corp | Thermally conductive sheet |
| JP2012039065A (en) * | 2010-01-29 | 2012-02-23 | Nitto Denko Corp | Heat-conductive sheet |
| JP2012039062A (en) * | 2010-01-29 | 2012-02-23 | Nitto Denko Corp | Heat-conductive sheet |
| JP2012039064A (en) * | 2010-01-29 | 2012-02-23 | Nitto Denko Corp | Heat-conductive sheet |
| JP2012049493A (en) * | 2010-01-29 | 2012-03-08 | Nitto Denko Corp | Imaging part |
| JP2012049495A (en) * | 2010-01-29 | 2012-03-08 | Nitto Denko Corp | Light-emitting diode device |
| JP2013062379A (en) * | 2011-09-13 | 2013-04-04 | Nitto Denko Corp | Thermally conductive sheet and method for manufacturing the same |
| JP2013249330A (en) * | 2012-05-30 | 2013-12-12 | Canon Inc | Molded article and method of producing the same |
| JP2021054922A (en) * | 2019-09-30 | 2021-04-08 | 富士フイルム株式会社 | Composition for forming thermally conductive material, thermally conductive material, thermally conductive sheet, device with thermally conductive layer |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000022289A (en) * | 1998-07-01 | 2000-01-21 | Denki Kagaku Kogyo Kk | Resin composition for circuit board and circuit board using the same |
| JP2002237554A (en) * | 2001-02-07 | 2002-08-23 | Denki Kagaku Kogyo Kk | Heat conductive resin formation and its use |
-
2007
- 2007-02-14 JP JP2007033353A patent/JP5002280B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000022289A (en) * | 1998-07-01 | 2000-01-21 | Denki Kagaku Kogyo Kk | Resin composition for circuit board and circuit board using the same |
| JP2002237554A (en) * | 2001-02-07 | 2002-08-23 | Denki Kagaku Kogyo Kk | Heat conductive resin formation and its use |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012039065A (en) * | 2010-01-29 | 2012-02-23 | Nitto Denko Corp | Heat-conductive sheet |
| JP2012039064A (en) * | 2010-01-29 | 2012-02-23 | Nitto Denko Corp | Heat-conductive sheet |
| JP2012039061A (en) * | 2010-01-29 | 2012-02-23 | Nitto Denko Corp | Heat-conductive sheet |
| JP2012039060A (en) * | 2010-01-29 | 2012-02-23 | Nitto Denko Corp | Heat-conductive sheet |
| JP2012036364A (en) * | 2010-01-29 | 2012-02-23 | Nitto Denko Corp | Heat-conductive sheet |
| JP2012036365A (en) * | 2010-01-29 | 2012-02-23 | Nitto Denko Corp | Thermally conductive sheet |
| JP2012039066A (en) * | 2010-01-29 | 2012-02-23 | Nitto Denko Corp | Heat-conductive sheet |
| JP2012039062A (en) * | 2010-01-29 | 2012-02-23 | Nitto Denko Corp | Heat-conductive sheet |
| JP2012049495A (en) * | 2010-01-29 | 2012-03-08 | Nitto Denko Corp | Light-emitting diode device |
| JP2012049493A (en) * | 2010-01-29 | 2012-03-08 | Nitto Denko Corp | Imaging part |
| JP2012031242A (en) * | 2010-07-29 | 2012-02-16 | Nitto Denko Corp | Heat-conductive sheet |
| JP2013062379A (en) * | 2011-09-13 | 2013-04-04 | Nitto Denko Corp | Thermally conductive sheet and method for manufacturing the same |
| JP2013249330A (en) * | 2012-05-30 | 2013-12-12 | Canon Inc | Molded article and method of producing the same |
| JP2021054922A (en) * | 2019-09-30 | 2021-04-08 | 富士フイルム株式会社 | Composition for forming thermally conductive material, thermally conductive material, thermally conductive sheet, device with thermally conductive layer |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5002280B2 (en) | 2012-08-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5002280B2 (en) | Resin molded product manufacturing method | |
| JP4889110B2 (en) | Thermally conductive resin composition, thermal conductive sheet and method for producing the same | |
| TWI687393B (en) | Agglomerated boron nitride particles, a method for producing agglomerated boron nitride particles, a resin composition including the agglomerated boron nitride particles, molding, and sheet | |
| JP5134824B2 (en) | Resin molded product manufacturing method | |
| WO2012070289A1 (en) | Thermal conductive sheet and power module | |
| WO2011104996A1 (en) | Thermosetting resin composition, b-stage thermally conductive sheet, and power module | |
| JP2014040533A (en) | Thermosetting resin composition; method for manufacturing a heat-conductive resin sheet; and heat-conductive resin sheet; and semiconductor device for power applications | |
| JP6801659B2 (en) | Epoxy resin composition, film epoxy resin composition and electronic device | |
| TWI642711B (en) | Thermosetting resin composition and thermal conducting sheet | |
| TWI690484B (en) | Manufacturing method of glass-coated aluminum nitride particles and manufacturing method of exothermic resin composition containing glass-coated aluminum nitride particles | |
| TWI679252B (en) | Glass-coated aluminum nitride particles, method for producing the same, and exothermic resin composition containing the same | |
| KR101898234B1 (en) | Resin composition, article prepared by using the same and method of preparing the same | |
| JP2009188142A (en) | Epoxy resin tablet for semiconductor sealing, and manufacturing method thereof | |
| WO2018150779A1 (en) | Resin composition, resin sheet, semiconductor device and method for producing semiconductor device | |
| JP7383971B2 (en) | Resin compositions, cured resin products and composite molded bodies | |
| CN112771123A (en) | Resin composition, cured resin, and composite molded article | |
| WO2014119449A1 (en) | Method for producing module substrate and electronic device | |
| JP2006089579A (en) | Thermally conductive sheet and method for producing the same | |
| JP2022151865A (en) | Laminated structure and manufacturing method thereof | |
| JP2019083342A (en) | Sealing sheet with separator, and manufacturing method of semiconductor device | |
| TWI643890B (en) | Resin sheet for hollow sealing and manufacturing method of hollow package | |
| TW202302740A (en) | Resin composition, cured product sheet, composite molded body and semiconductor device | |
| JP4883064B2 (en) | Manufacturing method of resin molding | |
| JP2013124342A (en) | Flaky molding material and molded article using the same | |
| JP2016204669A (en) | Thermosetting resin composition, manufacturing method of heat conductive resin sheet, heat conductive resin sheet and semiconductor device for electric power |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| RD04 | Notification of resignation of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7424 Effective date: 20080626 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20091116 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20110929 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20111007 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20111128 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20120511 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20120521 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150525 Year of fee payment: 3 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |