JP5370129B2 - Thermosetting resin composition, prepreg and laminate - Google Patents
Thermosetting resin composition, prepreg and laminate Download PDFInfo
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本発明は、熱伝導性の良い絶縁層を提供するための熱硬化性樹脂組成物に関する。また、当該熱硬化性樹脂組成物を用いたプリプレグ及び積層板に関する。この絶縁層は、発熱部品を実装するプリント配線板の絶縁層として好適である。 The present invention relates to a thermosetting resin composition for providing an insulating layer having good thermal conductivity. Moreover, it is related with the prepreg and laminated board using the said thermosetting resin composition. This insulating layer is suitable as an insulating layer of a printed wiring board on which a heat generating component is mounted.
電子機器に搭載する配線板は、電子機器の軽薄短小化に伴う微細配線・高密度実装の技術が求められる一方で、発熱に対応する高放熱の技術も求められている。特に、各種制御・操作に大電流を使用する自動車などにおける電子回路では、導電回路の抵抗に起因する発熱やパワー素子からの発熱が非常に多く、配線板の放熱特性は高レベルであることが必須となってきている。 A wiring board mounted on an electronic device is required to have a technology for fine wiring and high-density mounting in accordance with a reduction in the thickness and size of the electronic device, and a technology for high heat dissipation corresponding to heat generation is also required. In particular, in electronic circuits such as automobiles that use a large current for various controls and operations, heat generation due to the resistance of the conductive circuit and heat generation from the power element are very large, and the heat dissipation characteristics of the wiring board may be high. It has become essential.
そのような現状において、絶縁層の熱伝導性を向上させるために、熱硬化性樹脂に無機充填材を添加することは広く行われている。例えば、熱硬化性樹脂に鱗片状無機充填材と粒子状無機充填材との混合充填材を添加した熱伝導性樹脂シートが特許文献１に記載されている。この熱伝導性樹脂シートは、鱗片状無機充填材と粒子状無機充填材とを混合し、鱗片状無機充填材を厚さ方向に配向させることにより、樹脂シートの厚さ方向の熱伝導性を向上させるものである。 Under such circumstances, it is widely performed to add an inorganic filler to the thermosetting resin in order to improve the thermal conductivity of the insulating layer. For example, Patent Document 1 discloses a thermally conductive resin sheet in which a mixed filler of a scaly inorganic filler and a particulate inorganic filler is added to a thermosetting resin. This heat conductive resin sheet mixes the scale-like inorganic filler and the particulate inorganic filler, and orients the scale-like inorganic filler in the thickness direction, thereby increasing the heat conductivity in the thickness direction of the resin sheet. It is to improve.
また、無機充填材として窒化アルミニウムと酸化アルミニウムの混合充填材を添加した熱硬化性樹脂組成物が特許文献２に記載されている。この熱硬化性樹脂組成物は、高熱伝導性の窒化アルミニウムを使用することにより、樹脂組成物の熱伝導率を向上させるものである。 Patent Document 2 discloses a thermosetting resin composition to which a mixed filler of aluminum nitride and aluminum oxide is added as an inorganic filler. This thermosetting resin composition improves the thermal conductivity of the resin composition by using high thermal conductivity aluminum nitride.
熱硬化性樹脂組成物の熱伝導率を向上させる方法として、熱伝導率の高い鱗片状窒化ホウ素や窒化アルミニウムを添加する方法がある。しかし、これらの無機充填材を高充填した場合、吸湿後の絶縁特性が低下するという問題があり、この方法による放熱特性の向上には限界があった。また、前記樹脂組成物をプリプレグに適用する場合、樹脂組成物の粘度が高くなり、繊維基材への含浸性が悪化するという問題がある。 As a method for improving the thermal conductivity of the thermosetting resin composition, there is a method of adding scaly boron nitride or aluminum nitride having high thermal conductivity. However, when these inorganic fillers are highly filled, there is a problem that the insulation characteristics after moisture absorption is lowered, and there is a limit to the improvement of the heat dissipation characteristics by this method. Moreover, when applying the said resin composition to a prepreg, there exists a problem that the viscosity of a resin composition becomes high and the impregnation property to a fiber base material deteriorates.
本発明が解決しようとする第１の課題は、吸湿後の絶縁特性を低下させることなく、放熱特性を向上させた熱硬化性樹脂組成物を提供することである。また、本発明が解決しようとする第２の課題は、前記樹脂組成物をプリプレグに適用した場合においても、繊維基材への含浸性を悪化させることのない熱硬化性樹脂組成物を提供することである。 The first problem to be solved by the present invention is to provide a thermosetting resin composition having improved heat dissipation characteristics without deteriorating the insulation characteristics after moisture absorption. The second problem to be solved by the present invention is to provide a thermosetting resin composition that does not deteriorate the impregnation property to the fiber base material even when the resin composition is applied to a prepreg. That is.
上記課題を解決するために、本発明に係る熱硬化性樹脂組成物は、熱硬化性樹脂に、二次粒子の平均粒子径が２０〜４０μｍの窒化アルミニウムと、一次粒子の平均粒子径が異なる３種類の酸化アルミニウムとを含有させる。そして、前記熱硬化性樹脂固形分と窒化アルミニウムと酸化アルミニウムとの合計体積に対し、窒化アルミニウムを３５〜４５体積％、酸化アルミニウムを３０〜４５体積％で用いる。さらに、前記酸化アルミニウムの一次粒子の平均粒子径が、０．１μｍ以上１μｍ未満のもの（ａ群）と、１μｍ以上１０μｍ未満のもの（ｂ群）と、１０μｍ以上３５μｍ以下のもの（ｃ群）とで構成される。 In order to solve the above-described problems, the thermosetting resin composition according to the present invention is different from the thermosetting resin in that the average particle diameter of primary particles is different from that of aluminum nitride whose average particle diameter of secondary particles is 20 to 40 μm. Three types of aluminum oxide are contained. And 35-45 volume% of aluminum nitride and 30-45 volume% of aluminum oxide are used with respect to the total volume of the said thermosetting resin solid content, aluminum nitride, and aluminum oxide. Furthermore, the average particle diameter of the primary particles of the aluminum oxide is 0.1 μm or more and less than 1 μm (group a), 1 μm or more and less than 10 μm (group b), and 10 μm or more and 35 μm or less (group c). Ru is composed of a.
そして、前記窒化アルミニウムの二次粒子の平均粒子径（Ａ）と、前記ｃ群の酸化アルミニウムの一次粒子の平均粒子径（Ｂ）とが、（Ａ）／（Ｂ）を、０．８〜１．３とすることを特徴とする（請求項１）。 And the average particle diameter (A) of the secondary particles of the aluminum nitride and the average particle diameter (B) of the primary particles of the aluminum oxide of the c group have (A) / (B) of 0.8 to characterized by 1.3 (claim 1).
本発明に係るプリプレグは、上述の熱硬化性樹脂組成物を繊維基材に含浸し乾燥してなるものである（請求項２）。
本発明に係る積層板は、上述のプリプレグの層を一部ないし全部として加熱加圧成形してなるものである（請求項３）。
The prepreg according to the present invention is obtained by impregnating a fiber base material with the thermosetting resin composition described above and drying it (Claim 2 ).
The laminated board according to the present invention is formed by heating and press-molding a part or all of the above-described prepreg layer (Claim 3 ).
本発明に係る熱硬化性樹脂組成物は、窒化アルミニウムとそれと近似した平均粒子径を有する酸化アルミニウムを含有させ、かつ、窒化アルミニウム及び酸化アルミニウムの平均粒子径、含有量を最適化することにより、吸湿後の絶縁特性を低下させることなく、放熱特性を向上させることができる。また、前記樹脂組成物は、窒化アルミニウム及び酸化アルミニウムの平均粒子径、含有量を最適化することにより、樹脂組成物の粘度を低く抑えることができ、プリプレグに適用した場合においても、繊維基材への含浸性を悪化させることはない。 The thermosetting resin composition according to the present invention contains aluminum nitride and aluminum oxide having an average particle size approximate to that of aluminum nitride, and by optimizing the average particle size and content of aluminum nitride and aluminum oxide, The heat dissipation characteristics can be improved without deteriorating the insulation characteristics after moisture absorption. Further, the resin composition can suppress the viscosity of the resin composition by optimizing the average particle diameter and content of aluminum nitride and aluminum oxide, and even when applied to a prepreg, the fiber base material It does not deteriorate the impregnation property.
本発明に係る熱硬化性樹脂組成物は、熱硬化性樹脂に、二次粒子の平均粒子径が２０〜４０μｍの窒化アルミニウムと、一次粒子の平均粒子径が異なる３種類の酸化アルミニウムとを含有させる。そして、前記熱硬化性樹脂固形分と窒化アルミニウムと酸化アルミニウムとの合計体積に対し、窒化アルミニウムを３５〜４５体積％、酸化アルミニウムを３０〜４５体積％で用いる。さらに、前記酸化アルミニウムの一次粒子の平均粒子径が、０．１μｍ以上１μｍ未満のもの（ａ群）と、１μｍ以上１０μｍ未満のもの（ｂ群）と、１０μｍ以上３５μｍ以下のもの（ｃ群）とで構成される。 The thermosetting resin composition according to the present invention contains, in the thermosetting resin, aluminum nitride having an average secondary particle diameter of 20 to 40 μm and three types of aluminum oxide having different primary particle average particle diameters. Let And 35-45 volume% of aluminum nitride and 30-45 volume% of aluminum oxide are used with respect to the total volume of the said thermosetting resin solid content, aluminum nitride, and aluminum oxide. Furthermore, the average particle diameter of the primary particles of the aluminum oxide is 0.1 μm or more and less than 1 μm (group a), 1 μm or more and less than 10 μm (group b), and 10 μm or more and 35 μm or less (group c). It consists of.
ここで、一次粒子とは、無機充填材粉末を構成する最小の粒子単体のことであり、二次粒子とは、前記一次粒子が凝集した凝集体のことである。
また、平均粒子径は、公知のレーザー回折・散乱法による粒度測定装置（例えば、日機装株式会社製「マイクロトラックＳＰＡ−７９９７型」）を用いて測定したものである。ここで、レーザー回折・散乱法とは、充填材粒子にレーザー光を照射したとき、粒子径により散乱光の強度パターンが変化することを利用した測定法である。
Here, the primary particles are the smallest single particles constituting the inorganic filler powder, and the secondary particles are aggregates in which the primary particles are aggregated.
The average particle diameter is measured using a known particle size measuring apparatus by a laser diffraction / scattering method (for example, “Microtrack SPA-7997 type” manufactured by Nikkiso Co., Ltd.). Here, the laser diffraction / scattering method is a measurement method utilizing the fact that the intensity pattern of the scattered light changes depending on the particle diameter when the filler particles are irradiated with laser light.
本発明では、二次粒子の平均粒子径が２０〜４０μｍの窒化アルミニウムと、一次粒子の平均粒子径が異なる３種類の酸化アルミニウムとを含有させる。そして、前記酸化アルミニウムの一次粒子の平均粒子径が、０．１μｍ以上１μｍ未満のもの（ａ群）と、１μｍ以上１０μｍ未満のもの（ｂ群）と、１０μｍ以上３５μｍ以下のもの（ｃ群）とで構成される。 In the present invention, aluminum nitride having an average secondary particle diameter of 20 to 40 μm and three types of aluminum oxide having different primary particle average particle diameters are contained. And the average particle diameter of the primary particle of the aluminum oxide is 0.1 μm or more and less than 1 μm (group a), 1 μm or more and less than 10 μm (group b), and 10 μm or more and 35 μm or less (group c). It consists of.
窒化アルミニウム及び酸化アルミニウムの平均粒子径がそれぞれ上記の範囲より小さいと、無機充填材粒子の接触点が増えるため、すなわち樹脂の熱抵抗が増大するため、熱伝導率が向上しない。なお、酸化アルミニウムの平均粒子径が０．１μｍ未満では、無機充填材粒子の表面積が大きく、樹脂量を増やさないと無機充填材粒子を樹脂で覆いきれず、硬化物中にボイドが発生する。また樹脂組成物の粘度が高くなり繊維基材への含浸性が悪化する。
また、酸化アルミニウムの平均粒子径がそれぞれ上記の範囲より大きいと、無機充填材粒子の間に隙間が生じやすくなり、そのため、硬化物中にボイドが発生し、熱伝導率が向上しない。なお、窒化アルミニウムの平均粒子径が４０μｍを超えると、吸湿しやすくなるため吸湿後の絶縁特性が低下する。
When the average particle diameters of aluminum nitride and aluminum oxide are smaller than the above ranges, the contact points of the inorganic filler particles increase, that is, the thermal resistance of the resin increases, so that the thermal conductivity is not improved. When the average particle diameter of aluminum oxide is less than 0.1 μm, the surface area of the inorganic filler particles is large, and unless the amount of resin is increased, the inorganic filler particles cannot be covered with the resin, and voids are generated in the cured product. Moreover, the viscosity of a resin composition becomes high and the impregnation property to a fiber base material deteriorates.
Moreover, when the average particle diameter of aluminum oxide is larger than the above range, gaps are likely to be generated between the inorganic filler particles, so that voids are generated in the cured product and the thermal conductivity is not improved. In addition, when the average particle diameter of aluminum nitride exceeds 40 μm, it becomes easy to absorb moisture, so that the insulating properties after moisture absorption are deteriorated.
また、平均粒子径が異なる２種類の酸化アルミニウムを使用した場合、例えば、０．１μｍ以上１μｍ未満のもの（ａ群）と、１０μｍ以上３５μｍ以下のもの（ｃ群）とで構成すると、小粒径の酸化アルミニウムにより大粒径の無機充填材粒子の間の隙間を埋めることになり、接触点が増えるため、すなわち樹脂の熱抵抗が増大するため、熱伝導率が向上しない。また、１μｍ以上１０μｍ未満のもの（ｂ群）と、１０μｍ以上３５μｍ以下のもの（ｃ群）とで構成すると、無機充填材間の隙間が増えるため、硬化物中にボイドが発生し、熱伝導率が向上しない。異なる３種類の平均粒子径を混在させることにより、無機充填材間の隙間を少なくすることができ、熱伝導率を向上することができる。 Further, when two types of aluminum oxide having different average particle diameters are used, for example, when composed of 0.1 μm or more and less than 1 μm (group a) and 10 μm or more and 35 μm or less (group c), small particles Since the gap between the inorganic filler particles having a large particle diameter is filled with the aluminum oxide having a diameter, the number of contact points is increased, that is, the thermal resistance of the resin is increased, so that the thermal conductivity is not improved. In addition, when it is composed of a material of 1 μm or more and less than 10 μm (group b) and a material of 10 μm or more and 35 μm or less (group c), voids are generated in the cured product due to an increase in the gap between the inorganic fillers. The rate does not improve. By mixing three different types of average particle sizes, the gaps between the inorganic fillers can be reduced, and the thermal conductivity can be improved.
そして、窒化アルミニウムの二次粒子の平均粒子径（Ａ）と、ｃ群（１０μｍ以上３５μｍ以下）の酸化アルミニウムの一次粒子の平均粒子径（Ｂ）とが、（Ａ）／（Ｂ）を、０．８〜１．３とする。この範囲であれば、無機充填材粒子を高密度に充填することができるため、熱伝導率を向上することができる。また、無機充填材粒子の間の隙間が少なく、硬化物中にボイドの発生もない。 And the average particle diameter (A) of secondary particles of aluminum nitride and the average particle diameter (B) of primary particles of aluminum oxide of group c (10 μm or more and 35 μm or less) are (A) / (B), 0.8 to 1.3. If it is this range, since inorganic filler particle | grains can be filled with high density, thermal conductivity can be improved. Further, there are few gaps between the inorganic filler particles, and no voids are generated in the cured product.
本発明では、熱硬化性樹脂固形分と窒化アルミニウムと酸化アルミニウムとの合計体積に対し、窒化アルミニウムを３５〜４５体積％、酸化アルミニウムを３０〜４５体積％で用いる。
窒化アルミニウムの含有量が３５体積％より小さいと十分な熱伝導率が得られず、４５体積％より大きいと吸湿後の絶縁特性が低下する。また、樹脂組成物の粘度が高くなり繊維基材への含浸性が悪化する。また、酸化アルミニウムの含有量が３０体積％より小さいと十分な熱伝導率が得られず、４５体積％より大きいと樹脂組成物の粘度が高くなり繊維基材への含浸性が悪化する。
In the present invention, 35 to 45% by volume of aluminum nitride and 30 to 45% by volume of aluminum oxide are used with respect to the total volume of the thermosetting resin solid content, aluminum nitride and aluminum oxide.
If the content of aluminum nitride is less than 35% by volume, sufficient thermal conductivity cannot be obtained, and if it is more than 45% by volume, the insulating properties after moisture absorption are deteriorated. Moreover, the viscosity of a resin composition becomes high and the impregnation property to a fiber base material deteriorates. Further, if the aluminum oxide content is less than 30% by volume, sufficient thermal conductivity cannot be obtained, and if it is more than 45% by volume, the viscosity of the resin composition becomes high and the impregnation property to the fiber base material is deteriorated.
上記の無機充填材の総含有量は、６５〜９０体積％であることが好ましい。無機充填材の総含有量が６５体積％より小さいと、十分な熱伝導率が得られず、９０体積％より大きいと、樹脂組成物の粘度が高くなり繊維基材への含浸性が悪化する。 The total content of the inorganic filler is preferably 65 to 90% by volume. If the total content of the inorganic filler is less than 65% by volume, sufficient thermal conductivity cannot be obtained. If the total content is more than 90% by volume, the viscosity of the resin composition becomes high and the impregnation property to the fiber substrate is deteriorated. .
なお、平均粒子径が異なる３種類の酸化アルミニウムの含有比率は、酸化アルミニウムの合計体積に対し、０．１μｍ以上１μｍ未満のもの（ａ群）を３０〜４０体積％、１μｍ以上１０μｍ未満のもの（ｂ群）を３０〜４０体積％、１０μｍ以上３５μｍ以下のもの（ｃ群）を２０〜４０体積％とすることが好ましい。このような含有比率とすることにより、樹脂組成物の粘度を低く抑えることができ、繊維基材への含浸性を向上することができる。また、無機充填材間の隙間を少なくすることができ、熱伝導率を向上することができる。 In addition, the content ratio of three types of aluminum oxides having different average particle diameters is 30 to 40% by volume (group a) of 0.1 to 1 μm with respect to the total volume of aluminum oxide, and 1 to 10 μm. It is preferable that (b group) is 30 to 40% by volume, and 10 μm or more and 35 μm or less (c group) is 20 to 40% by volume. By setting it as such a content ratio, the viscosity of a resin composition can be restrained low and the impregnation property to a fiber base material can be improved. Moreover, the clearance gap between inorganic fillers can be decreased and thermal conductivity can be improved.
上記の無機充填材と熱硬化性樹脂組成物を混練・混合してワニスを調製する際、熱硬化性樹脂組成物に無機充填材を添加していくと無機充填材のチキソ性および凝集性のため、ワニスの粘度が増大する。そこで、強力なせん断力を発生する分散機を選択することで、無機充填材の分散性がよくなりワニスの粘度も低下するため、９０体積％までの無機充填材の添加が可能となる。強力なせん断力を発生する分散機は、例えば、ボールミル、ビーズミル、三本ロールミルやその原理を応用した分散機などが挙げられる。 When preparing the varnish by kneading and mixing the above inorganic filler and the thermosetting resin composition, if the inorganic filler is added to the thermosetting resin composition, the thixotropic and cohesive properties of the inorganic filler are increased. Therefore, the viscosity of the varnish increases. Therefore, by selecting a disperser that generates a strong shearing force, the dispersibility of the inorganic filler is improved and the viscosity of the varnish is reduced, so that it is possible to add up to 90% by volume of the inorganic filler. Examples of the disperser that generates a strong shearing force include a ball mill, a bead mill, a three-roll mill, and a disperser that applies the principle thereof.
本発明を実施するに当り、プリプレグの製造は、一般的に行なわれている製造法を適用することができる。すなわち、無機充填材を含む熱硬化性樹脂組成物のワニスを繊維基材に含浸し加熱乾燥して、半硬化状態とする。
本発明に使用できる繊維基材は、ガラス繊維や有機繊維の織布や不織布であり、特に限定するものではない。例えば、ガラス繊維織布を使用することができる。ガラスの種類は強度や電気特性が良好なＥガラスが好ましい。また、ワニスの含浸には目空き量の大きいものが好ましいため、開繊処理されていないガラス繊維織布がよい。
In practicing the present invention, a commonly used production method can be applied to the production of the prepreg. That is, the fiber base material is impregnated with a varnish of a thermosetting resin composition containing an inorganic filler, and is heated and dried to obtain a semi-cured state.
The fiber base material that can be used in the present invention is a woven or non-woven fabric of glass fiber or organic fiber, and is not particularly limited. For example, a glass fiber woven fabric can be used. The glass type is preferably E glass having good strength and electrical characteristics. In addition, a glass fiber woven fabric that has not been subjected to fiber opening treatment is preferable because a varnish impregnated material with a large open space is preferable.
プリプレグの層を加熱加圧成形して絶縁層とする際に、銅箔ないし銅板をプリプレグの層に重ねて成形し一体に接着することができる。無機充填材の総含有量を上述した９０体積％以下にすれば、銅箔ないし銅板との接着性に特に問題となるところはない。当該プリプレグは、予め準備したプリント配線板同士を重ねて一体化し多層プリント配線板とするとき、また、アルミベース基板への放熱性の高い接着層として使用することもできる。
本発明に係るプリプレグによる絶縁層を備えたプリント配線板やアルミベース基板は、実装部品や制御回路から発生した熱が絶縁層を介して反対面に配置した銅箔ないし銅板やアルミニウム板に伝わり熱放散される。
When the prepreg layer is heat-pressed to form an insulating layer, a copper foil or a copper plate can be overlaid on the prepreg layer and bonded together. If the total content of the inorganic filler is 90% by volume or less as described above, there is no particular problem with the adhesiveness with the copper foil or the copper plate. The prepreg can also be used as an adhesive layer with high heat dissipation to an aluminum base substrate when previously prepared printed wiring boards are stacked and integrated to form a multilayer printed wiring board.
In the printed wiring board and the aluminum base substrate provided with the insulating layer by the prepreg according to the present invention, the heat generated from the mounting component and the control circuit is transferred to the copper foil or the copper plate or the aluminum plate disposed on the opposite surface through the insulating layer. Dissipated.
本発明に使用できる熱硬化性樹脂は、エポキシ樹脂、フェノール樹脂、メラミン樹脂、不飽和ポリエステル樹脂等であり、特に限定するものではないが、例えば、エポキシ樹脂モノマと硬化剤とから生成されたものを用いることにより、接着性、耐湿性、耐熱性、耐薬品性が良好となるので好ましい。エポキシ樹脂モノマは、ビスフェノールＡ型エポキシ、ビスフェノールＦ型エポキシなど一般的なエポキシ樹脂モノマはいずれも使用できる。（式１）で示される分子構造式のビフェニル骨格あるいはビフェニル誘導体の骨格をもち、１分子中に２個以上のエポキシ基をもつエポキシ樹脂モノマは放熱性が向上するため好ましい。 The thermosetting resin that can be used in the present invention is an epoxy resin, a phenol resin, a melamine resin, an unsaturated polyester resin, and the like, and is not particularly limited. For example, the thermosetting resin is produced from an epoxy resin monomer and a curing agent. It is preferable because the adhesiveness, moisture resistance, heat resistance, and chemical resistance are improved. As the epoxy resin monomer, any general epoxy resin monomer such as bisphenol A type epoxy and bisphenol F type epoxy can be used. An epoxy resin monomer having a biphenyl skeleton or a biphenyl derivative skeleton of the molecular structural formula represented by (Formula 1) and having two or more epoxy groups in one molecule is preferable because heat dissipation is improved.
さらに好ましくは、（式２）で示される分子構造式のものを選択する。ビフェニル基がより配列しやすいため、熱伝導率をより高くすることができる。また、ビフェニル骨格あるいはビフェニル誘導体の骨格は同一分子内に２つ以上あってもよい。 More preferably, the molecular structure represented by (Formula 2) is selected. Since the biphenyl group is more easily arranged, the thermal conductivity can be further increased. Further, two or more biphenyl skeletons or biphenyl derivative skeletons may be present in the same molecule.
エポキシ樹脂モノマに配合する硬化剤は、エポキシ樹脂モノマの硬化反応を進行させるために従来用いられている硬化剤を使用することができる。例えば、フェノール類又はその化合物、アミン化合物やその誘導体、酸無水物、イミダゾールやその誘導体などが挙げられる。また、硬化促進剤は、エポキシ樹脂モノマとフェノール類又はその化合物、アミン類またはその化合物との重合反応を進行させるために従来用いられている硬化促進剤を使用することができる。例えば、トリフェニルホスフィン、イミダゾールやその誘導体、三級アミン化合物やその誘導体などが挙げられる。 As the curing agent to be blended with the epoxy resin monomer, a conventionally used curing agent can be used to advance the curing reaction of the epoxy resin monomer. Examples thereof include phenols or compounds thereof, amine compounds and derivatives thereof, acid anhydrides, imidazoles and derivatives thereof, and the like. Moreover, the hardening accelerator conventionally used in order to advance the polymerization reaction with an epoxy resin monomer, phenols or its compound, amines, or its compound can be used for a hardening accelerator. Examples thereof include triphenylphosphine, imidazole and derivatives thereof, tertiary amine compounds and derivatives thereof.
エポキシ樹脂モノマと硬化剤、無機充填材、硬化促進剤を配合したエポキシ樹脂組成物には、必要に応じて難燃剤や希釈剤、可塑剤、カップリング剤等を含むことができる。また、このエポキシ樹脂組成物をガラスクロス基材に含浸し乾燥してプリプレグを製造する際、必要に応じて溶剤を使用することができる。これらの使用が、硬化物の熱伝導性に影響を与えることはない。 The epoxy resin composition in which an epoxy resin monomer, a curing agent, an inorganic filler, and a curing accelerator are blended may contain a flame retardant, a diluent, a plasticizer, a coupling agent, and the like as necessary. Moreover, when impregnating this epoxy resin composition to a glass cloth base material and drying and manufacturing a prepreg, a solvent can be used as needed. These uses do not affect the thermal conductivity of the cured product.
本発明に係るプリプレグを全層ないし一部の層として用い、これを加熱加圧成形した絶縁層を備えたプリント配線板やアルミベース基板は、熱伝導率が向上するので、高温雰囲気下での使用が想定される自動車機器用のプリント配線板やアルミベース基板、パソコン等の高密度実装プリント配線板に好適である。 Since the prepreg according to the present invention is used as the whole layer or a part of the layer, and the printed wiring board or the aluminum base substrate provided with the insulating layer formed by heating and pressing is improved in thermal conductivity, it can be used in a high temperature atmosphere. It is suitable for printed wiring boards for automobile equipment that are expected to be used, high-density mounting printed wiring boards such as aluminum base boards and personal computers.
以下、本発明に係る実施例を示し、本発明について詳細に説明する。尚、以下の実施例および比較例において、「部」とは「質量部」を意味する。また、本発明は、その要旨を逸脱しない限り、本実施例に限定されるものではない。 Examples of the present invention will be described below, and the present invention will be described in detail. In the following examples and comparative examples, “part” means “part by mass”. Moreover, this invention is not limited to a present Example, unless it deviates from the summary.
参考例１
エポキシ樹脂モノマ成分としてビフェニル骨格をもつエポキシ樹脂モノマ（ジャパンエポキシレジン製「ＹＬ６１２１Ｈ」，エポキシ当量１７５）１００部を用意し、これをメチルイソブチルケトン（和光純薬製）１００部に１００℃で溶解し、室温に戻した。尚、「ＹＬ６１２１Ｈ」は、既述の分子構造式（式１）において、Ｒ＝−ＣＨ３，ｎ＝０．１であるエポキシ樹脂モノマと分子構造式（式２）において、ｍ＝０．１であるエポキシ樹脂モノマを等モルで含有するエポキシ樹脂モノマである。
次に、硬化剤としてフェノールノボラック系硬化剤（ＤＩＣ製「ＬＦ６１６１」，水酸基当量１２０）２５部を用意し、これをメチルイソブチルケトン（和光純薬製）１００部に１００℃で溶解し、室温に戻した。
Reference example 1
As an epoxy resin monomer component, prepare 100 parts of an epoxy resin monomer having a biphenyl skeleton (“YL6121H” manufactured by Japan Epoxy Resin, epoxy equivalent of 175) and dissolve it at 100 ° C. in 100 parts of methyl isobutyl ketone (manufactured by Wako Pure Chemical Industries). , Returned to room temperature. “YL6121H” is an epoxy resin monomer in which R = —CH 3 and n = 0.1 in the molecular structural formula (formula 1) described above and m = 0.1 in the molecular structural formula (formula 2). This is an epoxy resin monomer containing an equimolar amount of the epoxy resin monomer.
Next, 25 parts of a phenol novolac type curing agent (“LF6161” manufactured by DIC, hydroxyl group equivalent 120) is prepared as a curing agent, and this is dissolved at 100 ° C. in 100 parts of methyl isobutyl ketone (manufactured by Wako Pure Chemical Industries, Ltd.). Returned.
上記のエポキシ樹脂モノマ溶液と硬化剤溶液を混合・撹拌して均一なワニスを作製し、この混合物（熱硬化性樹脂ワニス）に、無機充填材として下記（ａ）〜（ｄ）およびジメチルホルムアミド（和光純薬製）を１４２部、メチルイソブチルケトン（和光純薬製）を４７部加えて混練し、エポキシ樹脂ワニスを調製した。
（ａ）窒化アルミニウムａ（古河電子製「ＦＡＮ−ｆ３０」，二次粒子の平均粒子径：３０μｍ）７１７部（熱硬化性樹脂固形分と無機充填材を合わせた体積中の４２体積％に相当、以下体積％のみ表記する）
（ｂ）酸化アルミニウムｂ（住友化学製「ＡＡ−０４」，一次粒子の平均粒子径：０．４μｍ）２０１部（１１体積％）
（ｃ）酸化アルミニウムｃ（住友化学製「ＡＡ−３」，一次粒子の平均粒子径：３μｍ）２２９部（１２体積％）
（ｄ）酸化アルミニウムｄ（住友化学製「ＡＡ−１８」，一次粒子の平均粒子径：１８μｍ）１４３部（７体積％）
上記のエポキシ樹脂ワニスを、厚さ８０μｍのガラス繊維不織布基材（日本バイリーン製「ＥＰＭ−４０１５」）に含浸し加熱乾燥して半硬化状態のプリプレグを得た。樹脂（無機充填材を含む）の含有量は、９６質量％である。
作製したプリプレグ４枚とその両側に１８μｍ銅箔（福田金属製「ＣＦ−Ｔ９Ｃ」）を配置し、温度１７５℃、圧力２５ＭＰａの条件で９０分間加熱加圧形成して一体化し、厚さ０．８mmの積層板を得た。
The epoxy resin monomer solution and the curing agent solution are mixed and stirred to prepare a uniform varnish, and the mixture (thermosetting resin varnish) is mixed with the following (a) to (d) and dimethylformamide (inorganic filler). 142 parts of Wako Pure Chemical Industries, Ltd.) and 47 parts of methyl isobutyl ketone (Wako Pure Chemical Industries, Ltd.) were added and kneaded to prepare an epoxy resin varnish.
(A) Aluminum nitride a (Furukawa Denshi "FAN-f30", secondary particle average particle size: 30 μm) 717 parts (corresponding to 42% by volume in the combined volume of the thermosetting resin solid content and the inorganic filler) , Below only volume%)
(B) Aluminum oxide b (“AA-04” manufactured by Sumitomo Chemical, average particle diameter of primary particles: 0.4 μm) 201 parts (11% by volume)
(C) Aluminum oxide c (“AA-3” manufactured by Sumitomo Chemical Co., Ltd., average particle diameter of primary particles: 3 μm) 229 parts (12% by volume)
(D) Aluminum oxide d (“AA-18” manufactured by Sumitomo Chemical, average particle diameter of primary particles: 18 μm) 143 parts (7% by volume)
The epoxy resin varnish was impregnated into a 80 μm thick glass fiber nonwoven fabric substrate (“EPM-4015” manufactured by Nippon Vilene) and dried by heating to obtain a semi-cured prepreg. The content of the resin (including the inorganic filler) is 96% by mass.
Four prepared prepregs and 18 μm copper foil (“CF-T9C” made by Fukuda Metals) are arranged on both sides of the prepregs, and they are integrally formed by heating and pressing for 90 minutes under the conditions of a temperature of 175 ° C. and a pressure of 25 MPa. An 8 mm laminate was obtained.
参考例１で得た積層板について厚さ方向の熱伝導率、素子発熱温度、耐湿絶縁性を測定した結果を、エポキシ樹脂組成物の各成分の含有量と共に表１にまとめて示す。測定方法は、以下に示すとおりである。
なお、無機充填材の平均粒子径は、日機装株式会社製「マイクロトラックＳＰＡ−７９９７型」を用いて測定した。
厚さ方向の熱伝導率：積層板から５０ｍｍ×５０mmの板状試料を切り出し、定常法に準拠して室温で測定した。
素子発熱温度：実使用に近い放熱性評価として、板状試料を放熱板へグリース接着させ、板状試料に実装したヒータチップに６０Ｗの電力を入力した時のヒータチップ温度を測定した。参考例１を標準として、以下に説明する各例の板状試料を相対評価した。参考例１のヒータ温度に対して１５０％以上の温度になる場合を「×」、１１０以上１５０％未満の温度になる場合を「△」、１１０％未満の温度になる場合を「○」とした。
耐湿絶縁性：８５℃−８５％の恒温恒湿槽中に板状試料を入れて５０Ｖの電圧をかけ、１０００時間経過後の絶縁抵抗を測定した。そのとき１×１０１０Ω以上であれば「○」、１×１０１０Ω未満であれば「×」とした。
参考例１においては、積層板の熱伝導率、素子発熱温度、耐湿絶縁性共に良好であった。
The results obtained by measuring the thermal conductivity in the thickness direction, the element heat generation temperature, and the moisture resistance insulation of the laminate obtained in Reference Example 1 are shown in Table 1 together with the content of each component of the epoxy resin composition. The measuring method is as follows.
In addition, the average particle diameter of the inorganic filler was measured using Nikkiso Co., Ltd. "Microtrac SPA-7997 type".
Thermal conductivity in the thickness direction: A plate-like sample of 50 mm × 50 mm was cut out from the laminate and measured at room temperature in accordance with a steady method.
Element heat generation temperature: As a heat dissipation evaluation close to actual use, the plate sample was grease-bonded to the heat dissipation plate, and the heater chip temperature when 60 W electric power was input to the heater chip mounted on the plate sample was measured. Using Reference Example 1 as a standard, the plate samples of each example described below were relatively evaluated. The case where the temperature is 150% or more with respect to the heater temperature of Reference Example 1 is “X”, the case where the temperature is 110 or more and less than 150% is “Δ”, and the case where the temperature is less than 110% is “◯”. did.
Humidity resistance: A plate-like sample was put in a constant temperature and humidity chamber at 85 ° C. to 85%, a voltage of 50 V was applied, and the insulation resistance after 1000 hours was measured. At that time, if it was 1 × 1010Ω or more, it was “◯”, and if it was less than 1 × 1010Ω, it was “x”.
In Reference Example 1, the thermal conductivity, element heat generation temperature, and moisture resistance insulation of the laminate were good.
比較例１
参考例１において、窒化アルミニウムａ「ＦＡＮ−ｆ３０」の含有量を４９体積％、酸化アルミニウムｄ「ＡＡ−１８」の含有量を０体積％とする以外は参考例１と同様にしてプリプレグおよび積層板を得た。比較例１においては、窒化アルミニウムの含有量を多くしたことにより、熱伝導率は８．３Ｗ／ｍ・Ｋと良好であるが、参考例１よりも耐湿絶縁性が大きく低下した。また、樹脂組成物の粘度が高くなりガラス繊維基材への含浸性が悪化した。
Comparative Example 1
In Reference Example 1, the prepreg and laminate were the same as Reference Example 1 except that the content of aluminum nitride a “FAN-f30” was 49% by volume and the content of aluminum oxide d “AA-18” was 0% by volume. I got a plate. In Comparative Example 1, the heat conductivity was as good as 8.3 W / m · K by increasing the content of aluminum nitride, but the moisture resistance insulation was significantly lower than in Reference Example 1. Moreover, the viscosity of the resin composition became high and the impregnation property to a glass fiber base material deteriorated.
参考例２
参考例１において、窒化アルミニウムａ「ＦＡＮ−ｆ３０」の含有量を３５体積％、酸化アルミニウムｄ「ＡＡ−１８」の含有量を１４体積％とする以外は参考例１と同様にしてプリプレグおよび積層板を得た。参考例２においては、窒化アルミニウムの含有量を減らしたことにより、熱伝導率及び素子発熱温度は若干低下したが、機能上問題ない範囲であった。なお耐湿絶縁性は良好であった。
Reference example 2
In Reference Example 1, the prepreg and the laminate were the same as Reference Example 1 except that the content of aluminum nitride a “FAN-f30” was 35% by volume and the content of aluminum oxide d “AA-18” was 14% by volume. I got a plate. In Reference Example 2, although the thermal conductivity and the element heat generation temperature were slightly reduced by reducing the content of aluminum nitride, it was in a range where there was no functional problem. The moisture resistance insulation was good.
実施例１
参考例１において、酸化アルミニウムｄ「ＡＡ−１８」の代わりに、酸化アルミニウムｅ（マイクロン製「Ａ３５−０１」，一次粒子の平均粒子径：３２μｍ）を用いる以外は、参考例１と同様にしてプリプレグおよび積層板を得た。実施例１においては、（Ａ）／（Ｂ）を０．９としたことにより、熱伝導率は、７．７Ｗ／ｍ・Ｋと良好であり、また素子発熱温度、耐湿絶縁性も良好であった。ここで、（Ａ）は窒化アルミニウムの二次粒子の平均粒子径、（Ｂ）はｃ群（１０μｍ以上３５μｍ以下）の酸化アルミニウムの一次粒子の平均粒子径である。
Example 1
In Reference Example 1, in the same manner as Reference Example 1 except that aluminum oxide e (“A35-01” manufactured by Micron, average particle diameter of primary particles: 32 μm) is used instead of aluminum oxide d “AA-18”. A prepreg and a laminate were obtained. In Example 1 , since (A) / (B) was set to 0.9, the thermal conductivity was good at 7.7 W / m · K, and the element heat generation temperature and moisture resistance insulation were also good. there were. Here, (A) is the average particle diameter of secondary particles of aluminum nitride, and (B) is the average particle diameter of primary particles of aluminum oxide of group c (10 μm or more and 35 μm or less).
参考例３
実施例１において、窒化アルミニウムａ「ＦＡＮ−ｆ３０」の代わりに、窒化アルミニウムｆ（古河電子製「ＦＡＮ−ｆ３０」を分粒し、二次粒子の平均粒子径を２０μｍとしたもの）を用いる以外は、実施例１と同様にしてプリプレグおよび積層板を得た。参考例３においては、窒化アルミニウムの二次粒子の平均粒子径を小さくしたことにより、熱伝導率及び素子発熱温度は若干低下したが、機能上問題ない範囲であった。なお耐湿絶縁性は良好であった。
Reference example 3
In Example 1 , instead of aluminum nitride a “FAN-f30”, aluminum nitride f (“FAN-f30” manufactured by Furukawa Electronics was sized and the average particle diameter of secondary particles was 20 μm) was used. Obtained a prepreg and a laminate in the same manner as in Example 1 . In Reference Example 3 , the average particle size of the aluminum nitride secondary particles was reduced, so that the thermal conductivity and the element heat generation temperature were slightly reduced, but they were in a range with no functional problems. The moisture resistance insulation was good.
比較例２
参考例１において、窒化アルミニウムａの含有量を３０体積％、酸化アルミニウムｄ「ＡＡ−１８」の含有量を１９体積％とする以外は、参考例１と同様にしてプリプレグ及び積層板を得た。比較例２においては、窒化アルミニウムの含有量を参考例２より更に減らしたことにより、熱伝導率が５．２Ｗ／ｍ・Ｋと大幅に低下した。また素子発熱温度も大幅に低下した。
Comparative Example 2
In Reference Example 1, a prepreg and a laminate were obtained in the same manner as in Reference Example 1 except that the content of aluminum nitride a was 30% by volume and the content of aluminum oxide d “AA-18” was 19% by volume. . In Comparative Example 2, the thermal conductivity was significantly reduced to 5.2 W / m · K by further reducing the aluminum nitride content as compared with Reference Example 2. In addition, the element heat generation temperature was significantly reduced.
比較例３
比較例２において、酸化アルミニウムｃ「ＡＡ−３」の含有量を２１体積％、酸化アルミニウムｄ「ＡＡ−１８」の含有量を２１体積％とする以外は、比較例２と同様にしてプリプレグ及び積層板を得た。比較例３においては、平均粒子径が異なる２種類の酸化アルミニウムを使用し、１μｍ以上１０μｍ未満のもの（ｂ群）と、１０μｍ以上３５μｍ以下のもの（ｃ群）とで構成したことにより、硬化物中にボイドが発生し、参考例１と比較して熱伝導率、素子発熱温度が大幅に低下した。また耐湿絶縁性も大幅に低下した。
Comparative Example 3
In Comparative Example 2, the prepreg and the prepreg were the same as Comparative Example 2 except that the content of aluminum oxide c “AA-3” was 21% by volume and the content of aluminum oxide d “AA-18” was 21% by volume. A laminate was obtained. In Comparative Example 3, two types of aluminum oxides having different average particle diameters were used, and they were composed of those having a particle size of 1 μm or more and less than 10 μm (group b) and those of 10 μm or more and 35 μm or less (group c). Voids were generated in the product, and the thermal conductivity and element heat generation temperature were significantly reduced as compared with Reference Example 1. In addition, the insulation against moisture was greatly reduced.
比較例４
参考例１において、窒化アルミニウムａ「ＦＡＮ−ｆ３０」の代わりに、窒化アルミニウムｇ（古河電子製「ＦＡＮ−ｆ５０」、二次粒子の平均粒子径：５０μｍ）を用いる以外は、参考例１と同様にしてプリプレグおよび積層板を得た。比較例４においては、窒化アルミニウムの二次粒子の平均粒子径を大きくしたことにより、熱伝導率は７．８Ｗ／ｍ・Ｋと良好であったが、耐湿絶縁性が大幅に低下した。
Comparative Example 4
Reference Example 1 in place of the aluminum nitride a "FAN-f30", aluminum nitride g (Furukawa Denshi "FAN-f50", average particle diameter of the secondary particles: 50 [mu] m) but using, as in Reference Example 1 Thus, a prepreg and a laminate were obtained. In Comparative Example 4, although the thermal conductivity was good at 7.8 W / m · K by increasing the average particle diameter of the aluminum nitride secondary particles, the moisture resistance insulation was greatly reduced.
比較例５
参考例１において、窒化アルミニウムａ「ＦＡＮ−ｆ３０」の代わりに、窒化アルミニウムｈ（古河電子製「ＦＡＮ−ｆ０５」、平均粒子径：５μｍ）を用いる以外は、参考例１と同様にしてプリプレグおよび積層板を得た。比較例５においては、窒化アルミニウムの二次粒子の平均粒子径を参考例３より更に小さくしたことにより、熱伝導率は５．７Ｗ／ｍ・Ｋと大幅に低下した。また耐湿絶縁性も大幅に低下した。
Comparative Example 5
In Reference Example 1, in place of aluminum nitride a “FAN-f30”, prepreg and aluminum nitride h (“FAN-f05” manufactured by Furukawa Denshi, average particle size: 5 μm) were used in the same manner as in Reference Example 1. A laminate was obtained. In Comparative Example 5, the thermal conductivity was significantly reduced to 5.7 W / m · K by making the average particle size of the aluminum nitride secondary particles even smaller than in Reference Example 3 . In addition, the insulation against moisture was greatly reduced.
表１、表２から明らかなように、本発明に係る熱硬化性樹脂組成物は、窒化アルミニウムとそれと近似した平均粒子径を有する酸化アルミニウムを含有させ、かつ、窒化アルミニウム及び酸化アルミニウムの平均粒子径、含有量を最適化することにより、吸湿後の絶縁特性を低下させることなく、放熱特性を向上させることができる。 As is apparent from Tables 1 and 2, the thermosetting resin composition according to the present invention contains aluminum nitride and aluminum oxide having an average particle diameter close to that of the aluminum nitride, and average particles of aluminum nitride and aluminum oxide. By optimizing the diameter and content, the heat dissipation characteristics can be improved without deteriorating the insulation characteristics after moisture absorption.
Claims (3)
前記窒化アルミニウムの二次粒子の平均粒子径（Ａ）と、前記ｃ群の酸化アルミニウムの一次粒子の平均粒子径（Ｂ）とが、（Ａ）／（Ｂ）を、０．８〜１．３とする熱硬化性樹脂組成物。 The thermosetting resin contains aluminum nitride having an average secondary particle diameter of 20 to 40 μm and three types of aluminum oxide having different average particle diameters of primary particles, and the thermosetting resin solid content and the aluminum nitride are contained in the thermosetting resin. Aluminium nitride is used in an amount of 35 to 45% by volume and aluminum oxide in an amount of 30 to 45% by volume with respect to the total volume of aluminum oxide, and the average particle diameter of primary particles of the aluminum oxide is 0.1 μm or more and less than 1 μm (Group a), 1 μm or more and less than 10 μm (Group b), and 10 μm or more and 35 μm or less (Group c) ,
The average particle diameter (A) of the secondary particles of the aluminum nitride and the average particle diameter (B) of the primary particles of the aluminum oxide of the c group are (A) / (B) of 0.8 to 1. 3 is a thermosetting resin composition.
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| JP5652307B2 (en) * | 2011-04-14 | 2015-01-14 | 新神戸電機株式会社 | Prepress and laminate for heat and pressure molding |
| JP2013129788A (en) * | 2011-12-22 | 2013-07-04 | Shin Kobe Electric Mach Co Ltd | Thermosetting resin composition, prepreg for heating pressure molding, and laminate |
| JP5909808B2 (en) * | 2012-01-30 | 2016-04-27 | 日立化成株式会社 | Pre-preg for heat and pressure molding and laminate |
| WO2020137086A1 (en) * | 2018-12-25 | 2020-07-02 | 富士高分子工業株式会社 | Heat-conductive composition and heat-conductive sheet employing same |
| JP6692512B1 (en) * | 2018-12-25 | 2020-05-13 | 富士高分子工業株式会社 | Thermally conductive composition and thermally conductive sheet using the same |
| JP7242019B2 (en) * | 2020-07-31 | 2023-03-20 | 長野県 | Thermally conductive resin composition and molding thereof |
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