JP2008013759A - Epoxy resin composition and cured epoxy resin - Google Patents
Epoxy resin composition and cured epoxy resin Download PDFInfo
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- JP2008013759A JP2008013759A JP2007150110A JP2007150110A JP2008013759A JP 2008013759 A JP2008013759 A JP 2008013759A JP 2007150110 A JP2007150110 A JP 2007150110A JP 2007150110 A JP2007150110 A JP 2007150110A JP 2008013759 A JP2008013759 A JP 2008013759A
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- 0 CC1C(C2)C2*(C)C1 Chemical compound CC1C(C2)C2*(C)C1 0.000 description 2
- QRMPKOFEUHIBNM-UHFFFAOYSA-N CC1CCC(C)CC1 Chemical compound CC1CCC(C)CC1 QRMPKOFEUHIBNM-UHFFFAOYSA-N 0.000 description 2
- WTCPAFWUNFLPEW-UHFFFAOYSA-N CC1=CC=C(C)CC1 Chemical compound CC1=CC=C(C)CC1 WTCPAFWUNFLPEW-UHFFFAOYSA-N 0.000 description 1
- QFZFKXVGQIODJN-UHFFFAOYSA-N CC1C=CC(C)=CC1 Chemical compound CC1C=CC(C)=CC1 QFZFKXVGQIODJN-UHFFFAOYSA-N 0.000 description 1
- ADPYSZNUBWNLDH-UHFFFAOYSA-N CC1C=CC(C)CC1 Chemical compound CC1C=CC(C)CC1 ADPYSZNUBWNLDH-UHFFFAOYSA-N 0.000 description 1
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Abstract
【課題】エポキシ樹脂組成物及びその硬化物を提供すること。
【解決手段】式（１）
（式中、Ａｒ１、Ａｒ２及びＡｒ３は、それぞれ同一又は相異なって、アルキル置換されても良い芳香族環及びアルキル置換されても良く不飽和部を有しても良いシクロヘキサン環のいずれかの二価基を表わす。また、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５及びＲ６は、それぞれ同一又は相異なって、水素原子又は炭素数１〜１８のアルキル基を表わす。Ｑ１及びＱ２は、それぞれ同一又は相異なって、炭素数１〜９の直鎖状アルキレン基を表わし、該直鎖状アルキレン基を構成するメチレン基は、炭素数１〜１８のアルキル基で置換されていてもよく、また、該メチレン基の間に−Ｏ−又はＮ（Ｒ７）−が挿入されていてもよい。ここで、Ｒ７は、水素原子又は炭素数１〜１８のアルキル基を表わす。）で示されるエポキシ化合物、硬化剤及びアルミナ粉末を含むエポキシ樹脂組成物。
【選択図】なしAn epoxy resin composition and a cured product thereof are provided.
SOLUTION: Formula (1)
(In the formula, Ar 1 , Ar 2, and Ar 3 are the same or different and are either an aromatic ring that may be alkyl-substituted or a cyclohexane ring that may be alkyl-substituted and may have an unsaturated portion. In addition, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. Q 1 and Q 2 are the same or different and each represents a linear alkylene group having 1 to 9 carbon atoms, and the methylene group constituting the linear alkylene group is an alkyl group having 1 to 18 carbon atoms. It may be substituted, and -O- or N (R 7 )-may be inserted between the methylene groups, wherein R 7 is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. An epoxy compound represented by the following formula: An epoxy resin composition comprising a curing agent and alumina powder.
[Selection figure] None
Description
本発明は、エポキシ樹脂組成物及びエポキシ樹脂硬化物に関する。 The present invention relates to an epoxy resin composition and a cured epoxy resin.
アルミナ粉末を含有するエポキシ樹脂組成物は知られている（特許文献１及び２）。
しかしながら、熱伝導性が必ずしも充分なものではなかった。
However, the thermal conductivity is not always sufficient.
このような状況のもと、本発明は、高い熱伝導性及び優れた加工性を有するエポキシ樹脂組成物を提供しようとするものである。 Under such circumstances, the present invention intends to provide an epoxy resin composition having high thermal conductivity and excellent processability.
本発明者らは、上記課題を解決するため鋭意検討した結果、本発明に至った。
すなわち、本発明は、
［１］：
式（１）
で示されるエポキシ化合物、硬化剤及びアルミナ粉末を含むエポキシ樹脂組成物であって、
アルミナ粉末が、
重量累積粒度分布の微粒側からの累積５０％の粒経をＤ５０としたとき、
Ｄ５０が２μｍ以上１００μｍ以下のアルミナ（Ａ）、
Ｄ５０が１μｍ以上１０μｍ以下のアルミナ（Ｂ）及び
Ｄ５０が０．０１μｍ以上５μｍ以下のアルミナ（Ｃ）の混合物であり、
アルミナ粉末の体積に対するアルミナ（Ａ）、（Ｂ）及び（Ｃ）の割合が、それぞれ、５０体積％以上９０体積％以下、５体積％以上４０体積％以下、及び１体積％以上３０体積％以下（ただし、アルミナ（Ａ）、（Ｂ）及び（Ｃ）の合計の体積％は、１００体積％である）
であるエポキシ樹脂組成物；
［２］：
アルミナ粉末が、α−アルミナ粉末である上記［１］に記載のエポキシ樹脂組成物；
［３］：
上記［１］に記載の式（１）で示されるエポキシ化合物が、式（２）
で示されるエポキシ化合物である上記［１］又は２に記載のエポキシ樹脂組成物；
［４］：
上記［３］に記載の式（２）で示されるエポキシ化合物において、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５及びＲ６が水素原子である上記［３］に記載のエポキシ樹脂組成物；
［５］：
上記［３］に記載の式（２）で示されるエポキシ化合物が、式（３）
で示されるエポキシ化合物である上記［３］に記載のエポキシ樹脂組成物；
［６］：
上記［５］に記載の式（３）で示されるエポキシ化合物において、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５及びＲ６が水素原子である上記［５］に記載のエポキシ樹脂組成物；
［７］：
上記［５］に記載の式（３）で示されるエポキシ化合物が、式（４）
で示されるエポキシ化合物である上記［５に記載のエポキシ樹脂組成物；
［８］：
硬化剤が、アミン系硬化剤、レゾルシンノボラック系硬化剤、フェノールノボラック系硬化剤又は酸無水物系硬化剤である上記［１］１〜［７］のいずれかに記載のエポキシ樹脂組成物；
［９］：
硬化剤が、アミン系硬化剤である上記［８］に記載のエポキシ樹脂組成物；
［１０］：
アミン系硬化剤が、４，４’−ジアミノジフェニルメタン、４，４’−ジアミノジフェニルエタン、１，５−ジアミノナフタレン又はｐ−フェニレンジアミンである上記［９］に記載のエポキシ樹脂組成物；
［１１］：
上記［１］に記載の式（１）で示されるエポキシ化合物、硬化剤及びアルミナ粉末に、さらに、アルミナを主成分とし、その数平均繊維径が１〜５０μｍである無機繊維を含む上記［１］〜［１０］のいずれかに記載のエポキシ樹脂組成物。
［１２］：
上記［１］〜［１１］のいずれかに記載のエポキシ樹脂組成物を硬化させてなるエポキシ樹脂硬化物；
を提供するものである。
As a result of intensive studies to solve the above problems, the present inventors have reached the present invention.
That is, the present invention
[1]:
Formula (1)
An epoxy resin composition comprising an epoxy compound represented by: a curing agent and alumina powder,
Alumina powder
When the 50% cumulative particle size from the fine particle side of the weight cumulative particle size distribution is D50,
Alumina (A) having a D50 of 2 μm or more and 100 μm or less,
A mixture of alumina (B) having a D50 of 1 μm to 10 μm and alumina (C) having a D50 of 0.01 μm to 5 μm,
The ratio of alumina (A), (B) and (C) to the volume of the alumina powder is 50% by volume to 90% by volume, 5% by volume to 40% by volume, and 1% by volume to 30% by volume, respectively. (However, the total volume% of alumina (A), (B) and (C) is 100 volume%)
An epoxy resin composition;
[2]:
The epoxy resin composition according to the above [1], wherein the alumina powder is α-alumina powder;
[3]:
The epoxy compound represented by the formula (1) according to the above [1] is represented by the formula (2).
The epoxy resin composition according to the above [1] or 2, which is an epoxy compound represented by:
[4]:
In the epoxy compound represented by the formula (2) according to the above [3], the epoxy resin composition according to the above [3], wherein R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are hydrogen atoms. object;
[5]:
The epoxy compound represented by the formula (2) described in the above [3] is represented by the formula (3).
The epoxy resin composition according to [3], which is an epoxy compound represented by:
[6]:
In the epoxy compound represented by the formula (3) according to the above [5], the epoxy resin composition according to the above [5], wherein R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are hydrogen atoms. object;
[7]:
The epoxy compound represented by the formula (3) described in the above [5] is represented by the formula (4).
The epoxy resin composition according to [5], which is an epoxy compound represented by:
[8]:
The epoxy resin composition according to any one of [1] to [7] above, wherein the curing agent is an amine curing agent, a resorcin novolac curing agent, a phenol novolac curing agent, or an acid anhydride curing agent;
[9]:
The epoxy resin composition according to the above [8], wherein the curing agent is an amine curing agent;
[10]:
The epoxy resin composition according to the above [9], wherein the amine curing agent is 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, 1,5-diaminonaphthalene or p-phenylenediamine;
[11]:
[1] The epoxy compound represented by the formula (1) described in [1], the curing agent, and the alumina powder further include inorganic fibers whose main component is alumina and whose number average fiber diameter is 1 to 50 μm. ] The epoxy resin composition in any one of [10].
[12]:
Cured epoxy resin obtained by curing the epoxy resin composition according to any one of [1] to [11];
Is to provide.
本発明のエポキシ樹脂組成物を硬化させたエポキシ樹脂硬化物は、高い熱伝導率を有するため、例えば、プリント配線基板等の高い熱放散性を要求される絶縁材料として有用である。 The cured epoxy resin obtained by curing the epoxy resin composition of the present invention has high thermal conductivity, and thus is useful as an insulating material that requires high heat dissipation such as a printed wiring board.
本発明で用いられる式（１）で示されるエポキシ化合物（以下、エポキシ化合物（１）と略記する。）において、Ｒは水素原子又は炭素数１〜１８のアルキル基を表わし、炭素数１〜１８のアルキル基としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ｎ−ペンチル基、ｎ−ヘキシル基、ｎ−オクチル基、イソオクチル基、ｎ−デシル基、ｎ−ドデシル基、ｎ−ペンタデシル基、ｎ−オクタデシル基等の直鎖状もしくは分枝鎖状の炭素数１〜１８のアルキル基が挙げられ、炭素数１〜１０のアルキル基が好ましく、炭素数１〜６のアルキル基がより好ましく、炭素数１〜４のアルキル基がさらに好ましく、とりわけメチル基が好ましい。 In the epoxy compound represented by formula (1) used in the present invention (hereinafter abbreviated as epoxy compound (1)), R represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and 1 to 18 carbon atoms. As the alkyl group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n- Examples thereof include linear or branched alkyl groups having 1 to 18 carbon atoms such as octyl group, isooctyl group, n-decyl group, n-dodecyl group, n-pentadecyl group, and n-octadecyl group. An alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, an alkyl group having 1 to 4 carbon atoms is further preferable, and a methyl group is particularly preferable.
二価基としては、
かかる二価基の具体例としては、シクロヘキサン−１，４−ジイル基、２−シクロヘキセン−１，４−ジイル基、１−シクロヘキセン−１，４−ジイル基、１，４−シクロヘキサジエン−３，６−ジイル基、１，３−シクロヘキサジエン−１，４−ジイル基、１，３−シクロヘキサジエン−２，５−ジイル基、１，４−シクロヘキサジエン−１，４−ジイル基、１，４−フェニレン基、２−メチルシクロヘキサン−１，４−ジイル基、３−メチル−１，４−フェニレン基等が挙げられ、シクロヘキサン−１，４−ジイル基、１−シクロヘキセン−１，４−ジイル基、１，４−フェニレン基、２−メチルシクロヘキサン−１，４−ジイル基、３−メチル−１，４−フェニレン基、２−メチル−１，４−フェニレン基、３−エチル−１，４−フェニレン基、２−エチル−１，４−フェニレン基、３−ｎ−プロピル−１，４−フェニレン基、３−イソプロピル−１，４−フェニレン基が好ましい。
As a divalent group,
Specific examples of such divalent groups include cyclohexane-1,4-diyl group, 2-cyclohexene-1,4-diyl group, 1-cyclohexene-1,4-diyl group, 1,4-cyclohexadiene-3, 6-diyl group, 1,3-cyclohexadiene-1,4-diyl group, 1,3-cyclohexadiene-2,5-diyl group, 1,4-cyclohexadiene-1,4-diyl group, 1,4 -Phenylene group, 2-methylcyclohexane-1,4-diyl group, 3-methyl-1,4-phenylene group and the like, cyclohexane-1,4-diyl group, 1-cyclohexene-1,4-diyl group 1,4-phenylene group, 2-methylcyclohexane-1,4-diyl group, 3-methyl-1,4-phenylene group, 2-methyl-1,4-phenylene group, 3-ethyl-1,4- Fe Ren group, 2-ethyl-1,4-phenylene group, 3-n-propyl-1,4-phenylene group, 3-isopropyl-1,4-phenylene group is preferred.
Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５及びＲ６は、それぞれ同一又は相異なって、水素原子又は炭素数１〜１８のアルキル基を表わし、炭素数１〜１８としては、上記したものと同様のものが挙げられる。 R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. The thing similar to a thing is mentioned.
Ｑ１及びＱ２は、それぞれ同一又は相異なって、炭素数１〜９の直鎖状アルキレン基を表わし、炭素数１〜９の直鎖状アルキレン基としては、メチレン基、エチレン基、トリメチレン基、テトラメチレン基、ヘキサメチレン基、ノナメチレン基等の１〜９個のメチレン基が直鎖状に結合した基が挙げられ、炭素数１〜４の直鎖状アルキレン基が好ましく、メチレン基がより好ましい。かかる炭素数１〜９の直鎖状アルキレン基を構成するメチレン基は、炭素数１〜１８のアルキル基で置換されていてもよく、また、該メチレン基の間に−Ｏ−又はＮ（Ｒ７）−が挿入されていてもよい。このような炭素数１〜１８のアルキル基で置換されるか、又は、該メチレン基の間に−Ｏ−又はＮ（Ｒ７）−が挿入されたアルキレン基としては、２−メチルトリメチレン基、１，２−ジメチルエチレン基、３−オキサテトラメチレン基、３−オキサペンタメチレン基等が挙げられ、３−オキサペンタメチレン基が好ましい。 Q 1 and Q 2 are the same or different and each represents a linear alkylene group having 1 to 9 carbon atoms. Examples of the linear alkylene group having 1 to 9 carbon atoms include a methylene group, an ethylene group, and a trimethylene group. , Tetramethylene group, hexamethylene group, nonamethylene group and the like, in which 1 to 9 methylene groups are bonded in a straight chain, a linear alkylene group having 1 to 4 carbon atoms is preferable, and a methylene group is more preferable. preferable. The methylene group constituting the linear alkylene group having 1 to 9 carbon atoms may be substituted with an alkyl group having 1 to 18 carbon atoms, and —O— or N (R 7 )-may be inserted. Examples of the alkylene group substituted with such an alkyl group having 1 to 18 carbon atoms or having —O— or N (R 7 ) — inserted between the methylene groups include a 2-methyltrimethylene group. 1,2-dimethylethylene group, 3-oxatetramethylene group, 3-oxapentamethylene group and the like, and 3-oxapentamethylene group is preferable.
かかるエポキシ化合物（１）の中でも、下記式（２）
で示されるエポキシ化合物が好ましく、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５及びＲ６が水素原子であるエポキシ化合物がより好ましい。
さらに、Ｑ３が下記
The epoxy compound shown by these is preferable and the epoxy compound whose R < 1 >, R < 2 >, R < 3 >, R < 4 >, R < 5 > and R < 6 > are hydrogen atoms is more preferable.
In addition, Q 3 is represented by the following
また、式（４）
で示されるエポキシ化合物が好ましい。
かかるエポキシ化合物（１）としては、１，４−ビス｛４−（オキシラニルメトキシ）フェニル｝−１−シクロヘキセン、１−｛３−メチル−４−（オキシラニルメトキシ）フェニル｝−４−｛４−（オキシラニルメトキシ）フェニル｝−１−シクロヘキセン、１−｛２−メチル−４−（オキシラニルメトキシ）フェニル｝−４−｛４−（オキシラニルメトキシ）フェニル｝−１−シクロヘキセン、１−｛３−エチル−４−（オキシラニルメトキシ）フェニル｝−４−｛４−（オキシラニルメトキシ）フェニル｝−１−シクロヘキセン、１−｛２−エチル−４−（オキシラニルメトキシ）フェニル｝−４−｛４−（オキシラニルメトキシ）フェニル｝−１−シクロヘキセン、１−｛３−ｎ−プロピル−４−（オキシラニルメトキシ）フェニル｝−４−｛４−（オキシラニルメトキシ）フェニル｝−１−シクロヘキセン、１−｛３−イソプロピル−４−（オキシラニルメトキシ）フェニル｝−４−｛４−（オキシラニルメトキシ）フェニル｝−１−シクロヘキセン、１，４−ビス｛４−（オキシラニルメトキシ）フェニル｝−２−シクロヘキセン、１−｛３−メチル−４−（オキシラニルメトキシ）フェニル｝−４−｛４−（オキシラニルメトキシ）フェニル｝−２−シクロヘキセン、１，４−ビス｛４−（オキシラニルメトキシ）フェニル｝−２，５−シクロヘキサジエン、１−｛３−メチル−４−（オキシラニルメトキシ）フェニル｝−４−｛４−（オキシラニルメトキシ）フェニル｝−２，５−シクロヘキサジエン、１，４−ビス｛４−（オキシラニルメトキシ）フェニル｝−１，５−シクロヘキサジエン、１−｛３−メチル−４−（オキシラニルメトキシ）フェニル｝−４−｛４−（オキシラニルメトキシ）フェニル｝−１，５−シクロヘキサジエン、１，４−ビス｛４−（オキシラニルメトキシ）フェニル｝−１，４−シクロヘキサジエン、１−｛３−メチル−４−（オキシラニルメトキシ）フェニル｝−４−｛４−（オキシラニルメトキシ）フェニル｝−１，４−シクロヘキサジエン、１，４−ビス｛４−（オキシラニルメトキシ）フェニル｝−１，３−シクロヘキサジエン、１−｛３−メチル−４−（オキシラニルメトキシ）フェニル｝−４−｛４−（オキシラニルメトキシ）フェニル｝−１，３−シクロヘキサジエン、１，４−ビス｛４−（オキシラニルメトキシ）フェニル｝ベンゼン、１−｛３−メチル−４−（オキシラニルメトキシ）フェニル｝−４−｛４−（オキシラニルメトキシ）フェニル｝ベンゼン、
１，４−ビス｛４−（オキシラニルメトキシ）フェニル｝シクロヘキサン、１−｛３−メチル−４−（オキシラニルメトキシ）フェニル｝−４−｛４−（オキシラニルメトキシ）フェニル｝シクロヘキサン、１，４−ビス｛４−（３−オキサ−５，６−エポキシヘキシルオキシ）フェニル｝−１−シクロヘキセン、１−｛４−（３−オキサ−５，６−エポキシヘキシルオキシ）−３−メチルフェニル｝−４−｛４−（３−オキサ−５，６−エポキシヘキシルオキシ）フェニル｝−１−シクロヘキセン、１，４−ビス｛４−（５−メチル−３−オキサ−５，６−エポキシヘキシルオキシ）フェニル｝−１−シクロヘキセン、１−｛４−（５−メチル−３−オキサ−５，６−エポキシヘキシルオキシ）−３−メチルフェニル｝−４−｛４−（５−メチル−３−オキサ−５，６−エポキシヘキシルオキシ）フェニル｝−１−シクロヘキセン、１，４−ビス｛４−（４−メチル−４，５−エポキシペンチルオキシ）フェニル｝−１−シクロヘキセン、１，４−ビス｛４−（３−オキサ−５，６−エポキシヘキシルオキシ）フェニル｝ベンゼン、１−｛４−（３−オキサ−５，６−エポキシヘキシルオキシ）−３−メチルフェニル｝−４−｛４−（３−オキサ−５，６−エポキシヘキシルオキシ）フェニル｝ベンゼン、１，４−ビス｛４−（５−メチル−３−オキサ−５，６−エポキシヘキシルオキシ）フェニル｝ベンゼン、１−｛４−（５−メチル−３−オキサ−５，６−エポキシヘキシルオキシ）−３−メチルフェニル｝−４−｛４−（５−メチル−３−オキサ−５，６−エポキシヘキシルオキシ）フェニル｝ベンゼン、１，４−ビス｛４−（４−メチル−４，５−エポキシペンチルオキシ）フェニル｝ベンゼン、１，４−ビス｛４−（３−オキサ−５，６−エポキシヘキシルオキシ）フェニル｝シクロヘキサン、１−｛４−（３−オキサ−５，６−エポキシヘキシルオキシ）−３−メチルフェニル｝−４−｛４−（３−オキサ−５，６−エポキシヘキシルオキシ）フェニル｝シクロヘキサン、１，４−ビス｛４−（５−メチル−３−オキサ−５，６−エポキシヘキシルオキシ）フェニル｝シクロヘキサン、１−｛４−（５−メチル−３−オキサ−５，６−エポキシヘキシルオキシ）−３−メチルフェニル｝−４−｛４−（５−メチル−３−オキサ−５，６−エポキシヘキシルオキシ）フェニル｝シクロヘキサン、１，４−ビス｛４−（４−メチル−４，５−エポキシペンチルオキシ）フェニル｝シクロヘキサン等が挙げられる。
なかでも、１，４−ビス｛４−（オキシラニルメトキシ）フェニル｝−１−シクロヘキセン、１−｛３−メチル−４−（オキシラニルメトキシ）フェニル｝−４−｛４−（オキシラニルメトキシ）フェニル｝−１−シクロヘキセン、１−｛２−メチル−４−（オキシラニルメトキシ）フェニル｝−４−｛４−（オキシラニルメトキシ）フェニル｝−１−シクロヘキセン、１−｛３−エチル−４−（オキシラニルメトキシ）フェニル｝−４−｛４−（オキシラニルメトキシ）フェニル｝−１−シクロヘキセン、１−｛２−エチル−４−（オキシラニルメトキシ）フェニル｝−４−｛４−（オキシラニルメトキシ）フェニル｝−１−シクロヘキセン、１−｛３−ｎ−プロピル−４−（オキシラニルメトキシ）フェニル｝−４−｛４−（オキシラニルメトキシ）フェニル｝−１−シクロヘキセン、１−｛３−イソプロピル−４−（オキシラニルメトキシ）フェニル｝−４−｛４−（オキシラニルメトキシ）フェニル｝−１−シクロヘキセン、１，４−ビス｛４−（オキシラニルメトキシ）フェニル｝ベンゼン、１−｛３−メチル−４−（オキシラニルメトキシ）フェニル｝−４−｛４−（オキシラニルメトキシ）フェニル｝ベンゼン、１，４−ビス｛４−（オキシラニルメトキシ）フェニル｝シクロヘキサン、１−｛３−メチル−４−（オキシラニルメトキシ）フェニル｝−４−｛４−（オキシラニルメトキシ）フェニル｝シクロヘキサン、１，４−ビス｛４−（３−オキサ−５，６−エポキシヘキシルオキシ）フェニル｝−１−シクロヘキセン、１−｛４−（３−オキサ−５，６−エポキシヘキシルオキシ）−３−メチルフェニル｝−４−｛４−（３−オキサ−５，６−エポキシヘキシルオキシ）フェニル｝−１−シクロヘキセン、１，４−ビス｛４−（３−オキサ−５，６−エポキシヘキシルオキシ）フェニル｝ベンゼン、１−｛４−（３−オキサ−５，６−エポキシヘキシルオキシ）−３−メチルフェニル｝−４−｛４−（３−オキサ−５，６−エポキシヘキシルオキシ）フェニル｝ベンゼン、１，４−ビス｛４−（３−オキサ−５，６−エポキシヘキシルオキシ）フェニル｝シクロヘキサン、１−｛４−（３−オキサ−５，６−エポキシヘキシルオキシ）−３−メチルフェニル｝−４−｛４−（３−オキサ−５，６−エポキシヘキシルオキシ）フェニル｝シクロヘキサンが好ましく、
１，４−ビス｛４−（オキシラニルメトキシ）フェニル｝−１−シクロヘキセン、１−｛３−メチル−４−（オキシラニルメトキシ）フェニル｝−４−｛４−（オキシラニルメトキシ）フェニル｝−１−シクロヘキセン、１−｛２−メチル−４−（オキシラニルメトキシ）フェニル｝−４−｛４−（オキシラニルメトキシ）フェニル｝−１−シクロヘキセン、１−｛３−エチル−４−（オキシラニルメトキシ）フェニル｝−４−｛４−（オキシラニルメトキシ）フェニル｝−１−シクロヘキセン、１−｛２−エチル−４−（オキシラニルメトキシ）フェニル｝−４−｛４−（オキシラニルメトキシ）フェニル｝−１−シクロヘキセン、１−｛３−ｎ−プロピル−４−（オキシラニルメトキシ）フェニル｝−４−｛４−（オキシラニルメトキシ）フェニル｝−１−シクロヘキセン、１−｛３−イソプロピル−４−（オキシラニルメトキシ）フェニル｝−４−｛４−（オキシラニルメトキシ）フェニル｝−１−シクロヘキセン、１，４−ビス｛４−（オキシラニルメトキシ）フェニル｝ベンゼン、１−｛３−メチル−４−（オキシラニルメトキシ）フェニル｝−４−｛４−（オキシラニルメトキシ）フェニル｝ベンゼン、１，４−ビス｛４−（オキシラニルメトキシ）フェニル｝シクロヘキサン、１−｛３−メチル−４−（オキシラニルメトキシ）フェニル｝−４−｛４−（オキシラニルメトキシ）フェニル｝シクロヘキサンがより好ましく、
１，４−ビス｛４−（オキシラニルメトキシ）フェニル｝−１−シクロヘキセン、１−｛３−メチル−４−（オキシラニルメトキシ）フェニル｝−４−｛４−（オキシラニルメトキシ）フェニル｝−１−シクロヘキセン、１−｛２−メチル−４−（オキシラニルメトキシ）フェニル｝−４−｛４−（オキシラニルメトキシ）フェニル｝−１−シクロヘキセン、１−｛３−エチル−４−（オキシラニルメトキシ）フェニル｝−４−｛４−（オキシラニルメトキシ）フェニル｝−１−シクロヘキセン、１−｛２−エチル−４−（オキシラニルメトキシ）フェニル｝−４−｛４−（オキシラニルメトキシ）フェニル｝−１−シクロヘキセン、１−｛３−ｎ−プロピル−４−（オキシラニルメトキシ）フェニル｝−４−｛４−（オキシラニルメトキシ）フェニル｝−１−シクロヘキセン、１−｛３−イソプロピル−４−（オキシラニルメトキシ）フェニル｝−４−｛４−（オキシラニルメトキシ）フェニル｝−１−シクロヘキセンがさらに好ましい。
かかるエポキシ化合物（１）は、例えば、特開２００５−２０６８１４号公報に記載の方法により製造することができる。
Moreover, Formula (4)
The epoxy compound shown by these is preferable.
Examples of the epoxy compound (1) include 1,4-bis {4- (oxiranylmethoxy) phenyl} -1-cyclohexene, 1- {3-methyl-4- (oxiranylmethoxy) phenyl} -4- {4- (oxiranylmethoxy) phenyl} -1-cyclohexene, 1- {2-methyl-4- (oxiranylmethoxy) phenyl} -4- {4- (oxiranylmethoxy) phenyl} -1- Cyclohexene, 1- {3-ethyl-4- (oxiranylmethoxy) phenyl} -4- {4- (oxiranylmethoxy) phenyl} -1-cyclohexene, 1- {2-ethyl-4- (oxira) Nylmethoxy) phenyl} -4- {4- (oxiranylmethoxy) phenyl} -1-cyclohexene, 1- {3-n-propyl-4- (oxiranylmethoxy) phenyl -4- {4- (oxiranylmethoxy) phenyl} -1-cyclohexene, 1- {3-isopropyl-4- (oxiranylmethoxy) phenyl} -4- {4- (oxiranylmethoxy) phenyl} -1-cyclohexene, 1,4-bis {4- (oxiranylmethoxy) phenyl} -2-cyclohexene, 1- {3-methyl-4- (oxiranylmethoxy) phenyl} -4- {4- ( Oxiranylmethoxy) phenyl} -2-cyclohexene, 1,4-bis {4- (oxiranylmethoxy) phenyl} -2,5-cyclohexadiene, 1- {3-methyl-4- (oxiranylmethoxy) ) Phenyl} -4- {4- (oxiranylmethoxy) phenyl} -2,5-cyclohexadiene, 1,4-bis {4- (oxiranylmethoxy) phenyl}- , 5-cyclohexadiene, 1- {3-methyl-4- (oxiranylmethoxy) phenyl} -4- {4- (oxiranylmethoxy) phenyl} -1,5-cyclohexadiene, 1,4-bis {4- (oxiranylmethoxy) phenyl} -1,4-cyclohexadiene, 1- {3-methyl-4- (oxiranylmethoxy) phenyl} -4- {4- (oxiranylmethoxy) phenyl} 1,4-cyclohexadiene, 1,4-bis {4- (oxiranylmethoxy) phenyl} -1,3-cyclohexadiene, 1- {3-methyl-4- (oxiranylmethoxy) phenyl}- 4- {4- (oxiranylmethoxy) phenyl} -1,3-cyclohexadiene, 1,4-bis {4- (oxiranylmethoxy) phenyl} benzene, 1- {3-methyl- 4- (oxiranylmethoxy) phenyl} -4- {4- (oxiranylmethoxy) phenyl} benzene,
1,4-bis {4- (oxiranylmethoxy) phenyl} cyclohexane, 1- {3-methyl-4- (oxiranylmethoxy) phenyl} -4- {4- (oxiranylmethoxy) phenyl} cyclohexane 1,4-bis {4- (3-oxa-5,6-epoxyhexyloxy) phenyl} -1-cyclohexene, 1- {4- (3-oxa-5,6-epoxyhexyloxy) -3- Methylphenyl} -4- {4- (3-oxa-5,6-epoxyhexyloxy) phenyl} -1-cyclohexene, 1,4-bis {4- (5-methyl-3-oxa-5,6- Epoxyhexyloxy) phenyl} -1-cyclohexene, 1- {4- (5-methyl-3-oxa-5,6-epoxyhexyloxy) -3-methylphenyl} -4- {4- (5- Til-3-oxa-5,6-epoxyhexyloxy) phenyl} -1-cyclohexene, 1,4-bis {4- (4-methyl-4,5-epoxypentyloxy) phenyl} -1-cyclohexene, , 4-bis {4- (3-oxa-5,6-epoxyhexyloxy) phenyl} benzene, 1- {4- (3-oxa-5,6-epoxyhexyloxy) -3-methylphenyl} -4 -{4- (3-oxa-5,6-epoxyhexyloxy) phenyl} benzene, 1,4-bis {4- (5-methyl-3-oxa-5,6-epoxyhexyloxy) phenyl} benzene, 1- {4- (5-Methyl-3-oxa-5,6-epoxyhexyloxy) -3-methylphenyl} -4- {4- (5-methyl-3-oxa-5,6-epoxyhexyl) Oxy) phenyl} benzene, 1,4-bis {4- (4-methyl-4,5-epoxypentyloxy) phenyl} benzene, 1,4-bis {4- (3-oxa-5,6-epoxyhexyl) Oxy) phenyl} cyclohexane, 1- {4- (3-oxa-5,6-epoxyhexyloxy) -3-methylphenyl} -4- {4- (3-oxa-5,6-epoxyhexyloxy) phenyl } Cyclohexane, 1,4-bis {4- (5-methyl-3-oxa-5,6-epoxyhexyloxy) phenyl} cyclohexane, 1- {4- (5-methyl-3-oxa-5,6- Epoxyhexyloxy) -3-methylphenyl} -4- {4- (5-methyl-3-oxa-5,6-epoxyhexyloxy) phenyl} cyclohexane, 1,4-bis { 4- (4-methyl-4,5-epoxypentyloxy) phenyl} cyclohexane and the like.
Among them, 1,4-bis {4- (oxiranylmethoxy) phenyl} -1-cyclohexene, 1- {3-methyl-4- (oxiranylmethoxy) phenyl} -4- {4- (oxira) Nylmethoxy) phenyl} -1-cyclohexene, 1- {2-methyl-4- (oxiranylmethoxy) phenyl} -4- {4- (oxiranylmethoxy) phenyl} -1-cyclohexene, 1- {3 -Ethyl-4- (oxiranylmethoxy) phenyl} -4- {4- (oxiranylmethoxy) phenyl} -1-cyclohexene, 1- {2-ethyl-4- (oxiranylmethoxy) phenyl}- 4- {4- (oxiranylmethoxy) phenyl} -1-cyclohexene, 1- {3-n-propyl-4- (oxiranylmethoxy) phenyl} -4- {4- (oxirani Methoxy) phenyl} -1-cyclohexene, 1- {3-isopropyl-4- (oxiranylmethoxy) phenyl} -4- {4- (oxiranylmethoxy) phenyl} -1-cyclohexene, 1,4-bis {4- (oxiranylmethoxy) phenyl} benzene, 1- {3-methyl-4- (oxiranylmethoxy) phenyl} -4- {4- (oxiranylmethoxy) phenyl} benzene, 1,4- Bis {4- (oxiranylmethoxy) phenyl} cyclohexane, 1- {3-methyl-4- (oxiranylmethoxy) phenyl} -4- {4- (oxiranylmethoxy) phenyl} cyclohexane, 1,4 -Bis {4- (3-oxa-5,6-epoxyhexyloxy) phenyl} -1-cyclohexene, 1- {4- (3-oxa-5,6-epoxy Sihexyloxy) -3-methylphenyl} -4- {4- (3-oxa-5,6-epoxyhexyloxy) phenyl} -1-cyclohexene, 1,4-bis {4- (3-oxa-5 , 6-epoxyhexyloxy) phenyl} benzene, 1- {4- (3-oxa-5,6-epoxyhexyloxy) -3-methylphenyl} -4- {4- (3-oxa-5,6- Epoxyhexyloxy) phenyl} benzene, 1,4-bis {4- (3-oxa-5,6-epoxyhexyloxy) phenyl} cyclohexane, 1- {4- (3-oxa-5,6-epoxyhexyloxy) ) -3-methylphenyl} -4- {4- (3-oxa-5,6-epoxyhexyloxy) phenyl} cyclohexane,
1,4-bis {4- (oxiranylmethoxy) phenyl} -1-cyclohexene, 1- {3-methyl-4- (oxiranylmethoxy) phenyl} -4- {4- (oxiranylmethoxy) Phenyl} -1-cyclohexene, 1- {2-methyl-4- (oxiranylmethoxy) phenyl} -4- {4- (oxiranylmethoxy) phenyl} -1-cyclohexene, 1- {3-ethyl- 4- (oxiranylmethoxy) phenyl} -4- {4- (oxiranylmethoxy) phenyl} -1-cyclohexene, 1- {2-ethyl-4- (oxiranylmethoxy) phenyl} -4- { 4- (oxiranylmethoxy) phenyl} -1-cyclohexene, 1- {3-n-propyl-4- (oxiranylmethoxy) phenyl} -4- {4- (oxiranylmethoxy) Phenyl} -1-cyclohexene, 1- {3-isopropyl-4- (oxiranylmethoxy) phenyl} -4- {4- (oxiranylmethoxy) phenyl} -1-cyclohexene, 1,4-bis {4 -(Oxiranylmethoxy) phenyl} benzene, 1- {3-methyl-4- (oxiranylmethoxy) phenyl} -4- {4- (oxiranylmethoxy) phenyl} benzene, 1,4-bis { 4- (oxiranylmethoxy) phenyl} cyclohexane, 1- {3-methyl-4- (oxiranylmethoxy) phenyl} -4- {4- (oxiranylmethoxy) phenyl} cyclohexane are more preferred,
1,4-bis {4- (oxiranylmethoxy) phenyl} -1-cyclohexene, 1- {3-methyl-4- (oxiranylmethoxy) phenyl} -4- {4- (oxiranylmethoxy) Phenyl} -1-cyclohexene, 1- {2-methyl-4- (oxiranylmethoxy) phenyl} -4- {4- (oxiranylmethoxy) phenyl} -1-cyclohexene, 1- {3-ethyl- 4- (oxiranylmethoxy) phenyl} -4- {4- (oxiranylmethoxy) phenyl} -1-cyclohexene, 1- {2-ethyl-4- (oxiranylmethoxy) phenyl} -4- { 4- (oxiranylmethoxy) phenyl} -1-cyclohexene, 1- {3-n-propyl-4- (oxiranylmethoxy) phenyl} -4- {4- (oxiranylmethoxy) Phenyl} -1-cyclohexene, 1- {3-isopropyl-4- (oxiranylmethoxy) phenyl} -4- {4- (oxiranylmethoxy) phenyl} -1-cyclohexene are still more preferred.
Such an epoxy compound (1) can be produced, for example, by the method described in JP-A-2005-206814.
本発明のエポキシ樹脂組成物は、アルミナ粉末を含んでおり、かかるアルミナ粉末は、 重量累積粒度分布の微粒側からの累積５０％の粒経をＤ５０としたとき、
Ｄ５０が２μｍ以上１００μｍ以下のアルミナ（Ａ）、
Ｄ５０が１μｍ以上１０μｍ以下のアルミナ（Ｂ）及び
Ｄ５０が０．０１μｍ以上５μｍ以下のアルミナ（Ｃ）の混合物であり、
アルミナ粉末の体積に対するアルミナ（Ａ）、（Ｂ）及び（Ｃ）の割合が、それぞれ、５０体積％以上９０体積％以下、５体積％以上４０体積％以下、及び１体積％以上３０体積％以下（ただし、アルミナ（Ａ）、（Ｂ）及び（Ｃ）の合計の体積％は、１００体積％である）である。
かかるアルミナ粉末としては、アルミナ粉末の体積に対するアルミナ（Ａ）、（Ｂ）及び（Ｃ）の割合が、それぞれ、６０体積％以上９０体積％以下、１０体積％以上４０体積％以下、５体積％以上３０体積％以下（ただし、アルミナ（Ａ）、（Ｂ）及び（Ｃ）の合計の体積％は、１００体積％である）であるアルミナ粉末が好ましく、アルミナ粉末の体積に対するアルミナ（Ａ）、（Ｂ）及び（Ｃ）の割合が、それぞれ、７０体積％以上９０体積％以下、１０体積％以上３０体積％以下、５体積％以上２０体積％以下（ただし、アルミナ（Ａ）、（Ｂ）及び（Ｃ）の合計の体積％は、１００体積％である）であるアルミナ粉末がより好ましい。
The epoxy resin composition of the present invention contains an alumina powder, and when the alumina powder has a cumulative particle size of 50% from the fine particle side of the weight cumulative particle size distribution as D50,
Alumina (A) having a D50 of 2 μm or more and 100 μm or less,
Alumina (B) having a D50 of 1 μm to 10 μm and
D50 is a mixture of alumina (C) of 0.01 μm or more and 5 μm or less,
The ratio of alumina (A), (B) and (C) to the volume of the alumina powder is 50% by volume to 90% by volume, 5% by volume to 40% by volume, and 1% by volume to 30% by volume, respectively. (However, the total volume% of alumina (A), (B) and (C) is 100 volume%).
As the alumina powder, the ratio of alumina (A), (B) and (C) to the volume of the alumina powder is 60% by volume to 90% by volume, 10% by volume to 40% by volume, and 5% by volume, respectively. The alumina powder is preferably 30% by volume or less (however, the total volume% of alumina (A), (B) and (C) is 100% by volume), and the alumina (A) relative to the volume of the alumina powder, The ratio of (B) and (C) is 70 volume% or more and 90 volume% or less, 10 volume% or more and 30 volume% or less, 5 volume% or more and 20 volume% or less (however, alumina (A), (B) And (C) is more preferably 100% by volume of alumina powder).
アルミナ（Ａ）、（Ｂ）及び（Ｃ）としては、市販のものを用いてもよいし、遷移アルミナ又は熱処理することにより遷移アルミナとなるアルミナ粉末を、塩化水素を含有する雰囲気ガス中で焼成することにより製造することができる（例えば、特開平６−１９１８３３号公報、特開平６−１９１８３６号公報参照）。アルミナ粉末は、かかるアルミナ（Ａ）、（Ｂ）及び（Ｃ）を適宜混合することにより調製することができる。
アルミナ粉末は、好ましくは、α−アルミナ粉末である。
かかるアルミナ（Ａ）及び（Ｂ）としては、α−アルミナ粒子からなるアルミナが好ましく、α−アルミナの単結晶粒子からなるアルミナがより好ましい。アルミナ（Ｃ）としては、α−アルミナ粒子からなるアルミナであってもよいし、γ−アルミナ、θ−アルミナ、δ−アルミナ等の遷移アルミナ粒子からなるアルミナであってもよく、好ましくはα−アルミナ粒子からなるアルミナであり、より好ましくは、α−アルミナの単結晶粒子からなるアルミナである。
As alumina (A), (B), and (C), commercially available products may be used, or transition alumina or alumina powder that becomes transition alumina by heat treatment is fired in an atmosphere gas containing hydrogen chloride. (See, for example, JP-A-6-191833 and JP-A-6-191836). The alumina powder can be prepared by appropriately mixing such aluminas (A), (B) and (C).
The alumina powder is preferably α-alumina powder.
As the alumina (A) and (B), alumina composed of α-alumina particles is preferable, and alumina composed of α-alumina single crystal particles is more preferable. The alumina (C) may be alumina composed of α-alumina particles, or alumina composed of transition alumina particles such as γ-alumina, θ-alumina, and δ-alumina, preferably α- Alumina composed of alumina particles, more preferably alumina composed of α-alumina single crystal particles.
本発明のエポキシ樹脂組成物は、エポキシ化合物（１）と硬化剤とアルミナ粉末との合計体積に対して、アルミナ粉末の体積が、通常３０〜９５％、好ましくは６０〜９５％となるように、アルミナ粉末の使用量が決められる。エポキシ化合物（１）と硬化剤とアルミナ粉末との合計体積に対して、アルミナ粉末の体積が、３０％未満では、エポキシ樹脂硬化物の熱伝導率を高める効果が小さく、また、９５％を越えるとエポキシ樹脂硬化物の成形性が低下する傾向にある。
本発明のエポキシ樹脂組成物は、アルミナ粉末に加えて、アルミナを主成分とし、その数平均繊維径が１〜５０μｍである無機繊維を含んでいてもよい。本発明において、「アルミナを主成分とする無機繊維」とは、アルミナを５０重量％以上含む無機繊維を意味する。なかでも、アルミナを７０重量％以上含む無機繊維が好ましく、アルミナを９０重量％以上含む無機繊維がより好ましい。かかる無機繊維の数平均繊維径は、１〜５０μｍであるが、好ましくは１〜３０μｍであり、より好ましくは１〜２０μｍである。また、かかる無機繊維の繊維長は、通常０．１〜１００ｍｍである。
かかる無機繊維としては、通常、市販されているものが使用され、具体的には、アルテックス（住友化学株式会社製）、デンカアルセン（電気化学工業株式会社製）、マフテックバルクファイバー（三菱化学産資株式会社製）等が挙げられる。
In the epoxy resin composition of the present invention, the volume of the alumina powder is usually 30 to 95%, preferably 60 to 95% with respect to the total volume of the epoxy compound (1), the curing agent and the alumina powder. The amount of alumina powder used is determined. When the volume of the alumina powder is less than 30% with respect to the total volume of the epoxy compound (1), the curing agent, and the alumina powder, the effect of increasing the thermal conductivity of the cured epoxy resin is small, and the volume exceeds 95%. And the moldability of the cured epoxy resin tends to decrease.
In addition to the alumina powder, the epoxy resin composition of the present invention may contain inorganic fibers whose main component is alumina and whose number average fiber diameter is 1 to 50 μm. In the present invention, “inorganic fiber mainly composed of alumina” means an inorganic fiber containing 50% by weight or more of alumina. Among these, inorganic fibers containing 70% by weight or more of alumina are preferable, and inorganic fibers containing 90% by weight or more of alumina are more preferable. The number average fiber diameter of such inorganic fibers is 1 to 50 μm, preferably 1 to 30 μm, and more preferably 1 to 20 μm. Moreover, the fiber length of this inorganic fiber is 0.1-100 mm normally.
As such inorganic fibers, commercially available fibers are usually used. Specifically, Artex (manufactured by Sumitomo Chemical Co., Ltd.), Denka Arsen (manufactured by Denki Kagaku Kogyo Co., Ltd.), Maftec Bulk Fiber (Mitsubishi Chemical) Sangyo Co., Ltd.).
かかる無機繊維を用いる場合のその使用量は、アルミナ粉末の体積に対して、通常５〜７０体積％、好ましくは５〜５０体積％であり、アルミナ粉末と無機繊維の合計体積が、エポキシ化合物（１）と硬化剤とアルミナ粉末と無機繊維との合計体積に対して、通常３０〜９５％となる量が用いられる。
硬化剤としては、その分子内に、エポキシ基と硬化反応し得る官能基を少なくとも２個有するものであればよく、該官能基がアミノ基であるアミン系硬化剤、該官能基が水酸基であるフェノール系硬化剤、該官能基がカルボキシル基である酸無水物系硬化剤等が挙げられ、アミン系硬化剤又はフェノール系硬化剤が好ましく、アミン系硬化剤がより好ましい。
The amount of the inorganic fiber used is usually 5 to 70% by volume, preferably 5 to 50% by volume, based on the volume of the alumina powder. The total volume of the alumina powder and the inorganic fiber is an epoxy compound ( An amount of 30 to 95% is usually used with respect to the total volume of 1), the curing agent, the alumina powder, and the inorganic fibers.
The curing agent only needs to have at least two functional groups capable of undergoing a curing reaction with an epoxy group in the molecule. The amine curing agent in which the functional group is an amino group, and the functional group is a hydroxyl group. Examples thereof include a phenolic curing agent and an acid anhydride curing agent in which the functional group is a carboxyl group. An amine curing agent or a phenolic curing agent is preferable, and an amine curing agent is more preferable.
アミン系硬化剤としては、エチレンジアミン、トリメチレンジアミン、テトラメチレンジアミン、ヘキサメチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン等の炭素数２〜２０の脂肪族多価アミン；ｐ−キシレンジアミン、ｍ−キシレンジアミン、１，５−ジアミノナフタレン、ｍ−フェニレンジアミン、ｐ−フェニレンジアミン、４，４’−ジアミノジフェニルメタン、４，４’−ジアミノジフェニルエタン、４，４’−ジアミノジフェニルプロパン、４，４’−ジアミノジフェニルエーテル、１，１−ビス（４−アミノフェニル）シクロヘキサン、４，４’−ジアミノジフェニルスルホン、ビス（４−アミノフェニル）フェニルメタン等の芳香族多価アミン；４，４’−ジアミノジシクロヘキサン、１，３−ビス（アミノメチル）シクロヘキサン等の脂環式多価アミン；及びジシアンジアミド等が挙げられ、芳香族多価アミンが好ましく、４，４’−ジアミノジフェニルメタン、４，４’−ジアミノジフェニルエタン、１，５−ジアミノナフタレン、ｐ−フェニレンジアミンがより好ましい。 Examples of the amine curing agent include aliphatic diamines having 2 to 20 carbon atoms such as ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, diethylenetriamine, and triethylenetetramine; p-xylenediamine, m-xylenediamine, 1,5-diaminonaphthalene, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether 1,4-bis (4-aminophenyl) cyclohexane, 4,4′-diaminodiphenylsulfone, aromatic polyvalent amines such as bis (4-aminophenyl) phenylmethane; 4,4′-diaminodicyclohexane, , 3-bis (ami Methyl) cyclohexane and other alicyclic polyvalent amines; and dicyandiamide and the like, and aromatic polyvalent amines are preferred, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, 1,5-diaminonaphthalene P-phenylenediamine is more preferable.
フェノール系硬化剤としては、フェノール樹脂、フェノールアラルキル樹脂（フェニレン骨格、ジフェニレン骨格等を有する）、ナフトールアラルキル樹脂、ポリオキシスチレン樹脂等が挙げられる。フェノール樹脂としては、アニリン変性レゾール樹脂、ジメチルエーテルレゾール樹脂等のレゾール型フェノール樹脂；フェノールノボラック樹脂、クレゾールノボラック樹脂、ｔｅｒｔ−ブチルフェノールノボラック樹脂、ノニルフェノールノボラック樹脂等のノボラック型フェノール樹脂；ジシクロペンタジエン変性フェノール樹脂、テルペン変性フェノール樹脂、トリフェノールメタン型樹脂等の特殊フェノール樹脂等が挙げられ、ポリオキシスチレン樹脂としては、ポリ（ｐ−オキシスチレン）等が挙げられる。 Examples of the phenolic curing agent include phenol resin, phenol aralkyl resin (having a phenylene skeleton, diphenylene skeleton, etc.), naphthol aralkyl resin, polyoxystyrene resin, and the like. Examples of the phenol resin include resol-type phenol resins such as aniline-modified resole resin and dimethyl ether resole resin; , Terpene-modified phenol resins, special phenol resins such as triphenolmethane type resins, and the like, and examples of polyoxystyrene resins include poly (p-oxystyrene).
酸無水物系硬化剤としては、無水マレイン酸、無水フタル酸、無水ピロメリット酸、無水トリメリット酸等が挙げられる。
かかる硬化剤は、該硬化剤中のエポキシ基と硬化反応し得る官能基の総量が、エポキシ化合物（１）中のエポキシ基の総量に対して、通常０．５〜１．５倍、好ましくは０．９〜１．１倍となる量が用いられる。
Examples of the acid anhydride curing agent include maleic anhydride, phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, and the like.
In such a curing agent, the total amount of functional groups capable of undergoing a curing reaction with the epoxy group in the curing agent is usually 0.5 to 1.5 times, preferably the total amount of epoxy groups in the epoxy compound (1). An amount of 0.9 to 1.1 times is used.
本発明のエポキシ樹脂組成物は、エポキシ化合物（１）、硬化剤及びアルミナ（さらに必要に応じ無機繊維）以外に、エポキシ樹脂組成物を硬化させてなるエポキシ樹脂硬化物の所望の性能を妨げない限り、他のエポキシ化合物を含んでいてもよく、また、各種添加剤を含んでいてもよい。
他のエポキシ化合物としては、ビスフェノールＡ型エポキシ化合物、オルソクレゾール型エポキシ化合物、ビフェノールジグリシジルエーテル、４，４’−ビス（３，４−エポキシブテン−１−イロキシ）フェニルベンゾエート、ナフタレンジグリシジルエーテル、α−メチルスチルベン−４，４’−ジグリシジルエーテル等が挙げられる。
添加剤としては、溶融破砕シリカ粉末、溶融球状シリカ粉末、結晶シリカ粉末、二次凝集シリカ粉末等のシリカ粉末；チタンホワイト、水酸化アルミニウム、タルク、クレイ、マイカ、ガラス繊維等の充填材；トリフェニルホスフィン、１，８−アザビシクロ［５．４．０］−７−ウンデセン、２−メチルイミダゾール等の硬化促進剤；γ−グリシドキシプロピルトリメトキシシラン等のカップリング剤；カーボンブラック等の着色剤；シリコーンオイル、シリコーンゴム等の低応力成分；天然ワックス、合成ワックス、高級脂肪酸又はその金属塩、パラフィン等の離型剤；酸化防止剤等が挙げられる。かかる他のエポキシ化合物や添加剤の含量は、本発明のエポキシ樹脂組成物を硬化させて得られるエポキシ樹脂硬化物の所望の性能を損なわない量であれば特に問題ない。
The epoxy resin composition of the present invention does not interfere with the desired performance of the cured epoxy resin composition obtained by curing the epoxy resin composition, in addition to the epoxy compound (1), the curing agent, and alumina (and inorganic fibers as necessary). As long as other epoxy compounds may be included, various additives may be included.
Other epoxy compounds include bisphenol A type epoxy compounds, ortho cresol type epoxy compounds, biphenol diglycidyl ether, 4,4′-bis (3,4-epoxybuten-1-yloxy) phenyl benzoate, naphthalene diglycidyl ether, α-methylstilbene-4,4′-diglycidyl ether and the like can be mentioned.
Additives include silica powder such as fused crushed silica powder, fused spherical silica powder, crystalline silica powder, secondary agglomerated silica powder; fillers such as titanium white, aluminum hydroxide, talc, clay, mica, glass fiber; Curing accelerators such as phenylphosphine, 1,8-azabicyclo [5.4.0] -7-undecene, 2-methylimidazole; coupling agents such as γ-glycidoxypropyltrimethoxysilane; coloring such as carbon black Agents; low stress components such as silicone oil and silicone rubber; natural waxes, synthetic waxes, higher fatty acids or metal salts thereof, mold release agents such as paraffin; and antioxidants. The content of such other epoxy compounds and additives is not particularly limited as long as it is an amount that does not impair the desired performance of the cured epoxy resin obtained by curing the epoxy resin composition of the present invention.
また、本発明のエポキシ樹脂組成物は、溶媒を含んでいてもよく、溶媒としては、エポキシ樹脂組成物の硬化反応を阻害しないものであれば特に制限されない。
本発明のエポキシ樹脂組成物を硬化させることにより、エポキシ樹脂硬化物を製造することができる。得られたエポキシ樹脂硬化物は、高い熱伝導率を示すため、例えばプリント配線基板等の高い熱放散性が要求される絶縁材料等として有用である。
The epoxy resin composition of the present invention may contain a solvent, and the solvent is not particularly limited as long as it does not inhibit the curing reaction of the epoxy resin composition.
A cured epoxy resin can be produced by curing the epoxy resin composition of the present invention. Since the obtained cured epoxy resin exhibits high thermal conductivity, it is useful as, for example, an insulating material that requires high heat dissipation such as a printed wiring board.
エポキシ樹脂硬化物を製造する方法としては、エポキシ樹脂組成物をそのまま所定温度まで加熱して硬化させる方法、エポキシ樹脂組成物を加熱溶融して金型等に注ぎ、該金型をさらに加熱して成形する方法、エポキシ樹脂組成物を溶融させ、得られる溶融物を予め加熱された金型に注入し硬化する方法、エポキシ樹脂組成物を部分硬化させ、得られる部分硬化物を粉砕してなる粉末を金型に充填し、該充填粉末を溶融成形する方法、エポキシ樹脂組成物を必要に応じて溶媒に溶解し、攪拌しながら部分硬化させ、得られた溶液をキャストした後、溶媒を通風乾燥等で乾燥除去し、必要に応じてプレス機等で圧力をかけながら所定時間加熱する方法等が挙げられる。 As a method for producing a cured epoxy resin, a method in which the epoxy resin composition is heated and cured as it is to a predetermined temperature, and the epoxy resin composition is heated and melted and poured into a mold, and the mold is further heated. A molding method, a method in which an epoxy resin composition is melted, a resulting melt is poured into a preheated mold and cured, and a powder obtained by partially curing an epoxy resin composition and grinding the resulting partially cured product A method of melt-molding the filled powder, dissolving the epoxy resin composition in a solvent as necessary, partially curing with stirring, casting the resulting solution, and then ventilating the solvent with air For example, there may be mentioned a method of drying and removing with a etc. and heating for a predetermined time while applying pressure with a press machine or the like, if necessary.
また、本発明のエポキシ樹脂組成物を、必要に応じて溶媒で希釈した後、基材に塗布もしくは含浸させた後、塗布もしくは含浸された基材を加熱して半硬化させることにより、プリプレグを製造することができる。基材としては、ガラス繊維織布等の無機質繊維の織布もしくは不織布、ポリエステル等の有機質繊維の織布もしくは不織布等が挙げられる。かかるプリプレグを用い、通常の方法により、積層板等を容易に製造することができる。 In addition, after the epoxy resin composition of the present invention is diluted with a solvent as necessary, the substrate is applied or impregnated, and then the coated or impregnated substrate is heated and semi-cured, whereby a prepreg is obtained. Can be manufactured. Examples of the substrate include woven or nonwoven fabrics of inorganic fibers such as glass fiber woven fabrics, and woven or nonwoven fabrics of organic fibers such as polyester. By using such a prepreg, a laminate or the like can be easily produced by a normal method.
以下、本発明を実施例によりさらに詳細に説明するが、本発明はこれら実施例に限定されるものではない。
［実施例１］
１−（３−メチル−４−オキシラニルメトキシフェニル）−４−（４−オキシラニルメトキシフェニル）−１−シクロヘキセン１００重量部と、１，５−ジアミノナフタレン（和光純薬工業株式会社製）２０重量部と、アルミナ粉末１１０７重量部（住友化学株式会社製α−アルミナ粉末；Ｄ５０が１８μｍのアルミナ８１９重量部（アルミナ粉末に対して、７４体積％）と、Ｄ５０が３μｍのアルミナ１５５重量部（アルミナ粉末に対して、１４体積％）と、Ｄ５０が０．４μｍのアルミナ１３３重量部（アルミナ粉末に対して、１２体積％）との混合物）と、メチルエチルケトン３００重量部とを混合し、得られた混合物を、真空条件下で脱気し、エポキシ樹脂組成物を得た。１−（３−メチル−４−オキシラニルメトキシフェニル）−４−（４−オキシラニルメトキシフェニル）−１−シクロヘキセンと１，５−ジアミノナフタレンとの混合物の密度を１．２ｇ／ｃｍ３、アルミナ粉末の密度を３．９７ｇ／ｃｍ３として、１−（３−メチル−４−オキシラニルメトキシフェニル）−４−（４−オキシラニルメトキシフェニル）−１−シクロヘキセンと１，５−ジアミノナフタレンとアルミナ粉末との合計体積に対するアルミナ粉末の割合を算出したところ、７４体積％であった。
アプリケータで、エポキシ樹脂組成物をポリエチレンテレフタレート基材上に厚みが４００μｍとなるように塗布した後、１時間室温で放置し、乾燥させた。温度６０℃、真空度１ｋＰａで、１０分間さらに乾燥させた後、真空プレス成形（プレス温度１４０℃、真空度１ｋＰａ、プレス圧２ＭＰａ、処理時間３．５分）を行い、プリプレグシートを得た。
得られたプリプレグシートの両面のポリエチレンテレフタレートフィルムを剥がした後、両面を銅箔（３５μｍ）で挟んで真空圧着（温度１４０℃、真空度１ｋＰａ、プレス圧４ＭＰａ、処理時間１０分間）した。その後、大気圧条件下、１４０℃で２時間、１８０℃で３時間加熱した。得られたシートを、１０×１０ｍｍの大きさに裁断した後、銅箔を除去し、厚み２００μｍの樹脂シートを得た。得られた樹脂シートの熱伝導率を、キセノンフラッシュ法、レーザーフラッシュ法及び温度波熱分析法で測定しところ、キセノンフラッシュ法では、９．４Ｗ／ｍ・Ｋ、温度波熱分析法では、１０．４Ｗ／ｍ・Ｋであったが、レーザーフラッシュ法では、熱伝導率を測定することができなかった。
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.
[Example 1]
100 parts by weight of 1- (3-methyl-4-oxiranylmethoxyphenyl) -4- (4-oxiranylmethoxyphenyl) -1-cyclohexene and 1,5-diaminonaphthalene (manufactured by Wako Pure Chemical Industries, Ltd.) ) 20 parts by weight, 1107 parts by weight of alumina powder (α-alumina powder manufactured by Sumitomo Chemical Co., Ltd .; 819 parts by weight of alumina having a D50 of 18 μm (74% by volume with respect to the alumina powder), and 155 weights of alumina having a D50 of 3 μm Parts (a mixture of 14% by volume with respect to alumina powder), 133 parts by weight of alumina having a D50 of 0.4 μm (12% by volume with respect to alumina powder), and 300 parts by weight of methyl ethyl ketone, The obtained mixture was deaerated under vacuum conditions to obtain an epoxy resin composition. The density of a mixture of 1- (3-methyl-4-oxiranylmethoxyphenyl) -4- (4-oxiranylmethoxyphenyl) -1-cyclohexene and 1,5-diaminonaphthalene is 1.2 g / cm 3. The density of the alumina powder was 3.97 g / cm 3 , and 1- (3-methyl-4-oxiranylmethoxyphenyl) -4- (4-oxiranylmethoxyphenyl) -1-cyclohexene and 1,5- The ratio of the alumina powder to the total volume of diaminonaphthalene and alumina powder was calculated to be 74% by volume.
The epoxy resin composition was applied on a polyethylene terephthalate substrate with an applicator so as to have a thickness of 400 μm, and then allowed to stand at room temperature for 1 hour and dried. After further drying for 10 minutes at a temperature of 60 ° C. and a vacuum of 1 kPa, vacuum press molding (press temperature of 140 ° C., vacuum of 1 kPa, press pressure of 2 MPa, treatment time of 3.5 minutes) was performed to obtain a prepreg sheet.
After peeling the polyethylene terephthalate film on both sides of the obtained prepreg sheet, both sides were sandwiched between copper foils (35 μm) and vacuum-pressed (temperature 140 ° C., vacuum degree 1 kPa, press pressure 4 MPa, treatment time 10 minutes). Thereafter, heating was performed at 140 ° C. for 2 hours and at 180 ° C. for 3 hours under atmospheric pressure conditions. After the obtained sheet was cut into a size of 10 × 10 mm, the copper foil was removed to obtain a resin sheet having a thickness of 200 μm. The thermal conductivity of the obtained resin sheet was measured by a xenon flash method, a laser flash method, and a temperature wave thermal analysis method. The xenon flash method was 9.4 W / m · K, and the temperature wave thermal analysis method was 10 Although it was 4 W / m · K, the thermal conductivity could not be measured by the laser flash method.
［実施例２］
１−（３−メチル−４−オキシラニルメトキシフェニル）−４−（４−オキシラニルメトキシフェニル）−１−シクロヘキセン１００重量部と、１，５−ジアミノナフタレン（和光純薬工業株式会社製）２０重量部と、アルミナ粉末３６４重量部（住友化学株式会社製α−アルミナ粉末；Ｄ５０が１８μｍのアルミナ２３８重量部（アルミナ粉末に対して、６５体積％）と、Ｄ５０が３μｍのアルミナ６８重量部（アルミナ粉末に対して、１９体積％）と、Ｄ５０が０．４μｍのアルミナ５８重量部（アルミナ粉末に対して、１６体積％）との混合物）と、アルミナ繊維（数平均繊維径：５μｍ）１２１重量部と、メチルエチルケトン３００重量部とを混合し、得られた混合物を、真空条件下で脱気し、エポキシ樹脂組成物を得た。１−（３−メチル−４−オキシラニルメトキシフェニル）−４−（４−オキシラニルメトキシフェニル）−１−シクロヘキセンと１，５−ジアミノナフタレンとの混合物の密度を１．２ｇ／ｃｍ３、アルミナ粉末及びアルミナ繊維の密度を３．９７ｇ／ｃｍ３として、１−（３−メチル−４−オキシラニルメトキシフェニル）−４−（４−オキシラニルメトキシフェニル）−１−シクロヘキセンと１，５−ジアミノナフタレンとアルミナ粉末とアルミナ繊維との合計体積に対するアルミナ粉末とアルミナ繊維の合計割合を算出したところ、５５体積％であった。
アプリケータで、エポキシ樹脂組成物をポリエチレンテレフタレート基材上に厚みが４００μｍとなるように塗布した後、１時間室温で放置し、乾燥させた。温度６０℃、真空度１ｋＰａで、１０分間さらに乾燥させた後、真空プレス成形（プレス温度１４０℃、真空度１ｋＰａ、プレス圧２ＭＰａ、処理時間３．５分）を行い、プリプレグシートを得た。
得られたプリプレグシートの両面のポリエチレンテレフタレートフィルムを剥がした後、両面を銅箔（３５μｍ）で挟んで真空圧着（温度１４０℃、真空度１ｋＰａ、プレス圧４ＭＰａ、処理時間１０分間）した。その後、大気圧条件下、１４０℃で２時間、１８０℃で３時間加熱した。得られたシートを、１０×１０ｍｍの大きさに裁断した後、銅箔を除去し、厚み２００μｍの樹脂シートを得た。得られた樹脂シートの熱伝導率を、キセノンフラッシュ法、レーザーフラッシュ法及び温度波熱分析法で測定したところ、キセノンフラッシュ法では、４．９Ｗ／ｍ・Ｋ、温度波熱分析法では、５．４Ｗ／ｍ・Ｋであったが、レーザーフラッシュ法では、熱伝導率を測定することができなかった。
[Example 2]
100 parts by weight of 1- (3-methyl-4-oxiranylmethoxyphenyl) -4- (4-oxiranylmethoxyphenyl) -1-cyclohexene and 1,5-diaminonaphthalene (manufactured by Wako Pure Chemical Industries, Ltd.) 20 parts by weight, 364 parts by weight of alumina powder (α-alumina powder manufactured by Sumitomo Chemical Co., Ltd .; 238 parts by weight of alumina having a D50 of 18 μm (65% by volume with respect to the alumina powder), and 68 parts by weight of alumina having a D50 of 3 μm Parts (19 volume% with respect to alumina powder), 58 parts by weight of alumina having a D50 of 0.4 μm (16 volume% with respect to alumina powder), and alumina fibers (number average fiber diameter: 5 μm) ) 121 parts by weight and 300 parts by weight of methyl ethyl ketone were mixed, and the resulting mixture was degassed under vacuum conditions to obtain an epoxy resin composition. The density of a mixture of 1- (3-methyl-4-oxiranylmethoxyphenyl) -4- (4-oxiranylmethoxyphenyl) -1-cyclohexene and 1,5-diaminonaphthalene is 1.2 g / cm 3. The density of alumina powder and alumina fiber was 3.97 g / cm 3 , and 1- (3-methyl-4-oxiranylmethoxyphenyl) -4- (4-oxiranylmethoxyphenyl) -1-cyclohexene and 1 The total ratio of alumina powder and alumina fiber to the total volume of 1,5-diaminonaphthalene, alumina powder and alumina fiber was calculated to be 55% by volume.
The epoxy resin composition was applied on a polyethylene terephthalate substrate with an applicator so as to have a thickness of 400 μm, and then allowed to stand at room temperature for 1 hour and dried. After further drying for 10 minutes at a temperature of 60 ° C. and a vacuum of 1 kPa, vacuum press molding (press temperature of 140 ° C., vacuum of 1 kPa, press pressure of 2 MPa, treatment time of 3.5 minutes) was performed to obtain a prepreg sheet.
After peeling the polyethylene terephthalate film on both sides of the obtained prepreg sheet, both sides were sandwiched between copper foils (35 μm) and vacuum-pressed (temperature 140 ° C., vacuum degree 1 kPa, press pressure 4 MPa, treatment time 10 minutes). Thereafter, heating was performed at 140 ° C. for 2 hours and at 180 ° C. for 3 hours under atmospheric pressure conditions. After the obtained sheet was cut into a size of 10 × 10 mm, the copper foil was removed to obtain a resin sheet having a thickness of 200 μm. When the thermal conductivity of the obtained resin sheet was measured by the xenon flash method, the laser flash method, and the temperature wave thermal analysis method, it was 4.9 W / m · K in the xenon flash method, and 5 in the temperature wave thermal analysis method. Although it was 4 W / m · K, the thermal conductivity could not be measured by the laser flash method.
［実施例３］
１−（３−メチル−４−オキシラニルメトキシフェニル）−４−（４−オキシラニルメトキシフェニル）−１−シクロヘキセン１００重量部と、１，５−ジアミノナフタレン（和光純薬工業株式会社製）２０重量部と、アルミナ粉末１１０７重量部（住友化学株式会社製α−アルミナ粉末；Ｄ５０が１０μｍのアルミナ８８６重量部（アルミナ粉末に対して、８０体積％）と、Ｄ５０が３μｍのアルミナ１１１重量部（アルミナ粉末に対して、１０体積％）と、Ｄ５０が０．４μｍのアルミナ１１０重量部（アルミナ粉末に対して、１０体積％）との混合物）と、メチルエチルケトン３００重量部とを混合し、得られた混合物を、真空条件下で脱気し、エポキシ樹脂組成物を得た。１−（３−メチル−４−オキシラニルメトキシフェニル）−４−（４−オキシラニルメトキシフェニル）−１−シクロヘキセンと１，５−ジアミノナフタレンとの混合物の密度を１．２ｇ／ｃｍ３、アルミナ粉末の密度を３．９７ｇ／ｃｍ３として、１−（３−メチル−４−オキシラニルメトキシフェニル）−４−（４−オキシラニルメトキシフェニル）−１−シクロヘキセンと１，５−ジアミノナフタレンとアルミナ粉末との合計体積に対するアルミナ粉末の割合を算出したところ、７４体積％であった。
アプリケータで、エポキシ樹脂組成物をポリエチレンテレフタレート基材上に厚みが４００μｍとなるように塗布した後、１時間室温で放置し、乾燥させた。温度６０℃、真空度１ｋＰａで、１０分間さらに乾燥させた後、真空プレス成形（プレス温度１４０℃、真空度１ｋＰａ、プレス圧４ＭＰａ、処理時間３．５分）を行い、プリプレグシートを得た。
得られたプリプレグシートの両面のポリエチレンテレフタレートフィルムを剥がした後、両面を銅箔（３５μｍ）で挟んで真空圧着（温度１４０℃、真空度１ｋＰａ、プレス圧４ＭＰａ、処理時間１０分間）した。その後、大気圧条件下、１４０℃で２時間、１８０℃で３時間加熱した。得られたシートを、１０×１０ｍｍの大きさに裁断した後、銅箔を除去し、厚み２００μｍの樹脂シートを得た。
[Example 3]
100 parts by weight of 1- (3-methyl-4-oxiranylmethoxyphenyl) -4- (4-oxiranylmethoxyphenyl) -1-cyclohexene and 1,5-diaminonaphthalene (manufactured by Wako Pure Chemical Industries, Ltd.) ) 20 parts by weight, 1107 parts by weight of alumina powder (α-alumina powder manufactured by Sumitomo Chemical Co., Ltd .; 886 parts by weight of alumina having a D50 of 10 μm (80% by volume with respect to the alumina powder), 111 parts by weight of alumina having a D50 of 3 μm Parts (a mixture of 10% by volume with respect to the alumina powder), 110 parts by weight of alumina having a D50 of 0.4 μm (10% by volume with respect to the alumina powder), and 300 parts by weight of methyl ethyl ketone, The obtained mixture was deaerated under vacuum conditions to obtain an epoxy resin composition. The density of a mixture of 1- (3-methyl-4-oxiranylmethoxyphenyl) -4- (4-oxiranylmethoxyphenyl) -1-cyclohexene and 1,5-diaminonaphthalene is 1.2 g / cm 3. The density of the alumina powder was 3.97 g / cm 3 , and 1- (3-methyl-4-oxiranylmethoxyphenyl) -4- (4-oxiranylmethoxyphenyl) -1-cyclohexene and 1,5- The ratio of the alumina powder to the total volume of diaminonaphthalene and alumina powder was calculated to be 74% by volume.
The epoxy resin composition was applied on a polyethylene terephthalate substrate with an applicator so as to have a thickness of 400 μm, and then allowed to stand at room temperature for 1 hour and dried. After further drying for 10 minutes at a temperature of 60 ° C. and a vacuum of 1 kPa, vacuum press molding (press temperature of 140 ° C., vacuum of 1 kPa, press pressure of 4 MPa, treatment time of 3.5 minutes) was performed to obtain a prepreg sheet.
After peeling the polyethylene terephthalate film on both sides of the obtained prepreg sheet, both sides were sandwiched between copper foils (35 μm) and vacuum-pressed (temperature 140 ° C., vacuum degree 1 kPa, press pressure 4 MPa, treatment time 10 minutes). Thereafter, heating was performed at 140 ° C. for 2 hours and at 180 ° C. for 3 hours under atmospheric pressure conditions. After the obtained sheet was cut into a size of 10 × 10 mm, the copper foil was removed to obtain a resin sheet having a thickness of 200 μm.
［比較例１］
ビスフェノールA型エポキシ化合物１００重量部と、１，５−ジアミノナフタレン（和光純薬工業株式会社製）２１重量部と、実施例１で用いたと同じアルミナ粉末１１０７重量部と、メチルエチルケトン３００重量部とを混合し、得られた混合物を、真空条件下で脱気し、比較組成物を得た。ビスフェノールA型エポキシ化合物と１，５−ジアミノナフタレンとの混合物の密度を１．２ｇ／ｃｍ３、アルミナ粉末の密度を３．９７ｇ／ｃｍ３として、ビスフェノールA型エポキシ化合物と１，５−ジアミノナフタレンとアルミナ混合粉末との合計体積に対するアルミナ粉末の割合を算出したところ、７４体積％であった。
アプリケータで、比較組成物をポリエチレンテレフタレート基材上に厚みが４００μｍとなるように塗布した後、１時間室温で放置し、乾燥させた。温度６０℃、真空度１ｋＰａで、１０分間さらに乾燥させた後、真空プレス成形（プレス温度１４０℃、真空度１ｋＰａ、プレス圧２ＭＰａ、処理時間３．５分）を行い、プリプレグシートを得た。
得られたプリプレグシートの両面のポリエチレンテレフタレートフィルムを剥がした後、両面を銅箔（３５μｍ）で挟んで真空圧着（温度１４０℃、真空度１ｋＰａ、プレス圧４ＭＰａ、処理時間１０分間）した。その後、大気圧条件下、１４０℃で２時間、１８０℃で３時間加熱した。得られたシートを、１０×１０ｍｍの大きさに裁断した後、銅箔を除去し、厚み２００μｍの樹脂シートを得た。得られた樹脂シートの熱伝導率を、キセノンフラッシュ法、レーザーフラッシュ法及び温度波熱分析法で測定したところ、キセノンフラッシュ法では、３．８Ｗ／ｍ・Ｋ、温度波熱分析法では、４．５Ｗ／ｍ・Ｋであったが、レーザーフラッシュ法では、熱伝導率は測定することができなかった。
[Comparative Example 1]
100 parts by weight of a bisphenol A type epoxy compound, 21 parts by weight of 1,5-diaminonaphthalene (manufactured by Wako Pure Chemical Industries, Ltd.), 1107 parts by weight of the same alumina powder used in Example 1, and 300 parts by weight of methyl ethyl ketone After mixing, the resulting mixture was degassed under vacuum conditions to obtain a comparative composition. The density of the mixture of the bisphenol A type epoxy compound and 1,5-diaminonaphthalene is 1.2 g / cm 3 , and the density of the alumina powder is 3.97 g / cm 3 , and the bisphenol A type epoxy compound and 1,5-diaminonaphthalene are set. It was 74 volume% when the ratio of the alumina powder with respect to the total volume of an alumina mixed powder was calculated.
The comparative composition was applied on a polyethylene terephthalate substrate with an applicator so as to have a thickness of 400 μm, and then allowed to stand at room temperature for 1 hour and dried. After further drying for 10 minutes at a temperature of 60 ° C. and a vacuum of 1 kPa, vacuum press molding (press temperature of 140 ° C., vacuum of 1 kPa, press pressure of 2 MPa, treatment time of 3.5 minutes) was performed to obtain a prepreg sheet.
After peeling the polyethylene terephthalate film on both sides of the obtained prepreg sheet, both sides were sandwiched between copper foils (35 μm) and vacuum-pressed (temperature 140 ° C., vacuum degree 1 kPa, press pressure 4 MPa, treatment time 10 minutes). Thereafter, heating was performed at 140 ° C. for 2 hours and at 180 ° C. for 3 hours under atmospheric pressure conditions. After the obtained sheet was cut into a size of 10 × 10 mm, the copper foil was removed to obtain a resin sheet having a thickness of 200 μm. When the thermal conductivity of the obtained resin sheet was measured by the xenon flash method, the laser flash method, and the temperature wave thermal analysis method, it was 3.8 W / m · K in the xenon flash method, and 4 in the temperature wave thermal analysis method. Although it was 0.5 W / m · K, the thermal conductivity could not be measured by the laser flash method.
本発明のエポキシ樹脂組成物を硬化させたエポキシ樹脂硬化物は、高い熱伝導率を有するため、例えばプリント配線基板等の高い熱放散性を要求される絶縁材料として有用である。 The cured epoxy resin obtained by curing the epoxy resin composition of the present invention has high thermal conductivity, and thus is useful as an insulating material that requires high heat dissipation such as a printed wiring board.
Claims (12)
で示されるエポキシ化合物、硬化剤及びアルミナ粉末を含むエポキシ樹脂組成物であって、
アルミナ粉末が、
重量累積粒度分布の微粒側からの累積５０％の粒経をＤ５０としたとき、
Ｄ５０が２μｍ以上１００μｍ以下のアルミナ（Ａ）、
Ｄ５０が１μｍ以上１０μｍ以下のアルミナ（Ｂ）及び
Ｄ５０が０．０１μｍ以上５μｍ以下のアルミナ（Ｃ）の混合物であり、
アルミナ粉末の体積に対するアルミナ（Ａ）、（Ｂ）及び（Ｃ）の割合が、それぞれ、５０体積％以上９０体積％以下、５体積％以上４０体積％以下、及び１体積％以上３０体積％以下（ただし、アルミナ（Ａ）、（Ｂ）及び（Ｃ）の合計の体積％は、１００体積％である）
であるエポキシ樹脂組成物。 Formula (1)
An epoxy resin composition comprising an epoxy compound represented by: a curing agent and alumina powder,
Alumina powder
When the 50% cumulative particle size from the fine particle side of the weight cumulative particle size distribution is D50,
Alumina (A) having a D50 of 2 μm or more and 100 μm or less,
A mixture of alumina (B) having a D50 of 1 μm to 10 μm and alumina (C) having a D50 of 0.01 μm to 5 μm,
The ratio of alumina (A), (B) and (C) to the volume of the alumina powder is 50% by volume to 90% by volume, 5% by volume to 40% by volume, and 1% by volume to 30% by volume, respectively. (However, the total volume% of alumina (A), (B) and (C) is 100 volume%)
An epoxy resin composition.
で示されるエポキシ化合物である請求項１又は２に記載のエポキシ樹脂組成物。 The epoxy compound represented by the formula (1) according to claim 1 is represented by the formula (2):
The epoxy resin composition of Claim 1 or 2 which is an epoxy compound shown by these.
で示されるエポキシ化合物である請求項３に記載のエポキシ樹脂組成物。 The epoxy compound represented by the formula (2) according to claim 3 is represented by the formula (3):
The epoxy resin composition of Claim 3 which is an epoxy compound shown by these.
で示されるエポキシ化合物である請求項５に記載のエポキシ樹脂組成物。 The epoxy compound represented by the formula (3) according to claim 5 is represented by the formula (4):
The epoxy resin composition of Claim 5 which is an epoxy compound shown by these.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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