JP2011046760A5 - - Google Patents
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- JP2011046760A5 JP2011046760A5 JP2009193888A JP2009193888A JP2011046760A5 JP 2011046760 A5 JP2011046760 A5 JP 2011046760A5 JP 2009193888 A JP2009193888 A JP 2009193888A JP 2009193888 A JP2009193888 A JP 2009193888A JP 2011046760 A5 JP2011046760 A5 JP 2011046760A5
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- Prior art keywords
- magnesium oxide
- oxide powder
- resin composition
- thermosetting resin
- thermal conductivity
- Prior art date
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- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 250
- 239000000395 magnesium oxide Substances 0.000 claims description 125
- 239000000843 powder Substances 0.000 claims description 105
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 92
- 239000000377 silicon dioxide Substances 0.000 claims description 43
- 229920001187 thermosetting polymer Polymers 0.000 claims description 40
- 239000002245 particle Substances 0.000 claims description 39
- 239000011342 resin composition Substances 0.000 claims description 39
- 239000011256 inorganic filler Substances 0.000 claims description 34
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 34
- 239000003822 epoxy resin Substances 0.000 claims description 31
- 229920000647 polyepoxide Polymers 0.000 claims description 31
- 239000000178 monomer Substances 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 16
- 229920005989 resin Polymers 0.000 claims description 15
- 239000011347 resin Substances 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 238000010304 firing Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000004381 surface treatment Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000009413 insulation Methods 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 18
- 239000002966 varnish Substances 0.000 description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N AI2O3 Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000011889 copper foil Substances 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K Aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 5
- VTHJTEIRLNZDEV-UHFFFAOYSA-L Magnesium hydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 5
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 5
- 239000003365 glass fiber Substances 0.000 description 5
- 239000000347 magnesium hydroxide Substances 0.000 description 5
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- -1 polyethylene terephthalate Polymers 0.000 description 5
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- 210000002356 Skeleton Anatomy 0.000 description 4
- 230000003247 decreasing Effects 0.000 description 4
- 239000005350 fused silica glass Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 230000017525 heat dissipation Effects 0.000 description 3
- 230000020169 heat generation Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 239000002759 woven fabric Substances 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L Calcium hydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N Imidazole Chemical compound C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N Silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N Triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 235000011116 calcium hydroxide Nutrition 0.000 description 2
- 230000000875 corresponding Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000007561 laser diffraction method Methods 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 238000000790 scattering method Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N Bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 0 CCC(C)(CC(*)COc(c(*)c1)c(*)cc1-c1cc(*)c(*C(C)(C)CC2OC2)c(*)c1)Oc(c(*)c1)c(*)cc1-c(cc1*)cc(*)c1OCC1OC1 Chemical compound CCC(C)(CC(*)COc(c(*)c1)c(*)cc1-c1cc(*)c(*C(C)(C)CC2OC2)c(*)c1)Oc(c(*)c1)c(*)cc1-c(cc1*)cc(*)c1OCC1OC1 0.000 description 1
- 210000000744 Eyelids Anatomy 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N N#B Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene (PE) Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N Silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N TiO Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PIGFYZPCRLYGLF-UHFFFAOYSA-N aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000002349 favourable Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910001929 titanium oxide Inorganic materials 0.000 description 1
Description
本発明は、酸化マグネシウム粉末の製造法に関する。また、この酸化マグネシウム粉末を含む熱硬化性樹脂組成物に関する。さらには、この樹脂組成物を用いたプリプレグの製造法、当該プリプレグにより構成される絶縁層又は絶縁層となる積層板の製造法に関する。この絶縁層は、耐湿特性、加工性に優れかつ熱伝導性が良好で、発熱部品を実装する配線板の絶縁層として好適である。 The present invention relates to a method of producing magnesium oxide powder. The present invention also relates to a thermosetting resin composition containing this magnesium oxide powder. Further, the present invention relates to a method for producing a prepreg using this resin composition, and a method for producing an insulating layer constituted by the prepreg or a laminate to be the insulating layer. This insulating layer is excellent in moisture resistance, processability and thermal conductivity, and is suitable as an insulating layer of a 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。 While the wiring board mounted on the electronic device is required to have a technology of fine wiring and high density mounting along with the reduction in the thickness and size of the electronic device, a technology of high heat dissipation corresponding to heat generation is also required. In particular, in an electronic circuit in an automobile or the like that uses a large current for various controls and operations, the heat generation due to the resistance of the conductive circuit and the heat generation from the power element are very large, and the heat dissipation characteristics of the wiring board are high level It has become essential.
そのような現状において、配線板の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、熱伝導率の高いアルミナを使用することで、樹脂組成物の熱伝導性を向上させることは知られている。しかし、アルミナは硬度が非常に高く、樹脂組成物の加工性が劣るため、アルミナ以外の無機充填材を使用する例もある。 Under such current circumstances, it is widely practiced to add an inorganic filler to a thermosetting resin in order to improve the thermal conductivity of the insulating layer of the wiring board. For example, it is known to improve the thermal conductivity of a resin composition by using alumina having a high thermal conductivity. However, since the hardness of alumina is very high and the processability of the resin composition is poor, there are also cases where inorganic fillers other than alumina are used.
酸化マグネシウムは、熱伝導率がアルミナと同等であり、かつ硬度もアルミナより低く、これを配合した樹脂成形物の加工性が良好である。しかしながら、酸化マグネシウムには吸湿性があり、配線板等の電子材料用途に使用する場合には、耐湿特性（特に、吸湿処理後の絶縁性）が低下するという問題がある。 Magnesium oxide has a thermal conductivity equivalent to that of alumina, and a hardness lower than that of alumina, and the processability of a resin molded product containing this is good. However, magnesium oxide has hygroscopicity, and when used for electronic materials such as wiring boards, there is a problem that the moisture resistance (in particular, the insulating property after the moisture absorption treatment) is lowered.
この対策として、例えば、特許文献１には、表面をシリカで被覆した酸化マグネシウム粉末が開示されている。その製造法は、１）酸化マグネシウム粉末にシリカを溶射する、２）酸化マグネシウム粉末にシリカを化学蒸着させる、３）酸化マグネシウム粉末に微粉シリカを噴霧接着させる、４）酸化マグネシウム粉末に微粉シリカをまぶし焼成するというものである。また、特許文献２には、シランカップリング剤により表面処理された酸化マグネシウム粉末が開示されている。 As a measure against this, for example, Patent Document 1 discloses a magnesium oxide powder whose surface is coated with silica. The manufacturing method includes 1) spraying silica on magnesium oxide powder, 2) chemically vapor depositing silica on magnesium oxide powder, 3) spray bonding fine silica to magnesium oxide powder, 4) finely powdered silica on magnesium oxide powder It is something that is fired with an eyelid. Patent Document 2 discloses a magnesium oxide powder surface-treated with a silane coupling agent.
しかしながら、特許文献１に記載された酸化マグネシウム粉末は、まず酸化マグネシウム粉末を焼成した後、さらにシリカを、溶射や化学蒸着、噴霧接着、まぶし焼成等の方法により被覆したものであるため、製造工程の増加とそのための製造設備が必要になるという問題がある。また、特許文献２に記載された技術では、配線板等の電子材料として使用する場合には、耐湿特性が不充分であるという問題がある。これは、配線板の吸湿処理試験を行った場合、シランカップリング剤により表面処理された僅かな隙間から吸湿が進行し、配線板が膨張したり、配線板の絶縁性が低下したりするためである。 However, the magnesium oxide powder described in Patent Document 1 is a manufacturing process because the magnesium oxide powder is first fired and then silica is further coated by a method such as thermal spraying, chemical vapor deposition, spray bonding, or baking. There is a problem that the increase of the cost and the manufacturing equipment for it are needed. Further, the technology described in Patent Document 2 has a problem that the moisture resistance is insufficient when used as an electronic material such as a wiring board. This is because when the wiring board is subjected to a moisture absorption treatment test, moisture absorption progresses from a slight gap surface-treated with a silane coupling agent, and the wiring board expands or the insulation of the wiring board is lowered. It is.
本発明が解決しようとする課題は、簡易な方法で吸湿性を改善できる酸化マグネシウム粉末を製造することである。また、この酸化マグネシウム粉末を含み、耐湿特性、加工性に優れかつ熱伝導性が良好な熱硬化性樹脂組成物を提供することである。さらには、この樹脂組成物を用いたプリプレグを製造し、当該プリプレグにより構成される積層板を提供することである。 The problem to be solved by the present invention is to produce magnesium oxide powder whose hygroscopicity can be improved by a simple method. Another object of the present invention is to provide a thermosetting resin composition which contains this magnesium oxide powder and which is excellent in moisture resistance, processability and thermal conductivity. Furthermore, the prepreg using this resin composition is manufactured, and it is providing the laminated board comprised with the said prepreg.
上記課題を解決するために、本発明に係る酸化マグネシウム粉末の製造法は、原料として、シリカ含有量が１〜６質量％である酸化マグネシウムを使用する。そして、これを１６５０〜１８００℃で焼成することにより、表面にシリカ膜を形成することを特徴とする（請求項１）。 In order to solve the said subject, the manufacturing method of the magnesium oxide powder which concerns on this invention uses the magnesium oxide whose silica content is 1-6 mass% as a raw material. And it is characterized by forming a silica film on the surface by baking this at 1650 to 1800 ° C. (Claim 1).
本発明の他の熱硬化性樹脂組成物は、上記の方法により得た酸化マグネシウム粉末を含む熱硬化性樹脂組成物であって、前記酸化マグネシウム粉末の平均粒径ｄ１を、１０μｍ≦ｄ１≦５０μｍの範囲とする。そして、前記酸化マグネシウム粉末の含有量が、熱硬化性樹脂固形分と酸化マグネシウム粉末を合わせた体積中に、２０〜８０体積％となるように混合することもできる。 Another thermosetting resin composition of the present invention is a thermosetting resin composition containing magnesium oxide powder obtained by the above method, wherein the average particle diameter d1 of the magnesium oxide powder is 10 μm ≦ d1 ≦ 50 μm. Range of And it can also be mixed so that content of the said magnesium oxide powder may be 20-80 volume% in the volume which united thermosetting resin solid content and magnesium oxide powder.
本発明に係る熱硬化性樹脂組成物は、上記の方法により得た酸化マグネシウム粉末を含む熱硬化性樹脂組成物であって、さらに、前記酸化マグネシウム粉末以外の無機充填材を含み、前記酸化マグネシウム粉末の平均粒径ｄ１を、１０μｍ≦ｄ１≦５０μｍの範囲とする。また、前記無機充填材は、平均粒径ｄ２を、０．１μｍ≦ｄ２≦５０μｍの範囲とする。そして、前記酸化マグネシウム粉末と無機充填材の総含有量が、熱硬化性樹脂固形分と酸化マグネシウム粉末と無機充填材を合わせた体積中に、２０〜８０体積％となるように混合することを特徴とする（請求項２）。 The thermosetting resin composition according to the present invention is a thermosetting resin composition containing a magnesium oxide powder obtained by the above method, and further contains an inorganic filler other than the magnesium oxide powder, and the magnesium oxide The average particle diameter d1 of the powder is in the range of 10 μm ≦ d1 ≦ 50 μm. The inorganic filler has an average particle diameter d2 in the range of 0.1 μm ≦ d2 ≦ 50 μm. Then, the total content of the magnesium oxide powder and the inorganic filler is 20-80% by volume in the combined volume of the thermosetting resin solid content, the magnesium oxide powder and the inorganic filler. It is characterized by (claim 2 ).
上記の樹脂組成物において、好ましくは、前記酸化マグネシウム粉末が、表面処理を施されたものである（請求項３）。 In the above resin composition, preferably, the magnesium oxide powder is subjected to surface treatment (claim 3).
また、好ましくは、熱硬化性樹脂組成物が、（式１）で示す分子構造のエポキシ樹脂モノマを配合したエポキシ樹脂組成物である（請求項４）。 In addition, preferably, the thermosetting resin composition is an epoxy resin composition in which an epoxy resin monomer having a molecular structure represented by (Formula 1) is blended (claim 4 ).
さらに好ましくは、上記（式１）においてＲが水素である、（式２）で示す分子構造のエポキシ樹脂モノマを配合したエポキシ樹脂組成物である（請求項５）。 More preferably, it is the epoxy resin composition which mix | blended the epoxy resin monomer of the molecular structure shown by (Formula 2) whose R is hydrogen in said (Formula 1) (Claim 5 ).
本発明に係るプリプレグの製造法は、上記の熱硬化性樹脂組成物を、シート状にし加熱乾燥することを特徴とする（請求項６）。
本発明に係る積層板の製造法は、上記の方法により製造したプリプレグを、プリプレグ層の全層ないしは一部の層として使用し加熱加圧成形することを特徴とする（請求項７）。
Preparation of the prepreg according to the present invention, the above-mentioned thermosetting resin composition, characterized by heating and drying the sheet (claim 6).
The method for producing a laminate according to the present invention is characterized in that the prepreg produced by the above method is used as the whole or a part of the prepreg layer and heat and pressure molded (Claim 8 ).
本発明に係る酸化マグネシウム粉末の製造法は、原料として、シリカ含有量が１〜６質量％である酸化マグネシウムを使用し、これを１６５０〜１８００℃（シリカの融点付近）で焼成する。これにより、酸化マグネシウム粉末の表面に溶け出したシリカは、酸化マグネシウム粉末と完全に分離することなく、酸化マグネシウム粉末の表面を被覆して、シリカ膜を形成することができる。このため、特許文献１に記載されたような特殊な工程を必要とせず、従来の酸化マグネシウム粉末の焼成工程のみで済み、製造工程を簡略化することができる。また、酸化マグネシウム粉末の表面がシリカ膜で被覆されているので、酸化マグネシウム粉末の吸湿性を改善することができる。 In the method for producing a magnesium oxide powder according to the present invention, magnesium oxide having a silica content of 1 to 6% by mass is used as a raw material, and this is calcined at 1650 to 1800 ° C. (around the melting point of silica). Thus, the silica dissolved on the surface of the magnesium oxide powder can cover the surface of the magnesium oxide powder without completely separating it from the magnesium oxide powder, thereby forming a silica film. For this reason, the special process as described in Patent Document 1 is not required, and only the process of firing the conventional magnesium oxide powder is sufficient, and the manufacturing process can be simplified. In addition, since the surface of the magnesium oxide powder is coated with a silica film, the hygroscopicity of the magnesium oxide powder can be improved.
また、本発明の他の熱硬化性樹脂組成物は、上記の方法により得た酸化マグネシウム粉末を含み、前記酸化マグネシウム粉末の平均粒径及び含有量を特定することにより、耐湿特性、加工性に優れかつ熱伝導性が良好な熱硬化性樹脂組成物とすることができる。 Moreover, the other thermosetting resin composition of this invention contains the magnesium oxide powder obtained by said method, By specifying the average particle diameter and content of the said magnesium oxide powder, it is in a moisture-resistant characteristic and processability. It is possible to obtain a thermosetting resin composition having excellent thermal conductivity.
さらに、本発明に係る熱硬化性樹脂組成物は、上記の方法により得た酸化マグネシウム粉末と無機充填材を含み、前記酸化マグネシウム粉末と無機充填材の平均粒径及び総含有量を特定することにより、耐湿特性、加工性に優れかつ熱伝導性が良好な熱硬化性樹脂組成物とすることができる。 Further, the thermosetting resin composition according to the present invention includes a magnesium oxide powder and an inorganic filler obtained by the method described above, to identify the average particle diameter and the total content of the magnesium oxide powder and an inorganic filler Thus, a thermosetting resin composition having excellent moisture resistance and processability and good thermal conductivity can be obtained.
上述のように、本発明によれば、原料となる酸化マグネシウム中のシリカ含有量と焼成温度を特定することで、耐湿特性、加工性に優れかつ熱伝導性が良好な絶縁層を製造することができ、当該絶縁層は配線板に好適に用いることができる。 As described above, according to the present invention, an insulating layer having excellent moisture resistance and processability and good thermal conductivity is specified by specifying the silica content in magnesium oxide as a raw material and the firing temperature. The insulating layer can be suitably used for a wiring board.
本発明の酸化マグネシウム粉末は、例えば、次のようにして製造することができる。まず、消石灰と海水を反応させ、水酸化マグネシウムとする。この水酸化マグネシウムを焼成することで原料となる酸化マグネシウムの１次粒子を製造する。そして、この原料となる酸化マグネシウムを焼成することにより、酸化マグネシウム粉末を製造する。 The magnesium oxide powder of the present invention can be produced, for example, as follows. First, slaked lime and seawater are reacted to form magnesium hydroxide. By firing the magnesium hydroxide, primary particles of magnesium oxide as a raw material are produced. And magnesium oxide powder is manufactured by baking the magnesium oxide used as this raw material.
このとき、原料となる酸化マグネシウムは、シリカ含有量が１〜６質量％であるものを使用する。シリカ含有量が１質量％より小さいと、溶融したシリカが酸化マグネシウム粉末の表面を充分に覆うことができず、酸化マグネシウム粉末の吸湿性を改善することができない。また、６質量％より大きいと、シリカ膜の厚みが厚くなるため、酸化マグネシウム本来の熱伝導率を発揮できず、樹脂成形物の熱伝導性が低下する。ここで、シリカ含有量とは、原料となる酸化マグネシウムの全質量（シリカ等を含む）を１００質量％としたときの値をいう。なお、原料となる酸化マグネシウムのシリカ含有量は、例えば海水中の珪酸の量を変えることで調整することができる。また、水酸化マグネシウムを焼成するときの焼成温度や焼成時間を変えることで調整することもできる。 At this time, the magnesium oxide used as a raw material has a silica content of 1 to 6% by mass. If the silica content is less than 1% by mass, the fused silica can not sufficiently cover the surface of the magnesium oxide powder, and the hygroscopicity of the magnesium oxide powder can not be improved. On the other hand, if the amount is more than 6% by mass, the thickness of the silica film becomes large, so that the thermal conductivity inherent to magnesium oxide can not be exhibited, and the thermal conductivity of the resin molded product is lowered. Here, the silica content refers to a value when the total mass (including silica and the like) of magnesium oxide as a raw material is 100% by mass. In addition, the silica content of the magnesium oxide used as a raw material can be adjusted, for example by changing the quantity of the silicic acid in seawater. Moreover, it can also adjust by changing the calcination temperature and calcination time at the time of baking magnesium hydroxide.
また、焼成温度は、１６５０〜１８００℃（シリカの融点付近）とする。焼成温度が１６５０℃より低いと、シリカが溶融しないため、酸化マグネシウム粉末の表面を覆うことができず、酸化マグネシウム粉末の吸湿性を改善することができない。また、１８００℃より高いと、溶融したシリカが酸化マグネシウム粉末と分離するため、シリカ膜を形成できず、酸化マグネシウム粉末の吸湿性を改善することができない。 In addition, the firing temperature is set to 1650 to 1800 ° C. (around the melting point of silica). If the firing temperature is lower than 1650 ° C., the silica does not melt, so the surface of the magnesium oxide powder can not be covered, and the hygroscopicity of the magnesium oxide powder can not be improved. Further, if the temperature is higher than 1800 ° C., the fused silica is separated from the magnesium oxide powder, so that the silica film can not be formed, and the hygroscopicity of the magnesium oxide powder can not be improved.
本発明の他の熱硬化性樹脂組成物は、上記の方法により得た酸化マグネシウム粉末を含み、酸化マグネシウム粉末の平均粒径ｄ１を、１０μｍ≦ｄ１≦５０μｍの範囲とする。平均粒径ｄ１が１０μｍより小さいと、酸化マグネシウム粉末の接触点が増えるため、樹脂との界面が熱抵抗となり、熱伝導率が向上しない。また、５０μｍより大きいと、吸湿しやすくなるため、耐湿特性（特に、吸湿処理後の絶縁性）が低下する。 Another thermosetting resin composition of the present invention contains the magnesium oxide powder obtained by the above method, and the average particle diameter d1 of the magnesium oxide powder is in the range of 10 μm ≦ d1 ≦ 50 μm. When the average particle diameter d1 is smaller than 10 μm, the contact point with the magnesium oxide powder is increased, the interface with the resin becomes a thermal resistance, and the thermal conductivity is not improved. If the thickness is larger than 50 μm, moisture absorption is likely to occur, and the moisture resistance (in particular, the insulating property after the moisture absorption treatment) is reduced.
なお、平均粒径ｄ１及び後述するｄ２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。 In addition, average particle diameter d1 and d2 mentioned later are measured using the particle size measuring apparatus (For example, Nikkiso Co., Ltd. "micro track SPA-7997 type") by a well-known laser diffraction and scattering method. Here, the laser diffraction / scattering method is a measuring method utilizing the fact that when filler particles are irradiated with laser light, the intensity pattern of scattered light changes with the particle diameter.
本発明に係る熱硬化性樹脂組成物は、さらに、上記酸化マグネシウム粉末以外の無機充填材を含む。無機充填材は、電気絶縁性を有していればよく、例えば、窒化ホウ素、アルミナ、シリカ、酸化チタン、窒化アルミニウム、窒化ケイ素等であり、特に限定するものではない。なお、無機充填材の熱伝導率が２０Ｗ／ｍ・Ｋ以上であることが好ましい。これにより、樹脂成形物の熱伝導率をさらに向上させることができる。また、平均粒径ｄ２を、０．１μｍ≦ｄ２≦５０μｍの範囲とする。平均粒径ｄ２が０．１μｍより小さいと、無機充填材の接触点が増えるため、樹脂との界面が熱抵抗となり、熱伝導率が向上しない。また、５０μｍより大きいと、吸湿しやすくなるため、耐湿特性（特に、吸湿処理後の絶縁性）が低下する。 The thermosetting resin composition according to the present invention further comprises an inorganic filler other than the magnesium oxide powder. The inorganic filler should just have electrical insulation, and is, for example, boron nitride, alumina, silica, titanium oxide, aluminum nitride, silicon nitride, etc., and is not particularly limited. The thermal conductivity of the inorganic filler is preferably 20 W / m · K or more. Thereby, the thermal conductivity of the resin molded product can be further improved. Further, the average particle diameter d2 is in the range of 0.1 μm ≦ d2 ≦ 50 μm. If the average particle diameter d2 is smaller than 0.1 μm, the contact point with the inorganic filler will increase, so the interface with the resin becomes a thermal resistance, and the thermal conductivity will not improve. If the thickness is larger than 50 μm, moisture absorption is likely to occur, and the moisture resistance (in particular, the insulating property after the moisture absorption treatment) is reduced.
なお、酸化マグネシウム粉末と無機充填材の混合比率は、前記酸化マグネシウム粉末の含有量が、酸化マグネシウム粉末と無機充填材を合わせた体積中に、５０体積％となるように混合することが好ましい。これにより、充分な耐湿特性、加工性及び熱伝導性を確保することができる。 The mixing ratio of the magnesium oxide powder and the inorganic filler is preferably 50% by volume in the combined volume of the magnesium oxide powder and the inorganic filler. Thereby, sufficient moisture resistance, processability and thermal conductivity can be secured.
上記酸化マグネシウム粉末が、表面処理を施されたものであると、耐湿特性が向上するため好ましい。表面処理は、シラン系カップリング剤、リン酸エステル類等によるものであり、特に限定するものではない。これらの処理は、簡易な工程を追加することで、実施することができる。 It is preferable that the above-mentioned magnesium oxide powder is subjected to surface treatment because the moisture resistance property is improved. The surface treatment is carried out with a silane coupling agent, phosphoric acid esters and the like, and is not particularly limited. These processes can be implemented by adding simple steps.
そして、本発明の他の熱硬化性樹脂組成物は、酸化マグネシウム粉末の含有量が、熱硬化性樹脂固形分と酸化マグネシウム粉末を合わせた体積中に、２０〜８０体積％となるように混合する。また、本発明に係る熱硬化性樹脂組成物は、酸化マグネシウム粉末と無機充填材の総含有量が、熱硬化性樹脂固形分と酸化マグネシウム粉末と無機充填材を合わせた体積中に、２０〜８０体積％となるように混合する。酸化マグネシウム粉末の含有量（本発明に係る熱硬化性樹脂組成物では、酸化マグネシウム粉末と無機充填材の総含有量）が２０体積％より小さいと、樹脂組成物の充分な熱伝導性が得られない。また、８０体積％より大きいと、樹脂組成物の粘度が上がりすぎるため、シート状に付形したり、シート状繊維基材に含浸することができず、外観の均一なプリプレグを製造することはできない。 And the other thermosetting resin composition of the present invention is mixed such that the content of the magnesium oxide powder is 20 to 80% by volume in the total volume of the thermosetting resin solid content and the magnesium oxide powder. Do. In the thermosetting resin composition according to the present invention, the total content of the magnesium oxide powder and the inorganic filler is 20 to 20 in the volume of the thermosetting resin solid content, the magnesium oxide powder and the inorganic filler. Mix to 80% by volume. When the content of the magnesium oxide powder (in the thermosetting resin composition according to the present invention, the total content of the magnesium oxide powder and the inorganic filler) is less than 20% by volume, sufficient thermal conductivity of the resin composition is obtained I can not. If the volume ratio is more than 80% by volume, the viscosity of the resin composition will be too high, so it can not be shaped into a sheet or impregnated into a sheet-like fiber substrate, and a prepreg having a uniform appearance can be produced. Can not.
上記の酸化マグネシウム粉末、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酸化マグネシウム粉末、無機充填材を添加していくと、酸化マグネシウム粉末、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、酸化マグネシウム粉末、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、８０体積％までの酸化マグネシウム粉末、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-mentioned magnesium oxide powder, inorganic filler and thermosetting resin composition, when magnesium oxide powder and inorganic filler are added to the thermosetting resin composition, oxidation is caused. The thixotropic and cohesive nature of the magnesium powder, mineral filler, increases the viscosity of the varnish. Therefore, by selecting a disperser that generates a strong shear force, the dispersibility of the magnesium oxide powder and the inorganic filler is improved and the viscosity of the varnish is also reduced, so magnesium oxide powder up to 80% by volume, inorganic filler Can be added. Examples of dispersers that generate strong shear force include ball mills, bead mills, triple roll mills, and dispersers to which the principle is applied.
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。例えば、酸化マグネシウム粉末、無機充填材を含む熱硬化性樹脂組成物のワニスをシート状繊維基材に含浸し加熱乾燥して、半硬化状態とする。また、前記ワニスを離型性のフィルム等に塗布し加熱乾燥して、半硬化状態としたものでもよい。 In the practice of the present invention, the production of a prepreg can be carried out by a commonly used production method. For example, a varnish of a thermosetting resin composition containing magnesium oxide powder and an inorganic filler is impregnated into a sheet-like fiber substrate and heated and dried to obtain a semi-cured state. The varnish may be applied to a releasable film or the like and dried by heating to form a semi-cured state.
本発明に使用できるシート状繊維基材は、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。また、ガラス繊維不織布基材に関しても特に限定するものではない。 The sheet-like fiber base material that can be used in the present invention is a woven fabric or non-woven fabric of glass fiber or organic fiber, and is not particularly limited. For example, glass fiber woven fabric can be used. The type of glass is preferably E glass having good strength and electrical characteristics. Further, since it is preferable to impregnate the varnish with a large amount of free space, it is preferable to use a glass fiber woven fabric which has not been subjected to fiber opening treatment. Moreover, it does not specifically limit regarding a glass fiber nonwoven fabric base material.
また、前記ワニスを離型性のフィルム等に塗布して半硬化状態とする場合の実施形態としては、ポリエチレンテレフタレート、ポリエチレン、ポリプロピレン、ポリスチレン等の離型性のフィルムに塗布して半硬化状態とした後に離型性のフィルムをはがして使用する形態や、銅箔やアルミ箔等の金属箔に塗布して半硬化とした後、そのまま金属板や金属箔に貼り付ける形態等があるが、特に限定するものではない。 In the embodiment in which the varnish is applied to a releasable film or the like to make it semi-cured, it is applied to a releasable film such as polyethylene terephthalate, polyethylene, polypropylene, polystyrene or the like to be semi-cured. There is a form that peels and uses a film of releasability after that, and there is a form that it is applied to metal foil such as copper foil and aluminum foil to make it semi-hard and then directly adheres to a metal plate or metal foil. It is not limited.
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８０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の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に伝わり熱放散される。
When the layer of the prepreg is heated and pressed to form the insulating layer, a copper foil or a copper plate can be overlaid on the layer of the prepreg and formed and integrally bonded. If the total content of the inorganic filler is 80% by volume or less as described above, there is no particular problem in adhesion to a copper foil or a copper plate. The said prepreg can also be used as an adhesive layer at the time of piling up and integrating previously prepared printed wiring boards, and setting it as a multilayer printed wiring board.
In the printed wiring board provided with the insulating layer by the prepreg according to the present invention, the heat generated from the mounted parts and the control circuit is transmitted to the copper foil or copper plate disposed on the opposite surface through the insulating layer and dissipated.
本発明に使用する熱硬化性樹脂は、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ができる。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、ターフェニル型エポキシやその誘導体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。 As the thermosetting resin used in the present invention, one produced from an epoxy resin monomer and a curing agent can be used. As the epoxy resin monomer, any of general epoxy resin monomers such as bisphenol A epoxy, bisphenol F epoxy, terphenyl epoxy and derivatives thereof can be used. An epoxy resin monomer having a biphenyl skeleton or a biphenyl derivative skeleton of a 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、上記（式１）においてＲが水素である、（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 structural formula represented by (Formula 2) in which R is hydrogen in the above (formula 1) is selected. Because the biphenyl groups are more easily arranged, the thermal conductivity can be further increased. In addition, two or more biphenyl skeletons or skeletons of biphenyl derivatives 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縮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 a curing agent to be added to the epoxy resin monomer, a curing agent conventionally used to advance the curing reaction of the epoxy resin monomer can be used. For example, phenols or compounds thereof, amine compounds or derivatives thereof, acid anhydrides, imidazoles or derivatives thereof and the like can be mentioned. Further, as a curing accelerator, a curing accelerator which is conventionally used to advance a polycondensation reaction between an epoxy resin monomer and a phenol or compounds thereof, an amine or a compound thereof can be used. For example, triphenylphosphine, imidazole and derivatives thereof, tertiary amine compounds and derivatives thereof and the like can be mentioned.
エポキシ樹脂モノマと硬化剤、酸化マグネシウム粉末、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、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、樹脂成形物の熱伝導性に影響を与えることはない。 The epoxy resin composition containing an epoxy resin monomer and a curing agent, magnesium oxide powder, an inorganic filler, and a curing accelerator can optionally contain a flame retardant, a diluent, a plasticizer, a coupling agent, etc. . Moreover, a solvent can be used as needed. Their use does not affect the thermal conductivity of the resin molding.
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、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 thermal conductivity is improved, the printed wiring board provided with the insulating layer obtained by using the prepreg according to the present invention as the entire layer or a part of the layer and heating and pressing it is expected to be used in a high temperature atmosphere Is suitable for printed wiring boards for automotive equipment and high density mounted printed wiring boards for personal computers and the like.
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。 Hereinafter, the present invention will be described in detail by showing examples according to the present invention. In the following Examples and Comparative Examples, "parts" means "parts by mass". Further, the present invention is not limited to the present embodiment unless it deviates from the gist of the present invention.
実施例１
酸化マグネシウム粉末を、次のようにして準備した。まず、消石灰と海水を反応させ、水酸化マグネシウムとする。この水酸化マグネシウムを焼成することで原料となる酸化マグネシウムの１次粒子を製造する。そして、この原料となる酸化マグネシウムを焼成することにより、酸化マグネシウム粉末を製造する。このとき、原料となる酸化マグネシウム中のシリカ含有量は１質量％、焼成温度は１７００℃、得られた酸化マグネシウム粉末の平均粒径は、２０μｍである。なお、原料となる酸化マグネシウム中のシリカ含有量は、海水中の珪酸の量により調整した。また、平均粒径は、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。
Example 1
Magnesium oxide powder was prepared as follows. First, slaked lime and seawater are reacted to form magnesium hydroxide. By firing the magnesium hydroxide, primary particles of magnesium oxide as a raw material are produced. And magnesium oxide powder is manufactured by baking the magnesium oxide used as this raw material. At this time, the content of silica in magnesium oxide as a raw material is 1% by mass, the firing temperature is 1700 ° C., and the average particle diameter of the obtained magnesium oxide powder is 20 μm. In addition, the silica content in magnesium oxide used as a raw material was adjusted with the quantity of the silicic acid in seawater. Moreover, the average particle diameter was measured using Nikkiso Co., Ltd. "Microtrac SPA-7997 type".
まず、エポキシ樹脂モノマ成分としてビスフェノールＡ型エポキシ樹脂（ジャパンエポキシレジン製「ＥＰ８２８」，エポキシ当量１８５）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。
次に、硬化剤として１，５−ジアミノナフタレン（和光純薬製「１，５−ＤＡＮ」，アミン当量４０）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。
First, 100 parts of bisphenol A type epoxy resin ("EP 828" made by Japan Epoxy Resin, epoxy equivalent 185) is prepared as an epoxy resin monomer component, and this is dissolved in 100 parts of methyl isobutyl ketone (made by Wako Pure Chemical Industries, Ltd.) at 100 ° C. , Returned to room temperature.
Next, 25 parts of 1,5-diaminonaphthalene ("1,5-DAN" manufactured by Wako Pure Chemical Industries, Ltd .; amine equivalent 40) is prepared as a curing agent, and 100 parts of this is added to 100 parts of methyl isobutyl ketone (manufactured by Wako Pure Chemical Industries, Ltd.) Melted at ° C and allowed to return to room temperature.
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、上記の酸化マグネシウム粉末３４０部（熱硬化性樹脂固形分と酸化マグネシウム粉末を合わせた体積中の４６体積％に相当、以下体積％のみ表記する）およびメチルイソブチルケトン（和光純薬製）６７部を加えて混練し、エポキシ樹脂ワニスを調製した。 The above epoxy resin monomer solution and curing agent solution are mixed and stirred to prepare a uniform varnish, and to this mixture (thermosetting resin varnish), 340 parts of the above magnesium oxide powder (thermosetting resin solid content and oxidation) An epoxy resin varnish was prepared by adding and corresponding to 46% by volume of the combined volume of magnesium powder, and the following volume%) and 67 parts of methyl isobutyl ketone (manufactured by Wako Pure Chemical Industries, Ltd.).
上記のエポキシ樹脂ワニスを、厚さ１００μｍのガラス繊維不織布基材に含浸し加熱乾燥して半硬化状態のプリプレグを得た。
作製したプリプレグ４枚とその両側に厚さ１８μｍの銅箔（福田金属製「ＣＦ−Ｔ９Ｃ」）を配置し、温度１７５℃、圧力４ＭＰａ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 above epoxy resin varnish was impregnated into a glass fiber non-woven fabric substrate having a thickness of 100 μm and dried by heating to obtain a semi-cured prepreg.
Four prepregs prepared and a copper foil with a thickness of 18 μm ("CF-T9C" made by Fukuda Metal) are placed on both sides, and heat and pressure are formed for 90 minutes under conditions of temperature 175 ° C and pressure 4MPa to integrate A laminated plate of 0.8 mm was obtained.
実施例１で得た積層板について厚さ方向の熱伝導率、耐湿絶縁性、ドリル加工性を測定した結果を、エポキシ樹脂組成物の配合組成と共に表１にまとめて示す。なお、エポキシ樹脂組成物の配合組成は、各成分の固形分の合計体積を１００体積％としたときの値を記載した。測定方法は、以下に示すとおりである。
厚さ方向の熱伝導率：積層板をエッチングにより銅箔を除去した後、５０mm×１２０mmの板状試料を切り出し、プローブ法に準拠して室温で測定した。
耐湿絶縁性：積層板に、導体幅１５０μｍ、導体間隔１５０μｍのくし型パターンを形成した。この試料を８５℃−８５％の恒温恒湿槽中に入れ、導体間に５０Ｖの電圧をかけた。そして、１０００時間経過後の絶縁抵抗を測定した。そのとき１．０×１０１０Ω以上であれば「○」、１．０×１０１０Ω未満であれば「×」とした。
ドリル加工性：積層板に、φ１．０ｍｍのドリルを使用して、孔明けを３０００穴行った前後のドリル刃の面積を測定した。そのときの摩耗量が２０％未満であれば「○」、２０％以上であれば「×」とした。
The thermal conductivity in the thickness direction, the moisture-proof insulation, and the drillability of the laminate obtained in Example 1 were measured. The results are shown in Table 1 together with the composition of the epoxy resin composition. In addition, the compounding composition of the epoxy resin composition described the value when the total volume of solid content of each component is 100 volume%. The measuring method is as follows.
Thermal conductivity in the thickness direction: After removing the copper foil by etching the laminate, a plate-like sample of 50 mm × 120 mm was cut out and measured at room temperature according to the probe method.
Moisture-proof insulation: A comb-shaped pattern having a conductor width of 150 μm and a conductor spacing of 150 μm was formed on the laminate. The sample was placed in a constant temperature and humidity chamber at 85 ° C. and 85%, and a voltage of 50 V was applied between the conductors. Then, the insulation resistance after 1000 hours was measured. At that time, if it is 1.0 × 10 10 Ω or more, “○”, and if it is less than 1.0 × 10 10 Ω, it is “×”.
Drillability: The laminated plate was measured for the area of the drill blade before and after 3,000 holes were drilled using a drill of φ 1.0 mm. If the amount of wear at that time is less than 20%, "○", and if 20% or more, "×".
実施例１においては、積層板の厚さ方向の熱伝導率が３．５Ｗ／ｍ・Ｋであり、耐湿絶縁性、ドリル加工性共に良好であった。 In Example 1, the thermal conductivity in the thickness direction of the laminate was 3.5 W / m · K, and both the moisture-proof insulation and the drillability were good.
比較例１
実施例１において、酸化マグネシウム粉末として、汎用の酸化マグネシウム（協和化学製「３３２０」，平均粒径２０μｍ）をシランカップリング剤処理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。
比較例１においては、酸化マグネシウム粉末の表面処理が充分でなく、耐湿絶縁性が悪化した。
Comparative Example 1
A prepreg and a laminate in the same manner as in Example 1 except that a general-purpose magnesium oxide ("3320" manufactured by Kyowa Chemical Co., Ltd., average particle diameter 20 μm) treated with a silane coupling agent is used as the magnesium oxide powder in Example 1. I got
In Comparative Example 1, the surface treatment of the magnesium oxide powder was not sufficient, and the moisture insulation resistance deteriorated.
比較例２
実施例１において、酸化マグネシウム粉末の代わりに、アルミナ（デンカ製「ＤＡＷ−１０」，平均粒径１０μｍ）を４６体積％使用する以外は実施例１と同様にしてプリプレグおよび積層板を得た。
比較例２においては、厚さ方向の熱伝導率と吸湿絶縁性は実施例１とほぼ同等であったが、ドリル加工性が悪化した。
Comparative example 2
A prepreg and a laminated board were obtained in the same manner as in Example 1 except that 46 volume% of alumina ("DAW-10" manufactured by Denka, average particle diameter 10 μm) was used instead of magnesium oxide powder in Example 1.
In Comparative Example 2, although the thermal conductivity in the thickness direction and the hygroscopic insulating property were substantially equivalent to those of Example 1, the drill processability was deteriorated.
実施例２
実施例１において、「ＥＰ８２８」の代わりに、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）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。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。
この積層板の厚さ方向の熱伝導率は５．７Ｗ／ｍ・Ｋと大きく向上した。
Example 2
A prepreg and a laminate were obtained in the same manner as in Example 1 except that instead of “EP 828”, an epoxy resin monomer having a biphenyl skeleton (“YL 6121 H” made by Japan Epoxy Resin, epoxy equivalent 175) was used. . Incidentally, “YL 6121 H” is an epoxy resin monomer where R = —CH 3 , n = 0.1 in the molecular structural formula (formula 1) described above, and m = 0.1 in the molecular structural formula (formula 2) An epoxy resin monomer containing an equimolar amount of the epoxy resin monomer.
The thermal conductivity of this laminate in the thickness direction was greatly improved to 5.7 W / m · K.
実施例３、４
実施例２において、原料となる酸化マグネシウム中のシリカ含有量を、それぞれ表１に示すように変えた酸化マグネシウム粉末を使用する以外は、実施例２と同様にしてプリプレグおよび積層板を得た。
これら積層板の厚さ方向の熱伝導率を測定した結果、シリカ含有量が増加すると厚さ方向の熱伝導率は若干低下したものの、良好な値であった。
Examples 3 and 4
A prepreg and a laminate were obtained in the same manner as in Example 2 except that magnesium oxide powders were used in which the content of silica in magnesium oxide as a raw material was changed as shown in Table 1 in Example 2.
As a result of measuring the thermal conductivity in the thickness direction of these laminates, when the silica content increased, the thermal conductivity in the thickness direction slightly decreased, but it was a good value.
比較例３、４
実施例２において、原料となる酸化マグネシウム中のシリカ含有量を、それぞれ表２に示すように変えた酸化マグネシウム粉末を使用する以外は、実施例２と同様にしてプリプレグおよび積層板を得た。
これら積層板の厚さ方向の熱伝導率を測定した結果、シリカ含有量が０．１質量％（比較例３）では、溶融したシリカが酸化マグネシウム粉末の表面を充分に覆うことができず、耐湿絶縁性が低下した。また、シリカの含有量が７．５質量％（比較例４）では、シリカ膜の厚みが厚くなるため、シリカの膜が熱抵抗になり、厚さ方向の熱伝導率が２．８Ｗ／ｍ・Ｋと実施例２より大きく悪化した。
Comparative Examples 3 and 4
A prepreg and a laminated board were obtained in the same manner as in Example 2 except that magnesium oxide powder in which the silica content in magnesium oxide as a raw material was changed as shown in Table 2 in Example 2 was used.
As a result of measuring the thermal conductivity in the thickness direction of these laminates, when the silica content is 0.1% by mass (Comparative Example 3), the fused silica can not sufficiently cover the surface of the magnesium oxide powder, Moisture resistant insulation decreased. Further, when the content of silica is 7.5% by mass (comparative example 4), the thickness of the silica film becomes large, so the film of silica becomes a thermal resistance, and the thermal conductivity in the thickness direction is 2.8 W / m K was much worse than in Example 2.
実施例５
実施例２において、酸化マグネシウム粉末の焼成温度を１８００℃にした酸化マグネシウム粉末を使用する以外は、実施例２と同様にしてプリプレグおよび積層板を得た。
実施例５においては、積層板の厚さ方向の熱伝導率、耐湿絶縁性、ドリル加工性共に良好であった。
Example 5
A prepreg and a laminate were obtained in the same manner as in Example 2 except that a magnesium oxide powder was used in which the sintering temperature of the magnesium oxide powder was set to 1800 ° C. in Example 2.
In Example 5, the thermal conductivity in the thickness direction of the laminate, the moisture-proof insulation, and the drillability were all good.
比較例５、６
実施例２において、酸化マグネシウム粉末の焼成温度を１５００℃（比較例５）、１９００℃（比較例６）にした酸化マグネシウム粉末を使用する以外は、実施例２と同様にしてプリプレグおよび積層板を得た。
焼成温度が１５００℃（比較例５）では、酸化マグネシウム中のシリカが溶融しないため、酸化マグネシウム粉末の表面を覆うことができず、耐湿絶縁性が悪化した。また、焼成温度が１９００℃（比較例６）では、溶融したシリカが揮発してしまい、酸化マグネシウム粉末表面にシリカ膜を形成することができず、耐湿絶縁性が悪化した。
Comparative Examples 5 and 6
A prepreg and a laminate were prepared in the same manner as in Example 2 except that magnesium oxide powder having a sintering temperature of 1500 ° C. (Comparative Example 5) and 1900 ° C. (Comparative Example 6) in Example 2 was used. Obtained.
At a firing temperature of 1500 ° C. (Comparative Example 5), the silica in the magnesium oxide was not melted, so the surface of the magnesium oxide powder could not be covered, and the moisture-proof insulation deteriorated. In addition, at a firing temperature of 1900 ° C. (Comparative Example 6), the fused silica is volatilized, so that a silica film can not be formed on the surface of the magnesium oxide powder, and the moisture-proof insulation property is deteriorated.
実施例６、７
実施例２において、酸化マグネシウム粉末の平均粒径を１０μｍ（実施例６）、５０μｍ（実施例７）にした酸化マグネシウム粉末を使用する以外は実施例２と同様にしてプリプレグおよび積層板を得た。
実施例６、７においては、厚さ方向の熱伝導率、吸湿絶縁性、ドリル加工性共に良好であった。
Examples 6, 7
A prepreg and a laminate were obtained in the same manner as in Example 2 except that a magnesium oxide powder having an average particle diameter of 10 μm (Example 6) and 50 μm (Example 7) in Example 2 was used. .
In Examples 6 and 7, the thermal conductivity in the thickness direction, the hygroscopic insulation property, and the drillability were all good.
参考例１、２
実施例２において、酸化マグネシウム粉末の平均粒径を５μｍ（参考例１）、７０μｍ（参考例２）にした酸化マグネシウム粉末を使用する以外は実施例２と同様にしてプリプレグおよび積層板を得た。
平均粒径が５μｍ（参考例１）では、粒径が小さいため、厚さ方向の熱伝導率が悪化した。また、平均粒径が７０μｍ（参考例２）では、粒径が大きいため、吸湿絶縁性が悪化した。
Reference Examples 1 and 2
A prepreg and a laminate were obtained in the same manner as in Example 2 except that magnesium oxide powder having an average particle diameter of 5 μm ( Reference Example 1 ) and 70 μm ( Reference Example 2 ) in Example 2 was used. .
When the average particle size is 5 μm ( Reference Example 1 ), the thermal conductivity in the thickness direction is deteriorated because the particle size is small. Further, in the case of the average particle diameter of 70 μm ( Reference Example 2 ), since the particle diameter is large, the hygroscopic insulation property is deteriorated.
実施例８、９
実施例２において、酸化マグネシウム粉末の含有量を２０体積％（実施例８）、８０体積％（実施例９）にした酸化マグネシウム粉末を使用する以外は実施例２と同様にしてプリプレグおよび積層板を得た。
酸化マグネシウム粉末の含有量が２０体積％（実施例８）では、厚さ方向の熱伝導率が若干低下したものの、良好な値であった。また、酸化マグネシウム粉末の含有量が８０体積％（実施例９）では、厚さ方向の熱伝導率が大きく向上し、また耐湿絶縁性、ドリル加工性も良好であった。
Examples 8 and 9
A prepreg and a laminate in the same manner as in Example 2 except that a magnesium oxide powder having a content of magnesium oxide powder of 20% by volume (Example 8) and 80% by volume (Example 9) in Example 2 is used. I got
When the content of the magnesium oxide powder was 20% by volume (Example 8), although the thermal conductivity in the thickness direction slightly decreased, it was a good value. In addition, when the content of the magnesium oxide powder was 80% by volume (Example 9), the thermal conductivity in the thickness direction was greatly improved, and the moisture insulation resistance and the drillability were also good.
参考例３、４
実施例２において、酸化マグネシウム粉末の含有量を１５体積％（参考例３）、８５体積％（参考例４）にした酸化マグネシウム粉末を使用する以外は実施例２と同様にしてプリプレグおよび積層板を得た。
酸化マグネシウム粉末の含有量が１５体積％（参考例３）では、厚さ方向の熱伝導率が大きく低下した。また、酸化マグネシウム粉末の含有量が８５体積％（参考例４）では、ワニスの粘性が高くなり、基材に均一に含浸できなかったため、積層板は得られなかった。
Reference Examples 3 and 4
A prepreg and a laminate were prepared in the same manner as in Example 2 except that a magnesium oxide powder was used in which the content of the magnesium oxide powder was changed to 15% by volume ( Reference Example 3 ) and 85% by volume ( Reference Example 4 ). I got
When the content of the magnesium oxide powder is 15% by volume ( Reference Example 3 ), the thermal conductivity in the thickness direction is greatly reduced. Further, when the content of the magnesium oxide powder was 85% by volume ( Reference Example 4 ), the viscosity of the varnish was high, and the base material could not be uniformly impregnated, so that a laminate was not obtained.
実施例１０〜１２
実施例２において、酸化マグネシウム粉末の含有量を２３体積％とし、さらに、無機充填材として、アルミナ（実施例１０）、水酸化アルミニウム（実施例１１）、シリカ（実施例１２）をそれぞれ含み、その含有量を２３体積％としたエポキシ樹脂ワニスを使用する以外は、実施例２と同様にしてプリプレグおよび積層板を得た。なお、使用した無機充填材は、下記のとおりである。
アルミナ （熱伝導率：３０Ｗ／ｍ・Ｋ、平均粒径：２０μｍ）
水酸化アルミニウム（熱伝導率：３Ｗ／ｍ・Ｋ、平均粒径：１０μｍ）
シリカ （熱伝導率：１Ｗ／ｍ・Ｋ、平均粒径：２０μｍ）
これら積層板の厚さ方向の熱伝導率を測定した結果、酸化マグネシウム（熱伝導率：３５Ｗ／ｍ・Ｋ）より熱伝導率の低い水酸化アルミニウム（実施例１１）やシリカ（実施例１２）では、厚さ方向の熱伝導率は若干低下したものの、良好な値であった。また、耐湿絶縁性やドリル加工性も良好であった。
Examples 10 to 12
In Example 2, the content of magnesium oxide powder is 23% by volume, and further contains alumina (Example 10), aluminum hydroxide (Example 11), and silica (Example 12) as inorganic fillers, A prepreg and a laminated board were obtained in the same manner as in Example 2 except that an epoxy resin varnish whose content was 23% by volume was used. In addition, the used inorganic filler is as follows.
Alumina (thermal conductivity: 30 W / m · K, average particle size: 20 μm)
Aluminum hydroxide (thermal conductivity: 3 W / m · K, average particle size: 10 μm)
Silica (thermal conductivity: 1 W / m · K, average particle size: 20 μm)
As a result of measuring the heat conductivity of the thickness direction of these laminated plates, aluminum hydroxide (Example 11) and silica (Example 12) whose heat conductivity is lower than magnesium oxide (heat conductivity: 35 W / m · K) Then, although the thermal conductivity in the thickness direction slightly decreased, it was a good value. Moreover, the moisture-proof insulation and drill processability were also favorable.
参考例５、６
実施例１０において、アルミナの平均粒径を０．０５μｍ（参考例５）、６０μｍ（参考例６）にしたアルミナを使用する以外は、実施例１０と同様にしてプリプレグおよび積層板を得た。
平均粒径が０．０５μｍ（参考例５）では、粒径が小さいため、厚さ方向の熱伝導率が３．０Ｗ/ｍ・Ｋと実施例１０より大きく悪化した。また、平均粒径が６０μｍ（参考例６）では、粒径が大きいため、吸湿絶縁性やドリル加工性が悪化した。
Reference Examples 5 and 6
A prepreg and a laminated board were obtained in the same manner as in Example 10 except that alumina having an average particle diameter of 0.05 μm ( Reference Example 5 ) and 60 μm ( Reference Example 6 ) in Example 10 was used.
When the average particle diameter is 0.05 μm ( Reference Example 5 ), the thermal conductivity in the thickness direction is greatly deteriorated to 3.0 W / m · K, which is larger than that of Example 10, because the particle diameter is small. Further, in the case of the average particle diameter of 60 μm ( Reference Example 6 ), since the particle diameter is large, the hygroscopic insulation property and the drill processability are deteriorated.
表１〜４から明らかなように、本発明に係る酸化マグネシウム粉末の製造法は、原料として、シリカ含有量が１〜６質量％である酸化マグネシウムを使用し、これを１６５０〜１８００℃で焼成することにより、耐湿特性、加工性に優れかつ熱伝導性が良好な絶縁層を製造することができることが理解できる（実施例２〜５と比較例３〜６の対照）。比較例３では、シリカ含有量が少ないため、耐湿絶縁性が低下している。比較例４では、シリカ含有量が多いため、厚さ方向の熱伝導率が低下している。また、比較例５では、焼成温度が低いため、耐湿絶縁性が低下している。比較例６では、焼成温度が高いため、耐湿絶縁性が低下している。 As apparent from Tables 1 to 4, the method for producing a magnesium oxide powder according to the present invention uses magnesium oxide having a silica content of 1 to 6% by mass as a raw material, and calcinates this at 1650 to 1800 ° C. It can be understood that by doing this, it is possible to produce an insulating layer having excellent moisture resistance and processability and good thermal conductivity (a control of Examples 2 to 5 and Comparative Examples 3 to 6). In Comparative Example 3, the moisture-proof insulation property is lowered because the silica content is small. In Comparative Example 4, since the silica content is large, the thermal conductivity in the thickness direction is lowered. Moreover, in Comparative Example 5, since the firing temperature is low, the moisture-proof insulation property is lowered. In Comparative Example 6, since the firing temperature is high, the moisture-proof insulation property is lowered.
また、本発明の他の熱硬化性樹脂組成物は、上記の方法により得た酸化マグネシウム粉末を含み、前記酸化マグネシウム粉末の平均粒径及び含有量を特定することにより、耐湿特性、加工性に優れかつ熱伝導性が良好な熱硬化性樹脂組成物とすることができることが理解できる（実施例２、６〜９と参考例１〜４の対照）。参考例１では、酸化マグネシウム粉末の平均粒径が小さいため、厚さ方向の熱伝導率が低下している。参考例２では、酸化マグネシウム粉末の平均粒径が大きいため、吸湿絶縁性が低下している。また、参考例３では、酸化マグネシウム粉末の含有量が小さいため、厚さ方向の熱伝導率が低下している。参考例４では、酸化マグネシウム粉末の含有量が大きいため、樹脂組成物の粘度が高くなり、シート状繊維基材に均一に含浸することができず、外観の均一なプリプレグを製造することができなかった。 Moreover, the other thermosetting resin composition of this invention contains the magnesium oxide powder obtained by said method, By specifying the average particle diameter and content of the said magnesium oxide powder, it is in a moisture-resistant characteristic and processability. It can be understood that a thermosetting resin composition having excellent thermal conductivity and good thermal conductivity can be obtained (control of Example 2, 6 to 9 and Reference Examples 1 to 4 ). In Reference Example 1 , since the average particle size of the magnesium oxide powder is small, the thermal conductivity in the thickness direction is reduced. In Reference Example 2 , since the average particle diameter of the magnesium oxide powder is large, the hygroscopic insulation property is lowered. Moreover, in the reference example 3 , since the content of the magnesium oxide powder is small, the thermal conductivity in the thickness direction is lowered. In Reference Example 4 , since the content of the magnesium oxide powder is large, the viscosity of the resin composition is high, and the sheet-like fiber substrate can not be uniformly impregnated, and a prepreg having a uniform appearance can be produced. It was not.
さらに、本発明に係る熱硬化性樹脂組成物は、上記の方法により得た酸化マグネシウム粉末と無機充填材を含み、前記酸化マグネシウム粉末と無機充填材の平均粒径及び総含有量を特定することにより、耐湿特性、加工性に優れかつ熱伝導性が良好な熱硬化性樹脂組成物を製造することができることが理解できる（実施例１０〜１２と参考例５〜６の対照）。参考例５では、無機充填材の平均粒径が小さいため、厚さ方向の熱伝導率が低下している。参考例６では、無機充填材の平均粒径が大きいため、吸湿絶縁性が低下している。 Further, the thermosetting resin composition according to the present invention includes a magnesium oxide powder and an inorganic filler obtained by the method described above, to identify the average particle diameter and the total content of the magnesium oxide powder and an inorganic filler It can be understood that a thermosetting resin composition having excellent moisture resistance and processability and good thermal conductivity can be produced (the control of Examples 10 to 12 and Reference Examples 5 to 6 ). In Reference Example 5 , since the average particle diameter of the inorganic filler is small, the thermal conductivity in the thickness direction is lowered. In the reference example 6 , since the average particle diameter of the inorganic filler is large, the hygroscopic insulation property is lowered.
Claims (7)
前記酸化マグネシウム粉末の平均粒径ｄ１が、１０μｍ≦ｄ１≦５０μｍの範囲であり、
前記無機充填材は、平均粒径ｄ２が、０．１μｍ≦ｄ２≦５０μｍの範囲であり、
前記酸化マグネシウム粉末と無機充填材の総含有量が、熱硬化性樹脂固形分と酸化マグネシウム粉末と無機充填材を合わせた体積中に、２０〜８０体積％となるように混合することを特徴とする熱硬化性樹脂組成物。 A thermosetting resin composition comprising magnesium oxide powder obtained by the method according to claim 1, further comprising an inorganic filler other than the magnesium oxide powder,
The average particle diameter d1 of the magnesium oxide powder is in the range of 10 μm ≦ d1 ≦ 50 μm,
The inorganic filler has an average particle diameter d2 in the range of 0.1 μm ≦ d2 ≦ 50 μm,
The total content of the magnesium oxide powder and the inorganic filler is 20% to 80% by volume in the total volume of the thermosetting resin solid content, the magnesium oxide powder and the inorganic filler. Thermosetting resin composition.
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