JP5919314B2 - Insulating resin composition manufacturing method, heat dissipation material manufacturing method, printed circuit board laminate manufacturing method, and printed circuit board manufacturing method - Google Patents
Insulating resin composition manufacturing method, heat dissipation material manufacturing method, printed circuit board laminate manufacturing method, and printed circuit board manufacturing method Download PDFInfo
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- JP5919314B2 JP5919314B2 JP2014010678A JP2014010678A JP5919314B2 JP 5919314 B2 JP5919314 B2 JP 5919314B2 JP 2014010678 A JP2014010678 A JP 2014010678A JP 2014010678 A JP2014010678 A JP 2014010678A JP 5919314 B2 JP5919314 B2 JP 5919314B2
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- 239000011342 resin composition Substances 0.000 title claims description 41
- 239000000463 material Substances 0.000 title claims description 18
- 230000017525 heat dissipation Effects 0.000 title claims description 6
- 238000004519 manufacturing process Methods 0.000 title claims 14
- 239000000843 powder Substances 0.000 claims description 86
- 229910052582 BN Inorganic materials 0.000 claims description 79
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 79
- 125000003277 amino group Chemical group 0.000 claims description 61
- 229920005989 resin Polymers 0.000 claims description 55
- 239000011347 resin Substances 0.000 claims description 55
- 229910052751 metal Inorganic materials 0.000 claims description 29
- 239000002184 metal Substances 0.000 claims description 29
- 239000000758 substrate Substances 0.000 claims description 27
- 239000011888 foil Substances 0.000 claims description 20
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims description 16
- 125000000524 functional group Chemical group 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 238000009832 plasma treatment Methods 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 16
- 239000011256 inorganic filler Substances 0.000 claims description 13
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 13
- 239000012298 atmosphere Substances 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 5
- 238000000059 patterning Methods 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229910000838 Al alloy Inorganic materials 0.000 claims description 3
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 3
- 239000012212 insulator Substances 0.000 claims 4
- 239000010410 layer Substances 0.000 description 24
- 239000004020 conductor Substances 0.000 description 13
- 239000007789 gas Substances 0.000 description 13
- 239000011159 matrix material Substances 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000004381 surface treatment Methods 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 239000001307 helium Substances 0.000 description 4
- 229910052734 helium Inorganic materials 0.000 description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000035939 shock Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000009864 tensile test Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NJNWCIAPVGRBHO-UHFFFAOYSA-N 2-hydroxyethyl-dimethyl-[(oxo-$l^{5}-phosphanylidyne)methyl]azanium Chemical group OCC[N+](C)(C)C#P=O NJNWCIAPVGRBHO-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 101100410148 Pinus taeda PT30 gene Proteins 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- ZSJHIZJESFFXAU-UHFFFAOYSA-N boric acid;phosphoric acid Chemical compound OB(O)O.OP(O)(O)=O ZSJHIZJESFFXAU-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 238000004147 desorption mass spectrometry Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Insulated Metal Substrates For Printed Circuits (AREA)
- Inorganic Insulating Materials (AREA)
Description
本発明は、表面にアミノ基が直接導入された窒化ホウ素粉末を含有する樹脂絶縁組成物、放熱材、プリント基板用積層板及びプリント基板に関する。本発明はまた、窒化ホウ素粉末の表面にアミノ基を直接導入する表面処理方法及び表面にアミノ基が直接導入された窒化ホウ素粉末に関する。 The present invention relates to a resin insulating composition containing a boron nitride powder in which amino groups are directly introduced on the surface, a heat dissipation material, a laminate for a printed circuit board, and a printed circuit board. The present invention also relates to a surface treatment method in which amino groups are directly introduced on the surface of boron nitride powder and a boron nitride powder in which amino groups are directly introduced on the surface.
近年、電気電子機器の高性能化及び小型化は急速に進行している。これに伴い、半導体素子の高密度化、高機能化が一層要求されると共に、それを実装するための回路基板も小型で高密度のものが要求されている。そのために、回路基板には、十分な耐熱性に加え、優れた放熱性が求められている。 In recent years, high performance and miniaturization of electrical and electronic equipment are rapidly progressing. Along with this, there is a further demand for higher density and higher functionality of semiconductor elements, and there is also a demand for small and high density circuit boards for mounting them. Therefore, the circuit board is required to have excellent heat dissipation in addition to sufficient heat resistance.
回路基板としてのプリント基板は、一般に、ベース基板の片面もしくは両面に絶縁層を介して回路パターンを形成した構造を有している。プリント基板の放熱性を高めるために、絶縁層には、母材となる樹脂に、熱伝導率が高く且つ絶縁性のシリカやアルミナ等の無機フィラー分散させた樹脂組成物が一般に広く用いられている。また分散させるフィラーとしては、様々な課題を解決する必要があるものの、高熱伝導率を有する窒化ホウ素や窒化アルミナが望ましいことがよく知られている。 A printed circuit board as a circuit board generally has a structure in which a circuit pattern is formed on one or both sides of a base substrate via an insulating layer. In order to increase the heat dissipation of the printed circuit board, a resin composition in which an inorganic filler such as silica or alumina having a high thermal conductivity and an insulating material is dispersed in a resin as a base material is generally widely used for the insulating layer. Yes. As fillers to be dispersed, it is well known that boron nitride and alumina nitride having high thermal conductivity are desirable, although various problems need to be solved.
六方晶窒化ホウ素については、グラファイトと同様の層状の結晶構造を有し、形状が鱗片状であるため、高充填し難いという問題があった。そこで、窒化ホウ素粉末と樹脂との親和性を向上させるという観点からこの問題を解決すべく、例えば、窒化ホウ素粉末を大気下または酸素雰囲気下にて加熱するという技術（例えば、特許文献１等を参照）や、窒化ホウ素粉末を超臨界水又は亜臨界水を用いて酸化し、酸化によって生じる水酸基に任意に有機修飾剤を吸着／結合させる技術（例えば、特許文献２等を参照）が開発されている。 Hexagonal boron nitride has a layered crystal structure similar to that of graphite and has a scaly shape, so that there is a problem that high filling is difficult. Therefore, in order to solve this problem from the viewpoint of improving the affinity between the boron nitride powder and the resin, for example, a technique of heating the boron nitride powder in the air or in an oxygen atmosphere (for example, Patent Document 1). And a technology (for example, see Patent Document 2), in which boron nitride powder is oxidized using supercritical water or subcritical water, and an organic modifier is arbitrarily adsorbed / bonded to a hydroxyl group generated by the oxidation. ing.
上述した技術以外の窒化ホウ素の表面処理技術として、樹脂との親和性を改善することを目的とするものではないが、例えば、所定のカップリング剤又は有機シリコン化合物を含むコーティング層で窒化ホウ素粉末の表面を処理することにより、窒化ホウ素粉末の充填性を高めたり、窒化ホウ素含有樹脂組成物の粘性を低下させる技術が開発されている（例えば、特許文献３又は４等を参照）。また、樹脂との親和性を改善することを目的とするものでもないが、紛体の表面処理技術として特許文献５には、所定のホスホリルコリン基を紛体表面に共有結合により直接導入する技術が開示されている。 The boron nitride surface treatment technology other than the above-described technology is not intended to improve the affinity with the resin. For example, the boron nitride powder is coated with a coating layer containing a predetermined coupling agent or an organic silicon compound. A technique for improving the filling property of boron nitride powder or reducing the viscosity of a boron nitride-containing resin composition has been developed by treating the surface of the material (for example, see Patent Document 3 or 4). Further, although it is not intended to improve the affinity with the resin, Patent Document 5 discloses a technique for directly introducing a predetermined phosphorylcholine group into the powder surface by covalent bonding as a powder surface treatment technique. ing.
未処理の窒化ホウ素粉末を樹脂組成物に充填材として使用した場合、高充填し難いという問題に加え、樹脂に対する密着性が悪いという問題がある。本発明者等が上述した先行技術に基づき表面処理した窒化ホウ素粉末を用いて樹脂絶縁組成物を調製し、これをプリント基板の絶縁層として使用した結果、耐熱衝撃性、耐ヒートサイクル性、熱抵抗性などのプリント基板としての特性を十分に満たすものは得られなかった。本発明者等の鋭意検討により、その主な原因は、窒化ホウ素粉末と樹脂との密着性が上述したような先行技術では十分に改善されないために、例えば放熱性シートとして成形された場合に所望とされる機械的強度が得られないことにあると推測された。 When untreated boron nitride powder is used as a filler in the resin composition, there is a problem that adhesion to the resin is poor in addition to the problem that high filling is difficult. As a result of preparing a resin insulation composition using boron nitride powder surface-treated based on the prior art described above by the present inventors and using this as an insulating layer of a printed circuit board, thermal shock resistance, heat cycle resistance, heat Those that sufficiently satisfy the characteristics of the printed circuit board such as resistance could not be obtained. Due to the diligent study by the present inventors, the main cause is that the adhesion between the boron nitride powder and the resin is not sufficiently improved by the prior art as described above. It was speculated that the mechanical strength assumed to be not obtained.
そこで、本発明は、マトリクスとしての樹脂と充填材としての窒化ホウ素粉末との密着性が改善された絶縁性樹脂組成物を提供することを目的とする。また、本発明は、機械的強度に優れる放熱材、この放熱材からなる絶縁層を具備するプリント基板用積層板及びプリント基板を提供することを目的とする。また、本発明は、マトリクスとしての樹脂との密着性に優れた窒化ホウ素を得るための窒化ホウ素粉末の表面処理方法及びこの方法により得られる窒化ホウ素粉末を提供することを目的とする。 Then, an object of this invention is to provide the insulating resin composition in which the adhesiveness of resin as a matrix and boron nitride powder as a filler was improved. Another object of the present invention is to provide a heat dissipating material having excellent mechanical strength, a printed board laminate and a printed circuit board having an insulating layer made of the heat dissipating material. Another object of the present invention is to provide a boron nitride powder surface treatment method for obtaining boron nitride having excellent adhesion to a resin as a matrix, and a boron nitride powder obtained by this method.
本発明の第１側面によると、樹脂と無機充填材を含有する絶縁性樹脂組成物であって、上記無機充填材として、アミノ基が表面に直接導入された窒化ホウ素粉末を少なくとも含有し、且つ、上記樹脂として、アミノ基と反応し化学結合を形成可能な官能基を有する樹脂を少なくとも含有する絶縁性樹脂組成物が提供される。 According to the first aspect of the present invention, there is provided an insulating resin composition containing a resin and an inorganic filler, wherein the inorganic filler contains at least boron nitride powder in which an amino group is directly introduced on the surface, and An insulating resin composition containing at least a resin having a functional group capable of reacting with an amino group to form a chemical bond is provided as the resin.
本発明の一形態において、上記絶縁性樹脂組成物における窒化ホウ素粉末表面に対するアミノ基の直接導入は、プラズマ処理により形成され得る。 In one embodiment of the present invention, the direct introduction of amino groups into the boron nitride powder surface in the insulating resin composition can be formed by plasma treatment.
また、本発明の他の形態において、上記絶縁性樹脂組成物の窒化ホウ素粉末におけるアミノ基の導入量は、ＴＰＤ−ＭＳによる測定において、質量数１７（ｍ／ｚ）に帰属する気体の発生量が１質量ｐｐｍ以上に相当する量であり得る。 In another embodiment of the present invention, the amount of amino groups introduced into the boron nitride powder of the insulating resin composition is a gas generation amount attributable to a mass number of 17 (m / z) as measured by TPD-MS. May be an amount corresponding to 1 ppm by mass or more.
また、本発明の他の形態において、上記絶縁性樹脂組成物は、アミノ基と反応し化学結合を形成可能な官能基を有する樹脂としてシアネート樹脂を少なくとも含有し得る。 In another embodiment of the present invention, the insulating resin composition may contain at least a cyanate resin as a resin having a functional group that can react with an amino group to form a chemical bond.
本発明の第２側面によると、上記絶縁性樹脂組成物を含む放熱材が提供される。
本発明の第３側面によると、ベース基板と、該ベース基板の少なくとも片面に設けられた絶縁層と、該絶縁層上に設けられた金属箔とを具備し、絶縁層が上記絶縁性樹脂組成物を用いて形成されたプリント基板用積層板が提供される。
According to the 2nd side surface of this invention, the heat radiating material containing the said insulating resin composition is provided.
According to the third aspect of the present invention, a base substrate, an insulating layer provided on at least one side of the base substrate, and a metal foil provided on the insulating layer are provided, and the insulating layer comprises the insulating resin composition. Provided is a laminate for a printed circuit board formed by using an object.
本発明の一形態において、プリント基板用積層板におけるベース基板は、銅板、銅合金板、アルミ板及びアルミ合金板から選択される金属基板であり得る。 In one form of the present invention, the base substrate in the laminate for a printed circuit board may be a metal substrate selected from a copper plate, a copper alloy plate, an aluminum plate, and an aluminum alloy plate.
本発明の第４側面によると、上記プリント基板用積層板の金属箔をパターニングすることによって得られるプリント基板が提供される。 According to the 4th side surface of this invention, the printed circuit board obtained by patterning the metal foil of the said laminated board for printed circuit boards is provided.
本発明の第５側面によると、窒化ホウ素粉末の表面にアミノ基を導入する窒化ホウ素粉末の表面処理方法であって、アミノ基の導入が、プラズマ処理により窒化ホウ素粉末の表面にアミノ基を直接導入することにより行われる、窒化ホウ素粉末の表面処理方法が提供される。 According to a fifth aspect of the present invention, there is provided a surface treatment method for boron nitride powder in which amino groups are introduced on the surface of the boron nitride powder, wherein the introduction of amino groups directly causes amino groups to be added to the surface of the boron nitride powder by plasma treatment. A surface treatment method for boron nitride powder, which is carried out by introducing, is provided.
本発明の第６側面によると、表面にアミノ基が直接導入された窒化ホウ素粉末が提供される。
本発明の一形態において、上記窒化ホウ素粉末におけるアミノ基の直接導入は、プラズマ処理により形成され得る。
According to the sixth aspect of the present invention, there is provided boron nitride powder having amino groups directly introduced on the surface.
In one form of the invention, the direct introduction of amino groups in the boron nitride powder can be formed by plasma treatment.
また、本発明の他の形態において、上記窒化ホウ素粉末の表面に直接導入されたアミノ基の導入量は、ＴＰＤ−ＭＳによる測定において、質量数１７（ｍ／ｚ）に帰属する気体の発生量が１質量ｐｐｍ以上に相当する量であり得る。 In another embodiment of the present invention, the amount of amino groups introduced directly on the surface of the boron nitride powder is the amount of gas generated attributable to a mass number of 17 (m / z) as measured by TPD-MS. May be an amount corresponding to 1 ppm by mass or more.
本発明により、マトリクスとしての樹脂と充填材としての窒化ホウ素との密着性が改善された絶縁性樹脂組成物の提供が可能となった。また、本発明により、機械的強度に優れる放熱材、この放熱材からなる絶縁層を具備するプリント基板用積層板及びプリント基板の提供が可能となった。このプリント基板用積層板及びプリント基板は、特に耐熱衝撃性、耐ヒートサイクル性、熱抵抗性に優れる。また、本発明により、マトリクスとしての樹脂との密着性に優れた窒化ホウ素粉末の提供が可能となった。 According to the present invention, it is possible to provide an insulating resin composition having improved adhesion between a resin as a matrix and boron nitride as a filler. In addition, according to the present invention, it is possible to provide a heat radiating material having excellent mechanical strength, a printed board laminate and a printed board having an insulating layer made of the heat radiating material. This laminated board for printed circuit boards and printed circuit boards are particularly excellent in thermal shock resistance, heat cycle resistance, and thermal resistance. In addition, according to the present invention, it is possible to provide a boron nitride powder excellent in adhesiveness with a resin as a matrix.
以下、本発明について詳細に説明する。
本発明に係る絶縁性樹脂組成物は、マトリクスである樹脂と無機充填材である窒化ホウ素粉末との密着性が改善された絶縁性樹脂組成物であり、窒化ホウ素粉末として、表面にアミノ基が直接導入された窒化ホウ素粉末（以下、「官能化窒化ホウ素粉末」ともいう）と、樹脂として、アミノ基と反応し化学結合を形成可能な官能基を有する樹脂を含有することを特徴とする。ここで「アミノ基」とは、−ＮＨ２基又は−ＮＨ−基を意味する。
Hereinafter, the present invention will be described in detail.
The insulating resin composition according to the present invention is an insulating resin composition having improved adhesion between a matrix resin and an inorganic filler boron nitride powder, and the boron nitride powder has an amino group on the surface. It is characterized by containing directly introduced boron nitride powder (hereinafter also referred to as “functionalized boron nitride powder”) and a resin having a functional group capable of reacting with an amino group to form a chemical bond. Here, the “amino group” means a —NH 2 group or a —NH— group.
窒化ホウ素粉末の表面に直接導入されたアミノ基とマトリクス樹脂中の官能基とが反応して化学結合を形成することにより、窒化ホウ素粉末とマトリクス樹脂との密着性が向上する結果、この絶縁性樹脂組成物を用いて形成される放熱材の機械的強度が向上する。そして、この放熱材を絶縁層としてプリント基板用積層板又はプリント基板に使用した場合、機械的強度が向上すると共に、耐熱衝撃性、耐ヒートサイクル性、熱抵抗性に優れたプリント基板用積層板又はプリント基板を得ることが可能となる。 As a result of the improved adhesion between the boron nitride powder and the matrix resin, the amino groups directly introduced onto the surface of the boron nitride powder react with the functional groups in the matrix resin to form a chemical bond. The mechanical strength of the heat dissipation material formed using the resin composition is improved. And when this heat-dissipating material is used as an insulating layer for a printed circuit board laminate or printed circuit board, the mechanical strength is improved and the printed circuit board laminate is excellent in thermal shock resistance, heat cycle resistance and thermal resistance. Or it becomes possible to obtain a printed circuit board.
本発明に係る絶縁性樹脂組成物が含有する官能化窒化ホウ素粉末は、上記の通り、窒化ホウ素粉末の表面にアミノ基（−ＮＨ２基）が直接導入されたものである。ここで「直接導入」とは、アミノ基が、窒化ホウ素粉末表面との間に他の原子や基を介さずに窒化ホウ素粉末表面に導入されることを意味し（図１を参照）、例えば、アミノ基を含む有機物によって窒化ホウ素が被覆されている状態や、アミノ基がヒドロキシ基などに吸着／結合する形で間接的に窒化ホウ素粉末の表面に連結している状態と明確に異なる。 As described above, the functionalized boron nitride powder contained in the insulating resin composition according to the present invention is obtained by directly introducing an amino group (—NH 2 group) onto the surface of the boron nitride powder. Here, “direct introduction” means that an amino group is introduced into the surface of the boron nitride powder without any other atom or group between the surface of the boron nitride powder (see FIG. 1). This is clearly different from a state in which boron nitride is coated with an organic substance containing an amino group, or a state in which the amino group is indirectly coupled to the surface of the boron nitride powder in a form of adsorbing / bonding to a hydroxy group or the like.
窒化ホウ素粉末表面に対するアミノ基の直接導入は、プラズマ処理により形成される。ここでプラズマ処理とは、特に限定されるものではなく、大気圧プラズマ処理や、低／高気圧プラズマ処理、液中プラズマ処理などが挙げられるが、例えば、簡便性などの観点から、大気圧下においてグロー放電プラズマを利用したプラズマ処理が好ましい。 The direct introduction of amino groups into the boron nitride powder surface is formed by plasma treatment. Here, the plasma treatment is not particularly limited, and examples thereof include atmospheric pressure plasma treatment, low / high pressure plasma treatment, in-liquid plasma treatment, and the like. Plasma treatment using glow discharge plasma is preferred.
大気圧プラズマ処理は、不活性気体雰囲気中で行うことが好ましく、特に、窒素ガスとヘリウムガス、又は、窒素ガスとアルゴンガスの混合ガス雰囲気中で行うことが好ましい。 The atmospheric pressure plasma treatment is preferably performed in an inert gas atmosphere, and particularly preferably performed in a mixed gas atmosphere of nitrogen gas and helium gas or nitrogen gas and argon gas.
官能化窒化ホウ素粉末において、窒化ホウ素粉末に対するアミノ基の導入量は、本発明の一形態において、ＴＰＤ−ＭＳによる測定において、質量数１７（ｍ／ｚ）に帰属する気体の発生量が１質量ｐｐｍ以上に相当する量であることが好ましい。より好ましくは、１〜５０質量ｐｐｍであり、更に好ましくは、２〜４０質量ｐｐｍである。 In the functionalized boron nitride powder, the amount of amino groups introduced into the boron nitride powder is 1 mass of the amount of gas attributed to a mass number of 17 (m / z) as measured by TPD-MS in one embodiment of the present invention. The amount is preferably equivalent to ppm or more. More preferably, it is 1-50 mass ppm, More preferably, it is 2-40 mass ppm.
本発明において、アミノ基が導入される前の窒化ホウ素粉末は、特に限定されるものではないが、例えば、鱗片状窒化ホウ素粉末、鱗片状窒化ホウ素粉末の凝集体、または窒化ホウ素の焼結体および結晶体を粉砕した粉末を用いることができる。 In the present invention, the boron nitride powder before the amino group is introduced is not particularly limited. For example, the flaky boron nitride powder, the aggregate of the flaky boron nitride powder, or the sintered body of boron nitride Further, a powder obtained by pulverizing a crystal body can be used.
本発明の一形態において、本発明に係る絶縁性樹脂組成物中に含有される官能化窒化ホウ素粉末の含有率は、絶縁性樹脂組成物を基準として４０〜９０体積％であることが好ましく、５０〜８０体積％であることがより好ましい。 In one embodiment of the present invention, the content of the functionalized boron nitride powder contained in the insulating resin composition according to the present invention is preferably 40 to 90% by volume based on the insulating resin composition, More preferably, it is 50-80 volume%.
本発明に係る絶縁性樹脂組成物は、上述した官能化窒化ホウ素以外の無機充填材を本発明の効果を損なわない範囲において更に含有していてもよい。そのような無機充填材としては、例えば、窒化アルミ、アルミナ、酸化亜鉛、シリカ等が挙げられる。 The insulating resin composition according to the present invention may further contain an inorganic filler other than the above-described functionalized boron nitride as long as the effects of the present invention are not impaired. Examples of such inorganic fillers include aluminum nitride, alumina, zinc oxide, and silica.
次にマトリクスとしての樹脂について説明する。
アミノ基と反応し化学結合を形成可能な官能基を有する樹脂としては、一般的に室温又は加熱下でアミノ基と化学結合を形成し得る官能基を有する樹脂であれば特に限定されるものではない。
Next, the resin as a matrix will be described.
The resin having a functional group capable of reacting with an amino group to form a chemical bond is not particularly limited as long as it is a resin having a functional group capable of forming a chemical bond with an amino group at room temperature or under heating. Absent.
アミノ基と反応し化学結合を形成可能な官能基としては、例えば、カルボキシル基、エポキシ基、イソシアネート基が挙げられる。そして、アミノ基と反応し化学結合を形成可能な官能基を有する樹脂としては、例えば、エポキシ樹脂、シアネート樹脂、ウレタン樹脂等が挙げられ、また、側鎖にアミノ基と反応し化学結合を形成可能な官能基を有する各種の変性樹脂であってもよい。本発明の一形態において、このような樹脂として、シアネート樹脂が好ましい。 Examples of the functional group capable of reacting with an amino group to form a chemical bond include a carboxyl group, an epoxy group, and an isocyanate group. Examples of the resin having a functional group capable of reacting with an amino group to form a chemical bond include an epoxy resin, a cyanate resin, a urethane resin, etc., and reacting with an amino group on a side chain to form a chemical bond. Various modified resins having possible functional groups may be used. In one embodiment of the present invention, a cyanate resin is preferable as such a resin.
シアネート樹脂を例に挙げて、官能化窒化ホウ素粉末とマトリクス樹脂との密着性向上のメカニズムを、図２を参照しながら説明する。すなわち、シアネート基の環化三量化反応と、シアネート基とアミノ基との反応では、シアネート基に比べてアミノ基の方が極性が高いため、樹脂中のシアネート基と窒化ホウ素粉末に直接導入されたアミノ基との反応が優先して進行する（図２の(ａ)）。シアネート基とアミノ基との反応が進行した後でシアネート基の環化三量化反応による樹脂同士の重合が進行する結果（図２の（ｂ））、樹脂と窒化ホウ素粉末との密着性が向上するものと推測している。 Taking a cyanate resin as an example, the mechanism for improving the adhesion between the functionalized boron nitride powder and the matrix resin will be described with reference to FIG. That is, in the cyclization trimerization reaction of a cyanate group and the reaction of a cyanate group and an amino group, the amino group is more polar than the cyanate group, so that it is directly introduced into the cyanate group and boron nitride powder in the resin. The reaction with the amino group proceeds preferentially ((a) of FIG. 2). As a result of the progress of the polymerization of the resins by the cyclization trimerization reaction of the cyanate group after the reaction between the cyanate group and the amino group ((b) in FIG. 2), the adhesion between the resin and the boron nitride powder is improved. I guess it will.
本発明に係る絶縁性樹脂組成物は、アミノ基と反応し化学結合を形成可能な官能基を有する樹脂を２種以上含有していてもよく、また、このような官能基を有さない１種以上の樹脂を本発明の効果を損なわない範囲において更に含有していてもよい。 The insulating resin composition according to the present invention may contain two or more kinds of resins having a functional group capable of reacting with an amino group to form a chemical bond, and does not have such a functional group. You may further contain the resin of a seed | species or more in the range which does not impair the effect of this invention.
本発明に係る絶縁性樹脂組成物は、上述した樹脂及び無機充填材以外に溶剤を含有していてもよい。溶剤の配合量としては、例えば、樹脂１００質量部に対して好ましくは１００〜９００質量部であり、より好ましくは１５０〜６００質量部である。溶剤としては、例えば、アセトン、メチルエチルケトン、メチルセロソルブ、トルエン、ジメチルアセトアミド、Ｎメチルピロリドン、エチレングリコールモノメチルエーテルなどが挙げられる。 The insulating resin composition according to the present invention may contain a solvent in addition to the above-described resin and inorganic filler. As a compounding quantity of a solvent, Preferably it is 100-900 mass parts with respect to 100 mass parts of resin, More preferably, it is 150-600 mass parts. Examples of the solvent include acetone, methyl ethyl ketone, methyl cellosolve, toluene, dimethylacetamide, N methylpyrrolidone, ethylene glycol monomethyl ether, and the like.
また、本発明に係る絶縁性樹脂組成物は、上述した樹脂及び無機充填材以外に種々の添加剤を更に含有していてもよい。そのような添加材としては、例えば、シランカップリング剤及びチタンカップリング剤などのカップリング剤、イオン吸着剤などが挙げられる。 Moreover, the insulating resin composition according to the present invention may further contain various additives in addition to the above-described resin and inorganic filler. Examples of such additives include coupling agents such as silane coupling agents and titanium coupling agents, and ion adsorbents.
本発明に係る絶縁性樹脂組成物は、例えば、以下の方法により調製することができる。 The insulating resin composition according to the present invention can be prepared, for example, by the following method.
シアネート樹脂と硬化促進剤（例えば、リン酸系ボレート錯体）をエチレングリコールモノメチルエーテルに溶解し、官能化窒化ホウ素粉末を添加して撹拌することで、本発明に係る絶縁樹脂組成物を調製することができる。撹拌方法として特に限定するものではないが、撹拌脱泡機を用いることで気泡の無い分散液（組成物）が得られる点で望ましい。 Preparing an insulating resin composition according to the present invention by dissolving a cyanate resin and a curing accelerator (for example, phosphoric acid borate complex) in ethylene glycol monomethyl ether, adding a functionalized boron nitride powder, and stirring. Can do. Although it does not specifically limit as a stirring method, It is desirable at the point from which the dispersion liquid (composition) without a bubble is obtained by using a stirring deaerator.
本発明に係る絶縁性樹脂組成物は、放熱材として各種用途に広く使用することができ、本発明に係る絶縁性樹脂組成物を用いて形成された放熱材は、機械的強度に優れるという特性を有する。このような放熱材としては、例えば、放熱シート、放熱接着剤・粘着剤、放熱封止材等が挙げられる。 The insulating resin composition according to the present invention can be widely used for various applications as a heat radiating material, and the heat radiating material formed using the insulating resin composition according to the present invention is excellent in mechanical strength. Have Examples of such a heat radiating material include a heat radiating sheet, a heat radiating adhesive / adhesive, and a heat radiating sealing material.
本発明の一態様において、本発明に係る絶縁性樹脂組成物を用いて形成された接着剤は、プリント配線板を構成する絶縁層として好適に用いられる。
図３及び図４は、本発明に係る絶縁性樹脂組成物を用いて形成された接着剤を絶縁層として具備するプリント基板用積層板の一態様を示す。ここに示されるプリント基板用積層板１は、ベース基板２の片面に絶縁層３が形成され、絶縁層３の上に金属箔４が形成された３層構造をしている。本発明の他の形態において、ベース基板２の両面に絶縁層３が形成され、更に各絶縁層３の上に金属箔４が形成された５層構造をしていてもよい。なお、図３及び図４において、Ｘ及びＹ方向はベース基板２の主面に平行であり且つ互いに直交する方向であり、Ｚ方向はＸ及びＹ方向に対して垂直な厚さ方向である。図３には、一例として矩形上のプリント基板用積層板１を示しているが、プリント基板用積層板１は他の形状を有していてもよい。
In one embodiment of the present invention, an adhesive formed using the insulating resin composition according to the present invention is suitably used as an insulating layer constituting a printed wiring board.
3 and 4 show an embodiment of a laminate for a printed circuit board having an adhesive formed using the insulating resin composition according to the present invention as an insulating layer. The printed board laminate 1 shown here has a three-layer structure in which an insulating layer 3 is formed on one side of a base substrate 2 and a metal foil 4 is formed on the insulating layer 3. In another embodiment of the present invention, the base substrate 2 may have a five-layer structure in which the insulating layers 3 are formed on both surfaces and the metal foil 4 is further formed on each insulating layer 3. 3 and 4, the X and Y directions are parallel to the main surface of the base substrate 2 and perpendicular to each other, and the Z direction is a thickness direction perpendicular to the X and Y directions. FIG. 3 shows a rectangular printed circuit board laminate 1 as an example, but the printed circuit board laminate 1 may have other shapes.
本発明に係る絶縁樹脂組成物を用いて形成された絶縁層３は、機械的強度が高いため、絶縁層３を具備するプリント基板用積層板１は、プリント基板用として重要な特性である機械的強度が向上すると共に、耐熱衝撃性、耐ヒートサイクル性及び熱抵抗性に優れる。 Since the insulating layer 3 formed using the insulating resin composition according to the present invention has high mechanical strength, the laminated board 1 for a printed circuit board provided with the insulating layer 3 is an important characteristic for a printed circuit board. The mechanical strength is improved and the thermal shock resistance, heat cycle resistance and thermal resistance are excellent.
ベース基板２は、例えば、単体金属、合金又は無機充填材を含む複合金属からなる。本発明の一形態において、ベース基板２は、銅板、銅合金板、アルミ板、アルミ合金板から選択される。 The base substrate 2 is made of, for example, a single metal, an alloy, or a composite metal containing an inorganic filler. In one embodiment of the present invention, the base substrate 2 is selected from a copper plate, a copper alloy plate, an aluminum plate, and an aluminum alloy plate.
金属箔４は、例えば、単体金属又は合金からなる。金属箔４の材料としては、例えば、銅又はアルミニウムを使用することができる。金属箔４の厚さは、例えば、１０〜５００μｍの範囲である。 The metal foil 4 is made of, for example, a single metal or an alloy. As a material of the metal foil 4, for example, copper or aluminum can be used. The thickness of the metal foil 4 is, for example, in the range of 10 to 500 μm.
このプリント基板用積層板１は、例えば、以下の方法により製造する。
まず、上述した本発明に係る絶縁樹脂組成物を、ベース基板２及び金属箔４の少なくとも一方に塗布する。分散液の塗布には、例えば、ロールコート法、バーコート法又はスクリーン印刷法などを使用することができる。連続式で行ってもよく、単板式で行ってもよい。
This laminated board 1 for printed circuit boards is manufactured by the following method, for example.
First, the insulating resin composition according to the present invention described above is applied to at least one of the base substrate 2 and the metal foil 4. For the application of the dispersion, for example, a roll coating method, a bar coating method, a screen printing method, or the like can be used. You may carry out by a continuous type and may carry out by a single plate type.
次いで、ベース基板２と金属箔４とが塗膜を挟んで向き合うように重ね合わせる。組成物が溶剤を含む場合は、重ね合わせる前に塗膜を乾燥させてもよい。塗膜を挟んで金属基板２と金属箔４とを重ね合わせた後、それらを熱プレスする。以上のようにして、プリント基板用積層板１を得る。 Next, the base substrate 2 and the metal foil 4 are superposed so as to face each other with the coating film interposed therebetween. When the composition contains a solvent, the coating film may be dried before superposition. After the metal substrate 2 and the metal foil 4 are overlapped with the coating film interposed therebetween, they are hot-pressed. As described above, the printed board laminate 1 is obtained.
この方法では、本発明の組成物である分散液をベース基板２及び金属箔４の少なくとも一方に塗布することにより塗膜を形成するが、他の態様において、分散液をＰＥＴフィルム等の基材に塗布し乾燥することにより予め塗膜を形成し、これをベース基板２及び金属箔４の一方に熱転写してもよい。 In this method, the dispersion liquid which is the composition of the present invention is applied to at least one of the base substrate 2 and the metal foil 4 to form a coating film. In another embodiment, the dispersion liquid is a base material such as a PET film. A coating film may be formed in advance by applying to the substrate and drying, and this may be thermally transferred to one of the base substrate 2 and the metal foil 4.
次に、上述したプリント基板用積層板１から得られるプリント基板１’について説明する。 Next, the printed circuit board 1 ′ obtained from the printed circuit board laminate 1 will be described.
図４に示すプリント基板１’は、図３及び図４に示すプリント基板用積層板１から得られるものであり、ベース基板２と、絶縁層３と、回路パターン４´とを含んでいる。回路パターン４´は、図３及び図４を参照しながら説明したプリント基板用積層板１の金属箔４をパターニングすることにより得られる。このパターニングは、例えば、金属箔４の上にマスクパターンを形成し、金属箔４の露出部をエッチングによって除去することにより得られる。プリント基板１’は、例えば、先のプリント基板用積層板１の金属箔４に対して上記のパターニングを行い、必要に応じて、切断及び穴あけ加工などの加工を行うことにより得ることができる。 A printed board 1 ′ shown in FIG. 4 is obtained from the printed board laminate 1 shown in FIGS. 3 and 4, and includes a base board 2, an insulating layer 3, and a circuit pattern 4 ′. The circuit pattern 4 ′ is obtained by patterning the metal foil 4 of the printed board laminate 1 described with reference to FIGS. 3 and 4. This patterning can be obtained, for example, by forming a mask pattern on the metal foil 4 and removing the exposed portion of the metal foil 4 by etching. The printed circuit board 1 ′ can be obtained, for example, by performing the above-described patterning on the metal foil 4 of the previous printed circuit board laminate 1 and performing processing such as cutting and drilling as necessary.
以下に、本発明の例を記載する。本発明はこれらに限定されるものでない。
＜実施例１−３＞
窒化ホウ素粉末へのアミノ基の導入
窒化ホウ素粉末（以下、「ＢＮ紛体」という）として、ＨＰ−４０（水島合金鉄株式会社製、平均粒径１８μｍ）を使用した。粉体用大気プラズマ処理装置（九州計測器株式会社製）を用い、ＢＮ粉体を以下の条件で処理した。
Examples of the present invention will be described below. The present invention is not limited to these.
<Example 1-3>
Introduction of amino group into boron nitride powder HP-40 (manufactured by Mizushima Alloy Iron Co., Ltd., average particle size 18 μm) was used as boron nitride powder (hereinafter referred to as “BN powder”). The BN powder was processed under the following conditions using an atmospheric plasma processing apparatus for powder (manufactured by Kyushu Keiki Co., Ltd.).
処理条件１：ＢＮ紛体４０ｇと、１片約５ｍｍの四角に切ったナイロン製絶縁紙２ｇとを、上記装置の反応セルに投入し、アルゴンガス２．０Ｌ／分と、窒素ガス０．２Ｌ／分を流しながら、プラズマ出力３００Ｗで１０分間処理を行い、ＴＰＤ−ＭＳによる測定において、アミノ基に由来するアンモニアガスの発生量が１３質量ｐｐｍに相当するアミノ基が導入された窒化ホウ素粉末ＢＮ１を得た。 Treatment condition 1: 40 g of BN powder and 2 g of nylon insulating paper cut into a square of about 5 mm each are put into a reaction cell of the above apparatus, and argon gas is 2.0 L / min and nitrogen gas is 0.2 L / min. The boron nitride powder BN1 introduced with an amino group corresponding to 13 mass ppm of ammonia gas derived from an amino group in the measurement by TPD-MS is performed for 10 minutes at a plasma output of 300 W. Obtained.
処理条件２：プラズマ処理におけるガス雰囲気として、ヘリウムガス４．０Ｌ／分と、窒素ガス０．２Ｌ／分を使用した以外は、処理条件１と同様に処理し、ＴＰＤ−ＭＳによる測定において、アミノ基に由来するアンモニアガスの発生量が２３質量ｐｐｍに相当するアミノ基が導入された窒化ホウ素粉末ＢＮ２を得た。
Treatment condition 2: Treated in the same manner as in treatment condition 1 except that helium gas 4.0 L / min and nitrogen gas 0.2 L / min were used as the gas atmosphere in the plasma treatment. Boron nitride powder BN2 into which an amino group corresponding to the generation amount of ammonia gas derived from the group corresponding to 23 mass ppm was introduced was obtained.
処理条件３：プラズマ処理におけるガス雰囲気として、ヘリウムガス２．０Ｌ／分と、窒素ガス０．２Ｌ／分を使用した以外は、処理条件１と同様に処理し、ＴＰＤ−ＭＳによる測定において、アミノ基に由来するアンモニアガスの発生量が４０質量ｐｐｍに相当するアミノ基が導入された窒化ホウ素粉末ＢＮ３を得た。 Treatment condition 3: Treated in the same manner as in treatment condition 1 except that helium gas 2.0 L / min and nitrogen gas 0.2 L / min were used as the gas atmosphere in the plasma treatment. Boron nitride powder BN3 into which an amino group corresponding to the generation amount of ammonia gas derived from the group corresponding to 40 ppm by mass was introduced was obtained.
ここで、ＢＮ粉末表面にアミノ基が直接導入されたことの確認は、ＦＴ−ＩＲ分析により行った。すなわち、プラズマ処理したＢＮ粉末（ＢＮ１、ＢＮ２、ＢＮ３）のＦＴ−ＩＲ分析結果においては、未処理のＢＮ粉末の分析結果からは確認できない３２００〜３５００ｃｍ−１にＮ−Ｈに起因する吸収ピークが確認できた。以上の結果より、ＢＮ粉末表面にアミノ基が直接導入されたことわかる。 Here, it was confirmed by FT-IR analysis that amino groups were directly introduced on the surface of the BN powder. That is, in the FT-IR analysis results of the plasma-treated BN powder (BN1, BN2, BN3), there is an absorption peak due to N—H at 3200-3500 cm −1 that cannot be confirmed from the analysis result of the untreated BN powder. It could be confirmed. From the above results, it can be seen that amino groups were directly introduced on the surface of the BN powder.
［アミノ基導入量の測定］
アミノ基の導入量については、ＴＰＤ−ＭＳ（Tempereture Programmed Desorption - Mass Spectrometry）により、ヘリウムガス雰囲気で室温〜１０００℃を昇温速度２０℃／分で測定し、質量数１７（ｍ／ｚ）に帰属する気体（アンモニアガス）の発生量で比較した。対照用に、プラズマ処理をしていない未処理ＢＮ粉末（ＢＮ４：ＨＰ−４０、水島合金鉄株式会社製、平均粒径１８μｍ）についても同様の測定を行った。
[Measurement of amino group introduction amount]
The amount of amino group introduced was measured at room temperature to 1000 ° C. at a heating rate of 20 ° C./min in a helium gas atmosphere by TPD-MS (Temperture Programmed Desorption-Mass Spectrometry), and the mass number was 17 (m / z). Comparison was made by the amount of gas (ammonia gas) generated. For the control, the same measurement was performed for untreated BN powder (BN4: HP-40, manufactured by Mizushima Alloy Iron Co., Ltd., average particle size 18 μm) that was not plasma-treated.
プラズマ処理したＢＮ粉末（ＢＮ１、ＢＮ２、ＢＮ３）から、未処理のＢＮ粉末（ＢＮ４）からは確認できなかったアミノ基に由来するアンモニアガスの発生量が定量できた。測定結果を表１に示す。
＜実施例４−６、比較例２＞
［絶縁性樹脂組成物の調製］
ビスフェノール型シアネート樹脂（ロンザ製、「ＢＡ２００」）と、ノボラック型シアネート樹脂（ロンザ製、「ＰＴ３０」）を、質量比３：１の割合で合計１００質量部と、硬化促進剤としてテトラフェニルホスホニウムテトラ・Ｐ・トリルボレート（北興化学製、「ＴＰＰ−ＭＫ」）１質量部を、エチレングリコールモノメチルエーテル５９５質量部に溶解した。このシアネート樹脂溶液に、上記の各ＢＮ粉末（ＢＮ１、ＢＮ２、ＢＮ３、又はＢＮ４）を、シアネート樹脂とＢＮを合わせた体積の６５体積％になるよう添加し、撹拌脱泡機を用いて撹拌することで気泡のない分散液（絶縁樹脂組成物）１〜４を得た。
<Example 4-6, Comparative Example 2>
[Preparation of insulating resin composition]
Bisphenol-type cyanate resin (Lonza, “BA200”) and novolac-type cyanate resin (Lonza, “PT30”) in a mass ratio of 3: 1 in total, and tetraphenylphosphonium tetra as a curing accelerator -1 part by mass of P.tolylborate (manufactured by Kitako Chemical Co., Ltd., “TPP-MK”) was dissolved in 595 parts by mass of ethylene glycol monomethyl ether. Each BN powder (BN1, BN2, BN3, or BN4) is added to the cyanate resin solution so that the volume of the cyanate resin and BN is 65% by volume, and the mixture is stirred using a stirring deaerator. Thus, dispersions (insulating resin compositions) 1 to 4 having no bubbles were obtained.
得られた分散液１〜４を用いて、以下に示す方法でサンプルを作製し、引っ張り強度及び導体の引き剥がし強さを測定した。 Using the obtained dispersions 1 to 4, a sample was prepared by the following method, and the tensile strength and the conductor peeling strength were measured.
［引っ張り強度］
各分散液を導体（厚さ７０μｍ銅箔）に塗布し１００℃で溶剤を乾燥させた後、３００℃で加熱硬化させて厚さ１２０μｍのシート状放熱材を作製した。これをダンベル形状に機械加工し、エッチングによって導体を除去することで引張試験片を得た。得られた引張試験片を、インストロン引張試験機を用い、ＪＩＳ Ｋ７１２７の規格に則って下記条件で試験した。
[Tensile strength]
Each dispersion was applied to a conductor (copper foil having a thickness of 70 μm), the solvent was dried at 100 ° C., and then heated and cured at 300 ° C. to prepare a sheet-like heat radiation material having a thickness of 120 μm. This was machined into a dumbbell shape, and the conductor was removed by etching to obtain a tensile test piece. The obtained tensile test piece was tested under the following conditions in accordance with the standard of JIS K7127 using an Instron tensile tester.
・引張速度：２０±１ｍｍ／ｍｉｎ
・引張試験片サイズ:ダンベル４号形（全長１００ｍｍ、平行部長：２０ｍｍ、平行部幅:５ｍｍ）
測定された応力の最大値を引張破断応力としてＭＰａに換算し、これを引っ張り強度とした。引張強度の換算にあたっては、引張試験片平行部幅を測定して算出した。測定結果を表２に示す。
・ Tensile speed: 20 ± 1mm / min
・ Tensile specimen size: Dumbbell No. 4 type (overall length 100 mm, parallel part length: 20 mm, parallel part width: 5 mm)
The maximum value of the measured stress was converted to MPa as the tensile breaking stress, and this was taken as the tensile strength. In converting the tensile strength, the tensile test piece parallel part width was measured and calculated. The measurement results are shown in Table 2.
［導体の引き剥がし強さ］
各分散液を導体（厚さ７０μｍ銅箔）に塗布し１００℃で溶剤を乾燥させた後、塗膜を挟むようにベース板（厚さ２ｍｍＡｌ板）を積層し３００℃で加圧加熱して、導体とベース板に挟まれた厚さ１２０μｍの絶縁層を有する金属ベース基板を作製した。得られた金属ベース基板の導体を幅１０ｍｍになるように切断して導体の引き剥がし強さの試験片を得た。得られた試験片を、インストロン引張試験機を用い、ＪＩＳ Ｃ５０１２の規格に則って下記条件で試験した。
[Peeling strength of conductor]
After applying each dispersion to a conductor (70 μm thick copper foil) and drying the solvent at 100 ° C., a base plate (2 mm thick Al plate) is laminated so as to sandwich the coating film, and heated at 300 ° C. under pressure. Then, a metal base substrate having an insulating layer having a thickness of 120 μm sandwiched between the conductor and the base plate was produced. The conductor of the obtained metal base substrate was cut so as to have a width of 10 mm to obtain a test piece having a conductor peeling strength. The obtained test piece was tested under the following conditions according to the standard of JIS C5012 using an Instron tensile tester.
・引き剥がし速度：１００ｍｍ／ｍｉｎ
・引き剥がし角度：９０度
測定によって得られた引き剥がし荷重を導体幅で割って、単位Ｎ／ｃｍの導体の引き剥がし強さを得た。測定結果を表２に示す。
Peeling angle: 90 degrees The peeling load obtained by measurement was divided by the conductor width to obtain the peeling strength of the conductor of unit N / cm. The measurement results are shown in Table 2.
上記結果から、プラズマ処理されたＢＮ粉末を使用した実施例４−６は、未処理のＢＮ粉末を使用した比較例１に比べ、引っ張り強度及び導体の引き剥がし強さが高く、機械的強度に優れることがわかる。 From the above results, Example 4-6 using the plasma-treated BN powder has higher tensile strength and higher conductor peeling strength than that of Comparative Example 1 using untreated BN powder. It turns out that it is excellent.
また、図６（ａ）及び図６（ｂ）は、導体の引き剥がし強さ試験後のサンプルにおける、銅箔が剥離した部分のベース基板上の絶縁層表面を示すＳＥＭ写真であり、図６（ａ）は実施例４、図６（ｂ）は比較例２のサンプルのＳＥＭ写真である。 6 (a) and 6 (b) are SEM photographs showing the surface of the insulating layer on the base substrate where the copper foil has peeled off in the sample after the conductor peel strength test. (A) is the SEM photograph of the sample of Example 4, and FIG.
図６（ｂ）では、ＢＮ表面に樹脂が付着しておらず、界面剥離が起こっているのに対し、図６（ａ）では、樹脂がＢＮ表面に付着していることから、界面剥離ではなく樹脂の脆性破壊が起こっていることがわかる。このことからも、アミノ基が表面に直接導入された窒化ホウ素粉末を使用することにより、窒化ホウ素粉末とマトリクス樹脂との密着性が向上することがわかる。 In FIG. 6B, the resin is not attached to the BN surface and the interface peeling occurs, whereas in FIG. 6A, the resin is attached to the BN surface. It can be seen that brittle fracture of the resin is occurring. This also shows that the adhesion between the boron nitride powder and the matrix resin is improved by using the boron nitride powder in which the amino group is directly introduced on the surface.
１・・・プリント基板用積層板、１’・・・プリント基板、２・・・ベース基板、３・・・絶縁層、４・・・金属箔、４’・・・回路パターン DESCRIPTION OF SYMBOLS 1 ... Laminated board for printed circuit boards, 1 '... Printed circuit board, 2 ... Base substrate, 3 ... Insulating layer, 4 ... Metal foil, 4' ... Circuit pattern
Claims (8)
前記絶縁層が、アミノ基と反応し化学結合を形成可能な官能基を有する樹脂と、無機充填材として、アミノ基が表面に直接導入された絶縁体である窒化ホウ素粉末とを少なくとも含有する絶縁性樹脂組成物を含む絶縁層であり、
前記窒化ホウ素粉末を、不活性気体雰囲気中でのプラズマ処理により、アミノ基を表面に直接導入して形成することを含む、プリント基板用積層板の製造方法。 A method for producing a laminate for a printed circuit board comprising a base substrate, an insulating layer provided on at least one side of the base substrate, and a metal foil provided on the insulating layer ,
Insulation in which the insulating layer contains at least a resin having a functional group capable of reacting with an amino group to form a chemical bond, and boron nitride powder as an inorganic filler, which is an insulator in which an amino group is directly introduced on the surface An insulating layer containing a conductive resin composition,
A method for producing a laminate for a printed circuit board , comprising forming the boron nitride powder by directly introducing an amino group onto a surface by plasma treatment in an inert gas atmosphere .
前記絶縁層が、アミノ基と反応し化学結合を形成可能な官能基を有する樹脂と、無機充填材として、アミノ基が表面に直接導入された絶縁体である窒化ホウ素粉末とを少なくとも含有する絶縁性樹脂組成物を含む絶縁層であり、
前記窒化ホウ素粉末を、不活性気体雰囲気中でのプラズマ処理により、アミノ基を表面に直接導入して形成すること、及び、
前記金属箔をパターニングすること、
を含むプリント基板の製造方法。 A printed circuit board manufacturing method using a printed circuit board laminate comprising a base substrate, an insulating layer provided on at least one side of the base substrate, and a metal foil provided on the insulating layer,
Insulation in which the insulating layer contains at least a resin having a functional group capable of reacting with an amino group to form a chemical bond, and boron nitride powder as an inorganic filler, which is an insulator in which an amino group is directly introduced on the surface An insulating layer containing a conductive resin composition,
Forming the boron nitride powder by introducing amino groups directly on the surface by plasma treatment in an inert gas atmosphere; and
Patterning the metal foil,
A method of manufacturing a printed circuit board including:
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