JP5597498B2 - Epoxy resin composition, circuit board, and light emitting device - Google Patents
Epoxy resin composition, circuit board, and light emitting device Download PDFInfo
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- JP5597498B2 JP5597498B2 JP2010211633A JP2010211633A JP5597498B2 JP 5597498 B2 JP5597498 B2 JP 5597498B2 JP 2010211633 A JP2010211633 A JP 2010211633A JP 2010211633 A JP2010211633 A JP 2010211633A JP 5597498 B2 JP5597498 B2 JP 5597498B2
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- 229920000647 polyepoxide Polymers 0.000 title claims description 113
- 239000003822 epoxy resin Substances 0.000 title claims description 105
- 239000000203 mixture Substances 0.000 title claims description 38
- 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 claims description 25
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 19
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 230000003746 surface roughness Effects 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 125000003700 epoxy group Chemical group 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 38
- 239000011256 inorganic filler Substances 0.000 description 19
- 229910003475 inorganic filler Inorganic materials 0.000 description 19
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 239000011889 copper foil Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 229910001120 nichrome Inorganic materials 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- -1 imidazole compound Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000012258 stirred mixture Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
Landscapes
- Fastening Of Light Sources Or Lamp Holders (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Insulated Metal Substrates For Printed Circuits (AREA)
Description
本発明は、ニッケルなどの難接着金属との接着性に優れ、アンカー効果の少ない平坦な金属に対する接着性にも優れるエポキシ樹脂組成物、これを絶縁層とした回路基板、及び、この回路基板を用いた発光装置に関する。 The present invention provides an epoxy resin composition excellent in adhesion to a difficult-to-adhere metal such as nickel and excellent in adhesion to a flat metal with little anchor effect, a circuit board using the epoxy resin composition as an insulating layer, and the circuit board. It relates to the light emitting device used.
熱伝導性について言及したエポキシ樹脂組成物及びこのエポキシ樹脂組成物を用いた回路基板としては、特許文献１がある。 There exists patent document 1 as an epoxy resin composition mentioned about heat conductivity, and a circuit board using this epoxy resin composition.
従来のエポキシ樹脂組成物では、ニッケルなどのエポキシ樹脂と難接着金属に対しては十分な接着強度が得られず、基板として使用するには被着体金属の表面を粗化処理し、アンカー効果により接着強度を向上させるか、あるいは接着界面にプライマー処理を施し、化学的に接着強度を向上させるなどの手法が用いられてきた。
しかし、これら処理は工程増となり、プライマー処理においては新しい樹脂層が形成され、エポキシ樹脂の特徴を十分に活かしきれなかった。
With conventional epoxy resin compositions, sufficient adhesion strength cannot be obtained for epoxy resins such as nickel and difficult-to-adhere metals, and the surface of the adherend metal is roughened for use as a substrate, resulting in an anchor effect. A technique has been used in which the adhesive strength is improved by applying a primer treatment to the adhesive interface to chemically improve the adhesive strength.
However, these treatments increased the process, and a new resin layer was formed in the primer treatment, and the characteristics of the epoxy resin could not be fully utilized.
本発明は、ニッケルなどの難接着金属との接着の際にも十分な接着強度を保つエポキシ樹脂組成物、及び、エポキシ樹脂組成物を絶縁層とした回路基板、発光装置を提供することを目的としたものである。 An object of the present invention is to provide an epoxy resin composition that maintains sufficient adhesion strength even when bonded to a difficult-to-bond metal such as nickel, and a circuit board and a light emitting device using the epoxy resin composition as an insulating layer. It is what.
本発明は、金属板と、回路層とを有し、金属板と回路層の間に介した絶縁層を有する回路基板であって、
絶縁層が、分子量１０００以上１００００以下の高分子量エポキシ樹脂と、分子量３００以上５００以下の低分子量エポキシ樹脂と、エーテル結合を分子内に含む硬化剤、及び、球状酸化アルミニウムを有するエポキシ樹脂組成物であり、
高分子量エポキシ樹脂は、主鎖骨格がビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂のいずれかで、かつ、その骨格の末端にエポキシ基をもつエポキシ樹脂であり、
低分子量エポキシ樹脂は、ビスフェノールＡ型エポキシ樹脂、水添ビスフェノールＡ型エポキシ樹脂から選択される１種以上のエポキシ樹脂組成物であり、
かつ、回路層の表面粗さが１μｍ以下であり、ＪＩＳ Ｃ ６４８１に基づき測定される、回路層と絶縁層の間における剥離強度が１０Ｎ／ｃｍ以上である回路基板である。
The present invention is a circuit board having a metal plate and a circuit layer, and having an insulating layer interposed between the metal plate and the circuit layer,
An insulating layer is an epoxy resin composition having a high molecular weight epoxy resin having a molecular weight of 1000 or more and 10,000 or less, a low molecular weight epoxy resin having a molecular weight of 300 or more and 500 or less, a curing agent containing an ether bond in the molecule, and spherical aluminum oxide. Yes,
The high molecular weight epoxy resin is an epoxy resin whose main chain skeleton is either a bisphenol A type epoxy resin or a bisphenol F type epoxy resin and has an epoxy group at the end of the skeleton,
The low molecular weight epoxy resin is one or more epoxy resin compositions selected from bisphenol A type epoxy resins and hydrogenated bisphenol A type epoxy resins.
In addition, the circuit board has a circuit layer having a surface roughness of 1 μm or less and a peel strength between the circuit layer and the insulating layer of 10 N / cm or more as measured in accordance with JIS C 6481.
このエポキシ樹脂組成物組成物は、上述のエポキシ樹脂と、該エポキシ樹脂組成物よりも熱伝導率の高い無機フィラーとが含有されているのが好ましい。 The epoxy resin composition preferably contains the above-described epoxy resin and an inorganic filler having a higher thermal conductivity than the epoxy resin composition.
本発明の他の形態である回路基板は、金属板と、回路層とを有し、金属板と回路層の間に介した絶縁層を有する回路基板であって、絶縁層が請求項１又は２記載のエポキシ樹脂組成物である回路基板である。
この回路基板としては、回路層の表面粗さが３μｍ以下であり、回路層と絶縁層の間における剥離強度が１０Ｎ／ｃｍ以上であるのが好ましい。
A circuit board according to another aspect of the present invention is a circuit board having a metal plate and a circuit layer, and having an insulating layer interposed between the metal plate and the circuit layer. 2. A circuit board which is the epoxy resin composition according to 2.
In this circuit board, the surface roughness of the circuit layer is preferably 3 μm or less, and the peel strength between the circuit layer and the insulating layer is preferably 10 N / cm or more.
この回路基板としては、回路層を構成する素材がニッケル、アルミニウム、銅のいずれか一つを回路層全体の５０％以上であり、回路層と絶縁層との間における剥離強度が１０Ｎ／ｃｍ以上であるのが好ましい。 In this circuit board, the material constituting the circuit layer is nickel, aluminum, or copper, which is 50% or more of the entire circuit layer, and the peel strength between the circuit layer and the insulating layer is 10 N / cm or more. Is preferred.
本発明の他の形態の発光装置は、上述の回路基板と、回路基板上に設けられたＬＥＤを有する発光装置である。 A light emitting device according to another aspect of the present invention is a light emitting device including the above-described circuit board and an LED provided on the circuit board.
本発明に係るエポキシ樹脂組成物は、上記構成により、ニッケルなどの難接着金属との接着性に優れ、アンカー効果の少ない平坦な金属に対する接着性にも優れ、本発明に係る回路基板は、層間剥離が少なく、本発明に係る発光装置は、ＬＥＤの発熱に対しても層間剥離が少ない。 The epoxy resin composition according to the present invention is excellent in adhesion to a difficult-to-adhere metal such as nickel and excellent in adhesion to a flat metal with little anchor effect, and the circuit board according to the present invention has an interlayer There is little peeling, and the light-emitting device according to the present invention has little delamination against the heat generated by the LED.
以下、本発明について詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明は、分子量１０００以上１００００以下の高分子量エポキシ樹脂と、分子量３００以上５００以下の低分子量エポキシ樹脂、及び、エーテル結合を分子内に含む硬化剤とを有するエポキシ樹脂組成物であって、高分子量エポキシ樹脂は、主鎖骨格がビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂又はビスフェノールＡ型エポキシ樹脂とビスフェノールＦ型エポキシ樹脂の共重合体のいずれかで、かつ末端にエポキシ基をもつエポキシ樹脂であり、低分子量エポキシ樹脂は、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、水添ビスフェノールＡ型エポキシ樹脂、水添ビスフェノールＦ型エポキシ樹脂の単体又は複合体であるエポキシ樹脂組成物である。 The present invention is an epoxy resin composition comprising a high molecular weight epoxy resin having a molecular weight of 1,000 or more and 10,000 or less, a low molecular weight epoxy resin having a molecular weight of 300 or more and 500 or less, and a curing agent containing an ether bond in the molecule. The molecular weight epoxy resin is an epoxy resin whose main chain skeleton is either a bisphenol A type epoxy resin, a bisphenol F type epoxy resin or a copolymer of a bisphenol A type epoxy resin and a bisphenol F type epoxy resin and having an epoxy group at the terminal. The low molecular weight epoxy resin is an epoxy resin composition which is a simple substance or a composite of a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a hydrogenated bisphenol A type epoxy resin, or a hydrogenated bisphenol F type epoxy resin.
これらの骨格を持つ高分子量エポキシ樹脂と低分子量エポキシ樹脂を混合して用いることにより、部分的に架橋点間分子量の大きい３次元網目構造を持つエポキシ樹脂硬化体となり、ひずみに対する応力緩和能力が大きくなるため、ニッケルなどの難接着金属に対しても良好な接着性を与えることができた。 By using a mixture of high molecular weight epoxy resin having these skeletons and low molecular weight epoxy resin, a partially cured epoxy resin having a three-dimensional network structure with a large molecular weight between cross-linking points is obtained. Therefore, it was possible to give good adhesion even to hard-to-bond metals such as nickel.
本発明において、硬化剤として、エーテル結合を分子内に含む硬化剤がある。硬化剤にエーテル結合を含ませることによって、エポキシ樹脂組成物の架橋点間の分子骨格を部分的に柔軟にして被着体剥離時のひずみに対する応力緩和能力を大きくし、ニッケルなどの難接着金属に対しても良好な接着性を与えることができた。エーテル結合を分子内に含む硬化剤としては、プロピレンオキシド、エチレンオキシドなどを繰り返し単位としてもつポリエーテル骨格の末端に１級アミノ基をもつ化合物や、プロピレンオキシド、エチレンオキシドなどを繰り返し単位としてもつポリエーテル骨格の末端に酸無水物を反応させた化合物がある。 In the present invention, as the curing agent, there is a curing agent containing an ether bond in the molecule. By including an ether bond in the curing agent, the molecular skeleton between the crosslinking points of the epoxy resin composition is partially softened to increase the stress relaxation ability against strain at the time of peeling the adherend, and difficult to adhere metals such as nickel It was also possible to give good adhesiveness. Curing agents containing an ether bond in the molecule include compounds having a primary amino group at the end of a polyether skeleton having propylene oxide, ethylene oxide or the like as a repeating unit, or a polyether skeleton having propylene oxide, ethylene oxide or the like as a repeating unit. There is a compound obtained by reacting an acid anhydride at the terminal.
本発明の他の形態である上記エポキシ樹脂組成物と上記エポキシ樹脂より熱伝導率の高い無機フィラーとが含有されたエポキシ樹脂組成物は、エポキシ樹脂より熱伝導率の高い無機フィラーを含有しているので、硬化後の熱伝導率を向上させることができた。 An epoxy resin composition containing the epoxy resin composition according to another embodiment of the present invention and an inorganic filler having higher thermal conductivity than the epoxy resin contains an inorganic filler having higher thermal conductivity than the epoxy resin. As a result, the thermal conductivity after curing could be improved.
本発明における無機フィラーは、上記エポキシ樹脂より熱伝導率の高いものであり、例えば、金属酸化物、炭化物、窒化物又は炭酸塩から選ばれた少なくとも１種以上のものがある。無機フィラーの形状は、充填性の面から球状（粒状）のものを単独又は併用して用いることが好ましく、高充填可能なアルミニウムの酸化物である酸化アルミニウムの球状体が特に好ましく、高周波で駆動する素子を搭載する場合に窒化ホウ素が、誘電率が低いため、特に好ましい。 The inorganic filler in the present invention has a higher thermal conductivity than the epoxy resin, and includes, for example, at least one selected from metal oxides, carbides, nitrides or carbonates. The shape of the inorganic filler is preferably spherical (granular) from the standpoint of filling properties, and is preferably used alone or in combination. Aluminum oxide spheres, which are highly filled aluminum oxides, are particularly preferred, and are driven at high frequency. Boron nitride is particularly preferable when mounting an element to be mounted because of its low dielectric constant.
熱硬化前の熱伝導用エポキシ樹脂組成物に対する無機フィラーの含有量は、絶縁層の厚さや用いる無機フィラーの種類から適宜選択してよいが、４０体積％以上が好ましく、さらに、６５体積％以上がより好ましい。無機フィラーの体積％とは、熱硬化前に含有された無機フィラーの体積が熱硬化後の熱伝導用エポキシ樹脂組成物の体積に占める割合であり、無機フィラーの体積は、含有される無機フィラーの重量を無機フィラーの真比重で除したものである。 The content of the inorganic filler with respect to the epoxy resin composition for heat conduction before thermosetting may be appropriately selected from the thickness of the insulating layer and the type of the inorganic filler used, but is preferably 40% by volume or more, and more preferably 65% by volume or more. Is more preferable. The volume% of the inorganic filler is the ratio of the volume of the inorganic filler contained before thermosetting to the volume of the epoxy resin composition for heat conduction after thermosetting, and the volume of the inorganic filler is the inorganic filler contained Is divided by the true specific gravity of the inorganic filler.
本発明のエポキシ樹脂組成物には、本発明の効果に影響を与えない範囲で、添加剤としての硬化促進剤、変色防止剤、界面活性剤、カップリング剤、着色剤、粘度調整剤を配合することができる。 In the epoxy resin composition of the present invention, a curing accelerator, a discoloration inhibitor, a surfactant, a coupling agent, a colorant, and a viscosity modifier as additives are added within a range that does not affect the effects of the present invention. can do.
本発明の他の形態である回路基板は、金属板と、回路層とを有し、金属板と回路層の間に介した絶縁層を有する回路基板であって、絶縁層が請求項１又は２記載のエポキシ樹脂組成物である回路基板である。 A circuit board according to another aspect of the present invention is a circuit board having a metal plate and a circuit layer, and having an insulating layer interposed between the metal plate and the circuit layer. 2. A circuit board which is the epoxy resin composition according to 2.
回路基板に用いられる金属板としては、アルミニウム、銅、鉄があり、軽量性と熱伝導性を考えるとアルミニウムが好ましく、高い熱容量をもつ銅も好ましい。金属板の厚みは用途によって選択でき、例えば０．１ｍｍ〜５ｍｍの厚みがある。 Examples of the metal plate used for the circuit board include aluminum, copper, and iron. Aluminum is preferable in view of lightness and thermal conductivity, and copper having a high heat capacity is also preferable. The thickness of the metal plate can be selected depending on the application, for example, a thickness of 0.1 mm to 5 mm.
回路基板としては、回路層の表面粗さが３μｍ以下であり、回路層と絶縁層の間における剥離強度が１０Ｎ／ｃｍ以上であるのが好ましい。上述のエポキシ樹脂組成物を絶縁層とした場合、剥離時のひずみに対する応力緩和能力により、表面粗さが３μｍ以下のアンカー効果が小さい回路材金属との接着でも、１０Ｎ／ｃｍ以上の良好な剥離強度が得られる。 As a circuit board, the surface roughness of the circuit layer is preferably 3 μm or less, and the peel strength between the circuit layer and the insulating layer is preferably 10 N / cm or more. When the above-mentioned epoxy resin composition is used as an insulating layer, good peeling of 10 N / cm or more is possible even when bonded to a circuit material metal having a surface roughness of 3 μm or less and a small anchor effect due to the stress relaxation ability against strain at the time of peeling. Strength is obtained.
回路基板としては、回路層を構成する素材がニッケル、アルミニウム、銅のいずれか一つを回路層全体の５０％以上であり、回路層と絶縁層との間における剥離強度が１０Ｎ／ｃｍ以上であるのが好ましい。 As a circuit board, the material constituting the circuit layer is nickel, aluminum, or copper that is 50% or more of the entire circuit layer, and the peel strength between the circuit layer and the insulating layer is 10 N / cm or more. Preferably there is.
本発明の他の形態の発光装置は、上述の回路基板と、回路基板上に設けられたＬＥＤを有する発光装置である。 A light emitting device according to another aspect of the present invention is a light emitting device including the above-described circuit board and an LED provided on the circuit board.
以下に実施例および比較例をあげて本発明をさらに説明する。 The present invention will be further described below with reference to examples and comparative examples.
＜エポキシ樹脂組成物＞
本発明の実施例１のエポキシ樹脂組成物は、
分子量１０００以上１００００以下の高分子量エポキシ樹脂として、高分子量エポキシ樹脂としてビスフェノールＦ型エポキシ樹脂（エピコート４０１０（登録商標）ジャパンエポキシレジン株式会社製 分子量８６００）を、
分子量３００以上５００以下の低分子量エポキシ樹脂として、水添ビスフェノールＡ型エポキシ樹脂ＹＸ８０００（ジャパンエポキシレジン株式会社製 分子量４００）を、
エーテル結合を分子内に含む硬化剤として、エーテル結合を分子内に含むポリオキシプロピレンアミン（ジェファーミンＤ２３０（登録商標）三井化学株式会社製）、及び、ポリオキシプロピレンアミン（ジェファーミンＤ２０００（登録商標）三井化学株式会社製）、
さらに、無機フィラーとして、球状アルミナＤＡＷ−１０（電気化学工業株式会社製）、球状アルミナＡＳＦＰ−３０（電気化学工業株式会社製）を、表１の配合比で作製したものである。表１の単位は容量％であり、実施例１で採用した無機フィラーは、実施例１で採用したエポキシ樹脂より熱伝導率の高いものである。
<Epoxy resin composition>
The epoxy resin composition of Example 1 of the present invention is
As a high molecular weight epoxy resin having a molecular weight of 1,000 or more and 10,000 or less, a bisphenol F type epoxy resin (Epicoat 4010 (registered trademark) Japan Epoxy Resin, Ltd., molecular weight 8600) as a high molecular weight epoxy resin,
As a low molecular weight epoxy resin having a molecular weight of 300 or more and 500 or less, hydrogenated bisphenol A type epoxy resin YX8000 (molecular weight 400, manufactured by Japan Epoxy Resin Co., Ltd.)
As a curing agent containing an ether bond in the molecule, polyoxypropyleneamine (Jefamine D230 (registered trademark) manufactured by Mitsui Chemicals, Inc.) containing an ether bond in the molecule and polyoxypropyleneamine (Jephamine D2000 (registered trademark)) (Mitsui Chemicals)
Furthermore, spherical alumina DAW-10 (manufactured by Denki Kagaku Kogyo Co., Ltd.) and spherical alumina ASFP-30 (manufactured by Denki Kagaku Kogyo Co., Ltd.) were produced as inorganic fillers at the mixing ratios shown in Table 1. The unit of Table 1 is% by volume, and the inorganic filler employed in Example 1 has a higher thermal conductivity than the epoxy resin employed in Example 1.
＜エポキシ樹脂組成物の製造方法＞
前述の高分子量エポキシ樹脂、低分子量エポキシ樹脂を１３０℃まで加熱した後、攪拌し溶解し、室温まで冷却した後、前述の硬化剤、無機フィラーをプラネタリーミキサーで１５分間、攪拌混合し、エポキシ樹脂組成物を作製した。
<Method for producing epoxy resin composition>
The above high molecular weight epoxy resin and low molecular weight epoxy resin are heated to 130 ° C., stirred and dissolved, cooled to room temperature, and then the above curing agent and inorganic filler were stirred and mixed with a planetary mixer for 15 minutes to obtain an epoxy. A resin composition was prepared.
＜回路基板の作製＞
本発明の形態の一つである回路基板は、金属板と、回路層とを有し、金属板と回路層の間に介した絶縁層を有する回路基板であって、絶縁層が実施例１のエポキシ樹脂組成物である回路基板である。
<Production of circuit board>
A circuit board which is one embodiment of the present invention is a circuit board having a metal plate and a circuit layer, and having an insulating layer interposed between the metal plate and the circuit layer. It is a circuit board which is an epoxy resin composition.
＜表１の測定試料＞
測定試料は、具体的には、金属板としての厚さ１．５ｍｍのアルミニウム板上に、実施例１のエポキシ樹脂組成物を厚さ１００μｍとなるように塗布し、１３０℃で１５分間加熱乾燥させた後、１ｃｍ幅に切断した７０μｍ銅箔ＧＴＳ−ＭＰ（古河サーキットフォイル株式会社製）の光沢面（表面粗さ約１μｍ）、７０μｍ銅箔ＧＴＳ−ＭＰの粗化面（表面粗さ約７μｍ）、３０μｍニクロム箔（株式会社ニラコ製）、３０μｍ銅ニッケル箔を基板上に配置し、プレス機によって面圧３０ｋｇｆ／ｃｍ２をかけながら１４０℃９０分間加熱硬化したものである。銅箔、ニクロム箔、ニッケル箔は、回路基板としての回路層である。
<Measurement sample of Table 1>
Specifically, the measurement sample was applied on an aluminum plate having a thickness of 1.5 mm as a metal plate so that the epoxy resin composition of Example 1 had a thickness of 100 μm, and was heated and dried at 130 ° C. for 15 minutes. After polishing, the glossy surface (surface roughness of about 1 μm) of 70 μm copper foil GTS-MP (manufactured by Furukawa Circuit Foil Co., Ltd.) cut to a width of 1 cm, and the roughened surface (surface roughness of about 7 μm) of 70 μm copper foil GTS-MP ), 30 μm Nichrome foil (manufactured by Niraco Co., Ltd.) and 30 μm copper-nickel foil are placed on the substrate and cured by heating at 140 ° C. for 90 minutes while applying a surface pressure of 30 kgf / cm 2 with a press. Copper foil, nichrome foil, and nickel foil are circuit layers as circuit boards.
＜剥離強度の測定＞
剥離強度は、ＪＩＳ Ｃ ６４８１に基づき、テンシロンＵ−１１６０（東洋ボールドウィン株式会社製）を用いて測定した。１０Ｎ／ｃｍ以上の値が望ましい。
<Measurement of peel strength>
The peel strength was measured using Tensilon U-1160 (manufactured by Toyo Baldwin Co., Ltd.) based on JIS C 6481. A value of 10 N / cm or more is desirable.
実施例２は、高分子量エポキシ樹脂として、ビスフェノールＦ型エポキシ樹脂のエピコート４００４（（登録商標）ジャパンエポキシレジン株式会社製、分子量１９００））を用いた以外は、実施例１と同様のエポキシ樹脂組成物である。実施例２は、実施例１の高分子量エポキシ樹脂より分子量の小さいものである。 Example 2 is the same epoxy resin composition as in Example 1 except that Epicoat 4004 ((registered trademark) Japan Epoxy Resin Co., Ltd., molecular weight 1900) of bisphenol F type epoxy resin was used as the high molecular weight epoxy resin. It is a thing. Example 2 has a lower molecular weight than the high molecular weight epoxy resin of Example 1.
実施例３は、高分子量エポキシ樹脂として、ビスフェノールＡ型エポキシ樹脂のエポトートＹＤ−０２０Ｇ（（登録商標）新日鐵化学株式会社製 分子量７０００））を用いた以外は、実施例１と同様のエポキシ樹脂組成物である。実施例３は、実施例１の高分子量エポキシ樹脂と主鎖骨格及び分子量が異なるものである。 Example 3 is the same epoxy as Example 1 except that Epototo YD-020G ((registered trademark) Nippon Steel Chemical Co., Ltd., molecular weight 7000), a bisphenol A type epoxy resin, was used as the high molecular weight epoxy resin. It is a resin composition. Example 3 is different from the high molecular weight epoxy resin of Example 1 in the main chain skeleton and molecular weight.
実施例４は、低分子量エポキシ樹脂として、ビスフェノールＡ型エポキシ樹脂ｅｐ８２８（ジャパンエポキシレジン株式会社製 分子量３９０）を用いた以外は、実施例１と同様のエポキシ樹脂組成物である。実施例４は、実施例１の低分子量エポキシ樹脂と主鎖骨格及び分子量が異なるものである。 Example 4 is an epoxy resin composition similar to Example 1 except that bisphenol A type epoxy resin ep828 (molecular weight 390 manufactured by Japan Epoxy Resin Co., Ltd.) was used as the low molecular weight epoxy resin. Example 4 is different from the low molecular weight epoxy resin of Example 1 in the main chain skeleton and molecular weight.
実施例５は、高分子量エポキシ樹脂としてのビスフェノールＦ型のエピコート４０１０（（登録商標）ジャパンエポキシレジン株式会社製 分子量８６００））５．１容量％、低分子量エポキシ樹脂としての水添ビスフェノールＡ型エポキシ樹脂ＹＸ８０００（ジャパンエポキシレジン株式会社製 分子量４００）１６．６容量％を１３０℃まで加熱した後、攪拌し溶解し室温まで冷却し、さらに、硬化剤として分子内にエーテル結合を含む酸無水物硬化剤リカシッドＨＦ−０８（（登録商標）新日本理化社製）２５．６容量％、硬化促進剤としてイミダゾール化合物 ２Ｅ４ＭＺ−ＣＮ（四国化成社製）２．０容量％（表１での記載省略）、無機フィラーとして球状アルミナＤＡＷ−１０（電気化学工業株式会社製）３５．９容量％、球状アルミナ、ＡＳＦＰ−３０（電気化学工業株式会社製）１４．８容量％をプラネタリーミキサーで１５分間、攪拌混合しエポキシ樹脂組成物を作製した。実施例５は、実施例１と比べ高分子量エポキシ樹脂の配合比、低分子量エポキシ樹脂の配合比、硬化剤の素材及び配合比、無機フィラーの配合比を変えたものである。 Example 5 is a bisphenol F type epicoat 4010 as a high molecular weight epoxy resin (Molecular weight 8600 manufactured by (registered trademark) Japan Epoxy Resin Co., Ltd.) 5.1 vol%, hydrogenated bisphenol A type epoxy as a low molecular weight epoxy resin. Resin YX8000 (Molecular weight 400, manufactured by Japan Epoxy Resins Co., Ltd.) 16.6% by volume is heated to 130 ° C, stirred and dissolved, cooled to room temperature, and further cured with an acid anhydride containing an ether bond in the molecule. Agent Ricacid HF-08 ((registered trademark) manufactured by Shin Nippon Rika Co., Ltd.) 25.6% by volume, imidazole compound 2E4MZ-CN (manufactured by Shikoku Kasei Co., Ltd.) as a curing accelerator 2.0% by volume (not shown in Table 1) Spherical alumina DAW-10 (manufactured by Denki Kagaku Kogyo Co., Ltd.) 35.9% by volume as an inorganic filler, spherical alumina Mina, ASFP-30 (manufactured by Denki Kagaku Kogyo Co., Ltd.) 14.8% by volume 15 min in a planetary mixer to prepare a stirred mixture was epoxy resin composition. Example 5 is different from Example 1 in that the mixing ratio of the high molecular weight epoxy resin, the mixing ratio of the low molecular weight epoxy resin, the material and the mixing ratio of the curing agent, and the mixing ratio of the inorganic filler are changed.
実施例６は、表への記載は省略したが、実施例１の無機フィラーを配合しなかった以外は、実施例１と同様なものである。実施例６の剥離強度は、実施例１と同等な値であった。 Example 6 was the same as Example 1 except that the description in the table was omitted, but the inorganic filler of Example 1 was not blended. The peel strength of Example 6 was a value equivalent to that of Example 1.
実施例１乃至５は、いずれも良好な剥離強度を有していた。表１の「≧２０」は２０Ｎ／ｃｍ以上であったという意味である。 Examples 1 to 5 all had good peel strength. “≧ 20” in Table 1 means 20 N / cm or more.
〔比較例１〕
比較例１は、表１に示すように、低分子量エポキシ樹脂としての水添ビスフェノールＡ型エポキシ樹脂ＹＸ８０００（ジャパンエポキシレジン株式会社製 分子量４００）２７．４％、硬化剤としてのエーテル結合を分子内に含むポリオキシプロピレンアミン ジェファーミンＤ２３０（（登録商標）三井化学株式会社製）１１．５容量％、ポリオキシプロピレンアミン ジェファーミンＤ２０００（（登録商標）三井化学株式会社製）７．９容量％、無機フィラーとして球状アルミナＤＡＷ−１０（電気化学工業株式会社製）３７．１容量％、球状アルミナ、ＡＳＦＰ−３０（電気化学工業株式会社製）１５．９容量％をプラネタリーミキサーで１５分間、攪拌混合しエポキシ樹脂組成物を作製した。比較例１は、高分子量エポキシ樹脂を含まないため、十分な応力緩和能力が得られず、銅箔光沢面、ニクロム箔及び銅ニッケル箔への剥離強度が不十分だった。
[Comparative Example 1]
As shown in Table 1, Comparative Example 1 is a hydrogenated bisphenol A type epoxy resin YX8000 (molecular weight 400, Japan Epoxy Resin Co., Ltd.) 27.4% as a low molecular weight epoxy resin, and an ether bond as a curing agent in the molecule. Polyoxypropyleneamine Jeffamine D230 (manufactured by Mitsui Chemicals, Inc.) 11.5% by volume, polyoxypropyleneamine Jeffamine D2000 (manufactured by Mitsui Chemicals, Inc.) 7.9% by volume, As inorganic filler, spherical alumina DAW-10 (manufactured by Denki Kagaku Kogyo Co., Ltd.) 37.1% by volume, spherical alumina, ASFP-30 (manufactured by Denki Kagaku Kogyo Co., Ltd.) 15.9% by volume were stirred with a planetary mixer for 15 minutes. An epoxy resin composition was prepared by mixing. Since Comparative Example 1 did not contain a high molecular weight epoxy resin, sufficient stress relaxation ability was not obtained, and peel strength to the copper foil glossy surface, nichrome foil and copper nickel foil was insufficient.
〔比較例２〕
比較例２は、エーテル結合を分子内に含まない硬化剤を使用したものであり、具体的には、高分子量エポキシ樹脂としてのビスフェノールＦ型エポキシ樹脂のエピコート４０１０（（登録商標）ジャパンエポキシレジン株式会社製 分子量８６００）９．１容量％、低分子量エポキシ樹脂としての水添ビスフェノールＡ型エポキシ樹脂ＹＸ８０００（ジャパンエポキシレジン株式会社製 分子量４００）２９．４容量％、硬化剤として芳香族アミン Ｈ８４Ｂ（日本合成加工株式会社製）８．６容量％、無機フィラーとして球状アルミナＤＡＷ−１０（電気化学工業株式会社製）３７．１容量％、球状アルミナ、ＡＳＦＰ−３０（電気化学工業株式会社製）１５．９容量％をプラネタリーミキサーで１５分間、攪拌混合しエポキシ樹脂組成物を作製した。比較例２は硬化剤に芳香族アミンを使用したため、十分な応力緩和能力が得られず、銅箔光沢面、ニクロム箔、銅ニッケル箔への接着力が不十分だった。
[Comparative Example 2]
Comparative Example 2 uses a curing agent that does not contain an ether bond in the molecule. Specifically, Epicoat 4010 of bisphenol F type epoxy resin as a high molecular weight epoxy resin ((registered trademark) Japan Epoxy Resin Co., Ltd.) 9.1% by volume, molecular weight 8600), hydrogenated bisphenol A type epoxy resin YX8000 (Molecular weight 400, manufactured by Japan Epoxy Resin Co., Ltd.) 29.4% by volume, aromatic amine H84B (Japan) Synthetic processing Co., Ltd.) 8.6% by volume, spherical alumina DAW-10 (manufactured by Denki Kagaku Kogyo Co., Ltd.) 37.1% by volume, inorganic alumina, ASFP-30 (manufactured by Denki Kagaku Kogyo Co., Ltd.) 15. 9 vol% is stirred and mixed with a planetary mixer for 15 minutes to produce an epoxy resin composition. It was. Since the comparative example 2 used the aromatic amine for the hardening | curing agent, sufficient stress relaxation capability was not acquired and the adhesive force to a copper foil glossy surface, nichrome foil, and copper nickel foil was inadequate.
本発明の他の形態である発光装置の実施例について説明する。この発光装置の実施例は、実施例１のエポキシ樹脂組成物を用いた回路基板と、回路基板上に設けられたＬＥＤを設けたものである。この実施例は、ＬＥＤを長時間発光させても、回路層と絶縁層の界面が剥離し難いものであった。 Examples of the light emitting device according to another embodiment of the present invention will be described. In this example of the light emitting device, a circuit board using the epoxy resin composition of Example 1 and an LED provided on the circuit board are provided. In this example, even when the LED was allowed to emit light for a long time, the interface between the circuit layer and the insulating layer was difficult to peel off.
Claims (3)
絶縁層が、分子量１０００以上１００００以下の高分子量エポキシ樹脂と、分子量３００以上５００以下の低分子量エポキシ樹脂と、エーテル結合を分子内に含む硬化剤、及び、球状酸化アルミニウムを有するエポキシ樹脂組成物であり、
高分子量エポキシ樹脂は、主鎖骨格がビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂のいずれかで、かつ、その骨格の末端にエポキシ基をもつエポキシ樹脂であり、
低分子量エポキシ樹脂は、ビスフェノールＡ型エポキシ樹脂、水添ビスフェノールＡ型エポキシ樹脂から選択される１種以上のエポキシ樹脂組成物であり、
かつ、回路層の表面粗さが１μｍ以下であり、ＪＩＳ Ｃ ６４８１に基づき測定される、回路層と絶縁層の間における剥離強度が１０Ｎ／ｃｍ以上である回路基板。 A circuit board having a metal plate and a circuit layer, and having an insulating layer interposed between the metal plate and the circuit layer,
An insulating layer is an epoxy resin composition having a high molecular weight epoxy resin having a molecular weight of 1000 or more and 10,000 or less, a low molecular weight epoxy resin having a molecular weight of 300 or more and 500 or less, a curing agent containing an ether bond in the molecule, and spherical aluminum oxide. Yes,
The high molecular weight epoxy resin is an epoxy resin whose main chain skeleton is either a bisphenol A type epoxy resin or a bisphenol F type epoxy resin and has an epoxy group at the end of the skeleton,
The low molecular weight epoxy resin is one or more epoxy resin compositions selected from bisphenol A type epoxy resins and hydrogenated bisphenol A type epoxy resins.
And the circuit board whose surface roughness of a circuit layer is 1 micrometer or less, and the peeling strength between a circuit layer and an insulating layer is 10 N / cm or more measured based on JISC6481.
A light emitting device comprising: the circuit board according to claim 2; and an LED provided on the circuit board.
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