JP5031639B2 - Flexible copper clad laminate - Google Patents
Flexible copper clad laminate Download PDFInfo
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- JP5031639B2 JP5031639B2 JP2008092283A JP2008092283A JP5031639B2 JP 5031639 B2 JP5031639 B2 JP 5031639B2 JP 2008092283 A JP2008092283 A JP 2008092283A JP 2008092283 A JP2008092283 A JP 2008092283A JP 5031639 B2 JP5031639 B2 JP 5031639B2
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- copper foil
- polyimide
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 81
- 229910052802 copper Inorganic materials 0.000 title claims description 15
- 239000010949 copper Substances 0.000 title claims description 15
- 229920001721 polyimide Polymers 0.000 claims description 86
- 239000004642 Polyimide Substances 0.000 claims description 70
- 239000011889 copper foil Substances 0.000 claims description 66
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 30
- 238000010521 absorption reaction Methods 0.000 claims description 20
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 18
- 125000005462 imide group Chemical group 0.000 claims description 18
- 229910052759 nickel Inorganic materials 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 230000003746 surface roughness Effects 0.000 claims description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 11
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims description 11
- 229910052725 zinc Inorganic materials 0.000 claims description 11
- 239000011701 zinc Substances 0.000 claims description 11
- 239000011888 foil Substances 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- KMKWGXGSGPYISJ-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=CC(N)=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=C(N)C=C1 KMKWGXGSGPYISJ-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000000962 organic group Chemical group 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 125
- 239000011347 resin Substances 0.000 description 43
- 229920005989 resin Polymers 0.000 description 43
- 229920005575 poly(amic acid) Polymers 0.000 description 42
- 230000015572 biosynthetic process Effects 0.000 description 38
- 238000003786 synthesis reaction Methods 0.000 description 36
- 239000009719 polyimide resin Substances 0.000 description 15
- 239000002253 acid Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 10
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 7
- 239000004952 Polyamide Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229920002647 polyamide Polymers 0.000 description 6
- XUSNPFGLKGCWGN-UHFFFAOYSA-N 3-[4-(3-aminopropyl)piperazin-1-yl]propan-1-amine Chemical compound NCCCN1CCN(CCCN)CC1 XUSNPFGLKGCWGN-UHFFFAOYSA-N 0.000 description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 4
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 4
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 4
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 4
- 150000004985 diamines Chemical class 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- QYIMZXITLDTULQ-UHFFFAOYSA-N 4-(4-amino-2-methylphenyl)-3-methylaniline Chemical group CC1=CC(N)=CC=C1C1=CC=C(N)C=C1C QYIMZXITLDTULQ-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 150000004984 aromatic diamines Chemical class 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 239000002335 surface treatment layer Substances 0.000 description 3
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- -1 3-aminopropoxy Chemical group 0.000 description 2
- WUPRYUDHUFLKFL-UHFFFAOYSA-N 4-[3-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(OC=2C=CC(N)=CC=2)=C1 WUPRYUDHUFLKFL-UHFFFAOYSA-N 0.000 description 2
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 2
- ZHBXLZQQVCDGPA-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)sulfonyl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(S(=O)(=O)C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 ZHBXLZQQVCDGPA-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 1
- DKKYOQYISDAQER-UHFFFAOYSA-N 3-[3-(3-aminophenoxy)phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=C(OC=3C=C(N)C=CC=3)C=CC=2)=C1 DKKYOQYISDAQER-UHFFFAOYSA-N 0.000 description 1
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 description 1
- JCRRFJIVUPSNTA-UHFFFAOYSA-N 4-[4-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 JCRRFJIVUPSNTA-UHFFFAOYSA-N 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- MBENFEACGFINFS-UHFFFAOYSA-N C1(=CC=CC=C1)NCCC[Si](OC)(OC)OC.C(CC)CO[Si](OC)(OC)CCCN Chemical compound C1(=CC=CC=C1)NCCC[Si](OC)(OC)OC.C(CC)CO[Si](OC)(OC)CCCN MBENFEACGFINFS-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 125000004427 diamine group Chemical group 0.000 description 1
- 125000006159 dianhydride group Chemical group 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000009429 electrical wiring Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000010365 information processing Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001690 polydopamine Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Manufacturing Of Printed Wiring (AREA)
- Parts Printed On Printed Circuit Boards (AREA)
Description
本発明は、ポリイミド樹脂からなる絶縁層とその片面又は両面に銅箔が設けられたフレキシブル銅張積層板に関する。 The present invention relates to an insulating layer made of polyimide resin and a flexible copper-clad laminate provided with a copper foil on one or both sides thereof.
近年、携帯電話やデジタルカメラ、デジタルビデオ、ＰＤＡ、カーナビゲータ、ハードディスクその他の各種電子機器の高機能化、小型化、そして軽量化に伴い、これらの電気配線用基板材料として従来用いられてきたリジット基板に変わって配線の自由度が高く、薄型化が容易なフレキシブルプリント基板が採用される例が増加している。そして、より高度化していくこれらの機器に用いられているフレキシブルプリント基板に関しては更なる小型高密度化、多層化、ファイン化、高耐熱化等の要求が高まっている。 In recent years, with the increasing functionality, miniaturization, and weight reduction of various electronic devices such as mobile phones, digital cameras, digital video, PDAs, car navigators, hard disks, etc., the rigid that has been used in the past as a substrate material for these electrical wiring There is an increasing number of cases where a flexible printed board is employed instead of a board, which has a high degree of freedom in wiring and can be easily thinned. With respect to flexible printed circuit boards used in these increasingly sophisticated devices, there are increasing demands for further miniaturization, higher density, multilayering, finer, higher heat resistance, and the like.
このような要求に応えるため、導体上に直接ポリイミド層を塗工形成し、かつ熱膨張係数の異なる複数のポリイミド層で多層化して形成することにより、温度変化に対する寸法安定性、接着力、更にはエッチング後の平面性等で信頼性に優れたフレキシブルプリント基板を提供する方法が特許文献１などに開示されている。 In order to meet such demands, a polyimide layer is directly coated on a conductor, and a plurality of polyimide layers having different thermal expansion coefficients are formed to form a multi-layered structure. Patent Document 1 discloses a method for providing a flexible printed circuit board having excellent reliability such as flatness after etching.
このようなフレキシブルプリント基板に用いられる接着剤層を有さない銅張積層板においては、例えば特許文献２、特許文献３、特許文献４等にあるように、樹脂層との接着力を高めるために銅箔表面が粗化処理された銅箔が用いられている。 In a copper clad laminate having no adhesive layer used for such a flexible printed circuit board, for example, as disclosed in Patent Document 2, Patent Document 3, Patent Document 4, and the like, in order to increase the adhesive force with the resin layer A copper foil having a roughened copper foil surface is used.
更に、近年電子機器における情報処理能力の向上を図るために、電子機器に用いられるプリント配線板上の回路を伝達する電気信号の高速化・高周波化が進められている。そのため、電気信号が高周波化された場合にも、プリント配線板の電気的信頼性を保ち、回路での電気信号の伝達速度の低下や電気信号の損失を抑制することが望まれる。そのようなプリント配線板には、通常、当該配線基板や回路を保護するための保護膜や、多層構造の配線基板における各層間の絶縁性を確保するための層間絶縁膜等の絶縁層が形成される。これらの層間絶縁膜等に用いられる接着剤については、例えば特許文献５等のように、接着剤層の組成を改良することで樹脂の絶縁特性を向上させている報告もある。 Furthermore, in recent years, in order to improve information processing capability in electronic devices, electrical signals that transmit circuits on printed wiring boards used in electronic devices have been increased in speed and frequency. Therefore, it is desired to maintain the electrical reliability of the printed wiring board even when the electrical signal is increased in frequency, and to suppress the decrease in the transmission speed of the electrical signal in the circuit and the loss of the electrical signal. Such a printed wiring board is usually formed with an insulating layer such as a protective film for protecting the wiring board or circuit, or an interlayer insulating film for ensuring insulation between layers in a multilayered wiring board. Is done. As for the adhesive used for these interlayer insulating films and the like, there is also a report of improving the insulating properties of the resin by improving the composition of the adhesive layer as disclosed in Patent Document 5, for example.
しかしながら、これまでは上記の要求に対し、樹脂と導体回路を形成する銅箔との間に十分な接着性を持たせるために銅箔表面に粗化処理を施したり、銅箔に接する樹脂に吸湿率の高い熱可塑性の樹脂を用いたりしていたため、低誘電正接性の絶縁層を有するフレキシブル銅張積層板を得ることが困難であった。
本発明は、ポリイミドの保有する耐熱性や寸法安定性等を保持しつつ、電子機器類の分野にて近年急速に進む高集積化や高密度化の要請に対応でき、かつ、銅箔とポリイミド層との接着信頼性を有し、高周波領域における誘電率及び誘電正接が低く、誘電特性に優れたフレキシブル銅張積層板を提供することを目的とする。 The present invention is capable of meeting the demands for high integration and high density which are rapidly progressing in recent years in the field of electronic equipment while maintaining the heat resistance and dimensional stability possessed by polyimide, and copper foil and polyimide. It is an object of the present invention to provide a flexible copper-clad laminate having adhesion reliability with a layer, having a low dielectric constant and dielectric loss tangent in a high frequency region, and having excellent dielectric properties.
上記課題を解決するために鋭意検討した結果、導体回路を形成する銅箔とそれに接するポリイミド層に特定のものを採用することで誘電特性に優れたフレキシブル銅張積層板を提供することが可能なことを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, it is possible to provide a flexible copper-clad laminate having excellent dielectric characteristics by adopting a specific copper foil that forms a conductor circuit and a polyimide layer that is in contact with the copper foil. As a result, the present invention has been completed.
すなわち、本発明は、線膨張係数が１×１０ -6 〜３０×１０ -6 [１／Ｋ]の範囲のポリイミド層（ii）と線膨張係数が３０×１０ -6 [１／Ｋ]を超えるポリイミド層（ｉ）とを含んでなるポリイミド層の片面又は両面に銅箔を有する銅張積層板において、前記銅箔のポリイミド層と接する面が粗化処理されておらず、その表面粗度Rｚが１．０μｍ以下であり、かつ、最外層にシランカップリング剤処理層を有し、また、該表面に接するポリイミド層（ｉ）が下記一般式（１）で表される繰返し単位を含み、このポリイミド層（ｉ）は吸湿率１．０％以下であって、かつイミド基濃度が３３％以下であることを特徴とするフレキシブル銅張積層板である。
ここで、銅箔は、無粗化電解銅箔又は無粗化圧延延箔であり、その表面にニッケル、コバルト、モリブデン、亜鉛、銅、鉄、及びアルミニウムからなる群から選ばれる１種以上の金属で処理された金属処理層、及びクロメート処理層を有すると共に、ポリイミド層（ｉ）と接する側の最外層にシランカップリング剤処理層を有し、また、ポリイミド層（ｉ）の誘電率が３．３以下であり、かつ、誘電正接が０．００２５以下であることは本発明の好ましい態様を示す。
That is, the present invention provides a polyimide layer (ii) having a linear expansion coefficient in the range of 1 × 10 −6 to 30 × 10 −6 [1 / K] and a linear expansion coefficient of 30 × 10 −6 [1 / K]. In a copper clad laminate having a copper foil on one or both sides of a polyimide layer comprising a polyimide layer (i) that exceeds, the surface of the copper foil in contact with the polyimide layer is not roughened, and its surface roughness Rz is 1.0 μm or less , the outermost layer has a silane coupling agent-treated layer, and the polyimide layer (i) in contact with the surface contains a repeating unit represented by the following general formula (1) the polyimide layer (i) is a flexible copper clad laminate, characterized in that a 1.0% or less moisture absorption, and imide group concentration is 33% or less.
Here, the copper foil is a non-roughened electrolytic copper foil or a non-roughened rolled rolled foil, and one or more kinds selected from the group consisting of nickel, cobalt, molybdenum, zinc, copper, iron, and aluminum on the surface thereof. It has a metal treatment layer treated with metal and a chromate treatment layer, and has a silane coupling agent treatment layer on the outermost layer in contact with the polyimide layer (i), and the dielectric constant of the polyimide layer (i) is It is 3.3 or less, and a dielectric loss tangent is 0.0025 or less shows the preferable aspect of this invention.
本発明のフレキシブル銅張積層板は、いわゆる高周波とされているGHｚ帯域での誘電率や誘電正接が低く、これらの優れた誘電特性を活かした用途に好適に用いることができる。 The flexible copper-clad laminate of the present invention has a low dielectric constant and dielectric loss tangent in the so-called high-frequency GHz band, and can be suitably used for applications utilizing these excellent dielectric properties.
以下、本発明を詳細に説明する。
本発明のフレキシブル銅張積層板は、絶縁層となるポリイミド層（絶縁層ともいう）と銅箔とを有する。銅箔は、例えば圧延銅箔、電解銅箔等の公知の製造方法によって得られたものを用いることができる。銅箔の好ましい厚み範囲は、６〜３５μｍであり、９〜１８μｍの範囲がより好ましい。銅箔の厚みが６μｍに満たないと、銅張積層板を大量生産する場合のようなライン製造の工程において、テンションの調整等が困難となるおそれがあり、反対に３５μｍを超えるとフレキシブル銅張積層板の屈曲性が劣る。
Hereinafter, the present invention will be described in detail.
The flexible copper-clad laminate of the present invention has a polyimide layer (also referred to as an insulating layer) that serves as an insulating layer and a copper foil. What was obtained by well-known manufacturing methods, such as rolled copper foil and electrolytic copper foil, can be used for copper foil, for example. The preferable thickness range of copper foil is 6-35 micrometers, and the range of 9-18 micrometers is more preferable. If the thickness of the copper foil is less than 6 μm, it may be difficult to adjust the tension in the line manufacturing process as in the case of mass production of copper clad laminates. The flexibility of the laminate is poor.
使用する銅箔は、絶縁層であるポリイミド層と接する面が粗化処理されていない無粗化の電解銅箔や無粗化の圧延銅箔を用いることができる。この銅箔は、粗化処理されていないため、ポリイミド層との密着力を向上させるため、表面がシランカップリング剤で処理されたシランカップリング剤処理層を有していることが好ましい。なお、本明細書において「粗化処理されていない」と「無粗化」は同義であり、銅箔を電解析出させた表面にこぶ付け処理をしない銅箔のことをいう。 As the copper foil to be used, a non-roughened electrolytic copper foil or a non-roughened rolled copper foil whose surface in contact with the polyimide layer as an insulating layer is not roughened can be used. Since this copper foil is not roughened, it preferably has a silane coupling agent-treated layer whose surface is treated with a silane coupling agent in order to improve adhesion to the polyimide layer. In this specification, “not roughened” and “non-roughened” are synonymous and refer to a copper foil that is not subjected to a bumping treatment on the surface on which the copper foil is electrolytically deposited.
銅箔は、表面処理をした後の状態において表面粗度（Ｒｚ）が１．０μｍ以下であることが必要であり、０．２〜１.０μｍの範囲が好ましい。ここで、表面粗度（Ｒｚ）とは、JIS B0601（１９９４）によって定義される１０点平均粗さをさす。 The copper foil needs to have a surface roughness (Rz) of 1.0 μm or less in the state after the surface treatment, and a range of 0.2 to 1.0 μm is preferable. Here, the surface roughness (Rz) refers to a 10-point average roughness defined by JIS B0601 (1994).
銅箔には、シランカップリング処理剤層の他、金属処理層及びクロメート処理層を有していることが好ましい。ここで、金属処理層としては、ニッケル、コバルト、モリブデン、亜鉛、銅、鉄、及びアルミニウムからなる群から選ばれる１種以上の金属が用いられる。具体的にはニッケル、ニッケル＋亜鉛、ニッケル＋コバルト、ニッケル＋コバルト＋銅などによる処理が挙げられる。銅のみを用いた場合は酸化されやすくなり、変色等が起こりやすくなる。また、銅＋ニッケル若しくはニッケルのみでは、銅張積層板を得た後に回路形成等を行う際の化学研磨に対する耐性は強くなるものの、回路加工時に用いられる銅エッチング液に溶解しにくくなり、エッチング残りが発生しやすくなる恐れがある。銅＋コバルト若しくはコバルトのみでは耐酸性が悪くなり、化学研磨の際に回路剥がれが発生しやすくなる恐れがある。またクロメート処理層としては、クロムの電解めっきや無電解めっきなどにより、直接酸化クロムや水酸化クロムを析出方法や亜鉛との置換めっきにより酸化クロムや水酸化クロムを析出させる方法が挙げられる。 The copper foil preferably has a metal treatment layer and a chromate treatment layer in addition to the silane coupling treatment agent layer. Here, as the metal treatment layer, one or more metals selected from the group consisting of nickel, cobalt, molybdenum, zinc, copper, iron, and aluminum are used. Specific examples include nickel, nickel + zinc, nickel + cobalt, nickel + cobalt + copper treatment. When only copper is used, it is likely to be oxidized and discoloration or the like is likely to occur. In addition, with copper + nickel or nickel alone, the resistance to chemical polishing when performing circuit formation after obtaining a copper-clad laminate is increased, but it becomes difficult to dissolve in a copper etching solution used during circuit processing, resulting in residual etching. May be more likely to occur. When only copper + cobalt or cobalt is used, the acid resistance is poor, and circuit peeling may occur easily during chemical polishing. Examples of the chromate treatment layer include a method of directly depositing chromium oxide or chromium hydroxide by electrolytic plating or electroless plating of chromium, or a method of depositing chromium oxide or chromium hydroxide by displacement plating with zinc.
シランカップリング剤処理層としては、絶縁層との密着力を更に向上させるために、アミノ基を有するシランカップリング剤が好ましく用いられる。このシランカップリング処理層は、表面処理層の最外層に存在することが好ましい。アミノ基を有するシランカップリング剤としてはN-2-（アミノエチル）γ-アミノプロピルトリメトキシシラン、N-3-（4-（3-アミノプロポキシ）プトキシ）プロピル-3-アミノプロピルトリメトキシシラン、N-フェニル-3-アミノプロピルトリメトキシシラン等が挙げられる。これらのシランカップリング剤は単独で用いても、２種以上組み合わせて用いてもよく、複数の場合はアミノ基を有するシランカップリング剤が１種類以上含まれていればよい。 As the silane coupling agent treatment layer, a silane coupling agent having an amino group is preferably used in order to further improve the adhesion to the insulating layer. This silane coupling treatment layer is preferably present in the outermost layer of the surface treatment layer. Examples of silane coupling agents having amino groups include N-2- (aminoethyl) γ-aminopropyltrimethoxysilane, N-3- (4- (3-aminopropoxy) ptoxy) propyl-3-aminopropyltrimethoxysilane N-phenyl-3-aminopropyltrimethoxysilane and the like. These silane coupling agents may be used alone or in combination of two or more. In the case of a plurality of these silane coupling agents, it is sufficient that at least one silane coupling agent having an amino group is contained.
シランカップリング剤処理方法は、例えば上記カップリング剤を用いる場合、先ず、溶媒としての水に所定量のカップリング剤を溶解させ、上記した金属析出処理した後の銅箔表面に塗布し、乾燥させる方法が例示される。この際、必要により加熱処理を行ってもよい。また、銅箔表面に対して水に溶解させたカップリング剤を塗布する方法としては、例えば浸漬法、シャワーリング法、噴霧法等の公知の方法を用いることができる。 The silane coupling agent treatment method is, for example, when using the above coupling agent, first, a predetermined amount of the coupling agent is dissolved in water as a solvent, applied to the copper foil surface after the above-described metal precipitation treatment, and dried. The method to make is illustrated. At this time, heat treatment may be performed as necessary. Moreover, as a method of apply | coating the coupling agent dissolved in water with respect to the copper foil surface, well-known methods, such as a dipping method, a showering method, a spraying method, can be used, for example.
ポリイミド層を構成するポリイミドは、一般的に下記一般式（１）で表され、ジアミン成分と酸二無水物成分とを実質的に等モル使用し、有機極性溶媒中で重合する公知の方法によって製造することができる。
酸二無水物としては、例えば、O（CO）2-Ａｒ1-（CO）2Oによって表される芳香族テトラカルボン酸二無水物が好ましく、下記芳香族酸無水物残基をＡｒ1として与えるものが例示される。
酸二無水物は単独で又は２種以上混合して用いることができる。これらの中でも、ピロメリット酸二無水物（PMDA）、3,3',4,4'-ビフェニルテトラカルボン酸二無水物（BPDA）、3,3',4,4'-ベンゾフェノンテトラカルボン酸二無水物（BTDA）、3,3',4,4'-ジフェニルスルホンテトラカルボン酸二無水物（DSDA）、及び4,4'-オキシジフタル酸二無水物（ODPA） から選ばれるものを使用することが好ましい。 An acid dianhydride can be used individually or in mixture of 2 or more types. Among these, pyromellitic dianhydride (PMDA), 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA), 3,3', 4,4'-benzophenone tetracarboxylic acid Use one selected from anhydride (BTDA), 3,3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride (DSDA), and 4,4'-oxydiphthalic dianhydride (ODPA) Is preferred.
ジアミンとしては、例えば、Ｈ2Ｎ−Ａｒ2−ＮＨ2によって表される芳香族ジアミンが好ましく、下記芳香族ジアミン残基をＡｒ2として与える芳香族ジアミンが例示される。
これらのジアミンの中でも、ジアミノジフェニルエーテル（DAPE）、2,2'−ジメチル−4,4'−ジアミノビフェニル（以下ｍ-TB）、パラフェニレンジアミン（ｐ−PDA）、1,3-ビス（4-アミノフェノキシ）ベンゼン（TPE-R）、1,3-ビス（3-アミノフェノキシ）ベンゼン（APB）、1,4-ビス（4-アミノフェノキシ）ベンゼン（TPE-Q）、及び2,2-ビス[4-（4-アミノフェノキシ）フェニル]プロパン（BAPP）が好適なものとして例示される。 Among these diamines, diaminodiphenyl ether (DAPE), 2,2′-dimethyl-4,4′-diaminobiphenyl (hereinafter referred to as m-TB), paraphenylenediamine (p-PDA), 1,3-bis (4- Aminophenoxy) benzene (TPE-R), 1,3-bis (3-aminophenoxy) benzene (APB), 1,4-bis (4-aminophenoxy) benzene (TPE-Q), and 2,2-bis [4- (4-Aminophenoxy) phenyl] propane (BAPP) is exemplified as a suitable example.
重合に用いる溶媒については、例えばジメチルアセトアミド、ｎ-メチルピロリジノン、2-ブタノン、ジグライム、キシレン等を挙げることができ、これらについては１種若しくは２種以上を併用して使用することもできる。また、重合して得られたポリアミド酸（ポリイミド前駆体）の樹脂粘度については、５００ｃｐｓ〜３５０００ｃｐｓの範囲とするのが好ましい。 Examples of the solvent used for polymerization include dimethylacetamide, n-methylpyrrolidinone, 2-butanone, diglyme, xylene, and the like. These can be used alone or in combination of two or more. The resin viscosity of the polyamic acid (polyimide precursor) obtained by polymerization is preferably in the range of 500 cps to 35000 cps.
本発明のフレキシブル銅張積層板のポリイミド層は、単層からなるものであっても複数層からなるものであってもよいが、フレキシブル銅張積層板の寸法安定性や、銅箔との接着強度を優れたものとするためには、複数層とすることが好ましい。本発明では、ポリイミド層が単層であるか複数層であるかに拘らず、少なくとも前記銅箔と接するポリイミド層（ｉ）については、吸湿率が１．０％以下であり、イミド基濃度が３３％以下であるポリイミド樹脂から形成する必要がある。吸湿率が１．０％を超えると、樹脂表面に吸着する水の影響による樹脂の絶縁特性の低下が顕著になり、また、イミド基濃度が３３％を超えると、樹脂自体の分子量が小さくなる構造になるため、熱特性や接着特性の低下が顕著になる。本発明では、これらの要件を充足することで、優れた樹脂の絶縁特性が得られる。本発明における、吸湿率は、後記実施例記載の測定方法によって測定されるものをいい、また、イミド基濃度は、分子構造にてイミド基部（-(ＣＯ)2-Ｎ-）の分子量を構造全体の分子量で割ることで求められる値をいう。 The polyimide layer of the flexible copper-clad laminate of the present invention may be composed of a single layer or a plurality of layers, but the dimensional stability of the flexible copper-clad laminate and adhesion to the copper foil In order to make the strength excellent, it is preferable to have a plurality of layers. In the present invention, regardless of whether the polyimide layer is a single layer or a plurality of layers, at least the polyimide layer (i) in contact with the copper foil has a moisture absorption rate of 1.0% or less and an imide group concentration. It is necessary to form from polyimide resin which is 33% or less. When the moisture absorption rate exceeds 1.0%, the resin insulation characteristics are significantly deteriorated due to the effect of water adsorbed on the resin surface. When the imide group concentration exceeds 33%, the molecular weight of the resin itself decreases. Due to the structure, the thermal characteristics and adhesive characteristics are significantly reduced. In the present invention, excellent resin insulation characteristics can be obtained by satisfying these requirements. In the present invention, the moisture absorption refers to that measured by the measurement method described in the Examples below, and the imide group concentration is the molecular structure of the molecular weight of the imide group (— (CO) 2 —N—) in the molecular structure. The value obtained by dividing by the total molecular weight.
ポリイミド層を複数層とする場合、線膨張係数（CTE）が３０×１０-6[１／Ｋ]以下、好ましくは１×１０-6〜３０×１０-6[１／Ｋ]の範囲の低線膨張係数の樹脂層を主たるポリイミド層（ii）とし、その片面又は両面にポリイミド樹脂層（ｉ）を設けることが好ましい。 When multiple polyimide layers are used, the coefficient of linear expansion (CTE) is as low as 30 × 10 −6 [1 / K] or less, preferably in the range of 1 × 10 −6 to 30 × 10 −6 [1 / K]. It is preferable that the resin layer having a linear expansion coefficient is the main polyimide layer (ii), and the polyimide resin layer (i) is provided on one side or both sides thereof.
ポリイミド層（ｉ）は、吸湿率が１．０％以下であり、イミド基濃度が３３％以下である要件を充足する他、線膨張係数（CTE）が３０×１０-6[１／Ｋ]を超え、ガラス転移温度が３３０℃以下にあるものを用いることがより好ましい。好ましいポリイミド層（ｉ）の線膨張係数は、３０×１０-6〜６０×１０-6[１／Ｋ]で、ガラス転移温度が２００〜３３０℃の範囲にあるものである。ポリイミド層（ii）のCTEが３０×１０-6／Ｋより大きいと、銅張積層板を形成した際のカールが激しくなるおそれがあり、また、寸法安定性が低下するため製品として好ましくない。ポリイミド層（ii）の厚みは、全ポリイミド層の厚みの５０％以上、好ましくは７０〜９５％であることがよい。 The polyimide layer (i) satisfies the requirements that the moisture absorption is 1.0% or less and the imide group concentration is 33% or less, and the linear expansion coefficient (CTE) is 30 × 10 −6 [1 / K]. It is more preferable to use those having a glass transition temperature of 330 ° C. or lower. A preferred polyimide layer (i) has a linear expansion coefficient of 30 × 10 −6 to 60 × 10 −6 [1 / K] and a glass transition temperature in the range of 200 to 330 ° C. When the CTE of the polyimide layer (ii) is larger than 30 × 10 −6 / K, curling when forming a copper-clad laminate may be severe, and the dimensional stability is lowered, which is not preferable as a product. The thickness of the polyimide layer (ii) is 50% or more, preferably 70 to 95% of the thickness of the entire polyimide layer.
ポリイミド層（ｉ）としては、吸湿率を下げるためにエーテル構造やカルボニル構造を持たない構造のモノマーを選択すること、またイミド基濃度を下げるために分子量の大きいモノマーを選択することが望ましい。例えば、吸湿率を下げるために、エーテル構造やカルボニル構造を持たない3,3', 4,4'−ビフェニルテトラカルボン酸二無水物（ＢＰＤＡ）を用いたり、その他、エステル構造、プロプリデン構造を持つモノマーを選択したり、イミド基濃度を下げるために2,2'−ジメチル−4,4'−ジアミノビフェニル（ｍ−ＴＢ）、2,2-ビス[4-（4-アミノフェノキシ）フェニル]プロパン（ＢＡＰＰ）を用いたり、その他、プロプリデン構造を持つモノマーを選択することで、吸湿率１．０％以下であり、イミド基濃度が３３％以下の特徴を持つポリイミドを得ることができる。 As the polyimide layer (i), it is desirable to select a monomer having a structure not having an ether structure or a carbonyl structure in order to lower the moisture absorption rate, and to select a monomer having a large molecular weight in order to lower the imide group concentration. For example, in order to reduce the moisture absorption rate, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) having no ether structure or carbonyl structure is used, or in addition, an ester structure or propylidene structure is used. 2,2'-dimethyl-4,4'-diaminobiphenyl (m-TB), 2,2-bis [4- (4-aminophenoxy) phenyl] propane for selecting monomers and reducing imide group concentration By using (BAPP) or by selecting a monomer having a proprylene structure, a polyimide having characteristics of a moisture absorption rate of 1.0% or less and an imide group concentration of 33% or less can be obtained.
ポリイミド層を形成する方法については特に限定されないが、例えば、ポリイミドの前駆体であるポリアミド酸の樹脂溶液を、表面処理された銅箔表面に直接塗布し、樹脂溶液に含まれる溶剤を１５０℃以下の温度である程度除去した後、更に、１００〜４５０℃、好ましくは３００〜４５０℃の温度範囲で５〜４０分間程度の熱処理を行って、溶媒の乾燥及びイミド化を行うことがよい。２層以上にポリイミド樹脂層を設ける場合は、第一のポリアミド酸の樹脂溶液を塗布、乾燥したのち、第二のポリアミド酸の樹脂溶液を塗布、乾燥し、以下同様にして第三以下のポリアミド酸の樹脂溶液を順次、塗布、乾燥したのち、まとめて３００〜４５０℃の温度範囲で５〜４０分間程度の熱処理を行って、イミド化を行うことがよい。熱処理の温度が１００℃より低いとポリイミドの脱水閉環反応が十分に進行せず、反対に４５０℃を超えると、ポリイミド樹脂層及び銅箔が酸化等により劣化するおそれがある。 The method for forming the polyimide layer is not particularly limited. For example, a polyamide acid resin solution, which is a polyimide precursor, is directly applied to the surface of the surface-treated copper foil, and the solvent contained in the resin solution is 150 ° C. or less. After removing to some extent at this temperature, it is preferable to further perform drying and imidization of the solvent by performing a heat treatment at 100 to 450 ° C., preferably 300 to 450 ° C. for about 5 to 40 minutes. When two or more polyimide resin layers are provided, the first polyamic acid resin solution is applied and dried, then the second polyamic acid resin solution is applied and dried. It is preferable to perform imidization by sequentially applying and drying the acid resin solution and then performing heat treatment at a temperature range of 300 to 450 ° C. for about 5 to 40 minutes. If the temperature of the heat treatment is lower than 100 ° C, the dehydration ring-closing reaction of polyimide does not proceed sufficiently. Conversely, if it exceeds 450 ° C, the polyimide resin layer and the copper foil may be deteriorated due to oxidation or the like.
ポリイミド層の厚さは、６〜４５μｍの範囲であるのがよく、好ましくは９〜４０μｍの範囲である。絶縁層の厚みが６μｍに満たないと、銅張積層板製造等における搬送時にシワが入るなどの不具合が生じるおそれがあり、反対に４５μｍを超えると銅張り積層板の製造時の寸法安定性や屈曲性等において問題が生じるおそれがある。なお、複数層からポリイミド層を形成する場合には、その合計の厚みが上記範囲内になるようにすればよい。 The thickness of the polyimide layer may be in the range of 6 to 45 μm, and preferably in the range of 9 to 40 μm. If the thickness of the insulating layer is less than 6 μm, there is a risk of problems such as wrinkling during transportation in the manufacture of copper-clad laminates, and conversely, if it exceeds 45 μm, dimensional stability during production of copper-clad laminates and There is a risk of problems in flexibility and the like. In addition, what is necessary is just to make it the total thickness in the said range, when forming a polyimide layer from multiple layers.
本発明のフレキシブル銅張積層板は、ポリイミド層の片面側のみに銅箔を備えた片面銅張積層板であってもよいことはもちろんのこと、ポリイミド樹脂層の両面に銅箔を備えた両面銅張積層板でもよい。なお、両面銅張積層板を得るためには、片面銅張積層板を形成した後、互いにポリイミド樹脂層を向き合わせて熱プレスによって圧着し形成することや、片面銅張積層板のポリイミド樹脂層に銅箔を圧着し形成すること等により得ることができる。 The flexible copper-clad laminate of the present invention may be a single-sided copper-clad laminate having a copper foil only on one side of the polyimide layer, as well as both sides having a copper foil on both sides of the polyimide resin layer. A copper-clad laminate may also be used. In addition, in order to obtain a double-sided copper-clad laminate, after forming a single-sided copper-clad laminate, the polyimide resin layers are faced to each other and bonded by hot pressing, or a polyimide resin layer of a single-sided copper-clad laminate It can be obtained by pressure-bonding and forming a copper foil.
以下、実施例等に基づき、本発明の内容をより具体的に説明する。なお、実施例等における各種測定は次のようにして行った。 Hereinafter, based on an example etc., the contents of the present invention are explained more concretely. Various measurements in Examples and the like were performed as follows.
［誘電率、誘電正接の測定］
空洞共振器摂動法誘電率評価装置（商品名、ベクトルネットワークアナライザ）を用い、次に示す条件にて、実施例等で形成したポリイミド層からなる硬化樹脂シートの誘電率および誘電正接を測定した。
測定周波数：１GHｚ
測定温度：２４℃〜２６℃
測定湿度：４５％〜５５％
測定試料：上記測定温度・測定湿度条件下で、２４時間放置した硬化樹脂シート
[Measurement of dielectric constant and dissipation factor]
Using a cavity resonator perturbation method dielectric constant evaluation apparatus (trade name, vector network analyzer), the dielectric constant and dielectric loss tangent of a cured resin sheet made of a polyimide layer formed in Examples and the like were measured under the following conditions.
Measurement frequency: 1 GHz
Measurement temperature: 24 ° C to 26 ° C
Measurement humidity: 45% to 55%
Measurement sample: cured resin sheet left for 24 hours under the measurement temperature and humidity conditions described above
［吸湿率の測定］
実施例等で形成したポリイミド層からなるポリイミドフィルム（４ｃｍ×２０ｃｍ）を１２０℃で２時間乾燥した後、２３℃／５０％RHの恒温恒湿機で２４時間静置し、その前後の重量変化から次式により求めた。
吸湿率（％）＝[（吸湿後重量−乾燥後重量）／乾燥後重量]×１００
[Measurement of moisture absorption rate]
A polyimide film (4 cm × 20 cm) composed of a polyimide layer formed in Examples and the like was dried at 120 ° C. for 2 hours, and then left standing for 24 hours in a constant temperature and humidity chamber of 23 ° C./50% RH. From the following equation.
Moisture absorption rate (%) = [(weight after moisture absorption−weight after drying) / weight after drying] × 100
合成例１
熱電対及び攪拌機を備えると共に窒素導入が可能な反応容器に、N,N−ジメチルアセトアミドを入れた。この反応容器に2,2-ビス[4-（4-アミノフェノキシ）フェニル]プロパン（ＢＡＰＰ）を容器中で撹拌しながら溶解させた。次に、ピロメリット酸二無水物（ＰＭＤＡ）を加えた。モノマーの投入総量が１５ｗｔ％となるように投入した。その後、３時間撹拌を続け、ポリアミド酸ａの樹脂溶液を得た。ポリアミド酸ａの樹脂溶液の溶液粘度は３,０００cpsであった。
Synthesis example 1
N, N-dimethylacetamide was placed in a reaction vessel equipped with a thermocouple and a stirrer and capable of introducing nitrogen. 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP) was dissolved in the reaction vessel with stirring. Next, pyromellitic dianhydride (PMDA) was added. The total amount of monomers charged was 15 wt%. Thereafter, stirring was continued for 3 hours to obtain a resin solution of polyamic acid a. The solution viscosity of the polyamic acid a resin solution was 3,000 cps.
合成例２
熱電対及び攪拌機を備えると共に窒素導入が可能な反応容器に、N,N−ジメチルアセトアミドを入れた。この反応容器に2,2-ビス[4-（4-アミノフェノキシ）フェニル]プロパン（ＢＡＰＰ）および1,3-ビス（4-アミノフェノキシ）ベンゼン（ＴＰＥ−Ｒ）を加えた。各ジアミンのモル比率（ＢＡＰＰ：ＴＰＥ−Ｒ）が５０：５０となるように投入した。次にピロメリット酸二無水物（ＰＭＤＡ）を加え、モノマーの投入総量が１２ｗｔ％となるようにした。その後、３時間撹拌を続け、ポリアミド酸ｂの樹脂溶液を得た。ポリアミド酸ｂの樹脂溶液の溶液粘度は３,０００cpsであった。
Synthesis example 2
N, N-dimethylacetamide was placed in a reaction vessel equipped with a thermocouple and a stirrer and capable of introducing nitrogen. 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP) and 1,3-bis (4-aminophenoxy) benzene (TPE-R) were added to the reaction vessel. It charged so that the molar ratio (BAPP: TPE-R) of each diamine might be set to 50:50. Next, pyromellitic dianhydride (PMDA) was added so that the total amount of monomer was 12 wt%. Thereafter, stirring was continued for 3 hours to obtain a resin solution of polyamic acid b. The solution viscosity of the polyamic acid b resin solution was 3,000 cps.
合成例３
熱電対及び攪拌機を備えると共に窒素導入が可能な反応容器に、N,N−ジメチルアセトアミドを入れた。この反応容器にジアミノジフェニルエーテル（ＤＡＰＥ）を加えた。次に3,3',4,4'-ベンゾフェノンテトラカルボン酸二無水物（ＢＴＤＡ）を加え、モノマーの投入総量が１２ｗｔ％となるようにした。その後、３時間撹拌を続け、ポリアミド酸ｃの樹脂溶液を得た。ポリアミド酸ｃの樹脂溶液の溶液粘度は３,０００cpsであった。
Synthesis example 3
N, N-dimethylacetamide was placed in a reaction vessel equipped with a thermocouple and a stirrer and capable of introducing nitrogen. Diaminodiphenyl ether (DAPE) was added to the reaction vessel. Next, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (BTDA) was added so that the total amount of monomer was 12 wt%. Thereafter, stirring was continued for 3 hours to obtain a resin solution of polyamic acid c. The solution viscosity of the polyamic acid c resin solution was 3,000 cps.
合成例４
熱電対及び攪拌機を備えると共に窒素導入が可能な反応容器に、N,N−ジメチルアセトアミドを入れた。この反応容器に2,2'−ジメチル−4,4'−ジアミノビフェニル（ｍ−ＴＢ）を投入した。次に3,3', 4,4'−ビフェニルテトラカルボン酸二無水物（ＢＰＤＡ）およびピロメリット酸二無水物（ＰＭＤＡ）を加えた。モノマーの投入総量が１５ｗｔ％で、各酸無水物のモル比率（ＢＰＤＡ：ＰＭＤＡ）が２０：８０となるように投入した。その後、３時間撹拌を続け、ポリアミド酸の樹脂溶液ｄを得た。ポリアミド酸ｄの樹脂溶液の溶液粘度は２０,０００cpsであった。
Synthesis example 4
N, N-dimethylacetamide was placed in a reaction vessel equipped with a thermocouple and a stirrer and capable of introducing nitrogen. 2,2′-Dimethyl-4,4′-diaminobiphenyl (m-TB) was charged into the reaction vessel. Then 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) and pyromellitic dianhydride (PMDA) were added. The total amount of monomers charged was 15 wt%, and the molar ratio of each acid anhydride (BPDA: PMDA) was 20:80. Thereafter, stirring was continued for 3 hours to obtain a resin solution d of polyamic acid. The solution viscosity of the polyamic acid d resin solution was 20,000 cps.
表面粗度Ｒｚが０．６μｍで、無粗化の電解銅箔（厚み12μｍ）を準備し、その表面にニッケル＋亜鉛から成る金属処理層とクロメート処理層を形成した後、N-2-（アミノエチル）γ-アミノプロピルトリメトキシシラン処理によるシランカップリング剤処理層を形成した。この銅箔上に、合成例１で調製したポリアミド酸a、合成例４で調製したポリアミド酸d、及び合成例１で調製したポリアミド酸aの樹脂溶液を順次塗布し、乾燥後、最終的に３００℃以上約１０分で熱処理を行い、ポリイミド層の厚みが２５μｍのフレキシブル片面銅張積層板を得た。なお、ポリイミド層のうち、合成例１のポリアミド酸aの樹脂溶液から得られた層は各２μｍであり、合成例４ポリアミド酸ｄの樹脂溶液から得られた層は２１μｍであった。銅箔に接する合成例１からなるポリイミド層の吸湿率は０．５％であり、また、イミド基濃度は２３．６％であった。更には、銅箔に接する面のポリイミド表面の誘電率は３．２５、誘電正接は０．００２２であった。 After preparing a non-roughened electrolytic copper foil (thickness 12 μm) with a surface roughness Rz of 0.6 μm, and forming a metal treatment layer and a chromate treatment layer made of nickel + zinc on its surface, N-2- ( A silane coupling agent-treated layer was formed by treatment with (aminoethyl) γ-aminopropyltrimethoxysilane. On this copper foil, the polyamic acid a prepared in Synthesis Example 1, the polyamic acid d prepared in Synthetic Example 4 and the polyamic acid a prepared in Synthetic Example 1 were sequentially applied, dried, and finally Heat treatment was performed at 300 ° C. or more for about 10 minutes to obtain a flexible single-sided copper-clad laminate having a polyimide layer thickness of 25 μm. Of the polyimide layers, the layers obtained from the polyamic acid a resin solution of Synthesis Example 1 were each 2 μm, and the layers obtained from the Synthesis Example 4 polyamic acid d resin solution were 21 μm. The moisture absorption rate of the polyimide layer made of Synthesis Example 1 in contact with the copper foil was 0.5%, and the imide group concentration was 23.6%. Furthermore, the dielectric constant of the polyimide surface on the surface in contact with the copper foil was 3.25, and the dielectric loss tangent was 0.0022.
表面粗度Ｒｚが０．７μｍであること以外は実施例１と同じ無粗化電解銅箔（厚み12μｍ）を準備した（金属処理層、クロメート処理層及びシランカップリング処理層の形成についても実施例１と同様）。この銅箔上に、合成例１で調製したポリアミド酸a、合成例４で調製したポリアミド酸ｄ、及び合成例１で調製したポリアミド酸aの樹脂溶液を順次塗布し、乾燥後、最終的に３００℃以上約１０分で熱処理を行い、ポリイミド樹脂層の厚みが２５μｍのフレキシブル片面銅張積層板を得た。なお、ポリイミド樹脂層のうち、合成例１のポリアミド酸aの樹脂溶液から得られた層は各２μｍであり、合成例４のポリアミド酸dの樹脂溶液から得られた層は２１μｍであった。銅箔に接する合成例１からなるポリイミド層の吸湿率は０．５％であり、また、イミド基濃度は２３．６％であった。更には、銅箔に接する面のポリイミド表面の誘電率は３．２３であり、誘電正接は０．００２４であった。 The same non-roughened electrolytic copper foil (thickness 12 μm) as in Example 1 was prepared except that the surface roughness Rz was 0.7 μm (also carried out for the formation of the metal treatment layer, chromate treatment layer and silane coupling treatment layer). Same as Example 1). On this copper foil, the polyamic acid a prepared in Synthesis Example 1, the polyamic acid d prepared in Synthetic Example 4 and the polyamic acid a prepared in Synthetic Example 1 were sequentially applied, dried, and finally Heat treatment was performed at 300 ° C. or more for about 10 minutes to obtain a flexible single-sided copper-clad laminate having a polyimide resin layer thickness of 25 μm. Of the polyimide resin layers, the layers obtained from the polyamide acid a resin solution of Synthesis Example 1 were each 2 μm, and the layers obtained from the polyamide acid d resin solution of Synthesis Example 4 were 21 μm. The moisture absorption rate of the polyimide layer made of Synthesis Example 1 in contact with the copper foil was 0.5%, and the imide group concentration was 23.6%. Furthermore, the dielectric constant of the polyimide surface on the surface in contact with the copper foil was 3.23, and the dielectric loss tangent was 0.0024.
表面粗度Ｒｚが０．６μｍの無粗化圧延銅箔（厚み12μｍ）を準備し、その表面にニッケル＋亜鉛から成る金属処理層とクロメート処理層を形成し、N-2-（アミノエチル）γ-アミノプロピルトリメトキシシラン処理によるシランカップリング剤処理層を形成した。この銅箔上に、合成例２で調製したポリアミド酸ｂ、合成例４で調製したポリアミド酸ｄ、及び合成例１で調製したポリアミド酸aの樹脂溶液を順次塗布し、乾燥後、最終的に３００℃以上約１０分で熱処理を行い、ポリイミド樹脂層の厚みが２５μｍのフレキシブル片面銅張積層板を得た。なお、ポリイミド樹脂層のうち、合成例２のポリアミド酸bの樹脂溶液から得られた層は２μｍであり、合成例４のポリアミド酸dの樹脂溶液から得られた層は２１μｍであり、合成例１のポリアミド酸aの樹脂溶液から得られた層は２μｍであった。銅箔に接する合成例２からなるポリイミド層の吸湿率は０．４％であり、また、イミド基濃度は２６．３％であった。更には、銅箔に接する面のポリイミド表面の誘電率は３．２８、誘電正接は０．００２１であった。 A non-roughened rolled copper foil (thickness 12 μm) with a surface roughness Rz of 0.6 μm was prepared, and a metal treatment layer and a chromate treatment layer composed of nickel + zinc were formed on the surface, N-2- (aminoethyl) A silane coupling agent-treated layer was formed by γ-aminopropyltrimethoxysilane treatment. On this copper foil, the polyamic acid b prepared in Synthesis Example 2, the polyamic acid d prepared in Synthetic Example 4 and the polyamic acid a prepared in Synthetic Example 1 were sequentially applied, dried, and finally Heat treatment was performed at 300 ° C. or more for about 10 minutes to obtain a flexible single-sided copper-clad laminate having a polyimide resin layer thickness of 25 μm. Of the polyimide resin layers, the layer obtained from the polyamide acid b resin solution of Synthesis Example 2 is 2 μm, and the layer obtained from the polyamide acid d resin solution of Synthesis Example 4 is 21 μm. The layer obtained from the polyamic acid a resin solution of 1 was 2 μm. The moisture absorption rate of the polyimide layer made of Synthesis Example 2 in contact with the copper foil was 0.4%, and the imide group concentration was 26.3%. Furthermore, the dielectric constant of the polyimide surface on the surface in contact with the copper foil was 3.28, and the dielectric loss tangent was 0.0021.
［比較例１］
表面粗度Ｒｚが２．１μｍの粗化電解箔（厚み12μｍ）を準備しその表面にニッケル＋亜鉛から成る金属処理層とクロメート処理層を形成し、N-2-（アミノエチル）γ-アミノプロピルトリメトキシシラン処理によるシランカップリング剤処理層を形成した。この銅箔上に、合成例１で調製したポリアミド酸a、合成例４で調製したポリアミド酸ｄ、及び合成例１で調製したポリアミド酸aの樹脂溶液を順次塗布し、乾燥後、最終的に３００℃以上約１０分で熱処理を行い、ポリイミド樹脂層の厚みが２５μｍのフレキシブル片面銅張積層板を得た。なお、ポリイミド樹脂層のうち、合成例１のポリアミド酸の樹脂溶液から得られた層は各２μｍであり、合成例４のポリアミド酸の樹脂溶液から得られた層は２１μｍであった。銅箔に接する合成例１からなるポリイミド層の吸湿率は０．５％であり、また、イミド基濃度は２３．６％であった。更には、銅箔に接する面のポリイミド表面の誘電率は２．９７、誘電正接は０．００３５であった。
[Comparative Example 1]
A roughened electrolytic foil (thickness 12 μm) having a surface roughness Rz of 2.1 μm was prepared, and a metal treatment layer made of nickel + zinc and a chromate treatment layer were formed on the surface. N-2- (aminoethyl) γ-amino A silane coupling agent treatment layer was formed by propyltrimethoxysilane treatment. On this copper foil, the polyamic acid a prepared in Synthesis Example 1, the polyamic acid d prepared in Synthetic Example 4 and the polyamic acid a prepared in Synthetic Example 1 were sequentially applied, dried, and finally Heat treatment was performed at 300 ° C. or more for about 10 minutes to obtain a flexible single-sided copper-clad laminate having a polyimide resin layer thickness of 25 μm. Of the polyimide resin layers, the layers obtained from the polyamic acid resin solution of Synthesis Example 1 were each 2 μm, and the layers obtained from the polyamic acid resin solution of Synthesis Example 4 were 21 μm. The moisture absorption rate of the polyimide layer made of Synthesis Example 1 in contact with the copper foil was 0.5%, and the imide group concentration was 23.6%. Furthermore, the dielectric constant of the polyimide surface on the surface in contact with the copper foil was 2.97, and the dielectric loss tangent was 0.0035.
［比較例２］
表面粗度Ｒｚが１．８μｍの粗化電解箔（厚み12μｍ）を準備しその表面にニッケル＋亜鉛から成る金属処理層とクロメート処理層を形成し、N-2-（アミノエチル）γ-アミノプロピルトリメトキシシラン処理層を形成した。この銅箔上に、合成例１で調製したポリアミド酸a、合成例４で調製したポリアミド酸d、及び合成例１で調製したポリアミド酸aの樹脂溶液を順次塗布し、乾燥後、最終的に３００℃以上約１０分で熱処理を行い、ポリイミド層の厚みが２５μｍのフレキシブル片面銅張積層板を得た。なお、ポリイミド層のうち、合成例１のポリアミド酸の樹脂溶液から得られた層は各２μｍであり、合成例４のポリアミド酸の樹脂溶液から得られた層は２１μｍであった。銅箔に接する合成例１からなるポリイミド層の吸湿率は０．５％であり、また、イミド基濃度は２３．６％であった。更には、銅箔に接する面のポリイミド表面の誘電率は３．１１、誘電正接は０．００２８であった。
[Comparative Example 2]
A roughened electrolytic foil (thickness 12 μm) having a surface roughness Rz of 1.8 μm was prepared, and a metal treatment layer made of nickel + zinc and a chromate treatment layer were formed on the surface. N-2- (aminoethyl) γ-amino A propyltrimethoxysilane-treated layer was formed. On this copper foil, the polyamic acid a prepared in Synthesis Example 1, the polyamic acid d prepared in Synthetic Example 4 and the polyamic acid a prepared in Synthetic Example 1 were sequentially applied, dried, and finally Heat treatment was performed at 300 ° C. or more for about 10 minutes to obtain a flexible single-sided copper-clad laminate having a polyimide layer thickness of 25 μm. Of the polyimide layers, the layers obtained from the polyamic acid resin solution of Synthesis Example 1 were each 2 μm, and the layers obtained from the polyamic acid resin solution of Synthesis Example 4 were 21 μm. The moisture absorption rate of the polyimide layer made of Synthesis Example 1 in contact with the copper foil was 0.5%, and the imide group concentration was 23.6%. Furthermore, the dielectric constant of the polyimide surface on the surface in contact with the copper foil was 3.11, and the dielectric loss tangent was 0.0028.
［比較例３］
表面粗度Ｒｚが０．９μｍの粗化圧延箔（厚み12μｍ）を準備しその表面にニッケル＋亜鉛から成る表面処理層とクロメート処理層を形成し、N-2-（アミノエチル）γ-アミノプロピルトリメトキシシラン処理によるシランカップリング剤処理層を形成した。この銅箔上に、合成例３で調製したポリアミド酸c、合成例４で調製したポリアミド酸d、及び合成例１で調製したポリアミド酸aの樹脂溶液を順次塗布し、乾燥後、最終的に３００℃以上約１０分で熱処理を行い、ポリイミド層の厚みが２５μｍのフレキシブル片面銅張積層板を得た。なお、ポリイミド層のうち、合成例３のポリアミド酸の樹脂溶液から得られた層は２μｍであり、合成例４のポリアミド酸の樹脂溶液から得られた層は２１μｍであり、合成例１のポリアミド酸の樹脂溶液から得られた層は２μｍであった。銅箔に接する合成例３からなるポリイミド層の吸湿率は１．３％であり、また、イミド基濃度は２８．８％であった。更には、銅箔に接する面のポリイミド表面の誘電率は３．６２、誘電正接は０．０１２２であった。
[Comparative Example 3]
A roughened rolled foil (thickness 12 μm) having a surface roughness Rz of 0.9 μm was prepared, and a surface treatment layer made of nickel + zinc and a chromate treatment layer were formed on the surface, and N-2- (aminoethyl) γ-amino was formed. A silane coupling agent treatment layer was formed by propyltrimethoxysilane treatment. On this copper foil, the polyamic acid c prepared in Synthesis Example 3, the polyamic acid d prepared in Synthesis Example 4 and the polyamic acid a prepared in Synthesis Example 1 were sequentially applied, dried, and finally Heat treatment was performed at 300 ° C. or more for about 10 minutes to obtain a flexible single-sided copper-clad laminate having a polyimide layer thickness of 25 μm. Of the polyimide layers, the layer obtained from the polyamic acid resin solution of Synthesis Example 3 is 2 μm, the layer obtained from the polyamic acid resin solution of Synthesis Example 4 is 21 μm, and the polyamide of Synthesis Example 1 The layer obtained from the acid resin solution was 2 μm. The moisture absorption of the polyimide layer made of Synthesis Example 3 in contact with the copper foil was 1.3%, and the imide group concentration was 28.8%. Furthermore, the dielectric constant of the polyimide surface on the surface in contact with the copper foil was 3.62, and the dielectric loss tangent was 0.0122.
［比較例４］
表面粗度Ｒｚが０．６μｍの無粗化電解箔（厚み12μｍ）を準備しその表面にニッケル＋亜鉛から成る表面処理層とクロメート処理層を形成し、N-2-（アミノエチル）γ-アミノプロピルトリメトキシシラン処理によるシランカップリング剤処理層を形成した。この銅箔上に、合成例４で調製したポリアミド酸ｄ、及び合成例１で調製したポリアミド酸aの樹脂溶液を順次塗布し、乾燥後、最終的に３００℃以上約１０分で熱処理を行い、ポリイミド層の厚みが２５μｍのフレキシブル片面銅張積層板を得た。なお、ポリイミド層のうち、合成例４のポリアミド酸の樹脂溶液から得られた層は２３μｍであり、合成例１のポリアミド酸の樹脂溶液から得られた層は２μｍであった。銅箔に接する合成例４からなるポリイミド層の吸湿率は０．９％であり、また、イミド基濃度は３４．２％であった。更には、銅箔に接する面のポリイミド表面の誘電率は３．３８、誘電正接は０．００３２であった。
[Comparative Example 4]
A non-roughened electrolytic foil (thickness 12 μm) having a surface roughness Rz of 0.6 μm was prepared, and a surface treatment layer made of nickel + zinc and a chromate treatment layer were formed on the surface, and N-2- (aminoethyl) γ- A silane coupling agent treatment layer was formed by aminopropyltrimethoxysilane treatment. On this copper foil, the polyamic acid d prepared in Synthesis Example 4 and the polyamic acid a resin prepared in Synthesis Example 1 are sequentially applied, dried, and finally heat treated at 300 ° C. or more for about 10 minutes. A flexible single-sided copper-clad laminate with a polyimide layer thickness of 25 μm was obtained. Of the polyimide layers, the layer obtained from the polyamic acid resin solution of Synthesis Example 4 was 23 μm, and the layer obtained from the polyamic acid resin solution of Synthesis Example 1 was 2 μm. The moisture absorption rate of the polyimide layer made of Synthesis Example 4 in contact with the copper foil was 0.9%, and the imide group concentration was 34.2%. Furthermore, the dielectric constant of the polyimide surface on the surface in contact with the copper foil was 3.38, and the dielectric loss tangent was 0.0032.
上記実施例及び比較例で得られた銅張積層板についての結果（表１）から明らかなように、無粗化電解箔または圧延箔であって、銅箔の表面粗度がＲｚ１．０μｍ以下である銅箔と吸湿率が１．０％もしくはイミド基濃度が３３％以下であることを特徴とするポリイミド樹脂からなるポリイミド層とを組み合わせることによって、表面の平滑性と樹脂の低吸湿性の効果により、ＧＨｚ帯域でも低誘電率かつ低誘電正接を示し十分な誘電特性も発揮することができる。そのため、フレキシブルプリント配線板やビルドアップ回路基板等の回路基板の製造等に好適に用いることができる。 As is clear from the results (Table 1) for the copper clad laminates obtained in the above examples and comparative examples, the surface roughness of the copper foil is Rz 1.0 μm or less, which is a non-roughened electrolytic foil or a rolled foil. By combining a copper foil and a polyimide layer made of a polyimide resin characterized by having a moisture absorption rate of 1.0% or an imide group concentration of 33% or less, surface smoothness and low hygroscopicity of the resin Due to the effect, even in the GHz band, a low dielectric constant and a low dielectric loss tangent can be exhibited and sufficient dielectric properties can be exhibited. Therefore, it can be suitably used for manufacturing circuit boards such as flexible printed wiring boards and build-up circuit boards.
なお本発明は、以上説示した各構成に限定されるものではなく、特許請求の範囲に示した範囲で種々の変更が可能であり、異なる実施形態や実施例にそれぞれ開示された技術的手段を適宜組み合わせて得られる実施形態についても本発明の技術的範囲に含まれる。 Note that the present invention is not limited to the configurations described above, and various modifications are possible within the scope of the claims, and technical means disclosed in different embodiments and examples respectively. Embodiments obtained by appropriate combinations are also included in the technical scope of the present invention.
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| JP2016193501A (en) * | 2015-03-31 | 2016-11-17 | 新日鉄住金化学株式会社 | Copper-clad laminate and printed wiring board |
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| JP2015127117A (en) * | 2013-12-27 | 2015-07-09 | 新日鉄住金化学株式会社 | Metal-clad laminate and circuit board |
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| JP2000080165A (en) * | 1998-09-02 | 2000-03-21 | Du Pont Toray Co Ltd | Copolyimide film, preparation thereof and metallic wiring board using same as substrate material |
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| JP4757666B2 (en) * | 2005-03-14 | 2011-08-24 | 新日鐵化学株式会社 | Copper-clad laminate |
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| JP2016193501A (en) * | 2015-03-31 | 2016-11-17 | 新日鉄住金化学株式会社 | Copper-clad laminate and printed wiring board |
| US10844175B2 (en) | 2016-03-17 | 2020-11-24 | Nippon Steel Chemical & Material Co., Ltd. | Polyamide acid, thermoplastic polyimide, resin film, metal-clad laminate and circuit board |
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