JP2017119361A - Copper foil with resin, copper-clad laminate, printed wiring board and multilayer wiring board - Google Patents
Copper foil with resin, copper-clad laminate, printed wiring board and multilayer wiring board Download PDFInfo
- Publication number
- JP2017119361A JP2017119361A JP2015255911A JP2015255911A JP2017119361A JP 2017119361 A JP2017119361 A JP 2017119361A JP 2015255911 A JP2015255911 A JP 2015255911A JP 2015255911 A JP2015255911 A JP 2015255911A JP 2017119361 A JP2017119361 A JP 2017119361A
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- JP
- Japan
- Prior art keywords
- resin
- copper foil
- bis
- wiring board
- component
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229920005989 resin Polymers 0.000 title claims abstract description 53
- 239000011347 resin Substances 0.000 title claims abstract description 53
- 239000011889 copper foil Substances 0.000 title claims abstract description 48
- -1 aromatic tetracarboxylic acid Chemical class 0.000 claims abstract description 45
- 229920001721 polyimide Polymers 0.000 claims abstract description 28
- 239000009719 polyimide resin Substances 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 239000011342 resin composition Substances 0.000 claims abstract description 19
- 150000004985 diamines Chemical class 0.000 claims abstract description 17
- 239000000539 dimer Substances 0.000 claims abstract description 11
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 6
- 229920000647 polyepoxide Polymers 0.000 claims description 33
- 239000003822 epoxy resin Substances 0.000 claims description 32
- 229910052802 copper Inorganic materials 0.000 claims description 13
- 239000010949 copper Substances 0.000 claims description 13
- 239000004643 cyanate ester Substances 0.000 claims description 9
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims description 7
- 229920003192 poly(bis maleimide) Polymers 0.000 claims description 6
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 3
- 239000010410 layer Substances 0.000 abstract description 9
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 239000011229 interlayer Substances 0.000 abstract description 3
- 238000005476 soldering Methods 0.000 abstract description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 30
- 239000000243 solution Substances 0.000 description 28
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 24
- 238000004519 manufacturing process Methods 0.000 description 24
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 22
- 239000002253 acid Substances 0.000 description 14
- 239000012790 adhesive layer Substances 0.000 description 13
- 150000001412 amines Chemical class 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 12
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 10
- 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 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 8
- 239000004205 dimethyl polysiloxane Substances 0.000 description 7
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 5
- 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 4
- MQAHXEQUBNDFGI-UHFFFAOYSA-N 5-[4-[2-[4-[(1,3-dioxo-2-benzofuran-5-yl)oxy]phenyl]propan-2-yl]phenoxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC2=CC=C(C=C2)C(C)(C=2C=CC(OC=3C=C4C(=O)OC(=O)C4=CC=3)=CC=2)C)=C1 MQAHXEQUBNDFGI-UHFFFAOYSA-N 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- MXPYJVUYLVNEBB-UHFFFAOYSA-N 2-[2-(2-carboxybenzoyl)oxycarbonylbenzoyl]oxycarbonylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)OC(=O)C1=CC=CC=C1C(=O)OC(=O)C1=CC=CC=C1C(O)=O MXPYJVUYLVNEBB-UHFFFAOYSA-N 0.000 description 3
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 3
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- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- KZTYYGOKRVBIMI-UHFFFAOYSA-N S-phenyl benzenesulfonothioate Natural products C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000007809 chemical reaction catalyst Substances 0.000 description 3
- 239000011162 core material Substances 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
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- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 3
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- SZUPZARBRLCVCB-UHFFFAOYSA-N 3-(2-undecylimidazol-1-yl)propanenitrile Chemical compound CCCCCCCCCCCC1=NC=CN1CCC#N SZUPZARBRLCVCB-UHFFFAOYSA-N 0.000 description 2
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 2
- NYRFBMFAUFUULG-UHFFFAOYSA-N 3-[4-[2-[4-(3-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=C(N)C=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=CC(N)=C1 NYRFBMFAUFUULG-UHFFFAOYSA-N 0.000 description 2
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- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- IMYZQPCYWPFTAG-UHFFFAOYSA-N Mecamylamine Chemical compound C1CC2C(C)(C)C(NC)(C)C1C2 IMYZQPCYWPFTAG-UHFFFAOYSA-N 0.000 description 2
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Landscapes
- Laminated Bodies (AREA)
Abstract
Description
本発明は、樹脂付銅箔、銅張積層板、プリント配線板及び多層配線板に関する。 The present invention relates to a resin-coated copper foil, a copper-clad laminate, a printed wiring board, and a multilayer wiring board.
樹脂付銅箔(RCCF:resin coated copper foil)とは、銅箔の片面に絶縁性樹脂を含む組成物からなる接着層を設けた複合フィルムであり、銅張積層板、プリント配線板及び多層配線板(ビルドアップ基板)を製造するための基本材料とされる。 Resin coated copper foil (RCCF) is a composite film in which an adhesive layer made of a composition containing an insulating resin is provided on one side of a copper foil. It is a copper-clad laminate, printed wiring board, and multilayer wiring. It is considered as a basic material for manufacturing a plate (build-up substrate).
樹脂付銅箔には、常温での接着層の引き剥がし強さや、はんだ付温度における層間密着性が要求される。そのような樹脂付銅箔としては、例えば、接着層としてエポキシ樹脂配合物、マレイミド化合物及び両者と反応可能な芳香族ポリマーを含む組成物を使用したもの(特許文献1)や、カルボキシル基含有ニトリルブタジエンゴムを含む組成物を使用したもの(特許文献2)、ポリアミドイミド樹脂を含む組成物を使用したもの(特許文献3)等が公知である The resin-coated copper foil is required to have a peel strength of the adhesive layer at room temperature and interlayer adhesion at a soldering temperature. As such a resin-coated copper foil, for example, an adhesive layer using an epoxy resin compound, a maleimide compound and a composition containing an aromatic polymer capable of reacting with both (Patent Document 1), a carboxyl group-containing nitrile The thing using the composition containing a butadiene rubber (patent document 2), the thing using the composition containing a polyamide-imide resin (patent document 3), etc. are well-known.
一方、携帯電話やスマートフォン等のモバイル型通信機器やその基地局装置、サーバー・ルーター等のネットワーク関連電子機器、大型コンピュータ等においては、大容量の情報を低損失かつ高速で伝送・処理する必要があり、それら製品のプリント配線板で扱う電気信号も高周波化が進んでいる。しかし、高周波の電気信号は減衰しやすいため、プリント配線板は伝送損失を一層低くする必要がある。そのため、低伝送損失のプリント配線板を得るためには、樹脂付銅箔の接着層を誘電率及び誘電正接を共に小さくする必要がある。この点、上記特許文献1〜3にはそのことについて何ら言及されていない。 On the other hand, mobile communication devices such as mobile phones and smartphones, their base station devices, network-related electronic devices such as servers and routers, large computers, etc. need to transmit and process large amounts of information with low loss and high speed. The electrical signals handled by the printed wiring boards of these products are also becoming higher in frequency. However, since high-frequency electrical signals are easily attenuated, the printed wiring board needs to further reduce transmission loss. Therefore, in order to obtain a printed wiring board with low transmission loss, it is necessary to reduce both the dielectric constant and dielectric loss tangent of the adhesive layer of the copper foil with resin. In this regard, the above Patent Documents 1 to 3 do not mention anything about this.
本発明は、接着層の常温での引き剥がし強さ(以下、常温密着性ともいう。)、はんだ付温度における層間密着性(以下、耐熱密着性ともいう。)が共に良好であり、かつ、接着層の誘電率及び誘電正接がいずれも低い(以下、低誘電特性と総称することがある。)ことを特徴とする樹脂付銅箔を提供することを主たる課題とする。 The present invention has good peel strength at normal temperature of the adhesive layer (hereinafter also referred to as normal temperature adhesion), interlayer adhesion at soldering temperature (hereinafter also referred to as heat resistant adhesion), and The main object is to provide a resin-coated copper foil characterized in that both the dielectric constant and dielectric loss tangent of the adhesive layer are low (hereinafter may be collectively referred to as low dielectric properties).
本発明者は鋭意検討の結果、所定の樹脂組成物からなる接着層を備える樹脂付銅箔が前記課題を解決し得るものであることを見出し、本発明を完成した。 As a result of intensive studies, the present inventor has found that a resin-attached copper foil provided with an adhesive layer made of a predetermined resin composition can solve the above problems, and has completed the present invention.
即ち本発明は、芳香族テトラカルボン酸無水物(a1)及びダイマージアミンを30モル%以上含むジアミン(a2)を反応成分とするポリイミド樹脂(A)並びに熱硬化性樹脂(B)を含む樹脂組成物からなる層と銅箔とを構成要素とする樹脂付銅箔、該樹脂付銅箔を一要素とする銅張積層板、該銅張積層板の少なくとも一の銅箔に回路パターンを形成してなるプリント配線板、並びに該プリント配線板を一要素とする多層配線板、に関する。 That is, the present invention relates to a resin composition comprising a polyimide resin (A) having a diamine (a2) containing 30 mol% or more of an aromatic tetracarboxylic acid anhydride (a1) and dimer diamine as a reaction component and a thermosetting resin (B). Forming a circuit pattern on at least one copper foil of the copper clad laminate, a copper clad laminate comprising the resin layer and a copper foil as constituent elements, a copper clad laminate comprising the resin copper foil as one element And a multilayer wiring board having the printed wiring board as one element.
本発明の樹脂付銅箔は、常温密着性、耐熱密着性及び低誘電特性が良好であるため、特に高周波プリント配線板用の銅張積層板として有用である。また、本発明のプリント配線板及び多層配線板は、高周波の電気信号の伝送損失が小さいため、例えばスマートフォンや携帯電話に代表されるモバイル型通信機器やその基地局装置、サーバー・ルーター等のネットワーク関連電子機器、大型コンピュータ等の用途に好適である。 The resin-coated copper foil of the present invention is particularly useful as a copper-clad laminate for high-frequency printed wiring boards because it has good room-temperature adhesion, heat-resistant adhesion, and low dielectric properties. In addition, since the printed wiring board and the multilayer wiring board of the present invention have low transmission loss of high-frequency electrical signals, for example, mobile communication devices represented by smartphones and mobile phones, their base station devices, networks such as servers and routers, etc. Suitable for applications such as related electronic equipment and large computers.
本発明の樹脂付銅箔は、芳香族テトラカルボン酸無水物(a1)(以下、(a1)成分ともいう。)及びダイマージアミンを30モル%以上含むジアミン(a2)(以下、(a2)成分ともいう。)を反応成分とするポリイミド樹脂(A)(以下、(A)成分ともいう。)並びに熱硬化性樹脂(B)(以下、(B)成分ともいう。)を含む樹脂組成物からなる層と銅箔とを構成要素とする物品である。該樹脂組成物は、銅箔上で接着層(以下、単に接着層ともいう。)を形成する。 The resin-coated copper foil of the present invention is a diamine (a2) (hereinafter referred to as (a2) component) containing 30 mol% or more of an aromatic tetracarboxylic acid anhydride (a1) (hereinafter also referred to as (a1) component) and dimer diamine. From a resin composition containing a polyimide resin (A) (hereinafter also referred to as component (A)) and a thermosetting resin (B) (hereinafter also referred to as component (B)). This is an article comprising a layer and a copper foil as constituent elements. The resin composition forms an adhesive layer (hereinafter also simply referred to as an adhesive layer) on the copper foil.
(a1)成分としては、各種公知の芳香族テトラカルボン酸無水物を使用できる。具体的には、例えば、ピロメリット酸二無水物、4,4’−オキシジフタル酸二無水物、3,3’,4,4’−ベンゾフェノンテトラカルボン酸二無水物、3,3’,4,4’−ジフェニルエーテルテトラカルボン酸二無水物、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、1,2,3,4−ベンゼンテトラカルボン酸無水物、1,4,5,8−ナフタレンテトラカルボン酸無水物、2,3,6,7−ナフタレンテトラカルボン酸無水物、3,3’,4,4’−ビフェニルテトラカルボン酸二無水物、2,2’,3,3’−ビフェニルテトラカルボン酸二無水物、2,3,3’,4’−ビフェニルテトラカルボン酸二無水物、2,3,3’,4’−ベンゾフェノンテトラカルボン酸二無水物、2,3,3’,4’−ジフェニルエーテルテトラカルボン酸二無水物、2,3,3’,4’−ジフェニルスルホンテトラカルボン酸二無水物、2,2−ビス(3,3’,4,4’−テトラカルボキシフェニル)テトラフルオロプロパン二無水物、2,2’−ビス(3,4−ジカルボキシフェノキシフェニル)スルホン二無水物、2,2−ビス(2,3−ジカルボキシフェニル)プロパン二無水物、2,2−ビス(3,4−ジカルボキシフェニル)プロパン二無水物、シクロペンタンテトラカルボン酸無水物、ブタン−1,2,3,4−テトラカルボン酸、2,3,5−トリカルボキシシクロペンチル酢酸無水物及び4,4’−[プロパン−2,2−ジイルビス(1,4−フェニレンオキシ)]ジフタル酸二無水物等が挙げられ、これらは二種以上組み合わせてもよい。これらの中でも、(A)成分と(B)成分の相溶性、常温密着性、及び耐熱密着性等の点より、3,3’,4,4’−ベンゾフェノンテトラカルボン酸二無水物、4,4’−[プロパン−2,2−ジイルビス(1,4−フェニレンオキシ)]ジフタル酸二無水物、及び4,4’−オキシジフタル酸無水物からなる群より選ばれる少なくとも一種が好ましい。 As the component (a1), various known aromatic tetracarboxylic acid anhydrides can be used. Specifically, for example, pyromellitic dianhydride, 4,4′-oxydiphthalic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4, 4'-diphenyl ether tetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic anhydride, 1,4,5 , 8-Naphthalenetetracarboxylic anhydride, 2,3,6,7-naphthalenetetracarboxylic anhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3 3′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-benzophenonetetracarboxylic dianhydride, 2,3 , 3 ', 4'-di Phenyl ether tetracarboxylic dianhydride, 2,3,3 ′, 4′-diphenylsulfone tetracarboxylic dianhydride, 2,2-bis (3,3 ′, 4,4′-tetracarboxyphenyl) tetrafluoro Propane dianhydride, 2,2'-bis (3,4-dicarboxyphenoxyphenyl) sulfone dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, cyclopentanetetracarboxylic anhydride, butane-1,2,3,4-tetracarboxylic acid, 2,3,5-tricarboxycyclopentylacetic anhydride and 4 , 4 ′-[propane-2,2-diylbis (1,4-phenyleneoxy)] diphthalic dianhydride, etc., may be used in combination of two or more.Among these, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, from the viewpoint of compatibility between the components (A) and (B), room temperature adhesion, heat resistance adhesion, and the like, At least one selected from the group consisting of 4 ′-[propane-2,2-diylbis (1,4-phenyleneoxy)] diphthalic dianhydride and 4,4′-oxydiphthalic anhydride is preferable.
(a2)成分を構成するダイマージアミンは、オレイン酸等の不飽和脂肪酸の二量体であるダイマー酸から誘導される化合物であり(特開平9−12712号公報等参照)、各種公知のダイマージアミンを特に制限なく使用できる。以下、ダイマージアミンの非限定的な構造式を示す(各式において、m+n=6〜17であり、p+q=8〜19であり、波線部は炭素−炭素単結合または炭素−炭素二重結合を意味する。) The dimeramine constituting the component (a2) is a compound derived from dimer acid which is a dimer of unsaturated fatty acid such as oleic acid (see JP-A-9-12712), and various known dimeramine amines. Can be used without any particular limitation. Hereinafter, non-limiting structural formulas of dimeramine are shown (in each formula, m + n = 6 to 17, p + q = 8 to 19, and the wavy line represents a carbon-carbon single bond or a carbon-carbon double bond. means.)
(a2)成分の市販品としては、例えばバーサミン551(BASFジャパン(株)製)、バーサミン552(コグニクスジャパン(株)製;バーサミン551の水添物)、PRIAMINE1075、PRIAMINE1074(いずれもクローダジャパン(株)製)等が挙げられる。 Examples of commercially available products of component (a2) include Versamine 551 (manufactured by BASF Japan), Versamine 552 (manufactured by Cognix Japan); Etc.).
本発明では、(a2)成分にダイマージアミンを30モル%以上含ませることにより、常温密着性、耐熱密着性及び低誘電特性を並立させることが可能になる。かかる観点より、(a2)成分におけるダイマージアミンの含有量は、好ましくは40〜80モル%程度である。 In the present invention, by incorporating 30 mol% or more of dimer diamine in the component (a2), it becomes possible to make room temperature adhesion, heat resistant adhesion, and low dielectric properties side by side. From this viewpoint, the content of dimerized amine in the component (a2) is preferably about 40 to 80 mol%.
(a2)成分には、必要に応じ、更に脂環式ジアミン及び/又はジアミノポリシロキサンを含めることができる。 The component (a2) can further contain an alicyclic diamine and / or diaminopolysiloxane as necessary.
脂環式ジアミンは、ダイマージアミンと同様、低誘電特性に寄与する。その具体例としては、α,ω−ビス(2−アミノエチル)ポリジメチルシロキサン、α,ω−ビス(3−アミノプロピル)ポリジメチルシロキサン、α,ω−ビス(4−アミノブチル)ポリジメチルシロキサン、α,ω−ビス(5−アミノペンチル)ポリジメチルシロキサン、α,ω−ビス[3−(2−アミノフェニル)プロピル]ポリジメチルシロキサン、α,ω−ビス[3−(4−アミノフェニル)プロピル]ポリジメチルシロキサン等が挙げられ、これらは二種以上組み合わせてもよい。(a2)成分におけるその含有量は特に限定されないが、低誘電特性等を考慮すると通常70モル%未満、好ましくは60〜20モル%程度である。 The alicyclic diamine contributes to the low dielectric property like the dimer diamine. Specific examples thereof include α, ω-bis (2-aminoethyl) polydimethylsiloxane, α, ω-bis (3-aminopropyl) polydimethylsiloxane, α, ω-bis (4-aminobutyl) polydimethylsiloxane. , Α, ω-bis (5-aminopentyl) polydimethylsiloxane, α, ω-bis [3- (2-aminophenyl) propyl] polydimethylsiloxane, α, ω-bis [3- (4-aminophenyl) Propyl] polydimethylsiloxane, etc., and two or more of these may be combined. Although the content in the component (a2) is not particularly limited, it is usually less than 70 mol%, preferably about 60 to 20 mol% in view of low dielectric properties and the like.
ジアミノポリシロキサンは、特に常温密着性に寄与する。その具体例としては、ジアミノシクロヘキサン、ジアミノジシクロヘキシルメタン、ジメチルージアミノジシクロヘキシルメタン、テトラメチルージアミノジシクロヘキシルメタン、ジアミノジシクロヘキシルプロパン、ジアミノビシクロ[2.2.1]ヘプタン、ビス(アミノメチル)−ビシクロ[2.2.1]ヘプタン、3(4),8(9)−ビス(アミノメチル)トリシクロ[5.2.1.02,6]デカン、1,3−ビスアミノメチルシクロヘキサン、イソホロンジアミンなどが例示される。これらの中でも、ジアミノシクロヘキサン、ジアミノジシクロヘキシルメタン、ジメチルージアミノジシクロヘキシルメタン、ジアミノビシクロ[2.2.1]ヘプタン、ビス(アミノメチル)−ビシクロ[2.2.1]ヘプタン、3(4),8(9)−ビス(アミノメチル)トリシクロ[5.2.1.02,6]デカン、イソホロンジアミン、4,4’−ジアミノジシクロヘキシルメタン及び1,3−ビスアミノメチルシクロヘキサン等が挙げられ、これらは二種以上組み合わせてもよい。(a2)成分におけるその含有量は特に限定されないが、常温密着性等を考慮すると通常70モル%未満、好ましくは60〜20モル%程度である。 Diaminopolysiloxane contributes particularly to room temperature adhesion. Specific examples thereof include diaminocyclohexane, diaminodicyclohexylmethane, dimethyl-diaminodicyclohexylmethane, tetramethyl-diaminodicyclohexylmethane, diaminodicyclohexylpropane, diaminobicyclo [2.2.1] heptane, bis (aminomethyl) -bicyclo [2 2.1] heptane, 3 (4), 8 (9) -bis (aminomethyl) tricyclo [5.2.1.02,6] decane, 1,3-bisaminomethylcyclohexane, isophoronediamine and the like. Is done. Among these, diaminocyclohexane, diaminodicyclohexylmethane, dimethyl-diaminodicyclohexylmethane, diaminobicyclo [2.2.1] heptane, bis (aminomethyl) -bicyclo [2.2.1] heptane, 3 (4), 8 (9) -bis (aminomethyl) tricyclo [5.2.1.02,6] decane, isophoronediamine, 4,4′-diaminodicyclohexylmethane, 1,3-bisaminomethylcyclohexane, and the like. Two or more kinds may be combined. The content of the component (a2) is not particularly limited, but is usually less than 70 mol%, preferably about 60 to 20 mol% in consideration of room temperature adhesion.
本発明においては、他のジアミンも併用できる。具体的には、例えば、2,2−ビス[4−(3−アミノフェノキシ)フェニル]プロパン、2,2−ビス[4−(4−アミノフェノキシ)フェニル]プロパン等のビスアミノフェノキシフェニルプロパン類; 3,3’−ジアミノジフェニルエーテル、3,4’−ジアミノジフェニルエーテル、4,4’−ジアミノジフェニルエーテル等のジアミノジフェニルエーテル類;p−フェニレンジアミン、m−フェニレンジアミン等のフェニレンジアミン類;3,3’−ジアミノジフェニルスルフィド、3,4’−ジアミノジフェニルスルフィド、4,4’−ジアミノジフェニルスルフィド等のジアミノジフェニルスルフィド類;3,3’−ジアミノジフェニルスルホン、3,4’−ジアミノジフェニルスルホン、4,4’−ジアミノジフェニルスルホン等のジアミノジフェニルスルホン類;3,3’−ジアミノベンゾフェノン、4,4’−ジアミノベンゾフェノン、3,4’−ジアミノベンゾフェノン等のジアミノベンゾフェノン類;3,3’−ジアミノジフェニルメタン、4,4’−ジアミノジフェニルメタン、3,4’−ジアミノジフェニルメタン等のジアミノジフェニルメタン類;2,2−ジ(3−アミノフェニル)プロパン、2,2−ジ(4−アミノフェニル)プロパン、2−(3−アミノフェニル)−2−(4−アミノフェニル)プロパン等のジアミノフェニルプロパン類;2,2−ジ(3−アミノフェニル)−1,1,1,3,3,3−ヘキサフルオロプロパン、2,2−ジ(4−アミノフェニル)−1,1,1,3,3,3−ヘキサフルオロプロパン、2−(3−アミノフェニル)−2−(4−アミノフェニル)−1,1,1,3,3,3−ヘキサフルオロプロパン等のジアミノフェニルヘキサフルオロプロパン類; 1,1−ジ(3−アミノフェニル)−1−フェニルエタン、1,1−ジ(4−アミノフェニル)−1−フェニルエタン、1−(3−アミノフェニル)−1−(4−アミノフェニル)−1−フェニルエタン等のジアミノフェニルフェニルエタン類;1,3−ビス(3−アミノフェノキシ)ベンゼン、1,3−ビス(4−アミノフェノキシ)ベンゼン、1,4−ビス(3−アミノフェノキシ)ベンゼン、1,4−ビス(4−アミノフェノキシ)ベンゼン等のビスアミノフェノキシベンゼン類;1,3−ビス(3−アミノベンゾイル)ベンゼン、1,3−ビス(4−アミノベンゾイル)ベンゼン、1,4−ビス(3−アミノベンゾイル)ベンゼン、1,4−ビス(4−アミノベンゾイル)ベンゼン等のビスアミノベンゾイルベンゼン類;1,3−ビス(3−アミノ−α,α−ジメチルベンジル)ベンゼン、1,3−ビス(4−アミノ−α,α−ジメチルベンジル)ベンゼン、1,4−ビス(3−アミノ−α,α−ジメチルベンジル)ベンゼン、1,4−ビス(4−アミノ−α,α−ジメチルベンジル)ベンゼン等のビスアミノジメチルベンゼン類;1,3−ビス(3−アミノ−α,α−ジトリフルオロメチルベンジル)ベンゼン、1,3−ビス(4−アミノ−α,α−ジトリフルオロメチルベンジル)ベンゼン、1,4−ビス(3−アミノ−α,α−ジトリフルオロメチルベンジル)ベンゼン、1,4−ビス(4−アミノ−α,α−ジトリフルオロメチルベンジル)ベンゼン等のビスアミノジトリフルオロメチルベンジルベンゼン類;2,6−ビス(3−アミノフェノキシ)ベンゾニトリル、2,6−ビス(3−アミノフェノキシ)ピリジン、4,4’−ビス(3−アミノフェノキシ)ビフェニル、4,4’−ビス(4−アミノフェノキシ)ビフェニル等のアミノフェノキシビフェニル類;ビス[4−(3−アミノフェノキシ)フェニル]ケトン、ビス[4−(4−アミノフェノキシ)フェニル]ケトン等のアミノフェノキシフェニルケトン類;ビス[4−(3−アミノフェノキシ)フェニル]スルフィド、ビス[4−(4−アミノフェノキシ)フェニル]スルフィド等のアミノフェノキシフェニルスルフィド類;ビス[4−(3−アミノフェノキシ)フェニル]スルホン、ビス[4−(4−アミノフェノキシ)フェニル]スルホン等のアミノフェノキシフェニルスルホン類;ビス[4−(3−アミノフェノキシ)フェニル]エーテル、ビス[4−(4−アミノフェノキシ)フェニル]エーテル等のアミノフェノキシフェニルエーテル類;2,2−ビス[4−(3−アミノフェノキシ)フェニル]プロパン、2,2−ビス[3−(3−アミノフェノキシ)フェニル]−1,1,1,3,3,3−ヘキサフルオロプロパン、2,2−ビス[4−(4−アミノフェノキシ)フェニル]−1,1,1,3,3,3−ヘキサフルオロプロパン等のアミノフェノキシフェニルプロパン類;その他、1,3−ビス[4−(3−アミノフェノキシ)ベンゾイル]ベンゼン、1,3−ビス[4−(4−アミノフェノキシ)ベンゾイル]ベンゼン、1,4−ビス[4−(3−アミノフェノキシ)ベンゾイル]ベンゼン、1,4−ビス[4−(4−アミノフェノキシ)ベンゾイル]ベンゼン、1,3−ビス[4−(3−アミノフェノキシ)−α,α−ジメチルベンジル]ベンゼン、1,3−ビス[4−(4−アミノフェノキシ)−α,α−ジメチルベンジル]ベンゼン、1,4−ビス[4−(3−アミノフェノキシ)−α,α−ジメチルベンジル]ベンゼン、1,4−ビス[4−(4−アミノフェノキシ)−α,α−ジメチルベンジル]ベンゼン、4,4’−ビス[4−(4−アミノフェノキシ)ベンゾイル]ジフェニルエーテル、4,4’−ビス[4−(4−アミノ−α,α−ジメチルベンジル)フェノキシ]ベンゾフェノン、4,4’−ビス[4−(4−アミノ−α,α−ジメチルベンジル)フェノキシ]ジフェニルスルホン、4,4’−ビス[4−(4−アミノフェノキシ)フェノキシ]ジフェニルスルホン、3,3’−ジアミノ−4,4’−ジフェノキシベンゾフェノン、3,3’−ジアミノ−4,4’−ジビフェノキシベンゾフェノン、3,3’−ジアミノ−4−フェノキシベンゾフェノン、3,3’−ジアミノ−4−ビフェノキシベンゾフェノン、6,6’−ビス(3−アミノフェノキシ)3,3,3,’3,’−テトラメチル−1,1’−スピロビインダン6,6’−ビス(4−アミノフェノキシ)3,3,3,’3,’−テトラメチル−1,1’−スピロビインダン、1,3−ビス(3−アミノプロピル)テトラメチルジシロキサン、1,3−ビス(4−アミノブチル)テトラメチルジシロキサン、ビス(アミノメチル)エーテル、ビス(2−アミノエチル)エーテル、ビス(3−アミノプロピル)エーテル、ビス(2−アミノメトキシ)エチル]エ−テル、ビス[2−(2−アミノエトキシ)エチル]エーテル、ビス[2−(3−アミノプロトキシ)エチル]エーテル、1,2−ビス(アミノメトキシ)エタン、1,2−ビス(2−アミノエトキシ)エタン、1,2−ビス[2−(アミノメトキシ)エトキシ]エタン、1,2−ビス[2−(2−アミノエトキシ)エトキシ]エタン、エチレングリコ−ルビス(3−アミノプロピル)エーテル、ジエチレングリコ−ルビス(3−アミノプロピル)エーテル、トリエチレングリコ−ルビス(3−アミノプロピル)エーテル、エチレンジアミン、1,3−ジアミノプロパン、1,4−ジアミノブタン、1,5−ジアミノペンタン、1,6−ジアミノヘキサン、1,7−ジアミノヘプタン、1,8−ジアミノオクタン、1,9−ジアミノノナン、1,10−ジアミノデカン、1,11−ジアミノウンデカン、1,12−ジアミノドデカン等が挙げられ、これらは二種以上組み合わせてもよい。これらの使用量は特に限定されないが、全ジアミン成分に対して通常75モル%未満である。 In the present invention, other diamines can be used in combination. Specifically, for example, bisaminophenoxyphenylpropanes such as 2,2-bis [4- (3-aminophenoxy) phenyl] propane and 2,2-bis [4- (4-aminophenoxy) phenyl] propane Diaminodiphenyl ethers such as 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, and 4,4′-diaminodiphenyl ether; phenylenediamines such as p-phenylenediamine and m-phenylenediamine; 3,3′- Diaminodiphenyl sulfides such as diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide; 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4 ' -Diaminodiphenyls Diaminodiphenyl sulfones such as Hong; diaminobenzophenones such as 3,3′-diaminobenzophenone, 4,4′-diaminobenzophenone and 3,4′-diaminobenzophenone; 3,3′-diaminodiphenylmethane, 4,4′- Diaminodiphenylmethanes such as diaminodiphenylmethane and 3,4′-diaminodiphenylmethane; 2,2-di (3-aminophenyl) propane, 2,2-di (4-aminophenyl) propane, 2- (3-aminophenyl) Diaminophenylpropanes such as -2- (4-aminophenyl) propane; 2,2-di (3-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-di (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2- (3-aminophenyl) Dienyl) -2- (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane and the like; 1,1-di (3-aminophenyl) -1- Diaminophenylphenylethanes such as phenylethane, 1,1-di (4-aminophenyl) -1-phenylethane, 1- (3-aminophenyl) -1- (4-aminophenyl) -1-phenylethane; 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) Bisaminophenoxybenzenes such as benzene; 1,3-bis (3-aminobenzoyl) benzene, 1,3-bis (4-aminobenzoyl) benzene, 1,4 -Bisaminobenzoylbenzenes such as bis (3-aminobenzoyl) benzene and 1,4-bis (4-aminobenzoyl) benzene; 1,3-bis (3-amino-α, α-dimethylbenzyl) benzene, 1 , 3-bis (4-amino-α, α-dimethylbenzyl) benzene, 1,4-bis (3-amino-α, α-dimethylbenzyl) benzene, 1,4-bis (4-amino-α, α -Bisaminodimethylbenzenes such as dimethylbenzyl) benzene; 1,3-bis (3-amino-α, α-ditrifluoromethylbenzyl) benzene, 1,3-bis (4-amino-α, α-ditrifluoro) Methylbenzyl) benzene, 1,4-bis (3-amino-α, α-ditrifluoromethylbenzyl) benzene, 1,4-bis (4-amino-α, α-ditrifluoromethyl) Bisaminoditrifluoromethylbenzylbenzenes such as benzyl) benzene; 2,6-bis (3-aminophenoxy) benzonitrile, 2,6-bis (3-aminophenoxy) pyridine, 4,4′-bis (3- Aminophenoxybiphenyls such as aminophenoxy) biphenyl and 4,4′-bis (4-aminophenoxy) biphenyl; bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl Aminophenoxyphenyl ketones such as ketone; aminophenoxyphenyl sulfides such as bis [4- (3-aminophenoxy) phenyl] sulfide and bis [4- (4-aminophenoxy) phenyl] sulfide; bis [4- ( 3-aminophenoxy) phenyl] sulfone, bis [4- (4-amino) Aminophenoxyphenyl sulfones such as nophenoxy) phenyl] sulfone; aminophenoxyphenyl ethers such as bis [4- (3-aminophenoxy) phenyl] ether and bis [4- (4-aminophenoxy) phenyl] ether; 2 , 2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, Aminophenoxyphenylpropanes such as 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane; other 1,3-bis [4- (3-Aminophenoxy) benzoyl] benzene, 1,3-bis [4- (4-aminophenoxy) benzoyl] benzene, 1,4- [4- (3-aminophenoxy) benzoyl] benzene, 1,4-bis [4- (4-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3-aminophenoxy) -α, α -Dimethylbenzyl] benzene, 1,3-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-aminophenoxy) -α, α-dimethyl Benzyl] benzene, 1,4-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 4,4′-bis [4- (4-aminophenoxy) benzoyl] diphenyl ether, 4,4 '-Bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzophenone, 4,4'-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy Diphenylsulfone, 4,4′-bis [4- (4-aminophenoxy) phenoxy] diphenylsulfone, 3,3′-diamino-4,4′-diphenoxybenzophenone, 3,3′-diamino-4,4 ′ -Dibiphenoxybenzophenone, 3,3'-diamino-4-phenoxybenzophenone, 3,3'-diamino-4-biphenoxybenzophenone, 6,6'-bis (3-aminophenoxy) 3,3,3'3 , '-Tetramethyl-1,1'-spirobiindane 6,6'-bis (4-aminophenoxy) 3,3,3,3', '-tetramethyl-1,1'-spirobiindane, 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (4-aminobutyl) tetramethyldisiloxane, bis (aminomethyl) ether, Bis (2-aminoethyl) ether, bis (3-aminopropyl) ether, bis (2-aminomethoxy) ethyl] ether, bis [2- (2-aminoethoxy) ethyl] ether, bis [2- ( 3-aminoprotoxy) ethyl] ether, 1,2-bis (aminomethoxy) ethane, 1,2-bis (2-aminoethoxy) ethane, 1,2-bis [2- (aminomethoxy) ethoxy] ethane, 1,2-bis [2- (2-aminoethoxy) ethoxy] ethane, ethylene glycol bis (3-aminopropyl) ether, diethylene glycol bis (3-aminopropyl) ether, triethylene glycol bis (3-amino Propyl) ether, ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopenta 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, etc. These may be used, and two or more of these may be combined. Although the usage-amount of these is not specifically limited, Usually, it is less than 75 mol% with respect to all the diamine components.
(A)成分は、各種公知の方法により製造できる。例えば、(a1)成分と(a2)成分を、通常60〜120℃程度(好ましくは80〜100℃程度)の温度において、通常0.1〜2時間程度(好ましくは0.1〜0.5時間程度)、重付加反応させる。次いで、得られた重付加物を更に80〜250℃程度、好ましくは100〜200℃の温度において、0.5〜50時間程度(好ましくは1〜20時間程度)、イミド化反応、即ち脱水閉環反応させることにより、目的とする(A)成分が得られる。 The component (A) can be produced by various known methods. For example, the components (a1) and (a2) are usually about 0.1 to 2 hours (preferably 0.1 to 0.5 hours) at a temperature of about 60 to 120 ° C. (preferably about 80 to 100 ° C.). Polyaddition reaction). Subsequently, the obtained polyaddition product is further subjected to imidation reaction, that is, dehydration ring closure, at a temperature of about 80 to 250 ° C., preferably about 100 to 200 ° C., for about 0.5 to 50 hours (preferably about 1 to 20 hours). By reacting, the desired component (A) is obtained.
なお、イミド化反応においては、各種公知の反応触媒、脱水剤、及び後述する有機溶剤を使用できる。反応触媒としては、トリエチルアミン等の脂肪族第3級アミン類、ジメチルアニリン等の芳香族第3級アミン類、ピリジン、ピコリン、イソキノリン等の複素環式第3級アミン類等が挙げられ、これらは二種以上組み合わせてもよい。また、脱水剤としては、例えば無水酢酸等の脂肪族酸無水物や無水安息香酸等の芳香族酸無水物等が挙げられ、これらは二種以上組み合わせてもよい。 In the imidization reaction, various known reaction catalysts, dehydrating agents, and organic solvents described later can be used. Examples of the reaction catalyst include aliphatic tertiary amines such as triethylamine, aromatic tertiary amines such as dimethylaniline, and heterocyclic tertiary amines such as pyridine, picoline and isoquinoline. Two or more kinds may be combined. Examples of the dehydrating agent include aliphatic acid anhydrides such as acetic anhydride and aromatic acid anhydrides such as benzoic anhydride, and these may be used in combination of two or more.
(a1)成分と(a2)成分の使用量比は特に限定されないが、後述の有機溶剤に対する(A)成分の溶解性や、常温密着性、耐熱密着性及び低誘電特性のバランス等の観点より、〔(a1)成分の使用モル数/(a2)成分の使用モル数〕が通常0.6〜1.4程度、好ましくは0.8〜1.2程度となる範囲であるのがよい。 Although the usage-amount ratio of (a1) component and (a2) component is not specifically limited, from viewpoints, such as the solubility of (A) component with respect to the below-mentioned organic solvent, and the balance of normal temperature adhesiveness, heat resistant adhesiveness, and a low dielectric property. The [number of moles of component (a1) / the number of moles of component (a2)] is usually in the range of about 0.6 to 1.4, preferably about 0.8 to 1.2.
(A)成分のイミド閉環率は特に限定されない。ここに「イミド閉環率」とは、(A)成分における環状イミド結合の含有量を意味し、例えばNMRやIR分析等の各種分光手段により決定できる。そして、(A)成分のイミド閉環率を通常70%以上、好ましくは85〜100%程度とすることにより、常温密着性及び耐熱密着性が良好となる。 The imide ring closure rate of the component (A) is not particularly limited. Here, the “imide ring closure rate” means the content of the cyclic imide bond in the component (A), and can be determined by various spectroscopic means such as NMR and IR analysis. And the normal temperature adhesiveness and heat-resistant adhesiveness become favorable by making the imide cyclization rate of (A) component into 70% or more normally, Preferably it is about 85-100%.
こうして得られる(A)成分の物性は特に限定されないが、常温密着性、耐熱密着性及び低誘電特性のバランスの観点より、通常、ガラス転移温度が20〜250℃程度、好ましくは30〜200℃程度である。また、重量平均分子量も特に限定されないが、同様の観点より、通常3000〜60000程度、好ましくは6000〜40000程度である。 Although the physical properties of the component (A) thus obtained are not particularly limited, the glass transition temperature is usually about 20 to 250 ° C., preferably 30 to 200 ° C. from the viewpoint of the balance between room temperature adhesion, heat resistant adhesion and low dielectric properties. Degree. Moreover, although a weight average molecular weight is not specifically limited, From the same viewpoint, it is about 3000-60000 normally, Preferably it is about 6000-40000.
(B)成分としては、ポリイミド樹脂の架橋剤として機能するものであれば、各種公知の熱硬化性樹脂を特に制限なく使用することができる。具体的には、例えば、エポキシ樹脂、ベンゾオキサジン樹脂、ビスマレイミド樹脂及びシアネートエステル樹脂からなる群より選ばれる少なくとも一種が好ましい。 As the component (B), various known thermosetting resins can be used without particular limitation as long as they function as a crosslinking agent for the polyimide resin. Specifically, for example, at least one selected from the group consisting of epoxy resins, benzoxazine resins, bismaleimide resins, and cyanate ester resins is preferable.
前記エポキシ樹脂としては、例えばフェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、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、ビスフェノールS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、スチルベン型エポキシ樹脂、トリアジン骨格含有エポキシ樹脂、フルオレン骨格含有エポキシ樹脂、線状脂肪族エポキシ樹脂、脂環式エポキシ樹脂、グリシジルアミン型エポキシ樹脂、トリフェノールフェノ−ルメタン型エポキシ樹脂、アルキル変性トリフェノールメタン型エポキシ樹脂、ビフェニル型エポキシ樹脂、ジシクロペンタジエン骨格含有エポキシ樹脂、ナフタレン骨格含有エポキシ樹脂、アリールアルキレン型エポキシ樹脂、テトラグリシジルキシリレンジアミン、これらエポキシ樹脂をダイマー酸で変性してなる変性エポキシ樹脂、ダイマー酸ジグリシジルエステル等が挙げられ、これらは二種以上組み合わせてもよい。また、市販品としては例えば、三菱化学(株)製の「jER828」や「jER834」、「jER807」、新日鐵化学(株)製の「ST−3000」、ダイセル化学工業(株)製の「セロキサイド2021P」、新日鐵化学(株)製の「YD−172−X75」、三菱ガス化学(株)製の「TETRADX」等が挙げられる。これらの中でも、当該接着剤組成物の透明性や耐熱性等の観点よりビスフェノール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型エポキシ樹脂及び脂環式エポキシ樹脂からなる群より選ばれる少なくとも一種が好ましい。 Examples of the epoxy resin include phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type. Epoxy resin, stilbene type epoxy resin, triazine skeleton containing epoxy resin, fluorene skeleton containing epoxy resin, linear aliphatic epoxy resin, alicyclic epoxy resin, glycidylamine type epoxy resin, triphenolphenol methane type epoxy resin, alkyl modified Triphenolmethane type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene skeleton-containing epoxy resin, naphthalene skeleton-containing epoxy resin, arylalkylene type epoxy resin, Tiger glycidyl xylylenediamine, these epoxy resin-modified epoxy resin obtained by modifying with dimer acid, and dimer acid diglycidyl ester and the like, which may be combined two or more. Examples of commercially available products include “jER828”, “jER834”, “jER807” manufactured by Mitsubishi Chemical Corporation, “ST-3000” manufactured by Nippon Steel Chemical Co., Ltd., and manufactured by Daicel Chemical Industries, Ltd. “Celoxide 2021P”, “YD-172-X75” manufactured by Nippon Steel Chemical Co., Ltd., “TETRADX” manufactured by Mitsubishi Gas Chemical Co., Ltd., and the like. Among these, it is selected from the group consisting of bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin and alicyclic epoxy resin from the viewpoint of transparency and heat resistance of the adhesive composition. At least one is preferred.
なお、熱硬化性樹脂としてエポキシ樹脂を用いる場合には、各種公知のエポキシ樹脂用硬化剤を併用できる。具体的には、例えば、無水コハク酸、無水フタル酸、無水マレイン酸、無水トリメリット酸、無水ピロメリット酸、ヘキサヒドロ無水フタル酸、3−メチル−ヘキサヒドロ無水フタル酸、4−メチル−ヘキサヒドロ無水フタル酸、あるいは4−メチル−ヘキサヒドロ無水フタル酸とヘキサヒドロ無水フタル酸との混合物、テトラヒドロ無水フタル酸、メチル−テトラヒドロ無水フタル酸、無水ナジック酸、無水メチルナジック酸、ノルボルナン−2,3−ジカルボン酸無水物、メチルノルボルナン−2,3−ジカルボン酸無水物、メチルシクロヘキセンジカルボン酸無水物、3−ドデセニル無水コハク酸、オクテニルコハク酸無水物等の酸無水物系硬化剤;ジシアンジアミド(DICY)、芳香族ジアミン(商品名「LonzacureM−DEA」、「LonzacureM−DETDA」等。いずれもロンザジャパン(株)製)、脂肪族アミン等のアミン系硬化剤;フェノールノボラック樹脂、クレゾールノボラック樹脂、ビスフェノールA型ノボラック樹脂、トリアジン変性フェノールノボラック樹脂、フェノール性水酸基含有ホスファゼン(大塚化学(株)製の商品名「SPH−100」等)等のフェノール系硬化剤、環状ホスファゼン系化合物、マレイン酸変性ロジンやその水素化物等のロジン系架橋剤等が挙げられ、これらは二種以上組み合わせてもよい。これらの中でもフェノール系硬化剤、特にフェノール性水酸基含有ホスファゼン系硬化剤が好ましい。これら硬化剤の使用量は特に制限されないが、通常、本発明の接着剤組成物の固形分を100重量%とした場合において0.1〜120重量%程度であり、好ましくは10〜40重量%程度である。 In addition, when using an epoxy resin as a thermosetting resin, various well-known hardening | curing agents for epoxy resins can be used together. Specifically, for example, succinic anhydride, phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, 3-methyl-hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride Acid, or a mixture of 4-methyl-hexahydrophthalic anhydride and hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl-tetrahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, norbornane-2,3-dicarboxylic anhydride Acid anhydride-based curing agents such as methylnorbornane-2,3-dicarboxylic anhydride, methylcyclohexene dicarboxylic anhydride, 3-dodecenyl succinic anhydride, octenyl succinic anhydride; dicyandiamide (DICY), aromatic diamine ( Product name "Lonacure M-" EA ”,“ Lonacure M-DETDA ”, etc., all manufactured by Lonza Japan Co., Ltd.), amine-based curing agents such as aliphatic amines; Phenolic hydroxyl group-containing phosphazenes (trade name “SPH-100” manufactured by Otsuka Chemical Co., Ltd.), etc., phenolic curing agents, cyclic phosphazene compounds, rosin crosslinking agents such as maleic acid-modified rosin and hydrides thereof, etc. These may be used, and two or more of these may be combined. Of these, phenol-based curing agents, particularly phenolic hydroxyl group-containing phosphazene-based curing agents are preferred. The amount of these curing agents used is not particularly limited, but is usually about 0.1 to 120% by weight, preferably 10 to 40% by weight when the solid content of the adhesive composition of the present invention is 100% by weight. Degree.
また、エポキシ樹脂とその硬化剤の反応を促進するための触媒を使用することもできる。具体的には、例えば、1,8−ジアザ−ビシクロ[5.4.0]ウンデセン−7、トリエチレンジアミン、ベンジルジメチルアミン、トリエタノールアミン、ジメチルアミノエタノール、トリス(ジメチルアミノメチル)フェノール等の三級アミン類;2−メチルイミダゾール、2−フェニルイミダゾール、2−フェニル−4−メチルイミダゾール、2−ヘプタデシルイミダゾール等のイミダゾ−ル類;トリブチルホスフィン、メチルジフェニルホスフィン、トリフェニルホスフィン、ジフェニルホスフィン、フェニルホスフィン等の有機ホスフィン類;テトラフェニルホスホニウム・テトラフェニルボレート、2−エチル−4−メチルイミダゾール・テトラフェニルボレート、N−メチルモルホリン・テトラフェニルボレート等のテトラフェニルボロン塩等が挙げられ、これらは二種以上組み合わせてもよい。また、当該触媒の使用量は特に制限されないが、通常、本発明の接着剤組成物の固形分を100重量%とした場合において0.01〜5重量%程度である。 A catalyst for promoting the reaction between the epoxy resin and its curing agent can also be used. Specifically, for example, 1,8-diaza-bicyclo [5.4.0] undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol and the like. Secondary amines; imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole; tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenyl Organic phosphines such as phosphine; tetraphenylphosphonium / tetraphenylborate, 2-ethyl-4-methylimidazole / tetraphenylborate, N-methylmorpholine / tetraphenylborate, etc. Niruboron salts and the like, they may be combined two or more. The amount of the catalyst used is not particularly limited, but is usually about 0.01 to 5% by weight when the solid content of the adhesive composition of the present invention is 100% by weight.
前記ベンゾオキサジン樹脂としては、例えば、6,6−(1−メチルエチリデン)ビス(3,4−ジヒドロ−3−フェニル−2H−1,3−ベンゾオキサジン)、6,6−(1−メチルエチリデン)ビス(3,4−ジヒドロ−3−メチル−2H−1,3−ベンゾオキサジン)等が挙げられ、これらは二種以上組み合わせてもよい。なお、オキサジン環の窒素にはフェニル基、メチル基、シクロヘキシル基等が結合していてもよい。また、市販品としては例えば、四国化成工業(株)社製の「ベンゾオキサジンF−a型」や「ベンゾオキサジンP−d型」、エア・ウォ−タ−社製の「RLV−100」等が挙げられる。 Examples of the benzoxazine resin include 6,6- (1-methylethylidene) bis (3,4-dihydro-3-phenyl-2H-1,3-benzoxazine) and 6,6- (1-methylethylidene). ) Bis (3,4-dihydro-3-methyl-2H-1,3-benzoxazine) and the like, and two or more of these may be combined. Note that a phenyl group, a methyl group, a cyclohexyl group, or the like may be bonded to nitrogen of the oxazine ring. In addition, examples of commercially available products include “benzoxazine Fa type” and “benzoxazine Pd type” manufactured by Shikoku Kasei Kogyo Co., Ltd., “RLV-100” manufactured by Air Water Co., etc. Is mentioned.
前記ビスマレイミド樹脂としては、例えば、4,4’−ジフェニルメタンビスマレイミド、m−フェニレンビスマレイミド、ビスフェノールAジフェニルエーテルビスマレイミド、3,3’−ジメチル−5,5’−ジエチル−4,4’−ジフェニルメタンビスマレイミド、4−メチル−1,3−フェニレンビスマレイミド、1,6’−ビスマレイミド−(2,2,4−トリメチル)ヘキサン、4,4’−ジフェニルエーテルビスマレイミド、4,4’−ジフェニルスルフォンビスマレイミド等が挙げられ、これらは二種以上組み合わせてもよい。また、市販品としては例えば、JFEケミカル(株)社製の「BAF−BMI」等が挙げられる。 Examples of the bismaleimide resin include 4,4′-diphenylmethane bismaleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethane. Bismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6′-bismaleimide- (2,2,4-trimethyl) hexane, 4,4′-diphenyl ether bismaleimide, 4,4′-diphenylsulfone A bismaleimide etc. are mentioned, These may combine 2 or more types. Examples of commercially available products include “BAF-BMI” manufactured by JFE Chemical Co., Ltd.
前記シアネートエステル樹脂としては、例えば、2−アリルフェノールシアネートエステル、4−メトキシフェノールシアネートエステル、2,2−ビス(4−シアナトフェノール)−1,1,1,3,3,3−ヘキサフルオロプロパン、ビスフェノールAシアネートエステル、ジアリルビスフェノールAシアネートエステル、4−フェニルフェノールシアネートエステル、1,1,1−トリス(4−シアナトフェニル)エタン、4−クミルフェノールシアネートエステル、1,1−ビス(4−シアナトフェニル)エタン、4,4’−ビスフェノールシアネートエステル、及び2,2‐ビス(4‐シアナトフェニル)プロパン等が挙げられ、これらは二種以上組み合わせてもよい。また、市販品としては例えば、「PRIMASET BTP−6020S(ロンザジャパン(株)製)」等が挙げられる。 Examples of the cyanate ester resin include 2-allylphenol cyanate ester, 4-methoxyphenol cyanate ester, 2,2-bis (4-cyanatophenol) -1,1,1,3,3,3-hexafluoro. Propane, bisphenol A cyanate ester, diallyl bisphenol A cyanate ester, 4-phenylphenol cyanate ester, 1,1,1-tris (4-cyanatophenyl) ethane, 4-cumylphenol cyanate ester, 1,1-bis ( 4-Cyanatophenyl) ethane, 4,4′-bisphenol cyanate ester, 2,2-bis (4-cyanatophenyl) propane and the like may be mentioned, and these may be used in combination of two or more. Moreover, as a commercial item, "PRIMASET BTP-6020S (Lonza Japan Co., Ltd. product)" etc. are mentioned, for example.
(B)成分の使用量は特に制限されないが、通常、(A)成分100重量部(固形分換算)に対して1〜150重量部程度、好ましくは3〜100重量部程度、一層好ましくは3〜75重量部程度である。 Although the usage-amount of (B) component is not restrict | limited, Usually, it is about 1-150 weight part with respect to 100 weight part (solid content conversion) of (A) component, Preferably it is about 3-100 weight part, More preferably, it is 3 About 75 parts by weight.
本発明に係る樹脂組成物は、前記(A)成分及び(B)成分を各種有機溶剤(以下、(C)成分ともいう。)に溶解させることにより得られる。(C)成分の具体例としては、N−メチル−2−ピロリドン、ジメチルホルムアミド、ジメチルアセトアミド、ジメチルスルホキシド、N−メチルカプロラクタム、メチルトリグライム、メチルジグライム等の非プロトン性極性溶剤や、シクロヘキサノン、メチルシクロヘキサン等の脂環式溶剤、メタノール、エタノール、プロパノール、ベンジルアルコール、クレゾ−ル等のアルコール系溶剤、トルエン等の芳香族系溶剤等が挙げられ、これらは二種以上組み合わせてもよい。また、該有機溶剤の使用量は特に制限されないが、通常、本発明に係る樹脂組成物の固形分重量が通常10〜60重量%程度となる範囲である。 The resin composition according to the present invention is obtained by dissolving the component (A) and the component (B) in various organic solvents (hereinafter also referred to as the component (C)). Specific examples of the component (C) include N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, N-methylcaprolactam, methyltriglyme, methyldiglyme, and other aprotic polar solvents, cyclohexanone, Examples include alicyclic solvents such as methylcyclohexane, alcohol solvents such as methanol, ethanol, propanol, benzyl alcohol, and cresol, aromatic solvents such as toluene, and the like. The amount of the organic solvent used is not particularly limited, but is usually in the range where the solid content weight of the resin composition according to the present invention is usually about 10 to 60% by weight.
また、本発明に係る樹脂組成物には、必要に応じ、前記開環エステル化反応触媒や脱水剤、可塑剤、耐候剤、酸化防止剤、熱安定剤、滑剤、帯電防止剤、増白剤、着色剤、導電剤、離型剤、表面処理剤、粘度調節剤、リン系難燃剤、難燃フィラー、シリカフィラー、フッ素フィラー等の添加剤を配合できる。 Further, the resin composition according to the present invention includes the ring-opening esterification reaction catalyst, dehydrating agent, plasticizer, weathering agent, antioxidant, thermal stabilizer, lubricant, antistatic agent, and whitening agent as necessary. Additives such as a colorant, a conductive agent, a release agent, a surface treatment agent, a viscosity modifier, a phosphorus flame retardant, a flame retardant filler, a silica filler, and a fluorine filler can be blended.
本発明の樹脂付銅箔は、各種公知の方法を採用できる。具体的には、例えば、本発明に係る樹脂組成物を銅箔の片面に塗工して接着層を形成することにより、目的の樹脂付銅箔が得られる。 Various well-known methods can be adopted for the resin-coated copper foil of the present invention. Specifically, for example, by applying the resin composition according to the present invention to one surface of a copper foil to form an adhesive layer, a target copper foil with resin is obtained.
銅箔としては、各種公知のものを特に制限なく使用できる。具体的には、例えば、圧延銅箔や電解銅箔が挙げられる。また、その厚みも特に限定されず、通常は1〜100μm程度、好ましくは2〜38μm程度である。また、該銅箔は、各種表面処理(粗化、防錆化等)が施されたものであってよい。防錆化処理としては、例えば、Ni,Zn,Sn等を含むメッキ液を用いたメッキ処理や、クロメート処理等の、所謂鏡面化処理が挙げられる。 Various known copper foils can be used without any particular limitation. Specifically, rolled copper foil and electrolytic copper foil are mentioned, for example. Moreover, the thickness is not specifically limited, Usually, about 1-100 micrometers, Preferably it is about 2-38 micrometers. The copper foil may be subjected to various surface treatments (roughening, rust prevention, etc.). Examples of the rust prevention treatment include so-called mirror finishing treatment such as plating treatment using a plating solution containing Ni, Zn, Sn and the like, and chromate treatment.
塗工手段は特に限定されず、カーテンコーター、ロールコーター、ラミネーター等が挙げられる。また、各種レベリング手段を併用してもよい。 A coating means is not specifically limited, A curtain coater, a roll coater, a laminator etc. are mentioned. Various leveling means may be used in combination.
接着層は、未硬化であってもよく、また、加熱下に部分硬化ないし完全硬化させたものであってもよい。部分硬化の接着層は、いわゆるBステージと呼ばれる状態にある。また、接着層の厚みも特に限定されず、通常、0.5〜30μm程度である。 The adhesive layer may be uncured, or may be partially cured or completely cured under heating. The partially cured adhesive layer is in a state called a so-called B stage. Further, the thickness of the adhesive layer is not particularly limited, and is usually about 0.5 to 30 μm.
本発明の銅張積層板は、本発明の樹脂付銅箔を一要素とする物品であり、CCL(Copper Clad Laminate)とも呼ばれる。具体的には、各種公知の絶縁性シートの少なくとも片面又は両面に、本発明の樹脂付銅箔を、加熱下に圧着させたものである。また、片面の場合には、他方の面に本発明の樹脂付銅箔とは異なるものを圧着させてもよい。また、当該銅張積層板における樹脂付銅箔と絶縁シートの枚数は特に制限されない。 The copper clad laminate of the present invention is an article having the resin-coated copper foil of the present invention as one element, and is also called CCL (Copper Clad Laminate). Specifically, the resin-coated copper foil of the present invention is pressure-bonded with heating on at least one surface or both surfaces of various known insulating sheets. Moreover, in the case of one side, you may crimp | bond the thing different from the resin-coated copper foil of this invention to the other side. Moreover, the number of the resin-coated copper foil and the insulating sheet in the copper-clad laminate is not particularly limited.
絶縁性シートとしては、プリプレグが好ましい。プリプレグとは、ガラス布等の補強材に樹脂を含浸させBステージまで硬化させたシート状材料のことをいい(JISC5603)、該樹脂としては、通常、ポリイミド樹脂、フェノール樹脂、エポキシ樹脂、ポリエステル樹脂、液晶ポリマー、アラミド樹脂等の絶縁性樹脂使用される。また、該プリプレグの厚みは特に限定されず、通常、20〜500μm程度である。 As the insulating sheet, a prepreg is preferable. A prepreg refers to a sheet-like material obtained by impregnating a reinforcing material such as a glass cloth with a resin and curing it to the B stage (JISC5603). As the resin, usually a polyimide resin, a phenol resin, an epoxy resin, or a polyester resin. Insulating resins such as liquid crystal polymers and aramid resins are used. Moreover, the thickness of this prepreg is not specifically limited, Usually, it is about 20-500 micrometers.
加熱・圧着条件は特に限定されず、通常150〜280℃程度(好ましくは170℃〜240℃程度)、及び0.5〜20MPa程度(好ましくは1〜8MPa程度)である。 The heating and pressure bonding conditions are not particularly limited, and are usually about 150 to 280 ° C. (preferably about 170 ° C. to 240 ° C.) and about 0.5 to 20 MPa (preferably about 1 to 8 MPa).
本発明のプリント配線板は、本発明の銅張積層板の少なくとも一の銅箔に回路パターンを形成してなる物品である。パターニング手段としては、例えばセミアディティブ法が挙げられる。具体的には、例えば、本発明の銅張積層板の銅箔面に、レジストフィルムでパターニングした後、電解銅メッキを行い、レジストを除去し、アルカリ液でエッチングする方法が挙げられる。また、該プリント配線板における回路パターン層は特に限定されない。 The printed wiring board of the present invention is an article formed by forming a circuit pattern on at least one copper foil of the copper-clad laminate of the present invention. Examples of the patterning means include a semi-additive method. Specifically, for example, the copper foil surface of the copper-clad laminate of the present invention may be patterned with a resist film, followed by electrolytic copper plating, removing the resist, and etching with an alkaline solution. Moreover, the circuit pattern layer in the printed wiring board is not particularly limited.
本発明の多層配線板は、本発明のプリント配線板を一要素とする物品である。具体的には、該プリント配線板をコア材とし、その片面ないし両面に本発明の樹脂付銅箔を積層した後、外層銅箔に回路パターンを描写したものがあげられる。また、コア材に対する樹脂付銅箔の積層数は特に限定されない。また、積層の都度、ビアホールを挿設し、内部をメッキ処理してもよい。 The multilayer wiring board of the present invention is an article having the printed wiring board of the present invention as one element. Specifically, the printed wiring board is used as a core material, the resin-coated copper foil of the present invention is laminated on one side or both sides, and then a circuit pattern is drawn on the outer layer copper foil. Further, the number of laminated copper foils with resin on the core material is not particularly limited. Moreover, a via hole may be inserted and the inside may be plated each time it is laminated.
以下、実施例及び比較例を通じて本発明を具体的に説明するが、それらによって本発明の範囲が限定されることはない。また、各例中、部及び%は特記しない限り重量基準である。 EXAMPLES Hereinafter, although this invention is demonstrated concretely through an Example and a comparative example, the scope of the present invention is not limited by them. In each example, parts and% are based on weight unless otherwise specified.
軟化点は、市販の測定器(「ARES−2KSTD−FCO−STD」、Rheometric Scientfic社製)を用いて測定した粘弾性プロファイルにおいて、剛性率が低下開始する温度である。 The softening point is a temperature at which the rigidity starts to decrease in a viscoelastic profile measured using a commercially available measuring instrument (“ARES-2KSTD-FCO-STD”, manufactured by Rheometric Scientific).
<ポリイミド樹脂の製造>
製造例1
撹拌機、分水器、温度計及び窒素ガス導入管を備えた反応容器に、3,3’,4,4’−ベンゾフェノンテトラカルボン酸二無水物(商品名「BTDA」、ダイセル化学工業(株)製。)53.00g、シクロヘキサノン249.10g、及びメチルシクロヘキサン49.82gを仕込み、60℃まで加熱した。次いで、ダイマージアミン(商品名「PRIAMINE1075」、クローダジャパン(株)製。以下、PRIAMINEと略す。)85.40gを滴下した後、140℃で1時間かけてイミド化反応させることにより、ポリイミド樹脂(A−1)の溶液(不揮発分30.6%)を得た。なお、該ポリイミド樹脂の酸成分/アミン成分のモル比は1.04であり、軟化点は80℃であった。
<Manufacture of polyimide resin>
Production Example 1
In a reaction vessel equipped with a stirrer, a water separator, a thermometer, and a nitrogen gas introduction tube, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (trade name “BTDA”, Daicel Chemical Industries, Ltd.) )) 53.00 g, cyclohexanone 249.10 g, and methylcyclohexane 49.82 g were charged and heated to 60 ° C. Next, 85.40 g of dimer diamine (trade name “PRIAMINE 1075”, manufactured by Croda Japan Co., Ltd., hereinafter abbreviated as PRIAMINE) was added dropwise, and then the polyimide resin ( A solution of A-1) (non-volatile content: 30.6%) was obtained. The polyimide resin had an acid component / amine component molar ratio of 1.04 and a softening point of 80 ° C.
製造例2
製造例1と同様の反応容器に、4,4’−[プロパン−2,2−ジイルビス(1,4−フェニレンオキシ)]ジフタル酸二無水物(商品名「BisDA−1000」、SABICイノベーティブプラスチックスジャパン合同会社製。以下、BisDAと略す。)を70.00g、シクロヘキサノンを266.00g及びメチルシクロヘキサンを53.20g仕込み、60℃まで加熱した。次いで、PRIAMINE 69.90gを徐々に添加した後、140℃まで加熱し、1時間かけてイミド化反応を実施することにより、ポリイミド樹脂(A−2)の溶液(不揮発分30.3%)を得た。なお、該ポリイミド樹脂の酸成分/アミン成分のモル比は1.04であり、軟化点は90℃であった。
Production Example 2
In a reaction vessel similar to Production Example 1, 4,4 ′-[propane-2,2-diylbis (1,4-phenyleneoxy)] diphthalic dianhydride (trade name “BisDA-1000”, SABIC Innovative Plastics) 70.00 g, manufactured by Japan GK (hereinafter abbreviated as BisDA), 266.00 g of cyclohexanone and 53.20 g of methylcyclohexane were charged and heated to 60 ° C. Next, after gradually adding 69.90 g of PRIAMINE, the mixture was heated to 140 ° C. and subjected to an imidization reaction over 1 hour, whereby a polyimide resin (A-2) solution (non-volatile content: 30.3%) was obtained. Obtained. The polyimide resin had an acid component / amine component molar ratio of 1.04 and a softening point of 90 ° C.
製造例3
製造例1と同様の反応容器に4,4’−オキシジフタル酸無水物(商品名「ODPA−1000」、SABICイノベーティブプラスチックスジャパン合同会社製。以下、ODPAともいう。)を50.00g、シクロヘキサノンを250.00g、メチルシクロヘキサンを50.00g仕込み、溶液を60℃まで加熱した。次いで、PRIAMINE 84.56gを徐々に添加した後、140℃まで加熱し、1時間かけてイミド化反応を実施することにより、不揮発分30.2%のポリイミド樹脂(A−3)の溶液を得た。なお、該ポリイミド樹脂の酸成分/アミン成分のモル比は1.03であり、軟化点は70℃であった。
Production Example 3
In a reaction container similar to Production Example 1, 50.00 g of 4,4′-oxydiphthalic anhydride (trade name “ODPA-1000”, manufactured by SABIC Innovative Plastics Japan G.K., hereinafter also referred to as ODPA) and cyclohexanone. 250.00 g and 50.00 g of methylcyclohexane were charged, and the solution was heated to 60 ° C. Next, after 84.56 g of PRIAMINE was gradually added, the solution was heated to 140 ° C. and subjected to an imidization reaction over 1 hour to obtain a polyimide resin (A-3) solution having a nonvolatile content of 30.2%. It was. The polyimide resin had an acid component / amine component molar ratio of 1.03 and a softening point of 70 ° C.
製造例4
製造例1と同様の反応容器にBisDAを65.00g、シクロヘキサノンを214.50g、メチルシクロヘキサンを35.75g仕込み、溶液を60℃まで加熱した。次いで、PRIAMINE 51.43gと、1,3−ビス(アミノメチル)シクロヘキサン(商品名「1,3−BAC」、三菱ガス化学製。)3.39gを徐々に添加した後、140℃まで加熱し、1時間かけてイミド化反応を実施することにより、ポリイミド樹脂(A−4)の溶液(不揮発分29.5%)を得た。なお、該ポリイミド樹脂の酸成分/アミン成分のモル比は1.05であり、軟化点は90℃であった。
Production Example 4
A reaction vessel similar to Production Example 1 was charged with 65.00 g of BisDA, 214.50 g of cyclohexanone, and 35.75 g of methylcyclohexane, and the solution was heated to 60 ° C. Next, 51.43 g of PRIAMINE and 3.39 g of 1,3-bis (aminomethyl) cyclohexane (trade name “1,3-BAC”, manufactured by Mitsubishi Gas Chemical Co., Ltd.) were gradually added and heated to 140 ° C. By performing imidation reaction over 1 hour, the solution (nonvolatile content 29.5%) of the polyimide resin (A-4) was obtained. The polyimide resin had an acid component / amine component molar ratio of 1.05 and a softening point of 90 ° C.
製造例5
製造例1と同様の反応容器にBisDAを65.00g、シクロヘキサノンを266.50g、メチルシクロヘキサンを44.42g仕込み、溶液を60℃まで加熱した。次いで、PRIAMINE 43.71gと、1,3−BAC 5.42gとを徐々に添加した後、140℃まで加熱し、1時間かけてイミド化反応を実施することにより、ポリイミド樹脂(A−5)の溶液(不揮発分29.5%)を得た。なお、該ポリイミド樹脂の酸成分/アミン成分のモル比は1.05であり、軟化点は100℃であった。
Production Example 5
A reaction vessel similar to Production Example 1 was charged with 65.00 g of BisDA, 266.50 g of cyclohexanone, and 44.42 g of methylcyclohexane, and the solution was heated to 60 ° C. Next, after gradually adding 43.71 g of PRIAMINE and 5.42 g of 1,3-BAC, the mixture was heated to 140 ° C. and subjected to an imidization reaction for 1 hour to obtain a polyimide resin (A-5). Solution (29.5% non-volatile content) was obtained. The polyimide resin had an acid component / amine component molar ratio of 1.05 and a softening point of 100 ° C.
製造例6
製造例1と同様の反応容器にBisDAを65.00g、シクロヘキサノンを144.19g、溶液を60℃まで加熱した。次いで、PRIAMINE 19.29gと、1,3−BAC11.85gとを徐々に添加した後、メチルシクロヘキサンを26.22g、エチレングリコールジメチルエーテルを91.8g仕込み、140℃まで加熱し、3時間かけてイミド化反応を実施することにより、ポリイミド樹脂(A−6)の溶液(不揮発分26.8%)を得た。なお、該ポリイミド樹脂の酸成分/アミン成分のモル比は1.04であり、軟化点は140℃であった。
Production Example 6
In the same reaction vessel as in Production Example 1, 65.00 g of BisDA, 144.19 g of cyclohexanone, and the solution were heated to 60 ° C. Next, after gradually adding 19.29 g of PRIAMINE and 11.85 g of 1,3-BAC, 26.22 g of methylcyclohexane and 91.8 g of ethylene glycol dimethyl ether were charged, heated to 140 ° C., and imide was added over 3 hours. By performing the chemical reaction, a solution of the polyimide resin (A-6) (nonvolatile content: 26.8%) was obtained. The polyimide resin had an acid component / amine component molar ratio of 1.04 and a softening point of 140 ° C.
製造例7
製造例1と同様の反応容器に、BTDAを53.00g、シクロヘキサノンを278.30g、メチルシクロヘキサンを55.65g仕込み、溶液を60℃まで加熱した。次いで、PRIAMINE 64.05gと、α,ω−ビス(3−アミノプロピル)ポリジメチルシロキサン(商品名「KF−8010」、信越化学工業(株)製。)34.79gを徐々に添加した後、140℃で1時間かけてイミド化反応させることにより、ポリイミド樹脂(A−7)の溶液(不揮発分30.2%)を得た。なお、該ポリイミド樹脂の酸成分/アミン成分のモル比は1.04であり、軟化点は40℃であった。
Production Example 7
A reaction vessel similar to Production Example 1 was charged with 53.00 g of BTDA, 278.30 g of cyclohexanone, and 55.65 g of methylcyclohexane, and the solution was heated to 60 ° C. Next, 64.05 g of PRIAMINE and 34.79 g of α, ω-bis (3-aminopropyl) polydimethylsiloxane (trade name “KF-8010”, manufactured by Shin-Etsu Chemical Co., Ltd.) were gradually added, A polyimide resin (A-7) solution (non-volatile content: 30.2%) was obtained by performing an imidization reaction at 140 ° C. over 1 hour. The polyimide resin had an acid component / amine component molar ratio of 1.04 and a softening point of 40 ° C.
製造例8
製造例1と同様の反応容器に、BTDAを53.00g、シクロヘキサノンを312.70g、メチルシクロヘキサンを62.54g仕込み、溶液を60℃まで加熱した。次いで、PRIAMINE 42.70gと、KF−8010 69.59gとを徐々に添加した後、140℃で1時間かけてイミド化反応させることにより、ポリイミド樹脂(A−8)の溶液(不揮発分30.2%)を得た。なお、該ポリイミド樹脂の酸成分/アミン成分のモル比は1.04であり、ガラス転移温度は30℃であった。
Production Example 8
A reaction vessel similar to Production Example 1 was charged with 53.00 g of BTDA, 312.70 g of cyclohexanone, and 62.54 g of methylcyclohexane, and the solution was heated to 60 ° C. Subsequently, 42.70 g of PRIAMINE and 69.59 g of KF-8010 were gradually added, and then an imidization reaction was performed at 140 ° C. over 1 hour, whereby a solution of the polyimide resin (A-8) (nonvolatile content 30.30). 2%). The polyimide resin had an acid component / amine component molar ratio of 1.04 and a glass transition temperature of 30 ° C.
比較製造例1
製造例1と同様の反応容器にBTDAを53.00g、シクロヘキサノンを212.00g、メチルシクロヘキサンを42.40g仕込み、溶液を60℃まで加熱した。次いでPRIAMINE 21.35g及びKF−8010 104.38gを徐々に添加し、徐々に添加した後、溶液を140℃まで加熱し、1時間かけてイミド化反応を実施することにより、ポリイミド樹脂(ロ)の溶液(不揮発分42.0%)を得た。なお、該ポリイミド樹脂の酸成分/アミン成分のモル比は1.04であり、ガラス転移温度は5℃であった。
Comparative production example 1
A reaction vessel similar to Production Example 1 was charged with 53.00 g of BTDA, 212.00 g of cyclohexanone, and 42.40 g of methylcyclohexane, and the solution was heated to 60 ° C. Next, 21.35 g of PRIAMINE and 104.38 g of KF-8010 were gradually added, and after gradually adding, the solution was heated to 140 ° C. and subjected to an imidization reaction for 1 hour to obtain a polyimide resin (B) Solution (non-volatile content: 42.0%) was obtained. The polyimide resin had an acid component / amine component molar ratio of 1.04 and a glass transition temperature of 5 ° C.
比較製造例2
製造例1と同様の反応容器にBTDA 53.00g、シクロヘキサノン212.00g、メチルシクロヘキサン42.40gを仕込み、溶液を60℃になるまで加熱した。次いで、KF−8010 139.17gを徐々に添加し、1時間かけてイミド化反応を実施することにより、ポリイミド樹脂(イ)の溶液(不揮発分42.0%)を得た。なお、該ポリイミド樹脂の酸成分/アミン成分のモル比は1.04であり、ガラス転移温度は10℃であった。
Comparative production example 2
A reaction vessel similar to Production Example 1 was charged with 53.00 g of BTDA, 212.00 g of cyclohexanone, and 42.40 g of methylcyclohexane, and the solution was heated to 60 ° C. Next, 139.17 g of KF-8010 was gradually added, and an imidization reaction was carried out over 1 hour to obtain a solution of polyimide resin (i) (nonvolatile content: 42.0%). The polyimide resin had an acid component / amine component molar ratio of 1.04 and a glass transition temperature of 10 ° C.
実施例1
ポリイミド樹脂(A−1)の溶液100.0g、(B)成分としてビスフェノールA型エポキシ樹脂(ジャパンエポキシレジン(株)製、商品名「jER828」、エポキシ当量190g/eq)11.1g、水酸基含有シクロフォスファゼン(商品名「SPH−100」大塚化学(株)製)13.9g、1−シアノエチル−2−ウンデシルイミダゾール(商品名「C11Z−CN」四国化成(株))0.03g、並びに有機溶剤としてシクロヘキサノン32.5g及びメチルエチルケトン16.4gを混合し、よく撹拌することによって、不揮発分32.0%の樹脂組成物を得た。
Example 1
100.0 g of polyimide resin (A-1) solution, as component (B), bisphenol A type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., trade name “jER828”, epoxy equivalent 190 g / eq) 11.1 g, hydroxyl group-containing 13.9 g of cyclophosphazene (trade name “SPH-100” manufactured by Otsuka Chemical Co., Ltd.), 0.03 g of 1-cyanoethyl-2-undecylimidazole (trade name “C11Z-CN” Shikoku Kasei Co., Ltd.), In addition, 32.5 g of cyclohexanone and 16.4 g of methyl ethyl ketone as an organic solvent were mixed and stirred well to obtain a resin composition having a nonvolatile content of 32.0%.
実施例2〜12
(A)成分、(B)成分及び有機溶剤として、表2で示す種類のものをそれぞれの量で使用した他は実施例1と同様にして、各樹脂組成物を得た。
Examples 2-12
As the component (A), the component (B), and the organic solvent, resin compositions were obtained in the same manner as in Example 1 except that the types shown in Table 2 were used in respective amounts.
比較例1
実施例1において、(A−1)成分の溶液に代えて、前記(イ)成分の溶液を表2で示す量で用い、かつ(B)成分及び有機溶剤として表3で示す種類のものをそれぞれの量で使用した他は同様にして、各樹脂組成物を得た。
Comparative Example 1
In Example 1, instead of the solution of component (A-1), the solution of component (a) was used in the amount shown in Table 2, and the component shown in Table 3 as the component (B) and organic solvent was used. Each resin composition was obtained in the same manner except that each amount was used.
比較例2
実施例1において、(A−1)成分の溶液に代えて、前記(ロ)成分の溶液を表2で示す量で用い、かつ(B)成分及び有機溶剤として表3で示す種類のものをそれぞれの量で使用した他は同様にして、各樹脂組成物を得た。
Comparative Example 2
In Example 1, instead of the solution of the component (A-1), the solution of the component (b) was used in the amount shown in Table 2, and the component (B) and the organic solvent shown in Table 3 were used. Each resin composition was obtained in the same manner except that each amount was used.
比較例3
実施例1において、(A−1)成分の溶液に代えてカルボキシル基含有NBR(商品名「XER−32C」、JSR(株)製)を表3で示す量で用い、かつ(B)成分及び(C)成分として、表2で示す種類のものをそれぞれの量で使用した他は同様にして、各樹脂組成物を得た。
Comparative Example 3
In Example 1, instead of the solution of component (A-1), carboxyl group-containing NBR (trade name “XER-32C”, manufactured by JSR Corporation) was used in the amounts shown in Table 3, and (B) component and (C) Each resin composition was obtained in the same manner except that the components shown in Table 2 were used in the respective amounts.
SPH−100(商品名):水酸基含有シクロフォスファゼン(大塚化学(株)製)
C11Z−CN(商品名):1−シアノエチル−2−ウンデシルイミダゾール(四国化成(株)製)
2E4MZ(商品名):2−エチル−4−メチルイミダゾール(四国化成工業(株)製)
BMI−TMH(商品名):1,6’−ビスマレイミド−(2,2,4−トリメチル)ヘキサン(大和化成工業(株)製)
パークミルD(商品名):ジクミルパーオキサイド(日油(株)製)
Primaset BA−3000 S(商品名):シアネートエステル樹脂(ロンザジャパン(株)製)
SPH-100 (trade name): Hydroxyl-containing cyclophosphazene (Otsuka Chemical Co., Ltd.)
C11Z-CN (trade name): 1-cyanoethyl-2-undecylimidazole (manufactured by Shikoku Kasei Co., Ltd.)
2E4MZ (trade name): 2-ethyl-4-methylimidazole (manufactured by Shikoku Chemicals Co., Ltd.)
BMI-TMH (trade name): 1,6′-bismaleimide- (2,2,4-trimethyl) hexane (manufactured by Daiwa Kasei Kogyo Co., Ltd.)
Park mill D (trade name): Dicumyl peroxide (manufactured by NOF Corporation)
Primeset BA-3000 S (trade name): Cyanate ester resin (manufactured by Lonza Japan Co., Ltd.)
<誘電率及び誘電正接の測定>
実施例1の樹脂組成物を、ナフロン(登録商標)PTFEテープ(「TOMBO No.9001」、ニチアス(株)製)上に塗工し、室温で12時間乾燥させた後、200℃で1時間硬化させることによって、膜厚50μmの硬化物シートを得た。
<Measurement of dielectric constant and dissipation factor>
The resin composition of Example 1 was coated on Naflon (registered trademark) PTFE tape (“TOMBO No. 9001”, manufactured by NICHIAS Corporation), dried at room temperature for 12 hours, and then at 200 ° C. for 1 hour. By curing, a cured product sheet having a thickness of 50 μm was obtained.
次いで、該硬化物シートについて、JIS C2565に準じ、10GHzにおける誘電率及び誘電正接を、市販の誘電率測定装置(空洞共振器タイプ、エーイーティー製)を用いて測定した。結果を表4に示す。 Next, according to JIS C2565, the dielectric constant and dielectric loss tangent of the cured product sheet at 10 GHz were measured using a commercially available dielectric constant measuring device (cavity resonator type, manufactured by AET). The results are shown in Table 4.
他の実施例及び比較例の樹脂組成物についても同様に硬化物シートを作製し、誘電率及び誘電正接を測定した。結果を表4に示す。 For the resin compositions of other examples and comparative examples, cured sheets were prepared in the same manner, and the dielectric constant and dielectric loss tangent were measured. The results are shown in Table 4.
<樹脂付銅箔の作製>
実施例1の樹脂組成物を、18μm厚の電解銅箔(商品名「F2−WS」、古河電気工業(株)製。幅25.4cmのロール状。)の鏡面に、乾燥後の厚みが5μmとなるようギャップコーターで塗布した後、200℃で3分間乾燥させた後、所定の長さで切りとり、樹脂付銅箔を得た。
<Production of copper foil with resin>
The thickness after drying of the resin composition of Example 1 on the mirror surface of an electrolytic copper foil having a thickness of 18 μm (trade name “F2-WS”, manufactured by Furukawa Electric Co., Ltd., 25.4 cm wide). After apply | coating with a gap coater so that it might become 5 micrometers, after making it dry for 3 minutes at 200 degreeC, it cut out by predetermined length and obtained copper foil with resin.
<銅張積層板の作製>
次いで、該樹脂付銅箔の接着面に、80μm厚のエポキシプリプレグ(商品名「5100」、(株)寺岡製作所製)を重ね、その上に該樹脂付銅箔を更に重ねてから、圧力4.5MPa、200℃及び30分間の条件で加熱プレスすることにより、銅張積層板を作製した。
<Preparation of copper-clad laminate>
Next, an 80 μm-thick epoxy prepreg (trade name “5100”, manufactured by Teraoka Seisakusho Co., Ltd.) is stacked on the adhesive surface of the resin-coated copper foil, and the resin-coated copper foil is further stacked thereon. A copper-clad laminate was produced by hot pressing under conditions of 0.5 MPa, 200 ° C. and 30 minutes.
<常温密着性の評価>
該銅張積層板について、JIS C 6481(プリント配線板用銅張積層板試験方法)に準じ、引き剥がし強さ(N/cm)を評価した。結果を表4に示す。
<Evaluation of room temperature adhesion>
About this copper clad laminated board, peeling strength (N / cm) was evaluated according to JIS C 6481 (copper clad laminated board test method for printed wiring boards). The results are shown in Table 4.
<耐熱密着性の評価>
該銅張り積層板を120℃で5分間加熱した後、300℃のはんだ浴に10分間浮かべた後、樹脂層の発泡や金属基材の剥がれの有無を評価した。結果を表4に示す。
<Evaluation of heat-resistant adhesion>
The copper-clad laminate was heated at 120 ° C. for 5 minutes, then floated in a 300 ° C. solder bath for 10 minutes, and then evaluated for foaming of the resin layer and peeling of the metal substrate. The results are shown in Table 4.
他の実施例及び比較例の樹脂組成物についても同様に銅張積層板を作製し、初期接着性及び耐熱接着性を評価した。結果を表4に示す。 For the resin compositions of other examples and comparative examples, copper-clad laminates were similarly prepared, and initial adhesiveness and heat-resistant adhesiveness were evaluated. The results are shown in Table 4.
<プリント配線板の作製>
実施例1に係る銅張積層板の両面の銅箔に、ライン/スペース=0.2/0.2(mm)のレジストパターンを形成したものを、濃度40%の塩化第二鉄水溶液に浸漬することによってエッチングし、銅回路を形成した。このようにして、プリント配線板が得られた。
<Production of printed wiring board>
A copper foil on both sides of the copper clad laminate according to Example 1 formed with a resist pattern of line / space = 0.2 / 0.2 (mm) was immersed in an aqueous ferric chloride solution having a concentration of 40%. Etching was performed to form a copper circuit. In this way, a printed wiring board was obtained.
<多層配線板の作製>
得られたプリント配線板をコア材とし、その両面に、実施例1に係る樹脂付銅箔を重ね、圧力4.5MPa、200℃及び30分間の条件で圧着させたものの外層の未処理銅箔に、ライン/スペース=0.2/0.2(mm)のレジストパターンを形成した。次いで、得られた基板を濃度40%の塩化第二鉄水溶液への浸漬によってエッチングすることにより、銅回路を形成した。このようにして、回路パターン層を4つ備える多層配線板が得られた。
<Production of multilayer wiring board>
The obtained printed wiring board is used as a core material, and the copper foil with resin according to Example 1 is overlapped on both sides thereof, and the outer layer untreated copper foil is bonded under pressure of 4.5 MPa, 200 ° C. and 30 minutes. Then, a resist pattern of line / space = 0.2 / 0.2 (mm) was formed. Next, a copper circuit was formed by etching the obtained substrate by immersion in a ferric chloride aqueous solution having a concentration of 40%. In this way, a multilayer wiring board having four circuit pattern layers was obtained.
他の実施例の接着剤組成物についても、同様の方法により、プリント配線板及び多層配線板が得られた。 For the adhesive compositions of other examples, printed wiring boards and multilayer wiring boards were obtained in the same manner.
Claims (6)
A multilayer wiring board comprising the printed wiring board according to claim 5 as one element.
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