JP2020132920A - Manufacturing method of copper-clad laminate - Google Patents
Manufacturing method of copper-clad laminate Download PDFInfo
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- JP2020132920A JP2020132920A JP2019025045A JP2019025045A JP2020132920A JP 2020132920 A JP2020132920 A JP 2020132920A JP 2019025045 A JP2019025045 A JP 2019025045A JP 2019025045 A JP2019025045 A JP 2019025045A JP 2020132920 A JP2020132920 A JP 2020132920A
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- copper
- copper plating
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- clad laminate
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 238000007747 plating Methods 0.000 claims abstract description 123
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 116
- 229910052802 copper Inorganic materials 0.000 claims abstract description 116
- 239000010949 copper Substances 0.000 claims abstract description 116
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000011593 sulfur Substances 0.000 claims abstract description 23
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 23
- 238000009713 electroplating Methods 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims description 29
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 8
- 239000000460 chlorine Substances 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- LMPMFQXUJXPWSL-UHFFFAOYSA-N 3-(3-sulfopropyldisulfanyl)propane-1-sulfonic acid Chemical group OS(=O)(=O)CCCSSCCCS(O)(=O)=O LMPMFQXUJXPWSL-UHFFFAOYSA-N 0.000 claims description 6
- OBDVFOBWBHMJDG-UHFFFAOYSA-N 3-mercapto-1-propanesulfonic acid Chemical compound OS(=O)(=O)CCCS OBDVFOBWBHMJDG-UHFFFAOYSA-N 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 abstract description 22
- 239000000758 substrate Substances 0.000 abstract description 4
- 230000003111 delayed effect Effects 0.000 abstract 1
- 238000000151 deposition Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 62
- -1 alkane sulfonic acid copper salt Chemical class 0.000 description 15
- 239000000126 substance Substances 0.000 description 10
- 150000001879 copper Chemical class 0.000 description 9
- 239000013078 crystal Substances 0.000 description 9
- 239000000654 additive Substances 0.000 description 8
- 239000010953 base metal Substances 0.000 description 8
- 238000005498 polishing Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000010409 thin film Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910000623 nickel–chromium alloy Inorganic materials 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- XXACTDWGHQXLGW-UHFFFAOYSA-M Janus Green B chloride Chemical compound [Cl-].C12=CC(N(CC)CC)=CC=C2N=C2C=CC(\N=N\C=3C=CC(=CC=3)N(C)C)=CC2=[N+]1C1=CC=CC=C1 XXACTDWGHQXLGW-UHFFFAOYSA-M 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical compound OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- RSJOBNMOMQFPKQ-UHFFFAOYSA-L copper;2,3-dihydroxybutanedioate Chemical compound [Cu+2].[O-]C(=O)C(O)C(O)C([O-])=O RSJOBNMOMQFPKQ-UHFFFAOYSA-L 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- BSXVKCJAIJZTAV-UHFFFAOYSA-L copper;methanesulfonate Chemical compound [Cu+2].CS([O-])(=O)=O.CS([O-])(=O)=O BSXVKCJAIJZTAV-UHFFFAOYSA-L 0.000 description 1
- SEGDGYCSRNUBHG-UHFFFAOYSA-N copper;propan-1-ol Chemical compound [Cu].CCCO SEGDGYCSRNUBHG-UHFFFAOYSA-N 0.000 description 1
- NPSDYIWFLLIHOT-UHFFFAOYSA-L copper;propane-1-sulfonate Chemical compound [Cu+2].CCCS([O-])(=O)=O.CCCS([O-])(=O)=O NPSDYIWFLLIHOT-UHFFFAOYSA-L 0.000 description 1
- FWBOFUGDKHMVPI-UHFFFAOYSA-K dicopper;2-oxidopropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[O-]C(=O)CC([O-])(C([O-])=O)CC([O-])=O FWBOFUGDKHMVPI-UHFFFAOYSA-K 0.000 description 1
- YIOJGTBNHQAVBO-UHFFFAOYSA-N dimethyl-bis(prop-2-enyl)azanium Chemical compound C=CC[N+](C)(C)CC=C YIOJGTBNHQAVBO-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229940045996 isethionic acid Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
Abstract
Description
本発明は、銅張積層板の製造方法に関する。さらに詳しくは、本発明は、フレキシブルプリント配線板（ＦＰＣ）などの製造に用いられる銅張積層板の製造方法に関する。 The present invention relates to a method for manufacturing a copper-clad laminate. More specifically, the present invention relates to a method for manufacturing a copper-clad laminate used for manufacturing a flexible printed wiring board (FPC) or the like.
液晶パネル、ノートパソコン、デジタルカメラ、携帯電話などには、樹脂フィルムの表面に配線パターンが形成されたフレキシブルプリント配線板が用いられる。フレキシブルプリント配線板は、例えば、銅張積層板から製造される。 Flexible printed wiring boards having a wiring pattern formed on the surface of a resin film are used for liquid crystal panels, notebook computers, digital cameras, mobile phones, and the like. The flexible printed wiring board is manufactured from, for example, a copper-clad laminate.
銅張積層板の製造方法としてメタライジング法が知られている。メタライジング法による銅張積層板の製造は、例えば、つぎの手順で行なわれる。まず、樹脂フィルムの表面にニッケルクロム合金からなる下地金属層を形成する。つぎに、下地金属層の上に銅薄膜層を形成する。つぎに、銅薄膜層の上に銅めっき被膜を形成する。銅めっきにより、配線パターンを形成するのに適した膜厚となるまで導体層を厚膜化する。メタライジング法により、樹脂フィルム上に直接導体層が形成された、いわゆる２層基板と称されるタイプの銅張積層板が得られる。 The metallizing method is known as a method for manufacturing a copper-clad laminate. The production of the copper-clad laminate by the metallizing method is performed, for example, by the following procedure. First, a base metal layer made of a nickel-chromium alloy is formed on the surface of the resin film. Next, a copper thin film layer is formed on the base metal layer. Next, a copper plating film is formed on the copper thin film layer. By copper plating, the conductor layer is thickened until the film thickness is suitable for forming the wiring pattern. By the metallizing method, a copper-clad laminate of a type called a so-called two-layer substrate in which a conductor layer is directly formed on a resin film can be obtained.
この種の銅張積層板を用いてフレキシブルプリント配線板を製造する方法としてセミアディティブ法が知られている。セミアディティブ法によるフレキシブルプリント配線板の製造は、つぎの手順で行なわれる（特許文献１参照）。まず、銅張積層板の銅めっき被膜の表面にレジスト層を形成する。つぎに、レジスト層のうち配線パターンを形成する部分に開口部を形成する。つぎに、レジスト層の開口部から露出した銅めっき被膜を陰極として電解めっきを行ない、配線部を形成する。つぎに、レジスト層を除去し、フラッシュエッチングなどにより配線部以外の導体層を除去する。これにより、フレキシブルプリント配線板が得られる。 A semi-additive method is known as a method for manufacturing a flexible printed wiring board using this type of copper-clad laminate. The flexible printed wiring board is manufactured by the semi-additive method according to the following procedure (see Patent Document 1). First, a resist layer is formed on the surface of the copper plating film of the copper-clad laminate. Next, an opening is formed in the portion of the resist layer that forms the wiring pattern. Next, electrolytic plating is performed using the copper plating film exposed from the opening of the resist layer as a cathode to form a wiring portion. Next, the resist layer is removed, and the conductor layer other than the wiring portion is removed by flash etching or the like. As a result, a flexible printed wiring board can be obtained.
セミアディティブ法において、銅めっき被膜の表面にレジスト層を形成するあたり、ドライフィルムレジストを用いることがある。この場合、銅めっき被膜の表面を化学研磨した後に、ドライフィルムレジストを貼り付ける。化学研磨により銅めっき被膜の表面に微細な凹凸をつけることで、アンカー効果によるドライフィルムレジストの密着性を高めている。しかし、銅めっき被膜の表面の凹凸が過剰であると、かえってドライフィルムレジストの密着性が悪化することがある。 In the semi-additive method, a dry film resist may be used to form a resist layer on the surface of the copper plating film. In this case, after the surface of the copper plating film is chemically polished, a dry film resist is attached. By making fine irregularities on the surface of the copper plating film by chemical polishing, the adhesion of the dry film resist due to the anchor effect is improved. However, if the surface of the copper plating film is excessively uneven, the adhesion of the dry film resist may be deteriorated.
化学研磨後の銅めっき被膜の表面粗さは、銅めっき被膜の結晶粒のサイズに影響される。結晶粒が小さいほど化学研磨後の銅めっき被膜の表面が滑らかになり、結晶粒が大きいほど化学研磨後の銅めっき被膜の表面が粗くなるという傾向がある。 The surface roughness of the copper plating film after chemical polishing is affected by the size of the crystal grains of the copper plating film. The smaller the crystal grains, the smoother the surface of the copper plating film after chemical polishing, and the larger the crystal grains, the rougher the surface of the copper plating film after chemical polishing.
銅めっき被膜の結晶粒はめっき処理後の再結晶の進行にともない、徐々に大きくなる。再結晶が進行中の銅めっき被膜に化学研磨を行なうと、化学研磨の時点におけるめっき処理からの経過時間によって、化学研磨後の銅めっき被膜の表面粗さが変化する。そのため、配線加工における工程管理が困難になる。また、再結晶が終了した銅めっき被膜は結晶粒が大きくなっていることから、化学研磨後の表面粗さが過剰となることがある。そこで、銅張積層板の銅めっき被膜には、再結晶の進行が遅いことが求められる場合がある。 The crystal grains of the copper plating film gradually increase in size as the recrystallization progresses after the plating treatment. When the copper plating film in which recrystallization is in progress is chemically polished, the surface roughness of the copper plating film after the chemical polishing changes depending on the elapsed time from the plating treatment at the time of the chemical polishing. Therefore, process control in wiring processing becomes difficult. Further, since the crystal grains of the copper-plated coating that has been recrystallized are large, the surface roughness after chemical polishing may be excessive. Therefore, the copper-plated coating of the copper-clad laminate may be required to have a slow progress of recrystallization.
本発明は上記事情に鑑み、再結晶の進行が遅い銅めっき被膜を有する銅張積層板の製造方法を提供することを目的とする。 In view of the above circumstances, an object of the present invention is to provide a method for producing a copper-clad laminate having a copper-plated coating film in which recrystallization proceeds slowly.
第１発明の銅張積層板の製造方法は、銅めっき液を用いた電解めっきにより、基材の表面に銅めっき被膜を成膜して銅張積層板を得る方法であって、前記銅めっき液中のブライトナー成分に含まれる硫黄の濃度が１．８〜９．１ｍｇ／Ｌであることを特徴とする。
第２発明の銅張積層板の製造方法は、第１発明において、前記ブライトナー成分がビス（３−スルホプロピル）ジスルフィドおよび／または３−メルカプトプロパン−１−スルホン酸であることを特徴とする。
第３発明の銅張積層板の製造方法は、第１または第２発明において、前記銅めっき液中の銅濃度が１５〜７０ｇ／Ｌ、硫酸濃度が２０〜２５０ｇ／Ｌ、塩素濃度が２０〜８０ｇ／Ｌであることを特徴とする。
第４発明の銅張積層板の製造方法は、第１〜第３発明のいずれかにおいて、前記電解めっきの電流密度が０．１〜４．５Ａ／ｄｍ2であることを特徴とする。
The method for producing a copper-clad laminate according to the first invention is a method for obtaining a copper-clad laminate by forming a copper plating film on the surface of a base material by electrolytic plating using a copper plating solution, and the copper plating The concentration of sulfur contained in the brightener component in the liquid is 1.8 to 9.1 mg / L.
The method for producing a copper-clad laminate of the second invention is characterized in that, in the first invention, the Brightener component is bis (3-sulfopropyl) disulfide and / or 3-mercaptopropane-1-sulfonic acid. ..
In the first or second invention, the method for producing a copper-clad laminate of the third invention has a copper concentration of 15 to 70 g / L, a sulfuric acid concentration of 20 to 250 g / L, and a chlorine concentration of 20 to 20 in the copper plating solution. It is characterized by being 80 g / L.
The method for producing a copper-clad laminate according to the fourth invention is characterized in that, in any one of the first to third inventions, the current density of the electrolytic plating is 0.1 to 4.5 A / dm 2 .
本発明によれば、銅めっき液のブライトナー成分に含まれる硫黄が銅めっき被膜に取り込まれる。銅めっき被膜に取り込まれた硫黄により再結晶が阻害されるため、銅めっき被膜の再結晶の進行を遅くできる。 According to the present invention, sulfur contained in the Brightener component of the copper plating solution is incorporated into the copper plating film. Since recrystallization is inhibited by the sulfur incorporated into the copper plating film, the progress of recrystallization of the copper plating film can be slowed down.
つぎに、本発明の実施形態を図面に基づき説明する。
図１に示すように、本発明の一実施形態に係る方法により製造される銅張積層板１は、基材１０と、基材１０の表面に形成された銅めっき被膜２０とからなる。図１に示すように基材１０の片面のみに銅めっき被膜２０を形成してもよいし、基材１０の両面に銅めっき被膜２０を形成してもよい。
Next, an embodiment of the present invention will be described with reference to the drawings.
As shown in FIG. 1, the copper-clad laminate 1 manufactured by the method according to the embodiment of the present invention comprises a base material 10 and a copper plating film 20 formed on the surface of the base material 10. As shown in FIG. 1, the copper plating film 20 may be formed on only one side of the base material 10, or the copper plating film 20 may be formed on both sides of the base material 10.
銅めっき被膜２０は電解めっきにより成膜される。したがって、基材１０は銅めっき被膜２０が成膜される側の表面に導電性を有する素材であればよい。例えば、基材１０は絶縁性を有するベースフィルム１１の表面に金属層１２が形成されたものである。ベースフィルム１１としてポリイミドフィルムなどの樹脂フィルムを用いることができる。金属層１２は、例えば、スパッタリング法により形成される。金属層１２は下地金属層１３と銅薄膜層１４とからなる。下地金属層１３と銅薄膜層１４とはベースフィルム１１の表面にこの順に積層されている。一般に、下地金属層１３はニッケル、クロム、またはニッケルクロム合金からなる。金属層１２と銅めっき被膜２０とにより導体層が構成されている。 The copper plating film 20 is formed by electrolytic plating. Therefore, the base material 10 may be a material having conductivity on the surface on the side where the copper plating film 20 is formed. For example, the base material 10 has a metal layer 12 formed on the surface of a base film 11 having an insulating property. A resin film such as a polyimide film can be used as the base film 11. The metal layer 12 is formed by, for example, a sputtering method. The metal layer 12 is composed of a base metal layer 13 and a copper thin film layer 14. The base metal layer 13 and the copper thin film layer 14 are laminated in this order on the surface of the base film 11. Generally, the base metal layer 13 is made of nickel, chromium, or a nickel-chromium alloy. The conductor layer is composed of the metal layer 12 and the copper plating film 20.
電解めっきは、例えば、図２に示すめっき装置３を用いて行なわれる。
めっき装置３は、ロールツーロールにより長尺帯状の基材１０を搬送しつつ、基材１０に対して電解めっきを行なう装置である。めっき装置３はロール状に巻回された基材１０を繰り出す供給装置３１と、めっき後の基材１０（銅張積層板１）をロール状に巻き取る巻取装置３２とを有する。
Electroplating is performed using, for example, the plating apparatus 3 shown in FIG.
The plating device 3 is a device that performs electrolytic plating on the base material 10 while transporting the long strip-shaped base material 10 by roll-to-roll. The plating device 3 has a supply device 31 for feeding out the base material 10 wound in a roll shape, and a winding device 32 for winding up the base material 10 (copper-clad laminate 1) after plating in a roll shape.
めっき装置３は基材１０を搬送する上下一対のエンドレスベルト３３（下側のエンドレスベルト３３は図示省略）を有する。各エンドレスベルト３３には基材１０を把持する複数のクランプ３４が設けられている。供給装置３１から繰り出された基材１０は、その幅方向が鉛直方向に沿う懸垂姿勢となり、両縁が上下のクランプ３４に把持される。基材１０はエンドレスベルト３３の駆動によりめっき装置３内を周回した後、クランプ３４から開放され、巻取装置３２で巻き取られる。 The plating apparatus 3 has a pair of upper and lower endless belts 33 (the lower endless belt 33 is not shown) that conveys the base material 10. Each endless belt 33 is provided with a plurality of clamps 34 for gripping the base material 10. The base material 10 unwound from the supply device 31 is in a suspended posture in the width direction along the vertical direction, and both edges are gripped by the upper and lower clamps 34. The base material 10 circulates in the plating device 3 by driving the endless belt 33, is released from the clamp 34, and is wound by the winding device 32.
基材１０の搬送経路には、前処理槽３５、めっき槽４０、および後処理槽３６が配置されている。めっき槽４０には銅めっき液が貯留されている。めっき槽４０内を搬送される基材１０は、その全体が銅めっき液に浸漬されている。基材１０はめっき槽４０内を搬送されつつ、電解めっきよりその表面に銅めっき被膜２０が成膜される。これにより、長尺帯状の銅張積層板１が得られる。 A pretreatment tank 35, a plating tank 40, and a posttreatment tank 36 are arranged in the transport path of the base material 10. A copper plating solution is stored in the plating tank 40. The entire base material 10 conveyed in the plating tank 40 is immersed in a copper plating solution. While the base material 10 is conveyed in the plating tank 40, a copper plating film 20 is formed on the surface of the base material 10 by electrolytic plating. As a result, a long strip-shaped copper-clad laminate 1 can be obtained.
銅めっき液は水溶性銅塩を含む。銅めっき液に一般的に用いられる水溶性銅塩であれば、特に限定されず用いられる。水溶性銅塩として、無機銅塩、アルカンスルホン酸銅塩、アルカノールスルホン酸銅塩、有機酸銅塩などが挙げられる。無機銅塩として、硫酸銅、酸化銅、塩化銅、炭酸銅などが挙げられる。アルカンスルホン酸銅塩として、メタンスルホン酸銅、プロパンスルホン酸銅などが挙げられる。アルカノールスルホン酸銅塩として、イセチオン酸銅、プロパノールスルホン酸銅などが挙げられる。有機酸銅塩として、酢酸銅、クエン酸銅、酒石酸銅などが挙げられる。 The copper plating solution contains a water-soluble copper salt. Any water-soluble copper salt generally used in the copper plating solution is used without particular limitation. Examples of the water-soluble copper salt include an inorganic copper salt, an alkane sulfonic acid copper salt, an alkanol sulfonic acid copper salt, and an organic acid copper salt. Examples of the inorganic copper salt include copper sulfate, copper oxide, copper chloride, and copper carbonate. Examples of the alkane sulfonic acid copper salt include copper methanesulfonate and copper propane sulfonate. Examples of the alkanol sulfonic acid copper salt include copper isethionic acid and copper propanol sulfonate. Examples of the organic acid copper salt include copper acetate, copper citrate, copper tartrate and the like.
銅めっき液に用いる水溶性銅塩として、無機銅塩、アルカンスルホン酸銅塩、アルカノールスルホン酸銅塩、有機酸銅塩などから選択された１種類を単独で用いてもよいし、２種類以上を組み合わせて用いてもよい。例えば、硫酸銅と塩化銅とを組み合わせる場合のように、無機銅塩、アルカンスルホン酸銅塩、アルカノールスルホン酸銅塩、有機酸銅塩などから選択された１つのカテゴリー内の異なる２種類以上を組み合わせて用いてもよい。ただし、銅めっき液の管理の観点からは、１種類の水溶性銅塩を単独で用いることが好ましい。 As the water-soluble copper salt used in the copper plating solution, one type selected from inorganic copper salt, alkane sulfonic acid copper salt, alkanol sulfonic acid copper salt, organic acid copper salt and the like may be used alone, or two or more types may be used. May be used in combination. For example, as in the case of combining copper sulfate and copper chloride, two or more different types in one category selected from inorganic copper salt, alkane sulfonic acid copper salt, alkanol sulfonic acid copper salt, organic acid copper salt, etc. It may be used in combination. However, from the viewpoint of controlling the copper plating solution, it is preferable to use one kind of water-soluble copper salt alone.
銅めっき液は硫酸を含んでもよい。硫酸の添加量を調整することで、銅めっき液のｐＨおよび硫酸イオン濃度を調整できる。 The copper plating solution may contain sulfuric acid. By adjusting the amount of sulfuric acid added, the pH and sulfate ion concentration of the copper plating solution can be adjusted.
銅めっき液は一般的にめっき液に添加される添加剤を含む。添加剤として、ブライトナー成分、レベラー成分、ポリマー成分、塩素成分などが挙げられる。添加剤として、ブライトナー成分、レベラー成分、ポリマー成分、塩素成分などから選択された１種類を単独で用いてもよいし、２種類以上を組み合わせて用いてもよい。 The copper plating solution contains additives that are generally added to the plating solution. Examples of the additive include a Brightner component, a leveler component, a polymer component, a chlorine component and the like. As the additive, one type selected from the Brightner component, the leveler component, the polymer component, the chlorine component and the like may be used alone, or two or more types may be used in combination.
ブライトナー成分として、特に限定されないが、ビス（３−スルホプロピル）ジスルフィド（略称ＳＰＳ）、３−メルカプトプロパン−１−スルホン酸（略称ＭＰＳ）などから選択された１種類を単独で、または２種類以上を組み合わせて用いることが好ましい。レベラー成分は窒素を含有するアミンなどで構成される。レベラー成分として、特に限定されないが、ジアリルジメチルアンモニウムクロライド、ヤヌス・グリーンＢなどから選択された１種類を単独で、または２種類以上を組み合わせて用いることが好ましい。ポリマー成分として、特に限定されないが、ポリエチレングリコール、ポリプロピレングリコール、ポリエチレングリコール−ポリプロピレングリコール共重合体から選択された１種類を単独で、または２種類以上を組み合わせて用いることが好ましい。塩素成分として、特に限定されないが、塩酸、塩化ナトリウムなどから選択された１種類を単独で、または２種類以上を組み合わせて用いることが好ましい。 The Brightener component is not particularly limited, but one type selected from bis (3-sulfopropyl) disulfide (abbreviated as SPS), 3-mercaptopropane-1-sulfonic acid (abbreviated as MPS), etc. may be used alone or as two types. It is preferable to use the above in combination. The leveler component is composed of nitrogen-containing amines and the like. The leveler component is not particularly limited, but it is preferable to use one selected from diallyldimethylammonium chloride, Janus Green B, etc. alone or in combination of two or more. The polymer component is not particularly limited, but it is preferable to use one selected from polyethylene glycol, polypropylene glycol, and polyethylene glycol-polypropylene glycol copolymer alone or in combination of two or more. The chlorine component is not particularly limited, but it is preferable to use one selected from hydrochloric acid, sodium chloride and the like alone or in combination of two or more.
銅めっき液の各成分の含有量は任意に選択できる。ただし、銅めっき液は銅を１５〜７０ｇ／Ｌ、硫酸を２０〜２５０ｇ／Ｌ含有することが好ましい。そうすれば、銅めっき被膜２０を十分な速度で成膜できる。銅めっき液はブライトナー成分を１〜５０ｍｇ／Ｌ含有することが好ましい。そうすれば、析出結晶を微細化し銅めっき被膜２０の表面を平滑にできる。銅めっき液はレベラー成分を１〜３００ｍｇ／Ｌ含有することが好ましい。そうすれば、突起を抑制し平坦な銅めっき被膜２０を形成できる。銅めっき液はポリマー成分を１０〜１，５００ｍｇ／Ｌ含有することが好ましい。そうすれば、基材１０端部への電流集中を緩和し均一な銅めっき被膜２０を形成できる。銅めっき液は塩素成分を２０〜８０ｍｇ／Ｌ含有することが好ましい。そうすれば、異常析出を抑制できる。 The content of each component of the copper plating solution can be arbitrarily selected. However, the copper plating solution preferably contains 15 to 70 g / L of copper and 20 to 250 g / L of sulfuric acid. Then, the copper plating film 20 can be formed at a sufficient speed. The copper plating solution preferably contains a Brightener component of 1 to 50 mg / L. Then, the precipitated crystals can be made finer and the surface of the copper plating film 20 can be smoothed. The copper plating solution preferably contains a leveler component of 1 to 300 mg / L. Then, the protrusions can be suppressed and the flat copper plating film 20 can be formed. The copper plating solution preferably contains a polymer component of 10 to 1,500 mg / L. Then, the current concentration on the end of the base material 10 can be relaxed and a uniform copper plating film 20 can be formed. The copper plating solution preferably contains a chlorine component of 20 to 80 mg / L. Then, abnormal precipitation can be suppressed.
銅めっき液の温度は２０〜３５℃が好ましい。また、めっき槽４０内の銅めっき液を撹拌することが好ましい。銅めっき液を撹拌する手段は、特に限定されないが、噴流を利用した手段を用いることができる。例えば、ノズルから噴出させた銅めっき液を基材１０に吹き付けることで、銅めっき液を撹拌できる。 The temperature of the copper plating solution is preferably 20 to 35 ° C. Further, it is preferable to stir the copper plating solution in the plating tank 40. The means for stirring the copper plating solution is not particularly limited, but a means using a jet can be used. For example, the copper plating solution can be agitated by spraying the copper plating solution ejected from the nozzle onto the base material 10.
めっき槽４０の内部には、基材１０の搬送方向に沿って複数のアノードが配置されている。アノードと基材１０との間に電流を流すことで、基材１０の表面に銅めっき被膜２０を成膜できる。複数のアノードは、それぞれに整流器が接続されている。したがって、アノードごとに異なる電流密度となるように設定できる。電流密度は０．１〜４．５Ａ／ｄｍ2が好ましい。 Inside the plating tank 40, a plurality of anodes are arranged along the transport direction of the base material 10. A copper plating film 20 can be formed on the surface of the base material 10 by passing an electric current between the anode and the base material 10. A rectifier is connected to each of the plurality of anodes. Therefore, the current density can be set to be different for each anode. The current density is preferably 0.1 to 4.5 A / dm 2 .
本願発明者は、以上のような電解めっきにおいて、銅めっき液中のブライトナー成分の濃度を適切な範囲に調整することにより、銅めっき被膜２０の再結晶時間を長くできるとの知見を得ている。 The inventor of the present application has obtained the finding that the recrystallization time of the copper plating film 20 can be lengthened by adjusting the concentration of the brightener component in the copper plating solution to an appropriate range in the above electrolytic plating. There is.
その理由は不明なところもあるが、概ねつぎのとおりであると考えられる。銅めっき液に添加剤を添加すると、添加剤に由来する不純物が銅めっき被膜２０に取り込まれる。例えば、銅めっき液にブライトナー成分を添加すると、ブライトナー成分に含まれる硫黄が銅めっき被膜２０に取り込まれる。銅めっき被膜２０に取り込まれた硫黄は銅めっき被膜２０の結晶粒界に存在し、結晶粒同士の結合を抑制する。これにより、結晶粒が大きく成長することが阻害されるため、再結晶の進行が遅くなる。 The reason for this is unknown, but it is thought to be as follows. When an additive is added to the copper plating solution, impurities derived from the additive are incorporated into the copper plating film 20. For example, when a Brightener component is added to a copper plating solution, sulfur contained in the Brightener component is incorporated into the copper plating film 20. Sulfur incorporated into the copper plating film 20 exists at the grain boundaries of the copper plating film 20 and suppresses the bonding between the crystal grains. This hinders the large growth of crystal grains, which slows down the progress of recrystallization.
具体的には、銅めっき液中のブライトナー成分に含まれる硫黄の濃度（以下、単に「硫黄濃度」と称する。）を１．８〜９．１ｍｇ／Ｌとすることが好ましい。ここで、硫黄濃度は銅めっき液の単位体積あたりのブライトナー成分中の硫黄の質量を意味する。例えば、式（１）に示すように、硫黄濃度Ｃsは、銅めっき液中のブライトナー成分の濃度ρbに、ブライトナー成分の分子量Ｍbに対するブライトナー成分に含まれる硫黄の原子量Ａr(Ｓ)の総和の比率をかけることで求められる。
硫黄濃度を基準として、銅めっき液へのブライトナー成分の添加量を調整する。再結晶の進行に影響するのは、ブライトナー成分そのものではなく、銅めっき被膜２０に取り込まれたブライトナー成分由来の硫黄である。そのため、ブライトナー成分に含まれる硫黄の濃度を基準とすることが好ましい。 The amount of the Brightener component added to the copper plating solution is adjusted based on the sulfur concentration. It is not the Brightner component itself that affects the progress of recrystallization, but the sulfur derived from the Brightner component incorporated into the copper plating film 20. Therefore, it is preferable to use the concentration of sulfur contained in the Breitner component as a reference.
つぎに、実施例を説明する。
（試験１）
つぎの手順で、基材を準備した。ベースフィルムとして、厚さ３５μｍのポリイミドフィルム（宇部興産社製 Ｕｐｉｌｅｘ−３５ＳＧＡＶ１）を用意した。ベースフィルムをマグネトロンスパッタリング装置にセットした。マグネトロンスパッタリング装置内にはニッケルクロム合金ターゲットと銅ターゲットとが設置されている。ニッケルクロム合金ターゲットの組成はＣｒが２０質量％、Ｎｉが８０質量％である。真空雰囲気下で、ベースフィルムの片面に、厚さ２５０Åのニッケルクロム合金からなる下地金属層を形成し、その上に厚さ１，５００Åの銅薄膜層を形成した。
Next, an embodiment will be described.
(Test 1)
The substrate was prepared by the following procedure. As a base film, a polyimide film having a thickness of 35 μm (Upilex-35SGAV1 manufactured by Ube Industries, Ltd.) was prepared. The base film was set in the magnetron sputtering apparatus. A nickel-chromium alloy target and a copper target are installed in the magnetron sputtering apparatus. The composition of the nickel-chromium alloy target is 20% by mass of Cr and 80% by mass of Ni. Under a vacuum atmosphere, a base metal layer made of a nickel-chromium alloy having a thickness of 250 Å was formed on one side of the base film, and a copper thin film layer having a thickness of 1,500 Å was formed on the base metal layer.
つぎに、銅めっき液を調整した。銅めっき液は銅を３０ｇ／Ｌ、硫酸を７０ｇ／Ｌ、レベラー成分を５０ｍｇ／Ｌ、ポリマー成分を１，１００ｍｇ／Ｌ、塩素成分を５０ｍｇ／Ｌ含有する。レベラー成分としてジアリルジメチルアンモニウムクロライド−二酸化硫黄共重合体（ニットーボーメディカル株式会社製 ＰＡＳ−Ａ―５）を用いた。ポリマー成分としてポリエチレングリコール−ポリプロピレングリコール共重合体（日油株式会社製 ユニルーブ５０ＭＢ−１１）を用いた。塩素成分として塩酸（和光純薬工業株式会社製の３５％塩酸）を用いた。 Next, the copper plating solution was adjusted. The copper plating solution contains 30 g / L of copper, 70 g / L of sulfuric acid, 50 mg / L of leveler component, 1,100 mg / L of polymer component, and 50 mg / L of chlorine component. A diallyldimethylammonium chloride-sulfur dioxide copolymer (PAS-A-5 manufactured by Nittobo Medical Co., Ltd.) was used as a leveler component. A polyethylene glycol-polypropylene glycol copolymer (Unilube 50MB-11 manufactured by NOF CORPORATION) was used as a polymer component. Hydrochloric acid (35% hydrochloric acid manufactured by Wako Pure Chemical Industries, Ltd.) was used as the chlorine component.
また、銅めっき液はブライトナー成分を含む。ブライトナー成分としてビス（３−スルホプロピル）ジスルフィド（ＲＡＳＣＨＩＧ ＧｍｂＨ社製の試薬、以下同じ）を用いた。ブライトナー成分の濃度が異なる６種類の銅めっき液（ブライトナー成分の濃度：１、５、１０、１５、２５、３５ｍｇ／Ｌ）を調整した。これらを銅めっき液１〜６と称する。 The copper plating solution also contains a Brightener component. Bis (3-sulfopropyl) disulfide (reagent manufactured by RASCHIG GmbH, the same applies hereinafter) was used as the Brightener component. Six types of copper plating solutions having different concentrations of the Brightener component (concentration of the Brightner component: 1, 5, 10, 15, 25, 35 mg / L) were adjusted. These are referred to as copper plating solutions 1 to 6.
ビス（３−スルホプロピル）ジスルフィドは以下の構造式で表される。分子量は３５４．４であり、１つの分子に４つの硫黄原子（原子量３２．１）が含まれる。ブライトナー成分の濃度が１０ｍｇ／Ｌの場合の硫黄濃度は３．６ｍｇ／Ｌ（＝１０［ｍｇ／Ｌ］×１２８．３／３５４．４）と求まる。以下、同様の手順で、ブライトナー成分としてビス（３−スルホプロピル）ジスルフィドを用いた場合の硫黄濃度を求める。
以上のとおり調整した銅めっき液が貯留されためっき槽に基材を供給した。電解めっきにより基材の片面に厚さ２．０μｍの銅めっき被膜を成膜した。ここで、銅めっき液の温度を３１℃とした。また、電解めっきの間、ノズルから噴出させた銅めっき液を基材の表面に対して略垂直に吹き付けることで、銅めっき液を撹拌した。 The base material was supplied to the plating tank in which the copper plating solution prepared as described above was stored. A copper plating film having a thickness of 2.0 μm was formed on one side of the base material by electrolytic plating. Here, the temperature of the copper plating solution was set to 31 ° C. In addition, during the electrolytic plating, the copper plating solution ejected from the nozzle was sprayed substantially perpendicular to the surface of the base material to stir the copper plating solution.
電解めっきにおいて、めっき開始から終了までの電流密度を０．４Ａ／ｄｍ2で５０秒、０．６Ａ／ｄｍ2で５０秒、０．８Ａ／ｄｍ2で５０秒、１．０Ａ／ｄｍ2で５０秒、１．２Ａ／ｄｍ2で５０秒、１．５Ａ／ｄｍ2で５０秒、２．０Ａ／ｄｍ2で１６０秒と変化させた。銅めっき液１〜６を用いて得られた銅張積層板を、それぞれ試料１〜６と称する。 In the electrolytic plating, the current density to the end from the plating after 50 seconds at 0.4A / dm 2, 0.6A / dm 2 at 50 seconds, 50 seconds at 0.8 A / dm 2, at 1.0A / dm 2 It was changed to 50 seconds, 1.2 A / dm 2 for 50 seconds, 1.5 A / dm 2 for 50 seconds, and 2.0 A / dm 2 for 160 seconds. Copper-clad laminates obtained by using the copper plating solutions 1 to 6 are referred to as samples 1 to 6, respectively.
以上の手順で得られた６つの試料１〜６について、銅めっき被膜の再結晶時間を測定した。再結晶時間は四探針法により銅めっき被膜の抵抗率の変化を観察することで測定した。銅めっき被膜の再結晶の進行にともない、結晶粒が大きくなり、抵抗率が変化する。抵抗率が一定になった時点で再結晶終了と判断する。めっき処理から再結晶終了までの経過時間を再結晶時間とした。なお、抵抗率の測定器として、三菱ケミカルアナリティック製のロレスタＡＸ ＭＣＰ−Ｔ３７０を用いた。 The recrystallization time of the copper plating film was measured for the six samples 1 to 6 obtained by the above procedure. The recrystallization time was measured by observing the change in resistivity of the copper plating film by the four-probe method. As the recrystallization of the copper plating film progresses, the crystal grains become larger and the resistivity changes. When the resistivity becomes constant, it is judged that recrystallization is completed. The elapsed time from the plating treatment to the end of recrystallization was defined as the recrystallization time. As a resistivity measuring instrument, Lola TAX MCP-T370 manufactured by Mitsubishi Chemical Analytical Co., Ltd. was used.
その結果を表１に示す。
表１より、硫黄濃度を１．８〜９．１ｍｇ／Ｌに調整すれば、銅めっき被膜の再結晶時間を４日以上にできることが分かる。また、硫黄濃度を３．６〜５．４ｍｇ／Ｌに調整すれば、銅めっき被膜の再結晶時間を５日にできることが分かる。 From Table 1, it can be seen that the recrystallization time of the copper plating film can be increased to 4 days or more by adjusting the sulfur concentration to 1.8 to 9.1 mg / L. It can also be seen that if the sulfur concentration is adjusted to 3.6 to 5.4 mg / L, the recrystallization time of the copper plating film can be set to 5 days.
（試験２）
試験１と同様の手順で基材を準備した。
つぎに、銅めっき液を調整した。レベラー成分の濃度を１５ｍｇ／Ｌとし、レベラー成分としてヤヌス・グリーンＢ（東京化成工業株式会社製の試薬）を用いたほかは、試験１と同様の条件で銅めっき液を調整した。
(Test 2)
The substrate was prepared in the same procedure as in Test 1.
Next, the copper plating solution was adjusted. The copper plating solution was prepared under the same conditions as in Test 1 except that the concentration of the leveler component was 15 mg / L and Janus Green B (a reagent manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the leveler component.
ブライトナー成分の濃度が異なる６種類の銅めっき液（ブライトナー成分の濃度：１、５、１０、１５、２５、３５ｍｇ／Ｌ）を銅めっき液７〜１２と称する。 Six types of copper plating solutions having different concentrations of Brightener components (concentrations of Brightener components: 1, 5, 10, 15, 25, 35 mg / L) are referred to as copper plating solutions 7 to 12.
つぎに、試験１と同様の手順で電解めっきを行なった。銅めっき液７〜１２を用いて得られた銅張積層板を、それぞれ試料７〜１２と称する。また、得られた６つの試料７〜１２について、試験１と同様の手順で、銅めっき被膜の再結晶時間を測定した。 Next, electrolytic plating was performed in the same procedure as in Test 1. The copper-clad laminates obtained by using the copper plating solutions 7 to 12 are referred to as samples 7 to 12, respectively. In addition, the recrystallization time of the copper plating film was measured for the obtained 6 samples 7 to 12 in the same procedure as in Test 1.
その結果を表２に示す。
表２より、銅めっき液のレベラー成分を変えたとしても、硫黄濃度を１．８〜９．１ｍｇ／Ｌに調整すれば、銅めっき被膜の再結晶時間を４日以上にできることが分かる。 From Table 2, it can be seen that even if the leveler component of the copper plating solution is changed, the recrystallization time of the copper plating film can be set to 4 days or more by adjusting the sulfur concentration to 1.8 to 9.1 mg / L.
１ 銅張積層板
１０ 基材
１１ ベースフィルム
１２ 金属層
１３ 下地金属層
１４ 銅薄膜層
1 Copper-clad laminate 10 Base film 11 Base film 12 Metal layer 13 Base metal layer 14 Copper thin film layer
Claims (4)
前記銅めっき液中のブライトナー成分に含まれる硫黄の濃度が１．８〜９．１ｍｇ／Ｌである
ことを特徴とする銅張積層板の製造方法。 It is a method of forming a copper plating film on the surface of a base material by electrolytic plating using a copper plating solution to obtain a copper-clad laminate.
A method for producing a copper-clad laminate, characterized in that the concentration of sulfur contained in the Brightner component in the copper plating solution is 1.8 to 9.1 mg / L.
ことを特徴とする請求項１記載の銅張積層板の製造方法。 The method for producing a copper-clad laminate according to claim 1, wherein the Brightener component is bis (3-sulfopropyl) disulfide and / or 3-mercaptopropane-1-sulfonic acid.
ことを特徴とする請求項１または２に記載の銅張積層板の製造方法。 The copper-clad laminate according to claim 1 or 2, wherein the copper concentration in the copper plating solution is 15 to 70 g / L, the sulfuric acid concentration is 20 to 250 g / L, and the chlorine concentration is 20 to 80 g / L. How to make a board.
ことを特徴とする請求項１〜３のいずれかに記載の銅張積層板の製造方法。 The method for producing a copper-clad laminate according to any one of claims 1 to 3, wherein the current density of the electrolytic plating is 0.1 to 4.5 A / dm 2 .
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