JP2005023301A - Adhered layer-forming liquid, method for producing bonded layer of copper with resin by using the liquid and laminated material of them - Google Patents
Adhered layer-forming liquid, method for producing bonded layer of copper with resin by using the liquid and laminated material of them Download PDFInfo
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Abstract
Description
本発明は、接着層形成液、その液を用いた銅と樹脂の接着層の製造方法及びその積層体に関する。さらに詳しくは、プリント配線基板、半導体実装品、液晶デバイス、エレクトロルミネッセンスなどの各種電子部品に使用される接着層形成液、その液を用いた銅と樹脂の接着層の製造方法及びその積層体に関する。 The present invention relates to an adhesive layer forming liquid, a method for producing an adhesive layer of copper and resin using the liquid, and a laminate thereof. More specifically, the present invention relates to an adhesive layer forming liquid used for various electronic components such as printed wiring boards, semiconductor mounting products, liquid crystal devices, and electroluminescence, a method for producing an adhesive layer of copper and resin using the liquid, and a laminate thereof. .
一般的な多層配線板は、表面に銅からなる導電層を有する内層基板が、プリプレグを挟んで他の内層基板や銅箔と積層プレスされて製造されている。導電層間は、孔壁が銅めっきされたスルーホールとよばれる貫通孔により、電気的に接続されている。前記内層基板の銅表面には、プリプレグとの接着性を向上させるために、ブラックオキサイドやブラウンオキサイドとよばれる針状の酸化銅が形成されている。この方法では、針状の酸化銅がプリプレグにくい込み、アンカー効果が生じて接着性が向上する。前記酸化銅はプリプレグとの接着性に優れているが、スルーホールめっきの工程において酸性液と接触した場合、溶解して変色し、ハローイングと呼ばれる欠陥を生じやすいという問題がある。 A general multilayer wiring board is manufactured by laminating and pressing an inner layer substrate having a conductive layer made of copper on the surface with another inner layer substrate or a copper foil with a prepreg interposed therebetween. The conductive layers are electrically connected by a through-hole called a through-hole whose hole wall is plated with copper. Needle-like copper oxide called black oxide or brown oxide is formed on the copper surface of the inner layer substrate in order to improve adhesion to the prepreg. In this method, acicular copper oxide is difficult to prepreg, an anchor effect is produced, and adhesion is improved. Although the copper oxide is excellent in adhesiveness with a prepreg, there is a problem that when it comes into contact with an acidic solution in the through-hole plating process, it dissolves and discolors and easily causes a defect called haloing.
そこで、ブラックオキサイドやブラウンオキサイドに代わる方法として、下記特許文献１や下記特許文献２に提案されているように、内層基板の銅表面にスズ層を形成する方法が提案されている。また、下記特許文献３には、銅と樹脂との接着性を向上させるため、銅表面にスズめっきしたのち、さらにシランカップリング剤で処理することが提案されている。また、下記特許文献４には、銅と樹脂との接着性を向上させるために、銅表面に銅スズ合金層を形成することが提案されている。また、エッチングにより銅表面を粗化し、アンカー効果を発現させることも提案されている。
しかし、前記のごとき銅表面にスズ層や銅スズ合金層を形成する方法では、樹脂の種類がガラス転移温度の高い、いわゆる硬い樹脂の場合、接着性向上効果が不充分な場合があった。また、前記特許文献３に記載の方法では、スズめっきすることにより、銅がメッキ液中に溶出し、配線が細くなる。さらに、シランカップリング剤は使用の際の取扱いが困難であるという問題がある。樹脂との接着性も不充分である。
本発明は、前記従来の問題を解決するため、銅と樹脂の接着力をさらに向上できる接着層形成液、その液を用いた銅と樹脂の接着層の製造方法及びその積層体を提供する。
However, in the method of forming a tin layer or a copper tin alloy layer on the copper surface as described above, the effect of improving the adhesion may be insufficient when the resin type is a so-called hard resin having a high glass transition temperature. In the method described in Patent Document 3, copper is eluted in the plating solution by thinning the tin, and the wiring becomes thin. Furthermore, the silane coupling agent has a problem that it is difficult to handle at the time of use. Adhesiveness with resin is also insufficient.
In order to solve the above-described conventional problems, the present invention provides an adhesive layer forming liquid that can further improve the adhesive force between copper and resin, a method for producing an adhesive layer of copper and resin using the liquid, and a laminate thereof.
本発明の銅と樹脂の接着層形成液は、
ａ 無機酸及び有機酸から選ばれる少なくとも１種の酸、
ｂ スズ塩又はスズ酸化物、
ｃ 銀、亜鉛、アルミニウム、チタン、ビスマス、クロム、鉄、コバルト、ニッケル、パラジウム、金及び白金から選ばれる少なくとも１種の金属の塩又は酸化物、
ｄ 反応促進剤、及び
ｅ 拡散系保持溶媒
を含有する水溶液であることを特徴とする。
The adhesive layer forming liquid of copper and resin of the present invention is
a at least one acid selected from inorganic acids and organic acids,
b Tin salt or tin oxide,
c A salt or oxide of at least one metal selected from silver, zinc, aluminum, titanium, bismuth, chromium, iron, cobalt, nickel, palladium, gold and platinum,
d It is an aqueous solution containing a reaction accelerator and e diffusion system holding solvent.
本発明の銅と樹脂の接着層の製造方法は、銅の表面に、
ａ 無機酸及び有機酸から選ばれる少なくとも１種の酸、
ｂ スズ塩又はスズ酸化物、
ｃ 銀、亜鉛、アルミニウム、チタン、ビスマス、クロム、鉄、コバルト、ニッケル、パラジウム、金及び白金から選ばれる少なくとも１種の金属の塩又は酸化物、
ｄ 反応促進剤及び
ｅ 拡散系保持溶媒
を含有する水溶液を含む樹脂接着層形成液を接触させ、スズ及び前記ｃの金属の合金層を形成させ、次いで前記銅と、前記スズ及び前記ｃの金属とが拡散している層を残して、前記スズ及び前記ｃの金属の合金層を除去することにより、銅の表面に、銅、スズ及び前記ｃ金属の合金を含む樹脂の接着層を形成することを特徴とする。
The method for producing an adhesive layer of copper and resin according to the present invention includes a copper surface,
a at least one acid selected from inorganic acids and organic acids,
b Tin salt or tin oxide,
c A salt or oxide of at least one metal selected from silver, zinc, aluminum, titanium, bismuth, chromium, iron, cobalt, nickel, palladium, gold and platinum,
a resin adhesion layer-forming liquid containing an aqueous solution containing a d reaction accelerator and e diffusion system holding solvent is contacted to form an alloy layer of tin and the c metal, and then the copper, the tin and the c metal And removing the alloy layer of the tin and c metal, leaving a layer in which the metal is diffused, thereby forming an adhesive layer of a resin containing copper, tin and the alloy of c metal on the copper surface. It is characterized by that.
本発明の銅と樹脂の積層体は、銅と樹脂とが一体化された積層体であって、銅の樹脂と接する表面に、銅、スズ、ならびに銀、亜鉛、アルミニウム、チタン、ビスマス、クロム、鉄、コバルト、ニッケル、パラジウム、金及び白金から選ばれる少なくとも１種の金属からなる合金を含む樹脂の接着層を存在させたことを特徴とする。 The copper-resin laminate of the present invention is a laminate in which copper and resin are integrated, and has copper, tin, silver, zinc, aluminum, titanium, bismuth, chromium on the surface in contact with the copper resin. And an adhesive layer of a resin containing an alloy made of at least one metal selected from iron, cobalt, nickel, palladium, gold and platinum.
本発明によれば、銅表面に銅とスズと第３の金属の合金からなる樹脂接着層を形成することにより、銅と樹脂の接着力を向上できる接着層形成液、その液を用いた銅と樹脂の接着層の製造方法及びその積層体を提供できる。 According to the present invention, by forming a resin adhesive layer made of an alloy of copper, tin and a third metal on the copper surface, an adhesive layer forming liquid capable of improving the adhesive force between copper and resin, and copper using the liquid And a method for producing a resin adhesive layer and a laminate thereof.
本発明の銅と樹脂の接着層の製造方法では、銅の表面に、銅、スズ、ならびに銀、亜鉛、アルミニウム、チタン、ビスマス、クロム、鉄、コバルト、ニッケル、パラジウム、金及び白金から選ばれる少なくとも１種の金属（以下「第３の金属」ともいう。）の合金からなる樹脂接着層を形成する。この樹脂接着層により、銅と樹脂の接着性を改良する。 In the method for producing an adhesive layer of copper and resin according to the present invention, the surface of copper is selected from copper, tin, and silver, zinc, aluminum, titanium, bismuth, chromium, iron, cobalt, nickel, palladium, gold and platinum. A resin adhesive layer made of an alloy of at least one metal (hereinafter also referred to as “third metal”) is formed. This resin adhesive layer improves the adhesion between copper and resin.
本発明の銅と樹脂の接着層形成液について説明する。まず、酸はスズ塩の種類の応じてｐＨを調整して接着性に優れた表面を形成するために配合される。本発明で使用できる酸は、塩酸、硫酸、硝酸、ホウフッ化水素酸、リン酸などの無機酸、ギ酸、酢酸、プロピオン酸、酪酸などのカルボン酸、メタンスルホン酸、エタンスルホン酸などのアルカンスルホン酸、ベンゼンスルホン酸、フェノールスルホン酸、クレゾールスルホン酸などの芳香族スルホン酸を含む水溶性の有機酸を挙げることができる。このうち、硫酸が樹脂接着層形成速度やスズ化合物の溶解性などの点から好ましい。酸の好ましい濃度は１〜５０％（質量％、以下同様）であり、さらに好ましくは５〜４０％、特に好ましくは１０〜３０％の範囲である。５０％を超えると樹脂に対する接着性が低下する傾向となる。また、１％未満では対樹脂接着層が形成されない。 The copper-resin adhesive layer forming liquid of the present invention will be described. First, the acid is blended in order to adjust the pH according to the type of tin salt to form a surface with excellent adhesion. Acids that can be used in the present invention include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, borofluoric acid, and phosphoric acid, carboxylic acids such as formic acid, acetic acid, propionic acid, and butyric acid, and alkane sulfones such as methanesulfonic acid and ethanesulfonic acid. Examples thereof include water-soluble organic acids including aromatic sulfonic acids such as acid, benzenesulfonic acid, phenolsulfonic acid, and cresolsulfonic acid. Of these, sulfuric acid is preferable from the viewpoint of the resin adhesive layer formation rate and the solubility of the tin compound. The preferable concentration of the acid is 1 to 50% (mass%, the same applies hereinafter), more preferably 5 to 40%, and particularly preferably 10 to 30%. If it exceeds 50%, the adhesiveness to the resin tends to decrease. On the other hand, if it is less than 1%, the adhesive layer for resin is not formed.
本発明において、スズ塩としては、可溶性のものである限り特に制限なく使用しうるが、その溶解性から前記酸との塩類が好ましい。例えば、硫酸第一スズ、硫酸第二スズ、ホウフッ化第一スズ、フッ化第一スズ、フッ化第二スズ、硝酸第一スズ、硝酸第二スズ、塩化第一スズ、塩化第二スズ、ギ酸第一スズ、ギ酸第二スズ、酢酸第一スズ、酢酸第二スズなどの第一スズ塩や第二スズ塩を使用できる。このなかでも樹脂接着層形成速度が速いという点からは第一スズ塩を用いるのが好ましく、溶解させた液中での安定性が高いという点からは第二スズ塩を用いるのが好ましい。スズ酸化物としては酸化第一スズが好ましい。 In the present invention, the tin salt can be used without particular limitation as long as it is soluble, but salts with the acid are preferred because of its solubility. For example, stannous sulfate, stannic sulfate, stannous borofluoride, stannous fluoride, stannic fluoride, stannous nitrate, stannic nitrate, stannous chloride, stannic chloride, Stannous salts and stannic salts such as stannous formate, stannic formate, stannous acetate, and stannic acetate can be used. Of these, stannous salts are preferably used from the viewpoint that the resin adhesive layer forming speed is high, and stannic salts are preferably used from the viewpoint of high stability in the dissolved liquid. As the tin oxide, stannous oxide is preferable.
スズ塩又はスズ酸化物の好ましい濃度は、スズの濃度として０．０５〜１０％の範囲が好ましく、さらに好ましくは０．１〜５％であり、特に好ましくは０．５〜３％の範囲である。１０％を超えると樹脂に対する接着性が低下する傾向となり、０．０５％未満では樹脂接着層が形成しにくくなる。 The preferable concentration of the tin salt or tin oxide is preferably in the range of 0.05 to 10%, more preferably 0.1 to 5%, and particularly preferably 0.5 to 3% as the concentration of tin. is there. If it exceeds 10%, the adhesiveness to the resin tends to decrease, and if it is less than 0.05%, it becomes difficult to form a resin adhesive layer.
第３の金属としては、銀、亜鉛、アルミニウム、チタン、ビスマス、クロム、鉄、コバルト、ニッケル、パラジウム、金及び白金から選ばれる少なくとも１種の金属が使用される。これらは、樹脂との接着性を著しく向上させる銅及びスズとの合金を形成し、かつ取扱いの容易な金属である。 As the third metal, at least one metal selected from silver, zinc, aluminum, titanium, bismuth, chromium, iron, cobalt, nickel, palladium, gold and platinum is used. These are metals that form an alloy with copper and tin that significantly improve the adhesion to the resin and are easy to handle.
第３の金属の塩又は酸化物としては可溶性のものである限り特に制限なく使用でき、金属の原子価に特に制限はない。例えばＡｇ2Ｏ，ＺｎＯ，Ａｌ2Ｏ3，ＴｉＯ2，Ｂｉ2Ｏ2，Ｃｒ2Ｏ3などの酸化物、ＡｇＣｌ，ＺｎＩ2，ＡｌＢｒ3，ＢｉＩ3，ＦｅＣｌ3、ＰｄＣｌ2、ＡｕＣｌなどのハロゲン物、Ａｇ2ＳＯ4，Ｚｎ（ＮＯ3）2，Ａｌ（ＮＯ3）2，ＮｉＳＯ4，ＣｏＳＯ4などの無機酸との塩、ＣＨ3ＣＯＯＡｇ，（ＨＣＯＯ）2Ｚｎなどの有機酸との塩などである。前記金属塩又は酸化物の好ましい濃度は、金属の濃度として０．１〜２０％であり、さらに好ましくは０．５〜１０％、特に好ましくは１〜５％である。２０％を超えるか、又は０．１％未満では、樹脂に対する接着性が低下する傾向となる。 The salt or oxide of the third metal can be used without particular limitation as long as it is soluble, and the metal valence is not particularly limited. For example, oxides such as Ag 2 O, ZnO, Al 2 O 3 , TiO 2 , Bi 2 O 2 , Cr 2 O 3 , halogens such as AgCl, ZnI 2 , AlBr 3 , BiI 3 , FeCl 3 , PdCl 2 , AuCl , Salts with inorganic acids such as Ag 2 SO 4 , Zn (NO 3 ) 2 , Al (NO 3 ) 2 , NiSO 4 , CoSO 4 , salts with organic acids such as CH 3 COOAg, (HCOO) 2 Zn Etc. A preferable concentration of the metal salt or oxide is 0.1 to 20% as a metal concentration, more preferably 0.5 to 10%, and particularly preferably 1 to 5%. If it exceeds 20% or less than 0.1%, the adhesion to the resin tends to decrease.
本明細書にいう反応促進剤とは、下地の銅に配位してキレートを形成し、銅表面に樹脂接着層を形成しやすくするものをいう。例えば、チオ尿素、1,3-ジメチルチオ尿素、1,3-ジエチル-2-チオ尿素、チオグリコール酸などのチオ尿素誘導体などである。反応促進剤の好ましい濃度は、１〜５０％の範囲、好ましくは５〜４０％、特に好ましくは１０〜３０％の範囲である。反応促進剤の濃度が５０％を超えると樹脂に対する接着性が低下する傾向となる。また、１％未満では樹脂接着層の形成速度が遅い傾向となる。 The reaction accelerator referred to in the present specification refers to an agent that coordinates with the underlying copper to form a chelate and facilitates the formation of a resin adhesive layer on the copper surface. Examples thereof include thiourea derivatives such as thiourea, 1,3-dimethylthiourea, 1,3-diethyl-2-thiourea, and thioglycolic acid. A preferable concentration of the reaction accelerator is in the range of 1 to 50%, preferably 5 to 40%, particularly preferably 10 to 30%. When the concentration of the reaction accelerator exceeds 50%, the adhesiveness to the resin tends to decrease. If it is less than 1%, the resin adhesive layer formation rate tends to be slow.
本明細書にいう拡散系保持溶媒とは、樹脂接着層形成に必要な反応成分濃度を、銅表面近傍に保持しやすくする溶媒をいう。拡散系保持溶媒の例としては、エチレングリコール、ジエチレングリコール、プロピレングリコールなどのグリコール類、セロソルブ、カルビトール、ブチルカルビトールなどのグリコールエステル類である。拡散系保持溶媒の好ましい濃度は、１〜８０％の範囲であり、より好ましくは５〜６０％、特に好ましくは１０〜５０％である。８０％を超えると樹脂に対する接着性が低下する傾向となる。また１％未満では樹脂接着層が形成しにくい傾向となる。 The diffusion system holding solvent referred to in this specification refers to a solvent that facilitates holding the reaction component concentration necessary for forming the resin adhesive layer in the vicinity of the copper surface. Examples of the diffusion system holding solvent include glycols such as ethylene glycol, diethylene glycol, and propylene glycol, and glycol esters such as cellosolve, carbitol, and butyl carbitol. A preferable concentration of the diffusion system holding solvent is in the range of 1 to 80%, more preferably 5 to 60%, and particularly preferably 10 to 50%. If it exceeds 80%, the adhesion to the resin tends to decrease. If it is less than 1%, it tends to be difficult to form a resin adhesive layer.
本発明の樹脂接着層形成液には、その他の成分としてＣｕＳＯ4，ＣｕＣｌ2などの銅塩を添加してもよい。 The resin adhesive layer forming solution of the present invention may be added a copper salt such as CuSO 4, CuCl 2 as other components.
また、均一な樹脂接着層を形成するための界面活性剤など、必要に応じて種々の添加剤を添加してもよい。 Moreover, you may add various additives as needed, such as surfactant for forming a uniform resin contact layer.
本発明の接着層形成液は、前記の各成分を水に溶解させることにより容易に調製することができる。前記水としては、イオン交換水、純水、超純水などのイオン性物質や不純物を除去した水が好ましい。 The adhesive layer forming liquid of the present invention can be easily prepared by dissolving the above-described components in water. The water is preferably water from which ionic substances and impurities such as ion-exchanged water, pure water, and ultrapure water have been removed.
前記接着層形成液を用いて樹脂接着層を形成するには、まず、銅の表面に、前記樹脂接着層形成液を接触させる。銅としては、樹脂と接着させる銅である限り特に制限はない。例えば、電子基板、リードフレームなどの電子部品、装飾品、建材などに使用される、箔（電解銅箔、圧延銅箔）、めっき膜（無電解銅めっき膜、電解銅めっき膜）、線、棒、管、板など、種々の用途の銅の表面を挙げることができる。前記銅は、黄銅、青銅、白銅、ヒ素銅、ケイ素銅、チタン銅、クロム銅など、その目的に応じて他の元素を含有したものであってもよい。前記銅表面の形状は、平滑であってもよく、エッチングなどにより粗化された表面であってもよい。例えば樹脂と積層した際のアンカー効果を得るためには粗化された表面であるのが好ましい。また、近年の高周波の電気信号が流れる銅配線の場合は、中心線平均粗さRaが０．１μｍ以下の平滑面であることが好ましい。特に微細な銅配線の場合は、本発明においては表面粗化によるアンカー効果にたよらず、平滑な表面であっても充分な接着性がえられるので、粗化のためのエッチングによる断線などのおそれがない。 In order to form a resin adhesive layer using the adhesive layer forming liquid, first, the resin adhesive layer forming liquid is brought into contact with the surface of copper. Copper is not particularly limited as long as it is copper to be bonded to a resin. For example, foil (electrolytic copper foil, rolled copper foil), plating film (electroless copper plating film, electrolytic copper plating film), wire, used for electronic parts such as electronic substrates, lead frames, ornaments, building materials, etc. Listed are copper surfaces for various applications such as rods, tubes, and plates. The copper may contain other elements depending on the purpose, such as brass, bronze, white copper, arsenic copper, silicon copper, titanium copper, and chromium copper. The copper surface may be smooth or roughened by etching or the like. For example, in order to obtain an anchor effect when laminated with a resin, a roughened surface is preferable. Further, in the case of copper wiring through which a high-frequency electrical signal flows in recent years, it is preferable that the center line has a smooth surface with an average roughness Ra of 0.1 μm or less. In particular, in the case of fine copper wiring, the present invention does not depend on the anchor effect due to surface roughening, and sufficient adhesion can be obtained even on a smooth surface, which may cause disconnection due to etching for roughening. There is no.
銅の表面に、前記接着層形成液を接触させる際の条件に特に限定はないが、たとえば浸漬法などにより、好ましくは１０〜７０℃、さらに好ましくは２０〜４０度で５秒〜５分間接触させればよい。これにより、銅の表面にスズ及び第３の金属の合金層を形成すると、拡散により銅とスズ及び第３の金属との界面に、銅、スズ及び第３の金属の合金層（接着層）が形成される。前記拡散を促進させるために、熱処理などを行なってもよい。 There are no particular limitations on the conditions when the adhesive layer forming liquid is brought into contact with the copper surface, but contact is preferably made at 10 to 70 ° C., more preferably at 20 to 40 ° C. for 5 seconds to 5 minutes, for example, by an immersion method. You can do it. Thus, when an alloy layer of tin and the third metal is formed on the surface of copper, an alloy layer (adhesion layer) of copper, tin and the third metal is formed at the interface between copper, tin and the third metal by diffusion. Is formed. In order to promote the diffusion, heat treatment or the like may be performed.
次に、前記銅、スズ及び第３の金属の合金層（接着層）を残して、その上層にあるスズ及び第３金属の合金層を選択的に除去すると、銅表面に接着層が形成される。前記スズ及び第３の金属の合金層を選択的に除去する方法としては、エッチング液によりスズ及び第３の金属の合金層を選択的にエッチングする方法があげられる。前記選択的エッチング液としては、例えばメック社製の商品名“メックリムーバーＳ−６５１Ａ"等を使用することができる。別な例としては、硝酸等の無機酸を含む水溶液も使用できる。前記接着層形成液の組成やこれを接触させる条件や、銅の表面状態を選択することにより、銅の表面に直接、銅、スズ及び第３の金属からなる接着層を形成してもよい。 Next, the alloy layer (adhesive layer) of the copper, tin, and the third metal is left, and the alloy layer of the tin and the third metal is selectively removed to form an adhesive layer on the copper surface. The As a method for selectively removing the alloy layer of tin and the third metal, there is a method of selectively etching the alloy layer of tin and the third metal with an etching solution. As the selective etching solution, for example, trade name “Mekku Remover S-651A” manufactured by MEC Co., Ltd. can be used. As another example, an aqueous solution containing an inorganic acid such as nitric acid can also be used. You may form the contact bonding layer which consists of copper, tin, and a 3rd metal directly on the copper surface by selecting the composition of the said contact bonding layer formation liquid, the conditions which make this contact, and the surface state of copper.
以上のように銅表面に形成された対樹脂接着層は、通常、厚さが１μｍ以下であり、銅と樹脂との接着性を著しく向上させる。 The resin-adhesive layer formed on the copper surface as described above usually has a thickness of 1 μm or less, and remarkably improves the adhesion between copper and the resin.
本発明において、銅と接着する樹脂は、ＡＳ樹脂、ＡＢＳ樹脂、フッ素樹脂、ポリアミド、ポリエチレン、ポリエチレンテレフタレート、ポリ塩化ビニリデン、ポリ塩化ビニル、ポリカーボネート、ポリスチレン、ポリサルホン、ポリプロピレン、液晶ポリマー等の熱可塑性樹脂や、エポキシ樹脂、フェノール樹脂、ポリイミド、ポリウレタン、ビスマレイミド・トリアジン樹脂、変性ポリフェニレンエーテル、シアネートエステル等の熱硬化性樹脂等を挙げることができる。これらの樹脂は官能基によって変性されていてもよく、ガラス繊維、アラミド繊維、その他の繊維などで強化されていてもよい。 In the present invention, the resin to be bonded to copper is a thermoplastic resin such as AS resin, ABS resin, fluororesin, polyamide, polyethylene, polyethylene terephthalate, polyvinylidene chloride, polyvinyl chloride, polycarbonate, polystyrene, polysulfone, polypropylene, and liquid crystal polymer. And thermosetting resins such as epoxy resin, phenol resin, polyimide, polyurethane, bismaleimide / triazine resin, modified polyphenylene ether, and cyanate ester. These resins may be modified with functional groups, and may be reinforced with glass fibers, aramid fibers, other fibers, and the like.
本発明の積層体が配線基板であって、導電層の表面に前記接着層が形成された場合には、層間絶縁樹脂（プリプレグ、無電解めっき用接着剤、フィルム状樹脂、液状樹脂、感光性樹脂、熱硬化性樹脂、熱可塑性樹脂、）、ソルダーレジスト、エッチングレジスト、導電性樹脂、導電性ペースト、導電性接着剤、誘電体樹脂、穴埋め用樹脂、フレキシブルカバーレイフィルム等との接着性に優れているため、信頼性の高い配線基板となる。 When the laminate of the present invention is a wiring board and the adhesive layer is formed on the surface of a conductive layer, an interlayer insulating resin (prepreg, electroless plating adhesive, film resin, liquid resin, photosensitive property Resin, thermosetting resin, thermoplastic resin), solder resist, etching resist, conductive resin, conductive paste, conductive adhesive, dielectric resin, hole filling resin, flexible coverlay film, etc. Since it is excellent, it becomes a highly reliable wiring board.
本発明の積層体は、とくに微細な銅配線とビアホールを形成するビルドアップ基板として有用である。前記ビルドアップ基板には一括ラミネーション方式のビルドアップ基板と、シーケンシャルビルドアップ方式のビルドアップ基板がある。 The laminate of the present invention is particularly useful as a build-up substrate for forming fine copper wiring and via holes. The build-up board includes a batch lamination type build-up board and a sequential build-up type build-up board.
また、いわゆるメタルコア基板とよばれる心材に銅板を用いた基板において、銅板の表面が前記対樹脂接着層となっている場合には、銅板とそれに積層された絶縁樹脂との接着性に優れたメタルコア基板である。 Further, in a substrate using a copper plate as a core material called a so-called metal core substrate, when the surface of the copper plate is the above-mentioned resin adhesive layer, the metal core having excellent adhesion between the copper plate and the insulating resin laminated thereon It is a substrate.
図１は本発明の一実施例の銅表面に形成された樹脂接着層の断面図である。すなわち、銅基材１の表面に樹脂接着層２が形成されている。
FIG. 1 is a cross-sectional view of a resin adhesive layer formed on a copper surface according to an embodiment of the present invention. That is, the
以下実施例を挙げて本発明をさらに具体的に説明する。 Hereinafter, the present invention will be described more specifically with reference to examples.
（実施例１〜１１）
（１）層間剥離試験
両面に厚さ１８μｍの銅箔を張り合わせたガラス布エポキシ樹脂含浸銅張積層板（ＦＲ−４グレード）の両面の銅箔を、５％の塩酸を１０秒間室温でスプレーして洗浄したのち、水洗、乾燥させた。
(Examples 1 to 11)
(1) Delamination test 5% hydrochloric acid was sprayed at room temperature for 10 seconds on a copper foil on both sides of a glass cloth epoxy resin impregnated copper clad laminate (FR-4 grade) with 18 μm thick copper foil laminated on both sides. After washing, it was washed with water and dried.
次に表１及び２に示される成分を混合した接着層形成液に３０℃、３０秒の条件で浸漬したのち水洗、乾燥させた。 Next, it was immersed in an adhesive layer forming liquid in which the components shown in Tables 1 and 2 were mixed at 30 ° C. for 30 seconds, washed with water and dried.
次にメック社製商品名“メックリムーバーＳ−６５１Ａ”（硝酸を主成分とする水溶液）に３０秒間室温で浸漬したのち、水洗し、乾燥させ、銅箔表面に樹脂接着層（合金層）を形成した。 Next, after being immersed in a product name “Mekuri Mover S-651A” (an aqueous solution containing nitric acid as a main component) for 30 seconds at room temperature, it is washed with water and dried, and a resin adhesive layer (alloy layer) is applied to the copper foil surface. Formed.
次に、得られた積層板の銅箔と樹脂との接着性を評価するため、前記積層板の両面に銅箔付きビルドアップ配線板用樹脂（味の素社製のＡＢＦ−ＳＨＣ銅箔付き樹脂）を重ね加熱しながらプレスした後、周辺部を切り取って縦１０ｃｍ、横１０ｃｍの積層体を作製した。次に両面にある銅箔付き樹脂の銅箔をエッチングして除去したのち、プレッシャークッカーにて１２１℃、１００％ＲＨ、２気圧、８時間の負荷を与えた後、ＪＩＳ Ｃ ６４８１に準じて２９０℃の溶融はんだ浴中に１分間浸漬し、銅箔と樹脂の剥離（樹脂のふくれ）を調べた。結果を表１及び２に示す。
（２）引き剥がし強さ試験
厚さ３５μｍの電解銅箔の表面を、前記層間剥離試験の試料と同様に処理し、表面に樹脂接着層を形成した。
Next, in order to evaluate the adhesiveness between the copper foil and the resin of the obtained laminated board, a resin for build-up wiring board with copper foil (resin with ABF-SHC copper foil manufactured by Ajinomoto Co., Inc.) on both sides of the laminated board. Was pressed while being heated, and then the peripheral part was cut off to produce a laminate of 10 cm in length and 10 cm in width. Next, after removing the copper foil of the resin with copper foil on both sides by etching, a pressure cooker was applied at 121 ° C., 100% RH, 2 atmospheres, 8 hours, and then 290 according to JIS C 6481. The film was immersed in a molten solder bath at 1 ° C. for 1 minute, and the peeling (resin blistering) of the copper foil and the resin was examined. The results are shown in Tables 1 and 2.
(2) Peel strength test The surface of an electrolytic copper foil having a thickness of 35 μm was treated in the same manner as the sample for the delamination test to form a resin adhesive layer on the surface.
次に、得られた銅箔の片面に銅箔付きビルドアップ配線板用樹脂（味の素（株）製のＡＢＦ−ＳＨＣ銅箔付き樹脂）を重ね加熱しながらプレスした。得られた積層体の電解銅箔の引き剥がし強さを、ＪＩＳ Ｃ ６４８１に準拠して調べた。結果を表１及び２に示す。 Next, a resin for a build-up wiring board with a copper foil (ABF-SHC resin with an ABF-SHC copper foil) manufactured by Ajinomoto Co., Inc. was pressed on one side of the obtained copper foil while being heated. The peel strength of the electrolytic copper foil of the obtained laminate was examined in accordance with JIS C 6481. The results are shown in Tables 1 and 2.
（実施例１２）
両面に厚さ１８μｍの銅箔を張り合わせたガラス布エポキシ樹脂含浸銅張積層板（ＦＲ−４グレード）の両面の銅箔を、５％の塩酸を１０秒間室温でスプレーして洗浄したのち、水洗、乾燥させた。次に表３に示される成分を混合した接着層形成液に３０℃、３０秒の条件で浸漬したのち、水洗、乾燥させ、銅箔表面に直接樹脂接着層を形成した。
(Example 12)
After washing the copper foil on both sides of a glass cloth epoxy resin impregnated copper clad laminate (FR-4 grade) with copper foil with a thickness of 18μm on both sides by spraying 5% hydrochloric acid at room temperature for 10 seconds, then washing with water , Dried. Next, it was immersed in an adhesive layer forming liquid in which the components shown in Table 3 were mixed at 30 ° C. for 30 seconds, washed with water and dried to form a resin adhesive layer directly on the copper foil surface.
次に実施例１と同様に、ビルドアップ配線板用樹脂を積層して積層体を作成し、評価した。結果を表３に示す。 Next, in the same manner as in Example 1, a laminate was prepared by laminating a resin for a build-up wiring board and evaluated. The results are shown in Table 3.
（実施例１３）
銅箔付きビルドアップ配線板用樹脂の代わりに、ガラス布エポキシ樹脂含浸プリプレグ２枚を用いた他は、実施例１と同様に積層体を作成し、評価した。結果を表３に示す。
(Example 13)
A laminate was prepared and evaluated in the same manner as in Example 1 except that two glass cloth epoxy resin-impregnated prepregs were used instead of the resin for the build-up wiring board with copper foil. The results are shown in Table 3.
（実施例１４）
銅箔付きビルドアップ配線板用樹脂の代わりに、ガラス布ビスマレイミド・トリアジン樹脂含浸プリプレグ２枚を用いた他は、実施例１と同様に積層体を作成し、評価した。結果を表３に示す。
(Example 14)
A laminate was prepared and evaluated in the same manner as in Example 1 except that two glass cloth bismaleimide / triazine resin-impregnated prepregs were used instead of the resin for the build-up wiring board with copper foil. The results are shown in Table 3.
（実施例１５）
銅箔付きビルドアップ配線板用樹脂の代わりに、ガラス布ポリフェニレンエーテル含浸プリプレグ２枚を用いた他は、実施例１と同様に積層体を作成し、評価した。結果を表３に示す。
(Example 15)
A laminate was prepared and evaluated in the same manner as in Example 1 except that two glass cloth polyphenylene ether-impregnated prepregs were used instead of the resin for the build-up wiring board with copper foil. The results are shown in Table 3.
（比較例１）
両面に厚さ１８μｍの銅箔を張り合わせたガラス布エポキシ樹脂含浸銅張積層板（ＦＲ−４グレード）の両面の銅箔を、５％の塩酸を１０秒間室温でスプレーして洗浄したのち、水洗、乾燥させた。次に表３に示される成分を混合したスズ層形成液に３０℃、３０秒の条件で浸漬したのち、水洗、乾燥させ、銅箔表面にスズ層を形成した。
(Comparative Example 1)
After washing the copper foil on both sides of a glass cloth epoxy resin impregnated copper clad laminate (FR-4 grade) with copper foil with a thickness of 18μm on both sides by spraying 5% hydrochloric acid at room temperature for 10 seconds, then washing with water , Dried. Next, it was immersed in a tin layer forming solution in which the components shown in Table 3 were mixed at 30 ° C. for 30 seconds, then washed with water and dried to form a tin layer on the surface of the copper foil.
次に実施例１と同様に、ビルドアップ配線板用樹脂を積層して積層体を作成し、評価した。結果を表３に示す。 Next, in the same manner as in Example 1, a laminate was prepared by laminating a resin for a build-up wiring board and evaluated. The results are shown in Table 3.
（比較例２）
比較例１と同様に銅箔表面にスズ層を形成した。次にメック社製商品名“メックリムーバーＳ−６５１Ａ”に３０秒間室温で浸漬したのち、水洗し、乾燥させ、銅箔表面に銅スズ合金層を形成した。
(Comparative Example 2)
Similar to Comparative Example 1, a tin layer was formed on the surface of the copper foil. Next, it was immersed in a product name “Mekku remover S-651A” manufactured by MEC at room temperature for 30 seconds, washed with water and dried to form a copper tin alloy layer on the surface of the copper foil.
次に実施例１と同様に、ビルドアップ配線板用樹脂を積層して積層体を作成し、評価した。結果を表３に示す。 Next, in the same manner as in Example 1, a laminate was prepared by laminating a resin for a build-up wiring board and evaluated. The results are shown in Table 3.
表１〜３から明らかなとおり、本実施例の樹脂接着層は、銅箔と樹脂の引き剥がし強力（接着力）が高いことが確認できた。 As is clear from Tables 1 to 3, it was confirmed that the resin adhesive layer of this example had high peel strength (adhesive strength) between the copper foil and the resin.
１ 銅基材
２ 樹脂接着層
1
Claims (19)
ａ 無機酸及び有機酸から選ばれる少なくとも１種の酸、
ｂ スズ塩又はスズ酸化物、
ｃ 銀、亜鉛、アルミニウム、チタン、ビスマス、クロム、鉄、コバルト、ニッケル、パラジウム、金及び白金から選ばれる少なくとも１種の金属の塩又は酸化物、
ｄ 反応促進剤、及び
ｅ 拡散系保持溶媒
を含有する水溶液であることを特徴とする銅と樹脂の接着層形成液。 An adhesive layer forming liquid of copper and resin,
a at least one acid selected from inorganic acids and organic acids,
b Tin salt or tin oxide,
c A salt or oxide of at least one metal selected from silver, zinc, aluminum, titanium, bismuth, chromium, iron, cobalt, nickel, palladium, gold and platinum,
d. Adhesive layer forming liquid of copper and resin, which is an aqueous solution containing a reaction accelerator and e diffusion system holding solvent.
ａ 無機酸及び有機酸から選ばれる少なくとも１種の酸、
ｂ スズ塩又はスズ酸化物、
ｃ 銀、亜鉛、アルミニウム、チタン、ビスマス、クロム、鉄、コバルト、ニッケル、パラジウム、金及び白金から選ばれる少なくとも１種の金属の塩又は酸化物、
ｄ 反応促進剤及び
ｅ 拡散系保持溶媒
を含有する水溶液を含む樹脂接着層形成液を接触させ、スズ及び前記ｃの金属の合金層を形成させ、
次いで前記銅と、前記スズ及び前記ｃの金属とが拡散している層を残して、前記スズ及び前記ｃの金属の合金層を除去することにより、銅の表面に、銅、スズ及び前記ｃの金属の合金を含む樹脂の接着層を形成することを特徴とする銅と樹脂の接着層の製造方法。 On the copper surface,
a at least one acid selected from inorganic acids and organic acids,
b Tin salt or tin oxide,
c A salt or oxide of at least one metal selected from silver, zinc, aluminum, titanium, bismuth, chromium, iron, cobalt, nickel, palladium, gold and platinum,
contacting a resin adhesive layer forming liquid containing an aqueous solution containing a d reaction accelerator and e diffusion system-retaining solvent to form an alloy layer of tin and the metal of c;
Next, leaving the layer in which the copper, the tin and the c metal are diffused, and removing the alloy layer of the tin and the c metal, copper, tin and the c are formed on the surface of the copper. A method for producing an adhesive layer of copper and resin, comprising forming an adhesive layer of a resin containing an alloy of the above metals.
A laminated body in which copper and a resin are integrated, and on the surface in contact with the copper resin, copper, tin, silver, zinc, aluminum, titanium, bismuth, chromium, iron, cobalt, nickel, palladium, gold and A copper-resin laminate comprising a resin adhesive layer containing an alloy made of at least one metal selected from platinum.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102009005691A1 (en) | 2008-02-01 | 2009-08-06 | MEC COMPANY LTD., Amagasaki | Electrically conductive layer, laminate using same and manufacturing method therefor |
| WO2009110364A1 (en) * | 2008-03-04 | 2009-09-11 | 日本ペイント株式会社 | Copper surface treatment agent and surface treatment method |
| DE102009031015A1 (en) | 2008-07-02 | 2010-01-07 | MEC COMPANY LTD., Amagasaki-shi | Adhesive layer forming liquid |
| JP2010111748A (en) * | 2008-11-05 | 2010-05-20 | Mec Kk | Adhesive layer forming liquid and adhesive layer forming process |
| KR20160140455A (en) | 2015-05-28 | 2016-12-07 | 이시하라 케미칼 가부시키가이샤 | Replacement nickel plating bath for the copper surface treatment, manufacturing method of the copper parts of using the plating bath and the copper parts |
| JPWO2020170638A1 (en) * | 2019-02-21 | 2020-08-27 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE102009005691A1 (en) | 2008-02-01 | 2009-08-06 | MEC COMPANY LTD., Amagasaki | Electrically conductive layer, laminate using same and manufacturing method therefor |
| US8828554B2 (en) | 2008-02-01 | 2014-09-09 | Mec Company Ltd. | Electroconductive layer, laminate using the same, and producing processes thereof |
| WO2009110364A1 (en) * | 2008-03-04 | 2009-09-11 | 日本ペイント株式会社 | Copper surface treatment agent and surface treatment method |
| JP5307117B2 (en) * | 2008-03-04 | 2013-10-02 | 日本ペイント株式会社 | Copper surface treatment agent and surface treatment method |
| DE102009031015A1 (en) | 2008-07-02 | 2010-01-07 | MEC COMPANY LTD., Amagasaki-shi | Adhesive layer forming liquid |
| JP2010013516A (en) * | 2008-07-02 | 2010-01-21 | Mec Kk | Adhesive layer-forming liquid |
| TWI467050B (en) * | 2008-07-02 | 2015-01-01 | Mec Co Ltd | Followed by layer formation |
| JP2010111748A (en) * | 2008-11-05 | 2010-05-20 | Mec Kk | Adhesive layer forming liquid and adhesive layer forming process |
| KR101312802B1 (en) * | 2008-11-05 | 2013-09-27 | 멕크 가부시키가이샤 | Bonding layer forming solution and method of forming bonding layer |
| KR20160140455A (en) | 2015-05-28 | 2016-12-07 | 이시하라 케미칼 가부시키가이샤 | Replacement nickel plating bath for the copper surface treatment, manufacturing method of the copper parts of using the plating bath and the copper parts |
| JPWO2020170638A1 (en) * | 2019-02-21 | 2020-08-27 | ||
| WO2020170638A1 (en) * | 2019-02-21 | 2020-08-27 | メック株式会社 | Adhesive composition, method for producing surface-treated metal member, and method for producing metal-resin composite body |
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