JP2014194068A5 - Copper foil with carrier, method for producing copper-clad laminate, and method for producing printed wiring board - Google Patents

Copper foil with carrier, method for producing copper-clad laminate, and method for producing printed wiring board Download PDF

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JP2014194068A5
JP2014194068A5 JP2013187782A JP2013187782A JP2014194068A5 JP 2014194068 A5 JP2014194068 A5 JP 2014194068A5 JP 2013187782 A JP2013187782 A JP 2013187782A JP 2013187782 A JP2013187782 A JP 2013187782A JP 2014194068 A5 JP2014194068 A5 JP 2014194068A5
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キャリア、中間層、極薄銅層をこの順に有するキャリア付銅箔であって、
前記極薄銅層表面には粗化処理層を有し、
以下の(A)〜(C)のいずれか一つ以上を満たし、
(A)前記極薄銅層の粗化処理層表面を非接触式粗さ計で測定したRzが1.6μm以下である、
(B)前記極薄銅層の粗化処理層表面を非接触式粗さ計で測定したRaが0.3μm以下である、
(C)前記極薄銅層の粗化処理層表面を非接触式粗さ計で測定したRtが2.3μm以下である、
前記中間層はNiを含み、
前記極薄銅層に絶縁基板を大気中、圧力:20kgf/cm2、220℃×2時間の条件下で熱圧着させ、JIS C 6471に準拠して前記極薄銅層を剥がしたとき、XPSによる表面からの深さ方向分析から得られた深さ方向(x:単位nm)のクロムの原子濃度(%)をe(x)とし、亜鉛の原子濃度(%)をf(x)とし、ニッケルの原子濃度(%)をg(x)とし、銅の原子濃度(%)をh(x)とし、酸素の合計原子濃度(%)をi(x)とし、炭素の原子濃度(%)をj(x)とし、その他の原子濃度(%)をk(x)とすると、
前記極薄銅層の前記中間層側の表面からの深さ方向分析の区間[0、1.0]において、∫g(x)dx/(∫e(x)dx +∫f(x)dx + ∫g(x)dx + ∫h(x)dx + ∫i(x)dx + ∫j(x)dx+ ∫k(x)dx )が20.0%以下を満たすキャリア付銅箔。
A carrier-attached copper foil having a carrier, an intermediate layer, and an ultrathin copper layer in this order,
The ultrathin copper layer surface has a roughening treatment layer ,
Satisfy any one or more of the following (A) to (C),
(A) Rz measured by a non-contact type roughness meter on the roughened layer surface of the ultrathin copper layer is 1.6 μm or less .
(B) Ra measured by the non-contact type roughness meter on the roughened layer surface of the ultrathin copper layer is 0.3 μm or less.
(C) Rt measured by a non-contact type roughness meter on the roughened layer surface of the ultrathin copper layer is 2.3 μm or less.
The intermediate layer includes Ni;
When the insulating substrate is thermocompression bonded to the ultrathin copper layer in the atmosphere under the conditions of pressure: 20 kgf / cm 2 and 220 ° C. × 2 hours, and the ultrathin copper layer is peeled off according to JIS C 6471, XPS E (x) is the atomic concentration (%) of chromium in the depth direction (x: unit nm), and f (x) is the atomic concentration (%) of zinc. The atomic concentration (%) of nickel is g (x), the atomic concentration (%) of copper is h (x), the total atomic concentration (%) of oxygen is i (x), and the atomic concentration of carbon (%) Is j (x) and other atomic concentration (%) is k (x),
In the section [0, 1.0] in the depth direction analysis from the surface on the intermediate layer side of the ultrathin copper layer, ∫g (x) dx / (∫e (x) dx + ∫f (x) dx + ∫g (x) dx + ∫h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x) dx) satisfying 20.0% or less.
前記極薄銅層に絶縁基板を大気中、圧力:20kgf/cm2、220℃×2時間の条件下で熱圧着させ、JIS C 6471に準拠して前記極薄銅層を剥がしたとき、前記極薄銅層の前記中間層側の表面からの深さ方向分析の区間[1.0、4.0]において、
∫g(x)dx/(∫e(x)dx +∫f(x)dx + ∫g(x)dx + ∫h(x)dx + ∫i(x)dx + ∫j(x)dx+ ∫k(x)dx )が10.0%以下を満たす請求項に記載のキャリア付銅箔。
When the insulating substrate is thermocompression bonded to the ultrathin copper layer under the conditions of pressure: 20 kgf / cm 2 , 220 ° C. × 2 hours in the atmosphere, and the ultrathin copper layer is peeled off in accordance with JIS C 6471, In the section [1.0, 4.0] of the depth direction analysis from the surface of the intermediate layer side of the ultrathin copper layer,
∫g (x) dx / (∫e (x) dx + ∫f (x) dx + ∫g (x) dx + ∫h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫ The copper foil with a carrier according to claim 1 , wherein k (x) dx) satisfies 10.0% or less.
以下の(D)〜(G)を一つ以上満たす請求項1または2のいずれか一項に記載のキャリア付銅箔。
(D)前記極薄銅層表面は、Sskが−0.3〜0.3である
(E)前記極薄銅層表面は、Skuが2.7〜3.3である、
(F)極薄銅層表面の表面積比が1.05〜1.5である、
(G)極薄銅層表面の面積66524μm 2 当たりの体積が300000〜500000μm 3 である。
The copper foil with a carrier as described in any one of Claim 1 or 2 which satisfy | fills one or more of the following (D)-(G).
(D) The ultrathin copper layer surface has Ssk of −0.3 to 0.3 ,
(E) The ultra-thin copper layer surface has a Sku of 2.7 to 3.3.
(F) The surface area ratio of the ultrathin copper layer surface is 1.05-1.5,
(G) The volume per area 66524 μm 2 of the ultrathin copper layer surface is 300,000 to 500,000 μm 3 .
前記極薄銅層に絶縁基板を大気中、圧力:20kgf/cm2、220℃×2時間の条件下で熱圧着させ、JIS C 6471に準拠して前記極薄銅層を剥がしたとき、前記極薄銅層の前記中間層側の表面からの深さ方向分析の区間[0、1.0]において、∫g(x)dx/(∫e(x)dx +∫f(x)dx + ∫g(x)dx + ∫h(x)dx + ∫i(x)dx + ∫j(x)dx+ ∫k(x)dx )が1.0%以上20.0%以下、且つ、区間[1.0、4.0]において、∫g(x)dx/(∫e(x)dx +∫f(x)dx + ∫g(x)dx + ∫h(x)dx + ∫i(x)dx + ∫j(x)dx+ ∫k(x)dx )が1.0%以上10.0%以下を満たす請求項1〜のいずれか一項に記載のキャリア付銅箔。 When the insulating substrate is thermocompression bonded to the ultrathin copper layer under the conditions of pressure: 20 kgf / cm 2 , 220 ° C. × 2 hours in the atmosphere, and the ultrathin copper layer is peeled off in accordance with JIS C 6471, In the interval [0, 1.0] of the depth direction analysis from the surface on the intermediate layer side of the ultrathin copper layer, ∫g (x) dx / (∫e (x) dx + ∫f (x) dx + ∫g (x) dx + ∫h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x) dx) is 1.0% or more and 20.0% or less, and the interval [ 1.0, 4.0], ∫g (x) dx / (∫e (x) dx + ∫f (x) dx + ∫g (x) dx + ∫h (x) dx + ∫i (x The copper foil with a carrier according to any one of claims 1 to 3 , wherein dx + dj (x) dx + ∫k (x) dx) satisfies 1.0% to 10.0%. 前記極薄銅層に絶縁基板を大気中、圧力:20kgf/cm2、220℃×2時間の条件下で熱圧着させ、JIS C 6471に準拠して前記極薄銅層を剥がしたとき、前記極薄銅層の前記中間層側のXPSによる表面からの深さ方向分析の区間[0、1.0]において、∫e(x)dx/(∫e(x)dx +∫f(x)dx + ∫g(x)dx + ∫h(x)dx + ∫i(x)dx + ∫j(x)dx+ ∫k(x)dx )が3.0%以下を満たす請求項1〜のいずれか一項に記載のキャリア付銅箔。 When the insulating substrate is thermocompression bonded to the ultrathin copper layer under the conditions of pressure: 20 kgf / cm 2 , 220 ° C. × 2 hours in the atmosphere, and the ultrathin copper layer is peeled off in accordance with JIS C 6471, In the interval [0, 1.0] of the depth direction analysis from the surface by XPS on the intermediate layer side of the ultrathin copper layer, ∫e (x) dx / (∫e (x) dx + ∫f (x) dx + ∫g (x) dx + ∫h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x) dx) of claim 1-4 which satisfy the following 3.0% The copper foil with a carrier as described in any one of Claims. 前記極薄銅層に絶縁基板を大気中、圧力:20kgf/cm2、220℃×2時間の条件下で熱圧着させ、JIS C 6471に準拠して前記極薄銅層を剥がしたとき、前記極薄銅層の前記中間層側の表面からの深さ方向分析の区間[0、1.0]において、∫g(x)dx/(∫e(x)dx +∫f(x)dx + ∫g(x)dx + ∫h(x)dx + ∫i(x)dx + ∫j(x)dx+ ∫k(x)dx )が11.0%以下を満たす請求項1〜のいずれか一項に記載のキャリア付銅箔。 When the insulating substrate is thermocompression bonded to the ultrathin copper layer under the conditions of pressure: 20 kgf / cm 2 , 220 ° C. × 2 hours in the atmosphere, and the ultrathin copper layer is peeled off in accordance with JIS C 6471, In the interval [0, 1.0] of the depth direction analysis from the surface on the intermediate layer side of the ultrathin copper layer, ∫g (x) dx / (∫e (x) dx + ∫f (x) dx + either ∫g (x) dx + ∫h ( x) dx + ∫i (x) dx + ∫j (x) according to claim 1-5 where dx + ∫k (x) dx) satisfies the following 11.0% The copper foil with a carrier according to one item. 前記極薄銅層に絶縁基板を大気中、圧力:20kgf/cm2、220℃×2時間の条件下で熱圧着させ、JIS C 6471に準拠して前記極薄銅層を剥がしたとき、前記極薄銅層の前記中間層側の表面からの深さ方向分析の区間[1.0、4.0]において、
∫g(x)dx/(∫e(x)dx +∫f(x)dx + ∫g(x)dx + ∫h(x)dx + ∫i(x)dx + ∫j(x)dx+ ∫k(x)dx )が7.0%以下を満たす請求項1〜のいずれか一項に記載のキャリア付銅箔。
When the insulating substrate is thermocompression bonded to the ultrathin copper layer under the conditions of pressure: 20 kgf / cm 2 , 220 ° C. × 2 hours in the atmosphere, and the ultrathin copper layer is peeled off in accordance with JIS C 6471, In the section [1.0, 4.0] of the depth direction analysis from the surface of the intermediate layer side of the ultrathin copper layer,
∫g (x) dx / (∫e (x) dx + ∫f (x) dx + ∫g (x) dx + ∫h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫ The copper foil with a carrier according to any one of claims 1 to 6 , wherein k (x) dx) satisfies 7.0% or less.
JIS C 6471に準拠して前記極薄銅層を剥がしたとき、XPSによる表面からの深さ方向分析から得られた深さ方向(x:単位nm)のクロムの原子濃度(%)をe(x)とし、亜鉛の原子濃度(%)をf(x)とし、ニッケルの原子濃度(%)をg(x)とし、銅の原子濃度(%)をh(x)とし、酸素の合計原子濃度(%)をi(x)とし、炭素の原子濃度(%)をj(x)とし、その他の原子濃度(%)をk(x)とすると、
前記極薄銅層の前記中間層側の表面からの深さ方向分析の区間[0、1.0]において、∫g(x)dx/(∫e(x)dx +∫f(x)dx + ∫g(x)dx + ∫h(x)dx + ∫i(x)dx + ∫j(x)dx+ ∫k(x)dx )が5.0%以下を満たす請求項1〜のいずれか一項に記載のキャリア付銅箔。
When the ultra-thin copper layer was peeled off according to JIS C 6471, the atomic concentration (%) of chromium in the depth direction (x: unit nm) obtained from the depth direction analysis from the surface by XPS was expressed as e ( x), the atomic concentration (%) of zinc is f (x), the atomic concentration (%) of nickel is g (x), the atomic concentration (%) of copper is h (x), and the total oxygen atoms If the concentration (%) is i (x), the carbon atomic concentration (%) is j (x), and the other atomic concentration (%) is k (x),
In the section [0, 1.0] in the depth direction analysis from the surface on the intermediate layer side of the ultrathin copper layer, ∫g (x) dx / (∫e (x) dx + ∫f (x) dx + ∫g (x) dx + ∫h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x) dx) is any of claims 1-7 which satisfy the following 5.0% A copper foil with a carrier according to claim 1.
JIS C 6471に準拠して前記極薄銅層を剥がしたとき、XPSによる表面からの深さ方向分析から得られた深さ方向(x:単位nm)のクロムの原子濃度(%)をe(x)とし、亜鉛の原子濃度(%)をf(x)とし、ニッケルの原子濃度(%)をg(x)とし、銅の原子濃度(%)をh(x)とし、酸素の合計原子濃度(%)をi(x)とし、炭素の原子濃度(%)をj(x)とし、その他の原子濃度(%)をk(x)とすると、
前記極薄銅層の前記中間層側の表面からの深さ方向分析の区間[1.0、4.0]において、∫g(x)dx/(∫e(x)dx +∫f(x)dx + ∫g(x)dx + ∫h(x)dx + ∫i(x)dx + ∫j(x)dx+ ∫k(x)dx )が1.0%以下又は0.1%以上又は0.1%以上1.0%以下のいずれかを満たす請求項1〜のいずれか一項に記載のキャリア付銅箔。
When the ultra-thin copper layer was peeled off according to JIS C 6471, the atomic concentration (%) of chromium in the depth direction (x: unit nm) obtained from the depth direction analysis from the surface by XPS was expressed as e ( x), the atomic concentration (%) of zinc is f (x), the atomic concentration (%) of nickel is g (x), the atomic concentration (%) of copper is h (x), and the total oxygen atoms If the concentration (%) is i (x), the carbon atomic concentration (%) is j (x), and the other atomic concentration (%) is k (x),
In the section [1.0, 4.0] of the depth direction analysis from the surface on the intermediate layer side of the ultrathin copper layer, ∫g (x) dx / (∫e (x) dx + ∫f (x ) dx + ∫g (x) dx + ∫h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫k (x) dx) is 1.0% or less or 0.1% or more The copper foil with a carrier according to any one of claims 1 to 8 , which satisfies any of 0.1% to 1.0% .
JIS C 6471に準拠して前記極薄銅層を剥がしたとき、前記極薄銅層の前記中間層側のXPSによる表面からの深さ方向分析の区間[0、1.0]において、∫e(x)dx/(∫e(x)dx +∫f(x)dx + ∫g(x)dx + ∫h(x)dx + ∫i(x)dx + ∫j(x)dx+ ∫k(x)dx )が2.0%以下を満たす請求項1〜のいずれか一項に記載のキャリア付銅箔。 When the ultra-thin copper layer is peeled in accordance with JIS C 6471, in the section [0, 1.0] in the depth direction analysis from the surface by XPS on the intermediate layer side of the ultra-thin copper layer, ∫e (x) dx / (∫e (x) dx + ∫f (x) dx + ∫g (x) dx + ∫h (x) dx + ∫i (x) dx + ∫j (x) dx + ∫k ( The copper foil with a carrier according to any one of claims 1 to 9 , wherein x) dx) satisfies 2.0% or less. 以下の(H)〜(Q)のいずれか一つを満たす請求項1〜10のいずれか一項に記載のキャリア付銅箔。
(H)前記中間層は、キャリア上にニッケルまたはニッケルを含む合金のいずれか1種の層、及びクロム、クロム合金、クロムの酸化物のいずれか1種以上を含む層がこの順で積層されて構成されている
(I)前記(H)を満たし、且つ、前記クロム、クロム合金、クロムの酸化物のいずれか1種以上を含む層がクロメート処理層を含む、
(J)前記中間層は、亜鉛を含む、
(K)前記中間層は、前記キャリア上にニッケル、ニッケル−亜鉛合金、ニッケル−リン合金、ニッケル−コバルト合金のいずれか1種の層、及び亜鉛クロメート処理層、純クロメート処理層、クロムめっき層のいずれか1種の層がこの順で積層されて構成されている、
(L)前記中間層は、前記キャリア上に、
ニッケル層またはニッケル−亜鉛合金層、及び、亜鉛クロメート処理層がこの順で積層されて構成されている、又は、
ニッケル−亜鉛合金層、及び、純クロメート処理層または亜鉛クロメート処理層がこの順で積層されて構成されており、
前記中間層におけるニッケルの付着量が100〜40000μg/dm 2 、クロムの付着量が5〜100μg/dm 2 、亜鉛の付着量が1〜70μg/dm 2 である、
(M)前記中間層は、前記キャリア上にニッケル層、及び、窒素含有有機化合物、硫黄含有有機化合物及びカルボン酸のいずれかを含む有機物層の順で積層されて構成されており、
前記中間層におけるニッケルの付着量が100〜40000μg/dm 2 である、
(N)前記中間層は、前記キャリア上に窒素含有有機化合物、硫黄含有有機化合物及びカルボン酸のいずれかを含む有機物層、及び、ニッケル層の順で積層されて構成されており、
前記中間層におけるニッケルの付着量が100〜40000μg/dm 2 である、
(O)前記中間層が有機物を厚みで25nm以上80nm以下含有する、
(P)前記(M)または前記(N)を満たし、且つ、前記中間層が有機物を厚みで25nm以上80nm以下含有する、
(Q)前記中間層は、前記キャリア上にニッケル層またはニッケルを含む合金層および、モリブデン、コバルト、モリブデンコバルト合金のいずれか1種以上を含む層の順で積層されて構成されており、
前記中間層におけるニッケルの付着量が100〜40000μg/dm 2 であり、モリブデンが含まれる場合にはモリブデンの付着量が10〜1000μg/dm 2 、コバルトが含まれる場合にはコバルトの付着量が10〜1000μg/dm 2 である。
The copper foil with a carrier as described in any one of Claims 1-10 which satisfy | fills any one of the following (H)-(Q).
(H) In the intermediate layer, any one layer of nickel or an alloy containing nickel and a layer containing any one or more of chromium, a chromium alloy, and an oxide of chromium are laminated in this order on the carrier. Configured ,
(I) The layer satisfying (H) and containing at least one of chromium, a chromium alloy, and a chromium oxide includes a chromate treatment layer.
(J) The intermediate layer includes zinc.
(K) The intermediate layer is formed on the carrier by any one of nickel, nickel-zinc alloy, nickel-phosphorus alloy, nickel-cobalt alloy, zinc chromate treatment layer, pure chromate treatment layer, chromium plating layer. Any one of the layers is laminated in this order,
(L) the intermediate layer is on the carrier;
A nickel layer or a nickel-zinc alloy layer and a zinc chromate treatment layer are laminated in this order, or
A nickel-zinc alloy layer and a pure chromate treatment layer or a zinc chromate treatment layer are laminated in this order.
The amount of adhered 100~40000μg / dm 2 of nickel in the intermediate layer, the adhesion amount of chromium 5~100μg / dm 2, the adhesion amount of the zinc is 1~70μg / dm 2,
(M) The intermediate layer is formed by laminating a nickel layer on the carrier and an organic material layer containing any one of a nitrogen-containing organic compound, a sulfur-containing organic compound and a carboxylic acid,
The adhesion amount of nickel in the intermediate layer is 100 to 40000 μg / dm 2 .
(N) The intermediate layer is configured by laminating on the carrier in order of a nitrogen-containing organic compound, a sulfur-containing organic compound and a carboxylic acid, and a nickel layer.
The adhesion amount of nickel in the intermediate layer is 100 to 40000 μg / dm 2 .
(O) The intermediate layer contains an organic substance in a thickness of 25 nm or more and 80 nm or less,
(P) Satisfying (M) or (N) above, and the intermediate layer contains an organic substance in a thickness of 25 nm to 80 nm.
(Q) The intermediate layer is formed by stacking a nickel layer or an alloy layer containing nickel on the carrier and a layer containing any one or more of molybdenum, cobalt, and a molybdenum cobalt alloy in this order.
The adhesion amount of nickel in the intermediate layer is 100 to 40000 μg / dm 2 , and when molybdenum is included, the adhesion amount of molybdenum is 10 to 1000 μg / dm 2 , and when cobalt is included, the adhesion amount of cobalt is 10 ˜1000 μg / dm 2 .
以下の(R)〜(T)のいずれか一つを満たす請求項1〜11のいずれか一項に記載のキャリア付銅箔。
(R)前記粗化処理層の表面に、耐熱層、防錆層、クロメート処理層及びシランカップリング処理層からなる群から選択された1種以上の層を有する
(S)前記粗化処理層の表面に、耐熱層、防錆層、クロメート処理層及びシランカップリング処理層からなる群から選択された1種以上の層を有し、且つ、前記耐熱層、防錆層、クロメート処理層及びシランカップリング処理層からなる群から選択された1種以上の層の上に樹脂層を備える、
(T)前記粗化処理層上に樹脂層を備える。
The copper foil with a carrier as described in any one of Claims 1-11 which satisfy | fills any one of the following (R)-(T).
(R) The surface of the roughening treatment layer has one or more layers selected from the group consisting of a heat-resistant layer, a rust prevention layer, a chromate treatment layer, and a silane coupling treatment layer .
(S) The surface of the roughening treatment layer has one or more layers selected from the group consisting of a heat resistance layer, a rust prevention layer, a chromate treatment layer, and a silane coupling treatment layer, and the heat resistance layer, A resin layer is provided on one or more layers selected from the group consisting of a rust prevention layer, a chromate treatment layer, and a silane coupling treatment layer.
(T) A resin layer is provided on the roughening treatment layer.
請求項1〜12のいずれか一項に記載のキャリア付銅箔を用いてプリント配線板を製造する方法 Method of making a print wiring board using the copper foil with carrier according to any one of claims 1 to 12. 請求項1〜12のいずれか一項に記載のキャリア付銅箔を用いて銅張積層板を製造する方法 Method of producing a copper-clad laminate using a copper foil with carrier according to any one of claims 1 to 12. 請求項1〜12のいずれか一項に記載のキャリア付銅箔と絶縁基板とを準備する工程、
前記キャリア付銅箔と絶縁基板とを積層する工程、
前記キャリア付銅箔と絶縁基板とを積層した後に、前記キャリア付銅箔のキャリアを剥がす工程を経て銅張積層板を形成し、
その後、セミアディティブ法、サブトラクティブ法、パートリーアディティブ法又はモディファイドセミアディティブ法のいずれかの方法によって、回路を形成する工程を含むプリント配線板の製造方法。
A step of preparing the carrier-attached copper foil according to any one of claims 1 to 12 and an insulating substrate,
Laminating the copper foil with carrier and an insulating substrate;
After laminating the carrier-attached copper foil and the insulating substrate, forming a copper-clad laminate through a step of peeling the carrier of the carrier-attached copper foil,
Then, the manufacturing method of a printed wiring board including the process of forming a circuit by any method of a semi-additive method, a subtractive method, a partly additive method, or a modified semi-additive method.
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