JP6277256B2 - Metal substrate with plating - Google Patents

Description

  The present invention relates to a metal substrate with plating. In addition, the present invention is provided with or using a metal substrate with plating, metal foil with carrier, connector, terminal, laminate, shield tape, shield material, printed wiring board, metal working member, electronic / electric equipment, And it is related with the manufacturing method of a printed wiring board.

  Printed circuit boards widely used in electronic and electrical equipment are generally bonded to insulating base materials such as synthetic resin boards and films by bonding metal foil under high temperature and pressure without using an adhesive. A metal-clad laminate is manufactured, and then a metal wiring is formed on the metal foil side through an etching process to form a printed wiring board. Various electronic components are mounted on the printed wiring board by soldering. Is manufactured.

Conventionally, a technique for forming a metal or alloy layer having a slower etching rate than copper on the etching surface side is known for the purpose of forming a circuit with high line width uniformity by improving the etching characteristics of a metal foil (Patent Literature). 1). According to Patent Document 1, by forming a metal or alloy layer having a slower etching rate than copper on the etching surface side, by controlling the etching rate in the thickness direction of the copper foil, a circuit having a uniform circuit width without sagging It is said that can be formed. Further, Patent Document 1 exemplifies cobalt, nickel, or an alloy layer thereof as a metal or alloy layer having a slower etching rate than copper, and the thickness may be 100 to 10,000 μg / dm ^2. It is disclosed.

JP 2002-176242 A

  However, in Patent Document 1, although the etching property of the copper foil at the time of producing the printed circuit board is considered, the adhesion strength between the solder and the metal wiring used when mounting the electronic component on the printed circuit board is concerned. No consideration has been given. In particular, copper foil does not pose a problem because of its excellent solder adhesion, but it cannot ensure solder adhesion when used as a metal substrate containing an element that is highly reactive with oxygen at room temperature. Does not show any solution. Further, it is conceivable that both etching properties and solderability are required in applications other than the printed wiring board. However, in Patent Document 1, only a printed circuit board is considered. Moreover, when considering the practicality of the metal substrate as a conductive material, consideration on weather resistance is also important, but such consideration is not seen. Thus, an object of the present invention is to provide a metal substrate that is excellent in solder adhesion and weather resistance while using a metal substrate containing an element that is highly reactive with oxygen at room temperature.

As a result of intensive studies to solve the above problems, the inventor of the present invention has a Co plating layer on the surface of the metal substrate, and an alloy plating layer containing two or more elements selected from the group consisting of Co, Ni and Mo. By forming a plating layer selected from the group consisting of Co, Ni and Mo in the plating layer so that the total adhesion amount is 500 μg / dm ² or more, solder adhesion and weather resistance are remarkably improved. I found. The present invention has been completed based on this finding.

In one aspect, the present invention provides a Co plating layer on a part or all of the surface of a metal substrate, and a group consisting of an alloy plating layer containing two or more elements selected from the group consisting of Co, Ni and Mo. A plated metal substrate on which a selected plating layer is formed, wherein the total adhesion amount of Co, Ni and Mo in the plating layer is 500 μg / dm ² or more,
Metal substrates are Ti, Si, Mg, P, Sn, Zn, Cr, Zr, V, W, Na, Ca, Ba, Cs, Mn, K, Ga, B, Nb, Ce, Be, Nd, Sc, Selected from the group consisting of Hf, Ho, Lu, Yb, Dy, Er, Pr, Y, Li, Gd, Pu, In, Fe, La, Th, Ta, U, Sm, Tb, Sr, Tm, and Al. A plated metal substrate containing one or more elements.

In one embodiment of the metal substrate with plating according to the present invention, the total adhesion amount of Co, Ni and Mo in the plating layer is 700 μg / dm ² or more.

In one embodiment of the metal substrate with plating according to the present invention, the total adhesion amount of Co, Ni and Mo in the plating layer is 1000 μg / dm ² or more.

In one embodiment of the metal substrate with plating according to the present invention, the total adhesion amount of Co, Ni and Mo in the plating layer is 2000 μg / dm ² or more.

In one embodiment of the metal base with plating according to the present invention, the total adhesion amount of Co, Ni and Mo in the plating layer is 3000 μg / dm ² or more.

In one embodiment of the metal substrate with plating according to the present invention, the total adhesion amount of Co, Ni and Mo in the plating layer is 5000 μg / dm ² or more.

In one embodiment of the metal substrate with plating according to the present invention, the total adhesion amount of Co, Ni and Mo in the plating layer is 7000 μg / dm ² or more.

In one embodiment of the metal substrate with plating according to the present invention, the total adhesion amount of Co, Ni and Mo in the plating layer is 180,000 μg / dm ² or less.

  In one embodiment of the metal substrate with plating according to the present invention, in the plating layer, the total adhesion amount of Ni and Mo with respect to the total adhesion amount of Co, Ni and Mo (hereinafter also referred to as “Ni + Mo ratio (%)”). .) Is 80% or less by mass ratio.

  In one embodiment of the metal substrate with plating according to the present invention, in the plating layer, the total adhesion amount of Ni and Mo with respect to the total adhesion amount of Co, Ni and Mo (hereinafter also referred to as “Ni + Mo ratio (%)”). .) Is 60% or less by mass ratio.

  In one embodiment of the metal substrate with plating according to the present invention, in the plating layer, the total adhesion amount of Ni and Mo with respect to the total adhesion amount of Co, Ni and Mo (hereinafter also referred to as “Ni + Mo ratio (%)”). .) Is 50% or less by mass ratio.

  In one embodiment of the metal substrate with plating according to the present invention, in the plating layer, the total adhesion amount of Ni and Mo with respect to the total adhesion amount of Co, Ni and Mo (hereinafter also referred to as “Ni + Mo ratio (%)”). Is 10% or more by mass ratio.

  In one embodiment of the metal substrate with plating according to the present invention, an underlayer and / or a roughening treatment layer is formed between the plating layer and the metal substrate.

  In one embodiment of the metal substrate with plating according to the present invention, the plating layer includes a Co—Ni alloy plating layer, a Co—Mo alloy plating layer, a Ni—Mo alloy plating layer, and a Co—Ni—Mo alloy plating layer. Selected from the group consisting of

  In one embodiment of the plated metal substrate according to the present invention, the plating layer includes Cu, As, Ag, Au, Pd, Pt, Bi, Os, Rh, Tl, Sb, Pb, Hg, Ir, Cd, One or more elements selected from the group consisting of Ru, Re, Tc and Gd are included.

In one embodiment of the plated metal substrate according to the present invention, the plating layer includes Cu, As, Ag, Au, Pd, Pt, Bi, Os, Rh, Tl, Sb, Pb, Hg, Ir, Cd, It contains 0 to 2000 μg / dm ^{2 in} total of one or more elements selected from the group consisting of Ru, Re, Tc and Gd.

In one embodiment of the plated metal substrate according to the present invention, the plating layer includes Cu, As, Ag, Au, Pd, Pt, Bi, Os, Rh, Tl, Sb, Pb, Hg, Ir, Cd, It contains 0 to 1000 μg / dm ^{2 in} total of one or more elements selected from the group consisting of Ru, Re, Tc and Gd.

In one embodiment of the plated metal substrate according to the present invention, the plating layer includes Cu, As, Ag, Au, Pd, Pt, Bi, Os, Rh, Tl, Sb, Pb, Hg, Ir, Cd, It contains 0 to 500 μg / dm ^{2 in} total of one or more elements selected from the group consisting of Ru, Re, Tc and Gd.

  In one embodiment of the plated metal substrate according to the present invention, the plating layer contains one or more elements selected from the group consisting of Cu, As, Ag, Au, Pd, and Pt.

In one embodiment of the plated metal substrate according to the present invention, the plating layer is a total of 0 to 2000 μg / dm of one or more elements selected from the group consisting of Cu, As, Ag, Au, Pd, and Pt. ² included.

In one embodiment of the plated metal substrate according to the present invention, the plating layer is a total of 0 to 1000 μg / dm of one or more elements selected from the group consisting of Cu, As, Ag, Au, Pd and Pt. ² included.

In one embodiment of the plated metal substrate according to the present invention, the plating layer is a total of 0 to 500 μg / dm of one or more elements selected from the group consisting of Cu, As, Ag, Au, Pd, and Pt. ² included.

  In one embodiment of the metal substrate with plating according to the present invention, the metal substrate is a copper alloy, aluminum, aluminum alloy, iron, iron alloy, stainless steel, nickel alloy, titanium, titanium alloy, gold alloy, silver alloy. Platinum group alloy, chromium, chromium alloy, magnesium, magnesium alloy, tungsten, tungsten alloy, molybdenum alloy, lead alloy, tantalum, tantalum alloy, zirconium, zirconium alloy, tin, tin alloy, indium, indium alloy, zinc, or It is made of zinc alloy.

  In one embodiment of the metal substrate with plating according to the present invention, the metal substrate is a copper alloy, aluminum, aluminum alloy, iron, iron alloy, stainless steel, nickel alloy, titanium, titanium alloy, zinc, or zinc. It is made of an alloy.

  In one embodiment of the plated metal substrate according to the present invention, the metal substrate is formed of titanium copper, phosphor bronze, Corson alloy, red brass, brass, white or other copper alloy.

  In one embodiment of the plated metal substrate according to the present invention, the metal substrate is in the form of a metal strip, a metal plate, or a metal foil.

  In one embodiment of the metal substrate with plating according to the present invention, the metal substrate is a rolled copper alloy foil or an electrolytic copper alloy foil.

  In one embodiment of the metal substrate with plating according to the present invention, a resin layer is provided on the surface of the plating layer.

  In one embodiment of the metal substrate with plating according to the present invention, the metal substrate has two main surfaces, and the plating layer is provided on one or both surfaces thereof.

  Another aspect of the present invention is a metal foil with a carrier having an intermediate layer and an ultrathin metal layer in this order on one or both sides of the carrier, wherein the ultrathin metal layer is included in the present invention. It is a metal foil with a carrier which is the metal base material with plating which concerns.

  In one embodiment of the metal foil with a carrier according to the present invention, the intermediate layer and the ultrathin metal layer are provided in this order on one surface of the carrier, and a roughening treatment layer is provided on the other surface of the carrier. .

  In one embodiment of the metal foil with a carrier according to the present invention, the metal substrate of the metal substrate with plating is made of a copper alloy.

  In yet another aspect, the present invention is a connector including the plated metal substrate according to the present invention.

  In still another aspect, the present invention provides a terminal including the plated metal substrate according to the present invention.

  In still another aspect, the present invention is a laminated plate produced by laminating a metal substrate with plating according to the present invention or a metal foil with carrier according to the present invention and a resin substrate.

  In yet another aspect, the present invention is a shield tape or a shield material provided with the laminate according to the present invention.

  In yet another aspect, the present invention is a printed wiring board including the laminate according to the present invention.

  In still another aspect of the present invention, there is provided a metal workpiece having the metal base with plating according to the present invention or the metal foil with carrier according to the present invention.

  In still another aspect, the present invention is an electronic / electrical device including the metal base with plating according to the present invention or the metal foil with carrier according to the present invention.

In yet another aspect of the present invention, a step of preparing the metal foil with a carrier and the insulating substrate according to the present invention,
Laminating the metal foil with carrier and an insulating substrate;
After laminating the metal foil with carrier and the insulating substrate, forming a metal-clad laminate through a process of peeling the carrier of the metal foil with carrier,
Thereafter, the printed wiring board manufacturing method includes a step of forming a circuit by any one of a semi-additive method, a subtractive method, a partly additive method, or a modified semi-additive method.

In yet another aspect of the present invention, the step of forming a circuit on the ultrathin metal layer side surface or the carrier side surface of the metal foil with a carrier according to the present invention,
Forming a resin layer on the ultrathin metal layer side surface or the carrier side surface of the metal foil with carrier so that the circuit is buried;
Forming a circuit on the resin layer;
After forming a circuit on the resin layer, peeling the carrier or the ultrathin metal layer; and
After the carrier or the ultrathin metal layer is peeled off, the ultrathin metal layer or the carrier is removed to be buried in the resin layer formed on the ultrathin metal layer side surface or the carrier side surface. It is a manufacturing method of a printed wiring board including the process of exposing the circuit which has been carried out.

  In still another aspect of the present invention, there is provided a joined body of a metal base with plating and solder according to the present invention.

  In one embodiment of the joined body according to the present invention, a thermal diffusion layer containing Sn and Co is present at the joint interface between the solder and the metal substrate.

  In yet another aspect of the present invention, the step of shape-processing the plated metal substrate according to the present invention by etching, and the shape-processed product of the obtained metal substrate with plating by soldering at a place having a plating layer It is the connection method of the metal base material with plating including the process of joining with an electroconductive member, and an electroconductive member.

  In yet another aspect, the present invention is an electronic component including the plated metal substrate according to the present invention.

  In still another aspect, the present invention is an autofocus module including the plated metal substrate according to the present invention as a spring material.

  In yet another aspect of the present invention, a lens, a spring member made of a plated metal base material according to the present invention that elastically biases the lens toward an initial position in the optical axis direction, and a biasing force of the spring member are resisted. An autofocus camera module having electromagnetic driving means capable of generating electromagnetic force to drive the lens in the optical axis direction, the electromagnetic driving means having a coil, and a spring member having the plating layer This is an autofocus camera module that is joined to a coil by soldering at a location.

  The metal substrate with plating according to the present invention is excellent in solder adhesion despite using a metal substrate that is inherently poor in solder adhesion. For this reason, it is suitable for connecting to various conductive members by soldering. Moreover, according to the metal base material with a plating which concerns on this invention, since it can have the improved weather resistance, it is suitable also for the utilization in severe environments, such as high temperature and humidity. Suitable for shape processing including circuit formation by etching by containing Co in the plating layer, taking advantage of such characteristics, the plated metal substrate according to the present invention performs circuit formation by etching, It can be suitably used as a conductive material for later use by connecting to an electronic component by soldering, for example, a printed circuit board. Further, it can be suitably used as a material for electronic components such as switches, connectors (in particular, fork type FPC connectors that do not require severe bending workability), autofocus camera modules, jacks, terminals, relays, and the like.

[Metal base material]
Examples of the metal substrate used in the present invention include Ti, Si, Mg, P, Sn, Zn, Cr, Zr, V, Na, Ca, Ba, Cs, Mn, K, Ga, B, Nb, Ce, and Be. Nd, Sc, Hf, Ho, Lu, Yb, Dy, Er, Pr, Y, Li, Gd, Pu, In, Fe, La, Th, Ta, U, Sm, Tb, Sr, Tm and Al Contains one or more elements selected from the group. These elements are elements having high reactivity with oxygen at room temperature, and are elements that hinder the solder adhesion of the metal substrate. Specifically, these elements are in the Ellingham diagram of oxides (see, for example, “Japan Iron and Steel Institute,“ Third Edition Steel Handbook Volume I Basics ”, 1983, Maruzen Co., Ltd.) The standard free energy of formation ΔG ° of the solid oxide is −500 kJ / mol O ₂ or less at a temperature of 300K.

  The metal substrate used in the present invention preferably contains a total of 0.0001% by mass or more of the above elements having high reactivity with oxygen from the viewpoint of exhibiting the effects of the present invention significantly. More preferably, it is more preferable to contain 0.007 mass% or more, still more preferably 0.01 mass% or more, still more preferably 0.02 mass% or more. In addition, the metal base material used in the present invention may be an element having a high reactivity with oxygen as described above for the entire constituent material, but the reactivity with the oxygen of the metal base material is reduced, so that the solder adhesion is further improved. In order to improve the above, it is preferable to contain a total of 100% by mass or less of the elements having high reactivity with oxygen, preferably less than 100% by mass, more preferably 99% by mass or less, more preferably 95% by mass. Even more preferably, 90% by mass or less, still more preferably 85% by mass or less, still more preferably 50% by mass or less, still more preferably 40% by mass or less, and even more preferably 40% by mass or less, It is even more preferable to include 30% by mass or less, still more preferable to include 20% by mass or less, and even more preferable to include 10% by mass or less.

  Examples of metal substrates that can be used in the present invention include copper alloy, aluminum, aluminum alloy, iron, iron alloy, stainless steel, nickel alloy, titanium, titanium alloy, gold alloy, silver alloy, platinum group alloy, chromium, chromium Alloy, magnesium, magnesium alloy, tungsten, tungsten alloy, molybdenum alloy, lead alloy, tantalum, tantalum alloy, zirconium, zirconium alloy, tin, tin alloy, indium, indium alloy, zinc, zinc alloy, etc. Known metal materials can also be used. In addition, a metal material standardized by JIS standard, CDA or the like can also be used. Further, the metal substrate may be in the form of a metal strip, a metal plate, or a metal foil.

  When a copper alloy foil is used as the metal foil, either an electrolytic copper alloy foil or a rolled copper alloy foil may be used. The copper alloy foil may be a copper alloy foil suitable for manufacturing an electronic component on which a circuit is formed by bonding a resin substrate to a laminated body and removing the laminated body by etching. There is no restriction | limiting in particular also about the thickness of the said copper alloy foil, For example, it can adjust and use suitably for the thickness suitable for a use. For example, it can be about 1 to 5000 μm or about 2 to 1000 μm. Especially when it is used by forming a circuit, it is as thin as 35 μm or less, and as a shield tape, it is 18 μm or less. When used as a shield material, a cover material, a spring or the like, it can be applied to a thick material such as 70 to 1000 μm, and the upper limit thickness is not particularly determined.

  As a copper alloy, a copper alloy containing 0.001 to 4.0 mass% in total of at least one of Sn, Cr, Fe, In, P, Si, Ti, Zn, B, Mn, and Zr is used. You can also. Note that other elements may be included including elements having low reactivity with oxygen, such as Ag, Au, Co, Ni, and Te.

  Examples of the copper alloy further include titanium copper, phosphor bronze, Corson alloy, red brass, brass, white and other copper alloys. Further, as the copper alloy, copper or a copper alloy standardized in JIS H 3100 to JIS H 3510, JIS H 5120, JIS H 5121, JIS C 2520 to JIS C 2801, JIS E 2101 to JIS E 2102 is also included in the present invention. Can be used. In the present specification, unless otherwise specified, the JIS standard listed to indicate the metal standard means the 2001 version of the JIS standard.

  Titanium copper typically contains Ti: 0.5 to 5.0% by mass, with the balance being composed of copper and inevitable impurities. Titanium copper further contains one or more of Fe, Co, V, Nb, Mo, B, Ni, P, Zr, Mn, Zn, Si, Mg, and Cr in total of 2.0% by mass or less. Also good.

  Phosphor bronze typically refers to a copper alloy containing copper as the main component and Sn and a lower mass of P. As an example, phosphor bronze contains Sn in an amount of 3.5 to 11% by mass and P in an amount of 0.03 to 0.35% by mass, and has a composition composed of the remaining copper and inevitable impurities. Phosphor bronze may contain a total of elements such as Ni and Zn of 1.0% by mass or less.

  A Corson alloy is typically a copper alloy in which, in addition to Si, an element that forms a compound with Si (for example, any one or more of Ni, Co, and Cr) is added, and precipitates as second phase particles in the parent phase. That means. As an example, the Corson alloy contains 1.0 to 5.0% by mass of Ni and 0.2 to 1.6% by mass of Si, and has a composition composed of the balance copper and inevitable impurities. As another example, the Corson alloy contains 1.0 to 5.0% by mass of Ni, 0.2 to 1.6% by mass of Si, 0.03 to 0.5% by mass of Cr, the remaining copper and unavoidable The composition is composed of mechanical impurities. As yet another example, the Corson alloy contains 1.0 to 5.0 mass% Ni, 0.2 to 1.6 mass% Si, 0.1 to 3.5 mass% Co, the balance copper and It has a composition composed of inevitable impurities. As yet another example, the Corson alloy has a Ni content of 1.0 to 5.0 mass%, a Si content of 0.2 to 1.6 mass%, a Co content of 0.1 to 3.5 mass%, and a Cr content of 0.03. It has a composition composed of ˜0.5% by mass and remaining copper and inevitable impurities. As yet another example, the Corson alloy contains 0.2 to 1.6 mass% of Si and 0.1 to 3.5 mass% of Co, and has a composition composed of the balance copper and unavoidable impurities. Optionally, other elements (eg, Mg, Sn, B, Ti, Mn, Ag, P, Zn, As, Sb, Be, Zr, Al, and Fe) may be added to the Corson alloy. These other elements are generally added up to about 4.0% by mass in total. For example, as yet another example, the Corson alloy has a Ni content of 1.0 to 5.0 mass%, a Si content of 0.2 to 1.6 mass%, a Sn content of 0.01 to 2.0 mass%, and a Zn content of 0. .01-2.0 mass%, and has a composition composed of the remaining copper and unavoidable impurities.

  In the present invention, the red copper is an alloy of copper and zinc and refers to a copper alloy containing 1 to 20% by mass of zinc, more preferably 1 to 10% by mass of zinc. Further, the red copper may contain 0.1 to 1.0% by mass of tin.

  In the present invention, brass means an alloy of copper and zinc, and particularly a copper alloy containing 20% by mass or more of zinc. The upper limit of zinc is not particularly limited, but is 60% by mass or less, preferably 45% by mass or less, or 40% by mass or less.

  In the present invention, “white” means copper containing 60% to 75% by weight of copper, 8.5% to 19.5% by weight of nickel, and 10% to 30% by weight of zinc. An alloy.

  In the present invention, the other copper alloy includes 8.0% by mass or less of Zn, Sn, Mg, Fe, Si, P, Mn, Zr, Cr, and Ti, or a total of 8.0% by mass or less. These elements are contained in an amount of 20% by mass or less, or optionally other elements are contained in an amount of 10% by mass or less, and the balance is an inevitable impurity and copper alloy. The other elements are not particularly limited, and may be elements having low reactivity with oxygen such as Ni and Co.

  As aluminum and aluminum alloy, for example, aluminum containing 40% by mass or more, 80% by mass or more, or 99% by mass or more can be used. For example, aluminum and aluminum alloys specified in JIS H 4000 to JIS H 4180, JIS H 5202, JIS H 5303, or JIS Z 3232 to JIS Z 3263 can be used. For example, aluminum alloy number 1085, 1080, 1070, 1050, 1100, 1200, 1N00, and 1N30, which are standardized in JIS H 4000, Al: 99.00% by mass or more of aluminum or an alloy thereof is used. be able to.

  As the nickel alloy, for example, an alloy containing 40 mass% or more of Ni, 80 mass% or more, or 99.0 mass% or more can be used. For example, a nickel alloy standardized in JIS H 4541 to JIS H 4554, JIS H 5701, JIS G 7604 to JIS G 7605, or JIS C 2531 on condition that the above-described element having high reactivity with oxygen is contained. Can be used. Further, for example, a nickel alloy of Ni: 99.0% by mass or more represented by alloy numbers NW2200 and NW2201 described in JIS H4551 can be used.

  As iron and iron alloy, for example, stainless steel, mild steel, carbon steel, iron-nickel alloy, steel and the like can be used. For example, iron or an iron alloy described in JIS G 3101 to JIS G 7603, JIS C 2502 to JIS C 8380, JIS A 5504 to JIS A 6514 or JIS E 1101 to JIS E 5402-1 can be used. As the stainless steel, SUS 301, SUS 304, SUS 310, SUS 316, SUS 430, SUS 631 (all of which are JIS standards) or the like can be used. As the mild steel, a mild steel having 0.15% by mass or less of carbon can be used, and a mild steel described in JIS G3141 can be used. The iron-nickel alloy contains 35 to 85% by mass of Ni and the balance is made of Fe and inevitable impurities. Specifically, an iron-nickel alloy described in JIS C2531 can be used.

  As zinc and a zinc alloy, for example, Zn containing 40% by mass or more, 80% by mass or more, or 99.0% by mass or more can be used. For example, zinc or a zinc alloy described in JIS H 2107 to JIS H 5301 can be used.

  As a lead alloy, for example, containing Pb in an amount of 40% by mass or more, 80% by mass or more, or 99.0% by mass or more, provided that the above-described element having high reactivity with oxygen is contained. can do. For example, lead or a lead alloy standardized in JIS H 4301 to JIS H 4312 or JIS H 5601 can be used.

  As magnesium and a magnesium alloy, for example, Mg containing 40% by mass or more, 80% by mass or more, or 99.0% by mass or more can be used. For example, magnesium and a magnesium alloy specified in JIS H 4201 to JIS H 4204, JIS H 5203 to JIS H 5303, and JIS H 6125 can be used.

  As tungsten and a tungsten alloy, for example, W containing 40% by mass or more, 80% by mass or more, or 99.0% by mass or more can be used. For example, tungsten and a tungsten alloy specified in JIS H 4463 can be used.

  As a molybdenum alloy, for example, containing Mo of 40% by mass or more, 80% by mass or more, or 99.0% by mass or more is used on condition that the above-described element having high reactivity with oxygen is contained. can do.

  As titanium and a titanium alloy, for example, Ti containing 40% by mass or more, 80% by mass or more, or 99.0% by mass or more can be used. For example, titanium and titanium alloys specified in JIS H 4600 to JIS H 4675 and JIS H 5801 can be used.

  As the tantalum and tantalum alloy, for example, Ta containing 40% by mass or more, 80% by mass or more, or 99.0% by mass or more can be used. For example, tantalum and tantalum alloy standardized in JIS H 4701 can be used.

  As zirconium and a zirconium alloy, for example, those containing 40 mass% or more, 80 mass% or more, or 99.0 mass% or more of Zr can be used. For example, zirconium and a zirconium alloy specified in JIS H 4751 can be used.

  As tin and a tin alloy, for example, Sn containing 40% by mass or more, 80% by mass or more, or 99.0% by mass or more can be used. For example, tin and tin alloy standardized in JIS H 5401 can be used.

  As indium and an indium alloy, for example, those containing 40 mass% or more of In, 80 mass% or more, or 99.0 mass% or more can be used.

  As chromium and a chromium alloy, for example, Cr containing 40% by mass or more, 80% by mass or more, or 99.0% by mass or more can be used.

  As the silver alloy, for example, containing Ag containing 40% by mass or more, containing 80% by mass or more, or containing 99.0% by mass or more, on condition that the above-described element having high reactivity with oxygen is contained. can do.

  As a gold alloy, for example, a material containing 40% by mass or more of Au, 80% by mass or more, or 99.0% by mass or more is used on condition that the above-described element having high reactivity with oxygen is contained. can do.

  The platinum group is a general term for ruthenium, rhodium, palladium, osmium, iridium, and platinum. The platinum group alloy contains at least one element selected from the element group of, for example, Pt, Os, Ru, Pd, Ir, and Rh, on the condition that the above-described element having high reactivity with oxygen is contained. Those containing 40% by mass or more, 80% by mass or more, or 99.0% by mass or more can be used.

  Although there is no restriction | limiting in particular as a shape of the metal base material used in this invention, You may be processed into the shape of the final electronic component, and may exist in the state by which press work was made partially. Shape processing is not performed and it may be in the form of a plate or foil. Note that in the case of “pre-plating” in which plating is performed before shape processing, unplated parts remain after press processing, and in the case of “post-plating” in which plating is performed after shape processing, the entire surface can be plated. However, what stage of surface processing should be performed may be appropriately determined in consideration of the portion to be plated.

[Plating layer]
In one embodiment, the metal substrate with plating according to the present invention is a plating selected from the group consisting of a Co plating layer and an alloy plating layer containing two or more elements selected from the group consisting of Co, Ni and Mo. A layer is provided on the surface of the metal substrate. In an exemplary embodiment, the alloy plating layer containing two or more elements selected from the group consisting of Co, Ni, and Mo is a Co—Ni alloy plating layer, a Co—Mo alloy plating layer, or a Ni—Mo alloy plating. Selected from the group consisting of a layer and a Co—Ni—Mo alloy plating layer.

When the total adhesion amount of Co, Ni, and Mo in the plating layer is 500 μg / dm ² or more, the adhesion strength and weather resistance between the metal substrate and the solder are improved. Moreover, the effect of improving the etching property can be obtained by including Co in the plating layer. Although it is not intended that the present invention be limited by theory, Ni, Co, and Mo are less reactive with oxygen and less likely to form oxides, and the main components that constitute solder during soldering Therefore, it is presumed that the effect of improving the adhesion strength and weather resistance of the solder is remarkably exhibited.

Preferably the total adhesion amount of Co, Ni and Mo in the plating layer is 700 [mu] g / dm ² or more, preferably 1000 [mu] g / dm ² or more, preferably 2000 [mu] g / dm ² or more, 3000μg / dm preferably ² or more, it is preferably 5000 [mu] g / dm ² or more, more preferably 7000μg / dm ² or more, and still more preferably at 8000μg / dm ² or more. On the other hand, even if the total adhesion amount of Co, Ni and Mo is excessively increased, the cost tends to increase and the effect tends to be saturated. In addition, the etching property is also adversely affected. Therefore, excellent from the viewpoint of ensuring the etch resistance, Co, the total deposition amount of Ni and Mo is preferably at most 90000μg / dm ^2, and more preferably 55000μg / dm ² or less.

  From the viewpoint of securing etching properties in addition to excellent solder adhesion and weather resistance, it is preferable that the Co ratio is high, that is, the total ratio of Ni and Mo is low, specifically, Co, Ni and The total adhesion amount of Ni and Mo with respect to the total adhesion amount of Mo (hereinafter also referred to as “Ni + Mo ratio (%)”) is preferably 80% by mass or less, more preferably 60% by mass or less, and 50 Even more preferably, the amount is not more than%. However, if the Ni + Mo ratio (%) is too low, the weather resistance will be adversely affected, and since Co is an expensive metal, the cost becomes high if it is made of a single Co layer. For this reason, when comprehensively considering the solder adhesion, weather resistance, etching property and economy, the Ni + Mo ratio (%) in the plating layer is preferably more than 0% by mass, more preferably 1% by mass or more. Preferably, it is still more preferably 2% by mass or more, still more preferably 10% by mass or more, and even more preferably 20% by mass or more.

Based on the above explanation, when referring to the adhesion amount of each element in the plating layer, the adhesion amount of Co is preferably 180 μg / dm ² or more, more preferably 250 μg / dm ² or more, from the viewpoint of securing etching properties, and 360 μg / dm ² or more, and more preferably from 720μg / dm ² or more, more preferably 1080Myug / dm ² or more, 1800 [mu] g / dm ² or more is preferred even more, even more preferably 3000Myug / dm ² or more, 4200Myug / dm ² or more Is more preferable, and 4800 μg / dm ² or more is even more preferable. Further, the adhesion amount of Co is preferably 108000μg / dm ² or less from the viewpoint of weather resistance and economic efficiency, more preferably 54000μg / dm ² or less, still more preferably 33000μg / dm ² or less.

The total coating weight of Ni and Mo from the viewpoint of securing the weather resistance, preferably 0 Pg / dm ² greater, more preferably 120 [mu] g / dm ² or more, still more preferably from 170μg / dm ² or more, 240 [mu] g / dm ² or more the preferred, even more preferably from 480μg / dm ² or more, preferably from 720μg / dm ² or more further, 1200 [mu] g / dm ² or more preferably even more, still more preferably 2000 [mu] g / dm ² or more, 3200μg / dm ² or more Is more preferable. The total coating weight of Ni and Mo is preferably 72000μg / dm ² or less from the viewpoint of etching resistance, more preferably 36000μg / dm ² or less, still more preferably 22000μg / dm ² or less. Ni and Mo have similar properties, but Mo is superior in weather resistance, but Mo is more likely to deteriorate the etching property. Therefore, it is preferable to coexist both from the viewpoint of the balance between weather resistance and etching property. . For example, the content ratio of Ni and Mo in the plating layer can be Ni: Mo = 10: 0 to 0:10 by mass ratio, preferably Ni: Mo = 9: 1 to 1: 9, and Ni: Mo = 8. : 2 to 2: 8 is more preferable, and Ni: Mo = 6: 4 to 4: 6 is even more preferable.

  The Co plating layer, the Co—Ni alloy plating layer, the Co—Mo alloy plating layer, the Ni—Mo alloy plating layer, the Co—Ni—Mo alloy plating layer, and the Co—Ni alloy plating layer each contain inevitable impurities. Can do. In addition, other elements can be contained in the plating layer as long as the object of the present invention is not impaired. Therefore, in the present invention, the Co plating layer refers to a plating layer in which Co occupies 50% by mass or more. Typically, the Co concentration in the Co plating layer is 60% by weight or more, more typically 80% by weight or more, still more typically 90% by weight or more, and even more typically. It is 98 mass% or more, and can also be 100 mass%. In the present invention, the Co—Ni alloy plating layer refers to a plating layer in which the total concentration of Co and Ni occupies 50 mass% or more. Typically, the total concentration of Co and Ni in the Co—Ni alloy plating layer is 60 mass% or more, more typically 80 mass% or more, and even more typically 90 mass% or more. Even more typically, it is 98 mass% or more, and may be 100 mass%. In the present invention, the Co—Mo alloy plating layer refers to a plating layer in which the total concentration of Co and Mo occupies 50 mass% or more. Typically, the total concentration of Co and Mo in the Co—Mo alloy plating layer is 60% by weight or more, more typically 80% by weight or more, and even more typically 90% by weight or more. Even more typically, it is 98 mass% or more, and may be 100 mass%. In the present invention, the Ni—Mo alloy plating layer refers to a plating layer in which the total concentration of Ni and Mo occupies 50 mass% or more. Typically, the total concentration of Ni and Mo in the Ni-Mo alloy plating layer is 60% by weight or more, more typically 80% by weight or more, and still more typically 90% by weight or more. Even more typically, it is 98 mass% or more, and may be 100 mass%. In the present invention, the Co—Ni—Mo alloy plating layer refers to a plating layer in which the total concentration of Co, Ni and Mo occupies 50% by mass or more. Typically, the total concentration of Co, Ni and Mo in the Co—Ni—Mo alloy plating layer is 60% by weight or more, more typically 80% by weight or more, and even more typically 90% by weight. % Or more, even more typically 98% by weight or more, and may be 100% by weight.

As an element other than Co, Ni and Mo that can be contained in the plating layer, an element having low reactivity with oxygen at room temperature, that is, an oxide Ellingham diagram (for example, “Japan Iron and Steel Institute,” Oxidation in which the standard free energy of formation ΔG ° of the solid oxide is −440 kJ / mol O ₂ or more at a temperature of 300 K in “Third Edition Steel Handbook Volume I Fundamentals”, 1983, Maruzen Co., Ltd. The element which has a thing is mentioned. Illustratively, the plating layer is selected from the group consisting of Cu, As, Ag, Au, Pd, Pt, Bi, Os, Rh, Tl, Sb, Pb, Hg, Ir, Cd, Ru, Re, Tc, and Gd. One or more elements may be included. In this case, illustratively, the adhesion amount of these elements in the plating layer can be 0 to 2000 μg / dm ^{2 in} total, typically 0 to 1000 μg / dm ^2, and more Typically, it can be 0 to 500 μg / dm ² .

Typically, the plating layer may contain one or more elements selected from the group consisting of Cu, As, Ag, Au, Pd, and Pt. In this case, illustratively, the adhesion amount of these elements in the plating layer can be 0 to 2000 μg / dm ^{2 in} total, typically 0 to 1000 μg / dm ^2, and more Typically, it can be 0 to 500 μg / dm ² .

  The plating layer may be formed on part or all of the metal substrate. Moreover, you may form a plating layer in the one or both surfaces of the main surface of a metal base material. In one embodiment of the metal substrate with plating according to the present invention, the metal substrate may be provided in the form of a foil, and the plating layer may be formed on one or both main surfaces of the metal foil. The plating layer can be obtained by, for example, wet plating such as electroplating, electroless plating, and immersion plating. Electroplating is preferable from the viewpoint of cost.

  A base layer is provided between the metal substrate and the plating layer as long as it does not hinder the function of Co plating or alloy plating containing two or more elements selected from the group consisting of Co, Ni and Mo. Also good. The underlayer is not limited, but includes a Cu plating layer, a Sn plating layer, a Ni plating layer, a Cu—Zn plating layer, a Zn—Ni plating layer, a Cu—Co—Ni plating layer, a Cu—Co plating layer, Cu -Ni plating layer, Ni-W plating layer, Ni-W-Sn plating layer, Cu-As plating layer, Cu-W plating layer, Cu-W-As plating layer, noble metal (Au, Ag, platinum group element) plating Examples include an underlayer composed of a layer, a chromate treatment layer, a silane coupling treatment layer, and the like.

  A roughening treatment layer may be provided between the metal substrate and the plating layer, or a matting process such as etching or polishing, or a glossing process such as smooth plating may be performed. By these processes, the glossiness of the finished product can be easily adjusted. When the gloss level is low, there is a preferable effect that the color becomes dull as a whole and a calm atmosphere is created. Further, when the glossiness is high, there is a preferable effect of giving the observer a bright, vivid and refreshing impression as a whole.

  The outermost layer on the plating layer is further composed of a chromium layer or a chromate treatment layer and / or a silane coupling treatment layer in a range that does not adversely affect the solder adhesion in order to enhance the rust prevention effect. An antirust treatment layer may be formed. Note that when the chromate treatment layer is formed under the usual chromate treatment conditions, the thickness is extremely thin, so that the solder adhesion is not adversely affected.

A laminated body such as a shield tape or a shield material can be manufactured by bonding the plated layer side of the metal base with plating according to the present invention or the side opposite to the plated layer to a resin substrate. Further, if necessary, a printed wiring board or the like can be manufactured by further processing the plated metal substrate to form a circuit. Examples of resin substrates include paper base phenolic resin, paper base epoxy resin, synthetic fiber cloth base epoxy resin, glass cloth / paper composite base epoxy resin, glass cloth / glass nonwoven cloth composite base epoxy for rigid PWB. Polyester film, polyimide film, liquid crystal polymer (LCP), PET film and the like can be used for FPC and tape using resin and glass cloth base epoxy resin. In the present invention, the “printed wiring board” includes a printed wiring board, a printed circuit board, and a printed board on which components are mounted. Further, it is possible to manufacture a printed wiring board in which two or more printed wiring boards are connected by connecting two or more printed wiring boards according to the present invention, and at least one printed wiring board according to the present invention. One printed wiring board of the present invention or a printed wiring board not corresponding to the printed wiring board of the present invention can be connected, and an electronic / electrical device can be manufactured using such a printed wiring board. In the present invention, “copper circuit” includes copper wiring.
Moreover, the metal substrate with plating of the present invention is used for a heat sink, a structural plate, a shield material, a shield plate, a reinforcing material, a cover, a housing, a case, a box, and the like to produce a metal processing member such as a heat sink. be able to. That is, the metal substrate with plating is a concept including a heat sink, a structural plate, a shield material, a shield plate, a reinforcing material, a cover, a casing, a case, and a box. Moreover, the metal processing member produced using the metal base material with plating of this invention for the said heat sink, a structural board, a shielding material, a shielding board, a reinforcing material, a cover, a housing | casing, a case, a box, etc. is used for electronic / electric equipment. Can be used.

  In the use as described above, the metal substrate with plating according to the present invention is a step of performing shape processing on the metal substrate with plating by etching, and joining the shape processed product to the conductive member by soldering at a place having the plating layer. Can be particularly preferably used. Accordingly, in one aspect, the present invention provides a joined body of a plated metal substrate and solder according to the present invention. In one embodiment of the joined body according to the present invention, a thermal diffusion layer containing Sn—Co exists at the joint interface between the solder and the metal substrate. The thermal diffusion layer can be formed by allowing Co contained in the plating layer on the surface of the metal base and Sn contained in the solder to diffuse to each other by heat during soldering. Although it is not intended that the present invention be limited by theory, it is believed that this thermal diffusion layer improves adhesion with solder.

[Metal foil with carrier]
The metal foil with a carrier which is another embodiment of the present invention has an intermediate layer and an ultrathin metal layer in this order on one side or both sides of the carrier. And the metal substrate with plating mentioned above can be used as the said ultra-thin metal layer. In this case, it is preferable to form the plating layer on at least the surface to be soldered of the metal substrate in consideration of etching and soldering in later circuit formation. The surface to be soldered can vary depending on the circuit formation process. The surface to be soldered can be the surface facing the intermediate layer of the ultrathin metal layer, the surface opposite the surface facing the intermediate layer of the ultrathin metal layer, or both of these surfaces. Can be.

<Career>
Carriers that can be used in the present invention are typically metal foils or resin films, such as copper foil, copper alloy foil, nickel foil, nickel alloy foil, iron foil, iron alloy foil, stainless steel foil, aluminum foil, aluminum. It is provided in the form of alloy foil, insulating resin film (for example, polyimide film, liquid crystal polymer (LCP) film, polyethylene terephthalate (PET) film, polyamide film, polyester film, fluororesin film, etc.).
It is preferable to use a copper foil as a carrier that can be used in the present invention. This is because the copper foil has a high electric conductivity, which makes it easy to form an intermediate layer and an ultrathin metal layer thereafter. The carrier is typically provided in the form of rolled copper foil or electrolytic copper foil. In general, the electrolytic copper foil is produced by electrolytic deposition of copper from a copper sulfate plating bath onto a drum of titanium or stainless steel, and the rolled copper foil is produced by repeating plastic working and heat treatment with a rolling roll. In addition to high-purity copper such as tough pitch copper and oxygen-free copper, the copper foil material is, for example, Sn-containing copper, Ag-containing copper, copper alloy added with Cr, Zr, Mg, etc., and Corson-based added with Ni, Si, etc. Copper alloys such as copper alloys can also be used.

  The thickness of the carrier that can be used in the present invention is not particularly limited, but may be appropriately adjusted to a thickness suitable for serving as a carrier, and may be, for example, 5 μm or more. However, if it is too thick, the production cost becomes high, so generally it is preferably 35 μm or less. Accordingly, the thickness of the carrier is typically 12-70 μm, more typically 18-35 μm.

Moreover, the electrolytic copper foil produced with the following method can be used for a carrier.
<Electrolytic solution composition>
Copper: 90-110 g / L
Sulfuric acid: 90-110 g / L
Chlorine: 50-100ppm
Leveling agent 1 (bis (3sulfopropyl) disulfide): 10 to 30 ppm
Leveling agent 2 (amine compound): 10 to 30 ppm
As the amine compound, an amine compound having the following chemical formula can be used.

(In the above chemical formula, R ₁ and R ₂ are selected from the group consisting of a hydroxyalkyl group, an ether group, an aryl group, an aromatic substituted alkyl group, an unsaturated hydrocarbon group, and an alkyl group.)

<Production conditions>
Current density: 70 to 100 A / dm ²
Electrolyte temperature: 50-60 ° C
Electrolyte linear velocity: 3-5 m / sec
Electrolysis time: 0.5 to 10 minutes (adjusted according to the thickness of copper to be deposited and current density)
In addition, you may provide a roughening process layer in the surface on the opposite side to the surface in the side which provides the ultra-thin metal layer of a carrier. The said roughening process layer may be provided using a well-known method, and may be provided by the above-mentioned roughening process. Providing a roughening treatment layer on the surface opposite to the surface on which the ultrathin metal layer of the carrier is provided, when laminating the carrier on a support such as a resin substrate from the surface side having the roughening treatment layer, There is an advantage that the carrier and the resin substrate are hardly peeled off.

<Intermediate layer>
An intermediate layer is provided on the carrier. Another layer may be provided between the carrier and the intermediate layer. The intermediate layer used in the present invention is such that the ultrathin metal layer is difficult to peel off from the carrier before the metal foil with carrier is laminated on the insulating substrate, while the ultrathin metal layer is not separated from the carrier after the lamination step on the insulating substrate. There is no particular limitation as long as it can be peeled off. For example, the intermediate layer of the metal foil with a carrier of the present invention is Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, alloys thereof, hydrates thereof, oxides thereof, One or two or more selected from the group consisting of organic substances may be included. The intermediate layer may be a plurality of layers.
Further, for example, the intermediate layer is a single metal layer composed of one kind of element selected from the element group composed of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn from the carrier side. Or forming an alloy layer composed of one or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, A hydrate or oxide of one or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn, or an organic substance It can comprise by forming the layer which consists of.
Further, for example, the intermediate layer is a single metal layer composed of one kind of element selected from the element group composed of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn from the carrier side. Or forming an alloy layer composed of one or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, A single metal layer made of one element selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, or Cr, Ni, Co , Fe, Mo, Ti, W, P, Cu, Al, and Zn can be formed by forming an alloy layer made of one or more elements selected from the group of elements.
Moreover, a well-known organic substance can be used for the intermediate | middle layer as said organic substance, and it is preferable to use any 1 or more types of a nitrogen containing organic compound, a sulfur containing organic compound, and carboxylic acid. For example, specific nitrogen-containing organic compounds include 1,2,3-benzotriazole, carboxybenzotriazole, N ′, N′-bis (benzotriazolylmethyl) urea, 1H, which are triazole compounds having a substituent. It is preferable to use -1,2,4-triazole and 3-amino-1H-1,2,4-triazole.
For the sulfur-containing organic compound, it is preferable to use mercaptobenzothiazole, 2-mercaptobenzothiazole sodium, thiocyanuric acid, 2-benzimidazolethiol, and the like.
As the carboxylic acid, it is particularly preferable to use a monocarboxylic acid, and it is particularly preferable to use oleic acid, linoleic acid, linolenic acid, or the like.
Further, for example, the intermediate layer can be configured by laminating a nickel layer, a nickel-phosphorus alloy layer or a nickel-cobalt alloy layer, and a chromium-containing layer in this order on a carrier. Since the adhesive force between nickel and copper is higher than the adhesive force between chromium and copper, when the ultrathin metal layer is peeled off, it peels at the interface between the ultrathin metal layer and the chromium-containing layer. In addition, the nickel in the intermediate layer is expected to have a barrier effect that prevents the copper component from diffusing from the carrier into the ultrathin metal layer. Adhesion amount of nickel in the intermediate layer is preferably 100 [mu] g / dm ² or more 40000μg / dm ² or less, more preferably 100 [mu] g / dm ² or more 4000μg / dm ² or less, more preferably 100 [mu] g / dm ² or more 2500 g / dm ² or less, more Preferably, it is 100 μg / dm ² or more and less than 1000 μg / dm ² , and the amount of chromium deposited on the intermediate layer is preferably 5 μg / dm ² or more and 100 μg / dm ² or less. When the intermediate layer is provided only on one side, it is preferable to provide a rust preventive layer such as a Ni plating layer on the opposite side of the carrier. The intermediate chromium layer can be provided by chromium plating or chromate treatment.
If the thickness of the intermediate layer becomes too large, the cost for forming the intermediate layer may increase. Therefore, the thickness of the intermediate layer is preferably 1 to 1000 nm, and preferably 1 to 500 nm. It is preferably ˜200 nm, preferably 2 to 100 nm, and more preferably 3 to 60 nm. The intermediate layer may be provided on both sides of the carrier.

<Ultrathin metal layer>
An ultrathin metal layer, that is, a plated metal substrate according to the present invention can be provided on the intermediate layer. Another layer may be provided between the intermediate layer and the ultrathin metal layer. The thickness of the ultrathin metal layer is not particularly limited, but is generally thinner than the carrier, for example, 35 μm or less, and for example, 12 μm or less. Typically, it is 0.5 to 12 μm, and more typically 1.5 to 5 μm. Further, before providing the ultrathin metal layer on the intermediate layer, strike plating with a copper-phosphorus alloy or the like may be performed in order to reduce pinholes in the ultrathin metal layer. Examples of the strike plating include a copper pyrophosphate plating solution. The ultrathin metal layer may be provided on both sides of the carrier. Ultra-thin metal layer is copper alloy, aluminum, aluminum alloy, iron, iron alloy, nickel alloy, gold alloy, silver alloy, platinum group alloy, chromium, chromium alloy, magnesium, magnesium alloy, tungsten, tungsten alloy, molybdenum alloy, lead An alloy, tantalum, tantalum alloy, tin, tin alloy, indium, indium alloy, zinc, or a thin metal layer containing or consisting of a metal such as a zinc alloy may be used, and a known metal material Can also be used as an ultrathin metal layer. Further, a metal material standardized by JIS standard or CDA can also be used as the ultrathin metal layer. It is preferable to use an ultrathin copper alloy layer as the ultrathin metal layer. This is because the ultrathin copper alloy layer has high conductivity and is suitable for applications such as circuits.

Further, the ultrathin metal layer of the present invention may be produced by forming the electrodeposited metal layer under the following conditions and then providing the above-described plating layer thereon, and the above-described plating layer on the intermediate layer. It may be manufactured by forming and forming an electrodeposited metal layer on the following conditions.
-Electrolyte composition Copper concentration: 80-130 g / L
Ti, Si, Mg, P, Sn, Zn, Cr, W, Zr, V, Na, Ca, Ba, Cs, Mn, K, Ga, B, Nb, Ce, Be, Nd, Sc, Hf, Ho, One or more elements selected from the group consisting of Lu, Yb, Dy, Er, Pr, Y, Li, Gd, Pu, In, Fe, La, Th, Ta, U, Sm, Tb, Sr, Tm and Al Element concentrations of: 0.001 to 30 g / L
Sulfuric acid concentration: 80-120 g / L
Chloride ion concentration: 30-100ppm
Moreover, you may use a leveling agent, a brightener, etc. as needed.

Manufacturing conditions Current density: 70-100 A / dm ²
Electrolyte temperature: 50-80 ° C
Electrolyte linear velocity: 1.5-5 m / sec
Electrolysis time: 0.5 to 10 minutes (adjusted by the thickness to be deposited and the current density)

[Resin layer on the plating layer]
A resin layer may be provided on the surface of the plating layer of the metal substrate with plating according to the present invention. The resin layer may be an insulating resin layer. In the metal substrate with plating of the present invention, the “plating layer surface” means that a surface treatment for providing a roughening treatment layer, a heat resistant layer, a rust prevention layer, a weather resistant layer, etc. is performed on the plating layer. The surface of the metal substrate with plating after the surface treatment is performed. In addition, when the metal base with plating is an ultra-thin metal layer of a metal foil with carrier, the “plating layer surface” is for providing a roughening treatment layer, a heat-resistant layer, a rust-proof layer, a weather-resistant layer, etc. When the surface treatment is performed, the surface of the ultrathin metal layer after the surface treatment is performed. In addition, it is preferable to use resin which has a light transmittance for the said resin layer, It is more preferable to use resin with high light transmittance, It is more preferable to use transparent resin.

  The resin layer may be an adhesive, or an insulating resin layer in a semi-cured state (B stage state) for bonding. The semi-cured state (B stage state) is a state in which there is no sticky feeling even if the surface is touched with a finger, the insulating resin layer can be stacked and stored, and a curing reaction occurs when subjected to heat treatment. Including that.

  The resin layer may be an adhesive resin, that is, an adhesive, or an adhesive semi-cured (B stage state) insulating resin layer. The semi-cured state (B stage state) is a state in which there is no sticky feeling even if the surface is touched with a finger, the insulating resin layer can be stacked and stored, and a curing reaction occurs when subjected to heat treatment. Including that.

  The resin layer may contain a thermosetting resin or may be a thermoplastic resin. The resin layer may include a thermoplastic resin. The resin layer may contain a known resin, resin curing agent, compound, curing accelerator, dielectric, reaction catalyst, crosslinking agent, polymer, prepreg, skeleton material, and the like. The resin layer may be, for example, International Publication No. WO2008 / 004399, International Publication No. WO2008 / 053878, International Publication No. WO2009 / 084533, JP-A-11-5828, JP-A-11-140281, Patent 3184485, International Publication. No. WO 97/02728, Japanese Patent No. 3676375, Japanese Patent Laid-Open No. 2000-43188, Japanese Patent No. 3612594, Japanese Patent Laid-Open No. 2002-179722, Japanese Patent Laid-Open No. 2002-359444, Japanese Patent Laid-Open No. 2003-302068, Japanese Patent No. 3992225, Japanese Patent Laid-Open No. 2003 No. 249739, Japanese Patent No. 4136509, Japanese Patent Application Laid-Open No. 2004-82687, Japanese Patent No. 4025177, Japanese Patent Application Laid-Open No. 2004-349654, Japanese Patent No. 4286060, Japanese Patent Application Laid-Open No. 2005-262506, Japanese Patent No. 4570070, Japanese Patent Application Laid-Open No. No. 5-53218, Japanese Patent No. 3949676, Japanese Patent No. 4178415, International Publication No. WO2004 / 005588, Japanese Patent Application Laid-Open No. 2006-257153, Japanese Patent Application Laid-Open No. 2007-326923, Japanese Patent Application Laid-Open No. 2008-11169, and Japanese Patent No. 5024930. No. WO 2006/028207, Japanese Patent No. 4828427, JP 2009-67029, International Publication No. WO 2006/134868, Japanese Patent No. 5046927, JP 2009-173017, International Publication No. WO 2007/105635, Patent No. 5180815, International Publication Number WO2008 / 114858, International Publication Number WO2009 / 008471, Japanese Patent Application Laid-Open No. 2011-14727, International Publication Number WO2009 / 001850, International Publication Number WO2009 / 145179, International Publication Number Nos. WO2011 / 068157, JP-A-2013-19056 (resins, resin curing agents, compounds, curing accelerators, dielectrics, reaction catalysts, crosslinking agents, polymers, prepregs, skeletal materials, etc.) and / or You may form using the formation method and formation apparatus of a resin layer.

  The type of the resin layer is not particularly limited. For example, epoxy resin, polyimide resin, polyfunctional cyanate ester compound, maleimide compound, polymaleimide compound, maleimide resin, aromatic maleimide resin , Polyvinyl acetal resin, urethane resin, polyethersulfone (also referred to as polyethersulfone or polyethersulfone), polyethersulfone (also referred to as polyethersulfone or polyethersulfone) resin, aromatic polyamide resin, aromatic Polyamide resin polymer, rubber resin, polyamine, aromatic polyamine, polyamideimide resin, rubber modified epoxy resin, phenoxy resin, carboxyl group-modified acrylonitrile-butadiene resin, polyphenylene oxide, bismaleimide triazine tree Fat, thermosetting polyphenylene oxide resin, cyanate ester resin, carboxylic acid anhydride, polyvalent carboxylic acid anhydride, linear polymer having crosslinkable functional group, polyphenylene ether resin, 2,2-bis (4 -Cyanatophenyl) propane, phosphorus-containing phenol compound, manganese naphthenate, 2,2-bis (4-glycidylphenyl) propane, polyphenylene ether-cyanate resin, siloxane-modified polyamideimide resin, cyanoester resin, phosphazene resin, Select from the group of rubber-modified polyamide-imide resin, isoprene, hydrogenated polybutadiene, polyvinyl butyral, phenoxy, polymer epoxy, aromatic polyamide, fluororesin, bisphenol, block copolymerized polyimide resin, and cyanoester resin It can be mentioned resins containing one or more kinds as suitable to be.

The epoxy resin has two or more epoxy groups in the molecule and can be used without any problem as long as it can be used for electric / electronic materials. The epoxy resin is preferably an epoxy resin epoxidized using a compound having two or more glycidyl groups in the molecule. Also, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, novolac type epoxy resin, cresol novolac type epoxy resin, alicyclic epoxy resin, brominated (brominated) epoxy Resin, phenol novolac type epoxy resin, naphthalene type epoxy resin, brominated bisphenol A type epoxy resin, orthocresol novolac type epoxy resin, rubber modified bisphenol A type epoxy resin, glycidylamine type epoxy resin, triglycidyl isocyanurate, N, N -Glycidyl amine compounds such as diglycidyl aniline, glycidyl ester compounds such as diglycidyl tetrahydrophthalate, phosphorus-containing epoxy resins, biphenyl type epoxy resins, One or two or more types selected from the group of phenyl novolac type epoxy resin, trishydroxyphenylmethane type epoxy resin, tetraphenylethane type epoxy resin can be used, or a hydrogenated product of the epoxy resin or Halogenated substances can be used.
As the phosphorus-containing epoxy resin, a known epoxy resin containing phosphorus can be used. The phosphorus-containing epoxy resin is, for example, an epoxy resin obtained as a derivative from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide having two or more epoxy groups in the molecule. Is preferred.

(When the resin layer contains a dielectric (dielectric filler))
The resin layer may include a dielectric (dielectric filler).
In the case where a dielectric (dielectric filler) is included in any of the above resin layers or resin compositions, it can be used for the purpose of forming the capacitor layer and increase the capacitance of the capacitor circuit. The dielectric (dielectric filler) includes a composite oxide having a perovskite structure such as BaTiO3, SrTiO3, Pb (Zr-Ti) O3 (common name PZT), PbLaTiO3 / PbLaZrO (common name PLZT), SrBi2Ta2O9 (common name SBT). Dielectric powder is used.

  The dielectric (dielectric filler) may be powdery. When the dielectric (dielectric filler) is in powder form, the powder characteristics of the dielectric (dielectric filler) are such that the particle size ranges from 0.01 μm to 3.0 μm, preferably 0.02 μm to 2.0 μm. It is preferable that. When the dielectric is photographed with a scanning electron microscope (SEM) and a straight line is drawn on the dielectric particle on the photograph, the length of the longest straight line across the dielectric particle is The length of the dielectric particle is defined as the diameter of the dielectric particle. Then, an average value of the diameters of the dielectric particles in the measurement visual field is defined as the dielectric particle size.

Examples of the resin and / or resin composition and / or compound contained in the resin layer include methyl ethyl ketone (MEK), cyclopentanone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, toluene, methanol, ethanol, propylene glycol monomethyl ether , Dimethylformamide, dimethylacetamide, cyclohexanone, ethyl cellosolve, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide and the like to obtain a resin liquid (resin varnish). On the roughened surface of the metal base with plating, for example, it is applied by a roll coater method or the like, and then heated and dried as necessary to remove the solvent to obtain a B stage state. For example, a hot air drying furnace may be used for drying, and the drying temperature may be 100 to 250 ° C, preferably 130 to 200 ° C. The composition of the resin layer is dissolved using a solvent, and the resin solid content is 3 wt% to 70 wt%, preferably 3 wt% to 60 wt%, preferably 10 wt% to 40 wt%, more preferably 25 wt% to 40 wt%. It is good also as a resin liquid. In addition, it is most preferable at this stage from an environmental standpoint to dissolve using a mixed solvent of methyl ethyl ketone and cyclopentanone. In addition, it is preferable to use the solvent whose boiling point is the range of 50 to 200 degreeC as a solvent.
The resin layer is preferably a semi-cured resin film having a resin flow in the range of 5% to 35% when measured according to MIL-P-13949G in the MIL standard.
In this specification, the resin flow is based on MIL-P-13949G in the MIL standard. Four 10 cm square samples are sampled from a plated metal substrate having a resin layer with a thickness of 55 μm. It was calculated based on Equation 1 from the result of measuring the resin outflow weight at the time when the samples were laminated (laminate) under the conditions of a press temperature of 171 ° C., a press pressure of 14 kgf / cm ² , and a press time of 10 minutes. Value.

  The plated metal substrate provided with the resin layer is formed by superposing the resin layer on the substrate and then thermocompressing the entire resin layer to thermally cure the resin layer. In the case of an ultra-thin metal layer, the carrier is peeled off to expose the ultra-thin metal layer (naturally it is the surface on the intermediate layer side of the ultra-thin metal layer), and a metal substrate with plating In this embodiment, a predetermined wiring pattern is formed from the surface on the opposite side to the roughened side.

  When the metal base with plating provided with this resin layer is used, the number of prepreg materials used at the time of manufacturing a multilayer printed wiring board can be reduced. In addition, the metal-clad laminate can be manufactured even when the thickness of the resin layer is such that interlayer insulation can be ensured or no prepreg material is used. At this time, the surface smoothness can be further improved by undercoating the surface of the substrate with an insulating resin.

In addition, when the prepreg material is not used, the material cost of the prepreg material is saved and the laminating process is simplified, which is economically advantageous. Moreover, the multilayer printed wiring board manufactured by the thickness of the prepreg material is used. The thickness is reduced, and there is an advantage that an extremely thin multilayer printed wiring board in which the thickness of one layer is 100 μm or less can be manufactured.
The thickness of the resin layer is preferably 0.1 to 120 μm.

When the thickness of the resin layer becomes thinner than 0.1 μm, the adhesive force decreases, and when a metal substrate with plating provided with this resin layer is laminated on a substrate provided with an inner layer material without interposing a prepreg material, It may be difficult to ensure interlayer insulation between the inner layer circuit and the circuit. On the other hand, if the thickness of the resin layer is greater than 120 μm, it is difficult to form a resin layer having a target thickness in a single coating process, which may be economically disadvantageous because of extra material costs and man-hours.
In addition, when the metal base with plating provided with the resin layer is used for manufacturing an extremely thin multilayer printed wiring board, the thickness of the resin layer is 0.1 μm to 5 μm, more preferably 0.5 μm to The thickness is preferably 5 μm, more preferably 1 μm to 5 μm, in order to reduce the thickness of the multilayer printed wiring board.

Below, some examples of the manufacturing process of the printed wiring board using the metal foil with a carrier which concerns on this invention are shown.
In one embodiment of the method for producing a printed wiring board according to the present invention, a step of preparing a metal foil with a carrier and an insulating substrate according to the present invention, a step of laminating the metal foil with a carrier and an insulating substrate, and with the carrier After laminating the metal foil and the insulating substrate so that the ultrathin metal layer side faces the insulating substrate, a metal-clad laminate is formed through a step of peeling the carrier of the metal foil with carrier, and then a semi-additive method, a modified semi-conductor A step of forming a circuit by any one of an additive method, a partial additive method, and a subtractive method. It is also possible for the insulating substrate to contain an inner layer circuit.

  In the present invention, the semi-additive method refers to a method in which a thin electroless plating is performed on an insulating substrate or a metal foil seed layer, a pattern is formed, and then a conductor pattern is formed using electroplating and etching.

Therefore, in one embodiment of the method for producing a printed wiring board according to the present invention using a semi-additive method, the step of preparing the metal foil with carrier and the insulating substrate according to the present invention, the metal foil with carrier and the insulating substrate, A step of laminating the metal foil with carrier and an insulating substrate, and then peeling off the carrier of the metal foil with carrier, and etching the exposed ultrathin metal layer using a corrosive solution such as an acid. The process of removing everything by methods such as
A step of providing a through hole or / and a blind via in the resin exposed by removing the ultrathin metal layer by etching, a step of performing a desmear treatment on a region including the through hole or / and the blind via, the resin and the A step of providing an electroless plating layer in a region including a through hole or / and a blind via, a step of providing a plating resist on the electroless plating layer, a region where a circuit is formed after the plating resist is exposed to light The step of removing the plating resist, the step of providing an electroplating layer in the region where the circuit from which the plating resist has been removed is formed, the step of removing the plating resist, and the region other than the region where the circuit is formed Remove an electroless plating layer by flash etching Including that step.

  In another embodiment of the method for producing a printed wiring board according to the present invention using a semi-additive method, a step of preparing a metal foil with a carrier and an insulating substrate according to the present invention, the metal foil with a carrier and the insulating substrate A step of laminating the metal foil with carrier and an insulating substrate, and then peeling off the carrier of the metal foil with carrier, and etching the exposed ultrathin metal layer using a corrosive solution such as an acid. Removing all by a method such as plasma or plasma, providing an electroless plating layer on the surface of the resin exposed by removing the ultrathin metal layer by etching, providing a plating resist on the electroless plating layer A step of exposing the plating resist, and then removing the plating resist in a region where a circuit is formed; A step of providing an electroplating layer in a region where the circuit from which the resist is removed is formed, a step of removing the plating resist, an electroless plating layer and an ultrathin metal layer in a region other than the region where the circuit is formed Is removed by flash etching or the like.

  In the present invention, the modified semi-additive method is a method in which a metal foil is laminated on an insulating layer, a non-circuit forming part is protected by a plating resist, and the copper is thickened in the circuit forming part by electroplating, and then the resist is removed. Then, a method of forming a circuit on the insulating layer by removing the metal foil other than the circuit forming portion by (flash) etching is indicated.

  Therefore, in one embodiment of the method for producing a printed wiring board according to the present invention using the modified semi-additive method, the step of preparing the metal foil with carrier and the insulating substrate according to the present invention, the metal foil with carrier and the insulation A step of laminating a substrate, a step of laminating the carrier of the metal foil with a carrier and an insulating substrate, a step of peeling the carrier of the metal foil with a carrier, a through hole or / A step of providing a blind via, a step of performing a desmear process on the region including the through hole or / and the blind via, a step of providing an electroless plating layer on the region including the through hole or / and the blind via, and exposing the substrate by peeling off the carrier Providing a plating resist on the surface of the ultrathin metal layer; After providing the strike, it comprises forming a circuit by electroplating, removing the plating resist, a step, is removed by flash etching ultrathin metal layer exposed by removing the plating resist.

  In addition, the step of forming a circuit on the resin layer includes attaching another metal foil with a carrier on the resin layer from the ultrathin metal layer side, and using the metal foil with a carrier bonded to the resin layer. It may be a step of forming a circuit. Moreover, the metal foil with a carrier of the present invention may be another metal foil with a carrier to be bonded onto the resin layer. Further, the step of forming a circuit on the resin layer may be performed by any one of a semi-additive method, a subtractive method, a partial additive method, or a modified semi-additive method. Moreover, the metal foil with a carrier which forms a circuit on the surface may have a substrate or a resin layer on the surface of the carrier of the metal foil with a carrier.

  In another embodiment of the method for producing a printed wiring board according to the present invention using the modified semi-additive method, the step of preparing the metal foil with carrier and the insulating substrate according to the present invention, the metal foil with carrier and the insulation A step of laminating the substrate, a step of peeling the carrier of the metal foil with carrier after laminating the metal foil with carrier and an insulating substrate, a step of providing a plating resist on the exposed ultrathin metal layer by peeling off the carrier, Exposing the plating resist and then removing the plating resist in a region where the circuit is formed; providing an electroplating layer in a region where the circuit where the plating resist is removed; The step of removing the resist, the electroless plating layer and the ultrathin metal layer in a region other than the region where the circuit is formed are flash-etched. Comprising the steps of removing the like ring.

  In the present invention, the partial additive method means that a catalyst circuit is formed on a substrate provided with a conductor layer, and if necessary, a substrate provided with holes for through holes or via holes, and etched to form a conductor circuit. Then, after providing a solder resist or a plating resist as necessary, it refers to a method of manufacturing a printed wiring board by thickening through holes, via holes, etc. on the conductor circuit by electroless plating.

  Therefore, in one embodiment of the method for producing a printed wiring board according to the present invention using the partly additive method, the step of preparing the metal foil with carrier and the insulating substrate according to the present invention, the metal foil with carrier and the insulating substrate, Laminating the metal foil with a carrier and an insulating substrate, then peeling the carrier of the metal foil with a carrier, peeling the carrier and exposing the ultrathin metal layer and the insulating substrate with a through hole or / and a blind A step of providing a via; a step of performing a desmear process on a region including the through hole or / and a blind via; a step of applying a catalyst nucleus in a region including the through hole or / and a blind via; and an electrode exposed by peeling off the carrier Providing an etching resist on the surface of the thin metal layer, the etching resist; Forming a circuit pattern, exposing the ultrathin metal layer and the catalyst nuclei by etching using a corrosive solution such as an acid or a method such as plasma to form a circuit, the etching A step of removing a resist, a step of providing a solder resist or a plating resist on the surface of the insulating substrate exposed by removing the ultrathin metal layer and the catalyst core by a method such as etching using an etching solution such as an acid or plasma. And a step of providing an electroless plating layer in a region where the solder resist or plating resist is not provided.

  In the present invention, the subtractive method refers to a method of forming a conductor pattern by selectively removing unnecessary portions of a copper foil on a copper clad laminate by etching or the like.

  Therefore, in one embodiment of the method for producing a printed wiring board according to the present invention using a subtractive method, the step of preparing the metal foil with carrier and the insulating substrate according to the present invention, the metal foil with carrier and the insulating substrate, Laminating the metal foil with a carrier and an insulating substrate, then peeling the carrier of the metal foil with a carrier, peeling the carrier and exposing the ultrathin metal layer and the insulating substrate with a through hole or / and a blind A step of providing a via, a step of performing a desmear process on a region including the through hole or / and the blind via, a step of providing an electroless plating layer on the region including the through hole or / and the blind via, a surface of the electroless plating layer A step of providing an electroplating layer, the electroplating layer and / or the ultrathin metal layer A step of providing an etching resist on the surface, a step of exposing the etching resist to form a circuit pattern, and etching the ultrathin metal layer, the electroless plating layer, and the electroplating layer using a corrosive solution such as an acid And a process of forming a circuit by removing the film by a method such as plasma or the like, and a process of removing the etching resist.

  In another embodiment of the method for producing a printed wiring board according to the present invention using a subtractive method, a step of preparing a metal foil with a carrier and an insulating substrate according to the present invention, the metal foil with a carrier and the insulating substrate Laminating the metal foil with a carrier and an insulating substrate, then peeling the carrier of the metal foil with a carrier, peeling the carrier and exposing the ultrathin metal layer and the insulating substrate with a through hole or / and a blind A step of providing a via, a step of performing a desmear process on a region including the through hole or / and the blind via, a step of providing an electroless plating layer on the region including the through hole or / and the blind via, a surface of the electroless plating layer Forming a mask on the surface of the electroless plating layer where the mask is not formed. A step of providing a layer, a step of providing an etching resist on the surface of the electroplating layer and / or the ultrathin metal layer, a step of exposing the etching resist to form a circuit pattern, the ultrathin metal layer and the non-thin layer A step of forming a circuit by removing the electrolytic plating layer by a method such as etching or plasma using a corrosive solution such as an acid, and a step of removing the etching resist.

  The process of providing a through hole or / and a blind via and the subsequent desmear process may not be performed.

Here, the specific example of the manufacturing method of the printed wiring board using the metal foil with a carrier of this invention is demonstrated in detail. Here, a metal foil with a carrier having an ultra-thin metal layer on which a roughened layer is formed will be described as an example. However, the present invention is not limited to this, and a carrier having an ultra-thin metal layer on which a roughened layer is not formed. Similarly, the following printed wiring board manufacturing method can be performed using the attached metal foil.
First, a metal foil with a carrier (first layer) having an ultrathin metal layer with a roughened layer formed on the surface is prepared.
Next, a resist is applied on the roughened layer of the ultrathin metal layer, exposed and developed, and the resist is etched into a predetermined shape.
Next, after forming the plating for the circuit, the resist is removed to form a circuit plating having a predetermined shape.
Next, an embedding resin is provided on the ultrathin metal layer so as to cover the circuit plating (so that the circuit plating is buried), and the resin layer is laminated, and then another metal foil with carrier (second layer) is applied to the electrode. Adhere from the thin metal layer side.
Next, the carrier is peeled off from the second layer of metal foil with carrier.
Next, laser drilling is performed at a predetermined position of the resin layer to expose the circuit plating and form a blind via.
Next, a via fill is formed by filling copper in the blind via.
Next, circuit plating is formed on the via fill as described above.
Next, the carrier is peeled off from the first layer of metal foil with carrier.
Next, the ultrathin metal layers on both surfaces are removed by flash etching, and the surface of the circuit plating in the resin layer is exposed.
Next, bumps are formed on the circuit plating in the resin layer, and copper pillars are formed on the solder. In this way, a printed wiring board using the metal foil with a carrier of the present invention is produced.

  As the other metal foil with carrier (second layer), the metal foil with carrier of the present invention may be used, a conventional metal foil with carrier may be used, and a normal copper foil may be used. Further, one or more circuits may be formed on the circuit of the second layer, and the circuit formation is performed by any of the semi-additive method, subtractive method, partly additive method, or modified semi-additive method. You may carry out by the method.

  A known resin or prepreg can be used as the embedding resin (resin). For example, a prepreg that is a glass cloth impregnated with BT (bismaleimide triazine) resin or BT resin, an ABF film or ABF manufactured by Ajinomoto Fine Techno Co., Ltd. can be used. Moreover, the resin layer and / or resin and / or prepreg as described in this specification can be used for the embedding resin (resin).

  Moreover, the metal foil with a carrier used for the first layer may have a substrate or a resin layer on the surface of the metal foil with a carrier. By having the substrate or the resin layer, the carrier-attached metal foil used for the first layer is supported, and wrinkles are less likely to be formed, so that there is an advantage that productivity is improved. As the substrate or resin layer, any substrate or resin layer can be used as long as it has an effect of supporting the metal foil with carrier used in the first layer. For example, as the substrate or resin layer, the carrier, prepreg, resin layer and known carrier, prepreg, resin layer, metal plate, metal foil, inorganic compound plate, inorganic compound foil, organic compound plate described in the present specification, Organic compound foils can be used.

  The metal substrate with plating of the present invention can be bonded to a resin substrate from the plating layer side to produce a laminate. The resin substrate is not particularly limited as long as it has characteristics applicable to a printed wiring board or the like. For example, a paper base phenol resin, a paper base epoxy resin, a synthetic fiber cloth base epoxy resin for rigid PWB Fluorine resin impregnated cloth, glass cloth / paper composite base epoxy resin, glass cloth / glass nonwoven fabric composite base epoxy resin and glass cloth base epoxy resin, etc., polyester film and polyimide for flexible printed circuit board (FPC) A film, a liquid crystal polymer (LCP) film, a fluororesin, and a fluororesin / polyimide composite material can be used. In addition, since a liquid crystal polymer (LCP) has a small dielectric loss, it is preferable to use a liquid crystal polymer (LCP) film for the printed wiring board for a high frequency circuit use.

  In the case of the rigid PWB, a prepreg is prepared by impregnating a base material such as a glass cloth with a resin and curing the resin to a semi-cured state. It can be performed by stacking a copper foil on a prepreg and heating and pressing. In the case of FPC, a liquid crystal polymer or a polyimide film is bonded to a copper foil under high temperature and pressure without using an adhesive, or a polyimide precursor is applied and dried via an adhesive. -A laminated body can be manufactured by performing hardening etc.

  The laminate of the present invention can be used for various printed wiring boards (PWB) and is not particularly limited. For example, from the viewpoint of the number of layers of the conductor pattern, the single-sided PWB, the double-sided PWB, and the multilayer PWB (3 It is applicable to rigid PWB, flexible PWB (FPC), and rigid flex PWB from the viewpoint of the type of insulating substrate material.

  Finally, description will be made on the case where the plated metal substrate according to the present invention is applied to a spring material for an autofocus module. In a typical autofocus module, a lens, a spring member made of a metal base with plating according to the present invention that elastically biases the lens to an initial position in the optical axis direction, and a biasing force of the spring member are resisted. Electromagnetic driving means capable of generating an electromagnetic force to drive the lens in the optical axis direction is provided. The electromagnetic drive means is illustratively a U-shaped cylindrical yoke, a coil housed inside the inner peripheral wall of the yoke, and surrounding the coil and housed inside the outer peripheral wall of the yoke. A magnet can be provided. The spring member can be joined to a coil (typically a lead wire of the coil) by soldering at a portion having the plating layer. Since the structure of the autofocus module itself is known in Japanese Patent Application Laid-Open No. 2014-102294, Japanese Patent Application Laid-Open No. 2014-084514, etc., detailed description thereof is omitted.

  EXAMPLES Examples of the present invention will be described below, but these examples are presented for better understanding of the present invention and its advantages, and are not intended to limit the present invention.

The metal base material which consists of metal foil with each material composition and thickness of Table 2 was prepared. After degreasing and pickling and cleaning the surface of the metal foil, Co plating, Co—Ni alloy plating, and Co—Mo alloy are applied to the entire surface of the metal foil according to the Ni, Co, and Mo adhesion conditions shown in Table 2. Plating, Ni—Mo alloy plating, or Co—Ni—Mo alloy plating was performed using a sulfuric acid acidic plating bath (pH: 2 to 3.5, liquid temperature: 40 to 60 ° C., current density: ² to 10 A / dm ² ). It carried out by electroplating and manufactured the metal foil with a plating of an invention example, a reference example, and a comparative example. The ion concentrations of Ni, Mo, and Co in the plating solution were set as shown in Table 1 according to the Ni + Mo ratio (%). The ion concentrations of other elements were set as shown in Table 1 according to the amount of adhesion. The amount of adhesion can be controlled by the amount of coulomb. In order to reduce the adhesion amount, the coulomb amount may be reduced. When the amount of adhesion is increased, the amount of coulomb may be increased. For example, when the total adhesion amount of Co, Ni and Mo is 3000 μg / dm ² , the coulomb amount is about 5 to 20 As / dm ² , and the total adhesion amount of Co, Ni and Mo is 14000 μg / dm ^2. In order to set the coulomb amount to about 45 to 80 As / dm ² and the total adhesion amount of Co, Ni and Mo to 180000 μg / dm ² , the coulomb amount is preferably set to about 700 to 900 As / dm ² . In order to increase the amount of Mo adhesion, the Mo concentration in the plating solution may be increased. In order to increase the amount of Co adhesion, the Co concentration in the plating solution may be increased. When it is desired to increase the Ni adhesion amount, the Ni concentration in the plating solution may be increased.

  Moreover, about the test numbers 90-93, the metal foil with a carrier which uses a metal base material for an ultra-thin metal layer was used. The metal foil with a carrier was manufactured as follows. JX Nippon Mining & Metals Co., Ltd. electrolytic copper foil JTC foil (thickness 18 μm) was used for the carriers of Test Nos. 90 and 91, and JX Nippon Mining & Metals Co., Ltd. Rolled copper foil Tough pitch copper (thickness 18 μm, JIS H3100 alloy number C1100) was used. And in order of Table 2, each layer was formed in the S surface (glossy surface) side of the said electrolytic copper foil, or the surface of a rolled copper foil.

The intermediate layers of test numbers 90 to 93 were formed as follows.
・ Test number 90
<Intermediate layer>
(1) Ni layer (Ni plating)
A Ni layer having an adhesion amount of 4000 μg / dm ² was formed on the carrier by electroplating on a roll-to-roll continuous plating line under the following conditions. Specific plating conditions are described below.
Nickel sulfate: 270-280 g / L
Nickel chloride: 35 to 45 g / L
Nickel acetate: 10-20g / L
Boric acid: 30-40 g / L
Brightener: Saccharin, butynediol, etc. Sodium dodecyl sulfate: 55-75 ppm
pH: 4-6
Bath temperature: 55-65 ° C
Current density: 10 A / dm ²
(2) Cr layer (electrolytic chromate treatment)
Next, after the surface of the Ni layer formed in (1) is washed with water and pickled, a Cr layer having an adhesion amount of 11 μg / dm ² is continuously formed on the Ni layer on a roll-to-roll-type continuous plating line. It was made to adhere by carrying out the electrolytic chromate process on the following conditions.
Potassium dichromate 1-10g / L
pH: 7-10
Liquid temperature: 40-60 degreeC
Current density: 2 A / dm ²

・ Test number 91
<Intermediate layer>
(1) Ni-Mo layer (nickel molybdenum alloy plating)
A Ni—Mo layer having an adhesion amount of 3000 μg / dm ² was formed on the carrier by electroplating using a roll-to-roll type continuous plating line under the following conditions. Specific plating conditions are described below.
(Liquid composition) Ni sulfate hexahydrate: 50 g / dm ³ , sodium molybdate dihydrate: 60 g / dm ³ , sodium citrate: 90 g / dm ³
(Liquid temperature) 30 ° C
(Current density) 1 to 4 A / dm ²
(Energization time) 3 to 25 seconds

・ Test number 92
<Intermediate layer>
(1) Ni layer (Ni plating)
A Ni layer was formed under the same conditions as in test number 90.
(2) Organic layer (Organic layer formation treatment)
Next, the surface of the Ni layer formed in (1) is washed with water and pickled, and subsequently contains carboxybenzotriazole (CBTA) at a concentration of 1 to 30 g / L with respect to the Ni layer surface under the following conditions. An organic layer was formed by spraying an aqueous solution of 40 ° C. and pH 5 after 20 to 120 seconds of showering.

・ Test number 93
<Intermediate layer>
(1) Co-Mo layer (cobalt molybdenum alloy plating)
A Co—Mo layer having an adhesion amount of 4000 μg / dm ² was formed on the carrier by electroplating using a roll-to-roll type continuous plating line under the following conditions. Specific plating conditions are described below.
(Liquid composition) Co sulfate 50 g / dm ³ , sodium molybdate dihydrate: 60 g / dm ³ , sodium citrate: 90 g / dm ³
(Liquid temperature) 30 ° C
(Current density) 1 to 4 A / dm ²
(Energization time) 3 to 25 seconds (2) Organic substance layer (organic substance layer formation treatment)
Next, after the surface of the Co-Mo layer formed in (1) is washed with water and pickled, it subsequently contains carboxybenzotriazole (CBTA) at a concentration of 1 to 30 g / L with respect to the Ni layer surface under the following conditions. An organic layer was formed by spraying an aqueous solution having a liquid temperature of 40 ° C. and a pH of 5 by showering for 20 to 120 seconds.

Moreover, the metal foil as an ultra-thin metal layer was formed on the intermediate layer or the plating layer so as to have the substrate thickness described in Table 2 under the following conditions.
<Metal foil>
Copper concentration: 90-110 g / L
Tin concentration: 1-30 g / L
Sulfuric acid concentration: 90-110 g / L
Chloride ion concentration: 50-90ppm
Electrolyte temperature: 50-80 ° C
Current density: 100 A / dm ²
Electrolyte linear velocity: 1.5-5 m / sec

(1) Adhesion amount of Ni, Co, Mo and other elements (μg / dm ² )
The adhesion amount (μg / dm ² ) of Ni, Co, Mo and other elements in the plating layer of the obtained metal foil with plating (test sample) was determined by dissolving the test sample with nitric acid having a concentration of 20% by mass. Measurement was performed by ICP emission spectrometry using an ICP emission spectroscopic analyzer (model: SPS3100) manufactured by the company. If the test sample is difficult to dissolve in nitric acid having a concentration of 20% by mass, a mixed solution of nitric acid and hydrochloric acid (nitric acid concentration: 20% by mass, hydrochloric acid concentration: 12% by mass) or a test sample can be dissolved. The test sample may be dissolved with a solution such as an acid aqueous solution. Further, the Ni + Mo ratio (%) in the plating layer was calculated from the measured adhesion amounts of Ni, Co, and Mo. Here, the definition of the Ni + Mo ratio (%) is as follows. Ni + Mo ratio (%) = {total adhesion amount of Ni and Mo (μg / dm ² ) / (total adhesion amount of Ni, Co and Mo (μg / dm ² ))} × 100

(2) Etching linearity Etching was performed on each test sample using an aqueous ferric chloride solution of 37% by mass and Baume degree of 40 °, and the line and space (L / S) was 100 mm / 200 μm in length of 150 mm. And a linear circuit having a length of 150 mm with a line and space (L / S) of 75 μm / 75 μm. The circuit was observed using a scanning electron microscope (Hitachi, S-4700) and evaluated according to the following criteria.
X: Waviness range is longer than 50% of circuit length. Δ: Waviness range is more than 25% to 50% of circuit length.
○: Waviness range is more than 15% to 25% of circuit length
○○: Waviness range is over 5% to 15% of circuit length
A: The waviness range is longer than 0% of the circuit length and not more than 5%. A: The waviness range is 0%. No waviness (straight)
Here, the swell is a photograph of the circuit taken from the top surface at 500 times with SEM, and two straight lines (thickness 1.9 μm) along the longitudinal direction connecting the corners of the circuit having a length of 186 μm in the photograph. When it is drawn, it means that the edge of the circuit is 5 μm or more away from the center line of each straight line. The measurement result was expressed as an average value when four photographs were taken.

(3) Solder adhesion strength test First, the foil thickness was reduced to 0.03 mm from one surface side of each test sample by wet etching. At this time, the opposite surface was masked with tape so that the plating would not peel off. And the plating layer side (the test sample which is not plating-formed is an arbitrary surface) and pure copper foil (JX Nippon Mining & Metals Co., Ltd. C1100, foil thickness 0.035 mm) are obtained from Senju Metal. Joined via Pb-free solder (ESC M705, solder containing flux (flux), Sn (remainder) -3.0 mass% Ag-0.5 mass% Cu) manufactured by Kogyo Co., Ltd., Aiko Engineering Co., Ltd. The adhesion strength was measured by conducting a 180 ° peeling test at a speed of 100 mm / min using a precision load measuring instrument (MODEL-1605NL) manufactured by the manufacturer. The sample foil has a strip shape with a width of 15 mm and a length of 200 mm, the pure copper foil has a strip shape with a width of 20 mm and a length of 200 mm, and an area of 30 mm × 15 mm in the central portion with respect to the length direction has a bonding temperature of 245 ° C. ± 5 ° C. As joined. The thickness of the pure copper foil is not a problem as long as it is close to the thickness of the sample foil to be evaluated, but is preferably 0.02 mm to 0.05 mm. In this example, 0.035 mm of pure copper foil was used. In the experimental example of the metal foil with carrier, the above-mentioned solder adhesion strength test was performed after peeling the carrier from the metal foil with carrier. In the case of test numbers 92 and 93 where the thickness of the metal foil of the carrier-attached metal foil is smaller than 0.03 mm, the thickness of the metal foil and the thickness of the Cu plating is increased by plating the metal foil with Cu. After making the total thickness of 0.03 mm, the carrier was peeled from the metal foil with a carrier, and then the above test was performed.

(4) Weather resistance test Investigate the degree of discoloration when each test sample is held for 100 hours or 200 hours in a constant temperature and humidity chamber (ESPEC Corporation (model number: PL-2E)) at 85 ° C. and 85% relative humidity. did. The degree of discoloration was obtained by taking a picture, overlaying a transparent resin film, painting the discolored portion with a black marker, binarizing it with image processing software, and obtaining the area of the discolored portion with the image processing software. A value obtained by dividing the obtained area by the area of the entire observation visual field by 100 was defined as the area ratio (%) of the discolored portion.

  Table 2 shows the test results of the plating adhesion amount, and Table 3 shows the test results of etching property, solder adhesion, and weather resistance. From Table 3, in the examples, the metal base material originally inferior in solder adhesion or weather resistance has obtained improved solder adhesion and weather resistance by forming the plating layer according to the present invention. I understand. Further, Examples (No. 1, 2, 2-2 to 2-6, 3 to 12, 15, 18 to 20, 22 to 27, 30, in which the total adhesion amount of Ni + Co + Mo and the Ni + Mo ratio (%) were appropriately controlled. It can be seen that high etchability is also obtained in 32-36, 38-44, 46, 48, 49, 78-81, 86, 88-97, while comparative examples show excellent etchability. However, there was no one that achieved both solder adhesion and weather resistance.

Claims (42)

A metal substrate with plating in which a Co—Ni alloy plating layer, a Co—Mo alloy plating layer, or a Co—Ni—Mo alloy plating layer is formed on a part or all of the surface of the metal substrate, the plating Co in the layer, the total deposition amount of Ni and Mo is 500 [mu] g / dm ² or more (excluding 13500μg / dm ² or more range), and and, Co, the sum of Ni and Mo to the total amount of adhered Ni and Mo adhesion amount (hereinafter, also referred to as "Ni + Mo ratio (%)".) is Ri der 10% to 50% by mass ratio,
Metal substrates are Ti, Si, Mg, P, Sn, Zn, Cr, Zr, V, Na, Ca, Ba, Cs, Mn, K, Ga, B, Nb, Ce, Be, Nd, Sc, Hf, One or more selected from the group consisting of Ho, Lu, Yb, Dy, Er, Pr, Y, Li, Gd, Pu, In, Fe, La, Th, Ta, U, Sm, Tb, Sr, Tm and Al A metal substrate with plating, which is formed of a copper alloy containing any of the above elements and is used in connection with an electronic component by soldering at a portion having the plating layer. A metal substrate with plating in which a Co—Mo alloy plating layer or a Co—Ni—Mo alloy plating layer is formed on a part or all of the surface of a metal substrate, wherein Co, Ni and Mo in the plating layer the total amount of deposited 500 [mu] g / dm ² or more (excluding 13500μg / dm ² or more range), and and, Co, the total deposition amount of Ni and Mo to the total deposition amount of Ni and Mo (hereinafter, "Ni + Mo Ratio (%) ") is a metal base material with plating in which the mass ratio is 10% or more and 50% or less, and the Mo adhesion amount in the plating layer is 259 μg / dm ² or more,
Metal substrates are Ti, Si, Mg, P, Sn, Zn, Cr, Zr, V, Na, Ca, Ba, Cs, Mn, K, Ga, B, Nb, Ce, Be, Nd, Sc, Hf, One or more selected from the group consisting of Ho, Lu, Yb, Dy, Er, Pr, Y, Li, Gd, Pu, In, Fe, La, Th, Ta, U, Sm, Tb, Sr, Tm and Al A metal substrate with plating, which is formed of a copper alloy containing any of the above elements and is used in connection with an electronic component by soldering at a portion having the plating layer. A metal substrate with plating in which a Co—Ni alloy plating layer, a Co—Mo alloy plating layer, or a Co—Ni—Mo alloy plating layer is formed on a part or all of the surface of the metal substrate, the plating Co in the layer, the total deposition amount of Ni and Mo is 500 [mu] g / dm ² or more (excluding 13500μg / dm ² or more range), and and, Co, the sum of Ni and Mo to the total amount of adhered Ni and Mo A metal base with plating having an adhesion amount (hereinafter also referred to as “Ni + Mo ratio (%)”) of 10% or more and 50% or less by mass ratio, and a Co adhesion amount in the plating layer of 1373 μg / dm ² or more. Yes,
Metal substrates are Ti, Si, Mg, P, Sn, Zn, Cr, Zr, V, Na, Ca, Ba, Cs, Mn, K, Ga, B, Nb, Ce, Be, Nd, Sc, Hf, One or more selected from the group consisting of Ho, Lu, Yb, Dy, Er, Pr, Y, Li, Gd, Pu, In, Fe, La, Th, Ta, U, Sm, Tb, Sr, Tm and Al A metal substrate with plating, which is formed of a copper alloy containing any of the above elements and is used in connection with an electronic component by soldering at a portion having the plating layer. A metal substrate with plating in which a Co—Ni alloy plating layer or a Co—Ni—Mo alloy plating layer is formed on a part or all of the surface of a metal substrate, wherein Co, Ni, and Mo in the plating layer the total amount of deposited 500 [mu] g / dm ² or more (excluding 13500μg / dm ² or more range), and and, Co, the total deposition amount of Ni and Mo to the total deposition amount of Ni and Mo (hereinafter, "Ni + Mo A ratio (also referred to as “% (%)”) is a metal base with plating having a mass ratio of 10% or more and 50% or less, and the Ni adhesion amount in the plating layer is 1008 μg / dm ² or more,
Metal substrates are Ti, Si, Mg, P, Sn, Zn, Cr, Zr, V, Na, Ca, Ba, Cs, Mn, K, Ga, B, Nb, Ce, Be, Nd, Sc, Hf, One or more selected from the group consisting of Ho, Lu, Yb, Dy, Er, Pr, Y, Li, Gd, Pu, In, Fe, La, Th, Ta, U, Sm, Tb, Sr, Tm and Al A metal substrate with plating, which is formed of a copper alloy containing any of the above elements and is used in connection with an electronic component by soldering at a portion having the plating layer. A metal substrate with plating in which a Co—Ni alloy plating layer is formed on a part or all of the surface of the metal substrate, and the total adhesion amount of Co and Ni in the plating layer is 500 μg / dm ² or more (however, , Except for the range of 13500 μg / dm ² or more), and the total deposition amount of Ni and Mo with respect to the total deposition amount of Co, Ni and Mo (hereinafter also referred to as “Ni + Mo ratio (%)”). Is a metal substrate with plating that is 10% or more and 50% or less,
Metal substrates are Ti, Si, Mg, P, Sn, Zn, Cr, Zr, V, Na, Ca, Ba, Cs, Mn, K, Ga, B, Nb, Ce, Be, Nd, Sc, Hf, One or more selected from the group consisting of Ho, Lu, Yb, Dy, Er, Pr, Y, Li, Gd, Pu, In, Fe, La, Th, Ta, U, Sm, Tb, Sr, Tm and Al A metal substrate with plating, which is formed of a copper alloy containing any of the above elements and is used in connection with an electronic component by soldering at a portion having the plating layer. A metal substrate with plating in which a Co—Ni alloy plating layer, a Co—Mo alloy plating layer, or a Co—Ni—Mo alloy plating layer is formed on a part or all of the surface of the metal substrate, the plating Co in the layer, the total deposition amount of Ni and Mo is 500 [mu] g / dm ² or more (excluding 13500μg / dm ² or more range), and and, Co, the sum of Ni and Mo to the total amount of adhered Ni and Mo The adhesion amount (hereinafter also referred to as “Ni + Mo ratio (%)”) is 10% or more and 50% or less by mass ratio, and the content ratio of Ni and Mo in the plating layer is Ni: Mo = 9: 1 by mass ratio. ~ 1: 9 plated metal substrate,
Metal substrates are Ti, Si, Mg, P, Sn, Zn, Cr, Zr, V, Na, Ca, Ba, Cs, Mn, K, Ga, B, Nb, Ce, Be, Nd, Sc, Hf, One or more selected from the group consisting of Ho, Lu, Yb, Dy, Er, Pr, Y, Li, Gd, Pu, In, Fe, La, Th, Ta, U, Sm, Tb, Sr, Tm and Al A metal substrate with plating, which is formed of a copper alloy containing any of the above elements and is used in connection with an electronic component by soldering at a portion having the plating layer.   The metal base with plating according to claim 6, wherein a content ratio of Ni and Mo in the plating layer is Ni: Mo = 6: 4 to 4: 6 in terms of mass ratio. The plated metal substrate according to any one of claims 1 to 7, wherein a total adhesion amount of Co, Ni, and Mo in the plating layer is 5000 µg / dm ² or more. The plated metal substrate according to any one of claims 1 to 7, wherein a total adhesion amount of Co, Ni, and Mo in the plating layer is 7000 µg / dm ² or more.   In the said plating layer, the total adhesion amount (henceforth "Ni + Mo ratio (%)") of Ni and Mo with respect to the total adhesion amount of Co, Ni, and Mo is 20% or more by mass ratio. The metal base material with plating as described in any one of these.   The metal substrate with plating as described in any one of Claims 1-10 in which the base layer and / or the roughening process layer were formed between the said plating layer and the said metal base material.   The metal base with plating according to any one of claims 1 to 5 and 8 to 11, wherein the content ratio of Ni and Mo in the plating layer is Ni: Mo = 9: 1 to 1: 9 in terms of mass ratio.   The metal base with plating according to any one of claims 1 to 5 and 8 to 11, wherein the content ratio of Ni and Mo in the plating layer is Ni: Mo = 6: 4 to 4: 6 in terms of mass ratio.   The plating layer is at least one selected from the group consisting of Cu, As, Ag, Au, Pd, Pt, Bi, Os, Rh, Tl, Sb, Pb, Hg, Ir, Cd, Ru, Re, Tc, and Gd. The metal substrate with plating as described in any one of Claims 1-13 containing these elements. The plating layer is at least one selected from the group consisting of Cu, As, Ag, Au, Pd, Pt, Bi, Os, Rh, Tl, Sb, Pb, Hg, Ir, Cd, Ru, Re, Tc, and Gd. The metal base material with plating of Claim 14 which contains 0-2000 microgram / dm < ² > in total of these elements. The plating layer is at least one selected from the group consisting of Cu, As, Ag, Au, Pd, Pt, Bi, Os, Rh, Tl, Sb, Pb, Hg, Ir, Cd, Ru, Re, Tc, and Gd. The metal base material with plating of Claim 14 which contains 0-1000 microgram / dm < ² > in total of these elements. The plating layer is at least one selected from the group consisting of Cu, As, Ag, Au, Pd, Pt, Bi, Os, Rh, Tl, Sb, Pb, Hg, Ir, Cd, Ru, Re, Tc, and Gd. The metal base material with plating of Claim 14 which contains 0-500 microgram / dm < ² > in total of these elements.   The plated metal substrate according to any one of claims 1 to 13, wherein the plating layer includes one or more elements selected from the group consisting of Cu, As, Ag, Au, Pd, and Pt. The plated metal substrate according to claim 18, wherein the plating layer contains a total of 0 to 2000 µg / dm ^{2 of} one or more elements selected from the group consisting of Cu, As, Ag, Au, Pd, and Pt. The plated metal substrate according to claim 18, wherein the plating layer contains a total of 0 to 1000 µg / dm ^{2 of} one or more elements selected from the group consisting of Cu, As, Ag, Au, Pd, and Pt. The plated metal substrate according to claim 18, wherein the plating layer contains a total of 0 to 500 µg / dm ^{2 of} one or more elements selected from the group consisting of Cu, As, Ag, Au, Pd, and Pt.   A copper alloy in which the metal substrate contains 0.001 to 4.0 mass% in total of at least one of Sn, Cr, Fe, In, P, Si, Ti, Zn, B, Mn, and Zr, or Zn, Sn, Mg, Fe, Si, P, Mn, Zr, Cr and Ti are formed of a copper alloy containing 8.0% by mass or less of one or more of them in total. The metal base material with plating as described in any one of Claims.   The metal substrate with plating according to any one of claims 1 to 22, wherein the metal substrate is in the form of a metal strip, a metal plate, or a metal foil.   The metal base material with plating as described in any one of Claims 1-23 which has a resin layer on the surface of the said plating layer.   The plated metal substrate according to any one of claims 1 to 24, wherein the metal substrate has two main surfaces, and the plated layer is provided on one or both surfaces thereof.   It is metal foil with a carrier which has an intermediate | middle layer and an ultra-thin metal layer in this order on one side or both sides of a carrier, Comprising: The said ultra-thin metal layer is any one of Claims 1-25. Metal foil with carrier, which is a metal substrate with plating.   27. The metal foil with a carrier according to claim 26, comprising the intermediate layer and the ultrathin metal layer in this order on one surface of the carrier, and a roughening treatment layer on the other surface of the carrier.   The connector provided with the metal base material with a plating as described in any one of Claims 1-25.   The terminal provided with the metal base material with plating as described in any one of Claims 1-25.   A laminated board produced by laminating the metal substrate with plating according to any one of claims 1 to 25 or the metal foil with carrier according to any one of claims 26 to 27 and a resin substrate.   A shield tape or a shield material comprising the laminate according to claim 30.   A printed wiring board comprising the laminate according to claim 30.   A metal workpiece comprising the metal substrate with plating according to any one of claims 1 to 25 or the metal foil with carrier according to any one of claims 26 to 27.   An electronic / electric device comprising the metal substrate with plating according to any one of claims 1 to 25 or the metal foil with carrier according to any one of claims 26 to 27. Preparing a metal foil with a carrier according to any one of claims 26 to 27 and an insulating substrate;
Laminating the metal foil with carrier and an insulating substrate;
After laminating the metal foil with carrier and the insulating substrate, forming a metal-clad laminate through a process of peeling the carrier of the metal foil with carrier,
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. A step of forming a circuit on the ultrathin metal layer side surface or the carrier side surface of the metal foil with a carrier according to any one of claims 26 to 27,
Forming a resin layer on the ultrathin metal layer side surface or the carrier side surface of the metal foil with carrier so that the circuit is buried;
Forming a circuit on the resin layer;
After forming a circuit on the resin layer, peeling the carrier or the ultrathin metal layer; and
After the carrier or the ultrathin metal layer is peeled off, the ultrathin metal layer or the carrier is removed to be buried in the resin layer formed on the ultrathin metal layer side surface or the carrier side surface. A method of manufacturing a printed wiring board including a step of exposing a circuit that is connected.   A joined body of the metal substrate with plating according to any one of claims 1 to 25 and solder.   38. The joined body according to claim 37, wherein a thermal diffusion layer containing Sn and Co is present at the joint interface between the solder and the metal substrate.   The process of shape-processing the metal substrate with plating according to any one of claims 1 to 25 by etching, and conducting the shape-processed product of the metal substrate with plating obtained by soldering at a place having a plating layer A method of connecting a metal base with plating and a conductive member, including a step of joining with a conductive member.   The electronic component provided with the metal base material with a plating as described in any one of Claims 1-25.   An autofocus module comprising the plated metal substrate according to any one of claims 1 to 25 as a spring material.   A lens, a spring member made of a plated metal base material according to any one of claims 1 to 25, which elastically biases the lens to an initial position in the optical axis direction, and resists a biasing force of the spring member. An autofocus camera module comprising electromagnetic driving means capable of driving the lens in the optical axis direction by generating electromagnetic force, the electromagnetic driving means comprising a coil, and a spring member having the plating layer Autofocus camera module joined to the coil by soldering.