TW201625414A - Metal substrate with plating - Google Patents

Abstract

The present invention provides a metal substrate with excellent solder adhesion and the weather resistance even if a substrate that contains elements having higher reactivity with oxygen at the room temperature is used. The metal substrate with plating according to the present invention is a metal substrate with plating, in which a coating in a group consisting of alloy coating layers of at least two elements selected from Co coating and a group consisting of Co, Ni and Mo, is formed on a portion or all of the surface of the metal substrate, and a total attachment amount of the Co, Ni and Mo in the coating is more than 500 [mu]g/dm2, and the metal substrate comprises at least one element selected from a group consisting of Ti, Si, Mg, P, Sn, Zn, Cr, Zr, V, W, Na, Ca, Ba, Cs, Mn, K, Ga, B, Nb, Ce, 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.

Description

Plated metal substrate

The invention relates to a plated metal substrate. Further, the present invention relates to a metal substrate including a plated metal or a carrier metal foil, a connector, a terminal, a laminate, a masking tape, a masking material, a printed wiring board, a metal working member, an electronic device, and a metal foil. Machines and methods of manufacturing printed wiring boards.

Printed circuit boards widely used in electronic and electrical machines are usually manufactured by adhering a metal foil to an insulating substrate such as a synthetic resin sheet or a synthetic resin film under high temperature and high pressure via an adhesive or without using an adhesive. After the metal-clad laminate is produced, a metal wiring is formed on the metal foil side by an etching step to form a printed wiring board, and various electronic components are mounted on the metal wiring of the printed wiring board by soldering.

A technique for forming a circuit having a high uniformity of line width by improving the etching characteristics of a metal foil has been known, and a technique in which an etching rate is slower than a metal or alloy layer of copper is formed on the side of the etching surface (Patent Document 1). According to Patent Document 1, the etching rate in the thickness direction of the copper foil is controlled by forming a metal or alloy layer having a slower etching rate on the etching surface side, whereby a circuit having a uniform circuit width without sag can be formed. Further, Patent Document 1 discloses a case where cobalt or nickel or an alloy layer thereof is exemplified as a metal or an alloy layer having an etching rate slower than copper, and the thickness thereof can be set to 100 to 10000 μg/dm ² .

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2002-176242

However, in Patent Document 1, although the etching property of the copper foil at the time of producing a printed circuit board has been considered, the adhesion strength between the solder and the metal wiring used when the electronic component is mounted on the printed circuit board is not performed. Research. In particular, the copper foil is not problematic because it has excellent solder adhesion, but when it is a metal substrate containing an element having high reactivity with oxygen at normal temperature, no problem has been proposed for the problem of ensuring solder adhesion. solution. In addition, it is also considered that both etching property and solderability are required for applications other than printed wiring boards, but Patent Document 1 only considers a printed circuit board. Further, in consideration of the practicality of the metal substrate as a conductive material, research on weather resistance is also important, but such research has not been found. Therefore, one of the problems of the present invention is to provide a metal substrate excellent in solder adhesion and weather resistance, although a metal substrate containing an element having high reactivity with oxygen at normal temperature is used.

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

The present invention is, in one aspect, a plated metal substrate formed on a portion or all of a surface of a metal substrate selected from the group consisting of a Co plating layer and a group selected from the group consisting of Co, Ni, and Mo. a metal substrate to which a plating layer of a plating layer composed of an alloy plating layer of two or more elements is applied, and a total adhesion amount of Co, Ni, and Mo in the plating layer is 500 μg/dm ² or more, and the metal substrate Containing from the group consisting of Ti, Si, Mg, P, Sn, Zn, Cr, Zr, V, W, Na, Ca, Ba, Cs, Mn, K, Ga, B, Nb, Ce, Be, Nd, Sc, Hf One of a 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 Or more than two elements.

In one embodiment of the plated metal substrate of 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 to be plated 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 to be plated 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 plated metal substrate of 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 to be plated 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 plated metal substrate of 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 to be plated 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 plated metal substrate of the present invention, the total amount of adhesion of Ni and Mo to the total amount of adhesion of Co, Ni, and Mo in the plating layer (hereinafter also referred to as "Ni+Mo ratio" (%)") is 80% or less by mass ratio.

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

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

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

In one embodiment of the plated metal substrate of the present invention, a base layer and/or a roughened layer is formed between the plating layer and the metal substrate.

In one embodiment of the plated metal substrate of the present invention, the plating layer is selected from the group consisting of 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. in.

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

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

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

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

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

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

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

In one embodiment of the plated metal substrate of the present invention, the metal substrate is made of a copper alloy, aluminum, aluminum alloy, iron, iron alloy, stainless steel, nickel alloy, titanium, titanium alloy, gold alloy, silver alloy. , platinum group alloys, chromium, chromium alloys, magnesium, magnesium alloys, tungsten, tungsten alloys, molybdenum alloys, lead alloys, niobium, tantalum alloys, zirconium, zirconium alloys, tin, tin alloys, indium, indium alloys, zinc, or zinc The alloy is formed.

In one embodiment of the plated metal substrate of the present invention, the metal substrate is made of a copper alloy, aluminum, aluminum alloy, iron, iron alloy, stainless steel, nickel alloy, titanium, titanium alloy, zinc, or zinc alloy. Formed.

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

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

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

In one embodiment of the plated metal substrate of the present invention, the metal substrate has two major surfaces, and the plating layer is provided on one or both sides thereof.

In yet another aspect of the invention, a metal foil with a carrier is one of the carriers The surface or both sides have a carrier metal foil with an intermediate layer and an extremely thin metal layer, and the extremely thin metal layer is a metal substrate to which the invention is applied.

In one embodiment of the metal foil with a carrier of the present invention, the intermediate layer and the ultra-thin metal layer are sequentially provided on one surface of the carrier, and the roughened layer is provided on the other surface of the carrier.

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

In still another aspect of the invention, a connector is provided with the plated metal substrate of the present invention.

In still another aspect of the invention, a terminal is provided with the plated metal substrate of the present invention.

In still another aspect of the invention, a laminated board is produced by laminating a metal substrate to be plated of the invention or a metal foil with a carrier of the invention and a resin substrate.

Still another aspect of the invention is a masking tape or masking material comprising the laminated board of the present invention.

Still another aspect of the present invention is a printed wiring board comprising the laminated board of the present invention.

Still another aspect of the present invention is a metal working member comprising the plated metal substrate of the present invention or the metal foil with a carrier of the present invention.

Still another aspect of the present invention is an electronic or electrical machine comprising the plated metal substrate of the present invention or the metal foil with a carrier of the present invention.

In still another aspect of the invention, a method of manufacturing a printed wiring board includes a step of preparing a metal foil with an insulating substrate and an insulating substrate of the present invention; a step of laminating the metal foil with a carrier and an insulating substrate; and laminating the metal foil with the insulating substrate after the carrier is laminated The step of stripping the carrier of the foil forms a metal-clad laminate, and thereafter, the step of forming the circuit is performed by any one of a semi-additive method, a subtractive method, a partial addition method, or a modified semi-additive method.

In still another aspect of the invention, a method of manufacturing a printed wiring board, comprising the steps of: forming a circuit on the side surface of the ultra-thin metal layer or the side surface of the carrier on the metal foil of the carrier of the present invention; a step of forming a resin layer on the side surface of the ultra-thin metal layer or the side of the carrier side of the metal foil with a carrier; a step of forming a circuit on the resin layer; and forming a circuit on the resin layer, a step of peeling off the carrier or the above-mentioned ultra-thin metal layer; and after peeling off the carrier or the ultra-thin metal layer, removing the ultra-thin metal layer or the carrier, thereby forming the surface of the ultra-thin metal layer or the carrier The step of burying the side surface of the circuit in the above resin layer is exposed.

In still another aspect of the invention, a bonded body is a bonded metal substrate of the present invention or a bonded metal foil and solder joint.

In one embodiment of the bonded body of the present invention, in solder and metal substrate A thermal diffusion layer containing Sn and Co exists in the bonding interface.

In still another aspect, the present invention provides a method of attaching a plated metal substrate or a carrier-attached metal foil to a conductive member, comprising the steps of: etching a metal substrate or attached to the present invention by etching a step of shape-working the carrier metal foil; and a step of bonding the portion having the plating layer of the obtained shaped metal substrate to the conductive member by welding.

Still another aspect of the present invention is an electronic component comprising the plated metal substrate of the present invention or a metal foil with a carrier.

Still another aspect of the present invention is an autofocus module comprising the plated metal substrate of the present invention or a metal foil with a carrier as a spring material.

According to still another aspect of the present invention, an autofocus camera module is a spring member made of a metal substrate with a plated surface and elastically biased at an initial position in the optical axis direction of the lens or a spring member with a carrier metal foil and an autofocus camera module that generates an electromagnetic driving means for driving the lens in the optical axis direction against an electromagnetic force acting against the force of the spring member, and the electromagnetic driving means includes a coil. The spring member is joined to the coil by welding at a portion having the plating layer.

[Effects of the Invention]

The metal substrate to which the plating of the present invention is excellent in solder adhesion is used although a metal substrate having insufficient solder adhesion is used. Therefore, it is also suitable to be connected to various conductive members by soldering. Further, the plated metal substrate according to the present invention can have improved weather resistance, and is therefore suitable for use in harsh environments such as high temperature and high humidity. By making the plating layer contain Co, it is suitable for the shape processing including the step of circuit formation by etching, and utilizing such a special The plated metal substrate of the present invention can be preferably used for circuit formation by etching, and then used for connection by soldering with electronic parts, for example, as a conductive material for printed circuit boards. In addition, it can be preferably used as a material for electronic components such as switches, connectors (especially FPC connectors for forks that do not require severe bending workability), autofocus camera modules, sockets, terminals, relays, and the like.

[Metal substrate]

The metal substrate used in the present invention contains a material selected from the group consisting of Ti, Si, Mg, P, Sn, Zn, Cr, Zr, V, Na, Ca, Ba, Cs, Mn, K, Ga, B, Nb, Ce, 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 One or two or more elements of the group consisting of Al. These elements are elements which have high reactivity with oxygen at normal temperature, and are elements which suppress the solder adhesion of a metal substrate. Specifically, these elements are in the Ellingham diagram of oxides (for example, refer to "Japan Iron and Steel Association, "The 3rd Edition of the Iron and Steel Handbook, Volume I Foundation", 1983, Maruzen Stock The standard production free energy ΔG° of the solid oxide in the company ") is -500 kJ/mol O ₂ or less at a temperature of 300 K.

In the metal base material to be used in the present invention, it is preferable that the above-mentioned effects of the present invention are contained in an amount of 0.0001% by mass or more, and the above-mentioned element having a high reactivity with oxygen is contained, and it is more preferable to contain 0.005 mass%. Further, the above-mentioned element having high reactivity with oxygen is more preferably contained in an amount of 0.007% by mass or more of the element having high reactivity with oxygen, and more preferably 0.01% by mass or more of the above-mentioned reactivity with oxygen. Further, it is more preferable that the element further contains 0.02% by mass or more of the above-mentioned element having high reactivity with oxygen. Further, the metal substrate used in the present invention may be an element having a high reactivity with oxygen as described above, but in order to make the metal base The reactivity of the material with oxygen is lowered, and the solder adhesion is further improved. It is preferable that the above-mentioned element having a high reactivity with oxygen is contained in a total amount of 100% by mass or less, and preferably less than 100% by mass of the above-mentioned reactivity with oxygen is high. It is more preferable that the element having a high reactivity with oxygen is contained in an amount of 99% by mass or less, and more preferably 95% by mass or less of the element having high reactivity with oxygen, and more preferably 90% by mass or less. Further, the element having high reactivity with oxygen is more preferably contained in an amount of 85% by mass or less of the element having high reactivity with oxygen, and more preferably 50% by mass or less of the above-mentioned reactivity with oxygen. Further, it is more preferable that the element further contains 40% by mass or less of the element having high reactivity with oxygen, and more preferably contains 30% by mass or less of the element having high reactivity with oxygen, and more preferably 20% by mass or less. Further, the element having high reactivity with oxygen is more preferably contained in an amount of 10% by mass or less of the above-mentioned element having high reactivity with oxygen.

Examples of the metal substrate usable 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, and the like. Chromium alloy, magnesium, magnesium alloy, tungsten, tungsten alloy, molybdenum alloy, lead alloy, niobium, tantalum alloy, zirconium, zirconium alloy, tin, tin alloy, indium, indium alloy, zinc, or zinc alloy, etc., and thus can also be used Known metal materials. In addition, a metal material such as a JIS standard or a CDA may 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, it may be any of an electrolytic copper alloy foil and a rolled copper alloy foil. In addition, the copper alloy foil may be a copper alloy foil suitable for producing an electronic component in which a copper alloy foil and a resin substrate are bonded to each other to form a laminate, which is removed by etching to form a circuit. The thickness of the copper alloy foil is not particularly limited, and for example, it can be appropriately adjusted to a thickness suitable for different uses. For example, it can be set to 1~5000 About μm or about 2 to 1000 μm, especially when used to form a circuit, the thickness is 35 μm or less, and as a mask tape, it is a thin copper alloy foil of 18 μm or less. Therefore, it is used as an electronic or electrical machine. In the case of a connector or a cover material, a cover, a spring, etc., it can also be applied to a thick material of 70 to 1000 μm, and the thickness of the upper limit is not particularly specified.

The copper alloy may be a copper alloy containing one or more of Sn, Cr, Fe, In, P, Si, Ti, Zn, B, Mn, and Zr in a total amount of 0.001 to 4.0% by mass. Further, other elements may be contained, and the other elements include elements having low reactivity with oxygen such as Ag, Au, Co, Ni, and Te.

Examples of the copper alloy include titanium copper, phosphor bronze, Carson alloy, red brass, brass, zinc white copper, and other copper alloys. Further, as the copper alloy, copper or copper alloys specified in JIS H 3100 to JIS H3510, JIS H 5120, JIS H 5121, JIS C 2520 to JIS C 2801, and JIS E 2101 to JIS E 2102 can be used in the present invention. . Further, as long as it is not specifically described in the present specification, the JIS standard listed for indicating the metal standard means the JIS standard of the 2001 edition.

The titanium copper is typically composed of a composition containing 0.5 to 5.0% by mass of Ti and the balance being composed of copper and unavoidable impurities. The titanium copper may further contain one or more of Fe, Co, V, Nb, Mo, B, Ni, P, Zr, Mn, Zn, Si, Mg, and Cr in a total amount of 2.0% by mass or less.

Regarding phosphor bronze, typically, phosphor bronze refers to a copper alloy containing copper as a main component and containing Sn and P having a mass less than Sn. As an example, phosphor bronze has a composition containing 3.5 to 11% by mass of Sn, 0.03 to 0.35% by mass of P, and the balance being composed of copper and unavoidable impurities. The phosphor bronze may further contain an element such as Ni or Zn in a total amount of 1.0% by mass or less.

The Carson alloy is typically added with an element (for example, any one of Ni, Co, and Cr) which forms a compound with Si in addition to Si, and a second phase particle in the parent phase. A copper alloy precipitated in the form. As an example, the Carson alloy has a composition containing 1.0 to 5.0% by mass of Ni, 0.2 to 1.6% by mass of Si, and the balance being composed of copper and unavoidable impurities. As another example, the Carson alloy has a composition containing 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, and the balance being composed of copper and unavoidable impurities. As still another example, the Carson alloy has a composition containing 1.0 to 5.0% by mass of Ni, 0.2 to 1.6% by mass of Si, and 0.1 to 3.5% by mass of Co, and the balance being composed of copper and unavoidable impurities. As still another example, the Carson alloy has the following composition: 1.0 to 5.0% by mass of Ni, 0.2 to 1.6% by mass of Si, 0.1 to 3.5% by mass of Co, 0.03 to 0.5% by mass of Cr, and the balance being copper and Inevitable impurities constitute. As still another example, the Carson alloy has a composition containing 0.2 to 1.6% by mass of Si, 0.1 to 3.5% by mass of Co, and the balance being composed of copper and unavoidable impurities. Other elements (for example, Mg, Sn, B, Ti, Mn, Ag, P, Zn, As, Sb, Be, Zr, Al, and Fe) may be optionally added to the Carson alloy. These other elements are usually added to a total of about 4.0% by mass. For example, as another example, the Carson alloy has a composition of 1.0 to 5.0% by mass of Ni, 0.2 to 1.6% by mass of Si, 0.01 to 2.0% by mass of Sn, and 0.01 to 2.0% by mass of Zn, and the remainder is Copper and inevitable impurities.

In the present invention, the term "red brass" means an alloy of copper and zinc, and contains 1 to 20% by mass of zinc, more preferably 1 to 10% by mass of zinc. In addition, the red brass may also contain 0.1 to 1.0% by mass of tin.

In the present invention, the term "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. It is preferably 45 mass% or less or 40 mass% or less.

In the present invention, zinc white copper refers to a copper alloy containing copper as a main component and containing 60% by mass to 75% by mass of copper, 8.5% by mass to 19.5% by mass of nickel, and 10% by mass to 30% by mass of zinc. .

In the present invention, the other copper alloys include one or more of Zn, Sn, Mg, Fe, Si, P, Mn, Zr, Cr, and Ti in a total amount of 8.0% by mass or less, and optionally It contains 20% by mass or less of other elements, or optionally contains 10% by mass or less of other elements, and the remainder is composed of unavoidable impurities and copper copper alloy. Further, the other elements are not particularly limited, and may be an element having low reactivity with oxygen such as Ni or Co.

As the aluminum and the aluminum alloy, for example, 40% by mass or more of Al or 80% by mass or more of Al or 99% by mass or more of Al and aluminum 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 or aluminum alloy represented by Al: 99.00% by mass or more represented by aluminum alloy numbers 1085, 1080, 1070, 1050, 1100, 1200, 1N00, and 1N30 specified by JIS H 4000 can be used.

As the nickel alloy, for example, a nickel alloy containing 40% by mass or more of Ni or 80% by mass or more of Ni or 99.0% by mass or more of Ni can be used. For example, a nickel alloy specified in JIS H 4541 to JIS H 4554, JIS H 5701, JIS G 7604 to JIS G 7605, and JIS C 2531 can be used as long as the element having high reactivity with oxygen is contained. Further, for example, a nickel alloy represented by Alloy No. NW2200 described in JIS H4551 and Ni: 99.0% by mass or more represented by NW2201 can be used.

As iron and iron alloys, for example, stainless steel, mild steel, carbon steel, iron-nickel alloy can be used. Gold, steel, etc. 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, and SUS 631 (all JIS standards) can be used. As the mild steel, soft steel having a carbon content of 0.15% by mass or less can be used, and mild steel described in JIS G3141 can be used. The iron-nickel alloy contains 35 to 85% by mass of Ni, and the remainder is composed of Fe and unavoidable impurities. Specifically, an iron-nickel alloy described in JIS C2531 or the like can be used.

As the zinc and the zinc alloy, for example, zinc or a zinc alloy containing 40% by mass or more of Zn or 80% by mass or more of Zn or 99.0% by mass or more of Zn 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, it is possible to use, for example, Pb containing 40% by mass or more, Pb containing 80% by mass or more, or Pb containing 99.0% by mass or more, as a condition of containing the above-mentioned element having high reactivity with oxygen. alloy. For example, lead or lead alloys as specified in JIS H 4301 to JIS H 4312 or JIS H 5601 can be used.

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

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

The molybdenum alloy may contain, for example, 40% by mass or more of Mo or 80% by mass or more of Mo, or an element having a high reactivity with oxygen as described above. A molybdenum alloy containing 99.0% by mass or more of Mo.

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

For the tantalum and niobium alloy, for example, Ta containing 40% by mass or more, Ta containing 80% by mass or more, or Ta containing 99.0% by mass or more of Ta and a niobium alloy can be used. For example, niobium and tantalum alloys as specified in JIS H 4701 can be used.

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

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

As the indium and the indium alloy, for example, 40% by mass or more of In, 80% by mass or more of In, or 99.0% by mass or more of In and Indium alloys can be used.

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

The silver alloy may be a silver alloy containing 40% by mass or more of Ag, 80% by mass or more of Ag, or 99.0% by mass or more of Ag, as long as the element having a high reactivity with oxygen is used. .

The gold alloy may contain, for example, 40% by mass or more of Au, 80% by mass or more of Au, or the like, as long as it contains the above-mentioned element having high reactivity with oxygen. There is a gold alloy of Au of 99.0% by mass or more.

The so-called platinum group is a general term for ruthenium, rhodium, palladium, osmium, iridium and platinum. As the platinum group alloy, for example, an element having a high reactivity with oxygen can be used. For example, at least one element selected from the group consisting of Pt, Os, Ru, Pd, Ir, and Rh can be used. 40% by mass or more, or 80% by mass or more, or 99.0% by mass or more of a platinum group alloy.

The shape of the metal substrate used in the present invention is not particularly limited, and it can be processed into the shape of the final electronic component, or the state in which the press working is partially completed. It may be in the form of a plate or a foil without performing shape processing. In the case of "pre-plating" in which plating is performed before the shape processing, in the case where the untreated portion of the plating remains after the press working, and the "post-plating" of the plating after the shape processing is performed, Although the entire surface may be subjected to a plating treatment, it is only necessary to appropriately determine the surface treatment stage in which the surface treatment is performed while maintaining the balance with the portion to be plated.

[plating]

In one embodiment, the plated metal substrate of the present invention has an alloy plating layer selected from a Co plating layer and an element containing two or more elements selected from the group consisting of Co, Ni, and Mo on the surface of the metal substrate. The coating in the group formed. An alloy plating layer containing two or more elements selected from the group consisting of Co, Ni, and Mo, and in a typical embodiment, is selected from the group consisting of a Co-Ni alloy plating layer, a Co-Mo alloy plating layer, a Ni-Mo alloy plating layer, and Co. - a group consisting of Ni-Mo alloy coatings.

The total adhesion amount of Co, Ni, and Mo in the plating layer is 500 μg/dm ² or more, whereby the adhesion strength and weather resistance between the metal substrate and the solder are improved. Further, by containing Co in the plating layer, an effect of improving etching properties can be obtained. Although it is not intended to limit the present invention by theory, it is presumed that Ni, Co, and Mo have low reactivity with oxygen, and it is difficult to form an oxide. Further, Sn, which is a main component of the solder, is easily thermally diffused at the time of soldering. Therefore, the effect of improving the adhesion strength or weather resistance of the solder is apparent.

The above coating layer of Co, Ni and Mo, the total deposition amount is preferably 700μg / dm ² or more, preferably 1000μg / dm ² or more, preferably 2000μg / dm ² or more, preferably 3000μg / dm ² or more, preferably 5000μg / dm ² or more, more preferably 7000 μg/dm ² or more, and more preferably 8000 μg/dm ² or more. On the other hand, even if the total adhesion amount of Co, Ni, and Mo is excessively increased, there is a tendency that the cost becomes high and the effect is saturated. In addition, it also has an adverse effect on the etching property. Therefore, from the viewpoint of ensuring excellent etching properties, the total adhesion amount of Co, Ni, and Mo is preferably 90,000 μg/dm ² or less, and more preferably 55,000 μg/dm ² or less.

In addition to ensuring 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, and specifically, it is preferable to compare the plating layers. The total adhesion amount of Ni and Mo (hereinafter also referred to as "Ni + Mo ratio (%)") in the total adhesion amount of Co, Ni, and Mo is 80% by mass or less, and more preferably 60% by mass or less. More preferably, it is 50 mass % or less. Among them, if the Ni+Mo ratio (%) is too low, the weather resistance is adversely affected, and Co is a high-priced metal. Therefore, if it is a separate plating layer of Co, the cost becomes high. Therefore, the Ni+Mo ratio (%) in the plating layer is preferably more than 0% by mass, more preferably 1% by mass or more, and still more preferably, in consideration of solder adhesion, weather resistance, etching property, and economy. It is 2% by mass or more, more preferably 10% by mass or more, and still more preferably 20% by mass or more.

According to the above explanation, if the adhesion amount mentioned elements of the coating, the deposition amount of Co ensures viewpoint of etching resistance, it is preferred 180μg / dm ² or more, more preferably 250 μg / dm ² or more, more preferably 360μg A / dm ^2, more preferably 720μg / dm ² or more, more preferably 1080μg / dm ² or more, still more preferably 1800μg / dm ² or more, still more preferably 3000 [mu A / dm ^2, still more preferably 4200μg / dm ² or more, and even more It is preferably 4800 μg/dm ² or more. In addition, the adhesion amount of Co is preferably 108,000 μg/dm ² or less, more preferably 54000 μg/dm ² or less, and still more preferably 33,000 μg/dm ² or less from the viewpoint of weather resistance and economy.

Ni and Mo, the total deposition amount of ensuring the viewpoint of weather resistance, it is preferred over 0μg / dm ^2, more preferably 120μg / dm ² or more, still more preferably 170μg / dm ² or more, still more preferably 240μg / dm ² or more, and more preferably 480μg / dm ² or more, still more preferably 720μg / dm ² or more, still more preferably 1200μg / dm ² or more, still more preferably 2000μg / dm ² or more, still more preferably 3200μg / dm ² or more. In addition, the total adhesion amount of Ni and Mo is preferably 72,000 μg/dm ² or less, more preferably 36,000 μg/dm ² or less, and still more preferably 22,000 μg/dm ² or less from the viewpoint of etching property. Ni has similar properties to Mo, but Mo is more excellent in weather resistance. On the other hand, Mo etching property is liable to be deteriorated. Therefore, from the viewpoint of balance between weather resistance and etching property, Ni and Mo are preferably coexistent. For example, the content ratio of Ni to Mo in the plating layer may be set to Ni:Mo=10:0 to 0:10, preferably Ni:Mo=9:1 to 1:9, more preferably Ni:Mo=8. 2~2:8, and more preferably Ni:Mo=6:4~4:6.

Further, 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 may contain unavoidable impurities, respectively. Further, other elements may be contained in the plating layer within the range not impairing the object of the present invention. Therefore, in the present invention, the Co plating layer means a plating layer in which Co accounts for 50% by mass or more. Typically, the Co concentration in the Co plating layer is 60% by mass or more, more typically 80% by mass or more, and more typically 90% by mass or more, and more typically 98% by mass or more. ,and also It can be set to 100% by 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 accounts for 50% by mass or more. Typically, the total concentration of Co and Ni in the Co—Ni alloy plating layer is 60% by mass or more, more typically 80% by mass or more, and still more typically 90% by mass or more, and more typically In other words, it is 98% by mass or more, and may be 100% by 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 accounts for 50% by mass or more. Typically, the total concentration of Co and Mo in the Co-Mo alloy plating layer is 60% by mass or more, more typically 80% by mass or more, and still more typically 90% by mass or more, and more typically In other words, it is 98% by mass or more, and may be 100% by 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 accounts for 50% by mass or more. Typically, the total concentration of Ni and Mo in the Ni-Mo alloy plating layer is 60% by mass or more, more typically 80% by mass or more, and still more typically 90% by mass or more, and more typically In other words, it is 98% by mass or more, and may be 100% by 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 accounts for 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 mass or more, more typically 80% by mass or more, and still more typically 90% by mass or more. More specifically, it is 98% by mass or more, and may be 100% by mass.

Examples of the elements other than Co, Ni, and Mo which may be contained in the plating layer include an element having a low reactivity with oxygen at a normal temperature, that is, an Ehringham graph having an oxide (for example, refer to "Japan Corporation" The standard free energy ΔG° of solid oxides in the Steel Association, “The 3rd Edition of the Iron and Steel Handbook Volume I Foundation, 1983, Maruzen Co., Ltd.” is -440kJ/mol O ₂ at a temperature of 300K. The above elements of the oxide. For example, the plating layer may contain a group 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 of the elements. In this case, for example, the adhesion amount of these elements in the plating layer may be set to 0 to 2000 μg/dm ^{2 in} total, and typically may be set to 0 to 1000 μg/dm ² , and more typically, it may be set to 0~500μg/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, for example, the adhesion amount of these elements in the plating layer may be set to 0 to 2000 μg/dm ^{2 in} total, and typically may be set to 0 to 1000 μg/dm ² , and more typically, it may be set to 0 ~ 500μg / dm ^2.

The above plating layer may also be formed on part or all of the metal substrate. Further, a plating layer may be formed on one or both sides of the main surface of the metal substrate. In one embodiment of the plated metal substrate of the present invention, the metal substrate may be provided in the form of a foil, and the plating layer may be formed on one surface or both main surfaces of the metal foil. The plating layer can be obtained, for example, by wet plating such as electroplating, electroless plating, or immersion plating. From the viewpoint of cost, electroplating is preferred.

A base layer may be provided between the metal substrate and the plating layer as long as it does not interfere with the plating of Co or an alloy plating function of two or more elements selected from the group consisting of Co, Ni, and Mo. The base layer is not limited, and examples thereof include 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, a Cu-Ni plating layer, and a Ni-W layer. Plating, Ni-W-Sn plating, Cu-As plating, Cu-W plating, Cu-W-As plating, precious metal (Au, Ag, platinum group element) plating, chromate treatment layer, decane coupling agent treatment layer, etc. The base layer formed.

A roughening treatment layer may be provided between the metal substrate and the plating layer, and a matte finish by etching or polishing or a glossing process by smooth plating or the like may be performed. By these processes, the gloss of the process can be easily adjusted. In the case of low gloss, there are The following preferred effect: as a whole, it becomes an opaque color tone, and exhibits a calm atmosphere. Further, in the case where the gloss is high, there is a preferable effect that the whole is brilliant, bright, and gives the viewer an impression of refreshing.

In the outermost layer on the plating layer, in order to improve the rust preventing effect, a layer treated with a chromium layer or a chromate layer and/or a decane coupling agent may be further formed within a range that does not adversely affect solder adhesion. The rust-preventing treatment layer is formed. Further, in the case where the chromate-treated layer is formed under the chromate treatment conditions which are generally used, since the thickness is extremely thin, the solder adhesion is not adversely affected.

The layered side of the plated metal substrate of the present invention or the side opposite to the plated layer can be bonded to the resin substrate to produce a laminate such as a mask tape or a mask. Further, if necessary, the plated metal substrate can be further processed to form an electric circuit, thereby producing a printed wiring board or the like. As the resin substrate, for example, for rigid PWB use, paper substrate phenol resin, paper substrate epoxy resin, synthetic fiber cloth substrate epoxy resin, glass cloth-paper composite substrate epoxy resin, glass cloth-glass can be used. A woven composite base material epoxy resin, a glass cloth base material epoxy resin, etc., as a FPC use or a tape use, a polyester film, a polyimine film, a liquid crystal polymer (ICP) film, a PET film, etc. can be used. Further, in the present invention, the "printed wiring board" also includes a printed wiring board on which components are mounted, a printed circuit board, and a printed circuit board. Further, two or more printed wiring boards of the present invention may be connected to each other to manufacture a printed wiring board in which two or more printed wiring boards are connected, and at least one printed wiring board of the present invention and another inventive invention may be used. The printed wiring board or the printed wiring board not belonging to the printed wiring board of the present invention is connected, and an electronic or electrical device can be manufactured using the printed wiring board. Further, in the present invention, the "copper circuit" also includes copper wiring.

In addition, the plated metal substrate of the present invention can be used for a heat dissipation plate, a structural plate, a mask material, A metal working member such as a heat sink is produced by a mask, a reinforcing material, a cover, an outer casing, a casing, a casing, and the like. That is, the metal substrate to be plated is a concept including a heat dissipation plate, a structural plate, a masking material, a masking plate, a reinforcing material, a cover, an outer casing, a casing, and a casing. In addition, the metal substrate coated with the present invention is used for the heat dissipating plate, the structural plate, the masking material, the masking plate, the reinforcing material, the outer cover, the outer casing, the casing, the casing, and the like to form a metal working member. This metal working member is used for an electronic or electrical machine.

The plated metal substrate of the present invention, in the above applications, can be particularly preferably used in the case of performing a shape processing on a metal substrate to be plated by etching, and borrowing a portion having a plating layer by etching The shaped product and the conductive member are joined by welding. Accordingly, the present invention provides, in one aspect, a bonded metal substrate of the present invention or a bonded metal foil and solder joint. In one embodiment of the joined body of the present invention, a thermal diffusion layer containing Sn-Co is present at a joint interface between the solder and the metal substrate or the metal foil with a carrier. The heat diffusion layer can be formed by dispersing Co contained in the plating layer on the surface of the metal substrate and Sn contained in the solder by mutual heat during soldering. Although the present invention is not intended to be limited by theory, it is considered that the adhesion to solder is improved by the thermal diffusion layer.

[with carrier metal foil]

The metal foil with a carrier according to another embodiment of the present invention has an intermediate layer or an extremely thin metal layer on one side or both sides of the carrier. Further, the above-mentioned plated metal substrate can be used as the above-mentioned extremely thin metal layer. In this case, in the case where etching is performed in the subsequent circuit formation and further welding is performed, the plating layer is preferably formed on at least the surface to be welded of the metal substrate. The surface to be welded may vary depending on the circuit forming process. The surface to be welded may be the surface side of the very thin metal layer opposite to the intermediate layer, or may be the surface of the very thin metal layer opposite to the intermediate layer. The surface on the opposite side can also be the above two surfaces.

<carrier>

The carrier which can be used in the present invention is typically a metal foil or a resin film such as a copper foil, a copper alloy foil, a nickel foil, a nickel alloy foil, an iron foil, a ferroalloy foil, a stainless steel foil, an aluminum foil, an aluminum alloy foil, An insulating resin film (for example, a polyimide film, a liquid crystal polymer (LCP) film, a polyethylene terephthalate (PET) film, a polyamide film, a polyester film, a fluororesin film, or the like) is provided.

As the carrier which can be used in the present invention, copper foil is preferably used. The reason for this is that the copper foil has a high electrical conductivity, so that it becomes easy to form an intermediate layer and an extremely thin metal layer thereafter. The carrier is typically provided in the form of a rolled copper foil or an electrolytic copper foil. Generally, the electrolytic copper foil is produced by electrolyzing copper from a copper sulfate or a stainless steel drum, and the rolled copper foil is repeatedly produced by plastic working and heat treatment using a calender roll. As a material of the copper foil, in addition to high-purity copper such as refined copper or oxygen-free copper, for example, copper to which Sn is added, copper to which Ag is added, copper alloy to which Cr, Zr or Mg is added, or the like may be added. Copper alloy such as Nixon and other Cason copper alloys.

The thickness of the carrier which can be used in the present invention is not particularly limited, and may be appropriately adjusted to a thickness suitable for the purpose of the carrier, and may be, for example, 5 μm or more. However, if it is too thick, the production cost becomes high, and therefore it is usually preferably 35 μm or less. Therefore, the thickness of the carrier is typically 12 to 70 μm, and more typically 18 to 35 μm.

Further, as the carrier, an electrolytic copper foil produced by the following method can be used.

<electrolyte composition>

Copper: 90~110g/L

Sulfuric acid: 90~110g/L

Chlorine: 50~100ppm

Leveling agent 1 (bis(trisulphonyl) disulfide): 10~30ppm

Leveling agent 2 (amine compound): 10~30ppm

As the above amine compound, an amine compound of the following chemical formula can be used.

(In the above chemical formula, R ₁ and R ₂ are a group 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).

<Manufacturing conditions>

Current density: 70~100A/dm ²

Electrolyte temperature: 50~60°C

Electrolyte line speed: 3~5m/sec

Electrolysis time: 0.5 to 10 minutes (adjusted according to copper thickness and current density)

Further, a roughened layer may be provided on the surface of the carrier opposite to the surface on the side where the ultra-thin metal layer is provided. The roughening treatment layer may be provided by a known method, or the roughening treatment layer may be provided by the above-described roughening treatment. The case where the roughened layer is provided on the surface of the carrier opposite to the surface on the side where the ultra-thin metal layer is provided has the advantage that the carrier is self-having the roughened layer. When the surface side is laminated on a support such as a resin substrate, the carrier and the resin substrate are less likely to be peeled off.

<intermediate layer>

An intermediate layer is provided on the carrier. Other layers may also be provided between the carrier and the intermediate layer. The intermediate layer used in the present invention is not particularly limited as long as the intermediate metal layer is deposited on the insulating substrate before the step of laminating the carrier metal foil, and it is difficult to peel off from the carrier. After the step, the extremely thin metal layer becomes peelable from the carrier. For example, the intermediate layer of the metal foil with a carrier of the present invention may also contain a compound selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, these, hydrates thereof, and the like. One or more of a group consisting of an oxide and an organic substance. In addition, the intermediate layer may also be a plurality of layers.

Further, for example, the intermediate layer may be configured by forming one of the element groups selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn from the carrier side. a single metal layer of an element or an alloy layer containing one or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn, a hydrate or an oxide containing one or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn, Or a layer of organic matter.

Further, for example, the intermediate layer may be configured by forming one of the element groups selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn from the carrier side. a single metal layer of an element or an alloy layer containing one or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn, Forming thereon a single metal layer containing one element selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, or containing a material selected from the group consisting of Cr and Ni An alloy layer of one or more of the element groups consisting of Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn.

In addition, as the organic substance, a known organic substance can be used as the intermediate layer, and any one or two or more of a nitrogen-containing organic compound, a sulfur-containing organic compound, and a carboxylic acid are preferably used. For example, as a specific nitrogen-containing organic compound, it is preferred to use 1,2,3-benzotriazole, carboxybenzotriazole, N', N'-bis(benzotriazole) as a triazole compound having a substituent. Methyl)urea, 1H-1,2,4-triazole and 3-amino-1H-1,2,4-triazole, and the like.

As the sulfur-containing organic compound, mercaptobenzothiazole, sodium 2-mercaptobenzothiazole, trimeric thiocyanate, 2-benzimidazolethiol or the like is preferably used.

As the carboxylic acid, a monocarboxylic acid is particularly preferably used, and among them, oleic acid, linoleic acid, linoleic acid or the like is preferably used.

Further, for example, the intermediate layer may be formed by sequentially laminating a nickel layer, a nickel-phosphorus alloy layer or a nickel-cobalt alloy layer, and a chromium-containing layer on the carrier. The adhesion between nickel and copper is higher than the adhesion between chromium and copper, so that when the ultra-thin metal layer is peeled off, peeling occurs at the interface between the extremely thin metal layer and the chromium-containing layer. Further, for the nickel of the intermediate layer, it is expected to have a barrier effect of preventing the copper component from diffusing from the carrier to the extremely thin metal layer. Adhesion amount of the intermediate layer of nickel, preferably 100μg / dm ² or more and 40000μg / ² or less dm, more preferably 100μg / dm ² or more and 4000μg / ² or less dm, more preferably 100μg / dm ² or more and 2500μg / ² or less dm, more It is preferably 100 μg/dm ² or more and less than 1000 μg/dm ² , and the adhesion amount of chromium in the intermediate layer is preferably 5 μg/dm ² or more and 100 μg/dm ² or less. In the case where the intermediate layer is provided only on one side, it is preferable to provide a rustproof layer such as a Ni plating layer on the opposite side of the carrier. The chromium layer of the above intermediate layer can be provided by chrome plating or chromate treatment.

If the thickness of the intermediate layer becomes too large, the cost of forming the intermediate layer is increased. Therefore, the thickness of the intermediate layer is preferably from 1 to 1000 nm, preferably from 1 to 500 nm, preferably from 2 to 200 nm, preferably from 2 to 100 nm, more preferably from 3 to 3. 60nm. Furthermore, the intermediate layer can also be arranged on both sides of the carrier.

<very thin metal layer>

An extremely thin metal layer, i.e., a plated metal substrate of the present invention, may be disposed on the intermediate layer. Other layers may also be provided between the intermediate layer and the very thin metal layer. The thickness of the ultra-thin metal layer is not particularly limited, but is usually thinner than the carrier, for example, 35 μm or less, and is, for example, 12 μm or less. Typically, it is from 0.5 to 12 μm, and more typically from 1.5 to 5 μm. Further, before the ultra-thin metal layer is provided on the intermediate layer, pre-plating using a copper-phosphorus alloy or the like may be performed to reduce pinholes of the ultra-thin metal layer. In the pre-plating, a copper pyrophosphate plating solution or the like can be mentioned. In addition, very thin metal layers can also be provided on both sides of the carrier. The ultra-thin metal layer may be composed of a 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, An extremely thin metal layer of a metal such as a lead alloy, tantalum, niobium alloy, tin, tin alloy, indium, indium alloy, zinc, or zinc alloy, or an extremely thin metal layer composed of the above metal, and further may be used A known metal material is used as an extremely thin metal layer. Further, a metal material specified by JIS standard or CDA or the like can also be used as the extremely thin metal layer. Further, it is preferable to use an extremely thin copper alloy layer as an extremely thin metal layer. The reason is that the extremely thin copper alloy layer has a high electrical conductivity and is suitable for circuits and the like.

Further, the ultra-thin metal layer of the present invention can be produced by forming the electroplated metal layer under the following conditions, and then providing the above-mentioned plating layer thereon, or by providing the above-mentioned plating layer on the intermediate layer, on which the following is It is produced by forming a plated metal layer under the conditions.

. Electrolyte composition

Copper concentration: 80~130g/L

Select 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, Lu, Yb, Dy, Er, Pr, The concentration of each element of one or more elements of the group consisting of Y, Li, Gd, Pu, In, Fe, La, Th, Ta, U, Sm, Tb, Sr, Tm, and Al: 0.001~ 30g/L

Sulfuric acid concentration: 80~120g/L

Chloride ion concentration: 30~100ppm

In addition, a leveling agent or a glossing agent may be used as needed.

. Manufacturing conditions

Current density: 70~100A/dm ²

Electrolyte temperature: 50~80°C

Electrolyte line speed: 1.5~5m/sec

Electrolysis time: 0.5 to 10 minutes (adjusted according to thickness and current density of precipitation)

[Resin layer on plating]

The surface of the plating of the plated metal substrate of the present invention may also include a resin layer. The above resin layer may also be an insulating resin layer. Further, in the metal substrate to which the plating of the present invention is applied, the term "plating surface" means that the surface of the plating layer is subjected to surface treatment for providing a roughened layer, a heat-resistant layer, a rustproof layer, a weather resistant layer or the like. In this case, the surface of the plated metal substrate after the surface treatment is performed. In addition, in the case where the metal substrate to which the plating is applied is an extremely thin metal layer with a carrier metal foil, the term "plating surface" means that the roughening layer, the heat-resistant layer, the rust-proof layer, and the weathering are provided. In the case of surface treatment such as a layer, the surface of the extremely thin metal layer after the surface treatment is performed. Further, as the resin layer, a resin having light transmissivity is preferably used, and a resin having high light transmittance is more preferably used, and a transparent resin is more preferably used.

The resin layer may be an adhesive or an insulating resin layer in a semi-hardened state (B-stage state) to be used next. The semi-hardened state (B-stage state) includes the following state: When the surface is in contact with the finger, there is no stickiness, and the insulating resin layer can be stacked for storage, and if it is further subjected to heat treatment, a hardening reaction occurs.

The resin layer may be a resin for subsequent use, that is, an adhesive, or an insulating resin layer in a semi-hardened state (B-stage state) to be used next. The semi-hardened state (B-stage state) includes a state in which there is no stickiness even when the surface is touched by a finger, and the insulating resin layer can be stacked and stored, and if it is further subjected to heat treatment, a hardening reaction occurs.

Further, the resin layer may contain a thermosetting resin or a thermoplastic resin. Further, the above resin layer may contain a thermoplastic resin. The resin layer may contain a known resin, a resin curing agent, a compound, a curing accelerator, a dielectric, a reaction catalyst, a crosslinking agent, a polymer, a prepreg, a skeleton, and the like. In addition, as the above-mentioned resin layer, for example, International Publication No. WO2008/004399, International Publication No. WO2008/053878, International Publication No. WO2009/084533, Japanese Patent Laid-Open No. Hei No. 11-5828, Japanese Patent Laid-Open No. Hei 11-140281, Japanese Patent No. No. 3,184,485, International Publication No. WO97/02728, Japanese Patent No. 3676375, Japanese Patent Laid-Open No. 2000-43188, Japanese Patent No. 3612594, Japanese Patent Laid-Open No. 2002-179772, Japanese Patent Laid-Open No. 2002-359444, Japanese Patent Laid-Open No. 2003 -304068, Japanese Patent No. 3992225, Japanese Patent Laid-Open No. 2003-249739, Japanese Patent No. 4136509, Japanese Patent Laid-Open No. 2004-82687, Japanese Patent No. 4025177, Japanese Patent Laid-Open No. 2004-349654, Japanese Patent No. 4286060 Japanese Patent Laid-Open No. 2005-262506, Japanese Patent No. 4570070, Japanese Patent Laid-Open No. 2005-53218, Japanese Patent No. 3949676, Japanese Patent No. 4178415, International Publication No. WO2004/005588, Japanese Patent Publication No. 2006-257153, Japanese Patent Laid-Open No. 2007-326923, Japanese Patent Laid-Open No. 2008-111169, Japanese Patent No. 5024930, International Publication No. WO2006/028207, Japanese Patent No. 4828427, and Japanese Special Publication 2009-6 No. 7029, International Japanese Patent No. WO2006/134868, Japanese Patent No. 5046927, Japanese Patent Laid-Open No. 2009-173017, International Publication No. WO2007/105635, Japanese Patent No. 5180815, International Publication No. WO2008/114858, International Publication No. WO2009/008471, Japanese Patent Laid-Open Substances (resin, resin hardener, compound, hardening accelerator, etc.) described in No. 2011-14727, International Publication No. WO2009/001850, International Publication No. WO2009/145179, International Publication No. WO2011/068157, and Japanese Patent Publication No. 2013-19056 It is formed by a method of forming a dielectric material, a reaction catalyst, a crosslinking agent, a polymer, a prepreg, a skeleton, or the like, and/or a resin layer.

Further, the type of the resin layer is not particularly limited, and examples thereof include an epoxy resin, a polyimide resin, a polyfunctional cyanate compound, a maleimide compound, and a polymaleimide compound. Maleic imine resin, aromatic maleimide resin, polyvinyl acetal resin, urethane resin, polyether oxime (also known as polyethersulphone, polyethersulphone), polyether oxime (also known as polyether oxime) Polyethersulphone, polyethersulphone) resin, aromatic polyamide resin, aromatic polyamide resin polymer, rubber resin, polyamine, aromatic polyamine, polyamidimide resin, rubber modified epoxy resin, benzene Oxygen resin, carboxyl modified acrylonitrile-butadiene resin, polyphenylene ether, bismaleimide III Resin, thermosetting polyphenylene ether resin, cyanate resin, carboxylic anhydride, polycarboxylic acid anhydride, linear polymer having crosslinkable functional groups, polyphenylene ether resin, 2,2-bis(4-cyanide) Acid ester phenyl) propane, phosphorus phenol compound, manganese naphthenate, 2,2-bis(4-glycidylphenyl)propane, polyphenylene ether-cyanate resin, decane modified poly Amidoxime resin, cyanoester resin, phosphazene resin, rubber modified polyamidoximine resin, isoprene, hydrogenated polybutadiene, polyvinyl butyral, phenoxy, high One or two or more resins selected from the group consisting of a molecular epoxy group, an aromatic polyamine, a fluororesin, a bisphenol, a block copolymerized polyimide resin, and a cyanoester resin are preferred as the above resin layer. kind.

Further, the epoxy resin is a resin having two or more epoxy groups in the molecule, and can be used as long as it is an epoxy resin which can be used for electrical and electronic materials, and has no particular problem. Further, the epoxy resin is preferably an epoxy resin obtained by epoxidizing a compound having two or more glycidyl groups in the molecule. In addition, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a bisphenol AD type epoxy resin, a novolak type epoxy resin, and a cresol novolac type may be used. Epoxy resin, alicyclic epoxy resin, brominated epoxy resin, phenolic novolak epoxy resin, naphthalene epoxy resin, brominated bisphenol A epoxy resin, o-cresol novolac Epoxy resin, rubber modified bisphenol A epoxy resin, glycidylamine epoxy resin, triglycidyl isocyanurate, N, N-diglycidylamine and other glycidylamine compounds, four a glycidyl ester compound such as hydrogen phthalic acid diglycidyl ester, a phosphorus-containing epoxy resin, a biphenyl type epoxy resin, a biphenol novolak type epoxy resin, a trishydroxyphenylmethane type epoxy resin, a tetraphenyl group One type of the group of the ethane type epoxy resins may be used in combination of two or more kinds, or a hydride or a halide of the above epoxy resin may be used.

A well-known phosphorus-containing epoxy resin can be used as the above phosphorus-containing epoxy resin. Further, the phosphorus-containing epoxy resin is preferably, for example, an epoxy resin derived from 9,10-dihydro-9-oxa-10-phosphonium having two or more epoxy groups in the molecule. The form of the derivative of phenanthrene-10-oxide is obtained.

(When the resin layer contains a dielectric (dielectric filler))

The above resin layer may further contain a dielectric (dielectric filler).

When any of the above resin layers or resin compositions contains a dielectric (dielectric filler), it can be used for forming a capacitor layer, and the capacitance of the capacitor circuit is increased. For the dielectric (dielectric filler), BaTiO ₃ , SrTiO ₃ , Pb(Zr-Ti)O ₃ (commonly known as PZT), and PbLaTiO _{3 are used} . A dielectric powder of a composite oxide having a perovskite structure such as PbLaZrO (commonly known as PLZT) or SrBi ₂ Ta ₂ O ₉ (commonly known as SBT).

The dielectric (dielectric filler) can also be in powder form. In the case where the dielectric (dielectric filler) is in a powder form, the powder characteristics of the dielectric (dielectric filler) are preferably from 0.01 μm to 3.0 μm, preferably from 0.02 μm to 2.0 μm. range. In addition, when a photo is taken on a dielectric by a scanning electron microscope (SEM), and a straight line is drawn on the dielectric particles on the photo, the length of the straight line that crosses the dielectric particles is the longest. The length of a portion of the dielectric particles is set to the particle size of the dielectric. Further, the average value of the diameters of the particles of the dielectric in the measurement field of view is defined as the particle diameter of the dielectric.

The resin and/or resin composition and/or compound contained in the above resin layer is dissolved in, for example, methyl ethyl ketone (MEK), cyclopentanone, dimethylformamide, dimethylacetamide, N- Methylpyrrolidone, toluene, methanol, ethanol, propylene glycol monomethyl ether, dimethylformamide, dimethylacetamide, cyclohexanone, ethyl stilbene, N-methyl-2-pyrrolidine A resin liquid (resin varnish) is prepared in a solvent such as ketone, N,N-dimethylacetamide or N,N-dimethylformamide, and the resin liquid is applied, for example, by a roll coating method or the like. On the surface of the roughened surface of the above-mentioned plated metal substrate, it is necessary to heat-dry and then remove the solvent to form a B-stage state. In the drying, for example, a hot air drying oven may be used, and the drying temperature may be 100 to 250 ° C, preferably 130 to 200 ° C. The solvent may be used to dissolve the composition of the above resin layer to form a resin solid content of from 3 wt% to 70 wt%, preferably from 3 wt% to 60 wt%, preferably from 10 wt% to 40 wt%, more preferably from 25 wt% to 40 wt%. Resin solution. Further, from the viewpoint of the environment, it is most preferable to use a mixed solvent of methyl ethyl ketone and cyclopentanone to dissolve at this stage. Further, as the solvent, a solvent having a boiling point of from 50 ° C to 200 ° C is preferably used.

Further, the resin layer is preferably a semi-cured resin film having a resin flow amount in the range of 5% to 35% when measured in accordance with MIL-P-13949G in the MIL standard.

In the present specification, the resin flow amount is based on MIL-P-13949G in the MIL standard, and four 10 cm square samples are taken from a plated metal substrate including a resin layer having a thickness of 55 μm. The state of the overlap (the layered body) is bonded at a pressurization temperature of 171 ° C, a pressurization pressure of 14 kgf / cm ² , and a pressurization time of 10 minutes, and the resin outflow weight is measured at this time, and based on the number 1, according to The value calculated from the obtained result.

The above-mentioned metal substrate including the plating of the resin layer is used in such a manner that after the resin layer is superposed on the substrate, the entire resin layer is thermocompression bonded to thermally cure the resin layer, and secondly, the metal plated with the plating is applied. In the case where the substrate is an extremely thin metal layer with a carrier metal foil, the carrier is peeled off to expose the extremely thin metal layer (of course, the surface of the intermediate layer side of the extremely thin metal layer is exposed), and the plating is self-attached. A surface of the metal substrate opposite to the side of the roughened side forms a specific wiring pattern.

When the metal substrate with the plating of the resin layer is used, the number of sheets of the prepreg used when manufacturing the multilayer printed wiring board can be reduced. Further, the thickness of the resin layer can be made such that the thickness of the interlayer insulation can be ensured, or the metal-clad laminate can be produced even if the prepreg material is not used at all. Further, at this time, the surface of the substrate may be coated with an insulating resin to further improve the smoothness of the surface.

In addition, without using a prepreg, it has the following advantages: saving pre- In addition, since the material cost of the immersion material is also simple, it is economically advantageous, and the thickness of the multilayer printed wiring board manufactured by only the thickness of the prepreg material is thinned, and one layer can be manufactured. An extremely thin multilayer printed wiring board having a thickness of 100 μm or less.

The thickness of the resin layer is preferably 0.1 to 120 μm.

If the thickness of the resin layer becomes thinner than 0.1 μm, there is a case where the force is lowered, and the plated metal substrate including the resin layer is laminated on the base including the inner layer without passing through the prepreg. In the case of a material, it becomes difficult to ensure interlayer insulation between the circuit and the inner layer. On the other hand, if the thickness of the resin layer is made thicker than 120 μm, it becomes difficult to form a resin layer of a target thickness by one coating step, which consumes an extra material cost and a number of steps, and thus becomes economically unfavorable.

Further, in the case where a metal substrate with a plating layer including a resin layer is used for producing an extremely thin multilayer printed wiring board, in order to make the thickness of the multilayer printed wiring board small, it is preferable to set the thickness of the above resin layer to 0.1 μm. ~5 μm, more preferably 0.5 μm to 5 μm, still more preferably 1 μm to 5 μm.

An example of the manufacturing steps of several printed wiring boards using the copper foil with a carrier of the present invention is shown below.

An embodiment of the method for producing a printed wiring board according to the present invention includes the steps of: preparing a metal foil with a carrier of the present invention and an insulating substrate, and stacking the metal foil with the insulating substrate; and The carrier-attached metal foil and the insulating substrate are laminated such that the ultra-thin metal layer side faces the insulating substrate, and then the metal-clad laminate is formed by peeling off the carrier with the carrier-attached metal foil, and thereafter, by semi-additive The steps of forming a circuit by any one of a method, a modified semi-additive method, a partial addition method, and a subtractive method. The insulating substrate may also be an insulating substrate to which an inner layer circuit is added.

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, and a pattern is formed, and a conductor pattern is formed by plating and etching.

Therefore, in an embodiment of the method for producing a printed wiring board of the present invention using a semi-additive method, the method comprises the steps of: preparing a metal foil with a carrier of the present invention and an insulating substrate; and insulating the metal foil with the carrier a step of laminating the substrate; and laminating the carrier-attached metal foil and the insulating substrate, and then peeling off the carrier with the carrier metal foil; and peeling off the carrier by etching or plasma etching using an acid or the like a step of completely removing the extremely thin metal layer; a step of providing a through hole or/and a blind hole in the resin exposed by removing the extremely thin metal layer by etching; for the region containing the through hole or/and the blind hole a step of removing the desmear; a step of providing an electroless plating layer for the region containing the resin and the through holes or/and the blind holes; a step of providing a plating resist on the electroless plating layer; and the plating resist Exposing, followed by a step of removing the plating resist in the region where the circuit is formed; and providing a plating layer in the region where the above-mentioned plating resist is removed Step; and removing the plating resist of the step; and the like by flash etching, present in the step of removing the non-plating area other than the area of the circuit is formed.

In another embodiment of the method for producing a printed wiring board of the present invention using a semi-additive method, the method comprises the steps of: preparing a metal foil with a carrier of the present invention and an insulating substrate; and the metal foil and the insulating substrate with the carrier a step of laminating; laminating the carrier-attached metal foil and the insulating substrate, and then peeling off the carrier of the carrier-attached metal foil; and peeling off the carrier by etching or plasma etching using an acid or the like Very thin metal layer a step of completely removing; a step of providing an electroless plating layer on a surface of the resin exposed by removing the ultra-thin metal layer by etching; a step of providing a plating resist on the electroless plating layer; and plating the plating a step of exposing the resist, and thereafter removing a plating resist in a region where the circuit is formed; a step of disposing a plating layer in the region where the plating resist is removed to form the circuit; and removing the plating resist And a step of removing the electroless plating layer and the extremely thin metal layer existing in the region outside the region where the circuit is formed by rapid etching or the like.

In the present invention, the modified semi-additive method refers to laminating a metal foil on an insulating layer, protecting a non-circuit forming portion by a plating resist, and performing copper plating thickening of the circuit forming portion by electroplating to remove the resist. A method of forming a circuit on an insulating layer by (fast) etching to remove a metal foil other than the above-described circuit forming portion.

Therefore, in one embodiment of the method for producing a printed wiring board of the present invention using the modified semi-additive method, the method comprises the steps of: preparing the metal foil with a carrier of the present invention and an insulating substrate; and the metal foil with the carrier a step of laminating the insulating substrate; and laminating the carrier-attached metal foil and the insulating substrate, and then removing the carrier of the carrier-attached metal foil; and providing a through-hole in the ultra-thin metal layer and the insulating substrate exposed by peeling the carrier; And a step of blinding the hole; performing a desmear treatment step on the region containing the through hole or/and the blind hole; and providing an electroless plating layer for the region including the through hole or/and the blind hole; peeling off the carrier And the step of providing a plating resist on the surface of the exposed ultra-thin metal layer; the step of forming a circuit by electroplating after the plating resist is disposed; the step of removing the plating resist; and by rapid etching, The step of removing the above-mentioned plating resist to expose the extremely thin metal layer.

Further, the step of forming a circuit on the resin layer may be a step of laminating another piece of metal foil with a carrier on the resin layer from the side of the ultra-thin metal layer, and bonding is used The above circuit is formed by attaching a carrier metal foil to the resin layer. Further, another sheet of the carrier-attached metal foil bonded to the above resin layer may be the metal foil with a carrier of the present invention. Further, the step of forming a circuit on the above resin layer can also be carried out by any one of a semi-additive method, a subtractive method, a partial addition method or a modified semi-additive method. Further, the carrier-attached metal foil on the surface forming circuit may have a substrate or a resin layer on the surface of the carrier of the carrier-attached metal foil.

In another embodiment of the method for producing a printed wiring board of the present invention using a modified semi-additive method, the method comprises the steps of: preparing a metal foil with a carrier of the present invention and an insulating substrate; and insulating the metal foil with the carrier a step of laminating the substrate; a step of laminating the carrier-attached metal foil and the insulating substrate, and then removing the carrier with the carrier metal foil; and a step of providing a plating resist on the extremely thin metal layer exposed by peeling the carrier; a step of exposing the plating resist, and thereafter forming a plating resist in a region where the circuit is formed; and a step of disposing a plating layer in the region where the plating resist is removed; forming the plating Step of removing the agent; removing the electroless plating layer and the ultra-thin metal layer existing in the region outside the region where the circuit is formed by rapid etching or the like.

In the present invention, the partial addition method is to apply a catalyst core to a substrate on which a conductor layer is provided, and a hole for a through hole or a via hole is required to be etched to form a conductor circuit, and a resistor is formed as needed. After the flux or the plating resist is applied, a method of manufacturing a printed wiring board by thickening a via hole or a via hole on the conductor circuit by electroless plating is used.

Therefore, in an embodiment of the method of manufacturing a printed wiring board of the present invention using a partial addition method, the method comprises the steps of: preparing a metal foil with a carrier of the present invention and an insulating substrate; and insulating the metal foil with the carrier a step of laminating the substrate; and laminating the carrier-attached metal foil and the insulating substrate, and then peeling off the carrier with the carrier metal foil; a step of providing a through hole or/and a blind hole in an extremely thin metal layer and an insulating substrate exposed from the carrier; a step of performing desmear treatment on a region including the through hole or/and the blind hole; and including the through hole or And a step of imparting a catalyst core to the region of the blind hole; a step of providing an etching resist on the surface of the extremely thin metal layer exposed by peeling off the carrier; and exposing the etching resist to form a circuit pattern; a method of etching an extremely thin metal layer and the catalyst core to form a circuit by etching or plasma etching of an acid or the like; a step of removing the etching resist; etching by etching an acid using an acid or the like a method of providing a solder resist or a plating resist on a surface of the insulating substrate exposed by removing the ultra-thin metal layer and the catalyst core by a method such as plasma; and an area in which the solder resist or plating resist is not provided Set the steps for the electroless plating.

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

Therefore, in another embodiment of the method for producing a printed wiring board of the present invention using the subtractive method, the method comprises the steps of: preparing the metal foil with a carrier of the present invention and an insulating substrate; and insulating the metal foil with the carrier a step of laminating the substrate; laminating the carrier with the carrier metal foil after laminating the carrier metal foil and the insulating substrate; and providing a through hole or/and a blind hole in the extremely thin metal layer and the insulating substrate exposed by peeling off the carrier a step of performing a desmear treatment on a region containing the above-mentioned through hole or/and a blind hole; a step of providing an electroless plating layer in a region containing the above-mentioned through hole or/and a blind hole; on the surface of the above electroless plating layer a step of providing a plating layer; a step of providing an etching resist on the surface of the plating layer or/and the ultra-thin metal layer; a step of exposing the etching resist to form a circuit pattern; and etching the solution by using an acid or the like Etching or plasma etching, removing the ultra-thin metal layer and the electroless plating layer and the plating layer to form a circuit; and etching the same The step of removing the resist.

In another embodiment of the method for producing a printed wiring board of the present invention using the subtractive method, the method comprises the steps of: preparing a metal foil with a carrier of the present invention and an insulating substrate; and performing the metal foil with the carrier and the insulating substrate a step of laminating; after laminating the carrier-attached metal foil and the insulating substrate, the step of peeling off the carrier with the carrier metal foil; and providing a through hole or/and a blind hole in the extremely thin metal layer and the insulating substrate exposed by peeling off the carrier a step of performing desmear treatment on a region containing the above-mentioned through holes or/and blind vias; a step of providing an electroless plating layer on a region containing the above-mentioned through holes or/and blind via holes; forming a mask on the surface of the above electroless plating plating layer a step of providing a plating layer on a surface of the electroless plating layer on which the mask is not formed; a step of providing an etching resist on the surface of the plating layer or/and the ultra-thin metal layer; and exposing the etching resist a step of forming a circuit pattern; the ultra-thin metal layer and the electroless plating layer are removed by etching or plasma etching using an acid or the like And forming a circuit; and removing the etching resist.

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

Here, a specific example of a method of manufacturing a printed wiring board using the metal foil with a carrier of the present invention will be described in detail. Further, here, a carrier-attached metal foil having an extremely thin metal layer in which a roughened layer is formed is exemplified, but not limited thereto, and an ultrathin metal layer having no roughened layer is used. In the carrier metal foil, the following method for producing a printed wiring board can be similarly performed.

First, a carrier-attached metal foil (first layer) having an extremely thin metal layer having a roughened layer formed on its surface is prepared.

Next, a resist is applied on the roughened layer of the extremely thin metal layer to perform exposure and development. The resist is etched into a specific shape.

Next, after the plating for the circuit is formed, the resist is removed, thereby forming a circuit plating of a specific shape.

Next, a resin layer is laminated on the ultra-thin metal layer to cover the circuit plating layer (the method of burying the circuit plating layer), and secondly, the other carrier-attached metal foil (the second layer) is next to the ultra-thin metal layer. .

Next, the carrier is peeled off from the carrier metal foil of the second layer.

Next, a laser opening is performed at a specific position of the resin layer to expose the circuit plating layer to form a blind hole.

Next, copper is buried in the blind hole to form a via filler.

Next, a circuit plating layer is formed on the via filler as described above.

Next, the carrier was peeled off from the carrier metal foil of the first layer.

Next, the extremely thin metal layers of the two surfaces are removed by rapid etching to expose the surface of the circuit plating layer in the resin layer.

Next, a bump is formed on the circuit plating layer in the resin layer, and a copper pillar is formed on the solder. A printed wiring board using the metal foil with a carrier of the present invention was produced in the above manner.

The above-mentioned another metal foil with a carrier (second layer) may be a metal foil with a carrier of the present invention, or a conventional metal foil with a carrier may be used, and a usual metal foil may be used. Further, one or more circuits may be further formed on the circuit of the second layer, or may be performed by any one of a semi-additive method, a subtractive method, a partial addition method, or a modified semi-additive method. The circuit is formed.

Further, a well-known resin or prepreg can be used as the embedded resin (RESIN). For example, BT (Bismaleimide III) can be used. A resin or a prepreg impregnated with a glass cloth impregnated with a BT resin, ABF film or ABF manufactured by Ajinomoto Fine Chemical Co., Ltd. Further, as the above-mentioned embedded resin (RESIN), the resin layer and/or the resin and/or the prepreg described in the present specification can be used.

Further, the carrier-attached metal foil used in the first layer may have a substrate or a resin layer on the surface of the carrier-attached metal foil. By having the substrate or the resin layer and supporting the carrier-attached metal foil used for the first layer, wrinkles are less likely to occur, and there is an advantage in that productivity is improved. Further, the substrate or the resin layer may be any substrate or resin layer as long as it functions as a substrate or a resin layer that supports the effect of the carrier-attached metal foil used for the first layer. For example, a carrier, a prepreg, a resin layer, or a known carrier, a prepreg, a resin layer, a metal plate, a metal foil, a plate of an inorganic compound, a foil of an inorganic compound, or a plate of an organic compound can be used as described in the specification of the present application. A foil of an organic compound is used as the above substrate or resin layer.

The metal substrate to which the plating of the present invention is applied can be bonded to the resin substrate from the side of the plating layer to produce a laminate. The resin substrate is not particularly limited as long as it has a property applicable to a printed wiring board or the like. For example, for rigid PWB use, a paper substrate phenol resin, a paper substrate epoxy resin, a synthetic fiber cloth substrate can be used. Epoxy resin, fluororesin impregnated cloth, glass cloth-paper composite substrate epoxy resin, glass cloth-glass non-woven composite substrate epoxy resin and glass cloth substrate epoxy resin, etc., for flexible printed circuit board (FPC) For the purpose, a polyester film or a polyimide film, a liquid crystal polymer (LCP) film, a fluororesin, and a fluororesin-polyimine composite material can be used. Further, since the liquid crystal polymer (LCP) has a small dielectric loss, it is preferable to use a liquid crystal polymer (LCP) film for a printed wiring board for high-frequency circuit use.

In the case of the rigid PWB application, the method of bonding is prepared by impregnating a resin with a base material such as a glass cloth to cure the resin to a semi-hardened state. By The copper foil is superposed on the prepreg and heated and pressurized. In the case of FPC, a substrate such as a liquid crystal polymer or a polyimide film is laminated under high temperature and high pressure via an adhesive or without an adhesive, followed by coating or drying the polyimide film or the polyimide precursor. , hardening, etc., whereby a laminate can be produced.

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, it can be applied to one-sided PWB, two-sided PWB, and multi-layer PWB (three or more layers). From the viewpoint of the kind of the insulating substrate material, it can be applied to rigid PWB, flexible PWB (FPC), and rigid-elastic PWB.

Finally, the case where the metal substrate to which the plating of the present invention is applied is applied to a spring material for an autofocus module will be described. A typical autofocus module includes a lens, a plated metal substrate of the present invention that elastically biases the lens toward an initial position in the optical axis direction, or a spring made of the carrier-attached metal foil of the present invention. The member and an electromagnetic driving means for generating an electromagnetic force against the urging force of the spring member to drive the lens in the optical axis direction. The electromagnetic driving means may include, for example, a U-shaped cylindrical yoke, a coil housed inside the inner peripheral wall of the yoke, and a magnet that is housed inside the peripheral wall of the yoke while being surrounded by the coil. . The spring member can be joined to the coil (typically, the wire of the coil) by welding at a portion having the plating layer described above. The structure of the autofocus module is known in the Japanese Patent Publication No. 2014-102294, and the Japanese Patent Publication No. 2014-084514, and the like.

[Examples]

In the following, the embodiments of the present invention are shown, but the embodiments are presented to better understand the present invention and its advantages, and are not intended to limit the invention.

A metal substrate composed of a metal foil having the composition and thickness of each material described in Table 2 was prepared. After degreasing and pickling the surface of the metal foil and purifying it, according to the adhesion conditions of Ni, Co and Mo described in Table 2, an acidic acid plating bath (pH: 2 to 3.5, liquid temperature: 40~) is used. 60 ° C, current density: 2 ~ 10A / dm ² ) plating, the entire surface of the metal foil is coated with Co, Co-Ni alloy plating, Co-Mo alloy plating, Ni-Mo alloy plating or Co- The Ni-Mo alloy was plated to produce a plated metal foil of the inventive examples, reference examples and comparative examples. The ion concentration of Ni, Mo, and Co in the plating solution was set to the conditions described in Table 1 depending on the Ni+Mo ratio (%). The ion concentration of the other elements was set as the conditions described in Table 1 depending on the amount of adhesion. The amount of adhesion can be controlled by the amount of coulomb. In the case of reducing the amount of adhesion, it is only necessary to make the amount of coulomb smaller. In the case of increasing the amount of adhesion, it is only necessary to increase the amount of coulomb. For example, when the total deposited mass of Co, Ni and Mo, the set 3000μg / dm ^2, the amount of coulombs can be set to 5 ~ 20As / dm about ^2, the total deposition amount of Co, Ni, and Mo in the set of 14000μg When /dm ² is used, the coulomb amount can be set to about 45 to 80 As/dm ² , and when the total adhesion amount of Co, Ni, and Mo is set to 180,000 μg/dm ² , the coulomb amount can be set to 700 to 900 As/dm ^{2 .} about. When it is desired to increase the amount of adhesion of Mo, the concentration of Mo in the plating solution may be increased. When it is desired to increase the amount of Co adhesion, the Co concentration in the plating solution may be increased. When it is desired to increase the amount of Ni deposited, the Ni concentration in the plating solution may be increased.

Further, regarding test Nos. 90 to 93, a metal foil with a metal substrate was used as the ultra-thin metal layer. The carrier-attached metal foil is produced in the following manner. The carrier of test Nos. 90 and 91 was an electrolytic copper foil JTC foil (thickness 18 μm) manufactured by JX Nippon Mining & Metal Co., Ltd., and the carrier of test No. 92 and 93 was manufactured by JX Nippon Mining & Metal Co., Ltd. Calendered copper foil copper (thickness 18 μm, JIS H3100 alloy number C1100). Then, in the order described in Table 2, each layer was formed on the S surface (glossy side) side of the electrodeposited copper foil or on the surface of the rolled copper foil.

The intermediate layers of Test Nos. 90 to 93 were formed in the following manner.

. Test No. 90

<intermediate layer>

(1) Ni layer (Ni plating)

With respect to the carrier, electroplating was performed on a continuous roll line of a roll-to-roll type under the following conditions, thereby forming an adhesion layer of Ni of 4000 μg/dm ² . The specific plating conditions are described below.

Nickel sulfate: 270~280g/L

Nickel chloride: 35~45g/L

Nickel acetate: 10~20g/L

Boric acid: 30~40g/L

Gloss agent: saccharin, butynediol, etc.

Sodium lauryl sulfate: 55~75ppm

pH: 4~6

Bath temperature: 55~65°C

Current density: 10A/dm ²

(2) Cr layer (electrolytic chromate treatment)

Next, the surface of the Ni layer formed in (1) was washed with water and pickled, and then subjected to electrolytic chromate treatment on a continuous roll line of a roll-to-roll type under the following conditions to obtain 11 μg/dm ^{2 .} The adhesion amount of the Cr layer adheres to the Ni layer.

Potassium dichromate 1~10g/L

pH: 7~10

Liquid temperature: 40~60°C

Current density: 2A/dm ²

. Test No. 91

<intermediate layer>

(1) Ni-Mo layer (nickel-molybdenum alloy plating)

With respect to the carrier, electroplating was performed on a continuous roll line of a roll-to-roll type under the following conditions, thereby forming a Ni-Mo layer having an adhesion amount of 3000 μg/dm ² . The specific plating conditions are described below.

(liquid composition) sulfuric acid Ni hexahydrate: 50 g/dm ³ , sodium molybdate dihydrate: 60 g/dm ³ , sodium citrate: 90 g/dm ³

(liquid temperature) 30 ° C

(current density) 1~4A/dm ²

(Power-on time) 3~25 seconds

. Test No. 92

<intermediate layer>

(1) Ni layer (Ni plating)

The Ni layer was formed under the same conditions as in Test No. 90.

(2) Organic layer (organic layer formation treatment)

Next, after washing the surface of the Ni layer formed in (1) with water and pickling, the liquid temperature of the carboxybenzotriazole (CBTA) having a concentration of 1 to 30 g/L is then 40 ° C and pH under the following conditions. The aqueous solution of value 5 was spray-washed to the surface of the Ni layer for 20 to 120 seconds, thereby forming an organic layer.

. Test No. 93

<intermediate layer>

(1) Co-Mo layer (cobalt-molybdenum alloy plating)

With respect to the carrier, electroplating was performed on a continuous roll line of a roll-to-roll type under the following conditions, thereby forming a Co-Mo layer of an adhesion amount of 4000 μg/dm ² . The specific plating conditions are described below.

(liquid composition) sulfuric acid Co: 50 g/dm ³ , sodium molybdate dihydrate: 60 g/dm ³ , sodium citrate: 90 g/dm ³

(liquid temperature) 30 ° C

(current density) 1~4A/dm ²

(Power-on time) 3~25 seconds

(2) Organic layer (organic layer formation treatment)

Next, after washing the surface of the Co-Mo layer formed in (1) with water and pickling, the liquid temperature of the hydroxybenzotriazole (CBTA) having a concentration of 1 to 30 g/L is then 40 ° C under the following conditions. The aqueous solution of pH 5 was spray-washed to the surface of the Ni layer for 20 to 120 seconds, thereby forming an organic layer.

Further, the metal foil as the ultra-thin metal layer was formed on the intermediate layer or on the plating layer so as to have the thickness of the substrate described in Table 2 under the following conditions.

<metal foil>

Copper concentration: 90~110g/L

Tin concentration: 1~30g/L

Sulfuric acid concentration: 90~110g/L

Chloride ion concentration: 50~90ppm

Electrolyte temperature: 50~80°C

Current density: 100A/dm ²

Electrolyte line speed: 1.5~5m/sec

(1) Adhesion of Ni, Co, Mo and other elements (μg/dm ² )

The adhesion amount (μg/dm ² ) of each of Ni, Co, Mo, and other elements in the plating layer of the obtained metal foil (test sample) obtained by the plating was obtained by dissolving the test sample with nitric acid having a concentration of 20% by mass. The measurement was carried out by ICP emission spectrometry using an ICP emission spectrometer (Model: SPS3100) manufactured by SII Corporation. Further, in the case where the test sample is difficult to be dissolved in nitric acid having a concentration of 20% by mass, the test sample may be dissolved by a mixture of nitric acid and hydrochloric acid (nitric acid concentration: 20% by mass; hydrochloric acid concentration: 12% by mass). A liquid such as another acid aqueous solution may dissolve the test sample. Further, the Ni+Mo ratio (%) in the plating layer was calculated from the measured adhesion amounts of Ni, Co, and Mo. Here, the Ni+Mo ratio (%) is defined as follows.

Ni + Mo ratio (%) = {Total deposition amount of Ni and Mo (μg / dm ² ) / (Total deposition amount of Ni, Co, and Mo (μg / dm ² ))} × 100

(2) etching linearity

Each test sample was etched using an aqueous solution of 37% by mass and a Baume 40 ° aqueous solution to form a linear circuit having a line and gap (L/S) of 100 μm/200 μm and a length of 150 mm, and a line and a gap (L). /S) is a linear circuit with a length of 150 mm of 75 μm/75 μm. The circuit was observed using a scanning electron microscope (manufactured by Hitachi, Ltd., S-4700), and evaluated according to the following criteria.

×: The bending range is longer than 50% of the length of the circuit

△: The bending range is more than 25% to 50% of the length of the circuit.

○: The bending range is more than 15% to 25% of the circuit length.

○○: The bending range is more than 5%~15% of the circuit length

◎: The bending range is longer than 0% of the length of the circuit and is 5% or less.

◎ ◎: The bending range is 0%. No bending (straight line)

Here, the term "bending" refers to taking a picture from the upper surface by the SEM at 500 times, and drawing two straight lines along the length direction connecting the crotch portions of the circuit having a length of 186 μm in the photo (thickness: 1.9 μm) In the case of the circuit, the ridge line of the circuit is 5 μm or more from the center line of each straight line. The measurement result is represented by the average value when photographs were taken at 4 places.

(3) Solder adhesion strength test

First, the foil thickness was thinned to 0.03 mm by wet etching from the surface side of one of the test samples. At this time, the opposite surface is shielded by a tape so that the plating layer does not peel off. Then, the plating side of the test sample obtained by thinning the obtained thickness (the test sample in which the plating layer is not formed is an arbitrary surface) and the pure copper foil (C1100 manufactured by JX Nippon Mining & Metal Co., Ltd., foil thickness 0.035 mm) via the living metal Lead-free solder manufactured by Industrial Co., Ltd. (ESC M705, solder with added resin deposit (flux), Sn (remaining part) - 3.0% by mass of Ag-0.5% by mass of Cu), joined by Japan Aiko Co., Ltd. The precision load measuring device (MODEL-1605NL) was subjected to a 180° peeling test at a speed of 100 mm/min, thereby measuring the adhesion strength of each test sample. The sample foil was formed into a short strip having a width of 15 mm and a length of 200 mm. The pure copper foil was a strip having a width of 20 mm and a length of 200 mm, and the joining temperature was 245 ° C ± 5 ° C, and the area of the center portion of 30 mm × 15 mm was joined to the length. In the direction. In addition, regarding the thickness of pure copper foil, if it is close to the sample foil for evaluation The thickness is then not problematic, but is preferably 0.02 mm to 0.05 mm, and 0.035 mm of pure copper foil is used in this embodiment. Further, in the experimental example of the metal foil with a carrier, the carrier was adhered to the metal foil of the carrier, and the solder adhesion strength test described above was carried out. Further, in the case of test numbers 92 and 93 in which the thickness of the metal foil with the carrier metal foil is less than 0.03 mm, Cu is plated on the metal foil to increase the thickness, and the thickness of the metal foil and the thickness of the Cu plating are combined. After setting to 0.03 mm, the carrier was peeled off from the carrier metal foil, and the above test was carried out.

(4) Weather resistance test

The degree of discoloration of each test sample at a constant temperature and humidity device (ESPEC Co., Ltd. (model: PL-2E)) having a temperature of 85 ° C and a relative humidity of 85% was maintained for 100 hours or 200 hours. Regarding the degree of discoloration, after the photograph is taken, the transparent resin film is overlapped, and the discolored portion is applied with the black mark, and the black and white binarization is performed by the image processing software, and the area of the discolored portion is obtained by the image processing software. . The value obtained by dividing the obtained area by the area of the entire observation field of view is 100 times the value obtained as the area ratio (%) of the discolored portion.

The test results of the plating adhesion amount are shown in Table 2, and the test results of etching property, solder adhesion, and weather resistance are shown in Table 3. As can be seen from Table 3, in the examples, the metal substrate having poor solder adhesion or weather resistance was excellent in solder adhesion and weather resistance by forming the plating layer of the present invention. Further, examples in which the total adhesion amount of Ni + Co + Mo and the Ni + Mo ratio (%) were appropriately controlled (No. 1, 2, 2-2 to 2-6, 3 to 12, 15, 18) In 20, 22~27, 30, 32~36, 38~44, 46, 48, 49, 78~81, 86, 88~97), a higher etching property is also obtained. On the other hand, in the comparative example, there is a metal substrate which exhibits excellent etching properties, but there is no metal substrate which has both solder adhesion and weather resistance.

Claims (53)

A plated metal substrate having an alloy selected from a Co plating layer and an element containing two or more elements selected from the group consisting of Co, Ni, and Mo, on a part or all of a surface of a metal substrate. a plating layer in a group of plating layers, wherein a total adhesion amount of Co, Ni, and Mo in the plating layer is 500 μg/dm ² or more, and the metal substrate contains a material selected from the group consisting of Ti, Si, Mg, P, Sn, Zn, Cr, and Zr. , V, W, Na, Ca, Ba, Cs, Mn, K, Ga, B, Nb, Ce, Be, Nd, Sc, Hf, Ho, Lu, Yb, Dy, Er, Pr, Y, Li, Gd One or two or more elements selected from the group consisting of Pu, In, Fe, La, Th, Ta, U, Sm, Tb, Sr, Tm, and Al. The metal substrate to be plated according to the first aspect of the invention, wherein the total adhesion amount of Co, Ni, and Mo in the plating layer is 700 μg/dm ² or more. The metal substrate to which the plating of the first aspect of the invention is applied, wherein the total adhesion amount of Co, Ni, and Mo in the plating layer is 1000 μg/dm ² or more. The metal substrate to be plated according to the first aspect of the invention, wherein the total adhesion amount of Co, Ni, and Mo in the plating layer is 2000 μg/dm ² or more. The metal substrate to which the plating of the first aspect of the invention is applied, wherein the total adhesion amount of Co, Ni, and Mo in the plating layer is 3000 μg/dm ² or more. The metal substrate to which the plating of the first aspect of the invention is applied, wherein the total adhesion amount of Co, Ni, and Mo in the plating layer is 5000 μg/dm ² or more. The metal substrate to which the plating of the first aspect of the invention is applied, wherein the total adhesion amount of Co, Ni, and Mo in the plating layer is 7000 μg/dm ² or more. The metal substrate to be plated according to the first aspect of the invention, wherein the total adhesion amount of Co, Ni, and Mo in the plating layer is 180,000 μg/dm ² or less. The metal substrate to be plated according to any one of the first to eighth aspects of the present invention, wherein the total amount of adhesion of Ni and Mo to the total amount of Co, Ni, and Mo adhered to the plating layer (hereinafter, Also referred to as "Ni+Mo ratio (%)"), the mass ratio is 80% or less. The metal substrate to be plated according to any one of the first to eighth aspects of the present invention, wherein the total amount of adhesion of Ni and Mo to the total amount of Co, Ni, and Mo adhered to the plating layer (hereinafter, Also referred to as "Ni+Mo ratio (%)"), the mass ratio is 60% or less. The metal substrate to be plated according to any one of the first to eighth aspects of the present invention, wherein the total amount of adhesion of Ni and Mo to the total amount of Co, Ni, and Mo adhered to the plating layer (hereinafter, Also referred to as "Ni+Mo ratio (%)"), the mass ratio is 50% or less. The metal substrate to be plated according to any one of the first to eighth aspects of the present invention, wherein the total amount of adhesion of Ni and Mo to the total amount of Co, Ni, and Mo adhered to the plating layer (hereinafter, Also referred to as "Ni+Mo ratio (%)"), the mass ratio is 10% or more. The metal substrate to be plated according to the ninth aspect of the invention, wherein the total amount of adhesion of Ni and Mo to the total amount of adhesion of Co, Ni, and Mo in the plating layer (hereinafter also referred to as "Ni+" The Mo ratio (%)") is 10% or more in terms of mass ratio. The plated metal substrate according to any one of claims 1 to 8, wherein a base layer and/or a roughened layer is formed between the plating layer and the metal substrate. The metal substrate to which the plating of claim 13 is applied, wherein a base layer and/or a roughened layer is formed between the plating layer and the metal substrate. The plated metal substrate according to any one of claims 1 to 8, wherein the plating layer is selected from the group consisting of a Co-Ni alloy plating layer, a Co-Mo alloy plating layer, a Ni-Mo alloy plating layer, and A group consisting of Co-Ni-Mo alloy coatings. The metal substrate for plating according to claim 15 , wherein the plating layer is selected from the group consisting of 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. In the group. The plated metal substrate according to any one of claims 1 to 8, wherein the plating layer is selected from the group consisting of Cu, As, Ag, Au, Pd, Pt, Bi, Os, Rh, Tl, Sb. One or two or more elements of the group consisting of Pb, Hg, Ir, Cd, Ru, Re, Tc, and Gd. The coated metal substrate according to claim 17, wherein the plating layer is selected from the group consisting of Cu, As, Ag, Au, Pd, Pt, Bi, Os, Rh, Tl, Sb, Pb, Hg, Ir One or more elements of the group consisting of Cd, Ru, Re, Tc, and Gd. The coated metal substrate according to claim 18, wherein the plating layer contains a total of 0 to 2000 μg/dm ² selected from the group consisting of Cu, As, Ag, Au, Pd, Pt, Bi, Os, Rh, Tl. One or two or more elements selected from the group consisting of Sb, Pb, Hg, Ir, Cd, Ru, Re, Tc, and Gd. The coated metal substrate according to claim 19, wherein the plating layer contains a total of 0 to 2000 μg/dm ² selected from the group consisting of Cu, As, Ag, Au, Pd, Pt, Bi, Os, Rh, Tl. One or two or more elements selected from the group consisting of Sb, Pb, Hg, Ir, Cd, Ru, Re, Tc, and Gd. The metal substrate for plating according to claim 18, wherein the plating layer contains a total of 0 to 1000 μg/dm ² selected from the group consisting of Cu, As, Ag, Au, Pd, Pt, Bi, Os, Rh, Tl, One or two or more elements of the group consisting of Sb, Pb, Hg, Ir, Cd, Ru, Re, Tc, and Gd. The metal substrate for plating according to claim 18, wherein the plating layer contains a total of 0 to 500 μg/dm ² selected from the group consisting of Cu, As, Ag, Au, Pd, Pt, Bi, Os, Rh, and Tl. One or two or more elements selected from the group consisting of Sb, Pb, Hg, Ir, Cd, Ru, Re, Tc, and Gd. The plated metal substrate according to any one of claims 1 to 8, wherein the plating layer contains one or two selected from the group consisting of Cu, As, Ag, Au, Pd, and Pt. Kind of above elements. The metal substrate to be plated according to claim 24, wherein the plating layer contains a total of 0 to 2000 μg/dm ² selected from the group consisting of Cu, As, Ag, Au, Pd, and Pt. Or more than two elements. The metal substrate to be plated according to claim 24, wherein the plating layer contains a total of 0 to 1000 μg/dm ² selected from the group consisting of Cu, As, Ag, Au, Pd, and Pt. Or more than two elements. The scope of the appended patent application 24 of the plated deposition of the metal substrate, wherein the coating layer contains one of the group consisting of total 0 ~ 500μg / dm selected from the group consisting of Cu ^2, As, Ag, Au, Pd and Pt of Or more than two elements. A plated metal substrate having an alloy selected from a Co plating layer and an element containing two or more elements selected from the group consisting of Co, Ni, and Mo, on a part or all of a surface of a metal substrate. a plating layer in a group consisting of plating layers, wherein a total adhesion amount of Co, Ni, and Mo in the plating layer is 500 μg/dm ² or more, and the metal substrate contains a material selected from the group consisting of Ti, Si, Mg, P, Sn, Zn, and Cr. , Zr, V, W, Na, Ca, Ba, Cs, Mn, K, Ga, B, Nb, Ce, Be, Nd, Sc, Hf, Ho, Lu, Yb, Dy, Er, Pr, Y, Li a plated metal substrate of one or more of the group consisting of Gd, Pu, In, Fe, La, Th, Ta, U, Sm, Tb, Sr, Tm, and Al, and One or more of the following items (1) to (21) are satisfied: (1): the total adhesion amount of Co, Ni, and Mo in the plating layer is 700 μg/dm ² or more; (2): in the above plating layer The total adhesion amount of Co, Ni, and Mo is 1000 μg/dm ² or more; (3): the total adhesion amount of Co, Ni, and Mo in the plating layer is 2000 μg/dm ² or more; (4): Co in the plating layer The total adhesion amount of Ni and Mo is 3000 μg/dm ² or more; (5) The total adhesion amount of Co, Ni, and Mo in the plating layer is 5000 μg/dm ² or more; (6): the total adhesion amount of Co, Ni, and Mo in the plating layer is 7000 μg/dm ² or more; (7): The total adhesion amount of Co, Ni, and Mo in the plating layer is 180000 μg/dm ² or less; (8): the total amount of adhesion of Ni and Mo to the total amount of adhesion of Co, Ni, and Mo in the plating layer (hereinafter also The "Ni+Mo ratio (%)" is 80% or less by mass ratio; (9): the total amount of adhesion of Ni and Mo to the total amount of adhesion of Co, Ni, and Mo in the plating layer (hereinafter) Also referred to as "Ni+Mo ratio (%)"), the mass ratio is 60% or less; (10): the total amount of adhesion of Ni and Mo relative to the total amount of adhesion of Co, Ni, and Mo in the plating layer ( The following is also referred to as "Ni+Mo ratio (%)"), which is 50% or less by mass ratio; (11): total adhesion amount of Ni and Mo with respect to the total amount of adhesion of Co, Ni, and Mo in the above-mentioned plating layer (hereinafter also referred to as "Ni+Mo ratio (%)") is 10% or more by mass ratio; (12): a base layer and/or a roughened layer is formed between the plating layer and the metal substrate; (13): The above plating layer is selected from Co-Ni a plating layer in a group consisting of a plating layer, a Co-Mo alloy plating layer, a Ni-Mo alloy plating layer, and a Co-Ni-Mo alloy plating layer; (14): the plating layer is selected from the group consisting of Cu, As, Ag, Au, Pd, Pt, One or more elements of the group consisting of Bi, Os, Rh, Tl, Sb, Pb, Hg, Ir, Cd, Ru, Re, Tc, and Gd; (15): The above plating layer contains a total of 0~ 2000 μg/dm ² 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 two or more elements; (16): the plating layer contains a total of 0 to 1000 μg/dm ² selected from the group consisting of Cu, As, Ag, Au, Pd, Pt, Bi, Os, Rh, Tl, Sb, Pb, One or more elements of the group consisting of Hg, Ir, Cd, Ru, Re, Tc, and Gd; (17): The plating layer contains a total of 0 to 500 μg/dm ² selected from Cu, As, Ag One or more elements of the group consisting of Au, Pd, Pt, Bi, Os, Rh, Tl, Sb, Pb, Hg, Ir, Cd, Ru, Re, Tc, and Gd; (18) The plating layer contains one or more elements selected from the group consisting of Cu, As, Ag, Au, Pd, and Pt; (19): Layer containing a group consisting of total 0 ~ 2000μg / dm selected from the group consisting of Cu ² of, As, Ag, Au, Pd and Pt of one or two or more kinds of elements; (20): the coating layer comprises in total 0 ~ 1000μg / The dm ^{2 is one} or more selected from the group consisting of Cu, As, Ag, Au, Pd, and Pt; (21): the plating layer contains a total of 0 to 500 μg/dm ² selected from Cu, One or more elements of the group consisting of As, Ag, Au, Pd, and Pt. A coated metal substrate according to any one of claims 1 to 8 and 28, wherein The metal substrate is made of 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, niobium, tantalum alloy, zirconium, zirconium alloy, tin, tin alloy, indium, indium alloy, zinc, or zinc alloy. The coated metal substrate according to claim 29, wherein the metal substrate is made of copper alloy, aluminum, aluminum alloy, iron, iron alloy, stainless steel, nickel alloy, titanium, titanium alloy, zinc, or zinc. The alloy is formed. A metal substrate for plating according to claim 29, wherein the metal substrate is formed of titanium copper, phosphor bronze, Carson alloy, red brass, brass, zinc white copper or other copper alloy. The metal substrate to be plated according to any one of claims 1 to 8, wherein the metal substrate is in the form of a metal strip, a metal plate, or a metal foil. The metal substrate to be plated according to any one of claims 1 to 8, wherein the metal substrate is a rolled copper alloy foil or an electrolytic copper alloy foil. The plated metal substrate according to any one of claims 1 to 8, wherein the surface of the plating layer has a resin layer. The plated metal substrate according to any one of claims 1 to 8, wherein the metal substrate has two main surfaces and has the plating layer on one or both sides thereof. A metal foil with a carrier having an intermediate layer or an extremely thin metal layer on one or both sides of the carrier, and the extremely thin metal layer is a plated metal substrate according to any one of claims 1 to 35. . A metal foil with a carrier as claimed in claim 36, wherein one of the above carriers The intermediate layer and the ultra-thin metal layer are sequentially provided, and the roughened layer is provided on the other surface of the carrier. The carrier metal foil of claim 36 or 37, wherein the metal substrate to which the plated metal substrate is attached is made of a copper alloy. A connector, which is provided with a plated metal substrate according to any one of claims 1 to 35, or a carrier-attached metal foil according to any one of claims 36 to 38. A terminal, which is provided with a plated metal substrate according to any one of claims 1 to 35, or a carrier-attached metal foil according to any one of claims 36 to 38. A laminated board which laminates a metal substrate to be plated according to any one of claims 1 to 35 or a metal foil with a carrier of any one of claims 36 to 38 and a resin substrate. And manufacturing. A masking tape or masking material having a laminate of claim 41. A printed wiring board having a laminate of the 41st patent application. A metal working member, which is provided with a metal substrate for plating according to any one of claims 1 to 35, or a metal foil with a carrier according to any one of claims 36 to 38. An electronic or electrical machine comprising the metal substrate with a plating of any one of claims 1 to 35, or the metal foil with a carrier of any one of claims 36 to 38. A manufacturing method of a printed wiring board, comprising the steps of: preparing a carrier-attached metal foil and an insulating substrate according to any one of claims 36 to 38; and laminating the carrier-attached metal foil and the insulating substrate And after laminating the above-mentioned carrier metal foil and the insulating substrate, passing the above-mentioned carrier metal foil The step of stripping the carrier forms a metal-clad laminate, and thereafter, the step of forming the circuit is performed by any one of a semi-additive method, a subtractive method, a partial addition method, or a modified semi-additive method. A manufacturing method of a printed wiring board, comprising the steps of: forming a circuit on the side surface of the above-mentioned ultra-thin metal layer or the side surface of the carrier side of the metal foil with a carrier of any one of claims 36 to 38; a step of forming a resin layer on the side surface of the ultra-thin metal layer or the side of the carrier side of the metal foil with a carrier; a step of forming a circuit on the resin layer; and forming a circuit on the resin layer, a step of peeling off the carrier or the ultra-thin metal layer; and after removing the carrier or the ultra-thin metal layer, removing the ultra-thin metal layer or the carrier, thereby forming the surface of the ultra-thin metal layer or the above The step of burying the circuit on the side surface of the carrier exposed in the above resin layer. A bonded body which is a bonded metal substrate of any one of claims 1 to 35, or a bonded metal foil and solder joint of any one of claims 36 to 38. The bonded body according to claim 48, wherein a heat diffusion layer containing Sn and Co is present at a joint interface between the solder and the metal substrate or the metal foil with a carrier. A method of joining a plated metal substrate or a metal foil with a carrier and a conductive member, comprising the steps of: plating the metal base of any one of claims 1 to 35 by etching Or a metal foil with a carrier of any one of claims 36 to 38 a step of processing, and a step of bonding the portion having the plating layer of the obtained shaped metal substrate to the conductive member by welding. An electronic component comprising the plated metal substrate of any one of claims 1 to 35, or the carrier-attached metal foil of any one of claims 36 to 38. An auto-focusing module, which is provided with a metal substrate for plating according to any one of claims 1 to 35, or a metal foil with a carrier of any one of claims 36 to 38 as a spring material. An autofocus camera module comprising: a lens; a spring member made of a plated metal substrate according to any one of claims 1 to 35, wherein the lens is elastically biased at an initial position in the optical axis direction; Or a spring member made of a carrier metal foil according to any one of claims 36 to 38; and an electromagnetic driving means for generating an electromagnetic force against the force of the spring member to drive the lens in the optical axis direction, The electromagnetic driving means includes a coil, and the spring member is joined to the coil by welding at a portion having the plating layer.