JP6449587B2 - Copper foil with carrier, laminated board using the same, printed wiring board, electronic device, and method for manufacturing printed wiring board - Google Patents

Description

  The present invention relates to a copper foil with a carrier and a laminated board, a printed wiring board, an electronic device, and a printed wiring board manufacturing method using the same, and in particular, the transparency of the remaining resin after etching the copper foil is required. The present invention relates to a copper foil with a carrier suitable for a field to be used, a laminated board using the same, a printed wiring board, an electronic device, and a method for manufacturing a printed wiring board.

  In a small electronic device such as a smartphone or a tablet PC, a flexible printed wiring board (hereinafter referred to as FPC) is adopted because of easy wiring and light weight. In recent years, with the enhancement of functions of these electronic devices, the signal transmission speed has been increased, and impedance matching has become an important factor in FPC. As a measure for impedance matching with respect to an increase in signal capacity, a resin insulation layer (for example, polyimide) serving as a base of an FPC has been increased in thickness. In addition, the demand for higher wiring density has further increased the number of FPC layers. On the other hand, processing such as bonding to a liquid crystal substrate and mounting of an IC chip is performed on the FPC, but the alignment at this time is the resin insulation remaining after etching the copper foil in the laminate of the copper foil and the resin insulating layer The visibility of the resin insulation layer is important because it is performed through a positioning pattern that is visible through the layer.

  Moreover, the copper clad laminated board which is a laminated board of copper foil and a resin insulating layer can also be manufactured even if it uses the rolled copper foil by which roughening plating was given to the surface. This rolled copper foil usually uses tough pitch copper (oxygen content of 100 to 500 ppm by weight) or oxygen-free copper (oxygen content of 10 ppm by weight or less) as a raw material, and after hot rolling these ingots, It is manufactured by repeating cold rolling and annealing to a thickness.

As such a technique, for example, in Patent Document 1, a polyimide film and a low-roughness copper foil are laminated, and a light transmittance at a wavelength of 600 nm of the film after copper foil etching is 40% or more, a haze value. An invention relating to a copper clad laminate having (HAZE) of 30% or less and an adhesive strength of 500 N / m or more is disclosed.
Further, Patent Document 2 has an insulating layer in which a conductive layer made of electrolytic copper foil is laminated, and the light transmittance of the insulating layer in the etching region when the circuit is formed by etching the conductive layer is 50% or more. In a flexible printed wiring board for chip-on-flex (COF), the electrolytic copper foil has a rust-proofing layer made of a nickel-zinc alloy on an adhesive surface bonded to an insulating layer, and the surface roughness (Rz) of the adhesive surface ) Is 0.05 to 1.5 μm, and the specular gloss at an incident angle of 60 ° is 250 or more, and an invention relating to a flexible printed wiring board for COF is disclosed.
Moreover, in patent document 3, in the processing method of the copper foil for printed circuits, after the roughening process by copper-cobalt-nickel alloy plating on the surface of copper foil, a cobalt-nickel alloy plating layer is formed, and also zinc-nickel An invention relating to a method for treating a copper foil for printed circuit, characterized by forming an alloy plating layer is disclosed.

  In addition, when the signal transmission speed is increased due to the higher functionality of electronic devices, the high frequency board is required to reduce transmission loss in order to ensure the quality of the output signal. The transmission loss mainly consists of a dielectric loss due to the resin (substrate side) and a conductor loss due to the conductor (copper foil side). The dielectric loss decreases as the dielectric constant and dielectric loss tangent of the resin decrease. In a high-frequency signal, the conductor loss is mainly caused by a decrease in the cross-sectional area through which the current flows due to the skin effect that only the surface of the conductor flows as the frequency increases, and the resistance increases.

  Patent Document 4 discloses an electrolytic copper foil characterized in that a part of the surface of the copper foil is a concavo-convex surface having a surface roughness of 2 to 4 μm made of bump-shaped protrusions. And according to this, it describes that the electrolytic copper foil excellent in the high frequency transmission characteristic can be provided.

JP 2004-98659 A WO2003 / 096776 Japanese Patent No. 2849059 JP 2004-244656 A

In Patent Document 1, a low-roughness copper foil obtained by improving adhesion with an organic treatment agent after blackening treatment or plating treatment is broken due to fatigue in applications where flexibility is required for a copper-clad laminate. May be inferior in resin transparency.
Moreover, in patent document 2, the roughening process is not made and the adhesive strength of copper foil and resin is low and inadequate in uses other than the flexible printed wiring board for COF.
Furthermore, in the processing method described in Patent Document 3, Cu-Co-Ni fine processing on the copper foil was possible, but the resin after bonding the copper foil with the resin and removing it by etching was excellent. Transparency is not realized.

As a result of intensive studies, the present inventors have made a mark on the polyimide substrate from which the surface-mean-square-root height Rq is controlled within a predetermined range by the surface treatment and is removed from the treated surface side by bonding. Paying attention to the slope of the lightness curve near the mark edge drawn in the observation point-lightness graph obtained from the image of the mark part taken by the CCD camera over the polyimide substrate with the printed material attached, Controlling the slope of the brightness curve affects the resin transparency and signal transmission loss after the copper foil is etched away without being affected by the type of substrate resin film or the thickness of the substrate resin film. I found out.
In addition, the inventors of the present invention are factors in which the surface treatment metal species of the copper foil and the amount of adhesion thereof affect the signal transmission loss, and these factors together with the number density and glossiness of the roughened particles on the copper foil surface It has been found that, by controlling, a carrier-attached copper foil with a small signal transmission loss can be obtained even when used for a high-frequency circuit board.

In one aspect, the present invention completed based on the above knowledge is a copper foil with a carrier having a carrier, an intermediate layer, and an ultrathin copper layer in this order, and the ultrathin copper layer is subjected to a surface treatment. A copper foil with a carrier whose root mean square height Rq is 0.14 to 0.63 μm, and the copper foil is applied to both surfaces of the polyimide resin substrate from the surface side where the surface treatment is performed. After the matching, the copper foils on both sides are removed by etching, and a printed matter on which a line-shaped mark is printed is laid under the exposed polyimide substrate, and the printed matter is photographed with a CCD camera through the polyimide substrate. In the observation point-brightness graph, an image obtained by the photographing was prepared by measuring the lightness at each observation point along a direction perpendicular to the direction in which the observed line-shaped mark extends. In the observation point-lightness graph, the difference between the top average value Bt and the bottom average value Bb of the lightness curve generated from the end of the mark to the part where the mark is not drawn is ΔB (ΔB = Bt−Bb). The value indicating the position of the intersection closest to the line-shaped mark among the intersections of the lightness curve and Bt is t1, and the depth range from the intersection of the lightness curve and Bt to 0.1ΔB with reference to Bt When the value indicating the position of the intersection closest to the line-shaped mark among the intersections of the lightness curve and 0.1ΔB is t2, Sv defined by the following equation (1) is 3.5 or more. Become.
Sv = (ΔB × 0.1) / (t1-t2) (1)

  In another embodiment of the copper foil with a carrier according to the present invention, the root mean square height Rq of the surface on which the surface treatment of the ultrathin copper layer is performed is 0.25 to 0.60 μm.

  In still another embodiment of the copper foil with a carrier according to the present invention, Sv defined by the formula (1) in the brightness curve is 3.9 or more.

  In still another embodiment of the copper foil with a carrier according to the present invention, Sv defined by the formula (1) in the brightness curve is 5.0 or more.

  In still another embodiment of the copper foil with a carrier according to the present invention, the 10-point average roughness Rz of the surface TD on which the surface treatment of the ultrathin copper layer is performed is 0.20 to 0.64 μm. .

  In still another embodiment of the copper foil with a carrier according to the present invention, the ten-point average roughness Rz of the surface TD on which the surface treatment of the ultrathin copper layer is performed is 0.26 to 0.62 μm. .

  In still another embodiment of the copper foil with a carrier according to the present invention, the ratio A / B between the three-dimensional surface area A and the two-dimensional surface area B of the surface on which the surface treatment of the ultrathin copper layer is performed is 1. 0 to 1.7.

  In still another embodiment of the copper foil with a carrier according to the present invention, the A / B is 1.0 to 1.6.

  In still another embodiment of the copper foil with carrier according to the present invention, the surface of the copper foil with carrier is subjected to surface treatment from copper, nickel, cobalt, phosphorus, tungsten, arsenic, molybdenum, chromium and zinc. Any one or more selected from the group consisting of:

  In still another embodiment of the copper foil with carrier according to the present invention, the copper foil with carrier comprises a resin layer on the surface where the surface treatment of the ultrathin copper layer is performed.

  In still another embodiment of the copper foil with a carrier according to the present invention, the resin layer includes a dielectric.

  In still another embodiment of the copper foil with a carrier according to the present invention, the ultrathin copper layer is provided on both surfaces of the carrier.

  In still another embodiment of the copper foil with a carrier according to the present invention, a roughening treatment layer is provided on the surface of the carrier opposite to the ultrathin copper layer side.

  In still another aspect, the present invention is a laminated board produced by laminating the copper foil with carrier of the present invention and a resin substrate.

  In still another aspect, the present invention is a printed wiring board using the copper foil with a carrier of the present invention.

  In still another aspect, the present invention is an electronic device using the printed wiring board of the present invention.

  In still another aspect, the present invention is a method of manufacturing a printed wiring board in which two or more printed wiring boards are connected by connecting two or more printed wiring boards of the present invention.

  In yet another aspect, the present invention includes a step of connecting at least one printed wiring board of the present invention and another printed wiring board of the present invention or a printed wiring board not corresponding to the printed wiring board of the present invention, This is a method for manufacturing a printed wiring board in which two or more printed wiring boards are connected.

  In still another aspect, the present invention is an electronic apparatus using one or more printed wiring boards to which at least one printed wiring board of the present invention is connected.

  In still another aspect, the present invention is a method for manufacturing a printed wiring board, including at least a step of connecting the printed wiring board of the present invention and a component.

  In yet another aspect of the present invention, the step of connecting at least one printed wiring board of the present invention to another printed wiring board of the present invention or a printed wiring board not corresponding to the printed wiring board of the present invention, and A method of manufacturing a printed wiring board having two or more printed wiring boards connected, comprising at least a step of connecting a printed wiring board of the present invention or a printed wiring board having two or more printed wiring boards of the present invention connected thereto and a component. It is.

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

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

  In another aspect of the present invention, in the step of forming a circuit on the resin layer, another carrier-attached copper foil is bonded to the resin layer from the ultrathin copper layer side and bonded to the resin layer. It is a manufacturing method of the printed wiring board which is the process of forming the said circuit using an attached copper foil.

  In another aspect of the present invention, there is provided a method for producing a printed wiring board, wherein another carrier-attached copper foil to be bonded onto the resin layer is the carrier-attached copper foil of the present invention.

  In another aspect of the present invention, the process for forming a circuit on the resin layer is performed by any one of a semi-additive method, a subtractive method, a partial additive method, or a modified semi-additive method. Is the method.

  In another aspect of the present invention, the copper foil with carrier for forming a circuit on the surface has a substrate or a resin layer on the carrier side surface of the copper foil with carrier or the surface on the ultrathin copper layer side. It is a manufacturing method of a board.

  According to the present invention, a copper foil with a carrier that adheres well to a resin and is excellent in transparency of a resin after removing the copper foil by etching and has a small signal transmission loss, and a laminate using the same Can be provided.

It is a schematic diagram which defines Bt and Bb. It is a schematic diagram which defines t1, t2, and Sv. It is a schematic diagram showing the structure of an imaging device and the measuring method of the inclination of a lightness curve in the case of evaluation of the lightness curve inclination. AC is a schematic diagram of the wiring board cross section in the process to circuit plating and the resist removal based on the specific example of the manufacturing method of the printed wiring board using the copper foil with a carrier of this invention. DF is a schematic diagram of a cross section of a wiring board in a process from lamination of a resin and copper foil with a second layer carrier to laser drilling according to a specific example of a method for producing a printed wiring board using a copper foil with a carrier of the present invention. It is. GI is a schematic diagram of the wiring board cross section in the process from the via fill formation to the first layer carrier peeling according to a specific example of the method for manufacturing a printed wiring board using the carrier-attached copper foil of the present invention. J to K are schematic views of a cross section of a wiring board in steps from flash etching to bump / copper pillar formation according to a specific example of a method of manufacturing a printed wiring board using the carrier-attached copper foil of the present invention. It is an external appearance photograph of the foreign material used in the Example. It is an external appearance photograph of the foreign material used in the Example.

[Form and manufacturing method of copper foil with carrier]
The copper foil with a carrier which is one embodiment of the present invention is useful for a copper foil used by making a laminate by bonding to a resin substrate and removing it by etching.
In general, the ultrathin copper layer of the carrier-attached copper foil is degreased for the purpose of improving the peel strength of the laminated copper foil on the (matte) surface to be bonded to the resin substrate, that is, the surface on the surface treatment side. A roughening treatment for performing fist-like electrodeposition may be performed on the surface of the subsequent copper foil. The ultrathin copper layer of the copper foil with carrier has irregularities at the time of production, but the irregularities can be further increased by enhancing the convexity of the ultrathin copper layer of the copper foil with carrier by roughening treatment. In the present invention, when the roughening treatment is performed on the ultrathin copper layer of the copper foil with carrier, the roughening treatment is performed by copper-cobalt-nickel alloy plating, copper-nickel-phosphorus alloy plating, or nickel-zinc alloy plating. It is performed by alloy plating such as. Moreover, Preferably it can carry out by copper alloy plating. As the copper alloy plating bath, for example, a plating bath containing one or more elements other than copper and copper, more preferably any selected from the group consisting of copper and cobalt, nickel, arsenic, tungsten, chromium, zinc, phosphorus, manganese and molybdenum It is preferable to use a plating bath containing at least one kind. And in this invention, the said roughening process makes a current density higher than the conventional roughening process, and shortens roughening processing time. Ordinary metal plating, alloy plating, copper plating, copper alloy plating, etc. may be performed as pre-treatment before roughening treatment, and normal copper plating to prevent electrodeposits from falling off as finishing treatment after roughening treatment Etc. may be performed. In the present invention, such pretreatment and finishing treatment may be performed.
Moreover, in this invention, when the said pre-processing is performed to the ultra-thin copper layer, the ultra-thin copper layer by which the said pre-processing was also made into an ultra-thin copper layer.

Copper as roughening treatment - cobalt - nickel alloy plating, by electrolytic plating, coating weight is to be the 15~40mg / dm ² of copper -250~2000μg / dm ² of cobalt -50~1000μg / dm ² of nickel It can be carried out so as to form a ternary alloy layer. When the Co adhesion amount is less than 250 μg / dm ² , the heat resistance may be deteriorated, and the etching property may be deteriorated. When the amount of Co deposition exceeds 2000 μg / dm ² , signal transmission loss may increase. In addition, etching spots may occur, and acid resistance and chemical resistance may deteriorate. If the Ni adhesion amount is less than 50 μg / dm ² , the heat resistance may deteriorate. On the other hand, if the Ni adhesion amount exceeds 1000 μg / dm ² , signal transmission loss may increase. In addition, etching residue may increase. A preferable Co adhesion amount is 300 to 1800 μg / dm ² , and a preferable nickel adhesion amount is 100 to 800 μg / dm ² . Here, the etching stain means that Co remains without being dissolved when etched with copper chloride, and the etching residue means that Ni remains without being dissolved when alkaline etching is performed with ammonium chloride. It means that.

An example of a plating bath and plating conditions for forming such a ternary copper-cobalt-nickel alloy plating is as follows:
Plating bath composition: Cu 10-20 g / L, Co 1-10 g / L, Ni 1-10 g / L
pH: 1-4
Temperature: 30-50 ° C
Current density D _k : 25 to 50 A / dm ²
Plating time: 0.2 to 3.0 seconds In one embodiment of the present invention, in the roughening treatment, the current density of the roughening treatment is set higher than the conventional roughening treatment conditions, and the roughening treatment time is set to be longer. Shorten.
The balance of the treatment liquid used in the present invention for electrolysis, surface treatment or plating is water unless otherwise specified.

  In the copper foil with carrier of the present invention, the “roughened surface” means the surface of the ultrathin copper layer after the roughening treatment is performed on the ultrathin copper layer of the copper foil with carrier. In addition, if the surface treatment for providing a heat-resistant layer, a rust-proof layer, a weather-resistant layer, etc. is performed after roughening the ultra-thin copper layer of the copper foil with carrier, the “roughened surface” Means the surface of the ultra-thin copper layer of the copper foil with carrier after the surface treatment. The “roughened surface” of the above-described copper foil with carrier includes “the roughened surface of the ultrathin copper layer of the copper foil with carrier”. One or more layers selected from the group consisting of a heat-resistant layer, a rust-proof layer, and a weather-resistant layer may be provided on the surface of the ultrathin copper layer after the roughening treatment or without the roughening treatment. In addition, each layer may be a plurality of layers such as two layers, three layers, and the order of stacking the layers may be any order, and the layers may be stacked alternately.

Here, a known heat-resistant layer can be used as the heat-resistant layer. Further, for example, the following surface treatment can be used.
As the heat-resistant layer and the rust-proof layer, known heat-resistant layers and rust-proof layers can be used. For example, the heat-resistant layer and / or the anticorrosive layer is a group of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, iron, tantalum A layer containing one or more elements selected from nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements Further, it may be a metal layer or an alloy layer made of one or more elements selected from the group consisting of iron, tantalum and the like. The heat-resistant layer and / or rust preventive layer is a group of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, iron, and tantalum. An oxide, nitride, or silicide containing one or more elements selected from the above may be included. Further, the heat-resistant layer and / or the rust preventive layer may be a layer containing a nickel-zinc alloy. Further, the heat-resistant layer and / or the rust preventive layer may be a nickel-zinc alloy layer. The nickel-zinc alloy layer may contain 50 wt% to 99 wt% nickel and 50 wt% to 1 wt% zinc, excluding inevitable impurities. The total adhesion amount of zinc and nickel in the nickel-zinc alloy layer may be 5 to 1000 mg / m ² , preferably 10 to 500 mg / m ² , preferably 20 to 100 mg / m ² . Further, the ratio of the nickel adhesion amount and the zinc adhesion amount of the layer containing the nickel-zinc alloy or the nickel-zinc alloy layer (= nickel adhesion amount / zinc adhesion amount) is 1.5 to 10. It is preferable. Further, the nickel - in adhesion amount of nickel in the zinc alloy layer is preferably from ^{0.5mg / m 2 ~500mg / m 2} , 1mg / m 2 ~50mg / m 2 - zinc alloy layer or the nickel containing More preferably. When the heat-resistant layer and / or rust prevention layer is a layer containing a nickel-zinc alloy, the interface between the copper foil and the resin substrate is eroded by the desmear liquid when the inner wall such as a through hole or via hole comes into contact with the desmear liquid. It is difficult to improve the adhesion between the copper foil and the resin substrate. The rust prevention layer may be a chromate treatment layer. A known chromate treatment layer can be used for the chromate treatment layer. For example, the chromate-treated layer refers to a layer treated with a liquid containing chromic anhydride, chromic acid, dichromic acid, chromate or dichromate. Chromate treatment layer is any element such as cobalt, iron, nickel, molybdenum, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic and titanium (metal, alloy, oxide, nitride, sulfide, etc.) May be included). Specific examples of the chromate treatment layer include a pure chromate treatment layer and a zinc chromate treatment layer. In the present invention, a chromate treatment layer treated with an anhydrous chromic acid or potassium dichromate aqueous solution is referred to as a pure chromate treatment layer. In the present invention, a chromate treatment layer treated with a treatment liquid containing chromic anhydride or potassium dichromate and zinc is referred to as a zinc chromate treatment layer.

For example heat-resistant layer and / or anticorrosive layer has coating weight of 1 mg / m ² -100 mg / m ^2, preferably from 5 mg / m ² and to 50 mg / m ² of nickel or nickel alloy layer, the adhesion amount is 1 mg / m ² to 80 mg / m ^2, preferably it may be obtained by sequentially laminating a tin layer of ^{5mg / m 2 ~40mg / m 2} , wherein the nickel alloy layer of nickel - molybdenum, nickel - zinc, nickel - molybdenum - cobalt You may be comprised by any one of these. The heat-resistant layer and / or anticorrosive layer, it is ^{preferably, 10mg / m 2 ~70mg / m} 2 total deposition amount of nickel or nickel alloy and tin is 2mg / m ² ~150mg / m 2 It is more preferable. Further, the heat-resistant layer and / or the rust preventive layer is preferably [nickel or nickel adhesion amount in nickel or nickel alloy] / [tin adhesion amount] = 0.25 to 10, preferably 0.33 to 3. More preferred. When the heat-resistant layer and / or rust-preventing layer is used, the carrier-clad copper foil is processed into a printed wiring board, and the subsequent circuit peeling strength, the chemical resistance deterioration rate of the peeling strength, and the like are improved.
Further, as the heat-resistant layer and / or the rust-preventing layer, a cobalt-nickel alloy plating layer of nickel having an adhesion amount of 200 to 2000 μg / dm ² and 50 to 700 μg / dm ² can be formed. This treatment can be regarded as a kind of rust prevention treatment in a broad sense. This cobalt-nickel alloy plating layer needs to be performed to such an extent that the adhesive strength between the copper foil and the substrate is not substantially reduced. If the amount of cobalt adhesion is less than 200 μg / dm ² , the heat-resistant peel strength is lowered, and the oxidation resistance and chemical resistance may be deteriorated. As another reason, if the amount of cobalt is small, the treated surface becomes reddish, which is not preferable. If the amount of deposited cobalt exceeds 2000 μg / dm ² , signal transmission loss increases, which is not preferable. In addition, etching spots may occur, and acid resistance and chemical resistance may deteriorate. As a heat-resistant layer and / or a rust-preventing layer, a preferable cobalt adhesion amount is 500 to 1000 μg / dm ² . On the other hand, if the nickel adhesion amount is less than 100 μg / dm ² , the heat-resistant peel strength is lowered, and the oxidation resistance and chemical resistance may be deteriorated. When nickel exceeds 1000 μg / dm ² , signal transmission loss increases. As a heat-resistant layer and / or a rust-preventing layer, a preferable nickel adhesion amount is 100 to 600 μg / dm ² .

An example of the conditions for cobalt-nickel alloy plating is as follows:
Plating bath composition: Co 1-20 g / L, Ni 1-20 g / L
pH: 1.5-3.5
Temperature: 30-80 ° C
Current density D _k : 6.0 to 20.0 A / dm ²
Plating time: 0.2 to 1 second

Moreover, you may form the zinc plating layer of 30-250 microgram / dm < ² > of the adhesion amount further on the said cobalt- nickel alloy plating. If the zinc adhesion amount is less than 30 μg / dm ² , the heat deterioration rate improving effect may be lost. On the other hand, when the zinc adhesion amount exceeds 250 μg / dm ² , the hydrochloric acid deterioration rate may be extremely deteriorated. Preferably, the zinc adhesion amount is 30 to 240 μg / dm ² , more preferably 80 to 220 μg / dm ² .

An example of the galvanizing conditions is as follows:
Plating bath composition: Zn 100 to 300 g / L
pH: 3-4
Temperature: 50-60 ° C
Current density D _k : 6.0 to 20.0 A / dm ²
Plating time: 0.2 to 1 second

  A zinc alloy plating layer such as zinc-nickel alloy plating may be formed in place of the zinc plating layer, and a rust prevention layer and a weather resistance layer are applied to the outermost surface by chromate treatment or application of a silane coupling agent. It may be formed.

Moreover, the roughening process is abbreviate | omitted, and the plating process by Ni plating bath of the following conditions can be used as a process which gives a heat-resistant plating layer and a rust prevention plating layer to the surface.
Ni: 15-25 g / L
pH: 2.5
Temperature: 35-45 ° C
Current density D _k : 6.0 to 20.0 A / dm ²
Plating time: 0.2 to 1 second

A known weathering layer can be used as the weathering layer. Moreover, as a weather resistance layer, a well-known silane coupling process layer can be used, for example, The silane coupling process layer formed using the following silanes can be used.
As the silane coupling agent used for the silane coupling treatment, a known silane coupling agent may be used. For example, an amino silane coupling agent, an epoxy silane coupling agent, or a mercapto silane coupling agent may be used. Silane coupling agents include vinyltrimethoxysilane, vinylphenyltrimethoxylane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, 4-glycidylbutyltrimethoxysilane, and γ-aminopropyl. Triethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-3- (4- (3-aminopropoxy) ptoxy) propyl-3-aminopropyltrimethoxysilane, imidazolesilane, triazinesilane, γ-mercaptopropyltrimethoxysilane or the like may be used.

  The silane coupling treatment layer may be formed using a silane coupling agent such as an epoxy silane, an amino silane, a methacryloxy silane, or a mercapto silane. In addition, you may use 2 or more types of such silane coupling agents in mixture. Especially, it is preferable to form using an amino-type silane coupling agent or an epoxy-type silane coupling agent.

  The amino silane coupling agent referred to here is N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane, 3- Aminopropyltriethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, N- (3 -Acryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, 4-aminobutyltriethoxysilane, (aminoethylaminomethyl) phenethyltrimethoxysilane, N- (2-aminoethyl-3-aminopropyl) Trimethoxysilane, N (2-Aminoethyl-3-aminopropyl) tris (2-ethylhexoxy) silane, 6- (aminohexylaminopropyl) trimethoxysilane, aminophenyltrimethoxysilane, 3- (1-aminopropoxy) -3,3- Dimethyl-1-propenyltrimethoxysilane, 3-aminopropyltris (methoxyethoxyethoxy) silane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, ω-aminoundecyltrimethoxysilane, 3- (2 -N-benzylaminoethylaminopropyl) trimethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, (N, N-diethyl-3-aminopropyl) trimethoxysilane, (N, N- Dimethyl-3-aminopropyl) Limethoxysilane, N-methylaminopropyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane, γ-aminopropyltriethoxysilane, N -Β (aminoethyl) γ-aminopropyltrimethoxysilane, N-3- (4- (3-aminopropoxy) ptoxy) propyl-3-aminopropyltrimethoxysilane Good.

The silane coupling treatment layer is 0.05 mg / m ^{2 to} 200 mg / m ² , preferably 0.15 mg / m ^{2 to} 20 mg / m ² , preferably 0.3 mg / m ^{2 to} 2.0 mg in terms of silicon atoms. / M ² is desirable. In the case of the above-mentioned range, the adhesiveness between the base resin and the carrier-attached copper foil can be further improved.

When the surface-treated copper foil of the present invention is not roughened, the current density is lower than that of the roughening treatment and higher than that of normal normal plating so that the plating film cannot be uneven as described above. By processing at a current density in a shorter time than normal normal plating, and when performing a roughening process, by increasing the current density to reduce the size of the roughened particles and plating in a short time The surface treatment with a small roughness is made possible, thereby controlling the root mean square height Rq of the surface.
In the present application, “normal plating” means plating that is not rough plating (burn plating).

[Root mean square height Rq of copper foil surface with carrier]
The surface of the ultrathin copper layer of the copper foil with a carrier of the present invention is controlled to have a root mean square height Rq of 0.14 to 0.63 μm. With such a configuration, the peel strength is increased and the resin is satisfactorily bonded to the resin, and the transparency of the resin after the copper foil is removed by etching is increased. As a result, alignment and the like when mounting an IC chip through a positioning pattern that is visible through the resin are facilitated. Moreover, since the surface unevenness | corrugation is very small, the length of the copper foil surface with a carrier equivalent to the length through which an electron flows becomes short, and a transmission loss becomes small. When the root mean square height Rq is less than 0.14 μm, the degree of unevenness on the surface of the copper foil becomes insufficient, causing a problem that the resin cannot be sufficiently bonded. On the other hand, if the root mean square height Rq is more than 0.63 μm, the unevenness of the resin surface after the copper foil is removed by etching becomes large, resulting in a problem that the transparency of the resin becomes poor. The root mean square height Rq of the surface on which the surface treatment is performed is more preferably 0.25 to 0.60 μm, and still more preferably 0.32 to 0.56 μm. In addition, in the copper foil with a carrier of the present invention, "surface subjected to surface treatment" is a surface treatment for providing a roughening treatment, a heat-resistant layer, a rust-proof layer, a weather-resistant layer, The surface of the ultra-thin copper layer of the copper foil with a carrier after performing the surface treatment.
Here, the root mean square height Rq of the surface is an index indicating the degree of unevenness in the surface roughness measurement with a non-contact type roughness meter in accordance with JIS B 0601 (2001), and is represented by the following formula: The surface roughness is the height of irregularities (peaks) in the Z-axis direction, and is the root mean square of the height Z (x) of the peaks at the reference length lr.
The root mean square height Rq of the height of the mountain at the reference length lr:
√ {(1 / lr) × ∫Z ² (x) dx (where integral is an integrated value from 0 to lr)}

[10-point average roughness Rz of the ultrathin copper layer surface of the copper foil with carrier]
Even if the ultra-thin copper layer of the copper foil with a carrier of the present invention is not subjected to a roughening treatment, it may be subjected to a roughening treatment in which roughened particles are formed, and is subjected to a surface treatment. Ten-point average roughness Rz (JIS B0601 1994) of surface TD (direction perpendicular to the carrier foil passing direction in the apparatus for forming an ultrathin copper layer on the carrier (width direction of the copper foil)) is 0.20 to 0.20. It is preferably 0.64 μm. With such a configuration, the peel strength becomes higher, the resin adheres well to the resin, and the transparency of the resin after the copper foil is removed by etching becomes higher. As a result, alignment and the like when mounting an IC chip through a positioning pattern that is visible through the resin can be made easier. Moreover, since the surface unevenness | corrugation is very small, the length of the copper foil surface with a carrier equivalent to the length through which an electron flows becomes short, and a transmission loss becomes small. When the ten-point average roughness Rz of TD is less than 0.20 μm, the degree of unevenness on the surface of the copper foil may be insufficient, and there may be a problem that the resin cannot be sufficiently bonded. On the other hand, if the ten-point average roughness Rz of TD is more than 0.64 μm, the unevenness of the resin surface after the copper foil is removed by etching may increase, resulting in a problem of poor resin transparency. May occur. The ten-point average roughness Rz of TD on the treated surface is more preferably 0.26 to 0.62 μm, still more preferably 0.40 to 0.55 μm.

[Surface morphology of carrier of copper foil with carrier]
Here, in order to obtain the visibility effect and the transmission loss reduction effect of the present invention, the TD ((ultra thin copper layer) of the surface of the copper foil with carrier on the side where the intermediate layer of the carrier before forming the intermediate layer is provided. It means the roughness (Rz (ten-point average roughness Rz (JIS B0601 1994)) of the direction perpendicular to the direction of foil passing through the carrier in the apparatus formed on the carrier (width direction of the copper foil). And the glossiness (meaning 60-degree glossiness (measured in accordance with JIS Z8741), the same in the present specification)). The surface roughness (Rz) of TD on the surface of the copper foil with carrier on the side where the carrier intermediate layer is provided before forming the intermediate layer is 0.20 to 0.55 μm, preferably 0.20. ~ 0.42 μm.
Further, the surface of the carrier-provided copper foil on the side where the intermediate layer of the carrier before forming the intermediate layer is provided has a TD 60 degree gloss of 400 to 710%, more preferably 500 to 710%. If the 60-degree glossiness of TD of the copper foil before the surface treatment is less than 400%, the transparency of the resin described above may be poorer than the case of 400% or more, and the signal transmission loss may increase. There is. If it exceeds 710%, it may be difficult to produce. As a carrier of such a copper foil with a carrier, rolling is performed by adjusting the oil film equivalent of the rolling oil (high gloss rolling), rolling is performed by adjusting the roughness of the rolling roll, or chemical etching is performed. It can be produced by chemical polishing or electrolytic polishing in a phosphoric acid solution. Moreover, it is producible by manufacturing electrolytic copper foil with a predetermined electrolyte solution and predetermined electrolysis conditions.

High gloss rolling can be performed by setting the oil film equivalent defined by the following formula to 13,000 to 24000 or less.
Oil film equivalent = {(rolling oil viscosity [cSt]) × (sheet feeding speed [mpm] + roll peripheral speed [mpm])} / {(roll biting angle [rad]) × (yield stress of material [kg / mm ² ])}
The rolling oil viscosity [cSt] is a kinematic viscosity at 40 ° C.
In order to set the oil film equivalent to 13,000 to 24,000, a known method such as using a low-viscosity rolling oil or slowing a sheet passing speed may be used.
The surface roughness of the rolling roll can be, for example, 0.01 to 0.25 μm in terms of arithmetic average roughness Ra (JIS B0601 1994). When the value of the arithmetic average roughness Ra of the rolling roll is large, the TD roughness (Rz) on the surface of the copper foil before the surface treatment becomes large, and the 60-degree glossiness of the TD on the surface of the copper foil before the surface treatment is Tend to be lower. Further, when the value of the arithmetic average roughness Ra of the rolling roll is small, the TD roughness (Rz) of the surface of the copper foil before the surface treatment becomes small, and the TD 60 degree gloss of the surface of the copper foil before the surface treatment becomes small. Tend to be higher.
Chemical polishing is performed over a long period of time using an etching solution such as sulfuric acid-hydrogen peroxide-water system or ammonia-hydrogen peroxide-water system at a concentration lower than usual.

Moreover, the manufacturing conditions etc. of the electrolytic copper foil which can be used for the carrier of the copper foil with a carrier of this invention are as follows.
-Electrolyte composition Copper: 80-120 g / L
Sulfuric acid: 80-120 g / L
Chlorine: 30-100ppm
Leveling agent 1 (bis (3sulfopropyl) disulfide): 10 to 30 ppm
Leveling agent 2 (amine compound): 10 to 30 ppm
As the amine compound, an amine compound having the following chemical formula can be used.

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

Manufacturing conditions Current density: 70-100 A / dm ²
Electrolyte temperature: 50-65 ° C
Electrolyte linear velocity: 1.5-5 m / sec
Electrolysis time: 0.5 to 10 minutes (adjusted according to the thickness of copper to be deposited and current density)
Moreover, as an electrolytic copper foil that can be used in the present invention, an electrolytic copper foil HLP foil manufactured by JX Nippon Mining & Metals Co., Ltd. can be used.

[Slope of brightness curve]
The copper foil with carrier of the present invention is bonded to both sides of the polyimide base resin from the surface side where the treated surface of the ultra thin copper layer of the copper foil with carrier is bonded, and then etched on both sides. When removing the copper foil and laying the printed matter on which the line-shaped mark is printed under the exposed polyimide substrate, and photographing the printed matter with the CCD camera through the polyimide substrate, the image obtained by photographing, In the observation point-lightness graph created by measuring the lightness of each observation point along the direction perpendicular to the direction in which the observed line-shaped mark extends, this occurs from the end of the mark to the part where no mark is drawn. The difference between the top average value Bt and the bottom average value Bb of the lightness curve is ΔB (ΔB = Bt−Bb), and the intersection of the lightness curve and Bt in the observation point-lightness graph. In the depth range from the intersection of the lightness curve and Bt to 0.1ΔB with reference to Bt, where t1 is the closest intersection to the line-shaped mark, the line shape is within the intersection of the lightness curve and 0.1ΔB. When the intersection closest to the mark is t2, Sv defined by equation (1) is 3.5 or more.
Sv = (ΔB × 0.1) / (t1-t2) (1)
In the observation position-lightness graph, the horizontal axis represents position information (pixel × 0.1), and the vertical axis represents the value of brightness (gradation).
Here, “top average value Bt of the lightness curve”, “bottom average value Bb of the lightness curve”, and “t1”, “t2”, and “Sv” described later will be described with reference to the drawings.
FIGS. 1A and 1B are schematic views for defining Bt and Bb when the mark width is about 0.3 mm. When the mark width is about 0.3 mm, a V-shaped brightness curve may be obtained as shown in FIG. 1A, or a brightness curve having a bottom as shown in FIG. 1B. . In any case, the “top average value Bt of the lightness curve” indicates the average value of lightness when measured at 5 locations (a total of 10 locations on both sides) at 30 μm intervals from the positions 50 μm away from the end positions on both sides of the mark. . On the other hand, the “bottom average value Bb of the lightness curve” indicates the minimum value of lightness at the tip of the V-shaped valley when the lightness curve is V-shaped as shown in FIG. When it has the bottom of (b), the value of the center part of about 0.3 mm is shown. The mark width may be about 0.2 mm, 0.16 mm, or 0.1 mm. Furthermore, the “top average value Bt of the lightness curve” is 5 points at 30 μm intervals from a position 100 μm apart, a position 300 μm apart, or a position 500 μm apart from the end positions on both sides of the mark (total 10 on both sides). Location) It may be the average value of brightness when measured.
FIG. 2 is a schematic diagram that defines t1, t2, and Sv. “T1 (pixel × 0.1)” is a value indicating an intersection point closest to the line-shaped mark among intersection points of the lightness curve and Bt and a position of the intersection point (value on the horizontal axis of the observation point-lightness graph) ). “T2 (pixel × 0.1)” is the line-shaped mark among the intersections of the lightness curve and 0.1ΔB in the depth range from the intersection of the lightness curve and Bt to 0.1ΔB with reference to Bt. And the value (the value on the horizontal axis of the observation point-brightness graph) indicating the position of the intersection closest to. At this time, regarding the slope of the brightness curve indicated by the line connecting t1 and t2, Sv (gradation / pixel × 0.1) calculated by 0.1 ΔB in the y-axis direction and (t1−t2) in the x-axis direction. ). One pixel on the horizontal axis corresponds to a length of 10 μm. Further, Sv is measured on both sides of the mark, and a small value is adopted. Further, when the shape of the lightness curve is unstable and there are a plurality of “intersections between the lightness curve and Bt”, the intersection closest to the mark is adopted.
In the image taken by the CCD camera, the brightness is high at the portion where the mark is not attached, but the brightness decreases as soon as the end of the mark is reached. If the visibility of the polyimide substrate is good, such a lowered state of brightness is clearly observed. On the other hand, if the visibility of the polyimide substrate is poor, the lightness does not suddenly drop from “high” to “low” in the vicinity of the mark end, but the state of decline is slow and the state of lightness decline is unclear. End up.
Based on such knowledge, the present invention is based on such a knowledge, the mark portion taken with a CCD camera over the polyimide substrate, with the printed matter with the mark placed on the polyimide substrate from which the carrier-attached copper foil of the present invention was bonded and removed. The inclination of the lightness curve near the mark end portion drawn in the observation point-lightness graph obtained from the image is controlled. More specifically, the difference between the top average value Bt and the bottom average value Bb of the lightness curve is ΔB (ΔB = Bt−Bb), and the line of the intersections of the lightness curve and Bt in the observation point-lightness graph. In the depth range from the intersection of the lightness curve and Bt to 0.1 ΔB with reference to Bt, the value indicating the position of the intersection closest to the shape mark (the value on the horizontal axis of the observation point-lightness graph) is t1. When the value indicating the position of the intersection closest to the line-shaped mark among the intersections of the lightness curve and 0.1ΔB (the observation point—the value on the horizontal axis of the lightness graph) is t2, the above equation (1) Sv defined by is 3.5 or more. According to such a configuration, the discrimination power of the mark over the polyimide by the CCD camera is improved without being affected by the type and thickness of the substrate resin. For this reason, it is possible to produce a polyimide substrate with excellent visibility, and the positioning accuracy by marking when performing a predetermined treatment on the polyimide substrate in an electronic substrate manufacturing process or the like is improved, thereby improving the yield. can get. Sv is preferably 3.9 or more, more preferably 4.5 or more, even more preferably 5.0 or more, and even more preferably 5.5 or more. The upper limit of Sv is not particularly limited, but is, for example, 70 or less, 30 or less, 15 or less, and 10 or less. According to such a configuration, the boundary between the mark and the non-mark portion becomes clearer, the positioning accuracy is improved, the error due to the mark image recognition is reduced, and the alignment can be performed more accurately.
Therefore, when the copper foil according to the embodiment of the present invention is used for a printed wiring board, when one printed wiring board and another printed wiring board are connected, connection failure is reduced and yield is improved.
In addition, it is preferable that the polyimide film used for the measurement of the inclination of a lightness curve is a polyimide film whose value of (DELTA) B ((DELTA) B (PI)) before bonding to copper foil is 50-65. This is because it becomes easier to measure Sv.

[Area ratio of ultra-thin copper layer surface of copper foil with carrier]
The ratio A / B between the three-dimensional surface area A and the two-dimensional surface area B of the surface of the ultrathin copper layer of the copper foil with carrier greatly affects the transparency of the resin. That is, if the surface roughness Rz is the same, the smaller the ratio A / B, the better the transparency of the resin. For this reason, as for the copper foil with a carrier of this invention, it is preferable that the said ratio A / B is 1.0-1.7, and it is more preferable that it is 1.0-1.6. Here, the ratio A / B between the three-dimensional surface area A and the two-dimensional surface area B of the roughened particles on the surface treated surface is, for example, when the surface is roughened, and the surface area A of the roughened particles, It can also be referred to as the ratio A / B to the area B obtained when the ultrathin copper layer of the carrier-attached copper foil is viewed from the ultrathin copper layer surface side.

  By controlling the current density and plating time of the surface treatment during the surface treatment such as the formation of roughened particles, the surface state of the copper foil after the surface treatment and the form and formation density of the roughened particles are determined. The height Rq, Sv, surface roughness Rz, glossiness, and area ratio A / B of the copper foil surface can be controlled.

[Transmission loss]
When the transmission loss is small, attenuation of the signal when performing signal transmission at a high frequency is suppressed, so that a stable signal transmission can be performed in a circuit that transmits the signal at a high frequency. Therefore, a smaller transmission loss value is preferable because it is suitable for use in a circuit for transmitting a signal at a high frequency. After bonding the copper foil with a carrier to the commercially available liquid crystal polymer resin (Vecstar CTZ-50 μm manufactured by Kuraray Co., Ltd.) from the surface side where the surface treatment of the ultrathin copper layer is performed, the characteristic impedance is 50Ω by etching. When the transmission coefficient is measured using a network analyzer HP8720C manufactured by HP and the transmission loss at a frequency of 20 GHz and a frequency of 40 GHz is obtained, the transmission loss at a frequency of 20 GHz is 5 Less than 0.0 dB / 10 cm is preferred, less than 4.1 dB / 10 cm is more preferred, and less than 3.7 dB / 10 cm is even more preferred.

[Copper foil with carrier]
The copper foil with a carrier which is one embodiment of the present invention includes a carrier, an intermediate layer laminated on the carrier, and an ultrathin copper layer laminated on the intermediate layer. Moreover, the copper foil with a carrier may include a carrier, an intermediate layer, and an ultrathin copper layer in this order. The copper foil with a carrier may have a surface treatment layer such as a roughening treatment layer on one or both of the surface on the carrier side and the surface on the ultrathin copper layer side.
When a roughening treatment layer is provided on the carrier-side surface of the carrier-attached copper foil, when the carrier-attached copper foil is laminated on the support such as a resin substrate from the carrier-side surface side, the carrier and the support such as the resin substrate Has the advantage that it becomes difficult to peel off.

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

The rolled copper foil that can be used for the carrier of the copper foil with carrier according to the present invention includes Ag, Sn, In, Ti, Zn, Zr, Fe, P, Ni, Si, Te, Cr, Nb, V, and the like. A copper alloy foil containing one or more of these elements is also included. When the concentration of the above elements increases (for example, 10% by mass or more in total), the conductivity may decrease. The conductivity of the rolled copper foil is preferably 50% IACS or more, more preferably 60% IACS or more, and still more preferably 80% IACS or more. The copper alloy foil may contain a total of elements other than copper of 0 mass% or more and 50 mass% or less, may contain 0.0001 mass% or more and 40 mass% or less, may contain 0.0005 mass% or more and 30 mass% or less, and 0.001 mass%. More than 20 mass% may be included.
In the present invention, the metal foil used for the carrier has a predetermined surface roughness Rz (ten-point average roughness (JIS B0601 1994) as described above for the surface on which the intermediate layer is formed before the intermediate layer is formed. Compliant)) as well as 60 degree gloss.

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

  Further, as described above, the carrier used in the present invention needs to have controlled surface roughness Rz and glossiness on the side where the intermediate layer is formed. This is for controlling the root mean square height Rq, Sv, surface roughness Rz, glossiness and area ratio A / B of the copper foil surface of the surface on which the surface treatment of the ultrathin copper layer is performed.

<Intermediate layer>
An intermediate layer is provided on the carrier. Another layer may be provided between the carrier and the intermediate layer. In the intermediate layer used in the present invention, the ultrathin copper layer is hardly peeled off from the carrier before the copper foil with the carrier is laminated on the insulating substrate, while the ultrathin copper layer is separated from the carrier after the lamination step on the insulating substrate. There is no particular limitation as long as it can be peeled off. For example, the intermediate layer of the copper foil with a carrier of the present invention is Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, alloys thereof, hydrates thereof, oxides thereof, One or two or more selected from the group consisting of organic substances may be included. The intermediate layer may be a plurality of layers.
Further, for example, the intermediate layer is a single metal layer composed of one kind of element selected from the element group composed of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn from the carrier side. Or forming an alloy layer composed of one or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, A layer made of a hydrate or oxide of one or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn. It can comprise by forming.
Moreover, a well-known organic substance can be used for the intermediate | middle layer as said organic substance, and it is preferable to use any 1 or more types of a nitrogen containing organic compound, a sulfur containing organic compound, and carboxylic acid. For example, specific nitrogen-containing organic compounds include 1,2,3-benzotriazole, carboxybenzotriazole, N ′, N′-bis (benzotriazolylmethyl) urea, 1H, which are triazole compounds having a substituent. It is preferable to use -1,2,4-triazole and 3-amino-1H-1,2,4-triazole.
For the sulfur-containing organic compound, it is preferable to use mercaptobenzothiazole, 2-mercaptobenzothiazole sodium, thiocyanuric acid, 2-benzimidazolethiol, and the like.
As the carboxylic acid, it is particularly preferable to use a monocarboxylic acid, and it is particularly preferable to use oleic acid, linoleic acid, linolenic acid, or the like.
Further, for example, the intermediate layer can be configured by laminating nickel, a nickel-phosphorus alloy or a nickel-cobalt alloy, and chromium in this order on a carrier. Since the adhesive strength between nickel and copper is higher than the adhesive strength between chromium and copper, when the ultrathin copper layer is peeled off, it peels at the interface between the ultrathin copper layer and chromium. Further, the nickel of the intermediate layer is expected to have a barrier effect that prevents the copper component from diffusing from the carrier into the ultrathin copper layer. Adhesion amount of nickel in the intermediate layer is preferably 100 [mu] g / dm ² or more 40000μg / dm ² or less, more preferably 100 [mu] g / dm ² or more 4000μg / dm ² or less, more preferably 100 [mu] g / dm ² or more 2500 g / dm ² or less, more Preferably, it is 100 μg / dm ² or more and less than 1000 μg / dm ² , and the amount of chromium deposited on the intermediate layer is preferably 5 μg / dm ² or more and 100 μg / dm ² or less. When the intermediate layer is provided only on one side, it is preferable to provide a rust preventive layer such as a Ni plating layer on the opposite side of the carrier.
If the thickness of the intermediate layer becomes too large, it may affect the glossiness of the roughened surface of the ultrathin copper layer after the surface treatment of the intermediate layer and the size and number of roughened particles. The thickness of the intermediate layer on the roughened surface of the layer is preferably 1-1000 nm, preferably 1-500 nm, preferably 2-200 nm, preferably 2-100 nm, More preferably, it is 60 nm. An intermediate layer may be provided on both sides of the carrier.

<Ultrathin copper layer>
An ultrathin copper layer is provided on the intermediate layer. Another layer may be provided between the intermediate layer and the ultrathin copper layer. Further, an ultrathin copper layer may be provided on both sides of the carrier. The ultrathin copper layer having the carrier is a copper foil with a carrier which is one embodiment of the present invention. The thickness of the ultrathin copper layer is not particularly limited, but is generally thinner than the carrier, for example, 12 μm or less. Typically, it is 0.5 to 12 μm, and more typically 1.5 to 5 μm. Further, strike plating with a copper-phosphorus alloy may be performed before reducing the pinholes in the ultrathin copper layer before providing the ultrathin copper layer on the intermediate layer. Examples of the strike plating include a copper pyrophosphate plating solution.
The ultra-thin copper layer of the present application is formed under the following conditions. By forming a smooth ultrathin copper layer, the root mean square height Rq, Sv, surface roughness Rz, glossiness, and surface area ratio A / B of the copper foil surface after the surface treatment of the ultrathin copper layer It is for controlling.
-Electrolyte composition Copper: 80-120 g / L
Sulfuric acid: 80-120 g / L
Chlorine: 30-100ppm
Leveling agent 1 (bis (3sulfopropyl) disulfide): 10 to 30 ppm
Leveling agent 2 (amine compound): 10 to 30 ppm
As the amine compound, an amine compound having the following chemical formula can be used.

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

Manufacturing conditions Current density: 70-100 A / dm ²
Electrolyte temperature: 50-65 ° C
Electrolyte linear velocity: 1.5-5 m / sec
Electrolysis time: 0.5 to 10 minutes (adjusted according to the thickness of copper to be deposited and current density)

[Resin layer on the surface where surface treatment is performed]
You may provide a resin layer on the surface where the surface treatment of the copper foil with a carrier of this invention is performed. The resin layer may be an insulating resin layer. In addition, in the copper foil with a carrier of the present invention, “the surface where the surface treatment is performed” is for providing a roughening treatment, a heat-resistant layer, a rust-proof layer, a weather-resistant layer, etc. on the ultra-thin copper layer of the copper foil with a carrier. When the surface treatment is performed, it means the surface of the ultrathin copper layer of the carrier-attached copper foil after the surface treatment.

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

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

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

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

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

  The epoxy resin obtained as a derivative from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is converted to 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide. After reacting naphthoquinone or hydroquinone to obtain a compound represented by the following chemical formula 3 (HCA-NQ) or chemical formula 4 (HCA-HQ), an epoxy resin is reacted with the OH group portion to obtain a phosphorus-containing epoxy resin. Is.

  The phosphorus-containing epoxy resin, which is the E component obtained using the above-mentioned compound as a raw material, is used by mixing one or two of the compounds having the structural formula shown in any one of the following chemical formulas 5 to 7. Is preferred. This is because the resin quality in a semi-cured state is excellent in stability, and at the same time, the flame retardant effect is high.

Further, as the brominated (brominated) epoxy resin, a known brominated (brominated) epoxy resin can be used. For example, the brominated (brominated) epoxy resin is a brominated epoxy resin having the structural formula shown in Chemical Formula 8 obtained as a derivative from tetrabromobisphenol A having two or more epoxy groups in the molecule. It is preferable to use one or two brominated epoxy resins having the structural formula shown in FIG.

As the maleimide resin, aromatic maleimide resin, maleimide compound or polymaleimide compound, known maleimide resins, aromatic maleimide resins, maleimide compounds or polymaleimide compounds can be used. For example, as maleimide resin or aromatic maleimide resin or maleimide compound or polymaleimide compound, 4,4′-diphenylmethane bismaleimide, polyphenylmethane maleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3′-dimethyl -5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenylsulfone bismaleimide, 1, It is possible to use 3-bis (3-maleimidophenoxy) benzene, 1,3-bis (4-maleimidophenoxy) benzene and a polymer obtained by polymerizing the above compound with the above compound or other compounds. The maleimide resin may be an aromatic maleimide resin having two or more maleimide groups in the molecule, and an aromatic maleimide resin having two or more maleimide groups in the molecule and a polyamine or aromatic polyamine. Polymerization adducts obtained by polymerizing and may be used.
As the polyamine or aromatic polyamine, known polyamines or aromatic polyamines can be used. For example, as polyamine or aromatic polyamine, m-phenylenediamine, p-phenylenediamine, 4,4′-diaminodicyclohexylmethane, 1,4-diaminocyclohexane, 2,6-diaminopyridine, 4,4′-diaminodiphenylmethane, 2,2-bis (4-aminophenyl) propane, 4,4′-diaminodiphenyl ether, 4,4′-diamino-3-methyldiphenyl ether, 4,4′-diaminodiphenyl sulfide, 4,4′-diaminobenzophenone, 4,4′-diaminodiphenylsulfone, bis (4-aminophenyl) phenylamine, m-xylenediamine, p-xylenediamine, 1,3-bis [4-aminophenoxy] benzene, 3-methyl-4,4 ′ -Diaminodiphenylmethane, 3,3'-diethyl-4 4'-diaminodiphenylmethane, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 2,2 ', 5,5'-tetrachloro-4,4'-diaminodiphenylmethane, 2,2-bis (3- Methyl-4-aminophenyl) propane, 2,2-bis (3-ethyl-4-aminophenyl) propane, 2,2-bis (2,3-dichloro-4-aminophenyl) propane, bis (2,3 -Dimethyl-4-aminophenyl) phenylethane, ethylenediamine and hexamethylenediamine, 2,2-bis (4- (4-aminophenoxy) phenyl) propane and the above compound and the above compound or other compounds were polymerized. A polymer or the like can be used. Moreover, 1 type, or 2 or more types of well-known polyamine and / or aromatic polyamine or the above-mentioned polyamine or aromatic polyamine can be used.
A known phenoxy resin can be used as the phenoxy resin. Moreover, what is synthesize | combined by reaction of bisphenol and a bivalent epoxy resin can be used as said phenoxy resin. As an epoxy resin, a well-known epoxy resin and / or the above-mentioned epoxy resin can be used.
As the bisphenol, known bisphenols can be used, and bisphenol A, bisphenol F, bisphenol S, tetrabromobisphenol A, 4,4′-dihydroxybiphenyl, HCA (9,10-Dihydro-9-Oxa- Bisphenol obtained as an adduct of 10-phosphophenanthrene-10-oxide) and quinones such as hydroquinone and naphthoquinone can be used.
As the linear polymer having a crosslinkable functional group, a known linear polymer having a crosslinkable functional group can be used. For example, the linear polymer having a crosslinkable functional group preferably has a functional group that contributes to the curing reaction of an epoxy resin such as a hydroxyl group or a carboxyl group. And it is preferable that the linear polymer which has this crosslinkable functional group is soluble in the organic solvent of the temperature of 50 to 200 degreeC of boiling points. Specific examples of the linear polymer having a functional group mentioned here include polyvinyl acetal resin, phenoxy resin, polyethersulfone resin, polyamideimide resin and the like.
The resin layer may contain a crosslinking agent. A known crosslinking agent can be used as the crosslinking agent. For example, a urethane-based resin can be used as the crosslinking agent.
A known rubber resin can be used as the rubber resin. For example, the rubber resin is described as a concept including natural rubber and synthetic rubber. The latter synthetic rubber includes styrene-butadiene rubber, butadiene rubber, butyl rubber, ethylene-propylene rubber, acrylonitrile butadiene rubber, acrylic rubber ( Acrylic ester copolymer), polybutadiene rubber, isoprene rubber and the like. Furthermore, when ensuring the heat resistance of the resin layer to be formed, it is also useful to select and use a synthetic rubber having heat resistance such as nitrile rubber, chloroprene rubber, silicon rubber, urethane rubber or the like. Regarding these rubber resins, it is desirable to have various functional groups at both ends in order to produce a copolymer by reacting with an aromatic polyamide resin or a polyamideimide resin. In particular, it is useful to use CTBN (carboxy group-terminated butadiene nitrile). Moreover, among acrylonitrile butadiene rubbers, a carboxyl-modified product can take a crosslinked structure with an epoxy resin and improve the flexibility of the cured resin layer. As the carboxyl-modified product, carboxy group-terminated nitrile butadiene rubber (CTBN), carboxy group-terminated butadiene rubber (CTB), and carboxy-modified nitrile butadiene rubber (C-NBR) can be used.
A known polyimide amide resin can be used as the polyamide imide resin. In addition, as the polyimide amide resin, for example, trimellitic anhydride, benzophenonetetracarboxylic anhydride and vitorylene diisocyanate are heated in a solvent such as N-methyl-2-pyrrolidone and / or N, N-dimethylacetamide. By heating the resin obtained by doing so, trimellitic anhydride, diphenylmethane diisocyanate and carboxyl group-terminated acrylonitrile-butadiene rubber in a solvent such as N-methyl-2-pyrrolidone and / or N, N-dimethylacetamide What is obtained can be used.
A known rubber-modified polyamideimide resin can be used as the rubber-modified polyamideimide resin. The rubber-modified polyamideimide resin is obtained by reacting a polyamideimide resin and a rubber resin. The reaction of the polyamide-imide resin and the rubber resin is performed for the purpose of improving the flexibility of the polyamide-imide resin itself. That is, the polyamideimide resin and the rubber resin are reacted to replace a part of the acid component (cyclohexanedicarboxylic acid or the like) of the polyamideimide resin with the rubber component. A known polyamideimide resin can be used as the polyamideimide resin. As the rubber resin, a known rubber resin or the aforementioned rubber resin can be used. Solvents used for dissolving the polyamideimide resin and the rubbery resin when polymerizing the rubber-modified polyamideimide resin include dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, nitromethane, nitroethane, tetrahydrofuran , Cyclohexanone, methyl ethyl ketone, acetonitrile, γ-butyrolactone, and the like are preferably used alone or in combination.
A known phosphazene resin can be used as the phosphazene resin. The phosphazene resin is a resin containing phosphazene having a double bond having phosphorus and nitrogen as constituent elements. The phosphazene resin can dramatically improve the flame retardancy due to the synergistic effect of nitrogen and phosphorus in the molecule. In addition, unlike 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivatives, it exists stably in the resin, and the effect of preventing the occurrence of migration is obtained.
A known fluororesin can be used as the fluororesin. Examples of the fluororesin include PTFE (polytetrafluoroethylene (tetrafluoroethylene)), PFA (tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer), FEP (tetrafluoroethylene / hexafluoropropylene copolymer (4.6). Fluoride)), ETFE (tetrafluoroethylene / ethylene copolymer), PVDF (polyvinylidene fluoride (difluoride)), PCTFE (polychlorotrifluoroethylene (trifluoride)), polyallylsulfone, aromatic A fluororesin composed of at least one thermoplastic resin selected from polysulfide and aromatic polyether and a fluororesin may be used.
The resin layer may contain a resin curing agent. A known resin curing agent can be used as the resin curing agent. For example, resin curing agents include amines such as dicyandiamide, imidazoles and aromatic amines, phenols such as bisphenol A and brominated bisphenol A, novolaks such as phenol novolac resins and cresol novolac resins, and acid anhydrides such as phthalic anhydride. Products, biphenyl type phenol resins, phenol aralkyl type phenol resins and the like can be used. The resin layer may contain one or more of the aforementioned resin curing agents. These curing agents are particularly effective for epoxy resins.
A specific example of the biphenyl type phenol resin is shown in Chemical formula 10.

  A specific example of the phenol aralkyl type phenol resin is shown in Chemical Formula 11.

Known imidazoles can be used, for example, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl- 2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5- Hydroxymethylimidazole etc. are mentioned, These can be used individually or in mixture.
Of these, imidazoles having the structural formula shown in Chemical Formula 12 below are preferably used. By using the imidazole having the structural formula shown in Chemical formula 12, the moisture absorption resistance of the semi-cured resin layer can be remarkably improved, and the long-term storage stability is excellent. This is because imidazoles function as a catalyst during curing of the epoxy resin and contribute as a reaction initiator that causes a self-polymerization reaction of the epoxy resin in the initial stage of the curing reaction.

As the amine resin curing agent, known amines can be used. As the amine resin curing agent, for example, the above-mentioned polyamines and aromatic polyamines can be used, and aromatic polyamines, polyamides, and these are obtained by polymerizing or condensing with epoxy resins or polyvalent carboxylic acids. One or more selected from the group of amine adducts to be used may be used. Examples of the resin curing agent for amines include 4,4′-diaminodiphenylenesulfone, 3,3′-diaminodiphenylenesulfone, 4,4-diaminodiphenylel, and 2,2-bis [4. It is preferable to use at least one of-(4-aminophenoxy) phenyl] propane and bis [4- (4-aminophenoxy) phenyl] sulfone.
The resin layer may contain a curing accelerator. A known curing accelerator can be used as the curing accelerator. For example, as the curing accelerator, tertiary amine, imidazole, urea curing accelerator and the like can be used.
The resin layer may include a reaction catalyst. A known reaction catalyst can be used as the reaction catalyst. For example, finely pulverized silica or antimony trioxide can be used as a reaction catalyst.

  The polyhydric carboxylic acid anhydride is preferably a component that contributes as a curing agent for the epoxy resin. The anhydride of the polyvalent carboxylic acid is phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, tetrahydroxyphthalic anhydride, hexahydroxyphthalic anhydride, methylhexahydroxyphthalic anhydride, nadine. Acid and methyl nadic acid are preferred.

The thermoplastic resin may be a thermoplastic resin having a functional group other than an alcoholic hydroxyl group polymerizable with an epoxy resin.
The polyvinyl acetal resin may have a functional group polymerizable with an epoxy resin or a maleimide compound other than an acid group and a hydroxyl group. The polyvinyl acetal resin may have a carboxyl group, an amino group or an unsaturated double bond introduced into the molecule.
Examples of the aromatic polyamide resin polymer include those obtained by reacting an aromatic polyamide resin and a rubber resin. Here, the aromatic polyamide resin is synthesized by condensation polymerization of an aromatic diamine and a dicarboxylic acid. As the aromatic diamine at this time, 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylsulfone, m-xylenediamine, 3,3′-oxydianiline and the like are used. As the dicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, fumaric acid or the like is used.
As the rubber resin to be reacted with the aromatic polyamide resin, a known rubber resin or the aforementioned rubber resin can be used.
This aromatic polyamide resin polymer is used for the purpose of not being damaged by under-etching by an etchant when etching a copper foil after being processed into a copper-clad laminate.

  The resin layer is a cured resin layer (the “cured resin layer” means a cured resin layer) and a half in order from the copper foil side (that is, the ultrathin copper layer side of the copper foil with carrier). The resin layer which formed the cured resin layer sequentially may be sufficient. The cured resin layer may be composed of a resin component of any one of a polyimide resin, a polyamideimide resin, and a composite resin having a thermal expansion coefficient of 0 ppm / ° C. to 25 ppm / ° C.

  Moreover, you may provide the semi-hardened resin layer whose thermal expansion coefficient after hardening is 0 ppm / degrees C-50 ppm / degrees C on the said cured resin layer. In addition, the thermal expansion coefficient of the entire resin layer after the cured resin layer and the semi-cured resin layer are cured may be 40 ppm / ° C. or less. The cured resin layer may have a glass transition temperature of 300 ° C. or higher. The semi-cured resin layer may be formed using a maleimide resin or an aromatic maleimide resin. The resin composition for forming the semi-cured resin layer preferably contains a maleimide resin, an epoxy resin, and a linear polymer having a crosslinkable functional group. As the epoxy resin, a known epoxy resin or an epoxy resin described in this specification can be used. In addition, as maleimide resins, aromatic maleimide resins, linear polymers having crosslinkable functional groups, known maleimide resins, aromatic maleimide resins, linear polymers having crosslinkable functional groups, or the aforementioned maleimide resins. An aromatic maleimide resin or a linear polymer having a crosslinkable functional group can be used.

Moreover, when providing the copper foil with a carrier which has a resin layer suitable for a three-dimensional molded printed wiring board manufacture use, it is preferable that the said cured resin layer is a polymeric polymer layer which has hardened | cured flexibility. The polymer layer is preferably made of a resin having a glass transition temperature of 150 ° C. or higher so that it can withstand the solder mounting process. The polymer layer is preferably composed of one or a mixture of two or more of a polyamide resin, a polyether sulfone resin, an aramid resin, a phenoxy resin, a polyimide resin, a polyvinyl acetal resin, and a polyamideimide resin. The thickness of the polymer layer is preferably 3 μm to 10 μm.
The polymer layer preferably contains one or more of epoxy resin, maleimide resin, phenol resin, and urethane resin. The semi-cured resin layer is preferably composed of an epoxy resin composition having a thickness of 10 μm to 50 μm.

Moreover, it is preferable that the said epoxy resin composition contains each component of the following A component-E component.
Component A: An epoxy resin having one or more selected from the group consisting of a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a bisphenol AD type epoxy resin that have an epoxy equivalent of 200 or less and are liquid at room temperature.
B component: High heat resistant epoxy resin.
Component C: Phosphorus-containing flame-retardant resin, which is any one of phosphorus-containing epoxy resin and phosphazene-based resin, or a resin obtained by mixing these.
Component D: A rubber-modified polyamide-imide resin modified with a liquid rubber component having a property that is soluble in a solvent having a boiling point in the range of 50 ° C. to 200 ° C.
E component: Resin curing agent.

The B component is a “high heat resistant epoxy resin” having a high so-called glass transition point Tg. The “high heat-resistant epoxy resin” referred to here is preferably a polyfunctional epoxy resin such as a novolac-type epoxy resin, a cresol novolac-type epoxy resin, a phenol novolac-type epoxy resin, or a naphthalene-type epoxy resin.
As the phosphorus-containing epoxy resin of component C, the aforementioned phosphorus-containing epoxy resin can be used. The phosphazene resin described above can be used as the C component phosphazene resin.
The rubber-modified polyamide-imide resin described above can be used as the rubber-modified polyamide-imide resin of component D. The resin curing agent described above can be used as the E component resin curing agent.

  A solvent is added to the resin composition shown above and used as a resin varnish, and a thermosetting resin layer is formed as an adhesive layer of a printed wiring board. The resin varnish is prepared by adding a solvent to the above resin composition so that the resin solid content is in the range of 30 wt% to 70 wt%, and the resin flow when measured in accordance with MIL-P-13949G in the MIL standard. A semi-cured resin film in the range of 5% to 35% can be formed. As the solvent, a known solvent or the aforementioned solvent can be used.

  The resin layer is a resin layer having a first thermosetting resin layer and a second thermosetting resin layer located on the surface of the first thermosetting resin layer in order from the copper foil side, The curable resin layer is formed of a resin component that does not dissolve in chemicals during desmear processing in the wiring board manufacturing process, and the second thermosetting resin layer dissolves in chemicals during desmear processing in the wiring board manufacturing process. Then, it may be formed using a resin that can be washed and removed. The first thermosetting resin layer may be formed using a resin component obtained by mixing one or more of polyimide resin, polyethersulfone, and polyphenylene oxide. The second thermosetting resin layer may be formed using an epoxy resin component. The thickness t1 (μm) of the first thermosetting resin layer is Rz (μm) of the roughened surface roughness of the copper foil with carrier, and the thickness of the second thermosetting resin layer is t2 (μm). Then, t1 is preferably a thickness that satisfies the condition of Rz <t1 <t2.

  The resin layer may be a prepreg in which a skeleton material is impregnated with a resin. The resin impregnated in the skeleton material is preferably a thermosetting resin. The prepreg may be a known prepreg or a prepreg used for manufacturing a printed wiring board.

The skeleton material may include aramid fibers, glass fibers, or wholly aromatic polyester fibers. The skeleton material is preferably an aramid fiber, a glass fiber, or a nonwoven fabric or woven fabric of wholly aromatic polyester fibers. The wholly aromatic polyester fiber is preferably a wholly aromatic polyester fiber having a melting point of 300 ° C. or higher. The wholly aromatic polyester fiber having a melting point of 300 ° C. or higher is a fiber produced using a resin called a so-called liquid crystal polymer, and the liquid crystal polymer contains 2-hydroxyl-6-naphthoic acid and p-hydroxybenzoic acid. The main component is an acid polymer. Since this wholly aromatic polyester fiber has a low dielectric constant and low dielectric loss tangent, it has excellent performance as a constituent material of an electrically insulating layer and can be used in the same manner as glass fiber and aramid fiber. is there.
In addition, in order to improve the wettability with the resin of the surface, it is preferable to perform the silane coupling agent process for the fiber which comprises the said nonwoven fabric and woven fabric. As the silane coupling agent at this time, a known amino-based or epoxy-based silane coupling agent or the aforementioned silane coupling agent can be used depending on the purpose of use.

  The prepreg is a prepreg obtained by impregnating a thermosetting resin into a nonwoven fabric using an aramid fiber or glass fiber having a nominal thickness of 70 μm or less, or a skeleton material made of glass cloth having a nominal thickness of 30 μm or less. Also good.

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

The dielectric (dielectric filler) may be powdery. When the dielectric (dielectric filler) is powdery, the powder characteristics of the dielectric (dielectric filler) are as follows. First, the particle size is 0.01 μm to 3.0 μm, preferably 0.02 μm to 2.0 μm. Must be in range. The particle size referred to here is indirect in which the average particle size is estimated from the measured values of the laser diffraction scattering type particle size distribution measurement method and the BET method because the particles form a certain secondary aggregation state. It cannot be used because the accuracy is inferior in measurement, and it refers to the average particle diameter obtained by directly observing a dielectric (dielectric filler) with a scanning electron microscope (SEM) and image analysis of the SEM image. It is. In this specification, the particle size at this time is indicated as DIA. The image analysis of the dielectric (dielectric filler) powder observed using a scanning electron microscope (SEM) in this specification is performed using IP-1000PC manufactured by Asahi Engineering Co., Ltd. Circular particle analysis was performed with a threshold value of 10 and an overlapping degree of 20, and the average particle diameter DIA was obtained.
According to the above-described embodiment, the resin layer containing the dielectric for forming the capacitor circuit layer having a low dielectric loss tangent is improved by improving the adhesion between the inner layer circuit surface of the inner layer core material and the resin layer containing the dielectric. The copper foil with a carrier which has can be provided.

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

  The copper foil with a carrier provided with the resin layer (copper foil with a carrier with resin) is superposed on the base material, and the whole is thermocompression bonded to thermally cure the resin layer, and then the carrier is peeled off. And expose the ultrathin copper layer (which is naturally the surface on the intermediate layer side of the ultrathin copper layer), and the surface opposite to the roughened side of the copper foil with carrier Are used in the form of forming a predetermined wiring pattern.

  If this resin-attached copper foil with a carrier is used, the number of prepreg materials used when manufacturing a multilayer printed wiring board can be reduced. In addition, the copper-clad laminate can be manufactured even if the resin layer is made thick enough to ensure interlayer insulation or no prepreg material is used. At this time, the surface smoothness can be further improved by undercoating the surface of the substrate with an insulating resin.

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

When the thickness of the resin layer is less than 0.1 μm, the adhesive strength is reduced, and when the copper foil with a carrier with the resin is laminated on the base material provided with the inner layer material without interposing the prepreg material, the circuit of the inner layer material It may be difficult to ensure interlayer insulation between the two. On the other hand, if the thickness of the resin layer is greater than 120 μm, it is difficult to form a resin layer having a target thickness in a single coating process, which may be economically disadvantageous because of extra material costs and man-hours.
In addition, when the copper foil with a carrier having a resin layer is used for manufacturing an extremely thin multilayer printed wiring board, the thickness of the resin layer is 0.1 μm to 5 μm, more preferably 0.5 μm to 5 μm, More preferably, the thickness is 1 μm to 5 μm in order to reduce the thickness of the multilayer printed wiring board.
When the resin layer includes a dielectric, the thickness of the resin layer is preferably 0.1 to 50 μm, preferably 0.5 μm to 25 μm, and more preferably 1.0 μm to 15 μm. preferable.
The total resin layer thickness with the cured resin layer and the semi-cured resin layer is preferably 0.1 μm to 120 μm, more preferably 5 μm to 120 μm, and preferably 10 μm to 120 μm, 10 μm to 60 μm. Are more preferred. The thickness of the cured resin layer is preferably 2 μm to 30 μm, preferably 3 μm to 30 μm, and more preferably 5 to 20 μm. Moreover, it is preferable that the thickness of a semi-hardened resin layer is 3 micrometers-55 micrometers, it is preferable that they are 7 micrometers-55 micrometers, and it is more desirable that it is 15-115 micrometers. If the total resin layer thickness exceeds 120 μm, it may be difficult to produce a thin multilayer printed wiring board. If the total resin layer thickness is less than 5 μm, a thin multilayer printed wiring board can be easily formed. This is because the resin layer may become too thin and the insulation between the circuits of the inner layer tends to become unstable. Moreover, when the cured resin layer thickness is less than 2 μm, it may be necessary to consider the surface roughness of the roughened surface of the copper foil with carrier. Conversely, if the cured resin layer thickness exceeds 20 μm, the effect of the cured resin layer may not be particularly improved, and the total insulating layer thickness becomes thick.

In the case where the thickness of the resin layer is 0.1 μm to 5 μm, in order to improve the adhesion between the resin layer and the copper foil with carrier, the heat-resistant layer and the roughened surface of the copper foil with carrier are provided. After providing the rust preventive layer and / or the weather resistant layer, it is preferable to form a resin layer on the heat resistant layer, the rust preventive layer or the weather resistant layer.
In addition, the thickness of the above-mentioned resin layer says the average value of the thickness measured by cross-sectional observation in arbitrary 10 points | pieces.

  Furthermore, as another product form when this copper foil with a carrier is a very thin copper layer of a copper foil with a carrier, on the roughened surface of the ultra thin copper layer (copper foil with carrier) After the resin layer is provided and the resin layer is in a semi-cured state, the carrier is then peeled off and can be manufactured in the form of an ultrathin copper layer with resin (copper foil with carrier) in which no carrier is present.

  Below, some examples of the manufacturing process of the printed wiring board using the copper foil with a carrier which concerns on this invention are shown.

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

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

Therefore, in one embodiment of a method for producing a printed wiring board according to the present invention using a semi-additive method, a step of preparing a copper foil with a carrier and an insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Removing all of the ultrathin copper layer exposed by peeling the carrier by a method such as etching or plasma using a corrosive solution such as acid,
Providing a through hole or / and a blind via in the resin exposed by removing the ultrathin copper layer by etching;
Performing a desmear process on the region including the through hole or / and the blind via,
Providing an electroless plating layer for the region including the resin and the through hole or / and the blind via;
Providing a plating resist on the electroless plating layer;
Exposing the plating resist, and then removing the plating resist in a region where a circuit is formed;
Providing an electrolytic plating layer in a region where the circuit from which the plating resist has been removed is formed;
Removing the plating resist;
Removing the electroless plating layer in a region other than the region where the circuit is formed by flash etching or the like;
including.

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

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

Therefore, in one embodiment of the method for producing a printed wiring board according to the present invention using the modified semi-additive method, the step of preparing the copper foil with carrier and the insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Providing a through hole or / and a blind via on the insulating substrate and the ultrathin copper layer exposed by peeling the carrier;
Performing a desmear process on the region including the through hole or / and the blind via,
Providing an electroless plating layer for the region including the through hole or / and the blind via;
Providing a plating resist on the surface of the ultrathin copper layer exposed by peeling the carrier,
Forming a circuit by electrolytic plating after providing the plating resist;
Removing the plating resist;
Removing the ultra-thin copper layer exposed by removing the plating resist by flash etching;
including.

In another embodiment of the method for producing a printed wiring board according to the present invention using the modified semi-additive method, the step of preparing the carrier-attached copper foil and the insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Providing a plating resist on the exposed ultrathin copper layer by peeling off the carrier;
Exposing the plating resist, and then removing the plating resist in a region where a circuit is formed;
Providing an electrolytic plating layer in a region where the circuit from which the plating resist has been removed is formed;
Removing the plating resist;
Removing the electroless plating layer and the ultrathin copper layer in a region other than the region where the circuit is formed by flash etching or the like;
including.

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

Therefore, in one embodiment of the method for producing a printed wiring board according to the present invention using a partly additive method, a step of preparing the copper foil with carrier and the insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Providing a through hole or / and a blind via on the insulating substrate and the ultrathin copper layer exposed by peeling the carrier;
Performing a desmear process on the region including the through hole or / and the blind via,
Applying catalyst nuclei to the region containing the through-holes and / or blind vias;
Providing an etching resist on the surface of the ultrathin copper layer exposed by peeling the carrier,
Exposing the etching resist to form a circuit pattern;
Removing the ultrathin copper layer and the catalyst nucleus by a method such as etching or plasma using a corrosive solution such as an acid to form a circuit;
Removing the etching resist;
A step of providing a solder resist or a plating resist on the surface of the insulating substrate exposed by removing the ultrathin copper layer and the catalyst core by a method such as etching or plasma using a corrosive solution such as an acid;
Providing an electroless plating layer in a region where the solder resist or plating resist is not provided,
including.

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

Therefore, in one embodiment of the method for producing a printed wiring board according to the present invention using a subtractive method, a step of preparing the carrier-attached copper foil and the insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Providing a through hole or / and a blind via on the insulating substrate and the ultrathin copper layer exposed by peeling the carrier;
Performing a desmear process on the region including the through hole or / and the blind via,
Providing an electroless plating layer for the region including the through hole or / and the blind via;
Providing an electroplating layer on the surface of the electroless plating layer;
A step of providing an etching resist on the surface of the electrolytic plating layer or / and the ultrathin copper layer;
Exposing the etching resist to form a circuit pattern;
Removing the ultrathin copper layer and the electroless plating layer and the electrolytic plating layer by a method such as etching or plasma using a corrosive solution such as an acid to form a circuit;
Removing the etching resist;
including.

In another embodiment of the method for producing a printed wiring board according to the present invention using a subtractive method, a step of preparing the carrier-attached copper foil and the insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Providing a through hole or / and a blind via on the insulating substrate and the ultrathin copper layer exposed by peeling the carrier;
Performing a desmear process on the region including the through hole or / and the blind via,
Providing an electroless plating layer for the region including the through hole or / and the blind via;
Forming a mask on the surface of the electroless plating layer;
Providing an electroplating layer on the surface of the electroless plating layer on which no mask is formed;
A step of providing an etching resist on the surface of the electrolytic plating layer or / and the ultrathin copper layer;
Exposing the etching resist to form a circuit pattern;
Removing the ultra-thin copper layer and the electroless plating layer by a method such as etching or plasma using a corrosive solution such as an acid to form a circuit;
Removing the etching resist;
including.

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

Here, the specific example of the manufacturing method of the printed wiring board using the copper foil with a carrier of this invention is demonstrated in detail using drawing. Here, the carrier-attached copper foil having an ultrathin copper layer on which a roughened layer is formed will be described as an example. However, the present invention is not limited thereto, and the carrier has an ultrathin copper layer on which a roughened layer is not formed. The following method for producing a printed wiring board can be similarly performed using an attached copper foil.
First, as shown to FIG. 4-A, the copper foil with a carrier (1st layer) which has the ultra-thin copper layer in which the roughening process layer was formed on the surface is prepared.
Next, as shown to FIG. 4-B, a resist is apply | coated on the roughening process layer of an ultra-thin copper layer, exposure and image development are performed, and a resist is etched to a defined shape.
Next, as shown in FIG. 4C, after forming a plating for a circuit, the resist is removed to form a circuit plating having a predetermined shape.
Next, as shown in FIG. 5-D, an embedded resin is provided on the ultrathin copper layer so as to cover the circuit plating (so that the circuit plating is buried), and then the resin layer is laminated, followed by another carrier attachment. A copper foil (second layer) is bonded from the ultrathin copper layer side.
Next, as shown to FIG. 5-E, a carrier is peeled from the copper foil with a carrier of the 2nd layer.
Next, as shown in FIG. 5-F, laser drilling is performed at a predetermined position of the resin layer to expose the circuit plating and form a blind via.
Next, as shown in FIG. 6-G, copper is embedded in the blind via to form a via fill.
Next, as shown in FIG. 6-H, circuit plating is formed on the via fill as shown in FIGS. 4-B and 4-C.
Next, as shown to FIG. 6-I, a carrier is peeled from the copper foil with a carrier of the 1st layer.
Next, as shown in FIG. 7-J, the ultrathin copper layers on both surfaces are removed by flash etching to expose the surface of the circuit plating in the resin layer.
Next, as shown in FIG. 7K, bumps are formed on the circuit plating in the resin layer, and copper pillars are formed on the solder. Thus, the printed wiring board using the copper foil with a carrier of this invention is produced.

  As the another copper foil with a carrier (second layer), the copper foil with a carrier of the present invention may be used, a conventional copper foil with a carrier may be used, and a normal copper foil may be further used. Further, one or more circuits may be formed on the second layer circuit shown in FIG. 6-H, and these circuits may be formed by the semi-additive method, the subtractive method, the partial additive method, or the modified semi-conductor method. You may carry out by any method of an additive method.

The copper foil with a carrier according to the present invention is preferably controlled so that the color difference on the surface of the ultrathin copper layer satisfies the following (1). In the present invention, the “color difference on the surface of the ultrathin copper layer” means the color difference on the surface of the ultrathin copper layer, or the color difference on the surface of the surface treatment layer when various surface treatments such as roughening treatment are applied. . That is, it is preferable that the copper foil with a carrier according to the present invention is controlled so that the color difference of the roughened surface of the ultrathin copper layer satisfies the following (1). In addition, in the copper foil with a carrier of the present invention, the “roughening treatment surface” refers to the surface when the surface treatment for providing a heat-resistant layer, a rust-proof layer, a weather-resistant layer, etc. is performed after the roughening treatment. The surface of the copper foil with a carrier after processing. In addition, when the copper foil with carrier is an ultrathin copper layer of the copper foil with carrier, the “roughening treatment surface” means that after the roughening treatment, a heat-resistant layer, a rust-proof layer, a weather-resistant layer, etc. are provided. When the surface treatment is performed, the surface of the ultrathin copper layer after the surface treatment is performed.
(1) The color difference on the surface of the ultrathin copper layer has a color difference ΔE * ab based on JIS Z8730 of 45 or more.

  Here, the color differences ΔL, Δa, and Δb are respectively measured with a color difference meter, and are shown using the L * a * b color system based on JIS Z8730, taking into account black / white / red / green / yellow / blue. It is a comprehensive index and is expressed as ΔL: black and white, Δa: reddish green, Δb: yellow blue. ΔE * ab is expressed by the following formula using these color differences.

The above-described color difference can be adjusted by increasing the current density when forming the ultrathin copper layer, decreasing the copper concentration in the plating solution, and increasing the linear flow rate of the plating solution.
Moreover, the above-mentioned color difference can also be adjusted by performing a roughening process on the surface of an ultra-thin copper layer and providing a roughening process layer. In the case of providing the roughening treatment layer, the current density is made higher than conventional (for example, 40 to 60 A) using an electrolytic solution containing copper and one or more elements selected from the group consisting of nickel, cobalt, tungsten, and molybdenum. / Dm ² ), and the processing time can be shortened (for example, 0.1 to 1.3 seconds). When a roughening layer is not provided on the surface of the ultrathin copper layer, use a plating bath in which the concentration of Ni is twice or more that of other elements, and use an ultrathin copper layer, heat resistant layer, rust preventive layer or chromate. Ni alloy plating (for example, Ni-W alloy plating, Ni-Co-P alloy plating, Ni-Zn alloy plating) is applied to the surface of the treatment layer or the silane coupling treatment layer at a lower current density (0.1 to 1.. 3A / dm ² ), and the processing time can be set long (20 to 40 seconds).

  When the color difference ΔE * ab based on JIS Z8730 is 45 or more when the color difference on the surface of the ultrathin copper layer is 45 or more, for example, when forming a circuit on the surface of the ultrathin copper layer of the copper foil with carrier, As a result, the visibility is improved and the circuit alignment can be performed with high accuracy. The color difference ΔE * ab based on JIS Z8730 on the ultrathin copper layer surface is preferably 50 or more, more preferably 55 or more, and even more preferably 60 or more.

  When the color difference on the surface of the ultrathin copper layer is controlled as described above, the contrast with the circuit plating becomes clear and the visibility becomes good. Therefore, in the manufacturing process of the printed wiring board as described above, for example, as shown in FIG. 4-C, the circuit plating can be accurately formed at a predetermined position. Further, according to the method for manufacturing a printed wiring board as described above, since the circuit plating is embedded in the resin layer, for example, removal of the ultrathin copper layer by flash etching as shown in FIG. At this time, the circuit plating is protected by the resin layer and the shape thereof is maintained, thereby facilitating the formation of a fine circuit. Further, since the circuit plating is protected by the resin layer, the migration resistance is improved, and the continuity of the circuit wiring is satisfactorily suppressed. For this reason, formation of a fine circuit becomes easy. Also, as shown in FIGS. 7-J and 7-K, when the ultra-thin copper layer is removed by flash etching, the exposed surface of the circuit plating is recessed from the resin layer, so that bumps are formed on the circuit plating. In addition, copper pillars can be easily formed thereon, and the production efficiency is improved.

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

  Moreover, the copper foil with a carrier used for the first layer may have a substrate or a resin layer on the surface of the copper foil with a carrier. By having the said board | substrate or resin layer, the copper foil with a carrier used for the first layer is supported, and since it becomes difficult to wrinkle, there exists an advantage that productivity improves. As the substrate or resin layer, any substrate or resin layer can be used as long as it has an effect of supporting the copper foil with carrier used in the first layer. For example, as the substrate or resin layer, the carrier, prepreg, resin layer and known carrier, prepreg, resin layer, metal plate, metal foil, inorganic compound plate, inorganic compound foil, organic compound plate described in the present specification, Organic compound foils can be used.

The copper foil with a carrier of the present invention can be bonded to a resin substrate from the surface-treated surface side to produce a laminate. The resin substrate is not particularly limited as long as it has characteristics applicable to a printed wiring board or the like. For example, a paper base phenol resin, a paper base epoxy resin, a synthetic fiber cloth base epoxy resin for rigid PWB Glass cloth / paper composite base material epoxy resin, glass cloth / glass nonwoven fabric composite base material epoxy resin and glass cloth base material epoxy resin, etc. are used, polyester film, polyimide film, liquid crystal polymer (LCP) film, fluorine for FPC Resin, Teflon (registered trademark) film, etc. can be used. In addition, when a liquid crystal polymer (LCP) film, a fluororesin film, or a Teflon (registered trademark) film is used, the peel strength between the film and the carrier-attached copper foil tends to be smaller than when a polyimide film is used. . Therefore, when a liquid crystal polymer (LCP) film or a fluororesin film is used, the copper circuit is covered with a coverlay after the copper circuit is formed, so that the film and the copper circuit are not easily peeled off, and the peel strength is reduced. The film can be prevented from peeling off from the copper circuit.
Since the liquid crystal polymer (LCP) film or fluororesin film has a small dielectric loss tangent, the copper-clad laminate using the liquid crystal polymer (LCP) film or fluororesin film and the copper foil with carrier according to the present invention, printed wiring Boards and printed circuit boards are suitable for high-frequency circuits (circuits that transmit signals at high frequencies). Further, the copper foil with a carrier according to the present invention has a small surface roughness Rz and a high glossiness, so that the surface is smooth and suitable for high frequency circuit applications. In the present invention, the “printed wiring board” includes a printed wiring board, a printed circuit board, and a printed board on which components are mounted.

In the case of the rigid PWB, a prepreg is prepared by impregnating a base material such as a glass cloth with a resin and curing the resin to a semi-cured state. The copper foil can be applied by heating and pressing the prepreg from the surface on which the surface treatment is performed. In the case of FPC, it is laminated on a copper foil under high temperature and high pressure without using an adhesive on a substrate such as a polyimide film, or a polyimide precursor is applied, dried, cured, etc. A laminated board can be manufactured by performing.
The thickness of the polyimide base resin is not particularly limited, but generally 25 μm or 50 μm can be mentioned.

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

(Laminated board and printed wiring board positioning method using the same)
A method for positioning the laminate of the copper foil with carrier and the resin substrate of the present invention will be described. First, the laminated board of copper foil with a carrier and a resin substrate is prepared. As a specific example of the laminated board of the copper foil with a carrier and the resin substrate of the present invention, at least one of a resin substrate such as a polyimide used for electrically connecting the main body substrate and the attached circuit substrate and them. In an electronic device composed of a flexible printed circuit board with copper wiring formed on the surface, a laminated board manufactured by accurately positioning the flexible printed circuit board and crimping it to the wiring ends of the main circuit board and the attached circuit board Is mentioned. That is, in this case, the laminate is a laminate in which the wiring end portions of the flexible printed circuit board and the main body substrate are bonded together by pressure bonding, or the wiring edge portions of the flexible printed circuit board and the circuit board are bonded together by pressure bonding. Laminated board. The laminated board has a mark formed of a part of the copper wiring and a separate material. The position of the mark is not particularly limited as long as it can be photographed by photographing means such as a CCD camera through the resin constituting the laminated plate. In addition, when the copper foil with a carrier of this invention is the ultra-thin copper layer (ultra-thin copper layer which has a carrier) of the copper foil with a carrier, from the laminated board of copper foil with a carrier and a resin substrate as needed Remove the carrier.

  In the laminated plate thus prepared, when the above-described mark is photographed by the photographing means through the resin, the position of the mark can be detected satisfactorily. And the position of the said mark can be detected in this way, and the positioning of the laminated board of copper foil with a carrier and a resin substrate can be favorably performed based on the detected position of the mark. Similarly, when a printed wiring board is used as the laminated board, the photographing means can detect the position of the mark well by such a positioning method, and the printed wiring board can be positioned more accurately.

  Therefore, when one printed wiring board and another printed wiring board are connected, it is considered that the connection failure is reduced and the yield is improved. In addition, as a method of connecting one printed wiring board and another printed wiring board, connection via soldering or anisotropic conductive film (ACF), anisotropic conductive paste (Anisotropic Conductive Paste, A known connection method such as connection via ACP) or connection via a conductive adhesive can be used. In the present invention, the “printed wiring board” includes a printed wiring board, a printed circuit board, and a printed board on which components are mounted. Also, it is possible to manufacture a printed wiring board in which two or more printed wiring boards are connected by connecting two or more printed wiring boards according to the present invention, and at least one printed wiring board according to the present invention. One printed wiring board of the present invention or a printed wiring board not corresponding to the printed wiring board of the present invention can be connected, and an electronic apparatus can be manufactured using such a printed wiring board. In the present invention, “copper circuit” includes copper wiring. Furthermore, the printed wiring board of the present invention may be connected to a component to produce a printed wiring board. Further, at least one printed wiring board of the present invention is connected to another printed wiring board of the present invention or a printed wiring board not corresponding to the printed wiring board of the present invention. A printed wiring board in which two or more printed wiring boards are connected may be manufactured by connecting two or more printed wiring boards and components. Here, as “components”, connectors, LCDs (Liquid Crystal Display), electronic components such as glass substrates used in LCDs, ICs (Integrated Circuits), LSIs (Large scale integrated circuits), VLSIs (Very Large scale circuits). ), Electronic components including semiconductor integrated circuits such as ULSI (Ultra-Large Scale Integrated Circuit) (for example, IC chip, LSI chip, VLSI chip, ULSI chip), components for shielding electronic circuits, and covers on printed wiring boards, etc. Examples of the parts necessary to fix the are included.

The positioning method according to the embodiment of the present invention may include a step of moving a laminated board (including a laminated board of copper foil and a resin substrate and a printed wiring board). In the moving process, for example, it may be moved by a conveyor such as a belt conveyor or a chain conveyor, may be moved by a moving device provided with an arm mechanism, or may be moved by floating a laminated plate using gas. It may be moved by a moving means, a moving device or moving means (including a roller or a bearing) that moves a laminated plate by rotating an object such as a substantially cylindrical shape, a moving device or moving means that uses hydraulic pressure as a power source, Moving devices and moving means powered by air pressure, moving devices and moving means powered by motors, gantry moving linear guide stages, gantry moving air guide stages, stacked linear guide stages, linear motor drive stages, etc. It may be moved by a moving device or moving means having a stage. Moreover, you may perform the movement process by a well-known moving means.
The positioning method according to the embodiment of the present invention may be used for a surface mounter or a chip mounter.
Moreover, the printed wiring board which has the circuit provided on the resin board and the said resin board may be sufficient as the laminated board of the copper foil with a carrier and resin board | substrate positioned in this invention. In that case, the mark may be the circuit.

In the present invention, “positioning” includes “detecting the position of a mark or an object”. In the present invention, “alignment” includes “after detecting the position of a mark or object, moving the mark or object to a predetermined position based on the detected position”.
In the printed wiring board, the circuit on the printed wiring board is used as a mark instead of the mark on the printed material, and the Sv value can be measured by photographing the circuit through a resin with a CCD camera. Also, for copper-clad laminates, after copper was etched into a line shape, the lined copper was used as a mark instead of a printed mark, and the lined copper was photographed with a CCD camera through the resin. Thus, the value of Sv can be measured.

As Examples 1 to 14 and Comparative Examples 1 to 5, various carriers shown in Table 1 were prepared, and an intermediate layer shown in Table 2 was formed on the surface of the carrier by a roll-to-roll type continuous plating line. . And the ultrathin copper layer of the thickness of Table 2 was formed on the surface of the intermediate layer on the following conditions. And it plated on the conditions of Table 2 as surface treatment of an ultra-thin copper layer.
In addition, for example, “Ni / electrolytic pure chromate” in the column of the intermediate layer in Table 2 indicates that electrolytic pure chromate was performed after Ni plating.
In addition, the copper foil with a carrier which does not perform a roughening process was also prepared. “No” in the “Roughening treatment” column of “Surface treatment” in Table 2 indicates that the surface treatment is not a roughening treatment, and “Yes” indicates that the surface treatment is a roughening treatment.

<Intermediate layer>
(1) “Ni”: indicates that Ni plating was performed under the following conditions.
Liquid composition: nickel sulfate: 270-280 g / L, nickel chloride: 35-45 g / L, nickel acetate: 10-20 g / L, boric acid: 30-40 g / L, brightener: saccharin, butynediol, dodecyl sulfate Sodium: 55-75 ppm
pH: 4-6
Bath temperature: 55-65 ° C
Current density: 10 A / dm ²
Ni adhesion amount: 500 to 20000 μg / dm ²
(2) “Electrolytically pure chromate”: Indicates that electrolytically pure chromate treatment was performed under the following conditions.
Liquid composition: potassium dichromate 1-10 g / L, zinc 0 g / L
pH: 7-10
Liquid temperature: 40-60 degreeC
Current density: 2 A / dm ²
Cr adhesion amount: 10 to 100 μg / dm ²
(3) “Electrolytic zinc chromate”: indicates that electrolytic zinc chromate treatment was performed under the following conditions.
Liquid composition: potassium dichromate 1-10 g / L, zinc 0.5-5 g / L
pH: 7-10
Liquid temperature: 40-60 degreeC
Current density: 2 A / dm ²
Cr adhesion amount: 10 to 100 μg / dm ²
(4) “Immersion pure chromate”: indicates that immersion pure chromate treatment was performed under the following conditions.
Liquid composition: potassium dichromate 1-10 g / L, zinc 0 g / L
pH: 7-10
Liquid temperature: 40-60 degreeC
Immersion time: 5 to 30 seconds (5) “Ni—Mo”: Indicates that nickel molybdenum alloy plating was performed under the following conditions.
Liquid composition: Ni sulfate sulfate hexahydrate: 50 g / dm ³ , sodium molybdate dihydrate: 60 g / dm ³ , sodium citrate: 90 g / dm ³
Liquid temperature: 30 ° C
Current density: 1-4 A / dm ²
Energizing time: 3 to 25 seconds Total adhesion amount of Ni and Mo: 500 to 5000 μg / dm ²
(6) “Co—Mo”: indicates that cobalt molybdenum alloy plating was performed under the following conditions.
Liquid composition: Co sulfate 50 g / L, sodium molybdate dihydrate: 60 g / L, sodium citrate: 90 g / L
Liquid temperature: 30 ° C
Current density: 1-4 A / dm ²
Energizing time: 3 to 25 seconds Total adhesion amount of Co and Mo: 200 to 2000 μg / dm ²

<Ultrathin copper layer>
As described above, after forming an intermediate layer on the carrier, an ultrathin copper layer with a predetermined thickness is formed on the intermediate layer by electroplating under the following conditions on a roll-to-roll type continuous plating line. A copper foil with a carrier was prepared.
Copper concentration: 90-110 g / L
Sulfuric acid concentration: 90-110 g / L
Chloride ion concentration: 50-90ppm
Leveling agent 1 (bis (3sulfopropyl) disulfide): 10 to 30 ppm
Leveling agent 2 (amine compound): 10 to 30 ppm
In addition, the following amine compound was used as the leveling agent 2.
(In the above chemical formula, R ₁ and R ₂ are selected from the group consisting of a hydroxyalkyl group, an ether group, an aryl group, an aromatic substituted alkyl group, an unsaturated hydrocarbon group, and an alkyl group.)
Electrolyte temperature: 50-80 ° C
Current density: 100 A / dm ²
Electrolyte linear velocity: 1.5-5 m / sec

In addition, the rolled copper foil ("Tough pitch copper" in the "Kind" column of Table 1 indicates that it is a rolled copper foil) was produced as follows. After manufacturing a predetermined copper ingot and performing hot rolling, annealing and cold rolling of a 300-800 degreeC continuous annealing line were repeated, and the rolled sheet of 1-2 mm thickness was obtained. This rolled plate was annealed and recrystallized in a continuous annealing line at 300 to 800 ° C., and finally cold-rolled to the thickness shown in Table 1 to obtain a copper foil. “Tough pitch copper” in Table 1 indicates tough pitch copper standardized in JIS H3100 C1100.
Table 1 shows the points of the copper foil preparation process before the surface treatment. “High gloss rolling” means that the final cold rolling (cold rolling after the final recrystallization annealing) was performed at the value of the oil film equivalent. In addition, about Example 1, 2, the copper foil whose thickness of copper foil is 6 micrometers, 12 micrometers, and 35 micrometers was also manufactured.
In addition, the leveling agent 1 and leveling agent 2 of Example 2 are the leveling agent 1 and leveling agent 2 used for the plating bath at the time of ultrathin copper layer formation in above-mentioned Examples 11-14. Same as above.

Various evaluation was performed as follows about each sample of the Example and comparative example which were produced as mentioned above.
(1) Measurement of surface roughness (Rz);
About the ultra-thin copper layer of the copper foil with a carrier after the surface treatment of each Example and Comparative Example, using a contact roughness meter Surfcorder SE-3C manufactured by Kosaka Laboratory Co., Ltd., ten points according to JIS B0601-1994 The average roughness was measured on the surface treated surface of the ultrathin copper layer. A direction perpendicular to the foil passing direction in an apparatus for forming an ultrathin copper layer on a carrier under the conditions of a measurement standard length of 0.8 mm, an evaluation length of 4 mm, a cut-off value of 0.25 mm, and a feed rate of 0.1 mm / sec. The measurement position was changed to (TD), 10 times each, and the average value in 10 measurements was obtained.
The surface roughness (Rz) of the carrier on the side where the intermediate layer is provided on the carrier before forming the intermediate layer was similarly determined.

(2) measurement of the root mean square height Rq of the surface;
About the surface treatment surface of the ultra-thin copper layer of the copper foil with a carrier after the surface treatment of each Example and a comparative example, the root mean square height Rq of the copper foil surface was measured with the Olympus laser microscope OLS4000. Values were obtained by measuring in a direction perpendicular to the foil passing direction (TD, width direction) in an apparatus for forming an ultrathin copper layer on a carrier under conditions of an evaluation length of 647 μm and a cutoff value of zero. In addition, the measurement environmental temperature of the root mean square height Rq of the surface by a laser microscope was 23-25 degreeC.

(3) Area ratio (A / B) of copper foil surface;
The surface area of the ultrathin copper layer surface of the copper foil with a carrier was measured by a laser microscope. About the surface treatment surface after the surface treatment of the ultrathin copper layer of the copper foil with a carrier of each Example and Comparative Example, using an Olympus laser microscope OLS4000, an area B equivalent to 647 μm × 646 μm at a magnification of 20 times the treatment surface In the data, the three-dimensional surface area A at 417,953 μm ² ) was measured, and setting was performed by a method of three-dimensional surface area A ÷ two-dimensional surface area B = area ratio (A / B). In addition, the measurement environmental temperature of the three-dimensional surface area A with a laser microscope was 23-25 degreeC.

(4) Glossiness;
Glossiness Handy Gloss Meter PG-1 manufactured by Nippon Denshoku Industries Co., Ltd. compliant with JIS Z8741 is used, and the rolled copper foil carrier has a glossiness at an incident angle of 60 degrees in the direction perpendicular to the rolling direction (TD). Or, for the carrier of the electrolytic copper foil, the glossiness at an incident angle of 60 degrees in the direction (TD) perpendicular to the traveling direction of the electrolytic copper foil in the electrolytic copper foil manufacturing apparatus, The surface on which the intermediate layer was formed was measured.

(5) Inclination of brightness curve From the surface side where the surface treatment of the ultra-thin copper layer of the copper foil with carrier is performed, the polyimide film (Kaneka thickness 25 μm and 50 μm (PIXEO (polyimide type: FRS), polyimide film with adhesive layer for copper clad laminates, PMDA (pyromellitic anhydride) based polyimide film (PMDA-ODA (4,4'-diaminodiphenyl ether) based polyimide film)), Toray DuPont thickness 50μm (Kapton (registered trademark), PMDA (pyromellitic anhydride) polyimide film (PMDA-ODA (4,4'-diaminodiphenyl ether) polyimide film))) , Remove ultrathin copper layer by etching (ferric chloride aqueous solution) to make sample film It was. Subsequently, a printed material on which a line-shaped black mark is printed is laid under the sample film, and the printed material is photographed with a CCD camera (line CCD camera of 8192 pixels) through the sample film. In the observation point-lightness graph created by measuring the lightness of each observation point along the direction perpendicular to the direction in which the observed line-shaped mark extends, this occurs from the end of the mark to the part where no mark is drawn. The slope (angle) of the brightness curve was measured. FIG. 3 is a schematic diagram showing the configuration of the photographing apparatus used at this time and the method of measuring the inclination of the brightness curve.
Further, ΔB, t1, t2, and Sv were measured by the following photographing apparatus as shown in FIG. One pixel on the horizontal axis corresponds to a length of 10 μm. For Sv, both sides of the mark are measured and a small value is adopted.
The polyimide film used for the measurement of the slope of the lightness curve may be any polyimide film as long as the value of ΔB (ΔB (PI)) before being bonded to the copper foil is 50 or more and 65 or less. In addition, the value of ΔB (PI) of the polyimide film used in this example and the comparative example was 50 or more and 65 or less (for example, 59).
The above-mentioned “printed matter printed with a line-shaped black mark” is printed on white glossy paper having a glossiness of 43.0 ± 2 according to JIS P8208 (1998) (a copy of the dust measurement chart of FIG. 1) and JIS P8145 (2011) ( Annex JA (normative) visual foreign matter comparison chart Figure JA.1-Copy of visual foreign matter comparison chart) Dirt with various lines printed on the transparent film shown in Fig. 8 (Contaminant) (Product name: Choyokai Co., Ltd. Product name: “Measurement table for dust-full size”, product number: JQA160-20151-1 (manufactured by the National Printing Bureau)) was used. .
The glossiness of the glossy paper was measured at an incident angle of 60 degrees using a gloss meter handy gloss meter PG-1 manufactured by Nippon Denshoku Industries Co., Ltd. based on JIS Z8741.
The photographing device is a CCD camera, a stage (white) on which a polyimide substrate is placed with a marked paper (glossy paper with impurities on it), an illumination power source that irradiates light onto the polyimide substrate photographing unit, and photographing. A transporting machine (not shown) is provided for transporting an evaluation polyimide substrate on which a paper with a mark of interest is placed on a stage. The main specifications of the camera are as follows:
・ Photographing device: Sheet inspection device Mujken manufactured by Nireco Corporation
CCD camera: 8192 pixels (160 MHz), 1024 gradation digital (10 bits)
・ Power supply for lighting: High-frequency lighting power supply (power supply unit x 2)
・ Lighting: fluorescent lamp (30W, model name: FPL27EX-D, twin fluorescent lamp)
Line for Sv measurements were used line indicated by arrows drawn in contaminants 8 of 0.7 mm ^2. The width of the line is 0.3 mm. Further, the line CCD camera field of view is arranged in a dotted line in FIG.
When shooting with a line CCD camera, the signal is confirmed at 256 gradations on the full scale, and the place where the black mark of the printed matter does not exist (on the white glossy paper above) without placing the polyimide film (polyimide substrate) to be measured. The lens aperture was adjusted so that the peak gradation signal of 230 ± 5 falls within the range (when a portion outside the mark printed on the contaminants is measured with a CCD camera from the transparent film side). The camera scan time (the time when the camera shutter is open and the time when light is captured) is fixed at 250 μs, and the lens aperture is adjusted so that it falls within the above gradation.
In the case of measuring ΔB and Sv using a line-shaped copper foil as a mark for a printed wiring board and a copper-clad laminate, a white gloss with a glossiness of 43.0 ± 2 is provided on the back surface of the line-shaped copper foil. Cover the paper, photograph with a CCD camera (line CCD camera of 8192 pixels) through the polyimide film, and for the image obtained by photographing, for each observation point along the direction perpendicular to the direction in which the observed copper foil extends In the observation point-lightness graph produced by measuring the lightness, the above-mentioned “line-shaped black mark is used except that ΔB and t1, t2, and Sv are measured from the lightness curve generated from the end of the mark to the portion without the mark. It is the same as the conditions for measuring ΔB and Sv using the “printed matter printed”.
For the lightness shown in FIG. 3, 0 means “black”, lightness 255 means “white”, and the gray level from “black” to “white” (black and white shading, gray scale) Is divided into 256 gradations for display.

(6) Visibility (resin transparency);
From the surface side where the surface treatment of the ultrathin copper layer is performed, the copper foil with a carrier is a polyimide film (Kaneka thickness 25 μm and 50 μm (PIXEO (polyimide type: FRS), polyimide film with an adhesive layer for a copper-clad laminate). , PMDA (pyromellitic anhydride) based polyimide film (PMDA-ODA (4,4′-diaminodiphenyl ether) based polyimide film)), Toray DuPont thickness 50 μm (Kapton (registered trademark), PMDA (pyromellitic acid) Anhydride) based polyimide film (PMDA-ODA (4,4'-diaminodiphenyl ether) based polyimide film))), and after removing the carrier, etching the ultrathin copper layer (ferric chloride) A sample film was prepared by removing with an aqueous solution. A printed material (black circle with a diameter of 6 cm) was attached to one surface of the obtained resin layer, and the visibility of the printed material was judged from the opposite surface through the resin layer. “◎” indicates that the outline of the black circle of the printed material is clear when the length is 90% or more of the circumference, and “Clear” indicates that the outline of the black circle is clear when the length is 80% or more and less than 90% of the circumference. “O” (passed above), a black circle with a clear outline of 0 to less than 80% of the circumference and a broken outline were evaluated as “x” (failed).

(7) Peel strength (adhesive strength);
Based on IPC-TM-650, the normal peel strength was measured with a tensile tester Autograph 100, and a normal peel strength of 0.7 N / mm or more could be used for laminated substrates. The peel strength was measured with an ultrathin copper layer thickness of 12 μm. The ultrathin copper layer having a thickness of less than 12 μm was subjected to copper plating so that the thickness of the ultrathin copper layer was 12 μm. In addition, when the ultrathin copper layer thickness was larger than 12 μm, etching was performed so that the ultrathin copper layer thickness was 12 μm. For the measurement of peel strength, polyimide film (Kaneka thickness 25 μm and 50 μm (PIXEO (polyimide type: FRS), polyimide film with adhesive layer for copper-clad laminate, PMDA (pyromellitic anhydride) based polyimide) Film (PMDA-ODA (4,4'-diaminodiphenyl ether) -based polyimide film)), Toray DuPont thickness 50 μm (Kapton (registered trademark), PMDA (pyromellitic anhydride) -based polyimide film (PMDA-ODA ( 4, 4′-diaminodiphenyl ether) -based polyimide film))) and the surface-treated surface of the ultrathin copper layer of the copper foil with carrier according to the examples and comparative examples of the present invention, and then the carrier removed sample Was used. During measurement, the polyimide film is fixed to a hard substrate (stainless steel plate or synthetic resin plate (which does not have to be deformed during peel strength measurement)) with double-sided tape or instant adhesive. did.

(8) Solder heat resistance evaluation;
From the surface side where the surface treatment of the ultrathin copper layer is performed, the copper foil with a carrier is a polyimide film (Kaneka thickness 25 μm and 50 μm (PIXEO (polyimide type: FRS), polyimide film with an adhesive layer for a copper clad laminate). , PMDA (pyromellitic anhydride) based polyimide film (PMDA-ODA (4,4′-diaminodiphenyl ether) based polyimide film)), Toray DuPont thickness 50 μm (Kapton (registered trademark), PMDA (pyromellitic acid) Anhydride) polyimide film (PMDA-ODA (4,4′-diaminodiphenyl ether) polyimide film))). About the obtained double-sided laminated board, the test coupon based on JISC6471 was created. The prepared test coupon was exposed to high temperature and high humidity of 85 ° C. and 85% RH for 48 hours, and then floated in a solder bath at 300 ° C. to evaluate solder heat resistance. After the solder heat resistance test, in the interface between the surface treatment surface of the ultra-thin copper layer and the polyimide resin adhesion surface, the surface of the ultra-thin copper layer in the test coupon is 5% or more of the area, and the interface is discolored due to blistering. (Fail), the case where the color change was less than 5% was evaluated as ◯, and the case where no color change occurred was evaluated as ◎.

(9) Yield A copper foil with a carrier is bonded to a polyimide film (Kaneka thickness 25 μm and 50 μm (PIXEO (polyimide type: FRS), copper clad laminate) from the surface side where the surface treatment of the ultra-thin copper layer is performed Layered polyimide film, PMDA (pyromellitic anhydride) based polyimide film (PMDA-ODA (4,4'-diaminodiphenyl ether) based polyimide film)), Toray DuPont thickness 50 μm (Kapton (registered trademark), PMDA) (Pyromellitic anhydride) -based polyimide film (PMDA-ODA (4,4'-diaminodiphenyl ether) -based polyimide film))), and the carrier is removed, and the ultrathin copper layer is etched (chlorinated Ferric aqueous solution), L / S 30 μm / 30 μm circuit and 20 μm × 20 μm It was to create a FPC with a mark of the corner. After that, an attempt was made to detect a 20 μm × 20 μm square mark with a CCD camera through polyimide. “◎” when 9 times or more out of 10 times can be detected, “◯” when 7 to 8 times can be detected, “△” when 6 times can be detected, and “Δ” when 5 times or less can be detected. Is “×”.

(10) Measurement of transmission loss After bonding the copper foil with a carrier with a commercially available liquid crystal polymer resin (Vecstar CTZ-50 μm manufactured by Kuraray Co., Ltd.) from the surface side where the surface treatment of the ultrathin copper layer is performed, After removing the carrier, a microstrip line is formed by etching so that the characteristic impedance is 50Ω, and the transmission coefficient is measured using a network analyzer HP8720C manufactured by HP, and transmission loss at a frequency of 20 GHz and a frequency of 40 GHz is obtained. It was. As an evaluation of transmission loss at a frequency of 20 GHz, 未 満 less than 3.7 dB / 10 cm, ◎ 3.7 dB / 10 cm or more and less than 4.1 dB / 10 cm, 、 ４ 4.1 dB / 10 cm or more and less than 5.0 dB / 10 cm, △, 5.0 dB / 10 cm or more was defined as x.
In the printed wiring board or copper-clad laminate, the above-mentioned (1) surface roughness (Rz) and (2) root mean square of the surface of the copper circuit or copper foil surface are obtained by dissolving and removing the resin. Height Rq and (3) area ratio (A / B) of the copper foil surface can be measured.
The conditions and evaluation results of the above tests are shown in Tables 1 to 3.

(Evaluation results)
In each of Examples 1 to 14, the root mean square height Rq of the surface is in the range of 0.14 to 0.63 μm, Sv is 3.5 or more, and the surface is subjected to surface treatment. When the surface contains Ni, the adhesion amount of Ni is 1000 μg / dm ² or less, and when the surface on which the surface treatment is performed contains Co, the adhesion amount of Co is 2000 μg / dm ² or less. Yes, visibility, peel strength, solder heat resistance evaluation and yield were good. Also, the transmission loss was small and good. In addition, the copper foils manufactured for Examples 1 and 2 and having thicknesses of 6 μm, 12 μm, and 35 μm had the same results as in Examples 1 and 2 having a thickness of 18 μm. That is, the copper foils manufactured for Examples 1 and 2 and having a thickness of 6 μm, 12 μm, and 35 μm all have a root mean square height Rq of 0.14 to 0.63 μm on the surface, and Sv is The visibility, peel strength, solder heat resistance evaluation, and yield were good.
In Comparative Example 1, the root mean square height Rq of the surface was less than 0.14 μm, and the peel strength and solder heat resistance were poor.
In Comparative Examples 2 to 5, the root mean square height Rq of the surface exceeded 0.63 μm, Sv was less than 3.5, and the visibility was poor.
In addition, after forming the intermediate layer and the ultra-thin copper layer on both sides of the carrier under the same conditions using the same carrier as each of the above examples and comparative examples, the same surface treatment is performed to produce a surface-treated copper foil. As a result of the evaluation, the same evaluation results as those of the respective Examples and Comparative Examples were obtained on both sides.
When surface treatment such as roughening treatment is performed on both surfaces of the copper foil, the surface treatment may be performed on both surfaces simultaneously, or the surface treatment may be separately performed on one surface and the other surface. In addition, when performing surface treatment on both surfaces simultaneously, it is good to perform surface treatment using the surface treatment apparatus (plating apparatus) which provided the anode on both surfaces side of copper foil. In this example, surface treatment was performed on both surfaces simultaneously.
In each of the above embodiments, the width of the mark is 0.3 mm to 0.16 mm (the third mark from the side closest to the description of 0.5 of the area 0.5 mm ² of the contaminant sheet). The same Sv value was measured after changing to the pointing mark)). In all cases, the Sv value was the same as when the mark width was 0.3 mm.
Further, in each of the above embodiments, with respect to the “top average value Bt of the lightness curve”, the position 50 μm away from the end positions on both sides of the mark is defined as a position 100 μm apart, a position 300 μm apart, and a position 500 μm apart. From the position, the Sv value was measured by changing to the average value of the brightness when measured at 5 locations at intervals of 30 μm (total of 10 locations on both sides). The average value of brightness when measuring 5 locations at a distance of 30 μm from a position 50 μm away from the part position (a total of 10 locations on both sides) is the same value as the Sv value when the “top average value Bt of the brightness curve” is used. .

Claims (27)

It is a copper foil with a carrier which has a carrier, an intermediate | middle layer, and an ultra-thin copper layer in this order, Comprising: Surface treatment is performed on the surface of the said ultra-thin copper layer, The ultra-thin copper layer in which the said surface treatment is performed The root mean square height Rq of the surface is 0.14 to 0.63 μm,
After bonding the copper foil with carrier on both sides of the polyimide resin substrate from the surface side where the surface treatment of the ultrathin copper layer is performed, the carrier is removed, and then the ultrathin copper layer on both sides is removed by etching. And
When a printed matter on which a line-shaped mark is printed is laid under the exposed polyimide substrate, and the printed matter is photographed with a CCD camera through the polyimide substrate,
For the image obtained by the photographing, an observation point-brightness graph prepared by measuring the brightness of each observation point along the direction perpendicular to the direction in which the observed line-shaped mark extends,
The difference between the top average value Bt and the bottom average value Bb of the brightness curve generated from the end of the mark to the part where the mark is not drawn is ΔB (ΔB = Bt−Bb). The value indicating the position of the intersection closest to the line-shaped mark among the intersections of the curve and Bt is t1, and the brightness is within a depth range from the intersection of the brightness curve and Bt to 0.1 ΔB with reference to Bt. A carrier in which Sv defined by the following equation (1) is 3.5 or more when a value indicating the position of the intersection closest to the line-shaped mark among the intersections of the curve and 0.1ΔB is t2. Copper foil.
Sv = (ΔB × 0.1) / (t1-t2) (1)   The copper foil with a carrier according to claim 1, wherein the root mean square height Rq of the surface of the ultrathin copper layer on which the surface treatment of the copper foil with a carrier is performed is 0.25 to 0.60 µm.   The copper foil with a carrier according to claim 1 or 2, wherein Sv defined by the formula (1) in the lightness curve is 3.9 or more.   The copper foil with a carrier as described in any one of Claims 1-3 from which Sv defined by (1) Formula in the said brightness curve becomes 5.0 or more.   The copper foil with a carrier according to any one of claims 1 to 4, wherein a ten-point average roughness Rz of TD of the surface of the ultrathin copper layer on which the surface treatment is performed is 0.20 to 0.64 µm. .   The copper foil with a carrier according to claim 5, wherein the ten-point average roughness Rz of TD of the surface of the ultrathin copper layer subjected to the surface treatment is 0.26 to 0.62 µm.   The ratio A / B between the three-dimensional surface area A and the two-dimensional surface area B of the surface of the ultrathin copper layer subjected to the surface treatment is 1.0 to 1.7. The copper foil with a carrier as described in 2.   The ratio A / B between the three-dimensional surface area A and the two-dimensional surface area B of the surface of the ultrathin copper layer on which the surface treatment is performed is 1.0 to 1.6. The copper foil with a carrier as described in 2.   The surface of the surface on which the surface treatment of the ultrathin copper layer is performed includes any one or more selected from the group consisting of copper, nickel, cobalt, phosphorus, tungsten, arsenic, molybdenum, chromium, and zinc. The copper foil with a carrier as described in any one of claim | item 1 -8.   The copper foil with a carrier as described in any one of Claims 1-9 provided with the resin layer on the surface of the surface where the surface treatment of the said ultra-thin copper layer is performed.   The copper foil with a carrier according to claim 10, wherein the resin layer includes a dielectric.   The copper foil with a carrier as described in any one of Claims 1-11 provided with the said ultra-thin copper layer on both surfaces of the said carrier.   The copper foil with a carrier as described in any one of Claims 1-11 provided with the roughening process layer in the surface on the opposite side to the said ultra-thin copper layer side of the said carrier.   The laminated board manufactured by laminating | stacking the copper foil with a carrier and resin substrate as described in any one of Claims 1-13.   The printed wiring board using the copper foil with a carrier as described in any one of Claims 1-13.   An electronic device using the printed wiring board according to claim 15.   A method for manufacturing a printed wiring board in which two or more printed wiring boards are connected by connecting two or more printed wiring boards according to claim 15.   At least a step of connecting at least one printed wiring board according to claim 15 and another printed wiring board according to claim 15 or a printed wiring board not corresponding to the printed wiring board according to claim 15 is included. A method of manufacturing a printed wiring board in which two or more printed wiring boards are connected.   An electronic apparatus using at least one printed wiring board to which at least one printed wiring board manufactured by the method according to claim 17 is connected.   A method for producing a printed wiring board, comprising at least a step of connecting the printed wiring board according to claim 15 and a component. Connecting at least one printed wiring board according to claim 15 to another printed wiring board according to claim 15 or a printed wiring board not corresponding to the printed wiring board according to claim 15, and
A printed circuit board having two or more printed wiring boards connected, comprising at least a step of connecting a printed wiring board according to claim 15 or two or more printed wiring boards according to claim 15 and a component. A method of manufacturing a wiring board. Preparing a copper foil with a carrier and an insulating substrate according to any one of claims 1 to 13,
Laminating the copper foil with carrier and an insulating substrate;
After laminating the carrier-attached copper foil and the insulating substrate, a copper-clad laminate is formed through a step of peeling the carrier of the carrier-attached copper foil,
Then, the manufacturing method of a printed wiring board including the process of forming a circuit by any method of a semi-additive method, a subtractive method, a partly additive method, or a modified semi-additive method. A step of forming a circuit on the ultrathin copper layer side surface or the carrier side surface of the copper foil with carrier according to any one of claims 1 to 13,
Forming a resin layer on the ultrathin copper layer side surface or the carrier side surface of the copper foil with carrier so that the circuit is buried;
Forming a circuit on the resin layer;
After forming a circuit on the resin layer, peeling the carrier or the ultra-thin copper layer; and
After the carrier or the ultra-thin copper layer is peeled off, the ultra-thin copper layer or the carrier is removed to be buried in the resin layer formed on the ultra-thin copper layer-side surface or the carrier-side surface. A method of manufacturing a printed wiring board including a step of exposing a circuit that is connected.   The step of forming a circuit on the resin layer includes attaching another carrier-attached copper foil on the resin layer from the ultrathin copper layer side, and using the carrier-attached copper foil attached to the resin layer to form the circuit. The method for manufacturing a printed wiring board according to claim 23, wherein the method is a forming step.   25. The method for producing a printed wiring board according to claim 24, wherein the carrier-attached copper foil to be bonded onto the resin layer is the carrier-attached copper foil according to any one of claims 1 to 11.   The print according to any one of claims 23 to 25, wherein the step of forming a circuit on the resin layer is performed by any one of a semi-additive method, a subtractive method, a partial additive method, and a modified semi-additive method. A method for manufacturing a wiring board.   27. The copper foil with a carrier that forms a circuit on the surface has a substrate or a resin layer on the surface on the carrier side or the surface on the ultrathin copper layer side of the copper foil with carrier. The manufacturing method of the printed wiring board of description.