JP6178360B2 - Surface-treated copper foil, copper foil with carrier, method for producing printed circuit board, method for producing copper-clad laminate, and method for producing printed wiring board - Google Patents

Description

  The present invention relates to a surface-treated copper foil, a copper foil with a carrier, a printed wiring board, a printed circuit board, a copper-clad laminate, and a method for producing a printed wiring board.

  The circuit forming method for the semiconductor package substrate and the printed wiring board is mainly a subtractive method. However, in recent years, with higher integration of semiconductors, miniaturization of circuits of semiconductor package substrates and printed wiring boards used therein has progressed, and it has become difficult to form microcircuits by a subtractive method.

  As a countermeasure for further miniaturization, MSAP (Modified Semi-Additive Construction Method) is known (for example, Patent Document 1).

Japanese Patent No. 4683769

  The MSAP method is useful for forming fine wiring as described above. Specifically, as shown in FIG. 1A, an ultrathin copper foil is formed as a power feeding layer on a resin layer (insulating material), and then pattern copper plating is applied on the ultrathin copper foil. Subsequently, as shown in FIG. 1B, desired wiring is formed by removing the ultrathin copper foil by flash etching. In FIG. 1, the wiring width is expressed as L (line) and the wiring interval is expressed as S (space).

  However, in general, a surface treatment layer such as a roughening treatment layer is formed on the surface of the resin layer in order to ensure adhesion to the resin layer in the ultrathin copper foil. When this ultra-thin copper foil, which is a surface-treated copper foil, is flash-etched to form wiring, the longer the removal of the surface-treated layer, the more the width of the copper foil part (wiring part) of the ultra-thin copper foil. Is removed more than necessary by etching, resulting in a problem that the wiring becomes thinner than a desired width.

  Then, this invention makes it a subject to provide the manufacturing method of the surface treatment copper foil excellent in fine wiring formation property, copper foil with a carrier, a printed wiring board, a printed circuit board, a copper clad laminated board, and a printed wiring board. .

  In order to achieve the above object, the present inventors have conducted extensive research and found that the etching rate of the surface treatment layer of the surface-treated copper foil is not less than a predetermined value with respect to the etching rate of the copper foil of the surface treatment copper foil. It was found that a surface-treated copper foil excellent in fine wiring formability can be provided by controlling so as to be.

The present invention has been completed on the basis of the above knowledge, and in one aspect, is a surface-treated copper foil in which a surface-treated layer having a roughened layer is formed on a copper foil, and the surface-treated layer is formed. From the surface opposite to the surface, the etching temperature is a liquid temperature 30 composed of 18 g / L H ₂ O ₂ , 92 g / L H ₂ SO ₄ , 8 g / L Cu and hydrogen peroxide stabilizer. upon spray etched in copper dissolution etchant ° C., when the 1 in the thickness direction of the etching rate of the copper foil, the etching rate in the thickness direction of the surface treatment layer becomes 0.5 or more, and, "the copper foil thickness ([mu] m), "" the copper foil and the surface treatment layer thickness was completely removed by etching the ([mu] m) - the ratio of the thickness ([mu] m) "of the copper foil with 0.04 to 0.21 Yes , the surface on which the surface treatment layer is formed Is a surface-treated copper foil having a surface roughness Sz of 0.8 to 3.2 μm.

  In one embodiment of the surface-treated copper foil of the present invention, when the etching rate in the thickness direction of the copper foil is 1, the etching rate in the thickness direction of the surface treatment layer is 0.75 or more.

  In another embodiment of the surface-treated copper foil of the present invention, when the etching rate in the thickness direction of the copper foil is 1, the etching rate in the thickness direction of the surface treatment layer is 1.0 or more.

Another aspect of the present invention is a surface-treated copper foil in which a surface-treated layer having a roughened layer is formed on a copper foil, from the surface opposite to the surface on which the surface-treated layer is formed, Spray etching is performed with a copper-dissolved etching solution having a temperature of 30 ° C., which is composed of 18 g / L H ₂ O ₂ , 92 g / L H ₂ SO ₄ , 8 g / L Cu and hydrogen peroxide stabilizer. The ratio of the etching treatment time in the thickness direction of the surface treatment layer to the etching treatment time of 1 μm thickness of the copper foil is 0.7 or less, and the etching treatment time in the thickness direction of the surface treatment layer is as follows: Calculated by equation A,
Formula A: Time required to completely remove the copper foil and the surface treatment layer by etching (s) —Time required to remove the thickness of the copper foil portion by etching (s)
The surface-treated copper foil has a surface roughness Sz of 0.8 to 3.2 μm on the surface on which the surface treatment layer is formed.

In the surface treatment copper foil another embodiment of the present invention, the relative etch time of thickness 1μm copper foil, the ratio of the etching time in the thickness direction of the surface treatment layer, Ri Do 0.4 or less, etching time in the thickness direction of the surface treatment layer, Ru is calculated by the following formula a.
Formula A: Time required to completely remove the copper foil and the surface treatment layer by etching (s) —Time required to remove the thickness of the copper foil portion by etching (s)

In the surface treatment copper foil another embodiment of the present invention, the relative etch time of thickness 1μm copper foil, the ratio of the etching time in the thickness direction of the surface treatment layer, Ri Do 0.2 or less, etching time in the thickness direction of the surface treatment layer, Ru is calculated by the following formula a.
Formula A: Time required to completely remove the copper foil and the surface treatment layer by etching (s) —Time required to remove the thickness of the copper foil portion by etching (s)

  In still another embodiment of the surface-treated copper foil of the present invention, the copper foil is formed of an electrolytic copper foil or a rolled copper foil.

  In another embodiment of the surface-treated copper foil of the present invention, the surface-treated layer is provided with a roughened layer, a heat-resistant layer, a rust-proof layer, a chromate-treated layer provided on the surface of the roughened layer, and And one or more layers selected from the group consisting of silane coupling treatment layers.

  In another embodiment of the surface-treated copper foil of the present invention, the surface-treated layer has at least one of the rust-proof layer and the heat-resistant layer, and at least one of the rust-proof layer and the heat-resistant layer is One or more elements selected from nickel, cobalt, copper, and zinc are included.

  In still another embodiment of the surface-treated copper foil of the present invention, the surface-treated layer has the roughened layer and the heat-resistant layer, and has the heat-resistant layer on the roughened layer.

  In another embodiment of the surface-treated copper foil of the present invention, the surface-treated layer has the roughened layer or the heat-resistant layer and the rust-proof layer, and the roughened layer or the heat-resistant layer. The rust preventive layer is provided on the top.

  In still another embodiment of the surface-treated copper foil of the present invention, the surface-treated layer has the rust-proof layer and the chromate-treated layer, and the chromate-treated layer is provided on the rust-proof layer.

  In another embodiment of the surface-treated copper foil of the present invention, the surface treatment layer has the chromate treatment layer and the silane coupling treatment layer, and the silane coupling treatment is provided on the chromate treatment layer. Has a layer.

  In still another embodiment, the surface-treated copper foil of the present invention includes a resin layer on the surface-treated layer.

  In another embodiment of the surface-treated copper foil of the present invention, the resin layer contains a dielectric.

  Another aspect of the present invention is a carrier-added copper foil in which an intermediate layer and an ultrathin copper layer are laminated in this order on one side or both sides of a carrier, and the ultrathin copper It is a copper foil with a carrier whose layer is the surface-treated copper foil of the present invention.

  In one embodiment, the copper foil with a carrier of the present invention has the intermediate layer and the ultrathin copper layer in this order on one surface of the carrier, and a roughening treatment layer on the other surface of the carrier.

The present invention in yet another aspect, a method for manufacturing a printed wiring board had use the surface treated copper foil of the present invention.

In the present invention yet another aspect, a method for manufacturing a printed wiring board had use copper foil with carrier of the present invention.

The present invention in yet another aspect, a method for manufacturing a printed circuit board which had use the surface treated copper foil of the present invention.

In the present invention yet another aspect, a method for manufacturing a printed circuit board which had use copper foil with carrier of the present invention.

The present invention in yet another aspect, a method for producing a copper-clad laminate had use the surface treated copper foil of the present invention.

In the present invention yet another aspect, a method for producing a copper-clad laminate had use copper foil with carrier of the present invention.

In yet another aspect of the present invention, a step of preparing the surface-treated copper foil of the present invention and an insulating substrate,
The surface-treated copper foil is laminated on an insulating substrate from the surface-treated layer side to form a copper-clad laminate,
Thereafter, the printed wiring board manufacturing method includes a step of forming a circuit by any one of the subtractive method, the partly additive method, and the modified semi-additive method.

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 on the insulating substrate from the ultrathin copper layer side,
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 either the partly additive method or the modified semi-additive method.

In yet another aspect of the present invention, a step of forming a circuit on the ultrathin copper layer side surface of the copper foil with a carrier of the present invention,
Forming a resin layer on the ultrathin copper layer side surface of the carrier-attached copper foil so that the circuit is buried;
Forming a circuit on the resin layer;
Forming the circuit on the resin layer, and then peeling the carrier; and
After the carrier is peeled off, the printed wiring board includes a step of exposing the circuit embedded in the resin layer formed on the surface of the ultrathin copper layer by removing the ultrathin copper layer Is the method.

  ADVANTAGE OF THE INVENTION According to this invention, the surface treatment copper foil excellent in fine wiring formation property can be provided.

A schematic diagram of the MSAP method is shown in (A) and (B). 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 a graph which shows the relationship between the etching process time of Examples 1-3 and the comparative example 1, and etching amount. It is an observation photograph of the residue appearance (L / S = 15 μm / 15 μm pitch part) between the wirings after flash etching of the wirings of Examples 1 to 3 and Comparative Example 1. It is an example of the cross-sectional observation photograph of a copper layer and a surface treatment layer.

[Surface treated copper foil]
The copper foil used in the surface-treated copper foil according to the present invention may be either an electrolytic copper foil or a rolled copper foil. The thickness of the copper foil used in the present invention is not particularly limited, but is, for example, 1 μm or more, 2 μm or more, 3 μm or more, 5 μm or more, for example, 3000 μm or less, 1500 μm or less, 800 μm or less, 300 μm or less, 150 μm or less, 100 μm. Below, it is 70 micrometers or less, 50 micrometers or less, and 40 micrometers or less.

  The rolled copper foil used in the present invention contains a copper alloy containing one or more elements such as Ag, Sn, In, Ti, Zn, Zr, Fe, P, Ni, Si, Te, Cr, Nb, V, B, and Co. Foil 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 rolled copper foil includes copper foil produced using tough pitch copper (JIS H3100 C1100) or oxygen-free copper (JIS H3100 C1020). In addition, when the term “copper foil” is used alone in this specification, a copper alloy foil is also included.

Moreover, about the electrolytic copper foil which can be used for this invention, it can produce on the following manufacturing conditions.
・ General electrolytic raw foil:
<Electrolyte composition>
Copper: 80-120 g / L
Sulfuric acid: 80-120 g / L
Chlorine: 30-100ppm
Leveling agent (Nika): 0.1-10ppm
・ Double-sided flat electrolytic foil, carrier copper foil of ultra-thin copper foil with carrier:
<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.)

<Production conditions>
Current density: 70 to 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)

  In the present invention, the surface treatment layer formed on the copper foil may be a roughening treatment layer. The roughening treatment is usually performed on the surface of the copper foil after degreasing for the purpose of improving the peel strength of the copper foil after being laminated on the surface of the copper foil to be bonded to the resin substrate, that is, the surface on the surface treatment side. A process for forming a fist-like electrodeposition. Although the electrolytic copper foil has irregularities at the time of manufacture, the irregularities can be further increased by enhancing the convex portions of the electrolytic copper foil by roughening treatment. The roughening treatment can be performed, for example, by forming roughened particles with copper or a copper alloy. The roughening process may be fine. The roughening treatment layer is a layer made of any single element selected from the group consisting of copper, nickel, cobalt, phosphorus, tungsten, arsenic, molybdenum, chromium and zinc, or an alloy containing one or more of them. Also good. Moreover, after forming the roughened particles with copper or a copper alloy, a roughening treatment can be performed in which secondary particles or tertiary particles are further formed of nickel, cobalt, copper, zinc alone or an alloy. Thus, when the surface treatment layer is a roughening treatment layer, the copper circuit formed by etching the ultrathin copper layer in the above-described MSAP method or the like is favorably suppressed from the resin layer. be able to.

As the roughening treatment, alloy plating such as copper-cobalt-nickel alloy plating, copper-nickel-phosphorus alloy plating, copper-nickel-tungsten alloy plating, copper-cobalt-tungsten alloy plating, and more preferably copper alloy plating is used. it can. Copper as roughening treatment - cobalt - nickel alloy plating, by electrolytic plating, coating weight is to be the 15~40mg / dm ² of copper -100~3000μg / dm ² of cobalt -100~1500μg / dm ² of nickel It can be carried out so as to form a ternary alloy layer. If the amount of deposited Co is less than 100 μg / dm ² , the heat resistance may deteriorate and the etching property may deteriorate. When the amount of Co deposition exceeds 3000 μg / dm ² , it is not preferable when the influence of magnetism must be taken into account, etching spots may occur, and acid resistance and chemical resistance may deteriorate. If the Ni adhesion amount is less than 100 μg / dm ² , the heat resistance may deteriorate. On the other hand, when the Ni adhesion amount exceeds 1500 μg / dm ² , the etching residue may increase. A preferable Co adhesion amount is 1000 to 2500 μg / dm ² , and a preferable nickel adhesion amount is 500 to 1200 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.

The plating bath and plating conditions for forming such ternary copper-cobalt-nickel alloy plating are 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 : 20 to 30 A / dm ²
Plating time: 1 to 5 seconds The plating solution immersion time after the end of plating: 20 seconds or less (because the particle shape is disturbed when immersed for longer than 20 seconds), preferably 10 seconds or less, more preferably 5 seconds or less Thereafter, if it is normal, it is not particularly quickly removed from the plating solution, but in the present invention, it is necessary to remove from the plating solution within a predetermined time after the completion of the plating. For this reason, as described above, the plating solution immersion time after the completion of the plating is set to 20 seconds or less. If the immersion time exceeds 20 seconds, a part of the roughened particles may be dissolved by the plating solution. It is considered that dissolution of a part of the roughened particles is one of the causes of the disturbance of the particle shape.
By shortening the plating solution immersion time after the completion of the plating to 10 seconds or less, or 5 seconds or less, the particle shape can be made more difficult to disturb, which is effective.
In addition, as with copper-cobalt-nickel alloy plating, alloy plating other than copper-cobalt-nickel alloy plating also has a plating solution immersion time of 20 seconds or less after completion of plating. Therefore, it is important to control to 10 seconds or less, more preferably 5 seconds or less. If the immersion time exceeds 20 seconds, a part of the roughened particles may be dissolved by the plating solution. It is considered that dissolution of a part of the roughened particles is one of the causes of the disturbance of the particle shape. Known conditions can be used for pH, temperature, current density, and plating time of alloy plating other than copper-cobalt-nickel alloy plating.
By shortening the plating solution immersion time after the completion of the plating to 10 seconds or less, or 5 seconds or less, the particle shape can be made more difficult to disturb, which is effective.
Moreover, you may perform copper plating as the following roughening processes as surface treatment. The surface treatment layer formed by copper plating as the following roughening treatment has a high copper concentration, and becomes a roughening treatment layer (plating layer) mostly composed of copper. A roughening layer (plating layer) having a high copper concentration is characterized by being hardly soluble in the plating solution. Copper plating as the following roughening treatment is performed in the order of copper plating 1 and copper plating 2.
・ Copper plating 1
(Liquid composition 1)
Cu concentration: 10-30 g / L
H ₂ SO ₄ concentration: 50 to 150 g / L
Tungsten concentration: 0.5-50 mg / L
Sodium dodecyl sulfate: 0.5-50 mg / L
(Electroplating condition 1)
Temperature: 30-70 ° C
(First stage current condition)
Current density: 18 to 70 A / dm ²
Roughening coulomb amount: 1.8 to 1000 A / dm ^2, preferably 1.8 to 500 A / dm ²
Plating time: 0.1 to 20 seconds (second stage current condition)
Current density: 0.5 to 13 A / dm ²
Roughening Coulomb amount: 0.05~1000A / dm ² preferably 0.05~500A / dm ²
Plating time: 0.1 to 20 seconds Note that the first and second steps may be repeated. Further, after the first stage is performed once or a plurality of times, the second stage may be performed once or a plurality of times. Further, after the first stage is performed once or a plurality of times, the second stage may be repeated once or a plurality of times.
・ Copper plating 2
(Liquid composition 2)
Cu concentration: 20-80 g / L
H ₂ SO ₄ concentration: 50 to 200 g / L
(Electroplating condition 2)
Temperature: 30-70 ° C
(Current condition)
Current density: 5 to 50 A / dm ²
Roughening coulomb amount: 50 to 300 A / dm ²
Plating time: 1 to 60 seconds In addition, the above-described copper plating may be combined with the above-described copper-cobalt-nickel alloy plating alloy plating. It is preferable to perform the alloy plating described above after the copper plating is performed on the copper foil.

  Moreover, you may form 1 or more types of layers selected from the group which consists of a heat-resistant layer, a rust prevention layer, a chromate processing layer, and a silane coupling processing layer on the surface of a roughening processing layer. Moreover, a heat-resistant layer may be formed on the roughened layer, a rust-proof layer may be formed on the roughened layer or the heat-resistant layer, and a chromate-treated layer is formed on the rust-proof layer. Alternatively, a silane coupling treatment layer may be formed on the chromate treatment layer.

  In the present invention, the surface treatment layer formed on the copper foil may be one or more layers selected from the group consisting of a heat-resistant layer, a rust prevention layer, a chromate treatment layer, and a silane coupling treatment layer. In addition, a heat-resistant layer may be formed on the copper foil, a rust-proof layer may be formed on the heat-resistant layer, a chromate-treated layer may be formed on the rust-proof layer, A silane coupling treatment layer may be formed thereon.

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 the rust preventive layer is a layer containing a nickel-zinc alloy, the adhesion between the copper foil and the resin substrate is improved.

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.
The chromate treatment 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.

  In addition, you may use a well-known silane coupling agent for the silane coupling agent used in order to provide a silane coupling process layer, for example, an amino-type silane coupling agent or an epoxy-type silane coupling agent, a mercapto-type silane coupling An 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 may be selected from the group consisting of 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 substrate and the surface-treated copper foil can be further improved.

[Etching rate]
In the production of printed wiring boards by MSAP (Modified Semi-Additive Method) etc., after surface-treated copper foil is laminated on the resin substrate from the surface-treated layer side, wiring may be formed by flash etching on the surface-treated copper foil. is there. In this flash etching, if it takes time to remove the surface treatment layer, the width of the copper foil wiring is removed more than necessary by etching, and the wiring becomes thinner than the desired width. As will be described later, when a printed wiring board is produced by a so-called embedding method in which a circuit is embedded in a resin substrate, the copper layer on the surface of the resin substrate is removed by flash etching as shown in FIG. Then, the surface of the circuit plating in the resin substrate is exposed. At this time, if it takes time to remove the surface treatment layer, the step between the resin substrate surface and the copper layer (circuit plating) surface becomes large. In other words, if it takes a long time to remove the surface treatment layer during flash etching, the copper surface will recede considerably from the resin substrate surface, so it is necessary to secure the corresponding copper plating thickness in advance. Not only the etching process, but also the productivity of the copper plating process is greatly reduced, leading to increased costs. On the other hand, the surface-treated copper foil of the present invention was spray-etched with a hydrogen peroxide / sulfuric acid-based copper-dissolved etching solution from the surface opposite to the surface on which the surface-treated layer was formed with the above-described configuration. At this time, when the etching rate in the thickness direction of the copper foil is set to 1, the etching rate in the thickness direction of the surface treatment layer is controlled to be 0.5 or more. When the etching rate in the thickness direction of the copper foil is set to 1, the etching rate in the thickness direction of the surface treatment layer becomes 0.5 or more, so that the time to be removed by flash etching is shortened compared to the conventional case, and the copper Etching of the foil portion more than necessary can be suppressed, and the copper foil wiring can be formed to a desired width. In addition, it is possible to satisfactorily suppress the occurrence of a step between the resin substrate surface, which is likely to occur in the embedding method, and the copper layer (circuit plating) surface. When the etching rate in the thickness direction of the copper foil is 1, the etching rate in the thickness direction of the surface treatment layer is preferably 0.6 or more, more preferably 0.7 or more. More preferably 0.75 or more, even more preferably 0.8 or more, even more preferably 0.9 or more, even more preferably 1.0 or more, typically 0.6 to 1.0, more Typically, it is 0.7 to 1.0. In addition, when the surface roughness Sz on the surface side of the surface-treated copper foil is large, the etching rate of the surface-treated layer tends to be low. Further, when the surface roughness Sz is small, the etching rate of the surface treatment layer tends to be high. Therefore, the surface roughness Sz of the surface-treated surface of the surface-treated copper foil is preferably 0.8 to 3.2 μm, more preferably 0.9 to 3.0 μm. It is still more preferably 0.0 to 3.0 μm, still more preferably 1.4 to 3.0 μm, and even more preferably 1.6 to 2.8 μm.
Further, when the crystal grain size of the copper foil is large, the etching rate of the copper foil tends to be low. In addition, when the crystal grain size of the copper foil is small, the etching rate of the copper foil tends to be high. A rolled copper foil or an electrolytic copper foil produced with an electrolytic solution containing chlorine, bis (3sulfopropyl) disulfide and an amine compound tends to have a large crystal grain size. Moreover, the electrolytic copper foil manufactured with the electrolyte solution with a high concentration of glue tends to have a small crystal grain size of the copper foil. Further, when the surface treatment layer contains an element that is difficult to be etched (for example, nickel, chromium, tungsten, vanadium, etc.), the etching rate of the surface treatment layer tends to be low. Further, when the surface treatment layer contains an element that is easily etched (for example, zinc, cobalt, iron, etc.), the etching rate of the surface treatment layer tends to be high.

[Etching time]
In addition, as described above, in flash etching, if it takes time to remove the surface treatment layer, the width of the copper foil wiring is removed more than necessary by etching, and the wiring becomes thinner than the desired width. . Further, when the printed wiring board is manufactured by the embedding method, as shown in FIG. 5J, the copper layer on the surface of the resin substrate is removed by flash etching to expose the surface of the circuit plating in the resin substrate. At this time, if it takes a long time to remove the surface treatment layer, the step between the resin substrate surface and the copper layer (circuit plating) surface becomes large, and the circuit becomes an unfavorable shape buried in the resin substrate. . On the other hand, the surface-treated copper foil of the present invention is a surface-treated copper foil in which a surface-treated layer is formed on the copper foil, and hydrogen peroxide / When spray etching is performed with a sulfuric acid-based copper-dissolved etching solution, the ratio of the etching treatment time in the thickness direction of the surface treatment layer to the etching treatment time of 1 μm thickness of the copper foil is controlled to be 0.7 or less. Yes. The ratio of the etching treatment time in the thickness direction of the surface treatment layer to the etching treatment time of 1 μm in thickness of the copper foil is 0.7 or less, so that the time to be removed by flash etching is shorter than before, the copper Etching of the foil portion more than necessary can be suppressed, and the copper foil wiring can be formed to a desired width. In addition, it is possible to satisfactorily suppress the occurrence of a step between the resin substrate surface, which is likely to occur in the embedding method, and the copper layer (circuit plating) surface. In the surface-treated copper foil of the present invention, the ratio of the etching treatment time in the thickness direction of the surface treatment layer to the etching treatment time of 1 μm thickness of the copper foil is preferably 0.4 or less, more preferably 0.3 or less. More preferably 0.2 or less, still more preferably 0.1 or less, typically 0.2 to 0.7, more typically 0.2 to 0.4. When the surface roughness Sz of the surface-treated surface of the surface-treated copper foil is large, the etching time required for removing the surface treatment layer tends to be long. In addition, when the surface roughness Sz is small, the etching processing time required for removing the surface treatment layer tends to be short. For this reason, it is preferable that the surface roughness Sz of the surface by which the surface treatment copper foil is surfaced is 0.8-3.2 micrometers, and it is more preferable that it is 0.9-3.0 micrometers. It is still more preferable that it is 0-3.0 micrometers, it is still more preferable that it is 1.4-3.0 micrometers, and it is still more preferable that it is 1.6-2.8 micrometers.
Further, when the crystal grain size of the copper foil is large, the etching processing time required for removing the copper foil tends to be long. Further, when the crystal grain size of the copper foil is small, the etching processing time required for removing the copper foil tends to be short. A rolled copper foil or an electrolytic copper foil produced with an electrolytic solution containing chlorine, bis (3sulfopropyl) disulfide and an amine compound tends to have a large crystal grain size. Moreover, the electrolytic copper foil manufactured with the electrolyte solution with a high concentration of glue tends to have a small crystal grain size of the copper foil. When the surface treatment layer contains an element that is difficult to be etched (for example, nickel, chromium, tungsten, vanadium, etc.), the etching treatment time required for removing the surface treatment layer tends to be long. When the surface treatment layer contains an element that is easily etched (for example, zinc, cobalt, iron, etc.), the etching treatment time required for removing the surface treatment layer tends to be short.

The etching conditions for the flash etching can be defined as follows:
・ Etching type: Spray etching ・ Spray nozzle: Full cone type ・ Spray pressure: 0.10 MPa
・ Etching temperature: 30 ℃
・ Etching solution composition:
H ₂ O ₂ 18g / L
H ₂ SO ₄ 92 g / L
Cu 8g / L
Additive (add commercially available additive as hydrogen peroxide stabilizer)

[Copper foil with carrier]
The copper foil with a carrier of this invention has an intermediate | middle layer and an ultra-thin copper layer in this order on the one surface of a carrier, or both surfaces. And the said ultra-thin copper layer is the surface treatment copper foil which is one embodiment of the above-mentioned this invention.

<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 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.
In addition, you may provide a roughening process layer in the surface on the opposite side to the surface in the side which provides the ultra-thin copper layer of a carrier. The said roughening process layer may be provided using a well-known method, and may be provided by the above-mentioned roughening process. Providing a roughened layer on the surface opposite to the surface on which the ultrathin copper layer of the carrier is provided, when laminating the carrier from the surface side having the roughened layer to a support such as a resin substrate, There is an advantage that the carrier and the resin substrate are hardly separated.

<Intermediate layer>
An intermediate layer is provided on one or both sides of 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, From hydrates or oxides or organic substances of one or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn It can comprise by forming the layer which becomes.
Further, for example, the intermediate layer is a single metal layer composed of one kind of element selected from the element group composed of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn from the carrier side. Or forming an alloy layer composed of one or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, A single metal layer made of one element selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, or Cr, Ni, Co , Fe, Mo, Ti, W, P, Cu, Al, and Zn can be formed by forming an alloy layer made of one or more elements selected from the group of elements.
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. When the intermediate layer is provided by chromate treatment, zinc chromate treatment, or plating treatment, it is considered that some of the attached metal such as chromium and zinc may be hydrates or oxides.
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.

<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. The ultrathin copper layer is the surface-treated copper foil 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 may be provided on both sides of the carrier.

[Resin layer on the surface treatment layer]
A resin layer may be provided on the surface treatment layer of the surface-treated copper foil of the present invention. The resin layer may be an insulating resin layer.

  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. 2002-179772, Japanese Patent Laid-Open No. 2002-359444, Japanese Patent Laid-Open No. 2003-302068, Japanese Patent No. 3992225, Japanese Patent Laid-Open No. 2003 No. 249739, Japanese Patent No. 4136509, Japanese Patent Application Laid-Open No. 2004-82687, Japanese Patent No. 4025177, Japanese Patent Application Laid-Open No. 2004-349654, Japanese Patent No. 4286060, Japanese Patent Application Laid-Open No. 2005-262506, Japanese Patent No. 4570070, Japanese Patent Application Laid-Open No. No. 5-53218, Japanese Patent No. 3949676, Japanese Patent No. 4178415, International Publication No. WO2004 / 005588, Japanese Patent Application Laid-Open No. 2006-257153, Japanese Patent Application Laid-Open No. 2007-326923, Japanese Patent Application Laid-Open No. 2008-11169, and Japanese Patent No. 5024930. No. WO2006 / 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, acrylic 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, bismaleimi Dotriazine resin, 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 phenolic compound, manganese naphthenate, 2,2-bis (4-glycidylphenyl) propane, polyphenylene ether-cyanate resin, siloxane-modified polyamideimide resin, cyanoester resin, phosphazene Resin, rubber modified polyamideimide 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 at least one selected from the group of a suitable.

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 -Glycidylamine compounds such as diglycidylaniline, glycidyl ester compounds such as diglycidyl tetrahydrophthalate, phosphorus-containing epoxy resins, biphenyl type epoxy resins , Biphenyl novolac type epoxy resin, trishydroxyphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, or a mixture of two or more types, or a hydrogenated product of the epoxy resin Or a halogenated compound can be used.
As the phosphorus-containing epoxy resin, a known epoxy resin containing phosphorus can be used. The phosphorus-containing epoxy resin is, for example, an epoxy resin obtained as a derivative from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide having two or more epoxy groups in the molecule. Is preferred.

(When the resin layer contains a dielectric (dielectric filler))
The resin layer may include a dielectric (dielectric filler).
In the case where a dielectric (dielectric filler) is included in any of the above resin layers or resin compositions, it can be used for the purpose of forming the capacitor layer and increase the capacitance of the capacitor circuit. Examples of the dielectric (dielectric filler) include BaTiO ₃ , SrTiO ₃ , Pb (Zr—Ti) O ₃ (common name PZT), PbLaTiO ₃ · PbLaZrO (common name PLZT), SrBi ₂ Ta ₂ O ₉ (common name SBT), and the like. A composite oxide dielectric powder having a perovskite structure is used.

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

For example, 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). The surface-treated copper foil is coated on the roughened surface by, for example, a roll coater method, 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 resin-treated surface-treated copper foil with 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 surface-treated copper foil (resin-treated surface-treated copper foil) provided with the resin layer is obtained by superposing the resin layer on a substrate and then thermocompressing the whole to thermally cure the resin layer, and then the surface-treated copper foil. When is an ultra-thin copper layer of a copper foil with a carrier, the carrier is peeled off to expose the ultra-thin copper layer (of course, the surface on the intermediate layer side of the ultra-thin copper layer is exposed) The surface-treated copper foil is used in a form in which a predetermined wiring pattern is formed from the surface opposite to the surface subjected to the roughening treatment.

  When this surface-treated copper foil with resin is used, the number of prepreg materials used in the production of the 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 laminating process is simplified, which is economically advantageous. Moreover, the multilayer printed wiring board manufactured by the thickness of the prepreg material is used. The thickness is reduced, and there is an advantage that an extremely thin multilayer printed wiring board in which the thickness of one layer is 100 μm or less can be manufactured.
The thickness of the resin layer is preferably 0.1 to 120 μm.

When the thickness of the resin layer becomes thinner than 0.1 μm, the adhesive strength is reduced, and when this surface-treated copper foil with 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 surface-treated copper foil 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.

<Printed wiring boards, printed circuit boards>
The printed wiring board and printed circuit board of the present invention can be produced using the surface-treated copper foil and carrier-attached copper foil of the present invention. As for the copper foil with carrier, its own usage is well known to those skilled in the art. For example, the surface of the ultra-thin copper layer is made of paper base phenol resin, paper base epoxy resin, synthetic fiber cloth base epoxy resin, 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, polyester film, polyimide film, etc. The ultra-thin copper layer adhered to the substrate is etched into the intended conductor pattern, and finally a printed wiring board or a printed circuit board can be manufactured. Moreover, you may manufacture a copper clad laminated board. In addition, after preparing an insulating layer for the shield film and bonding the copper foil with a carrier on the surface from the ultrathin copper layer side, the copper foil carrier is peeled off from the ultrathin copper layer, and the electrode after the copper foil carrier is peeled off A shield film can be manufactured by providing an anisotropic conductive adhesive on the surface of the thin copper layer. The printed wiring board and the printed circuit board can be mounted on, for example, various electronic components that require high-density mounting of the mounted components.

  Below, some examples of the manufacturing process of the printed wiring board using the surface-treated copper foil which concerns on this invention, or copper foil with a carrier are shown. Moreover, a printed circuit board is completed by mounting electronic components on the printed wiring board produced at the said process.

  In one embodiment of the method for producing a printed wiring board according to the present invention using a semi-additive method, the step of preparing the surface-treated copper foil and the insulating substrate according to the present invention, the surface-treated copper foil, the surface-treated layer side Laminating to the insulating substrate, removing the surface-treated copper foil on the insulating substrate, and forming a circuit on the surface of the insulating substrate from which the surface-treated copper foil has been removed.

  In the semi-additive construction method, the surface profile of copper foil is used. Specifically, first, the copper foil of the present invention is laminated on a resin base material to produce a copper clad laminate. Next, the entire surface of the copper foil of the copper clad laminate is etched. Next, electroless copper plating is applied to the surface of the resin substrate (entire etching substrate) to which the copper foil surface profile has been transferred. Then, a portion of the resin base material (entire etching base material) where the circuit is not formed is covered with a dry film or the like, and electroless (electrolytic) copper plating is applied to the surface of the electroless copper plating layer not covered with the dry film. Then, after removing the dry film, a fine circuit is formed by removing the electroless copper plating layer formed in the portion where the circuit is not formed. Since the fine circuit formed in the present invention is in close contact with the etching surface of the resin base material (entire etching base material) to which the copper foil surface profile of the present invention is transferred, the adhesion force (peel strength) is good. It has become.

  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 conductor pattern is formed using electroplating and etching.

  In one embodiment of the method for manufacturing a printed wiring board according to the present invention using a semi-additive method, the step of preparing the copper foil with a carrier and the insulating substrate of the present invention, the copper foil with a carrier on the ultrathin copper layer side Laminating to the insulating substrate, laminating the carrier-attached copper foil and insulating substrate, then peeling the carrier of the carrier-attached copper foil, removing the ultra-thin copper layer on the insulating substrate after peeling the carrier And a step of forming a circuit on the surface of the insulating substrate from which the ultrathin copper layer has been removed.

  In one embodiment of the method for producing a printed wiring board according to the present invention, a step of preparing the surface-treated copper foil and the insulating substrate of the present invention, the surface-treated copper foil is laminated on the insulating substrate from the surface-treated layer side. Forming a copper-clad laminate, and then forming a circuit by any one of a subtractive method, a partly additive method, or a modified semi-additive method.

  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.

  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.

  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.

  In one embodiment of the method for producing a printed wiring board according to the present invention, a step of preparing the copper foil with carrier and the insulating substrate of the present invention, the copper foil with carrier is laminated on the insulating substrate from the ultrathin copper layer side. Forming a copper-clad laminate through a step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate, and then either the partial additive method or the modified semi-additive method A method includes forming a circuit.

  In one embodiment of a printed wiring board manufacturing method according to the present invention using a semi-additive method, a step of preparing a metal foil on which a circuit is formed, a resin layer is provided on the surface of the metal foil so that the circuit is buried The step of forming, the step of laminating the surface-treated copper foil of the present invention on the resin layer from the surface-treated layer side, the step of removing the surface-treated copper foil on the resin layer, the resin layer from which the surface-treated copper foil has been removed Forming a circuit on the surface, and removing the metal foil to expose a circuit formed on the surface of the metal foil and buried in the resin layer.

  In one embodiment of the method for producing a printed wiring board according to the present invention using a semi-additive method, the copper foil with a carrier of the present invention is a first copper foil with a carrier, and the pole of the first copper foil with a carrier A step of forming a circuit on the surface of the thin copper layer, a step of forming a resin layer on the surface of the ultrathin copper layer of the first copper foil with carrier so that the circuit is buried, a second copper foil with carrier And laminating the second carrier-attached copper foil on the resin layer from the ultrathin copper layer side, laminating the second carrier-attached copper foil on the resin layer, and then attaching the second carrier A step of peeling the carrier of the copper foil, a step of removing the ultrathin copper layer on the resin layer after peeling the carrier of the second copper foil with carrier, a circuit on the surface of the resin layer from which the ultrathin copper layer has been removed Forming a circuit on the resin layer, and then forming the first The step of peeling the carrier of the copper foil with carrier, and after peeling the carrier of the first copper foil with carrier, removing the ultrathin copper layer of the first copper foil with carrier, A step of exposing a circuit buried in the resin layer formed on the surface of the copper foil with carrier 1 on the side of the ultrathin copper layer.

  In one embodiment of a method for producing a printed wiring board according to the present invention, a step of preparing a metal foil on which a circuit is formed, a step of forming a resin layer on the surface of the metal foil so that the circuit is buried, the present invention A step of laminating the surface-treated copper foil on the resin layer from the surface-treated layer side, and forming a circuit on the resin layer by any one of the subtractive method, the partial additive method, or the modified semi-additive method; and The step of exposing the circuit buried in the resin layer formed on the surface of the metal foil by removing the metal foil is included.

  In one embodiment of the method for producing a printed wiring board according to the present invention, the copper foil with a carrier of the present invention is a first copper foil with a carrier, and the ultrathin copper layer side surface of the first copper foil with a carrier is used. A step of forming a circuit, a step of forming a resin layer on the ultrathin copper layer side surface of the first carrier-attached copper foil so that the circuit is buried, and preparing a second carrier-attached copper foil, A method of any one of the subtractive method, the partly additive method, or the modified semi-additive method, wherein the carrier layer of the second carrier-attached copper foil is peeled off from the ultrathin copper layer side of the carrier-attached copper foil. Forming a circuit on the resin layer, forming a circuit on the resin layer, and then peeling the carrier of the first copper foil with carrier, and carrier of the first copper foil with carrier Strip Then, the ultrathin copper layer of the first carrier-attached copper foil is removed, thereby being buried in the resin layer formed on the ultrathin copper layer side surface of the first carrier-attached copper foil. Exposing the circuit.

  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 a 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 an insulating substrate, etching or plasma using a corrosive solution such as an acid on the exposed ultrathin copper layer by peeling off the carrier A step of removing all by a method such as, a step of providing a through hole or / and a blind via in the resin exposed by removing the ultrathin copper layer by etching, a desmear for a region including the through hole or / and the blind via In the region containing the resin and the through-hole or / and blind via A step of providing an electroless plating layer, a step of providing a plating resist on the electroless plating layer, a step of exposing the plating resist, and then removing the plating resist in a region where a circuit is formed, the plating The step of providing an electrolytic plating layer in the region where the circuit from which the resist has been removed is formed, the step of removing the plating resist, and the electroless plating layer in a region other than the region where the circuit is formed by flash etching or the like Removing.

  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, the copper foil with a carrier and the insulating substrate Laminating the copper foil with carrier and the insulating substrate, then peeling off the carrier of the copper foil with carrier, etching the exposed ultrathin copper layer with a corrosive solution such as an acid. Removing all by a method such as plasma or plasma, providing an electroless plating layer on the surface of the resin exposed by removing the ultrathin copper layer by etching, and providing a plating resist on the electroless plating layer Exposing the plating resist to a step, and then removing the plating resist in a region where a circuit is formed; A step of providing an electrolytic plating layer in a region where the circuit is left, a step of removing the plating resist, and flushing an electroless plating layer and an ultrathin copper layer in a region other than the region where the circuit is formed A step of removing by etching or the like.

  In one embodiment of the method for producing a printed wiring board according to the present invention using the modified semi-additive method, a step of preparing the copper foil with carrier and the insulating substrate according to the present invention, the copper foil with carrier and the insulating substrate are prepared. A step of laminating, a step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and an insulating substrate, a through hole or / and a blind via in the ultrathin copper layer and the insulating substrate exposed by peeling the carrier A step of performing a desmear process on the region including the through hole or / and the blind via, a step of providing an electroless plating layer on the region including the through hole or / and the blind via, and an electrode exposed by peeling off the carrier Step of providing a plating resist on the surface of the thin copper layer, after providing the plating resist Forming a circuit by electroplating, removing the plating resist, comprising the step of removing by flash etching ultrathin copper layer exposed by removing the plating resist.

  In another embodiment of the method for manufacturing 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, the copper foil with carrier and the insulation A step of laminating the substrate, a step of laminating the carrier-attached copper foil and an insulating substrate, a step of peeling the carrier of the copper foil with carrier, a step of 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 where the plating resist is removed; The step of removing the resist, the electroless plating layer and the ultrathin copper layer in a region other than the region where the circuit is formed for flash etching, etc. Ri, including the step of removing.

  In one embodiment of a method for producing a printed wiring board according to the present invention using a partly 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 a 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, a through hole or / and a blind via on the exposed ultrathin copper layer and the insulating substrate after peeling the carrier. A step of performing a desmear process on the region including the through hole or / and the blind via, a step of applying a catalyst nucleus to the region including the through hole or / and the blind via, and an ultrathin copper exposed by peeling off the carrier A step of providing an etching resist on the surface of the layer; exposing the etching resist; A step of forming a pattern, a step of forming a circuit by 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, a step of 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 nuclei by a method such as etching or plasma using a corrosive solution such as an acid, the solder resist or the plating resist The process of providing an electroless-plating layer in the area | region where is not provided.

  In one embodiment of a method for producing a printed wiring board according to the present invention using a subtractive 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 a 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, a through hole or / and a blind via on the exposed ultrathin copper layer and the insulating substrate after peeling the carrier. A step of providing, a step of performing a desmear process on the region including the through hole or / and the blind via, a step of providing an electroless plating layer on the region including the through hole or / and the blind via, on the surface of the electroless plating layer, An electrolytic plating layer is formed on the surface of the electrolytic plating layer and / or the ultrathin copper layer. A step of providing a strike, a step of exposing the etching resist to form a circuit pattern, etching of the ultrathin copper layer, the electroless plating layer, and the electrolytic plating layer using a corrosive solution such as an acid or plasma. And removing the etching resist.

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

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

  Here, the specific example of the manufacturing method of the printed wiring board using the 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. 2-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 in FIG. 2B, a resist is applied on the roughened layer of the ultrathin copper layer, exposed and developed, and the resist is etched into a predetermined shape.
Next, as shown in FIG. 2C, 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. 3D, 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. A copper foil (second layer) is bonded from the ultrathin copper layer side.
Next, as shown to FIG. 3-E, a carrier is peeled from the copper foil with a carrier of the 2nd layer.
Next, as shown in FIG. 3F, laser drilling is performed at a predetermined position of the resin layer to expose circuit plating and form a blind via.
Next, as shown in FIG. 4-G, copper is embedded in the blind via to form a via fill.
Next, as shown in FIG. 4-H, circuit plating is formed on the via fill as shown in FIGS. 2-B and 2-C.
Next, as shown to FIG. 4-I, a carrier is peeled from the copper foil with a carrier of the 1st layer.
Next, as shown in FIG. 5J, 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. 5K, 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. 4-H, and these circuits may be formed using a semi-additive method, a subtractive method, a partial additive method, or a modified semi-conductor method. You may carry out by any method of an additive method.

  Moreover, the copper foil with a carrier used for the said 1st layer may have a board | substrate on the carrier side surface of the said copper foil with a carrier. By having the said board | substrate or resin layer, since the copper foil with a carrier used for the 1st layer is supported and it becomes difficult to wrinkle, there exists an advantage that productivity improves. Any substrate can be used as long as it has the effect of supporting the copper foil with carrier used in the first layer. For example, the carrier, prepreg, resin layer or known carrier, prepreg, resin layer, metal plate, metal foil, inorganic compound plate, inorganic compound foil, organic compound plate, organic compound A foil can be used.

  Although there is no restriction | limiting in particular about the timing which forms a board | substrate in the carrier side surface, It is necessary to form before peeling a carrier. In particular, it is preferably formed before the step of forming a resin layer on the ultrathin copper layer side surface of the copper foil with carrier, and the step of forming a circuit on the ultrathin copper layer side surface of the copper foil with carrier More preferably, it is formed before.

  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).

  Examples of the present invention are shown below, but these examples are provided for better understanding of the present invention and its advantages, and are not intended to limit the invention.

  The following copper foil bulk layers (raw foils) were prepared as Examples 1 to 11 and Comparative Examples 1 to 4.

・ General electrolytic green foil Copper concentration of 80 to 120 g / L, sulfuric acid concentration of 80 to 120 g / L, chloride ion concentration of 30 to 100 ppm, glue concentration of 1 to 5 ppm, and electrolytic solution temperature of 57 to 62 ° C. The electrolytic solution flowing between the anode and the cathode (a metal drum for electrodeposition for copper foil) as a plating bath has a linear velocity of 1.5 to 2.5 m / sec, a current density of 70 A / dm ² and a thickness of 12 μm (weight thickness 95 g). / M ² ) general electrolytic green foil was prepared.

-Double-sided flat electrolytic green foil Copper concentration 80-120 g / L, sulfuric acid concentration 80-120 g / L, chloride ion concentration 30-100 ppm, leveling agent 1 (bis (3sulfopropyl) disulfide): 10-30 ppm, leveling agent 2 (Amine compound): The linear velocity of the electrolyte flowing between the anode and the cathode (electrodeposition metal drum for copper foil) using a copper sulfate electrolyte of 10 to 30 ppm and an electrolyte temperature of 57 to 62 ° C. as an electrolytic copper plating bath Was produced at a current density of 70 A / dm ² and a thickness of 12 μm (weight thickness 95 g / m ² ). 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.)

-Ultra-thin raw copper foil with carrier A double-sided flat electrolytic raw foil having a thickness of 18 µm was produced under the above-mentioned double-sided flat electrolytic raw foil manufacturing conditions. Using this as a copper foil carrier, a peeling layer, an ultrathin copper layer having a thickness described in Table 1, was formed by the following method to obtain an ultrathin copper foil with a carrier.
(1) Ni layer (peeling layer: base plating 1)
An Ni layer having an adhesion amount of 1000 μg / dm ² was formed on the S surface of the copper foil carrier by electroplating with a roll-to-roll type continuous plating line under the following conditions. Specific plating conditions are described below.
Nickel sulfate: 270-280 g / L
Nickel chloride: 35 to 45 g / L
Nickel acetate: 10-20g / L
Boric acid: 30-40 g / L
Brightener: Saccharin, butynediol, etc. Sodium dodecyl sulfate: 55-75 ppm
pH: 4-6
Bath temperature: 55-65 ° C
Current density: 10 A / dm ²
(2) Cr layer (peeling layer: base plating 2)
Next, after the surface of the Ni layer formed in (1) is washed with water and pickled, a Cr layer having an adhesion amount of 11 μg / dm ² is continuously formed on the Ni layer on a roll-to-roll-type continuous plating line. It was made to adhere by carrying out the electrolytic chromate process on the following conditions.
Potassium dichromate 1-10g / L, zinc 0g / L
pH: 7-10
Liquid temperature: 40-60 degreeC
Current density: 2 A / dm ²
(3) Ultra-thin copper layer Next, after the surface of the Cr layer formed in (2) was washed with water and pickled, the thickness 1. on the Cr layer on a continuous roll-to-roll type continuous plating line. A 5 μm, 2 μm, 3 μm, or 5 μm ultrathin copper layer was formed by electroplating under the following conditions to produce an ultrathin copper foil with a carrier.
Copper concentration: 80-120 g / L
Sulfuric acid concentration: 80-120 g / L
Chloride ion concentration: 30-100ppm
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

  Next, each surface treatment of roughening treatment, barrier treatment, rust prevention treatment, silane coupling material application on the M (matte) surface or S (shiny) surface, which is the surface of the green foil bonded to the resin base material Were applied in this order. Each processing condition is shown below.

[Roughening treatment]
・ Spherical roughening (normal):
The roughening process was performed on the M surface or S surface of the various raw foils described above under the following conditions.
(Electrolytic solution composition)
Cu: 20-30 g / L (added with copper sulfate pentahydrate, the same applies hereinafter)
H ₂ SO ₄ : 80-120 g / L
Arsenic: 1.0-2.0 g / L
(Electrolyte temperature)
35-40 ° C
(Current condition)
Current density: 70 A / dm ²

  Cover the M surface of various copper foils roughened under the above conditions and the surface of the ultrathin copper foil with carrier with a copper electrolytic bath made of sulfuric acid and copper sulfate to prevent the removal of the roughened particles and improve the peel strength. Plating was performed. The covering plating conditions are described below.

(Electrolytic solution composition)
Cu: 40-50 g / L
H ₂ SO ₄ : 80-120 g / L
(Electrolyte temperature)
43-47 ° C
(Current condition)
Current density: 29 A / dm ²

-Fine roughening (1):
The roughening process was performed on the M surface of various raw foils previously described, and the surface of the ultra-thin raw copper foil with a carrier on the following conditions.
(Electrolytic solution composition)
Cu concentration: 10 to 20 g / L
H ₂ SO ₄ concentration: 80 to 120 g / L
Tungsten concentration: 1 to 10 mg / L (added with sodium tungstate dihydrate)
Sodium dodecyl sulfate concentration: 1 to 10 mg / L
(Electrolyte temperature)
35-45 ° C
(Current condition)
In order to obtain a predetermined surface roughness Sz, a current was applied in a four-stage manner.
The current density was as follows.
First stage: 30 A / dm ²
Second stage: 10 A / dm ²
Third stage: 30 A / dm ²
Fourth stage: 10 A / dm ²

Cover the M surface of various copper foils roughened under the above conditions and the surface of the ultrathin copper foil with carrier with a copper electrolytic bath made of sulfuric acid and copper sulfate to prevent the removal of the roughened particles and improve the peel strength. Plating was performed. The covering plating conditions are described below.
(Electrolytic solution composition)
Cu: 40-50 g / L
H ₂ SO ₄ : 80-120 g / L
(Electrolyte temperature)
43-47 ° C
(Current condition)
Current density: 41 A / dm ²

-Fine roughening (2):
The surface of the ultrathin raw copper foil with a carrier described above was roughened under the following conditions.
(Electrolytic solution composition)
Cu concentration: 10 to 20 g / L
H ₂ SO ₄ concentration: 80 to 120 g / L
Tungsten concentration: 1 to 10 mg / L (added with sodium tungstate dihydrate)
Sodium dodecyl sulfate concentration: 1 to 10 mg / L
(Electrolyte temperature)
35-45 ° C
(Current condition)
In order to obtain a predetermined surface roughness Sz, a two-stage system was applied.
The current density was as follows.
First stage: 50 A / dm ²
Second stage: 10 A / dm ²

Cover the M surface of various copper foils roughened under the above conditions and the surface of the ultrathin copper foil with carrier with a copper electrolytic bath made of sulfuric acid and copper sulfate to prevent the removal of the roughened particles and improve the peel strength. Plating was performed. The covering plating conditions are described below.
(Electrolytic solution composition)
Cu: 40-50 g / L
H ₂ SO ₄ : 80-120 g / L
(Electrolyte temperature)
43-47 ° C
(Current condition)
Current density: 41 A / dm ²

-Fine roughening (3):
The roughening process was performed on the M surface of the double-sided flat electrolytic raw foil described above and the surface of the ultrathin raw copper foil with a carrier under the following conditions.
(Electrolytic solution composition)
Cu: 10 to 20 g / L
Co: 1-10 g / L
Ni: 1-10g / L
pH: 1-4
(Electrolyte temperature)
40-50 ° C
(Current condition)
Current density: 25 A / dm ²
(Immersion time in plating solution after plating)
In order to obtain a predetermined surface roughness Sz, the time was set within 5 seconds.

Co-Ni plating was performed on the M surface of the double-sided flat copper foil subjected to the roughening treatment under the above conditions and the surface of the ultrathin copper foil with carrier. The covering plating conditions are described below.
(Electrolytic solution composition)
Co: 1-30 g / L
Ni: 1-30 g / L
pH: 1.0-3.5
(Electrolyte temperature)
30-80 ° C
(Current condition)
Current density 5.0A / dm ²

-Fine roughening (4):
The surface of the ultrathin raw copper foil with a carrier described above was subjected to a roughening treatment for forming primary particles and secondary particles under the following conditions.
Primary particle formation:
(Electrolytic solution composition)
Cu concentration: 10 to 20 g / L
H ₂ SO ₄ concentration: 80 to 120 g / L
Tungsten concentration: 1 to 10 mg / L (added with sodium tungstate dihydrate)
Sodium dodecyl sulfate concentration: 1 to 10 mg / L
(Electrolyte temperature)
35-45 ° C
(Current condition)
In order to obtain a predetermined surface roughness Sz, a two-stage system was applied.
The current density was as follows.
First stage: 50 A / dm ²
Second stage: 10 A / dm ²

The surface of the ultrathin copper foil with carrier on which the primary roughened particles are formed under the above conditions is covered with a copper electrolytic bath composed of sulfuric acid and copper sulfate to prevent the primary roughened particles from falling off and improve the peel strength. Went. The covering plating conditions are described below.
(Electrolytic solution composition)
Cu: 40-50 g / L
H ₂ SO ₄ : 80-120 g / L
(Electrolyte temperature)
43-47 ° C
(Current condition)
Current density: 41 A / dm ²

Primary particle formation:
Next, the roughening process for forming a secondary coarse particle on the primary coarse particle of the ultra-thin copper foil with a carrier was performed.
(Electrolytic solution composition)
Cu: 10 to 20 g / L
Co: 1-10 g / L
Ni: 1-10g / L
pH: 1-4
(Electrolyte temperature)
40-50 ° C
(Current condition)
Current density: 25 A / dm ²
(Immersion time in plating solution after plating)
In order to obtain a predetermined surface roughness Sz, the time was set within 5 seconds.

Co-Ni covering plating was performed on the surface of the ultrathin copper foil with a carrier that had been subjected to secondary particle roughening treatment under the above conditions. The covering plating conditions are described below.
(Electrolytic solution composition)
Co: 1-30 g / L
Ni: 1-30 g / L
pH: 1.0-3.5
(Electrolyte temperature)
30-80 ° C
(Current condition)
Current density 5.0A / dm ²

-Fine roughening (5):
The surface of the ultrathin raw copper foil with a carrier described above was subjected to a roughening treatment for forming primary particles and secondary particles under the following conditions.
Primary particle formation:
(Electrolytic solution composition)
Cu concentration: 10 to 20 g / L
H ₂ SO ₄ concentration: 80 to 120 g / L
Tungsten concentration: 1 to 10 mg / L (added with sodium tungstate dihydrate)
Sodium dodecyl sulfate concentration: 1 to 10 mg / L
(Electrolyte temperature)
35-45 ° C
(Current condition)
In order to obtain a predetermined surface roughness Sz, a two-stage system was applied. The current density was as follows.
First stage: 20 A / dm ²
Second stage: 10 A / dm ²

The surface of the ultrathin copper foil with carrier on which the primary roughened particles are formed under the above conditions is covered with a copper electrolytic bath composed of sulfuric acid and copper sulfate to prevent the primary roughened particles from falling off and improve the peel strength. Went. The covering plating conditions are described below.
(Electrolytic solution composition)
Cu: 40-50 g / L
H ₂ SO ₄ : 80-120 g / L
(Electrolyte temperature)
43-47 ° C
(Current condition)
Current density: 41 A / dm ²

Secondary particle formation:
Next, the roughening process for forming a secondary coarse particle on the primary coarse particle of the ultra-thin copper foil with a carrier was performed.
(Electrolytic solution composition)
Cu: 10 to 20 g / L
Co: 1-10 g / L
Ni: 1-10g / L
pH: 1-4
(Electrolyte temperature)
40-50 ° C
(Current condition)
Current density: 25 A / dm ²
(Immersion time in plating solution after plating)
In order to obtain a predetermined surface roughness Sz, the time was set to 15 to 20 seconds.

Co-Ni covering plating was performed on the surface of the ultrathin copper foil with a carrier that had been subjected to secondary particle roughening treatment under the above conditions. The covering plating conditions are described below.
(Electrolytic solution composition)
Co: 1-30 g / L
Ni: 1-30 g / L
pH: 1.0-3.5
(Electrolyte temperature)
30-80 ° C
(Current condition)
Current density 5.0A / dm ²

-Fine roughening (6):
The surface of the ultrathin raw copper foil with a carrier described above was subjected to a roughening treatment for forming primary particles and secondary particles under the following conditions.
Primary particle formation:
(Electrolytic solution composition)
Cu concentration: 10 to 20 g / L
H ₂ SO ₄ concentration: 80 to 120 g / L
Tungsten concentration: 1 to 10 mg / L (added with sodium tungstate dihydrate)
Sodium dodecyl sulfate concentration: 1 to 10 mg / L
(Electrolyte temperature)
35-45 ° C
(Current condition)
In order to obtain a predetermined surface roughness Sz, a three-stage system was applied. The current density was as follows.
First stage: 25 A / dm ²
Second stage: 10 A / dm ²
Third stage: 5 A / dm ²

The surface of the ultrathin copper foil with carrier on which the primary roughened particles are formed under the above conditions is covered with a copper electrolytic bath composed of sulfuric acid and copper sulfate to prevent the primary roughened particles from falling off and improve the peel strength. Went. The covering plating conditions are described below.
(Electrolytic solution composition)
Cu: 40-50 g / L
H ₂ SO ₄ : 80-120 g / L
(Electrolyte temperature)
43-47 ° C
(Current condition)
Current density: 41 A / dm ²

Secondary particle formation:
Next, the roughening process for forming a secondary coarse particle on the primary coarse particle of the ultra-thin copper foil with a carrier was performed.
(Electrolytic solution composition)
Cu: 10 to 20 g / L
Co: 1-10 g / L
Ni: 1-10g / L
pH: 1-4
(Electrolyte temperature)
40-50 ° C
(Current condition)
Current density: 25 A / dm ²
(Immersion time in plating solution after plating)
In order to obtain a predetermined surface roughness Sz, the time was set to 5 to 10 seconds.

Co-Ni covering plating was performed on the surface of the ultrathin copper foil with a carrier that had been subjected to secondary particle roughening treatment under the above conditions. The covering plating conditions are described below.
(Electrolytic solution composition)
Co: 1-30 g / L
Ni: 1-30 g / L
pH: 1.0-3.5
(Electrolyte temperature)
30-80 ° C
(Current condition)
Current density 5.0A / dm ²

[Barrier (heat resistant) treatment]
A barrier (heat resistant) treatment was performed under the following conditions to form a brass plating layer or a zinc / nickel alloy plating layer.

Conditions for forming barrier layers (zinc / nickel plating) in Examples 2 and 6 and Comparative Example 2:
Ni: 10 g / L to 30 g / L, Zn: 1 g / L to 15 g / L, sulfuric acid (H ₂ SO ₄ ): 1 g / L to 12 g / L, chloride ion: 0 g / L to 5 g / L Using a plating bath, a plating electric quantity of 5.5 As / dm ² was applied to the M surface on which the roughening treatment layer was formed at a current density of 1.3 A / dm ² .

Barrier layer (brass plating) formation conditions of Example 8 and Comparative Examples 3 and 4:
Using a brass plating bath having a copper concentration of 50 to 80 g / L, a zinc concentration of 2 to 10 g / L, a sodium hydroxide concentration of 50 to 80 g / L, a sodium cyanide concentration of 5 to 30 g / L, and a temperature of 60 to 90 ° C. The plating electric quantity of 30 As / dm ² was applied to the M surface on which the roughening treatment layer was formed by 5 to 10 A / dm ² (multistage treatment).

[Rust prevention treatment]
Rust prevention treatment (chromate treatment) was performed under the following conditions to form a rust prevention treatment layer.
(Chromate conditions) CrO ₃ : 2.5 g / L, Zn: 0.7 g / L, Na ₂ SO ₄ : 10 g / L, pH 4.8, an electric quantity of 0.7 As / dm ^{2 in} a chromate bath at 54 ° C. Addition. Furthermore, immediately after completion of the rust prevention treatment in the chromate bath, the entire roughened surface was showered using the same chromate bath using a liquid shower pipe.
[Silane coupling material application]
A silane coupling material coating treatment was performed by spraying a solution having a pH of 7 to 8 containing 0.2 to 2% of alkoxysilane on the roughened surface of the copper foil.

About Example 9, the resin layer was formed on the following conditions after the antirust process and silane coupling material application | coating.
(Resin synthesis example)
To a 2-liter three-necked flask equipped with a stainless steel vertical stirring bar, a trap with a nitrogen inlet tube and a stopcock, and a reflux condenser with a ball condenser, 117.68 g (400 mmol) of 4′-biphenyltetracarboxylic dianhydride, 87.7 g (300 mmol) of 1,3-bis (3-aminophenoxy) benzene, 4.0 g (40 mmol) of γ-valerolactone, 4. 8 g (60 mmol), 300 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) and 20 g of toluene were added, heated at 180 ° C. for 1 hour, cooled to near room temperature, and then 3, 4, 3 ′, 4′— 29.42 g (100 mmol) of biphenyltetracarboxylic dianhydride, 2,2-bis {4- (4-aminophenoxy) phenyl} propane 82.12 (200 mmol), 200 g of NMP, toluene 40g added and after 1 hour mixing at room temperature, and heated for 3 hours at 180 ° C., to obtain a 38% solids polyimide block copolymer. The block copolymerized polyimide had the following general formula (1): general formula (2) = 3: 2, number average molecular weight: 70000, and weight average molecular weight: 150,000.

  The block copolymerized polyimide solution obtained in the synthesis example was further diluted with NMP to obtain a block copolymerized polyimide solution having a solid content of 10%. In this block copolymerized polyimide solution, bis (4-maleimidophenyl) methane (BMI-H, Kay-Isei Chemical Co., Ltd.) has a solid content weight ratio of 35 and a solid content weight ratio of block copolymerized polyimide of 65 (that is, included in the resin solution). Bis (4-maleimidophenyl) methane solid content weight: block copolymerized polyimide solid content weight contained in resin solution = 35: 65) A resin solution was prepared by dissolving and mixing at 60 ° C. for 20 minutes. Thereafter, the resin solution was applied to the surface of the ultrathin copper layer using a reverse roll coating machine, dried at 120 ° C. for 3 minutes and 160 ° C. for 3 minutes in a nitrogen atmosphere, and finally at 300 ° C. A heat treatment was performed for 2 minutes to prepare a copper foil provided with a resin layer. The thickness of the resin layer was 2 μm.

(Various evaluations of surface-treated copper foil and copper foil with carrier)
The surface-treated copper foil and the carrier-attached copper foil obtained as described above were evaluated by the following methods.

<Etching rate>
The following resin base material having a 6.25 cm square and a thickness of 100 μm was prepared, and the resin base material and the copper foil were laminated and pressed so that the surface having the surface treatment layer of the copper foil was in contact with the resin base material. The lamination press was performed under the conditions of press pressure: 3 MPa, heating temperature and time: 220 ° C. × 2 hours.
Resin: GHPL-830MBT manufactured by Mitsubishi Gas Chemical Company

Next, in the case of the surface-treated copper foil, the copper foil of the starting material in which the copper foil was laminated on the resin base material was etched under the following conditions. In addition, in the case of a copper foil with a carrier, prepared by peeling the carrier from the copper foil with a carrier on the resin substrate, the ultra thin copper layer of the starting material in which an ultra thin copper layer was laminated on the resin substrate, Etching was performed under the following conditions.
(Etching conditions)
・ Etching type: Spray etching ・ Spray nozzle: Full cone type ・ Spray pressure: 0.10 MPa
・ Etching temperature: 30 ℃
・ Etching solution composition:
H ₂ O ₂ 18g / L
H ₂ SO ₄ 92 g / L
Cu 8g / L
Additives FE-830IIW3C appropriate amount manufactured by JCU Corporation Etching time: 10 to 300 seconds

The etching amount and the etching rate were calculated from the weight difference before and after the etching process (weight before etching process−weight after etching process) by the following formula.
Etching amount (μm) = weight difference (g) ÷ [copper density (8.93 g / cm ² ) ÷ area (6.25 × 2 cm ² )] × 10000
Etching rate (μm / s) = etching amount (μm) ÷ etching time (s)
Moreover, the graph which shows the relationship between the etching process time of Examples 1-3 and the comparative example 1 and the etching amount in FIG. 6 was created. According to FIG. 6, during the etching process of the ultrathin copper layer part (in the case of surface-treated copper foil, the copper foil part, in the case of copper foil with carrier, the ultrathin copper layer part is shown), the processing time and the etching amount Is a straight line, and after etching the thickness of the ultrathin copper layer part (3 μm for the ultrathin copper layer with a thickness of 3 μm), an inflection point appears in the graph when the surface treatment layer is reached. It can be seen that the etching amount becomes gentle (the etching rate is lowered) and approaches the horizontal while drawing a curve. From these points, in the present invention, the calculation formula for the etching rate of the ultrathin copper layer portion, the calculation formula for the etching rate of the surface treatment layer portion, the calculation formula for the etching treatment time in the thickness direction of the surface treatment layer, and the copper The calculation formula of the etching treatment time for the foil thickness of 1 μm was defined as follows.
(A) Formula for calculating the etching rate of the ultrathin copper layer portion:
・ "Thickness of ultrathin copper layer (μm)" ÷ "Time required to remove the thickness of the ultrathin copper layer by etching (s)"
(B) Formula for calculating the etching rate of the surface treatment layer portion:
・ "Thickness of the ultrathin copper layer and surface treatment layer completely removed by etching (μm)-Thickness of the ultrathin copper layer (μm)" ÷ "The ultrathin copper layer and surface treatment layer are completely removed by etching. Time required for (s)-Time required for etching to remove the thickness of the ultrathin copper layer portion (s) "
The precision balance used for the weight measurement can measure up to 4 digits after the decimal point, and the measured value is rounded off to the fourth digit.
(C) Formula for calculating the etching time in the thickness direction of the surface treatment layer:
-Time required to completely remove the ultrathin copper layer and surface treatment layer by etching (s)-Time required to remove the thickness of the ultrathin copper layer portion by etching (s)
(D) Formula for calculating etching time for copper foil having a thickness of 1 μm:
・ Thickness of ultrathin copper layer 1μm / etching rate of ultrathin copper layer part (μm / s)
In addition, the measurement for preparation of the graph which shows the relationship between the etching time of FIG. 6 and the etching amount was performed at the following etching time intervals.
・ Ultra-thin copper layer part: 10 seconds interval ・ Inflection point vicinity: 1 to 3 seconds interval ・ Surface treatment layer: 1 to 2 seconds interval The above measurement interval is an example, and the relationship between the etching time and the etching amount is accurate. The measurement time interval that can be measured at a time may be determined as appropriate. As other measurement examples, the ultrathin copper layer, the vicinity of the inflection point, and the surface treatment layer may be measured at intervals of 0.1 to 2 seconds.
Here, when there is an inflection point in FIG. 6, the thickness (etching amount (μm)) at which the inflection point is generated is defined as the thickness of the ultrathin copper layer portion (μm). . Also, if the inflection point is not clear, or if the inflection point and the ultrathin copper layer are not likely to match the thickness of the sample, the sample will remain in the vicinity of the inflection point. Etching was performed. And the cross-section observation of the etched sample was performed with FIB (focused ion beam) -SIM (scanning ion microscope), and the interface between the ultrathin copper layer and the surface treatment layer was determined from the crystal structure (metal structure) of copper. Here, FIG. 8 shows an example of a cross-sectional observation photograph of a copper layer (corresponding to an ultrathin copper layer here) and a surface treatment layer. In FIG. 8, a particulate surface treatment layer is confirmed on the surface of the ultrathin copper layer together with the resin derived from the resin base material. The interface indicates a boundary surface between the ultrathin copper layer and the surface treatment layer. Etching is performed by etching to expose a part or all of the interface between the ultrathin copper layer and the surface treatment layer (or a part when the thickness variation of the ultrathin copper layer is large). The etching processing time was set to complete the removal of the copper layer by etching. And the etching amount in the etching process time which the etching of the said ultra-thin copper layer is completed was made into the thickness (micrometer) of the ultra-thin copper layer part.
The “time required for removing the thickness of the ultrathin copper layer portion by etching (s)” is the time required for removing the thickness (μm) of the ultrathin copper layer portion (ultrathin copper layer portion). The etching processing time for completing the etching was determined.
In addition, “thickness (μm) obtained by completely removing the ultrathin copper layer and the surface treatment layer by etching” indicates that the change in the etching weight in the section in Table 2 is 0.001 g or less per 2 seconds of etching time. The section immediately before is the end point, and is the etching amount from the etching start to the end point. In addition, when the etching time of each section is less than 2 seconds, the total amount of change in the etching time for each section is 2 seconds. Measure the weight change of the sample.
The “time (s) required to completely remove the ultrathin copper layer and the surface treatment layer by etching” was the time required from the start of etching to the end point.

<Surface roughness: Sz>
Surface treatment layer of surface-treated copper foil and copper foil with carrier using an Olympus laser microscope (tester: OLYMPUS LEXT OLS 4000, resolution: XY-0.12 μm, Z-0.0 μm, cut-off: none) The surface roughness Sz of the side surface was measured according to ISO25178.

<Wiring formability>
6. Prepare the following resin base material of 6.25 cm square and thickness 100 μm, and contact the resin base material, the surface-treated copper foil, and the copper foil with carrier with the surface having the surface treatment layer of the copper foil in contact with the resin base material. And laminated press. The lamination press was performed under the conditions of press pressure: 3 MPa, heating temperature and time: 220 ° C. × 2 hours.
Resin: GHPL-830MBT manufactured by Mitsubishi Gas Chemical Company

Next, the surface-treated copper foil on the resin substrate was microetched under the following etching conditions to adjust the thickness of the surface-treated copper foil to 1.4 μm. In addition, for the copper foil with carrier on the resin substrate, after peeling the carrier, micro-etching the ultra-thin copper layer under the following etching conditions to adjust the thickness of the surface-treated ultra-thin copper layer to 1.4 μm did. The microetching improves the DF adhesion during the DF patterning process described later.
(Micro etching conditions)
・ Etching type: Spray etching ・ Spray nozzle: Full cone type ・ Spray pressure: 0.10 MPa
・ Etching temperature: 30 ℃
・ Etching solution composition:
H ₂ O ₂ 18g / L
H ₂ SO ₄ 92 g / L
Cu 8g / L
Additive FE-830IIW3C appropriate amount made by JCU Corporation

Next, DF (dry film) patterning processing was performed according to the following processing steps and processing conditions.
-DF lamination process: Hitachi Chemical Co., Ltd. RY-5325 was used as DF, and the said DF was bonded together to the said micro etching surface. The temperature of the laminate roll used for bonding was 110 ° C., the pressure was 0.4 MPa, and the rotation speed was 1.0 m / min.
DF exposure step: An exposure mask of L (line) / S (space) = 21 μm / 9 μm was used, and the DF was irradiated with light through the exposure mask. The DF used was a negative type, and the portion that was exposed to light was photocured. The exposure amount was 100 mJ / cm ² .
-DF development process: By developing by spray etching with an aqueous solution of sodium carbonate (developer), a portion not exposed to light in the exposure process was dissolved and removed with a developer. The sodium carbonate concentration was 1 wt / vol%, the spray pressure was 0.16 MPa, and the spraying time was 36 seconds.
-Water washing step: Water was sprayed by spraying, and the development surface was washed with water. The spray pressure was 0.16 MPa and the spray spraying time was 36 seconds.

Next, pattern copper plating was performed on the surface of the copper foil and the ultrathin copper layer using a treatment solution having the following plating solution composition.
Pattern copper plating solution composition:
Copper sulphate pentahydrate: 100 g / L
・ Sulfuric acid: 180 g / L
・ Chlorine ion: 50ppm
-Additive: CU-BRITE-RF appropriate amount manufactured by JCU Corporation The additive is used for the purpose of improving the gloss and smoothness of the plating surface.

Next, DF peeling was performed with a sodium hydroxide solution. The sodium hydroxide concentration was 3 wt / vol%, the liquid temperature was 55 ° C., and the treatment time was 5 minutes.
Next, flash etching was performed on the surfaces of the copper foil and the ultrathin copper layer under the following conditions.
(Etching conditions)
・ Etching type: Spray etching ・ Spray nozzle: Full cone type ・ Spray pressure: 0.10 MPa
・ Etching temperature: 30 ℃
・ Etching solution composition:
H ₂ O ₂ 18g / L
H ₂ SO ₄ 92 g / L
Cu 8g / L
Additives FE-830IIW3C appropriate amount manufactured by JCU Corporation ・ Processing time [10 to 200 seconds]

  With respect to Examples 1 to 3 and Comparative Example 1, optical micrographs of the upper surface appearance were taken when the wiring formability was evaluated. Optical micrographs (magnification: 500 times) were taken for each of those focused on the top surface of the wiring and those focused on the bottom surface of the wiring. The observation photograph of the residue appearance (L / S = 15 μm / 15 μm pitch portion) between the wirings after flash etching of the wirings of Examples 1 to 3 and Comparative Example 1 is shown in FIG.

(Wiring formability evaluation 1)
In the observation photograph when focusing on the bottom surface of the wiring, when the removal of the copper residue on the resin surface between the wirings was completed, the width of the formed wiring was measured and evaluated according to the following criteria.
(Evaluation criteria) A: Wiring width exceeds 15 μm, O: Wiring width is 10-15 μm, X: Wiring width is less than 10 μm

(Wiring formability evaluation 2)
In the observation photograph when focusing on the bottom surface of the wiring, when the wiring width became 13.5 μm, the remaining level of the copper residue on the resin surface between the wirings was relatively evaluated according to the following criteria.
(Evaluation criteria) ○: No residue, ×: Residue confirmation, XX: Large amount of residue confirmation

(Wiring formability evaluation 3)
At the time when the removal of the copper residue on the resin surface between the wirings was completed, the step between the surface of the formed wiring and the resin surface was measured and relatively evaluated according to the following criteria.
(Evaluation criteria) (double-circle): A level | step difference is less than 1.5 micrometers, (circle): A level | step difference is 1.5-4 micrometers, X: A level | step difference exceeds 4 micrometers Test conditions and a result are shown to Tables 1-4.

(Evaluation results)
In each of Examples 1 to 11, when the etching rate in the thickness direction of the copper foil was 1, the etching rate in the thickness direction of the surface treatment layer was 0.5 or more, so the fine wiring formability was good. It was.
In each of Comparative Examples 1 to 4, when the etching rate in the thickness direction was 1, the etching rate in the thickness direction of the surface treatment layer was less than 0.5, so the fine wiring formability was poor.

Claims (28)

A surface-treated copper foil in which a surface-treated layer having a roughened layer is formed on the copper foil,
Stabilization of 18 g / L H ₂ O ₂ , 92 g / L H ₂ SO ₄ , 8 g / L Cu and hydrogen peroxide from the surface opposite to the surface on which the surface treatment layer is formed When spray etching is performed with a copper-dissolved etching solution having a liquid temperature of 30 ° C. composed of an agent,
When the etching rate in the thickness direction of the copper foil is 1, the etching rate in the thickness direction of the surface treatment layer is 0.5 or more, and
The ratio of “thickness (μm) of the copper foil and the surface treatment layer completely removed by etching−thickness of the copper foil (μm)” to “thickness (μm) of the copper foil” is 0.04 to 0.00. 21
The surface-treated copper foil whose surface roughness Sz of the surface in which the said surface treatment layer was formed is 0.8-3.2 micrometers.   The surface-treated copper foil according to claim 1, wherein an etching rate in the thickness direction of the surface treatment layer is 0.75 or more when an etching rate in the thickness direction of the copper foil is 1.   The surface-treated copper foil according to claim 2, wherein an etching rate in the thickness direction of the surface treatment layer is 1.0 or more when an etching rate in the thickness direction of the copper foil is 1. A surface-treated copper foil in which a surface-treated layer having a roughened layer is formed on the copper foil,
Stabilization of 18 g / L H ₂ O ₂ , 92 g / L H ₂ SO ₄ , 8 g / L Cu and hydrogen peroxide from the surface opposite to the surface on which the surface treatment layer is formed When spray etching is performed with a copper-dissolved etching solution having a liquid temperature of 30 ° C. composed of an agent,
The ratio of the etching treatment time in the thickness direction of the surface treatment layer to the etching treatment time of 1 μm thickness of the copper foil is 0.7 or less,
The etching treatment time in the thickness direction of the surface treatment layer is calculated by the following formula A,
Formula A: Time required to completely remove the copper foil and the surface treatment layer by etching (s) —Time required to remove the thickness of the copper foil portion by etching (s)
The surface-treated copper foil whose surface roughness Sz of the surface in which the said surface treatment layer was formed is 0.8-3.2 micrometers. It is a surface-treated copper foil in which a surface treatment layer is formed on the copper foil,
Stabilization of 18 g / L H ₂ O ₂ , 92 g / L H ₂ SO ₄ , 8 g / L Cu and hydrogen peroxide from the surface opposite to the surface on which the surface treatment layer is formed When spray etching is performed with a copper-dissolved etching solution having a liquid temperature of 30 ° C. composed of an agent,
For etching time of thickness 1μm of the copper foil, the ratio of the etching time in the thickness direction of the surface treatment layer, Ri Do 0.7 or less, etching time in the thickness direction of the surface treatment layer, the following formula The surface-treated copper foil as described in any one of Claims 1-3 calculated by A.
Formula A: Time required to completely remove the copper foil and the surface treatment layer by etching (s) —Time required to remove the thickness of the copper foil portion by etching (s) For etching time of thickness 1μm of the copper foil, the ratio of the etching time in the thickness direction of the surface treatment layer, Ri Do 0.4 or less, etching time in the thickness direction of the surface treatment layer, the following formula The surface-treated copper foil of Claim 4 or 5 calculated by A.
Formula A: Time required to completely remove the copper foil and the surface treatment layer by etching (s) —Time required to remove the thickness of the copper foil portion by etching (s) For etching time of thickness 1μm of the copper foil, the ratio of the etching time in the thickness direction of the surface treatment layer, Ri Do 0.2 or less, etching time in the thickness direction of the surface treatment layer, the following formula The surface-treated copper foil according to claim 6 calculated by A.
Formula A: Time required to completely remove the copper foil and the surface treatment layer by etching (s) —Time required to remove the thickness of the copper foil portion by etching (s) A surface-treated copper foil in which a surface-treated layer having a roughened layer is formed on the copper foil,
Stabilization of 18 g / L H ₂ O ₂ , 92 g / L H ₂ SO ₄ , 8 g / L Cu and hydrogen peroxide from the surface opposite to the surface on which the surface treatment layer is formed When spray etching is performed with a copper-dissolved etching solution having a liquid temperature of 30 ° C. composed of an agent
When the etching rate in the thickness direction of the copper foil is 1, the etching rate in the thickness direction of the surface treatment layer is 0.5 or more, and
The surface treatment layer has a thickness of 0.13 μm to 0.65 μm,
The surface-treated copper foil whose surface roughness Sz of the surface in which the said surface treatment layer was formed is 0.8-3.2 micrometers.   The surface-treated copper foil according to any one of claims 1 to 8, wherein the copper foil is formed of an electrolytic copper foil or a rolled copper foil.   The surface treatment layer is at least one selected from the group consisting of a roughening treatment layer and a heat-resistant layer, a rust prevention layer, a chromate treatment layer and a silane coupling treatment layer provided on the surface of the roughening treatment layer. The surface-treated copper foil as described in any one of Claims 1-9 which has a layer.   The surface treatment layer has at least one of the rust prevention layer and the heat resistant layer, and at least one of the rust prevention layer and the heat resistant layer is one or more elements selected from nickel, cobalt, copper, and zinc. The surface-treated copper foil of Claim 10 containing.   The surface-treated copper foil according to claim 10 or 11, wherein the surface-treated layer has the heat-resistant layer on the roughened layer.   The said surface treatment layer has the said heat-resistant layer and the said rust preventive layer, and has the said rust preventive layer on the said roughening process layer or the said heat resistant layer as described in any one of Claims 10-12. Surface treated copper foil.   The surface-treated copper foil as described in any one of Claims 10-13 in which the said surface treatment layer has the said rust prevention layer and the said chromate treatment layer, and has the said chromate treatment layer on the said rust prevention layer. .   The surface treatment layer has the chromate treatment layer and the silane coupling treatment layer, and has the silane coupling treatment layer on the chromate treatment layer. Surface treated copper foil.   The surface-treated copper foil as described in any one of Claims 1-15 provided with a resin layer on the said surface-treated layer.   The surface-treated copper foil according to claim 16, wherein the resin layer includes a dielectric.   A carrier-attached copper foil in which an intermediate layer and an ultrathin copper layer are laminated in this order on one or both sides of a carrier, wherein the ultrathin copper layer is any one of claims 1 to 17. A copper foil with a carrier, which is the surface-treated copper foil according to claim 1.   The copper foil with a carrier according to claim 18, comprising the intermediate layer and the ultrathin copper layer in this order on one surface of the carrier, and a roughening treatment layer on the other surface of the carrier.   The manufacturing method of the printed wiring board using the surface-treated copper foil as described in any one of Claims 1-17.   The manufacturing method of the printed wiring board using the copper foil with a carrier of Claim 18 or 19.   The manufacturing method of the printed circuit board using the surface-treated copper foil as described in any one of Claims 1-17.   The manufacturing method of the printed circuit board using the copper foil with a carrier of Claim 18 or 19.   The manufacturing method of the copper clad laminated board using the surface-treated copper foil as described in any one of Claims 1-17.   The manufacturing method of the copper clad laminated board using the copper foil with a carrier of Claim 18 or 19. A step of preparing the surface-treated copper foil and the insulating substrate according to any one of claims 1 to 17,
The surface-treated copper foil is laminated on an insulating substrate from the surface-treated layer side to form a copper-clad laminate,
Thereafter, a printed wiring board manufacturing method including a step of forming a circuit by any one of a subtractive method, a partly additive method, and a modified semi-additive method. A step of preparing the carrier-attached copper foil and the insulating substrate according to claim 18 or 19,
Laminating the copper foil with carrier on the insulating substrate from the ultrathin copper layer side,
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 the method of either the partly additive method or the modified semiadditive method. Forming a circuit on the ultra-thin copper layer side surface of the carrier-attached copper foil according to claim 18 or 19,
Forming a resin layer on the ultrathin copper layer side surface of the carrier-attached copper foil so that the circuit is buried;
Forming a circuit on the resin layer;
Forming the circuit on the resin layer, and then peeling the carrier; and
After the carrier is peeled off, the printed wiring board includes a step of exposing the circuit embedded in the resin layer formed on the surface of the ultrathin copper layer by removing the ultrathin copper layer Method.