TWI581684B - The preparation method of the copper foil, the method of making the copper clad sheet, the manufacturing method of the printed wiring board, the manufacturing method of the electronic machine, and the like - Google Patents

Description

Method for preparing carrier copper foil, method for manufacturing copper-clad laminate, method for manufacturing printed wiring board, method for manufacturing electronic device, and the like

The present invention relates to a method for producing a copper foil with a carrier, a method for producing a copper clad laminate, a method for producing a printed wiring board, a method for producing an electronic device, a copper foil with a carrier, a laminate, a printed wiring board, and an electronic device.

The printed wiring board is usually produced by forming a conductor pattern on the copper foil surface by etching after the insulating substrate and the copper foil are bonded to each other to form a copper clad laminate. In recent years, with the increase in the demand for miniaturization and high performance of electronic devices, high-density mounting of components and high-frequency signals have been promoted, and wiring patterns have been required to be fine-grained (narrow pitch). ) or high frequency response.

Corresponding to narrow pitching, copper foils having a thickness of 9 μm or less and even a thickness of 5 μm or less have recently been required. However, such extremely thin copper foils have low mechanical strength and are easily broken or wrinkled during the manufacture of printed wiring boards. Therefore, a copper foil with a carrier having a thickness of a metal foil as a carrier and electrodepositing an extremely thin copper layer thereon via a peeling layer was developed. After bonding the surface of the ultra-thin copper layer to the insulating substrate and thermocompression bonding, the carrier is peeled off by the peeling layer. Sulfuric acid-peroxidation after forming a circuit pattern on the exposed ultra-thin copper layer by a resist The hydrogen-based etching solution is used to etch away the ultra-thin copper layer, and a fine circuit is formed by the method (MSAP: Modified-Semi-Additive-Process).

Here, the surface of the ultra-thin copper layer which is the copper foil with a carrier which is the adhesive surface of the resin is required to have sufficient peeling strength of the ultra-thin copper layer and the resin substrate, and the peel strength is high-temperature heating, wet processing, and soldering. After chemical treatment, etc., it is also sufficient. The method for increasing the peel strength between the ultra-thin copper layer and the resin substrate is generally represented by the following method: a very thin copper layer having a large number of roughened particles attached to the surface (concavity, roughness, and roughness) on.

However, even in a printed wiring board, if a very thin copper layer having a large profile (concavity, roughness, and roughness) is used for a semiconductor package substrate having a particularly fine circuit pattern, it is not necessary to be left in the circuit etching. The copper particles cause problems such as poor insulation between circuit patterns.

Therefore, in WO2004/005588 (Patent Document 1), a copper foil with a carrier which is not subjected to a roughening treatment on the surface of the ultra-thin copper layer is attempted as a carrier-attached copper foil for a fine circuit including a semiconductor package substrate. Due to the influence of the low profile (concavity, roughness, roughness), the adhesion between the ultra-thin copper layer which is not subjected to the roughening treatment and the resin (peeling strength) is compared with that of a general copper foil for a printed wiring board. Reduce the tendency. Therefore, it is required to further improve the copper foil with a carrier.

In JP-A-2007-007937 (Patent Document 2) and JP-A-2010-006071 (Patent Document 3), the present invention discloses a polyimide-based resin substrate with an ultra-thin copper foil attached thereto. The surface of the contact (subsequent) is provided with a Ni layer or/and a Ni alloy layer, a chromate layer, a Cr layer or/and a Cr alloy layer, a Ni layer and a chromate layer, and a Ni layer and a Cr layer. By providing the surface treatment layer, the polyimide substrate and the carrier are provided The adhesion strength of the thin copper foil can be obtained without the roughening treatment or the degree of roughening treatment (fineness) to obtain the desired bonding strength. Further, surface treatment or rust-preventing treatment using a decane coupling agent is also described.

[Patent Document 1] WO2004/005588

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2007-007937

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2010-006071

In the development of the carrier-attached copper foil, the peel strength of the ultra-thin copper layer and the resin substrate has been considered as the focus until now. Therefore, the circuit formation of the ultra-thin copper layer has not been fully explored, and there is still room for improvement.

The circuit for forming an ultra-thin copper layer is usually performed by laminating an ultra-thin copper layer on a resin substrate, and then removing the carrier under a photoresist having a specific pattern on the ultra-thin copper layer. An etching process is performed using a specific etching solution to remove a copper layer that is not covered by the photoresist. Thereafter, a circuit having a desired conductor pattern is formed by removing the photoresist.

Here, when the etching treatment is performed by using a specific etching liquid, if the wettability of the portion near the interface between the ultra-thin copper layer and the resin substrate is poor, the wettability range of the etching liquid is insufficient. In this case, a portion where the etching is uneven in the vicinity of the interface with the resin substrate causes the circuit linearity to become poor. The present invention provides a method for producing a copper foil with a carrier which is excellent in circuit formation properties for an extremely thin copper layer. Further, a copper foil with a carrier having good wettability of the etching liquid is provided.

The invention completed on the basis of the above findings is a kind of attachment A method for producing a bulk copper foil comprising the step of heat-treating a carrier-attached copper foil having a carrier, an intermediate layer, an ultra-thin copper layer, and a surface treatment layer containing a decane coupling treatment layer in this order for 1 hour to 8 hours. The heating temperature is 100 ° C ~ 220 ° C heat treatment, or 1 hour ~ 6 hours heating temperature is 100 ° C ~ 220 ° C heat treatment, or 2 hours ~ 4 hours heating temperature 160 ° C ~ 220 ° C heat treatment .

In another aspect, the present invention provides a method for producing a copper foil with a carrier, comprising the following heat treatment step: a carrier copper foil with a carrier, an intermediate layer, an ultra-thin copper layer, and a surface treatment layer; The heating rate until reaching the heating temperature is more than 50 ° C / hour, and the heating temperature is from 100 ° C to 220 ° C for 1 hour to 8 hours, or the heating temperature is from 100 ° C to 220 ° C for 1 hour to 6 hours. The heat treatment, or the heating temperature of 2 hours to 4 hours, is 160 ° C ~ 220 ° C heat treatment.

In the method for producing a copper foil with a carrier according to the present invention, in the embodiment, the temperature increase rate in the heat treatment is 200 ° C /hr or less.

In another embodiment of the method for producing a copper foil with a carrier according to the present invention, the tensile strength of the carrier measured at room temperature after the heat treatment step is 300 MPa or more.

In still another embodiment of the method for producing a copper foil with a carrier according to the present invention, in the heat treatment step, heat treatment is performed in an inert gas atmosphere.

In still another embodiment of the method for producing a copper foil with a carrier according to the present invention, in the heat treatment step, heat treatment is performed in a state in which the copper foil with a carrier is wound into a hollow tube made of metal.

In still another embodiment of the method for producing a copper foil with a carrier according to the present invention, in the heat treatment step, the tension of the copper foil with a carrier is rolled into a hollow tube made of metal. It is heat-treated at 5 to 100 kgf/m or 20 to 100 kgf/m.

In still another embodiment of the method for producing a copper foil with a carrier according to the present invention, in the heat treatment step, the copper foil with a carrier is wound into a hollow tube made of metal, and 0.01 to 600 is used. The hollow tube was rotated at a rotation/hour speed while being subjected to heat treatment.

In still another embodiment of the present invention, the copper foil with a carrier before the heat treatment further includes an intermediate layer and an ultra-thin copper layer on the surface of the carrier side.

In still another embodiment of the present invention, the copper foil with a carrier before the heat treatment further has a surface treatment layer on the surface of the carrier side.

In still another embodiment of the present invention, the surface treated layer comprises a roughened layer.

In still another embodiment of the present invention, the surface of the surface treated layer is a roughened layer further comprising a heat-resistant layer, a rust-proof layer, a chromate-treated layer, and a decane coupling treatment. One or more layers of the group formed by the layers.

In still another embodiment of the present invention, the copper foil with a carrier before the heat treatment has a surface selected from the roughened layer, the heat-resistant layer, the rust-proof layer, and the surface of the ultra-thin copper layer. A layer of one or more layers of the group consisting of the chromate treatment layer and the decane coupling treatment layer is used as the surface treatment layer.

In still another embodiment of the present invention, the copper foil with a carrier before the heat treatment is provided with a resin layer on the surface treatment layer.

In still another aspect of the invention, there is provided a method for producing a copper-clad laminate comprising the copper foil with a carrier obtained by the method of the invention.

In still another aspect of the invention, there is provided a method of producing a printed wiring board using the copper foil with a carrier obtained by the method of the invention.

In still another aspect, the invention provides a method for manufacturing a printed wiring board, comprising the steps of: preparing a carrier copper foil and an insulating substrate prepared by the method of the invention; and insulating the above-mentioned carrier copper foil After laminating the carrier-attached copper foil and the insulating substrate, the copper-clad laminate is formed by peeling off the carrier of the carrier-attached copper foil, and then, by a semi-additive method, a subtractive method, A method of forming a circuit by either a partial addition method or a modified semi-additive method (Modified Semi Additive).

In still another aspect, the present invention provides a method of manufacturing a printed wiring board comprising the steps of: said ultra-thin copper layer side surface of said carrier copper foil obtained by the method of the present invention or said carrier side Forming a circuit; forming a resin layer on the surface of the ultra-thin copper layer side or the side of the carrier side of the copper foil with a carrier; and forming a circuit on the resin layer; after forming a circuit on the resin layer, Stripping the carrier or the ultra-thin copper layer; and after removing the carrier, removing the ultra-thin copper layer or the carrier, thereby embedding the surface of the ultra-thin copper layer or the side surface of the carrier on the resin layer The circuit is exposed.

In still another aspect of the invention, there is provided a method of manufacturing an electronic machine using the printed wiring board produced by the method of the invention.

In still another aspect of the invention, there is provided a carrier copper foil which is produced by the method of the invention.

In still another aspect, the invention is a copper foil with a carrier, which is provided with a carrier, an intermediate layer, an ultra-thin copper layer, a surface treatment layer containing a decane coupling treatment layer, and a very thin copper foil side on a horizontal surface. The surface treatment layer was placed on the above method to place the carrier copper foil (except for those having a resin layer), and 30 μL of sulfuric acid was added to a portion by using a pipette to have 24% by weight of sulfuric acid and 15% by weight of hydrogen peroxide (the remaining portion was water). After the etching liquid was left to stand for 30 seconds, the difference between the maximum diameter and the minimum diameter of the trace of the etching liquid was 10 mm or less.

In still another aspect, the invention is a copper foil with a carrier, which is provided with a carrier, an intermediate layer, an ultra-thin copper layer, a surface treatment layer containing a decane coupling treatment layer, and a very thin copper foil side on a horizontal surface. The surface treatment layer was placed on the above method to place the carrier copper foil (except for those having a resin layer), and 30 μL of sulfuric acid was added to a portion by using a pipette to have 24% by weight of sulfuric acid and 15% by weight of hydrogen peroxide (the remaining portion was water). The etching liquid of the composition is placed for 30 seconds, and after the etching liquid is wiped off, the maximum diameter of the trace of the etching liquid is 25 mm or more.

In still another aspect, the invention is a copper foil with a carrier, which is provided with a carrier, an intermediate layer, an ultra-thin copper layer and a surface treatment layer in sequence, and a surface treatment layer on the surface of the ultra-thin copper foil on the horizontal surface is on the surface. To place the carrier-attached copper foil (except for the resin layer), and use a pipette to add 30 μL of an etching solution having a composition of 24% by weight of sulfuric acid to 15% by weight of hydrogen peroxide (the remainder being water). After the etching liquid was wiped off after being left for 30 seconds, the difference between the maximum diameter and the minimum diameter of the trace of the etching liquid was 10 mm or less.

In still another aspect, the invention is a copper foil with a carrier, which is provided with a carrier, an intermediate layer, an ultra-thin copper layer and a surface treatment layer in sequence, and is on the surface of the extremely thin copper foil on the horizontal surface. In the above manner, the carrier-attached copper foil (except for the resin layer) is placed, and 30 μL of sulfuric acid having 24% by weight of hydrogen peroxide (15% by weight of hydrogen peroxide) is added to one portion using a pipette. After the etching liquid was left to stand for 30 seconds, the etching liquid was wiped off, and the maximum diameter of the trace of the etching liquid was 25 mm or more.

In still another aspect of the copper foil with a carrier of the present invention, the difference between the maximum diameter and the minimum diameter of the trace of the etching liquid is 5 mm or less.

In still another aspect of the copper foil with a carrier of the present invention, the trace of the etching liquid has a maximum diameter of 35 mm or more.

In still another aspect, the present invention is a laminate which is produced by using the copper foil with a carrier of the present invention.

In still another aspect, the present invention provides a laminate comprising the copper foil with a carrier of the present invention and a resin, and one or both of the end faces of the copper foil with the carrier are covered with the resin.

In still another aspect, the present invention provides a laminate in which a copper foil with a carrier of the present invention is laminated from the carrier side or the surface treatment layer to another carrier of the copper foil with carrier of the present invention. The side or the surface treatment layer side is formed.

In one embodiment of the present invention, the carrier side surface or the surface treatment layer side surface of the one of the carrier-attached copper foils and the carrier side surface of the other carrier copper foil or the surface of the surface treatment layer are It is necessary to be directly laminated by an adhesive.

In another embodiment of the present invention, the carrier or the surface treatment layer of the one of the copper foils with a carrier is bonded to the carrier or the surface treatment layer of the other copper foil with a carrier.

In still another embodiment of the laminated body of the present invention, part or all of the end faces of the laminated body are covered with a resin.

In still another aspect of the invention, there is provided a printed wiring board produced by using the copper foil with a carrier of the invention.

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

According to still another aspect of the present invention, a method of manufacturing a printed wiring board includes the steps of: preparing a copper foil with an insulating substrate of the present invention and an insulating substrate; laminating the copper foil with the carrier and the insulating substrate; After the carrier-attached copper foil is laminated with the insulating substrate, the copper-clad laminate is formed by the step of peeling off the carrier with the carrier copper foil, and then, by semi-additive method, subtractive method, partial addition method or modification Any of the methods of the semi-additive method forms a circuit.

In still another aspect, the present invention provides a method of manufacturing a printed wiring board comprising the steps of: forming a circuit on the side surface of the ultra-thin copper layer of the copper foil with carrier of the present invention or the side surface of the carrier; In the above circuit, a resin layer is formed on the surface of the ultra-thin copper layer side of the copper foil with a carrier or the surface of the carrier; after the resin layer is formed, the carrier or the ultra-thin copper layer is peeled off; and the carrier is peeled off or After the ultra-thin copper layer is removed, the ultra-thin copper layer or the carrier is removed. Thereby, the circuit buried in the resin layer formed on the side surface of the ultra-thin copper layer or the side surface of the carrier is exposed.

In still another aspect, the present invention provides a method of manufacturing a printed wiring board comprising the steps of: forming a circuit on the side surface of the ultra-thin copper layer of the copper foil with carrier of the present invention or the side surface of the carrier; In the above circuit, a resin layer is formed on the surface of the ultra-thin copper layer side surface or the carrier side surface of the copper foil with a carrier; a circuit is formed on the resin layer; after the circuit is formed on the resin layer, the carrier or the pole is peeled off a thin copper layer; and after the carrier or the ultra-thin copper layer is peeled off, the ultra-thin copper layer or the carrier is removed, whereby the surface of the ultra-thin copper layer or the side surface of the carrier is buried in the resin layer The circuit is exposed.

According to still another aspect of the invention, there is provided a method of producing a printed wiring board comprising the steps of: laminating the surface of the ultra-thin copper layer or the surface of the carrier side of the copper foil with a carrier of the present invention and a resin substrate a resin layer and a circuit layer are provided at least once on the surface of the ultra-thin copper layer side opposite to the side on which the resin substrate is laminated with the copper foil on the carrier or the carrier side surface; and the resin layer is formed and After the two layers of the circuit, the carrier or the ultra-thin copper layer is peeled off from the copper foil with a carrier.

In still another aspect, the present invention is a method of manufacturing a printed wiring board, The method includes the steps of: laminating the carrier side surface of the copper foil with a carrier of the present invention and a resin substrate; and providing at least 1 on the side surface of the ultra-thin copper layer on the side opposite to the side of the copper foil with the carrier copper foil laminated on the resin substrate. The two layers of the sub-resin layer and the circuit; and after forming the two layers of the resin layer and the circuit, the ultra-thin copper layer is peeled off from the copper foil with a carrier.

According to the present invention, it is possible to provide a method for producing a copper foil with a carrier which is excellent in circuit formation property to an extremely thin copper layer. Further, a copper foil with a carrier having good wettability of the etching liquid is provided.

Fig. 1 is a schematic view showing a cross section of a wiring board in a step from the exposure-development to the circuit plating-removal of the photoresist in the specific example of the method for producing a printed wiring board with a copper foil with a carrier of the present invention; .

Fig. 2 is a wiring board in the step of the self-laminated resin and the second layer-attached carrier copper foil to the laser opening of the specific example of the method for producing a printed wiring board with a carrier copper foil according to the present invention; Schematic diagram of the section.

Fig. 3 is a schematic view showing a cross section of the wiring board in the step from the formation of the via filler to the peeling of the first carrier, in a specific example of the method for producing a printed wiring board with a copper foil with a carrier of the present invention.

Fig. 4 is a schematic view showing a cross section of a wiring board in a step from rapid etching to formation of a bump-copper column in a specific example of a method of manufacturing a printed wiring board with a copper foil with a carrier of the present invention; Figure.

Fig. 5 is a plan view of a system circuit showing a method of measuring a difference (μm) between the maximum value and the minimum value of the width of the lower end of the circuit obtained from the observation of the circuit in the experimental example.

<Method for Producing Carrier Copper Foil>

As a form of use of a carrier-attached copper foil having a carrier, an intermediate layer, and an ultra-thin copper layer, first, the surface of the ultra-thin copper layer is bonded to an insulating substrate, and after thermocompression bonding, the carrier is peeled off. Next, a photoresist of a specific pattern is placed on the extremely thin copper layer that has been bonded to the insulating substrate. Next, an etching process is performed using a specific etching liquid, and an extremely thin copper layer which is not covered by the photoresist is removed to form a target conductor pattern. For example, a printed wiring board having a specific circuit or the like is formed. Here, when the etching treatment is performed by a specific etching liquid, if the wettability of the portion near the interface between the ultra-thin copper layer and the resin substrate is poor, the wettability range of the etching liquid becomes insufficient. In this case, a portion where etching is uneven in the vicinity of the interface with the resin substrate causes a circuit linearity to be deteriorated.

In this regard, the method for producing a copper foil with a carrier of the present invention is in the form of a carrier-attached copper foil which is provided with a carrier, an intermediate layer, an extremely thin copper layer, and a surface treatment layer containing a decane coupling treatment layer. The carrier copper foil is subjected to heat treatment at a heating temperature of 100 ° C to 220 ° C for 1 hour to 8 hours. Further, the above 100 ° C to 220 ° C indicates the ambient temperature in the heating device. Thus, by performing a heat treatment at a heating temperature of 100 ° C to 220 ° C for 1 hour to 8 hours, the unreacted hydrogen group in the decane coupling treatment layer undergoes a dehydration condensation reaction, so that the treatment layer becomes more Strong and improved adhesion to the resin substrate, it also makes the ultra-thin copper layer In the vicinity of the interface between the surface treatment layers, and in the case of having a plurality of surface treatment layers, the discontinuous portions of the atomic composition in the vicinity of the interface between the plurality of layers are formed into a continuous atomic composition distribution by mutual diffusion, and thus an extremely thin copper layer The wettability with respect to the etching liquid in the vicinity of the interface with the resin substrate is good, and the etching is uniform in the vicinity of the interface with the resin substrate, and the circuit linearity of the extremely thin copper layer is improved. Furthermore, typically, an extremely thin copper layer consists essentially of copper. Further, the surface treatment layer may have a roughening treatment layer and/or a heat-resistant layer and/or a rust-preventive layer and/or a chromate treatment layer and a decane coupling treatment layer in this order, or may be provided in any order. The roughened layer is preferably mainly composed of an alloy such as a copper alloy or a nickel alloy or a cobalt alloy. The roughening layer can also be mainly composed of copper. The chromate treatment layer is preferably composed mainly of a metal oxide. The decane coupling treatment layer is preferably composed of an organic ruthenium compound.

Usually, when the copper foil with a carrier is bonded to a resin substrate, the temperature is about 160 to 120 minutes, and the temperature is 160 to 220 ° C. Therefore, the above-mentioned mutual diffusion is performed to some extent. However, depending on the conditions, there will be situations where there is insufficient mutual diffusion. Therefore, the effect of improving the etching property and the uniformity can be further improved by performing the above heat treatment before the resin substrate.

Further, in the case where Si is detected on the surface of the ultra-thin copper layer of the carrier copper foil, the presence of the decane coupling treatment layer can be judged by surface analysis such as XPS.

In the heat treatment, when the temperature is less than 100 ° C or the heating time is less than 1 hour, the interdiffusion in the vicinity of the interface between the respective treatment layers becomes insufficient. Further, in the heat treatment, when the temperature exceeds 220 ° C or the heating time exceeds 8 hours, there is a possibility that the peel strength of the carrier and the ultra-thin copper foil is changed, or the grain growth of the extremely thin copper layer occurs. This causes other problems such as a decrease in mechanical strength. In the heat treatment step, it is preferably carried out for 1 hour. ~6 hours heating temperature is 100 ° C ~ 220 ° C heat treatment, preferably for 1 hour ~ 6 hours heating temperature is 120 ° C ~ 220 ° C heating treatment, more preferably for 2 hours ~ 4 hours heating temperature It is heat treated at 160 ° C ~ 220 ° C.

In another aspect of the method for producing a copper foil with a carrier of the present invention, the following heat treatment step is included: a copper foil with a carrier, an intermediate layer, an ultra-thin copper layer, and a surface treatment layer, which are sequentially provided, will reach the heating The temperature increase rate until the temperature is more than 50 ° C / hour, and the heating temperature of 1 hour to 8 hours is 100 ° C to 220 ° C. Here, the temperature increase rate is a temperature increase rate from the start of heating to the first time the heating temperature is reached. When the temperature increase rate is 50 ° C /hr or less, the productivity of the heat treatment is lowered, and since the heat treatment time is long, the surface of the copper foil with the carrier may be oxidized. Further, the temperature increase rate is preferably 200 ° C / hour or less. In the case where the temperature increase rate exceeds 200 ° C / hour, there is a case where the degree of elongation differs due to the difference in the coefficient of thermal expansion between the core and the copper foil with the carrier, and wrinkles are generated. Moreover, in the case of exceeding 200 ° C / hour, the wettability of the copper foil with a carrier to the etching liquid deteriorates. The reason for this is not clear, but it may be because the copper foil with the carrier is violently expanded, causing friction or offset between the surface treatment layer and the carrier which are wound when wound into a coil shape, or stress on the surface treatment layer. Concentration, the friction/offset/stress concentration and the like are related to the displacement of a portion of the surface treatment layer which affects the diffusion state of the elements of the surface treatment layer.

The temperature increase rate up to the above heating temperature is more preferably from 70 ° C / hr to 200 ° C / hr, still more preferably from 100 ° C / hr to 200 ° C / hr, still more preferably from 150 ° C / hr to 200 ° C / hr.

In the method for producing a copper foil with a carrier of the present invention, in the heat treatment step, it is preferred to contain oxygen and water which may cause oxidation or deterioration of the surface of the carrier and the surface of the ultra-thin copper layer. The heat treatment is carried out in the atmosphere of a gas such as steam. For example, it is preferably subjected to heat treatment in an inert gas atmosphere of cerium, neon, argon, nitrogen or the like and a mixed gas thereof.

In the method for producing a copper foil with a carrier of the present invention, in the heat treatment step, it is preferred to carry out heat treatment in a state in which the copper foil with a carrier is wound into a hollow tube made of metal. By heat-treating the copper foil with a carrier in a state in which it is wound in a metal hollow tube, it is possible to ventilate the metal tube which is excellent in heat conduction, or to heat the copper foil with a carrier from the inside. Effective heat treatment is possible. The hollow tube made of metal is not particularly limited. For example, it is preferably made of carbon steel or stainless steel. The outer diameter is 7 cm to 20 cm and the thickness is 0.5 cm to 3.0 cm.

In the method for producing a copper foil with a carrier according to the present invention, in the heat treatment step, it is preferred to carry out a heat treatment in which the tension when the copper foil with a carrier is wound into a hollow metal tube is set to 5 ~100kgf/m. This tension is the tension per unit width (width 1 m) of the carrier copper foil. By setting the tension to 5 kgf/m or more, it is possible to suppress the entrapment of oxygen and thereby prevent oxidation of the copper foil with a carrier. Moreover, by setting the tension to 100 kgf/m or less, it is possible to prevent wrinkles which are generated during winding.

The tension is more preferably 10 kgf/m or more, more preferably 20 kgf/m or more, still more preferably 20 to 100 kgf/m, still more preferably 20 to 50 kgf/m, still more preferably 20 to 30 kgf/m.

In the method for producing a copper foil with a carrier of the present invention, in the heat treatment step, it is preferable to rotate the carrier copper foil in a state of 0.01 to 600 while being wound into a hollow tube made of metal. Heat treatment was performed while rotating the hollow tube at an hourly speed. By rotating the hollow tube at a relatively low speed of 0.01 rotation/hour or more and 600 rotation/hour or less, heat treatment is performed to remove the wound between the wound copper foil and the copper foil. oxygen, Thereby, oxidation of the copper foil with a carrier in the heat treatment is prevented. The rotation speed of the hollow tube is preferably 0.01 to 180 rotations/hour, more preferably 0.01 to 120 rotations/hour, more preferably 0.01 to 70 rotations/hour, and even more preferably 1 to 70 rotations/hour.

In the method for producing a copper foil with a carrier according to the present invention, it is preferred that the tensile strength of the carrier measured at room temperature after the heat treatment step is 300 MPa or more. When the tensile strength of the carrier measured at room temperature after the heat treatment step as described above is 300 MPa or more, the rigidity of the ultra-thin copper layer to function as a carrier can be sufficiently maintained.

The tensile strength of the carrier is more preferably 350 MPa or more, still more preferably 380 MPa or more, still more typically 350 to 500 MPa, and still more typically 380 to 450 MPa.

<With carrier copper foil>

Hereinafter, unless otherwise stated, the embodiment of the copper foil with a carrier is described above for the heat treatment of the present invention, but the embodiment is the same as the heat treatment (the method of manufacturing the copper foil with a carrier of the present invention) The same applies to the carrier copper foil).

The copper foil with carrier of the present invention has a carrier, an intermediate layer, an extremely thin copper layer, and a surface treatment layer in this order. The method of using the carrier copper foil itself is well known. For example, the surface of the ultra-thin copper layer can be bonded to the paper substrate phenol resin, paper substrate epoxy resin, synthetic fiber cloth substrate epoxy resin, glass cloth - Paper composite substrate epoxy resin, glass cloth-glass non-woven composite substrate epoxy resin and glass cloth substrate epoxy resin, polyester film, polyimide film, liquid crystal polymer film, fluororesin film and other insulating substrates After the thermocompression bonding, the carrier is peeled off, and the ultra-thin copper layer adhered to the insulating substrate is etched into a target conductor pattern to finally produce a printed wiring board.

<carrier>

The carrier which can be used in the present invention is typically a metal foil or a resin film such as copper foil or copper. The alloy foil, nickel foil, nickel alloy foil, iron foil, iron alloy foil, stainless steel foil, aluminum foil, aluminum alloy foil, insulating resin film, polyimide film, and LCP film are provided.

The carrier which can be used in the present invention is typically provided in the form of a rolled copper foil or an electrolytic copper foil. Usually, the electrolytic copper foil is produced by electrically analyzing copper from a copper sulfate plating bath onto a drum of titanium or stainless steel, and the rolled copper foil is produced by repeatedly performing plastic working and heat treatment by a calender roll. As the material of the copper foil, in addition to high-purity copper such as refined copper (JIS H3100 alloy No. C1100) or oxygen-free copper (JIS H3100 alloy number C1020 or JIS H3510 alloy number C1011), for example, Sn-doped copper or Ag-doped copper may be used. A copper alloy such as Cr, Zr or Mg or a copper alloy such as a Cason copper alloy such as Ni or Si is added.

Further, the electrolytic copper foil can be produced by the following electrolyte composition and production conditions.

In addition, the remainder of the treatment liquid used for the production of the copper foil, the surface treatment of the copper foil, the plating of the copper foil, and the like described in the present specification is water unless otherwise specified.

<electrolyte composition>

Copper: 90~110g/L

Sulfuric acid: 90~110g/L

Chlorine: 50~100ppm

Leveling agent 1 (bis(3-sulfopropyl) disulfide): 10~30ppm

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

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

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

<Manufacturing conditions>

Current density: 70~100A/dm ²

Electrolyte temperature: 50~60°C

Electrolyte line speed: 3~5m/sec

Electrolysis time: 0.5~10 minutes

In addition, when the term "copper foil" is used alone in this specification, it also includes a copper alloy foil.

The thickness of the carrier which can be used in the present invention is not particularly limited, and may be appropriately adjusted to a thickness suitable for the function as a carrier, and may be, for example, 5 μm or more. However, if it is too thick, the production cost is increased, so it is usually preferably 35 μm or less. Therefore, the thickness of the carrier is typically from 8 to 70 μm, more typically from 12 to 70 μm, and more typically from 18 to 35 μm. Further, from the viewpoint of reducing the cost of the raw material, the thickness of the carrier is preferably small. Therefore, the thickness of the carrier is typically 5 μm or more and 35 μm or less, preferably 5 μm or more and 18 μm or less, preferably 5 μm or more and 12 μm or less, preferably 5 μm or more and 11 μm or less, preferably 5 μm or more and 10 μm or less. . In addition, in the thickness of the carrier In the small case, wrinkles are likely to occur when the carrier is passed through the foil. In order to prevent wrinkles from occurring, it is effective to smooth the conveyance roller of the carrier-attached copper foil manufacturing apparatus, for example, or to shorten the distance between the conveyance roller and the next conveyance roller. Further, in the case of using a copper foil with a carrier as an encapsuladed process for manufacturing a printed wiring board, the rigidity of the carrier must be high. Therefore, in the case of the embedding method, the thickness of the carrier is preferably 18 μm or more and 300 μm or less, preferably 25 μm or more and 150 μm or less, preferably 35 μm or more and 100 μm or less, and more preferably 35 μm or more. 70 μm or less.

<intermediate layer>

An intermediate layer is provided on the carrier. Other layers may also be provided between the carrier and the intermediate layer. The intermediate layer used in the present invention is not particularly limited as long as it is a structure in which the ultra-thin copper layer is not easily peeled off from the carrier before the step of laminating the carrier copper foil to the insulating substrate, and on the other hand, after the step of laminating the insulating substrate The very thin copper layer can be peeled off from the carrier. For example, the intermediate layer of the copper foil with a carrier of the present invention may further contain a compound selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, such alloys, and the like, One or more of the group consisting of such oxides and organic substances. Also, the intermediate layer may be a plurality of layers. Further, the intermediate layer may be disposed on both sides of the carrier.

Further, for example, the intermediate layer may be formed by forming an element selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn from the carrier side. a single metal layer constituting or 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, and Zn, Forming thereon a single metal layer composed of one element selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, or selected from Cr, Ni One or more elements of a group consisting of Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn An alloy layer composed of a hydrate, or a hydrate or oxidation of one or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn. a layer of matter or organic matter.

Further, an intermediate layer containing Ni may be provided on one side or both sides of the carrier. The intermediate layer is preferably formed by sequentially laminating a layer of nickel or a nickel-containing alloy on the carrier, and a layer containing at least one of chromium, a chromium alloy, and an oxide of chromium. Further, it is preferable that zinc is contained in any one of layers of nickel or a nickel-containing alloy and/or one or more layers containing chromium, a chromium alloy, and an oxide of chromium. Here, the alloy containing nickel means one or more elements selected from the group consisting of nickel and cobalt, iron, chromium, molybdenum, zinc, bismuth, copper, aluminum, phosphorus, tungsten, tin, arsenic, and titanium. The alloy that is formed. The nickel-containing alloy may be an alloy composed of three or more elements. Further, the term "chromium alloy" means an alloy composed of chromium and one or more elements selected from the group consisting of cobalt, iron, nickel, molybdenum, zinc, bismuth, copper, aluminum, phosphorus, tungsten, tin, arsenic, and titanium. . The chromium alloy may also be an alloy composed of three or more elements. Further, the layer containing at least one of chromium, a chromium alloy, and an oxide of chromium may be a chromate-treated layer. Here, the chromate treatment layer means a layer treated with a liquid containing chromic anhydride, chromic acid, dichromic acid, chromate or dichromate. The chromate treatment layer may also contain elements such as cobalt, iron, nickel, molybdenum, zinc, bismuth, copper, aluminum, phosphorus, tungsten, tin, arsenic and titanium (may also be metals, alloys, oxides, nitrides, sulfides). Any form of matter). Specific examples of the chromate treatment layer include a pure chromate treatment layer or a zinc chromate treatment layer. In the present invention, the chromate treatment layer treated with an aqueous solution of chromic anhydride or potassium dichromate is referred to as a pure chromate treatment layer. Further, in the present invention, the chromate treatment layer treated with the treatment liquid containing chromic acid anhydride or potassium dichromate and zinc is referred to as a zinc chromate treatment layer.

Moreover, the intermediate layer is preferably laminated on the carrier in sequence with nickel, nickel-zinc alloy, nickel- a layer of any one of a phosphorus alloy and a nickel-cobalt alloy, and a layer of any one of a zinc chromate treatment layer, a pure chromate treatment layer, and a chrome plating layer, and the intermediate layer is further preferably a carrier. The nickel layer or the nickel-zinc alloy layer and the zinc chromate treatment layer are sequentially laminated, or a nickel-zinc alloy layer, a pure chromate treatment layer or a zinc chromate treatment layer are sequentially laminated. The adhesion between nickel and copper is higher than the adhesion between chromium and copper. Therefore, when the ultra-thin copper layer is peeled off, the interface between the ultra-thin copper layer and the chromate-treated layer is peeled off. Further, for the nickel of the intermediate layer, it is expected to prevent the barrier effect of the copper component from diffusing from the carrier to the extremely thin copper layer. Further, it is preferred that the intermediate layer is not chrome-plated to form a chromate treatment layer. Since chrome plating forms a dense chromium oxide layer on the surface, when an extremely thin copper foil is formed by plating, the electric resistance rises and pinholes are likely to occur. The surface on which the chromate-treated layer is formed is formed with a chromium oxide layer which is not denser than chromium plating. Therefore, it is difficult to form an electric resistance when forming an extremely thin copper foil by electroplating, and pinholes can be reduced. Here, by forming the zinc chromate treatment layer as the chromate treatment layer, the electric resistance when forming an extremely thin copper foil by electroplating is lower than that of the usual chromate treatment layer, and the occurrence of pinholes can be further suppressed.

In the case of using an electrolytic copper foil as a carrier, it is preferable to provide an intermediate layer on the shiny side from the viewpoint of reducing pinholes.

When the chromate treatment layer in the intermediate layer is thinly present at the interface of the ultra-thin copper layer, the ultra-thin copper layer is not peeled off from the carrier before the step of laminating the insulating substrate, and on the other hand, the insulating substrate can be obtained. It is preferred to carry out the step of laminating to remove the ultra-thin copper layer from the carrier. When the nickel layer or the nickel-containing alloy layer (for example, a nickel-zinc alloy layer) is not provided and the chromate-treated layer is present at the boundary between the carrier and the ultra-thin copper layer, the peeling property is hardly improved, and the chromic acid is not removed. When the salt layer is directly treated with a nickel layer or a nickel-containing alloy layer (for example, a nickel-zinc alloy layer) and an extremely thin copper layer, a nickel layer or a nickel-containing alloy layer (for example, a nickel-zinc alloy layer) is used. The amount of nickel in the peeling strength is too strong or too weak to obtain a suitable peel strength.

Moreover, if the chromate treatment layer is present at the boundary between the support and the nickel layer or the nickel-containing alloy layer (for example, a nickel-zinc alloy layer), the intermediate layer is also peeled off when the ultra-thin copper layer is peeled off, that is, on the carrier and Peeling occurs between the intermediate layers, which is not preferable. Such a situation occurs not only when a chromate treatment layer is provided at the interface with the carrier, but also when the chromate treatment layer is provided at the interface with the ultra-thin copper layer. The reason for this is that copper and nickel are easily dissolved in a solid state. Therefore, if these contacts are made, the adhesion force is increased by mutual diffusion, and the adhesion is less likely to occur. On the other hand, since chromium and copper are not easily dissolved, it is less likely to occur. Diffusion, so the interface between chromium and copper is weaker and easy to peel off. Further, when the amount of nickel in the intermediate layer is insufficient, only a trace amount of chromium is present between the carrier and the ultra-thin copper layer, so that the two are in close contact with each other and become difficult to peel off.

The nickel layer of the intermediate layer or the alloy layer containing nickel (for example, a nickel-zinc alloy layer) may be, for example, wet plating such as electroplating, electroless plating, and immersion plating, or dry plating such as sputtering, CVD, and PDV. Formed by plating. From the viewpoint of cost, electroplating is preferred. Further, in the case where the carrier is a resin film, the intermediate layer can be formed by dry plating such as CVD and PDV or wet plating such as electroless plating and immersion plating.

Further, the chromate treatment layer may be formed, for example, by electrolytic chromate or impregnated chromate. However, since the chromium concentration is increased and the peel strength of the ultra-thin copper layer from the carrier is improved, it is preferably electrolytic chromic acid. Salt formation.

The intermediate layer of the copper foil with a carrier of the present invention may be formed by sequentially laminating a nickel layer on the carrier, and an organic layer containing any one of a nitrogen-containing organic compound, a sulfur-containing organic compound, and a carboxylic acid. Further, the intermediate layer of the copper foil with a carrier of the present invention may be formed by sequentially laminating an organic layer containing any of a nitrogen-containing organic compound, a sulfur-containing organic compound, and a carboxylic acid, and a nickel layer on the carrier. Further, as the organic compound containing a nitrogen-containing organic compound and containing sulfur Examples of the organic substance of any one of the substance and the carboxylic acid include BTA (benzotriazole), MBT (mercaptobenzothiazole), and the like.

In addition, as the organic substance contained in the intermediate layer, one or two or more kinds selected from the group consisting of organic compounds containing nitrogen, organic compounds containing sulfur, and carboxylic acids are preferably used. Among the nitrogen-containing organic compounds, sulfur-containing organic compounds, and carboxylic acids, the nitrogen-containing organic compound includes a nitrogen-containing organic compound having a substituent. As the specific nitrogen-containing organic compound, it is preferred to use a triazole compound having a substituent, that is, 1,2,3-benzotriazole, carboxybenzotriazole, N', N'-bis(benzotriazole). Methyl)urea, 1H-1,2,4-triazole and 3-amino-1H-1,2,4-triazole and the like.

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

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

The organic substance preferably contains a thickness of 25 nm or more and 80 nm or less, and more preferably 30 nm or more and 70 nm or less. The intermediate layer may also contain a plurality of (one or more) of the above organic substances.

Further, the thickness of the organic substance can be measured as follows.

<intermediate layer organic matter thickness>

After the ultra-thin copper layer with the carrier copper foil was peeled off from the carrier, the intermediate layer side surface of the exposed ultra-thin copper layer and the intermediate layer side surface of the exposed carrier were subjected to XPS measurement to prepare a depth profile. Then, the depth from the intermediate layer side surface of the ultra-thin copper layer to the carbon concentration of 3 at% or less is set to A (nm), and the depth from the intermediate layer side surface of the carrier to the carbon concentration is initially set to 3 at% or less. In the case of B (nm), the total of A and B is set as the thickness (nm) of the organic substance in the intermediate layer.

The operating conditions of XPS are shown below.

‧Device: XPS measuring device (ULVAC-PHI, model 5600MC)

‧ ultimate vacuum: 3.8 × 10 ^-7 Pa

‧X-ray: Monochromatic AlK α or non-monochromatic MgK α, X-ray output 300W, detection area 800μm , the angle between the sample and the detector is 45°

‧Ion beam: ion type Ar ⁺ , accelerating voltage 3kV, scanning area 3mm × 3mm, sputtering rate 2.8nm / min (SiO ₂ conversion)

Regarding the method of using the organic substance contained in the intermediate layer, the method of forming the intermediate layer on the carrier foil will be described below. The intermediate layer is formed on the carrier, and the organic substance is dissolved in a solvent, and the carrier is immersed in the solvent, or the surface to be formed with the intermediate layer may be subjected to a shower method, a spray method, a dropping method, an electrodeposition method, or the like, without A specially defined method is employed. In this case, the concentration of the organic solvent in the solvent is preferably in the range of 0.01 g/L to 30 g/L and the liquid temperature of 20 to 60 ° C in all of the above organic matters. The concentration of the organic substance is not particularly limited, and the original concentration is higher or lower without any problem. Further, there is a tendency that the higher the concentration of the organic substance, the longer the contact time of the carrier with the solvent for dissolving the organic substance, and the greater the thickness of the organic substance of the intermediate layer. Further, when the thickness of the organic material in the intermediate layer is thick, the effect of suppressing the diffusion of Ni to the extremely thin copper layer side tends to be large.

<very thin copper layer>

An extremely thin copper layer is provided on the intermediate layer. Other layers may be provided between the intermediate layer and the ultra-thin copper layer. The ultra-thin copper layer can be formed by electroplating using an electrolytic bath of copper sulfate, copper pyrophosphate, copper sulfonate, copper cyanide or the like, and is preferable in terms of forming a copper layer at a high current density. It is a copper sulfate bath. The thickness of the ultra-thin copper layer is not particularly limited and is usually thinner than the carrier, for example, 12 μm. under. It is typically 0.5 to 12 μm, more typically 1 to 5 μm, and more typically 1.5 to 5 μm, and more typically 2 to 5 μm. Furthermore, an extremely thin copper layer may be provided on both sides of the carrier.

<Coarsening and other surface treatment>

The roughening treatment can be provided by performing a roughening treatment on the surface of the ultra-thin copper layer, for example, in order to improve the adhesion to the insulating substrate. The roughening treatment can be carried out, for example, by forming roughened particles using copper or a copper alloy. The roughening process can also be fine. The roughening treatment layer may be any element selected from the group consisting of copper, nickel, cobalt, phosphorus, tungsten, arsenic, molybdenum, chromium, and zinc, or a layer containing any one or more alloys. Further, after the roughened particles are formed of copper or a copper alloy, the secondary particles or the tertiary particles may be further subjected to a roughening treatment using a simple substance such as nickel, cobalt, copper or zinc or an alloy. Further, the heat-resistant layer and/or the rust-preventing layer may be formed of a single substance or an alloy of nickel, cobalt, copper or zinc, or may be further subjected to a treatment such as chromate treatment or decane coupling treatment on the surface. Alternatively, the heat-resistant layer or the rust-preventive layer may be formed of a simple substance such as nickel, cobalt, copper or zinc or an alloy without performing the roughening treatment, and further subjected to a treatment such as chromate treatment or decane coupling treatment on the surface. That is, one or more layers selected from the group consisting of a heat-resistant layer, a rust-preventive layer, a chromate-treated layer, and a decane coupling treatment layer may be formed on the surface of the roughened layer, or may be in a very thin copper layer. The surface is formed of one or more layers selected from the group consisting of a heat resistant layer, a rust preventive layer, a chromate treated layer, and a decane coupling treatment layer. Further, each of the heat-resistant layer, the rust-preventive layer, the chromate-treated layer, and the decane coupling treatment layer may be formed in multiple layers (for example, two or more layers, three or more layers, or the like). Here, the chromate treatment layer may be the chromate treatment layer or other chromate treatment layer.

Furthermore, the above-described decane coupling treatment layer, in the method for producing a copper foil with a carrier according to another aspect of the invention of the present invention, is a necessary constituent element as described above, and further, another aspect of the invention of the present invention The method for producing a carrier-attached copper foil includes the following heat treatment step: a heating foil with a carrier, an intermediate layer, an ultra-thin copper layer, and a surface-treated layer, which are sequentially provided with a carrier copper foil, which reaches a heating temperature It is set to exceed 50 ° C / hour, and then heat-treated at 100 ° C to 220 ° C for 1 hour to 8 hours.

As the heat-resistant layer and the rust-preventing layer, a known heat-resistant layer or rust-preventing layer can be used. For example, the heat-resistant layer and/or the rust-preventing layer may also contain a component selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, and platinum. The layer of one or more elements of the group of iron and antimony may also be selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, A metal layer or an alloy layer composed of one or more elements of a group of platinum group elements, iron, and antimony. Moreover, the heat-resistant layer and/or the rust-preventing layer may further comprise a component selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, and platinum. Oxides, nitrides, and tellurides of one or more elements of the group of iron and antimony. 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% by weight to 99% by weight of nickel and 50% by weight to 1% by weight of zinc, in addition to unavoidable impurities. The total adhesion of zinc and nickel in the nickel-zinc alloy layer is 5 to 1000 mg/m ² , preferably 10 to 500 mg/m ² , and more preferably 20 to 100 mg/m ² . Further, the ratio of the nickel adhesion amount to the zinc adhesion amount of the nickel-zinc alloy-containing layer or the nickel-zinc alloy layer (=the adhesion amount of nickel/the adhesion amount of zinc) is preferably 1.5 to 10. Further, the nickel-zinc alloy-containing layer or the nickel-zinc alloy layer preferably has a nickel adhesion amount of 0.5 mg/m ² to 500 mg/m ² , more preferably 1 mg/m ² to 50 mg/m ² . When the heat-resistant layer and/or the rust-preventive layer is a layer containing a nickel-zinc alloy, the inner wall portion of a through hole or a via hole is in contact with the desmear liquid. The interface between the foil and the resin substrate is hard to be corroded by the desmear liquid, and the adhesion between the copper foil and the resin substrate is improved.

For example, the heat-resistant layer and/or the rust-preventive layer may be a nickel or nickel alloy layer having an adhesion amount of 1 mg/m ² to 100 mg/m ² , preferably 5 mg/m ² to 50 mg/m ² , and an adhesion amount of 1 mg/ The tin layer having m ² to 80 mg/m ² , preferably 5 mg/m ² to 40 mg/m ² is sequentially laminated, and the nickel alloy layer may also be composed of nickel-molybdenum, nickel-zinc, nickel-molybdenum-cobalt. Any of the components. Further, the total adhesion amount of the nickel or nickel alloy of the heat-resistant layer and/or the rust-preventing layer to tin is preferably 2 mg/m ² to 150 mg/m ² , more preferably 10 mg/m ² to 70 mg/m ² . Further, the heat-resistant layer and/or the rust-preventive layer are preferably [the amount of nickel deposited in the nickel or nickel alloy] / [the amount of tin adhesion] = 0.25 to 10, more preferably 0.33 to 3. When the heat-resistant layer and/or the rust-preventing layer are used, the peeling strength of the circuit after processing the copper foil with a carrier to a printed wiring board, the chemical-resistant deterioration rate of the peeling strength, and the like are improved.

Further, a known decane coupling agent can be used as the decane coupling agent used in the decane coupling treatment, and for example, an amine decane coupling agent, an epoxy decane coupling agent, or a decyl decane coupling agent can be used. Further, as the decane coupling agent, vinyl trimethoxy decane, vinyl phenyl trimethoxy decane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxy can also be used. Γ-glycidoxypropyltrimethoxysilane, 4-epoxypropylbutyltrimethoxydecane, γ-aminopropyltriethoxydecane, N-β(aminoethyl)γ-amino Propyltrimethoxydecane, N-3-(4-(3-aminopropoxy)butoxy)propyl-3-aminopropyltrimethoxydecane, imidazolium, three Decane, γ-mercaptopropyltrimethoxydecane, and the like.

The decane coupling treatment layer may be formed using a decane coupling agent such as epoxy decane, amine decane, methacryloxy decane or decyl decane. Further, such a decane coupling agent may be used in combination of two or more. Among them, it is preferred to use an amine decane coupling agent or epoxy. It is formed by a decane coupling agent.

The amine decane coupling agent herein may also be selected from the group consisting of N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-(N-benzene). Vinylmethyl-2-aminoethylamino)propyltrimethoxydecane, 3-aminopropyltriethoxydecane, bis(2-hydroxyethyl)-3-aminopropyltriethyl Oxydecane, aminopropyltrimethoxydecane, N-methylaminopropyltrimethoxydecane, N-phenylaminopropyltrimethoxydecane, N-(3-propenyloxy-2- Hydroxypropyl)-3-aminopropyltriethoxydecane, 4-aminobutyltriethoxydecane, (aminoethylaminomethyl)phenethyltrimethoxydecane, N-( 2-Aminoethyl-3-aminopropyl)trimethoxydecane, N-(2-aminoethyl-3-aminopropyl)tris(2-ethylhexyloxy)decane, 6- (Aminohexylaminopropyl)trimethoxynonane, aminophenyltrimethoxydecane, 3-(1-aminopropoxy)-3,3-dimethyl-1-propenyltrimethoxy Decane, 3-aminopropyltris(methoxyethoxyethoxy)decane, 3-aminopropyltriethoxydecane, 3-aminopropyltrimethoxydecane, ω-aminol Monoalkyl tri Baseline, 3-(2-N-decylaminoethylaminopropyl)trimethoxydecane, bis(2-hydroxyethyl)-3-aminopropyltriethoxydecane, (N, N-Diethyl-3-aminopropyl)trimethoxydecane, (N,N-dimethyl-3-aminopropyl)trimethoxydecane, N-methylaminopropyltrimethoxy Decane, N-phenylaminopropyltrimethoxydecane, 3-(N-styrylmethyl-2-aminoethylamino)propyltrimethoxydecane, γ-aminopropyltriethyl Oxydecane, N-β(aminoethyl)γ-aminopropyltrimethoxydecane, N-3-(4-(3-aminopropoxy)butoxy)propyl-3-amine Propyltrimethoxydecane.

The decane coupling treatment layer is preferably 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 ruthenium atom. The range of m ² . In the case of the above range, the adhesion between the base resin and the surface-treated copper foil can be further improved.

Further, the surface of the ultra-thin copper layer, the roughened layer, the heat-resistant layer, the rust-proof layer, the decane coupling treatment layer or the chromate-treated layer may be subjected to surface treatment as described in the following patent: International Publication No. WO2008/053878, Japanese Patent Publication No. 2008-111169, Japanese Patent No. 5024930, International Publication No. WO2006/028207, Japanese Patent No. 4828427, International Publication No. WO2006/134868, Japanese Patent No. 5046927, International Publication No. WO2007/105635, Japanese Patent No. No. 5180815, Japan Special Open 2013-19056.

Further, one or more selected from the group consisting of a roughened layer, a heat-resistant layer, a rust-proof layer, a chromate-treated layer, and a decane coupling treatment layer may be provided on one surface or both surfaces of the ultra-thin copper layer. The layer may also be provided with a surface treatment layer. The surface treatment layer may be one or more selected from the group consisting of a roughened layer, a heat-resistant layer, a rustproof layer, a chromate-treated layer, and a decane coupling treatment layer.

Further, the carrier-attached copper foil may have one or more layers selected from the group consisting of a heat-resistant layer, a rust-preventing layer, a chromate-treated layer, and a decane coupling treatment layer on the roughened layer.

Further, the heat-treated layer and the rust-preventing layer may be provided on the roughened layer, and a chromate-treated layer may be provided on the heat-resistant layer or the rust-preventing layer, and a decane coupling may be provided on the chromate-treated layer. Processing layer.

Further, the copper foil with a carrier may be provided with a resin layer on the ultra-thin copper layer or the roughened layer or the heat-resistant layer, the rust-proof layer, the chromate-treated layer or the decane coupling treatment layer. The above resin layer may also be an insulating resin layer.

Further, the carrier copper foil may have a roughening treatment layer on the carrier, or may have a layer on the carrier. The above is selected from the group consisting of a roughened layer, a heat-resistant layer, a rustproof layer, a chromate-treated layer, and a decane coupling treatment layer. The roughening layer, the heat-resistant layer, the rust-preventing layer, the chromate-treated layer, and the decane coupling treatment layer may be provided by a known method, or may be set by the method described in the specification, the patent application, and the drawings. . When the carrier is laminated on a surface of the resin substrate or the like from the surface side having the roughening layer or the like, one or more layers selected from the above-described roughening layer, heat-resistant layer, rust-proof layer, and chromate are disposed on the carrier. The layer or the layer in the decane coupling treatment layer has the advantage that the carrier and the support are not easily peeled off.

The resin layer may be an adhesive or an insulating resin layer which is followed by a semi-hardened state (B-stage state). The semi-hardened state (B-stage state) includes a state in which the insulating resin layer can be stacked and stored even if the surface is touched with a finger, and the heat-treated reaction is caused by further heat treatment.

Further, the resin layer may contain a thermosetting resin or a thermoplastic resin. Further, the resin layer may contain a thermoplastic resin. The resin layer may contain a known resin, a resin curing agent, a compound, a curing accelerator, a dielectric, a reaction catalyst, a crosslinking agent, a polymer, a prepreg, a skeleton material, and the like. Further, as the resin layer, for example, a resin (resin, a resin curing agent, a compound, a curing accelerator, a dielectric, a reaction catalyst, a crosslinking agent, a polymer, a prepreg, a skeleton material, etc.) can be used. And/or a method of forming a resin layer, and forming a device, the document is International Publication No. WO2008/004399, International Publication No. WO2008/053878, International Publication No. WO2009/084533, Japanese Patent Laid-Open No. 11-5828, Japanese Special Kaiping No. 11-140281, Japanese Patent No. 3184485, International Publication No. WO97/02728, Japanese Patent No. 3676375, Japanese Patent Laid-Open No. 2000-43188, Japanese Patent No. 3612594, Japanese Patent Laid-Open No. 2002-179772, Japanese Patent Laid-Open 2002-359444, Japan Japanese Patent No. 2003-304068, Japanese Patent No. 3992225, Japanese Patent Laid-Open No. 2003-249739, Japanese Patent No. 4136509, Japanese Patent Laid-Open No. 2004-82687, Japanese Patent No. 4025177, Japanese Patent Publication No. 2004-349654, Japan Patent No. 4,286,060, Japanese Patent Laid-Open No. 2005-262506, Japanese Patent No. 4570070, Japanese Patent Laid-Open No. 2005-53218, Japanese Patent No. 3949676, Japanese Patent No. 4178415, International Publication No. WO2004/005588, Japanese Patent Publication No. 2006 -257153, Japanese Laid-Open Patent Publication No. 2007-326923, Japanese Laid-Open Patent Publication No. 2008-111169, Japanese Patent No. 5024930, International Publication No. WO2006/028207, Japanese Patent No. 4828427, Japanese Patent Laid-Open No. 2009-67029, International Publication No. WO2006/134868, Japanese Patent No. 5046927, Japanese Patent Laid-Open No. 2009-173017, International Publication No. WO2007/105635, Japanese Patent No. 5180815, International Publication No. WO2008/114858, International Publication No. WO2009/008471, Japan Special Open 2011- No. 14727, International Publication No. WO2009/001850, International Publication No. WO2009/145179, International Publication No. WO2011/068157, Japanese Patent Publication No. 2013-19056.

In addition, the type of the resin layer is not particularly limited, and examples thereof include a resin containing at least one selected from the group consisting of epoxy resins, polyimine resins, and polyfunctional cyanates. a compound, a maleimide compound, a polys-methyleneimine compound, a maleimide resin, an aromatic maleimide resin, a polyvinyl acetal resin, Urethane resin, polyether oxime (also known as polyethersulphone, polyethersulfone), polyether oxime (also known as polyethersulphone, polyethersulfone) resin, aromatic polyamide resin, aromatic polyamide resin polymer, rubber Resin, polyamine, aromatic polyamine, polyamidoximine resin, rubber modified epoxy resin, phenoxy resin, carboxyl modified acrylonitrile-butadiene resin, polyphenylene ether, di-n-butylene Imine three Resin, thermosetting polyphenylene ether resin, cyanate ester resin, acid anhydride, acid anhydride, linear polymer having crosslinkable functional group, polyphenylene ether resin, 2,2- Bis(4-cyanate phenyl)propane, phosphorus-containing phenol compound, manganese naphthenate, 2,2-bis(4-epoxypropylphenyl)propane, polyphenylene ether-cyanate resin , oxoxane modified polyamidoximine resin, cyanoester resin, phosphazene resin, rubber modified polyamidoximine resin, isoprene, hydrogenated polybutadiene, polyvinyl butyral, Phenoxy group, polymer epoxy resin, aromatic polyamine, fluororesin, bisphenol, block copolymer polyimine resin and cyanoester resin.

Further, the epoxy resin has two or more epoxy groups in its molecule, and can be used without any problem as long as it can be used for electrical or electronic materials. Further, the epoxy resin is preferably an epoxy resin obtained by epoxidizing a compound having two or more epoxy propyl groups in the molecule. Further, one or two or more selected from the group consisting of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, and bisphenol may be used. AD type epoxy resin, novolak type epoxy resin, cresol novolak type epoxy resin, alicyclic epoxy resin, brominated epoxy resin, phenolic novolac type epoxy resin, naphthalene ring Oxygen resin, brominated bisphenol A type epoxy resin, o-cresol novolak type epoxy resin, rubber modified bisphenol A type epoxy resin, epoxidized propylamine type epoxy resin, triglycidyl isocyanurate , a glycidyl compound such as N,N-diepoxypropylaniline, a glycidyl ester compound such as diglycidyl tetrahydrophthalate, a phosphorus-containing epoxy resin, a biphenyl type epoxy resin, or a combination A novolac type epoxy resin, a trishydroxyphenylmethane type epoxy resin, a tetraphenylethane type epoxy resin, or a hydrogenated body or a halogenated body of the above epoxy resin can be used.

A well-known phosphorus-containing epoxy resin can be used as the above phosphorus-containing epoxy resin. Further, the phosphorus-containing epoxy resin preferably has, for example, two or more epoxy groups in the molecule from 9,10-dihydrogen. An epoxy resin obtained in the form of a derivative of -9-oxa-10-phosphaphenanthrene-10-oxide.

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

The resin layer may also contain a dielectric (dielectric filler).

When a dielectric material (dielectric filler) is contained in any of the above resin layers or resin compositions, it can be used for forming a capacitor layer to increase the capacitance of the capacitor circuit. The dielectric (dielectric filler) is BaTiO ₃ , SrTiO ₃ , Pb(Zr-Ti)O ₃ (commonly known as PZT), PbLaTiO ₃ ‧PbLaZrO (commonly known as PLZT), and SrBi ₂ Ta ₂ O ₉ (commonly known as SBT). A dielectric powder having a composite oxide of a perovskite structure.

The dielectric (dielectric filler) may also be in powder form. When the dielectric (dielectric filler) is in the form of a powder, the powder property of the dielectric (dielectric filler) is preferably from 0.01 μm to 3.0 μm, preferably from 0.02 μm to 2.0. The range of μm. Furthermore, when a photo is taken by a scanning electron microscope (SEM) on a dielectric body, the straight line length of the particles transverse to the dielectric body is the longest when a straight line is drawn on the particles of the dielectric body on the photo. The particle length of a portion of the dielectric is set to the particle diameter of the dielectric. Further, the average value of the particle diameters of the dielectric bodies in the measurement field of view is defined as the particle diameter of the dielectric body.

The resin and/or resin composition and/or compound contained in the above resin layer is dissolved in, for example, methyl ethyl ketone (MEK), cyclopentanone, dimethylformamide, dimethylacetamide, N -methylpyrrolidone, toluene, methanol, ethanol, propylene glycol monomethyl ether, dimethylformamide, dimethylacetamide, cyclohexanone, ethyl cellosolve, N-methyl-2-pyrrole A resin liquid (resin varnish) is prepared in a solvent such as ketone, N,N-dimethylacetamide or N,N-dimethylformamide, and is coated by, for example, a roll coating method. On the side surface of the extremely thin copper layer of the above-mentioned carrier copper foil, it is then heated and dried as necessary to remove the solvent to be in a B-stage state. Drying, for example, by using hot air drying The drying furnace can be used, and the drying temperature is preferably 100 to 250 ° C, preferably 130 to 200 ° C. The composition of the above resin layer may be dissolved in a solvent to form a resin solid content of 3 wt% to 70 wt%, preferably 3 wt% to 60 wt%, preferably 10 wt% to 40 wt%, more preferably 25 wt% to 40 wt%. Resin solution. Further, from the viewpoint of the atmosphere, it is most preferable to use a mixed solvent of methyl ethyl ketone and cyclopentanone for dissolution at this stage. Further, the solvent is preferably a solvent having a boiling point of from 50 ° C to 200 ° C.

Moreover, it is preferable that the resin layer is a semi-hardened resin film in the range of 5% to 35% of the resin flow amount measured according to MIL-P-13949G in the MIL standard.

In the present specification, the amount of resin flow refers to four pieces of 10 cm square samples taken from a surface-treated copper foil with a resin thickness of 55 μm according to MIL-P-13949G in the MIL standard, so that the four pieces are made. In the state in which the samples were overlapped (layered body), the bonding was carried out under the conditions of a pressing temperature of 171 ° C, a pressing pressure of 14 kgf/cm ² , and a pressing time of 10 minutes, and based on the result of measuring the resin outflow weight at this time, based on the number 1 And calculate the value.

The surface-treated copper foil (resin-treated copper foil with resin) provided with the above-mentioned resin layer is used in such a manner that the resin layer is superposed on the substrate and then thermally bonded to the entire resin layer to thermally cure the resin layer, followed by surface curing. When the copper foil is treated as an extremely thin copper layer with a carrier copper foil, the carrier is peeled off to expose an extremely thin copper layer (of course, the intermediate layer side surface of the extremely thin copper layer is exposed), which is thick from the surface-treated copper foil. The surface on the opposite side of the processing side forms a specific wiring pattern.

If the surface treated copper foil with the resin is used, the multilayer printing can be reduced. The number of sheets of prepreg material used for the wire substrate. Further, the copper clad laminate can be produced even if the thickness of the resin layer is such that the thickness of the interlayer insulation can be ensured or the prepreg material is not used at all. Further, at this time, the insulating resin primer may be applied to the surface of the substrate to further improve the smoothness of the surface.

Moreover, when the prepreg material is not used, the material cost of the prepreg material can be saved, and the lamination step is also simplified, so that it is economically advantageous, and has the following advantages: only the prepreg is manufactured. The thickness of the multilayer printed wiring board of the thickness of the material is reduced, and it is possible to manufacture a very thin multilayer printed wiring board having a thickness of 100 μm or less.

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

When the thickness of the resin layer is less than 0.1 μm, there is a case where the adhesion is lowered, and it is difficult to ensure that the surface-treated copper foil with the resin is laminated on the substrate having the inner layer material without interposing the prepreg material. Interlayer insulation between the inner layer material and the circuit. On the other hand, when the thickness of the resin layer is thicker than 120 μm, it is difficult to form a resin layer of a desired thickness in one coating step, and an unnecessary material cost and number of steps are required, so that it is economically disadvantageous. .

In the case where a surface-treated copper foil having a resin layer is used for producing an extremely thin multilayer printed wiring board, the thickness of the resin layer is set to be 0.1 μm to 5 μm, more preferably 0.5 μm to 5 μm, and more preferably When the thickness is from 1 μm to 5 μm, the thickness of the multilayer printed wiring board can be reduced, which is preferable.

Further, the printed circuit board is completed by mounting electronic components on the printed wiring board. In the present invention, the "printed wiring board" also includes a printed wiring board, a printed circuit board, and a printed circuit board on which electronic components are mounted.

In addition, an electronic device can be produced by using the printed wiring board, and an electronic device can be produced by using a printed circuit board on which the electronic component is mounted, and an electronic device can be manufactured by using the printed circuit board on which the electronic component is mounted. Hereinafter, a plurality of printed wirings using the copper foil with a carrier of the present invention are shown An example of a manufacturing step of a board.

An embodiment of the method for producing a printed wiring board according to the present invention includes the steps of: preparing a copper foil with an insulating substrate of the present invention and an insulating substrate; laminating the copper foil with the insulating substrate; and forming the ultra-thin copper layer side After the insulating substrate is laminated, the copper foil with the carrier and the insulating substrate are laminated, and then the copper-clad laminate is formed by peeling off the carrier of the copper foil with the carrier, and then the half-addition method is used to improve the half-addition. Any one of the method of forming, partial addition, and subtraction forms a circuit. The insulating substrate can also be set as an inner layer circuit inlet.

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, and a pattern is formed by plating and etching.

Therefore, an embodiment of a method for producing a printed wiring board of the present invention using a semi-additive method includes the steps of: preparing a copper foil with an insulating substrate of the present invention and an insulating substrate; and laminating the copper foil with the insulating substrate; After laminating the copper foil with the carrier and the insulating substrate, the carrier of the copper foil with the carrier is peeled off; and the ultra-thin copper layer exposed by peeling off the carrier is completely removed by etching or plasma etching using an etching solution such as acid; Providing a through hole or/and a blind hole in the resin exposed by removing the ultra-thin copper layer by etching; removing a region containing the through hole or/and the blind hole; and containing the resin and the above An electroless plating layer is disposed in a region of the through hole or/and the blind hole; And providing a photoresist on the electroless plating layer; exposing the photoresist to the photoresist, and then removing the photoresist formed in the circuit region; and forming the circuit region in which the photoresist is removed Electrolytic plating; removing the photoresist; and removing the electroless plating layer located in a region other than the region in which the circuit is formed by rapid etching or the like.

Another embodiment of the method for producing a printed wiring board of the present invention using a semi-additive method comprises the steps of: preparing a copper foil with a carrier of the present invention and an insulating substrate; laminating the copper foil with the carrier and the insulating substrate; After the carrier-attached copper foil is laminated with the insulating substrate, the carrier of the carrier-attached copper foil is peeled off; the ultra-thin copper layer exposed by peeling off the carrier and the insulating resin substrate are provided with through holes or/and blind vias; The area of the through hole or/and the blind hole is subjected to desmear treatment; the extremely thin copper layer exposed by peeling off the carrier is completely removed by etching or plasma etching using an acid or the like; the inclusion is removed by etching or the like. An electroless plating layer is provided in a region of the resin and the through hole or/and the blind hole exposed by the ultra-thin copper layer; a photoresist is disposed on the electroless plating layer; and the photoresist is exposed; After removing the photoresist formed in the region of the circuit; and providing an electrolytic plating layer in the region where the photoresist is formed in the circuit; The photoresist is removed; and the electroless plating layer located in a region other than the region in which the circuit is formed is removed by rapid etching or the like.

Another embodiment of the method for producing a printed wiring board of the present invention using a semi-additive method comprises the steps of: preparing a copper foil with a carrier of the present invention and an insulating substrate; laminating the copper foil with the carrier and the insulating substrate; After the carrier-attached copper foil is laminated with the insulating substrate, the carrier of the carrier-attached copper foil is peeled off; the ultra-thin copper layer exposed by peeling off the carrier and the insulating resin substrate are provided with through holes or/and blind vias; Etching or plasma etching of an etching solution such as acid to completely remove the extremely thin copper layer which is peeled off from the carrier; and performing desmear treatment on the region containing the above-mentioned through holes or/and blind vias; An electroless plating layer is disposed in the region of the resin and the through hole or/and the blind hole exposed by removing the ultra-thin copper layer; a photoresist is disposed on the electroless plating layer; and the photoresist is exposed. Thereafter, the photoresist formed in the region where the circuit is formed is removed; the electrolytic plating layer is disposed in the region where the photoresist is formed in the circuit-formed region; the photoresist is removed; and the etching is performed by rapid etching or the like Located in addition to the aforementioned electroless plating is formed in the region other than the region of the cladding layer circuit.

Another embodiment of the method for producing a printed wiring board of the present invention using a semi-additive method comprises the steps of: preparing a copper foil with a carrier of the present invention and an insulating substrate; laminating the copper foil with the carrier and the insulating substrate; After laminating the copper foil with the carrier and the insulating substrate, the carrier of the copper foil with the carrier is peeled off; and the ultra-thin copper layer exposed by peeling off the carrier is completely removed by etching or plasma etching using an etching solution such as acid; An electroless plating layer is provided on the surface of the resin exposed by removing the ultra-thin copper layer by etching; a photoresist is disposed on the electroless plating layer; the photoresist is exposed, and then removed to form a photoresist having a circuit region; an electrolytic plating layer disposed in the circuit-formed region from which the photoresist is removed; removing the photoresist; and removing the region formed by the circuit by rapid etching or the like Electroless plating and ultra-thin copper layers in areas other than those.

In the present invention, the modified semi-additive method refers to laminating a metal foil on an insulating layer, protecting a non-circuit forming portion by a photoresist, and thickening the thickness of the circuit forming portion by electrolytic plating to remove the anti-resistance. The etching agent is a method of forming a circuit on the insulating layer by (fast) etching to remove the metal foil other than the above-described circuit forming portion.

Therefore, an embodiment of a method of manufacturing a printed wiring board of the present invention using a modified semi-additive method includes the following steps: Preparing the copper foil and the insulating substrate with the carrier of the present invention; laminating the copper foil with the carrier and the insulating substrate; and laminating the carrier copper foil and the insulating substrate, and then peeling off the carrier of the copper foil with the carrier; And forming a through hole or/and a blind hole on the exposed ultra-thin copper layer and the insulating substrate; performing desmear treatment on the area containing the through hole or/and the blind hole; and the above-mentioned area containing the through hole or/and the blind hole Providing an electroless plating layer; providing a photoresist on a surface of the extremely thin copper layer exposed by peeling off the carrier; forming a circuit by electrolytic plating after the photoresist is disposed; removing the photoresist; and using rapid etching The extremely thin copper layer exposed by removing the above photoresist is removed.

Another embodiment of the method for producing a printed wiring board of the present invention using the modified semi-additive method comprises the steps of: preparing a copper foil with a carrier of the present invention and an insulating substrate; and laminating the copper foil with the carrier and the insulating substrate; After laminating the carrier-attached copper foil and the insulating substrate, the carrier of the carrier-attached copper foil is peeled off; a photoresist is provided on the ultra-thin copper layer exposed by peeling off the carrier; and the photoresist is exposed; Removing the photoresist formed in the circuit-formed region; providing an electrolytic plating layer in the region where the photoresist is formed in the circuit-forming region; removing the photoresist; and An extremely thin copper layer located in a region other than the above-described region in which the circuit is formed is removed by rapid etching or the like.

In the present invention, the partial addition method refers to a substrate in which a conductor layer is provided, a catalyst core is provided on a substrate formed by passing through a via hole or an auxiliary hole, and etching is performed to form a conductor circuit. After the solder resist or the photoresist is required to be provided, the via hole or the auxiliary hole or the like is thickened on the conductor circuit by electroless plating treatment (electroplating treatment is further performed as necessary), thereby manufacturing a printed wiring board. method.

Therefore, an embodiment of the method for producing a printed wiring board of the present invention using a partial addition method includes the steps of: preparing a copper foil with an insulating substrate of the present invention and an insulating substrate; and laminating the copper foil with the insulating substrate; After laminating the copper foil with the carrier and the insulating substrate, the carrier of the copper foil with the carrier is peeled off; and the through hole or/and the blind hole are provided on the ultra-thin copper layer and the insulating substrate exposed by peeling off the carrier; The area of the hole or/and the blind hole is subjected to desmear treatment; the catalyst core is provided in the above-mentioned region containing the through hole or/and the blind hole; and the etching resist is provided on the surface of the extremely thin copper layer exposed by peeling off the carrier; The etching resist is exposed to form a circuit pattern; the ultra-thin copper layer and the catalyst core are removed by etching or plasma etching using an acid or the like to form a circuit; and the etching resist is removed; Providing a solder resist or a photoresist on the surface of the insulating substrate exposed by removing the ultra-thin copper layer and the catalyst core by etching or plasma etching using an etching solution such as an acid; and removing the solder resist or the light An electroless plating layer is provided in the region of the resist.

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

Therefore, one embodiment of the method for producing a printed wiring board of the present invention using the subtractive method includes the steps of: preparing a copper foil with an insulating substrate of the present invention and an insulating substrate; and laminating the copper foil with the insulating substrate; After laminating the copper foil with the carrier and the insulating substrate, the carrier of the copper foil with the carrier is peeled off; and the through hole or/and the blind hole are provided on the ultra-thin copper layer and the insulating substrate exposed by peeling off the carrier; Or / and the area of the blind hole is subjected to desmear treatment; an electroless plating layer is disposed in the region containing the through hole or/and the blind hole; an electrolytic plating layer is disposed on the surface of the electroless plating layer; An etching resistor is disposed on the surface of the plating layer or/and the ultra-thin copper layer; the etching resist is exposed to form a circuit pattern; and the ultra-thin copper layer is removed by etching or plasma using an etching solution such as acid or the like. The electroless plating layer and the electrolytic plating layer are formed to form a circuit; and the etching resist is removed.

Another implementation of a method of manufacturing a printed wiring board of the present invention using a subtractive method The form includes the steps of: preparing a copper foil and an insulating substrate with a carrier of the present invention; laminating the copper foil with the carrier and the insulating substrate; and laminating the copper foil with the insulating substrate and the carrier of the copper foil with the carrier Peeling; providing a through hole or/and a blind hole in the ultra-thin copper layer and the insulating substrate exposed by peeling off the carrier; performing desmear treatment on the region containing the through hole or/and the blind hole; And an area of the blind hole is provided with an electroless plating layer; a mask is formed on the surface of the electroless plating layer; an electrolytic plating layer is provided on the surface of the electroless plating layer where the mask is not formed; An etching resistor is disposed on the surface of the cladding layer or/and the ultra-thin copper layer; the etching resist is exposed to form a circuit pattern; and the ultra-thin copper layer is removed by etching or plasma etching using an acid or the like An electroless plating layer is formed to form a circuit; and the above etching resist is removed.

The step of providing a through hole or/and a blind hole, and the subsequent desmear step may also be omitted.

The method for producing a printed wiring board of the present invention may further comprise the steps of: forming a circuit on the side surface of the surface treatment layer or the side surface of the carrier side of the copper foil with carrier of the present invention, and embedding the circuit in the manner described above a step of forming a resin layer on the side surface of the surface treatment layer or the side surface of the carrier side of the carrier copper foil, a step of forming a circuit on the resin layer, After the circuit is formed on the resin layer, the step of peeling off the carrier or the ultra-thin copper layer, and peeling off the carrier or the ultra-thin copper layer, and then removing the ultra-thin copper layer or the carrier, The step of embedding the circuit in the resin layer on the side surface of the surface treatment layer or the surface of the carrier side. Moreover, the method of manufacturing a printed wiring board may include the steps of forming a circuit on the side surface of the surface treatment layer or the side surface of the carrier side of the copper foil with a carrier of the present invention, and embedding the circuit in the manner described above. a step of forming a resin layer on the side surface of the surface treatment layer or the surface of the carrier side of the carrier copper foil, a step of peeling off the carrier or the ultra-thin copper layer, and peeling off the carrier or the ultra-thin copper layer, by removing the above An ultra-thin copper layer or the above-described carrier, and a step of embedding the circuit embedded in the resin layer on the side surface of the surface treatment layer or the side surface of the carrier.

Here, a specific example of a method of manufacturing a printed wiring board using the copper foil with a carrier of the present invention will be described in detail with reference to the drawings. Here, a copper foil with a carrier having an extremely thin copper layer as a surface treatment layer formed with a roughened layer is described as an example, but the invention is not limited thereto, and the surface treatment layer is not roughened. The carrier copper foil to which the layer is attached can also be similarly produced by the following method of manufacturing a printed wiring board.

First, as shown in Fig. 1-A, a carrier-attached copper foil (first layer) having an extremely thin copper layer having a roughened layer formed thereon is prepared.

Next, as shown in FIG. 1-B, a resist is applied onto the roughened layer of the ultra-thin copper layer, exposed and developed, and the resist is etched into a specific shape.

Next, as shown in FIG. 1-C, a circuit plating of a specific shape is formed by forming a plating layer for a circuit and removing the resist.

Secondly, as shown in Figure 2-D, the coating is coated on the circuit (to the side of the buried circuit plating) A resin layer is laminated on the ultra-thin copper layer to form a resin layer, and then another carrier copper foil (second layer) is attached from the side of the ultra-thin copper layer.

Next, as shown in Fig. 2-E, the carrier is peeled off from the carrier copper foil of the second layer.

Next, as shown in Fig. 2-F, a laser opening is performed at a specific position of the resin layer to expose the circuit plating layer to form a blind hole.

Next, as shown in FIG. 3-G, copper is buried in the blind via to form a via fill.

Next, as shown in FIG. 3-H, a circuit plating layer is formed on the via fill material in the manner of FIGS. 1-B and 1-C described above.

Next, as shown in Fig. 3-I, the carrier was peeled off from the carrier copper foil of the first layer.

Next, as shown in Fig. 4-J, the extremely thin copper layer on both surfaces is removed by rapid etching to expose the surface of the circuit plating layer in the resin layer.

Next, as shown in Fig. 4-K, bumps are formed on the circuit plating layer in the resin layer, and copper pillars are formed on the solder. A printed wiring board using the copper foil with a carrier of the present invention was produced in this manner.

The above-mentioned other carrier copper foil (second layer) may be a copper foil with a carrier of the present invention, and a conventional copper foil with a carrier may be used, and a usual copper foil may be used. Further, a layer 1 or a plurality of layers may be further formed on the second layer circuit shown in FIG. 3-H, and may be a semi-additive method, a subtractive method, a partial addition method or a modified semi-additive method. One method forms the circuits.

Further, the copper foil with a carrier used in the first layer may have a substrate on the side of the carrier side of the copper foil with the carrier. By having such a substrate, the copper foil with a carrier used for the first layer is supported, and wrinkles are less likely to occur, so that productivity is improved. Further, all of the substrates can be used as long as the substrate exhibits an effect of supporting the copper foil with a carrier used in the first layer. For example, a carrier, a prepreg, a resin layer or a known carrier described in the specification can be used. A prepreg, a resin layer, a metal plate, a metal foil, a plate of an inorganic compound, a foil of an inorganic compound, a plate of an organic compound, and a foil of an organic compound are used as the above substrate.

The time at which the substrate is formed on the side surface of the carrier is not particularly limited, but it must be formed before the carrier is peeled off. In particular, it is preferably formed before the step of forming a resin layer on the surface of the ultra-thin copper layer side of the copper foil with a carrier, and more preferably a step of forming a circuit on the side surface of the ultra-thin copper layer of the copper foil with a carrier. Formed before.

Further, a well-known resin or prepreg can be used as the resin. For example, BT (bis-non-butenylene diimide III can be used A resin or a glass cloth impregnated with a BT resin, that is, a prepreg, an ABF film manufactured by Ajinomoto Fine-Techno Co., Ltd. or ABF. Further, the embedded resin may contain a thermosetting resin or a thermoplastic resin. Further, the embedded resin may contain a thermoplastic resin. The type of the embedded resin is not particularly limited, and examples thereof include an epoxy resin, a polyimide resin, a polyfunctional cyanate compound, a maleimide compound, and polyethylene. a resin such as an acetal resin, an amine ester resin, a block copolymerized polyimine resin, a block copolymerized polyimide resin, or a paper base material phenol resin or paper substrate epoxy resin, Synthetic fiber cloth substrate epoxy resin, glass cloth-paper composite substrate epoxy resin, glass cloth-glass non-woven composite substrate epoxy resin and glass cloth substrate epoxy resin, polyester film, polyimide film, A liquid crystal polymer film, a fluororesin film, or the like.

Moreover, the method for producing a printed wiring board according to the present invention may be a method for producing a printed wiring board (coreless method) comprising the above-mentioned ultra-thin copper layer side surface of the copper foil with a carrier of the present invention or the carrier a step of laminating the side surface with the resin substrate; and providing at least one resin layer and the circuit layer on the surface of the carrier-attached copper foil on the side opposite to the surface-treated layer side surface or the carrier-side surface laminated with the resin substrate a step; and forming the above resin layer and circuit After the two layers, the carrier or the ultra-thin copper layer is peeled off from the copper foil with a carrier. Regarding the above-described coreless method, as a specific example, first, the surface treatment layer side surface or the carrier side surface of the copper foil with a carrier of the present invention and a resin substrate are laminated. Then, a resin layer is formed on the surface of the carrier-attached copper foil on the side opposite to the surface-treated layer side surface or the above-described carrier-side surface laminated with the resin substrate. It is also possible to laminate another resin-attached copper foil on the side of the carrier side or the surface treatment layer from the resin layer formed on the side surface of the carrier side or the side surface of the surface treatment layer. In this case, the resin substrate is centered on the both surface sides of the resin substrate in the order of the carrier/intermediate layer/very thin copper layer/surface treatment layer or the surface treatment layer/very thin copper layer/ The intermediate layer/carrier is sequentially laminated with a carrier copper foil. It is also possible to provide another resin layer on the surface of the surface treatment layer or the carrier exposed at both ends, and further to provide a copper layer or a metal layer, and then process the copper layer or the metal layer, thereby forming an electric circuit. Further, another resin layer may be provided on the above circuit so as to fill the above-mentioned circuit. Further, the formation of such a circuit and the resin layer may be performed once or more (growth method). Further, regarding the laminate (hereinafter also referred to as laminate) B formed as described above, the ultra-thin copper layer or carrier of each of the carrier-attached copper foils can be peeled off from the carrier or the ultra-thin copper layer to form a coreless substrate. Further, in the production of the coreless substrate described above, it is also possible to use two copper foils with a carrier to produce the following surface treatment layer/very thin copper layer/intermediate layer/carrier/carrier/intermediate layer/very thin copper layer/surface treatment. a laminated body composed of layers, or a laminated body having a carrier/intermediate layer/very thin copper layer surface treatment layer/surface treatment layer/very thin copper layer/intermediate layer/carrier, or having a carrier/intermediate layer/very thin A laminate of a copper layer/surface treatment layer/carrier/intermediate layer/very thin copper layer/surface treatment layer, and the above-mentioned laminate is used for the center. The resin layer and the circuit layer may be provided one or more times on the surface of the ultra-thin copper layer or the carrier on both sides of the laminated body (hereinafter also referred to as the laminated body A), and the resin layer and the circuit are provided one time or more. After that, each with a carrier copper foil The ultra-thin copper layer or carrier is peeled off from the carrier or the ultra-thin copper layer to form a coreless substrate. The above laminated body is between the surface of the surface treatment layer, the surface treatment layer and the ultra-thin copper layer, the surface of the carrier, the carrier and the carrier, the surface treatment layer and the surface treatment layer, and between the extremely thin copper layer and the carrier. There may be other layers. In the present specification, the "surface of the surface treatment layer", the "surface of the surface treatment layer", the surface of the carrier, the surface of the carrier, the surface of the carrier, the surface of the laminate, and the surface of the laminate When the surface treatment layer, the carrier, and the laminate have other layers on the surface of the surface treatment layer, the surface of the carrier, and the surface of the laminate, the concept is to include the surface (the outermost surface) of the other layer. Further, the laminate preferably has a composition of a surface treatment layer/very thin copper layer/intermediate layer/carrier/carrier/intermediate layer/very thin copper layer/surface treatment layer. This is because when the coreless substrate is produced by using the laminated body described above, since the ultra-thin copper layer is disposed on the coreless substrate side, it is easy to form a circuit on the coreless substrate by using the improved semi-additive method. Further, since the ultra-thin copper layer has a small thickness, the extremely thin copper layer can be easily removed, and after the ultra-thin copper layer is removed, it is easy to form a circuit on the coreless substrate by using a semi-additive method.

In the present specification, the "layered body" which is not particularly described as "layered body A" or "layered body B" means a layered body including at least the layered body A and the layered body B.

Further, in the method for producing a coreless substrate, by covering a part or all of the end faces of the copper foil or the laminate (layered product A) with a resin, it is possible to prevent the printed wiring board from being produced by the build-up method. The chemical solvent penetrates between the intermediate layer or a piece of the carrier-attached copper foil constituting the laminated body and the other copper foil with the carrier, and can prevent the separation of the extremely thin copper layer and the carrier caused by the penetration of the chemical solvent or the carrier-attached copper foil. Corrosion can increase yield. As the "resin covering a part or all of the end surface of the copper foil with a carrier" or "resin covering a part or all of the end surface of the laminated body", a resin which can be used for the resin layer can be used. again In the method for producing a coreless substrate, when the carrier copper foil or the laminate is viewed in plan, a laminated portion of the carrier copper foil or the laminate (a laminate portion of the carrier and the ultra-thin copper layer, or a carrier copper foil and a carrier) is attached. At least a portion of the outer periphery of the other laminated portion of the carrier-attached copper foil may be covered with a resin or a prepreg. Moreover, the laminated body (layered product A) formed by the above-described method for producing a coreless substrate may be configured such that a pair of copper foils with a carrier are detachably contacted with each other. Further, in the plan view of the copper foil with a carrier, the laminated portion of the carrier copper foil or the laminate may be covered with a resin or a prepreg (the laminated portion of the carrier and the ultra-thin copper layer, or a piece of copper foil with a carrier and The outer periphery of the other laminated portion of the carrier copper foil). With such a configuration, when the carrier copper foil or the laminate is viewed in a plan view, the laminated portion of the carrier copper foil or the laminate is covered with a resin or a prepreg, and it is possible to prevent other components from being laterally, that is, relative to each other. Collision in the lateral direction in the direction of the lamination, as a result, peeling of the carrier and the ultra-thin copper layer or the copper foil with the carrier in operation can be reduced. Further, by covering with the resin or the prepreg so as not to expose the outer periphery of the laminated portion with the carrier copper foil or the laminate, it is possible to prevent the penetration of the chemical solvent into the interface of the laminate portion in the chemical solvent treatment step as described above. It can prevent corrosion or erosion of the copper foil with the carrier. Further, when a carrier copper foil is separated from a pair of copper foils of a laminate, or when a carrier with a carrier copper foil and a copper foil (very thin copper layer) are separated, it is necessary to remove the resin or by cutting or the like. The laminated portion of the carrier-attached copper foil or laminate covered with the prepreg (the laminated portion of the carrier and the ultra-thin copper layer, or the laminated portion of the one-piece copper foil and the other carrier-attached copper foil).

The copper foil with a carrier of the present invention may be laminated from the side of the carrier side or the surface treatment layer to the side of the carrier or the surface of the surface of the copper foil with a carrier of the present invention to form a laminate. Further, the laminated body may be: the carrier side surface of the one piece of the carrier-attached copper foil or the surface treatment layer side surface and the carrier side surface or the surface of the other sheet of the carrier copper foil The side surface of the layer is obtained by directly laminating via an adhesive as needed. Further, the carrier or the surface-treated layer of the one piece of the copper foil with a carrier may be bonded to the carrier or the surface treatment layer of the other copper foil with the carrier. Further, a part or all of the end faces of the laminate may be covered with a resin.

The laminate of the carriers can be carried out, for example, by the following method, except for simply overlapping.

(a) Metallurgical joining method: welding (arc welding, TIG (tungsten inert gas) welding, MIG (metal inert gas) welding, resistance welding, seam welding, spot welding), crimping (ultrasonic welding, friction stir welding), soldering; (b) Mechanical joining method: caulking, joining by rivets (joining by self-piercing riveting, joining by rivets), binding machine; (c) Physical bonding method: adhesive, (double-sided) tape

By joining a part or all of one carrier to a part or all of the other carrier by the above-described joining method, it is possible to manufacture a laminated body in which one carrier and another carrier layer are brought into contact with each other in a separable manner. If one carrier and the other carrier are weakly connected, in the case of one carrier and another carrier layer, one carrier can be separated from the other carrier without removing the connection between one carrier and the other carrier. In addition, in the case where one carrier and the other carrier are strongly connected, a carrier and a portion to which the other carrier is connected may be separated by cutting or chemical polishing (etching, etc.), mechanical polishing, or the like, thereby separating a carrier and Another carrier.

Further, a printed wiring board can be produced by performing the steps of: providing at least one step of the resin layer and the circuit layer in the laminated body configured as described above; and forming the resin layer and the circuit layer at least once. Thereafter, the step of peeling off the ultra-thin copper layer or the carrier from the copper foil with a carrier of the above laminated body is carried out. Furthermore, it is also possible to provide one surface or two surfaces of the laminated body. The resin layer and the circuit are two layers.

[Examples]

Hereinafter, description will be made based on an experimental example. Furthermore, this experimental example is merely an example and is not limited to this example.

1. Manufacture of carrier copper foil

The carrier copper foil was produced by the following procedure.

First, a long electrolytic copper foil or a rolled copper foil having the thickness shown in Table 1 was prepared as a carrier.

The electrolytic copper foil was produced under the following conditions.

(electrolytic bath composition)

Cu: 80~120g/L

H ₂ SO ₄ : 80~120g/L

Cl: 20~80mg/L

Varnish: 0.1~6.0mg/L

(electrolysis conditions)

Liquid temperature: 55~65°C

Current density: 100A/dm ²

Electrolyte flow rate: 1.5m / sec

In the rolled copper foil, fine copper (fine copper specified in JIS H3100 C1100) was used in Examples 9 and 12, and oxygen-free copper (oxygen-free copper specified in JIS H3100 C1020) was used in Examples 10 and 11. The "rolled copper foil (Ag 180 ppm)" in the type column of the carrier of Table 1 means that 180 mass ppm of Ag is added to the refined copper.

<Intermediate layer of experimental example>

The shiny surface of the copper foil was formed on the continuous plating line of the roll-to-roll type by the following conditions, and an intermediate layer was formed by electroplating.

‧Ni layer

Nickel sulfate: 250~300g/L

Nickel chloride: 35~45g/L

Nickel acetate: 10~20g/L

Trisodium citrate: 15~30g/L

Gloss agent: saccharin, butynediol, etc.

Sodium lauryl sulfate: 30~100ppm

pH: 4~6

Bath temperature: 50~70°C

Current density: 3~15A/dm ²

Adhesion: 4000μg/dm ²

After washing with water and pickling, a Cr layer having an adhesion amount of 10 μg/dm ² was adhered to the Ni layer by electrolytic chromate treatment on a continuous roll line of a roll-to-roll type under the following conditions.

‧ electrolytic chromate treatment

Liquid composition: potassium dichromate 1~10g/L, zinc 0~5g/L

pH: 3~4

Liquid temperature: 50~60°C

Current density: 0.1~2.6A/dm ²

Coulomb amount: 0.5~30As/dm ²

<Extremely thin copper layer of experimental example>

Next, on the continuous plating line of the roll-to-roll type, an extremely thin copper layer having a thickness of 3 μm was formed on the intermediate layer by electroplating under the following conditions, thereby producing a copper foil with a carrier.

‧ very thin copper layer

Copper concentration: 30~120g/L

H ₂ SO ₄ concentration: 20~120g/L

Electrolyte temperature: 20~80°C

Current density: 10~100A/dm ²

<surface treatment layer of experimental example>

The surface of the above ultra-thin copper layer was subjected to surface treatment using the following surface treatment conditions. The layer constitution of the surface treatment layer formed by the surface treatment is shown in Table 1.

In a part of the experimental examples, the surface of the ultra-thin copper layer is subjected to a plating selected from the group consisting of Cu-W alloy plating, Cu-P alloy plating, and Cu-Co-Ni alloy plating under the following conditions. Come as a roughing process.

‧Cu-W alloy plating (examples 1, 2, 15, 16)

Liquid composition: Cu 15g / liter, sulfuric acid 100g / liter, W 5mg / liter

Temperature: 25 ° C

(The first stage)

Current density (D _k ): 90A/dm ²

Time: 1.5 seconds

(second stage)

Current density (D _k ): 20A/dm ²

Time: 3 seconds

‧Cu-P alloy plating (Examples 3 and 4)

Liquid composition: Cu 30g / liter, sulfuric acid 100g / liter, P 500mg / liter

Temperature: 30 ° C

(The first stage)

Current density (D _k ): 140A/dm ²

Time: 0.6 seconds

(second stage)

Current density (D _k ): 20A/dm ²

Time: 2.0 seconds

‧Cu-Co-Ni alloy plating (Examples 5, 6, 14)

Liquid composition: Cu 15g / liter, Co 8g / liter, Ni 8g / liter

pH: 1~3

Temperature: 40 ° C

(The first stage)

Current density (D _k ): 45A/dm ²

Time: 0.6 seconds

(second stage)

Current density (D _k ): 30A/dm ²

Time: 0.8 seconds

Next, at least one or more types of heat treatment, rust prevention treatment, chromate treatment, and decane coupling treatment selected from the following are sequentially performed. The surface was washed with water before each treatment.

‧ Heat-resistant treatment (formation of heat-resistant layer)

Liquid composition: Co 1~8g/L, Ni 10~20g/L

pH: 2~3

Temperature: 40 ° C

Current density (D _k ): 5A/dm ²

Time: 1.0 seconds

‧Anti-rust treatment (formation of anti-rust layer)

Liquid composition: Ni 15~30g/L, Zn 1~10g/L

pH: 2~4

Temperature: 40 ° C

Current density (D _k ): 5A/dm ²

Time: 1.0 seconds

‧ electrolytic chromate treatment (formation of chromate treatment layer)

Liquid composition: K ₂ Cr ₂ O ₇ : 1~10g / liter, Zn: 0 ~ 5g / liter

pH: 2~4

Temperature: 40 ° C

Current density (D _k ): 1A/dm ²

Time: 1.0 seconds

‧ decane coupling treatment (formation of decane coupling treatment layer)

After the decane coupling agent is applied by spraying a 1.0% by volume aqueous solution of 3-glycidoxypropyltrimethoxydecane on the treated surface, the solution is applied in an environment of 70° C. or higher and 200° C. or lower for 2 seconds or more. Dry to remove moisture from the surface.

‧Resin layer (Examples 13, 14, 15)

The coating of the resin layer was applied to the side surface of the ultra-thin copper layer by a gravure coating method, and then the thickness of the resin coating film was adjusted to 10 μm using a doctor blade, and the solvent was volatilized in a dry environment at 200 ° C. The resin component is hardened. Further, an epoxy resin (bisphenol A type epoxy resin manufactured by DIC Corporation) was used as the resin to be used.

Further, in Example 16, the surface of the carrier opposite to the side of the ultra-thin copper layer was subjected to the above-described roughening treatment (Cu-W alloy plating), heat-resistant layer, rust-preventing layer, chromate-treated layer, and decane. The surface treatment of the coupling treatment layer.

- Heat treatment -

Next, each of the carrier-attached copper foils was subjected to heat treatment as follows: heat treatment was carried out under the conditions of the conditions described in Tables 2 to 4 in a nitrogen atmosphere having a purity of 99.9% or more. The temperature increase rate in Tables 2 to 4 is the temperature increase rate up to the temperature (heating temperature) described in the first heat treatment condition. The cooling time until the normal temperature after the heat treatment is 1 to 6 hours.

Further, in the examples 1 to 16, the heat-treated treatment was carried out in a state in which the copper foil with a carrier was taken up in a hollow tube (outer diameter: 11 cm, thickness: 0.5 cm) made of stainless steel.

Further, in Examples 1 to 16, the tensions when the hollow tubes were wound were set to the settings described in Tables 2 to 4, and heat treatment was performed.

Further, the rotation speed of the hollow tube was set to the settings described in Tables 2 to 4, and heat treatment was performed.

2. Evaluation of carrier copper foil

The copper foil with respect to the examples 1 to 16 obtained in the above manner was subjected to the following evaluation tests before and after the heat treatment. The evaluation results are shown in Tables 2 to 4. In addition, in the description of the number of the experimental examples after the heating in Tables 2 to 4, for example, "Example 1-1" to "Example 1-50" indicate that "Example 1" which is a sample before heating is heated. After the sample.

- Evaluation of wettability of etching solution -

Place the copper foil with a carrier on the surface of the ultra-thin copper foil on the upper surface in the above manner (except for the resin layer), and add 30 μL of sulfuric acid to a portion by using a pipette to absorb 24% by weight of sulfuric acid. An etching solution having a composition of 15% by weight of hydrogen (the remainder being water) was left for 30 seconds and then the etching solution was wiped off. Since the sulfuric acid-hydrogen peroxide-based etching liquid dissolves the surface of the surface treatment layer and the extremely thin copper layer of the base thereof, it can be judged that if the trace of the liquid droplet is close to a perfect circle, the etching liquid near the surface The wettability is uniform, and if it is elliptical, it is uneven. Further, the larger the maximum diameter of the trace of the droplet, the better the wetting of the etching liquid, and the removability by the etching solution is good.

‧ Wetting uniformity

Here, the maximum diameter and the minimum diameter of the trace of the droplet are measured. If the difference between the maximum diameter and the minimum diameter is 10 mm or less, it is evaluated that the wettability of the etching liquid is very uniform (Table 2 to 4: Wetting uniformity column) "○"), if it is 5 mm or less, it is evaluated to be even more uniform (Tables 2 to 4: Wet uniformity column "◎"). Further, in the case where the difference between the maximum diameter and the minimum diameter of the trace of the liquid droplet is larger than 10 mm, it is evaluated that the wettability of the etching liquid is not uniform enough (Tables 2 to 4: "X" in the column of wettability uniformity). Here, the "wet uniformity maximum-minimum" of Tables 2 to 4 is calculated by "the maximum diameter (mm) of the trace of the droplet - the minimum diameter (mm) of the trace of the droplet".

‧ wettability

When the maximum diameter of the trace of the liquid droplet is measured, if the maximum diameter is 25 mm or more, it is evaluated that the wettability of the etching liquid is good enough (Tables 2 to 4: column of wettability "○"), and if it is 35 mm or more, it is evaluated as More preferably, it is good (Tables 2 to 4: column of wettability "◎"). Further, in the case where the maximum diameter was less than 25 mm, it was evaluated that the wettability of the etching liquid was insufficient (Tables 2 to 4: "X" in the column of wettability). Here, the "waste maximum diameter" in Tables 2 to 4 is "the maximum diameter (mm) of the trace of the droplet".

Furthermore, in the evaluation of "wet uniformity" and "wetability" described above, the minimum diameter of the circle surrounding the trace of the droplet is referred to as "the maximum diameter of the trace of the droplet", and the droplet is The maximum diameter of the circle contained in the trace is set to "the minimum diameter of the trace of the droplet".

- Evaluation of tensile strength of the carrier -

The tensile strength of the carrier measured at room temperature after the heat treatment step was measured in the following manner.

First, the carrier was peeled off from the obtained carrier copper foil. Next, the tensile strength (tensile strength) of the carrier was determined by a tensile test in accordance with JIS Z 2241.

- Evaluation of circuit straight line (circuit formation) -

The extremely thin copper foil side of the copper foil with a carrier is attached to the bis-s-butylene diimide by thermocompression bonding After the resin prepreg, the carrier was peeled off and removed, and then a pattern copper plating layer having a width of 21 μm was formed on the surface of the exposed ultra-thin copper layer in an L/S=21 μm/9 μm (very thin copper layer and pattern copper plating) The thickness of the layer was 16.5 μm in total. Further, the pattern copper plating layer was quickly etched by the following etching conditions until a copper plating layer having a width of 12 to 15 μm at the upper end of the circuit was formed to form a circuit. Next, as shown in FIG. 5, the difference (μm) between the maximum value and the minimum value of the width of the lower end of the circuit observed from the upper surface of the circuit was measured, and the average value obtained by measuring five parts was obtained. When the difference between the maximum value and the minimum value was 2 μm or less, it was judged to have good circuit linearity, and it was evaluated as ◎. Further, when the difference between the maximum value and the minimum value exceeds 2 μm and is 4 μm or less, it is evaluated as ○. Further, when the difference between the maximum value and the minimum value exceeds 4 μm, it is evaluated as ×.

(etching conditions)

‧ etching form: spray etching

‧Nozzle: solid conical

‧ spray pressure: 0.10MPa

‧ etching solution temperature: 30 ° C

‧ etching solution composition:

H ₂ O ₂ 18g/L

H ₂ SO ₄ 92g/L

Cu 8g/L

Additive: FE-830IIW3C manufactured by JCU Co., Ltd.

- observation of wrinkles -

The surface of the ultra-thin copper layer after the heat treatment of each experimental example was visually observed to have wrinkles in the range of 5 m in length. When the number of the wrinkles having a length of 10 cm or more was zero, it was evaluated as ◎, and when it was one site, it was evaluated as ○, when it was two sites, it was evaluated as Δ, and when it was three sites or more, it was evaluated as ×.

- Degree of oxidation -

For each experimental example, after the heat treatment, one roll was wound up, and the sample of the second roll having a length of 1 m was visually observed. In this case, the area of discoloration caused by oxidation was 5% or less, and the area of discoloration due to oxidation was more than 5%, and when it was 10% or less, it was evaluated as ○○, and the area of discoloration caused by oxidation was more than 10% and at 15 % or less was evaluated as ○, the area of discoloration caused by oxidation was more than 15%, and when it was 20% or less, it was evaluated as Δ, and the area of discoloration caused by oxidation was more than 20%, and it was evaluated as ×.

The test conditions and evaluation results are shown in Tables 1 to 4.

(Evaluation results)

Examples 1-1 to 1-4, 2-1 to 2-3, 3-5 to 3-13, and 4-1 to 16-1 have good circuit linearity (circuit formation). . In Examples 1 to 4, Examples 7 to 10, and Examples 14 to 16, it was found that although the circuit linearity (circuit formation property) was poor before the heat treatment, the circuit linearity (circuitry) was performed by appropriate heat treatment. Formative) was improved.

Further, regarding Examples 1-1 to 1-48, Examples 2-1 to 2-6, Examples 3-5 to 3-13, Examples 4-1 to 8-1, and Examples 11-1 and Examples 16-1, the wettability of the etching solution is also good.

In Example 1-49, the temperature of the heat treatment was low, and the circuit linearity (circuit formation property) was poor.

In Example 1-50, the heat treatment time was short, and the circuit linearity (circuit formation property) was poor.

In Example 2-4, the heat treatment time was long, and the crystal grain coarsening caused the circuit linearity (circuit formation property) to become poor.

In Examples 2-5 and 2-6, the temperature of the heat treatment was high, and the crystal grain was coarsened, which caused the circuit linearity (circuit formation property) to be poor.

In Examples 3-1 to 3-4, the heating rate of the heat treatment was small, and the circuit linearity (circuit formation property) was poor.

Claims (45)

A method for producing a copper foil with a carrier comprising the step of heat-treating a carrier-attached copper foil having a carrier, an intermediate layer, an ultra-thin copper layer, and a surface treatment layer containing a decane coupling treatment layer in this order for 1 hour. 8 hours heating temperature is 100 ° C ~ 220 ° C heating treatment, or 1 hour ~ 6 hours heating temperature is 100 ° C ~ 220 ° C heating treatment, or 2 hours ~ 4 hours heating temperature is 160 ° C ~ 220 ° C Heat treatment; after the above heat treatment step, the tensile strength of the carrier measured at room temperature is 300 MPa or more. A method for producing a copper foil with a carrier, comprising a heat treatment step of providing a carrier copper foil having a carrier, an intermediate layer, an ultra-thin copper layer, and a surface treatment layer in sequence, and setting a temperature increase rate up to a heating temperature More than 50 ° C / hour, 1 hour ~ 8 hours of heating temperature of 100 ° C ~ 220 ° C heat treatment, or 1 hour ~ 6 hours of heating temperature of 100 ° C ~ 220 ° C heat treatment, or 2 hours ~ 4 hours The heating temperature is 160 ° C to 220 ° C heat treatment. The method for producing a copper foil with a carrier according to the second aspect of the invention, wherein the temperature increase rate in the heat treatment is 200 ° C /hr or less. The method for producing a copper foil with a carrier according to the second aspect of the invention, wherein the tensile strength of the carrier measured at room temperature after the heat treatment step is 300 MPa or more. The method for producing a copper foil with a carrier according to the third aspect of the invention, wherein the tensile strength of the carrier measured at room temperature after the heat treatment step is 300 MPa or more. The method for producing a copper foil with a carrier according to any one of claims 1 to 5, wherein in the heat treatment step, heat treatment is performed in an inert gas atmosphere. The method for producing a copper foil with a carrier according to any one of claims 1 to 5, wherein in the heat treatment step, the copper foil with a carrier is wound into a hollow tube made of metal. Heat treatment in the state. The method for producing a copper foil with a carrier according to the seventh aspect of the invention, wherein in the heat treatment step, the tension when the copper foil with a carrier is wound into a hollow tube made of metal is set to 5 to 100 kgf/ m or 20~100kgf/m for heat treatment. The method for producing a copper foil with a carrier according to the seventh aspect of the invention, wherein in the heat treatment step, the copper foil with a carrier is wound into a hollow tube made of metal, and 0.01 to 600 is used. The hollow tube was rotated at a rotation/hour speed while being subjected to heat treatment. The method for producing a copper foil with a carrier according to the eighth aspect of the invention, wherein in the heat treatment step, the copper foil with a carrier is wound into a hollow tube made of metal, and 0.01 to 600 is used. The hollow tube was rotated at a rotation/hour speed while being subjected to heat treatment. The method for producing a copper foil with a carrier according to any one of claims 1 to 5, wherein the copper foil with a carrier before the heat treatment further has an intermediate layer and an extremely thin copper layer on the surface of the carrier side. . The method for producing a copper foil with a carrier according to any one of claims 1 to 5, wherein the copper foil with a carrier before the heat treatment further has a surface treatment layer on the surface of the carrier side. The method for producing a copper foil with a carrier according to any one of claims 1 to 5, wherein the surface treatment layer comprises a roughened layer. The method for producing a copper foil with a carrier according to claim 13 , wherein the surface of the surface treatment layer is further provided with a surface selected from the group consisting of a heat resistant layer, a rustproof layer, a chromate layer and a decane coupling treatment. One or more layers of the group formed by the layers. A method for producing a copper foil with a carrier according to any one of claims 1 to 5, wherein The copper foil with a carrier before the heat treatment has a surface selected from the group consisting of a roughened layer, a heat-resistant layer, a rust-proof layer, a chromate-treated layer, and a decane coupling treatment layer on the surface of the ultra-thin copper layer. More than one layer is used as the surface treatment layer. The method for producing a copper foil with a carrier according to any one of claims 1 to 5, wherein the copper foil with a carrier before the heat treatment has a resin layer on the surface treatment layer. A copper-clad laminate produced by the method of producing a copper foil with a carrier according to any one of claims 1 to 16 of the invention. A method of producing a printed wiring board using the copper foil with a carrier obtained by the method for producing a copper foil with a carrier according to any one of claims 1 to 16. A method of manufacturing a printed wiring board, comprising the steps of: preparing a copper foil with a carrier and an insulating substrate prepared by the method for producing a copper foil with a carrier according to any one of claims 1 to 16; a carrier copper foil and an insulating substrate are laminated; and after the carrier-attached copper foil and the insulating substrate are laminated, the copper-clad laminate is formed by peeling off the carrier of the carrier-attached copper foil, and then, by a half-addition A method of forming a circuit by any one of a method, a subtractive method, a partial addition method, or a modified semi-additive method (Modified Semi Additive). A method of manufacturing a printed wiring board, comprising the step of: forming the ultra-thin copper layer of a copper foil with a carrier prepared by the method for producing a copper foil with a carrier according to any one of claims 1 to 16 Forming a circuit on the side surface or the side surface of the carrier; forming a resin layer on the side surface of the ultra-thin copper layer of the copper foil with a carrier or the side surface of the carrier in such a manner as to embed the above-mentioned circuit; Forming a circuit on the resin layer; after forming a circuit on the resin layer, peeling off the carrier or the ultra-thin copper layer; and after peeling off the carrier, removing the ultra-thin copper layer or the carrier, thereby forming the above An electric circuit buried in the resin layer is exposed on the side surface of the ultra-thin copper layer or the side surface of the carrier. A method of manufacturing an electronic device using the printed wiring board produced by the method for producing a printed wiring board according to any one of claims 18 to 20. A copper foil with a carrier produced by the method for producing a copper foil with a carrier according to any one of claims 1 to 16. A copper foil with a carrier, which is provided with a carrier, an intermediate layer, an ultra-thin copper layer, and a surface treatment layer containing a decane coupling treatment layer, and is placed on the surface of the surface of the ultra-thin copper foil on the horizontal surface. Carrier copper foil (except for those having a resin layer), using a pipette to add 30 μL of an etching solution having a composition of 24% by weight of sulfuric acid and 15% by weight of hydrogen peroxide (the remainder being water) was placed in one portion, and left for 30 seconds. After the etching solution is wiped off, the difference between the maximum diameter and the minimum diameter of the trace of the etching liquid is 10 mm or less. The copper foil with carrier of claim 23, which is provided with a carrier, an intermediate layer, an ultra-thin copper layer, a surface treatment layer containing a decane coupling treatment layer, and a surface treatment layer having a very thin copper foil side on a horizontal surface. In the above manner, the carrier-attached copper foil (except for the resin layer) was placed, and 30 μL of a composition having 24% by weight of sulfuric acid and 15% by weight of hydrogen peroxide (the remainder being water) was added dropwise at one site using a pipette. After the etching solution was left for 30 seconds, the etching liquid was wiped off, and the maximum diameter of the trace of the etching liquid was 25 mm or more. A copper foil with carrier, which is provided with a carrier, an intermediate layer, an ultra-thin copper layer, and a surface treatment layer containing a decane coupling treatment layer, and a surface treatment layer on the surface of the ultra-thin copper foil on the horizontal surface To place the carrier-attached copper foil (except for the resin layer), and use a pipette to add 30 μL of an etching solution having a composition of 24% by weight of sulfuric acid to 15% by weight of hydrogen peroxide (the remainder being water). After the etching liquid is wiped off after being left for 30 seconds, the maximum diameter of the trace of the etching liquid is 25 mm or more. A carrier-attached copper foil, which is provided with a carrier, an intermediate layer, an ultra-thin copper layer, and a surface treatment layer in this order, and is provided with a carrier copper foil on the surface of the surface of the ultra-thin copper foil side on the horizontal surface (except for having In addition to the resin layer, 30 μL of an etching solution having a composition of 24% by weight of sulfuric acid and 15% by weight of hydrogen peroxide (the remainder being water) was added dropwise at one portion using a pipette, and after leaving the etching solution for 30 seconds, the etching liquid was wiped off. The difference between the maximum diameter and the minimum diameter of the trace of the etching liquid is 10 mm or less. The copper foil with carrier of claim 26, which is provided with a carrier, an intermediate layer, an ultra-thin copper layer and a surface treatment layer, and is placed on the surface of the surface of the ultra-thin copper foil on the horizontal surface. With a carrier copper foil (except for those having a resin layer), 30 μL of an etching solution having a composition of 24% by weight of sulfuric acid and 15% by weight of hydrogen peroxide (the remainder being water) was added dropwise to one portion using a pipette, and left for 30 seconds. After the etching liquid is wiped off, the maximum diameter of the trace of the etching liquid is 25 mm or more. A carrier-attached copper foil, which is provided with a carrier, an intermediate layer, an ultra-thin copper layer, and a surface treatment layer in this order, and is provided with a carrier copper foil on the surface of the surface of the ultra-thin copper foil side on the horizontal surface (except for having In addition to the resin layer, 30 μL of an etching solution having a composition of 24% by weight of sulfuric acid and 15% by weight of hydrogen peroxide (the remainder being water) was added dropwise at one portion using a pipette, and after leaving the etching solution for 30 seconds, the etching liquid was wiped off. The maximum diameter of the trace of the etching liquid is 25 mm or more. The carrier copper foil according to any one of claims 23 to 28, wherein The difference between the maximum diameter and the minimum diameter of the trace of the etching liquid is 5 mm or less. The carrier-attached copper foil according to any one of claims 23 to 28, wherein the trace of the etching liquid has a maximum diameter of 35 mm or more. The carrier copper foil according to claim 29, wherein the trace of the etching liquid has a maximum diameter of 35 mm or more. A laminate which is obtained by using the carrier copper foil of any one of claims 22 to 31. A laminated body comprising the copper foil with a carrier and a resin according to any one of claims 22 to 31, wherein one or all of the end faces of the copper foil with the carrier are covered with the resin. A laminated body in which a copper foil with a carrier of any one of claims 22 to 31 is laminated from the side of the carrier or the surface of the surface treatment layer to any of the 22nd to 31st patents of another patent application. The carrier side of the carrier copper foil is formed on the side of the carrier or the side of the surface treatment layer. The laminate according to claim 34, wherein the carrier side surface of the one of the carrier-attached copper foils or the surface treatment layer side surface and the carrier side surface of the other carrier copper foil or the surface treatment layer side The surface is formed by directly laminating via an adhesive as needed. The laminate according to claim 34, wherein the carrier or the surface treatment layer of the one of the copper foils with a carrier is bonded to the carrier or the surface treatment layer of the other copper foil with a carrier. The laminate according to claim 35, wherein the carrier or the surface treatment layer of the one of the carrier-attached copper foil is bonded to the carrier or the surface treatment layer of the other copper foil with a carrier. The laminate of any one of claims 32 to 37, wherein the laminate One or all of the end faces of the body are covered with resin. A printed wiring board manufactured by using the carrier-attached copper foil according to any one of claims 22 to 31. An electronic device manufactured by using a printed wiring board of the 39th patent application. A method of manufacturing a printed wiring board, comprising the steps of: preparing a carrier copper foil and an insulating substrate according to any one of claims 22 to 31; laminating the copper foil with the carrier and the insulating substrate; After laminating the carrier copper foil and the insulating substrate, the copper-clad laminate is formed by the step of peeling off the carrier with the carrier copper foil, and thereafter, by semi-additive method, subtractive method, partial addition method or modified half Any of the methods of addition forms a circuit. A manufacturing method of a printed wiring board, comprising the steps of: forming an electric circuit on the side surface of the ultra-thin copper layer or the side surface of the carrier side of the copper foil with a carrier of any one of claims 22 to 31; a method of forming a resin layer on the surface of the ultra-thin copper layer side of the copper foil with a carrier or the side surface of the carrier; after forming the resin layer, peeling off the carrier or the ultra-thin copper layer; and peeling off the carrier or the above After the ultra-thin copper layer is removed, the ultra-thin copper layer or the carrier is removed, whereby the circuit buried on the surface of the ultra-thin copper layer or the side surface of the carrier is exposed. A method of manufacturing a printed wiring board, comprising the steps of: The above-mentioned ultra-thin copper layer side surface or the carrier-side surface of the carrier-attached copper foil according to any one of claims 22 to 31, wherein an electric circuit is formed on the above-mentioned carrier copper foil in such a manner as to embed the above-mentioned circuit; a copper layer side surface or the carrier side surface forming a resin layer; forming a circuit on the resin layer; after forming a circuit on the resin layer, peeling off the carrier or the ultra-thin copper layer; and peeling off the carrier or the ultra-thin copper After the layer, the ultra-thin copper layer or the carrier is removed, whereby the circuit buried on the surface of the ultra-thin copper layer or the side surface of the carrier is exposed to the resin layer. A manufacturing method of a printed wiring board, comprising the steps of: laminating the ultra-thin copper layer side surface or the carrier side surface of the copper foil with a carrier of any one of claims 22 to 31 with a resin substrate; a resin layer and a circuit layer are provided at least once on the surface of the ultra-thin copper layer side opposite to the side on which the resin substrate is laminated with the carrier copper foil or the carrier side surface; and the resin layer and the circuit are formed After the two layers, the carrier or the ultra-thin copper layer is peeled off from the copper foil with a carrier. A method of manufacturing a printed wiring board, comprising the steps of: laminating the carrier side surface of the copper foil with a carrier of any one of claims 22 to 31 with a resin substrate; The surface of the ultra-thin copper layer on the side opposite to the resin substrate is provided with at least one resin layer and two layers of the circuit; and after the two layers of the resin layer and the circuit are formed, the pole is peeled off from the copper foil with the carrier thin Copper layer.