WO2014051123A1 - Copper foil provided with carrier, and copper-clad laminate using said copper foil provided with carrier - Google Patents
Copper foil provided with carrier, and copper-clad laminate using said copper foil provided with carrier Download PDFInfo
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- WO2014051123A1 WO2014051123A1 PCT/JP2013/076429 JP2013076429W WO2014051123A1 WO 2014051123 A1 WO2014051123 A1 WO 2014051123A1 JP 2013076429 W JP2013076429 W JP 2013076429W WO 2014051123 A1 WO2014051123 A1 WO 2014051123A1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
- C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/389—Improvement of the adhesion between the insulating substrate and the metal by the use of a coupling agent, e.g. silane
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/46—Manufacturing multilayer circuits
- H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
- H05K3/4652—Adding a circuit layer by laminating a metal foil or a preformed metal foil pattern
Definitions
- the present invention relates to a copper foil with a carrier. More specifically, the present invention relates to a carrier-attached copper foil used as a material for printed wiring boards and shield materials.
- Copper and copper alloy foils have greatly contributed to the development of electrical and electronic industries, and are indispensable particularly as printed circuit materials.
- Copper foils for printed circuits are generally laminated and bonded to substrates such as synthetic resin boards and polyimide films via adhesives, or without using adhesives at high temperature and high pressure, or by applying polyimide precursors.
- the necessary circuit is printed through a resist coating and exposure process, and then an etching process is performed to remove unnecessary portions. Is done. Finally, the required elements are soldered to form various printed circuit boards for the electronic device.
- the copper foil for printed circuit boards differs in the surface (roughening surface) adhere
- the requirements for the roughened surface formed on the copper foil are as follows: 1) No oxidation discoloration during storage, 2) High peel strength with substrate, high temperature heating, wet processing, soldering, chemicals It is sufficient even after treatment or the like, and 3) that there is no so-called lamination stain that occurs after lamination with the substrate and etching.
- the roughening treatment of the copper foil plays a major role as determining the adhesiveness between the copper foil and the base material.
- a copper roughening treatment in which electrodeposition of copper was initially employed was adopted, but various techniques were proposed thereafter, and copper--for the purpose of improving the heat-resistant peel strength, hydrochloric acid resistance and oxidation resistance.
- Nickel roughening is established as one typical processing method.
- Tsujimoto has proposed a copper-nickel roughening treatment (see Patent Document 1) and has achieved results.
- the surface of the copper-nickel treatment is black, and particularly in the rolled foil for flexible substrates, this copper-nickel treatment black has been recognized as a symbol as a product.
- the copper-nickel roughening treatment is excellent in heat-resistant peel strength, oxidation resistance, and hydrochloric acid resistance, it is difficult to etch with an alkaline etchant that has recently become important as a fine pattern treatment, and has a pitch of 150 ⁇ m.
- an alkaline etchant that has recently become important as a fine pattern treatment, and has a pitch of 150 ⁇ m.
- the processing layer becomes an etching residue. Therefore, the present applicant has previously developed a Cu—Co treatment (see Patent Documents 2 and 3) and a Cu—Co—Ni treatment (see Patent Document 4) as fine pattern treatments.
- the present applicant forms a cobalt plating layer or a cobalt-nickel alloy plating layer on the surface of the copper foil and then forms a cobalt plating layer or a cobalt-nickel alloy plating layer.
- it has many of the above-mentioned general characteristics, and in particular has the above-mentioned characteristics comparable to the Cu-Ni treatment, and does not decrease the heat-resistant peel strength when an acrylic adhesive is used.
- the present inventors have succeeded in developing a copper foil treatment method having excellent oxidation resistance and a black surface color (see Patent Document 5).
- a cobalt-nickel alloy plating layer is formed on the surface of the copper foil referred to in Patent Document 6 after a roughening process by copper-cobalt-nickel alloy plating.
- the surface etching solution erodes the interface between the copper foil circuit and the substrate resin, and the copper foil circuit and the substrate resin. This causes a problem that an electric circuit failure occurs as an FPC characteristic, and it is required to solve this problem.
- the applicant of the present application disclosed a roughening treatment layer by copper-cobalt-nickel alloy plating on the surface of a copper foil, a cobalt-nickel alloy plating layer formed on the roughening treatment layer, and the cobalt- In the copper foil for printed circuits in which a zinc-nickel alloy plating layer is formed on the nickel alloy plating layer, a technique has been proposed in which the total amount of zinc-nickel alloy plating layer, the amount of nickel, and the ratio of nickel are predetermined.
- Ni can be contained not only in the zinc-nickel alloy layer but also in the roughened layer, heat-resistant layer, and weather-resistant layer.
- Zn can be contained not only in the zinc-nickel alloy layer but also in the weather resistant layer and the rust preventive layer, the total Zn content in all of the weather resistant layer and the rust preventive layer is further compared with the above total Ni content. It turns out that the ratio needs to be considered.
- a printed wiring board is generally manufactured through a process of forming a copper-clad laminate by bonding an insulating substrate to a copper foil and then forming a conductor pattern on the copper foil surface by etching.
- higher density mounting of components and higher frequency of signals have progressed, and conductor patterns have become finer (fine pitch) and higher frequency than printed circuit boards. Response is required.
- the peel strength between the ultrathin copper layer and the resin substrate is mainly sufficient, and the peel strength Is required to be sufficiently retained after high-temperature heating, wet processing, soldering, chemical processing, and the like.
- a method of increasing the peel strength between the ultrathin copper layer and the resin base material generally, a large amount of roughened particles are adhered on the ultrathin copper layer having a large surface profile (unevenness, roughness). The method is representative.
- JP-A-52-145769 Japanese Patent Publication No.63-2158 JP-A-2-292895 JP-A-2-292894 Japanese Patent Publication No. 6-54831 Japanese Patent Publication No. 9-87889 WO2009 / 041292 WO2004 / 005588
- the present invention relates to a carrier-attached copper foil and a copper-clad laminate, and in particular, after a roughening treatment is formed on the surface of the copper foil, a heat-resistant layer, a weather-resistant layer, and a rust-proof layer are formed thereon, and then a silane cup
- copper-clad laminates using ring-treated copper foil with carrier when the substrate is subjected to acid treatment or chemical etching after fine pattern printed circuit formation, the acid to the interface between the copper foil circuit and the substrate resin
- copper foil with a carrier which can improve the suppression of the adhesive fall by "dipping" of this, is excellent in acid-proof adhesion strength, and was excellent in alkali etching property.
- the miniaturization and high integration of semiconductor devices have further advanced, and the processing performed in the manufacturing process of these printed circuits has become more severe. It is an object of the present invention to provide a technique that meets these requirements.
- the total Zn amount in the surface treatment layer / (total Zn amount + total Ni amount) is 0.02 or more and 0.23 or less, and the total Ni amount in the surface treatment layer is 1150 ⁇ g / dm 2 or less.
- the total amount of Co in the surface treatment layer is 770 to 3200 ⁇ g / dm 2 , and the total Co amount / (total Zn amount + total Ni amount) is 3.4 or less.
- the copper foil with a carrier as described in any one of 1). 6) Any one of 1) to 5) above, wherein the total amount of Co in the surface treatment layer is 770 to 2500 ⁇ g / dm 2 and total Co / (total Zn + total Ni) is 3.0 or less.
- the present application also provides the following invention. 8)
- the copper foil with a carrier according to any one of 1) to 9), wherein the roughened layer comprises fine particles having an average particle diameter of 0.05 to 0.60 ⁇ m.
- the roughening layer is composed of a primary particle layer having an average particle diameter of 0.25 to 0.45 ⁇ m and a secondary particle layer having an average particle diameter of 0.05 to 0.25 ⁇ m formed thereon.
- the roughening layer comprises a primary particle layer of Cu having an average particle diameter of 0.25 to 0.45 ⁇ m, and Cu, Co, Ni having an average particle diameter of 0.05 to 0.25 ⁇ m formed thereon.
- a copper foil for a printed circuit comprising the ultrathin copper layer of the copper foil with a carrier according to any one of 1) to 13) above.
- a copper-clad laminate obtained by laminating and bonding a printed circuit copper foil according to 14) above to a resin substrate.
- the present invention relates to a copper foil for a printed circuit and a copper foil with a carrier for a copper-clad laminate, and in particular, the ultra-thin copper foil with a carrier in which a carrier, an intermediate layer, and an ultra-thin copper layer are laminated in this order.
- the present invention relates to a copper foil with a carrier, which has excellent acid-resistant adhesion strength and excellent alkali etching properties.
- FIG. 1 is an explanatory view showing a state in which an etching solution is eroded from the periphery of a copper foil circuit when surface etching is performed using a solution of hydrogen peroxide and sulfuric acid.
- FIG. 2 shows the result of observing “soaking” of the etchant into the interface between the copper foil circuit and the substrate resin when the substrate is subjected to surface etching (by a solution of hydrogen peroxide and sulfuric acid) after the fine pattern printed circuit is formed.
- FIG. The upper diagram (photo) shows no “stain”, and the lower diagram (photo) shows “stain”.
- FIG. 3 shows a copper foil with carrier (A) having an ultrathin copper layer having a roughened layer formed on the surface, a resist is applied on the roughened layer of the ultrathin copper layer, and exposure and development are performed.
- FIG. 4B is an explanatory view for explaining that a resist plating is formed by etching a resist into a predetermined shape (B) and then forming a circuit plating having a predetermined shape by removing the resist (C).
- FIG. 4 shows that an embedded resin is provided on an ultrathin copper layer so as to cover circuit plating, and a resin layer is laminated, and then another carrier-attached copper foil (second layer) is adhered from the ultrathin copper layer side ( D)
- D Explanatory drawing explaining peeling a carrier from the copper foil with a carrier of the second layer (E), performing laser drilling at a predetermined position of the resin layer, exposing circuit plating, and forming a blind via (F) It is.
- FIG. 5 illustrates that copper is embedded in a blind via to form a via fill (G), circuit plating is formed on the via fill (H), and the carrier is peeled from the first layer of copper foil with carrier (I). It is explanatory drawing.
- FIG. 5 illustrates that copper is embedded in a blind via to form a via fill (G), circuit plating is formed on the via fill (H), and the carrier is peeled from the first layer of copper foil with carrier (I). It is explanatory drawing.
- the main object of the present invention is to prevent circuit erosion that occurs during surface etching in the pretreatment process in the manufacturing process of the FPC multilayer substrate.
- the copper foil with a carrier of the present invention is a roughened layer formed by subjecting a copper foil or a copper alloy foil to a roughening (treat) treatment, and a Ni-- formed on the roughened layer. It has a heat-resistant layer made of a Co layer, and a plurality of surface treatment layers made of a weather-resistant layer containing Zn, Ni, and Cr and a rust-proof layer formed on the heat-resistant layer.
- the total Zn content / (total Zn content + total Ni content) in the surface treatment layer is set to 0.02 or more and 0.35 or less.
- Zn is a component of a weathering layer and a rust prevention layer in the surface treatment layer of copper foil
- Ni is a component of a roughening treatment layer, a heat-resistant layer, and a weathering layer
- Zn and Ni are the surfaces of the copper foil It is an important component as a constituent component of the treatment layer.
- Zn is a component having an effect on weather resistance, but it is an unfavorable component for chemical resistance characteristics in the fine pattern circuit forming process, and “soaking” easily occurs in etching for circuit formation.
- Ni is an effective component for “soaking”, but if it is too much, the alkaline etching property is lowered and it is not suitable for printed circuit.
- the present invention has found that the balance between Zn and Ni is important. That is, the total Zn amount / (total Zn amount + total Ni amount) in the surface treatment layer is 0.02 or more and 0.35 or less. In a preferred embodiment, the total Zn content / (total Zn content + total Ni content) in the surface treatment layer can be 0.02 or more and 0.23 or less, more preferably 0.04 or more and 0.03 or less. 23 or less. If it is less than 0.02, there are cases where Zn is too little and cases where Ni is too much. In cases where Zn is too little, the weather resistance deteriorates. In cases where Ni is too much, etching properties become a problem. Is also not preferred. On the other hand, if it exceeds 0.35, the acid resistance tends to be deteriorated, so that “soaking” tends to occur during etching, which is not preferable.
- the definition of the total amount of Zn is “total amount of Zn contained in the roughened layer, the heat resistant layer, the weather resistant layer, and the rust preventive layer on the copper foil”.
- the total amount of Zn is the sum of the amounts of Zn contained in the two layers of the weather resistant layer and the rust preventive layer.
- the ultrathin copper layer is peeled from the carrier.
- the definition of the total amount of Ni is “the amount of Ni contained in the roughened layer, the heat-resistant layer, the weather-resistant layer, and the rust-proof layer on the copper foil (the ultra-thin copper layer of the copper foil with carrier)”.
- the total amount of Ni is the sum of the amounts of Ni in the roughening treatment layer, the heat resistant layer, and the weather resistant layer.
- the ultrathin copper layer is peeled from the carrier.
- the definition of the Ni adhesion amount at the roughening treatment stage is “the amount of Ni contained in the roughening treatment layer on the copper foil (the ultrathin copper layer of the copper foil with carrier)”.
- the amount of Ni deposited in the roughening treatment stage was the same as that of each example and each comparative example, and after manufacturing a copper foil with a carrier, only the roughening layer was provided under the same conditions as each example and each comparative example. Thereafter, a sample was taken and measured by measuring the Ni adhesion amount in the same manner as the total Ni amount.
- the definition of the total amount of Co is “the amount of Co contained in a roughened layer, a heat-resistant layer, a weather-resistant layer, and a rust-proof layer on a copper foil (an ultra-thin copper layer of a copper foil with a carrier)”.
- the total amount of Co is the total amount of Co in the roughening treatment layer, the heat resistant layer, and the weather resistant layer.
- the ultrathin copper layer is peeled from the carrier.
- the definition of the total Cr amount is “the amount of Cr contained in the roughened layer, the heat-resistant layer, the weather-resistant layer, and the rust-proof layer on the copper foil (ultra-thin copper layer of the copper foil with carrier)”.
- the total Cr amount is the sum of the Cr amounts in the roughened layer and the rust preventive layer.
- the ultrathin copper layer is peeled from the carrier.
- the Ni adhesion amount, the total Ni amount, the total Co amount, the total Cr amount, and the total Zn amount in the roughening treatment stage are the adhesion masses of Ni, Co, Cr, and Zn per unit area (dm 2 ) of the sample, respectively. Displayed in ( ⁇ g).
- the “soaking” is shown in FIG. 1, but when the surface is etched using a solution of hydrogen peroxide and sulfuric acid, or the circuit is formed using an etching solution made of a cupric chloride solution, a ferric chloride solution, or the like.
- This refers to a phenomenon in which an etchant penetrates into the interface between a copper foil and a resin when the formation is etched.
- the left side of FIG. 1 is a conceptual diagram showing a state ( ⁇ portion) in which the circuit surfaces of the resin layer and the copper foil with a surface treatment layer are in close contact with each other.
- the right side of FIG. 1 is a conceptual diagram showing a state ( ⁇ portion) in which permeation occurs on both edges of the circuit and adhesion is slightly reduced.
- FIG. 2 after the fine pattern printed circuit was formed, the “soaking” of the acid into the interface between the copper foil circuit and the substrate resin was observed when the substrate was soft-etched (by a solution of hydrogen peroxide and sulfuric acid).
- the figure (photograph) which shows a result is shown.
- the upper figure (photo) shows the case where there is no stain at the edge of the linear circuit, and the lower figure (photo) shows the case where there is “stain”. It can be observed that the edge of the linear circuit is disturbed.
- Ni is a component contained in the roughened layer, heat resistant layer, weather resistant layer, and rust preventive layer of the surface treatment layer as described above, and is an extremely important component in the surface treatment layer of the ultrathin copper layer. And it is a component effective in "sinking" which is a problem to be solved by the present invention.
- the total Ni content of the surface treatment layer is at 1600 ⁇ g / dm 2 or less, preferably 1150 ⁇ g / dm 2 or less.
- the total amount of Ni in the surface treatment layer is preferably 350 to 1350 ⁇ g / dm 2 , more preferably 450 to 1100 ⁇ g / dm 2 .
- Ni contained in the roughened layer needs to have the surface of the surface-treated copper foil appear black, it may be necessary to contain Ni in an amount of 50 ⁇ g / dm 2 or more. Furthermore, since Ni is also included in the heat-resistant layer and the weather-resistant layer, 350 ⁇ g / dm 2 or more may be necessary as the total Ni amount, and 450 ⁇ g / dm 2 or more may be necessary. However, if the total amount of Ni exceeds 1350 ⁇ g / dm 2 or 1100 ⁇ g / dm 2 , there may occur a problem that the alkali etching property deteriorates or the roughened particles remain on the substrate resin surface during circuit etching. Ni amount may desirable 1350 ⁇ g / dm 2 or less, it can be said that there is a case 1100 ⁇ g / dm 2 or less is more preferable.
- Co is an important component by contributing to heat resistance as a component used for the surface treatment layer of the copper foil, and the amount used is larger than other components. However, it is an unfavorable component for “soaking”. Accordingly, in the copper foil with a surface treatment layer of the present invention, it may be desirable that the total amount of Co in the surface treatment layer is 770 to 3200 ⁇ g / dm 2 . In a preferred embodiment, the total amount of Co in the surface treatment layer can be 770 to 2500 ⁇ g / dm 2 , more preferably 940 to 2500 ⁇ g / dm 2 .
- the total amount of Co in the surface treatment layer is particularly preferably 940 ⁇ g / dm 2 or more. Further, the total Co amount / (total Zn amount + total Ni amount) is preferably 3.0 or less. Even if the total Co amount is in the above range, the “penetration” tends to deteriorate when the total Co amount is large relative to the total of the total Zn amount and the total Ni amount as other main components. Because there are cases.
- the total Cr amount in the surface treatment layer is preferably 50 to 120 ⁇ g / dm 2 .
- the total Cr amount within this range has the effect of suppressing the penetration amount similarly.
- the effective Ni for the roughened layer of the copper foil with a surface-treated layer of the present invention is 50 to 550 ⁇ g / dm 2 .
- a roughened layer made of Co, Cu, or Ni is effective.
- the roughening treatment layer is preferably made of fine particles having an average particle size of 0.05 to 0.60 ⁇ m, and fine particles of a ternary alloy composed of Cu, Co, Ni having an average particle size of 0.05 to 0.60 ⁇ m. It can also be an aggregate of particles.
- the fine particles having an average particle diameter of 0.05 to 0.60 ⁇ m can be formed by burn plating (roughening plating treatment) of alloy plating containing copper.
- the roughening treatment layer may be a primary particle layer having an average particle size of 0.25 to 0.45 ⁇ m and a secondary particle layer having an average particle size of 0.05 to 0.25 ⁇ m formed thereon. preferable. Further, for the roughening treatment layer, a primary particle layer of Cu having an average particle diameter of 0.25 to 0.45 ⁇ m, and Cu, Co having an average particle diameter of 0.05 to 0.25 ⁇ m formed thereon, A secondary particle layer made of a ternary alloy made of Ni can be formed.
- the primary particle layer is preferably a copper plating burn plating (roughening plating treatment). Moreover, the said secondary particle layer can be formed by the baking plating (roughening plating process) of the alloy plating containing copper.
- the heat-resistant layer made of the Ni—Co layer, the weather-resistant layer containing Zn, Ni, and Cr, and the rust-preventing layer the following electrolytic plating conditions can be used.
- metal layer plating may be performed between the copper foil and the primary particles before forming the primary particles.
- a copper plating layer and a copper alloy plating layer are typically considered.
- the copper plating layer when using only copper sulfate and an aqueous copper sulfate solution mainly composed of sulfuric acid, sulfuric acid, an organic sulfur compound having a mercapto group, a surfactant such as polyethylene glycol, and a chloride ion The method of forming a copper plating layer by electroplating using the copper sulfate aqueous solution which combined these.
- Liquid composition Co 1 to 20 g / liter, Ni 1 to 20 g / liter pH: 1 to 4 Temperature: 30-60 ° C Current density (D k ): 1 to 20 A / dm 2 Time: 1-5 seconds
- Liquid composition Ni 1-30 g / liter, Zn 1-30 g / liter pH: 2-5 Temperature: 30-50 ° C Current density (D k ): 1 to 3 A / dm 2 Time: 1-5 seconds
- Liquid composition K 2 Cr 2 O 7 : 1 to 10 g / liter, Zn: 0 to 10 g / liter pH: 2 to 5 Temperature: 30-50 ° C Current density (D k ): 0.01 to 5 A / dm 2 Time: 0.01-5 seconds
- the immersion chromate treatment can be performed at a plating current density of 0 A / dm 2 .
- silane coupling treatment A silane coupling treatment for applying a silane coupling agent to at least the roughened surface on the anticorrosive layer is performed.
- the silane coupling agent include olefin silanes, epoxy silanes, acrylic silanes, amino silanes, and mercapto silanes, which can be appropriately selected and used.
- silane coupling agent may be used for the silane coupling agent used for a silane coupling process, for example, using an amino-type silane coupling agent or an epoxy-type silane coupling agent, a mercapto-type silane coupling agent.
- Silane coupling agents include vinyltrimethoxysilane, vinylphenyltrimethoxylane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, 4-glycidylbutyltrimethoxysilane, and ⁇ -aminopropyl.
- Triethoxysilane N- ⁇ (aminoethyl) ⁇ -aminopropyltrimethoxysilane, N-3- (4- (3-aminopropoxy) ptoxy) propyl-3-aminopropyltrimethoxysilane, imidazolesilane, triazinesilane, ⁇ -mercaptopropyltrimethoxysilane or the like may be used.
- the silane coupling treatment layer may be formed using a silane coupling agent such as epoxy silane, amino silane, methacryloxy silane, mercapto silane, or the like.
- a silane coupling agent such as epoxy silane, amino silane, methacryloxy silane, mercapto silane, or the like.
- you may use 2 or more types of such silane coupling agents in mixture.
- it is preferable to form using an amino-type silane coupling agent or an epoxy-type silane coupling agent.
- the amino silane coupling agent referred to here is N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane, 3- Aminopropyltriethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, N- (3 -Acryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, 4-aminobutyltriethoxysilane, (aminoethylaminomethyl) phenethyltrimethoxysilane, N- (2-aminoethyl-3-aminopropyl
- the silane coupling treatment layer is 0.05 mg / m 2 to 200 mg / m 2 , preferably 0.15 mg / m 2 to 20 mg / m 2 , preferably 0.3 mg / m 2 to 2.0 mg in terms of silicon atoms. / M 2 is desirable. In the case of the above-mentioned range, the adhesiveness between the base resin and the surface-treated copper foil can be further improved.
- the cocoon coating method may be any of silane coupling agent solution spraying, coater coating, dipping, pouring and the like. Since these are already known techniques (see, for example, Japanese Patent Publication No. 60-15654), details are omitted.
- the carrier of the copper foil with a carrier of the present invention a foil of copper foil, aluminum foil, aluminum alloy foil or iron alloy, stainless steel, nickel, nickel alloy or the like can be used.
- the carrier is preferably a copper foil.
- the copper foil used for the carrier is typically provided in the form of a rolled copper foil or an electrolytic copper foil.
- the electrolytic copper foil is produced by electrolytically depositing copper on a titanium or stainless steel drum from a copper sulfate plating bath. Moreover, a rolled copper foil is manufactured by repeating plastic working and heat treatment with a rolling roll.
- the copper foil is made of high purity copper such as tough pitch copper (JIS H3100 C1100) or oxygen-free copper (JIS H3100 C1020), for example, copper alloy containing Sn, copper containing Ag, Cr, Zr or Mg. Further, a copper alloy such as a Corson copper alloy to which Ni, Si, or the like is added can also be used. In addition, when the term “copper foil” is used alone in this specification, a copper alloy foil is also included.
- the thickness of the carrier there is no particular limitation on the thickness of the carrier that can be used in the present invention, but it may be appropriately adjusted to a thickness suitable for serving as a carrier, for example, 12 ⁇ m or more. However, if it is too thick, the production cost becomes high, so generally it is preferably 35 ⁇ m or less. Accordingly, the thickness of the carrier is typically 12-70 ⁇ m, more typically 18-35 ⁇ m.
- the intermediate layer is provided on the carrier. Another layer may be provided between the carrier and the intermediate layer.
- the intermediate layer of the carrier-attached copper foil of the present invention is made of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, or an alloy thereof, or a hydrate thereof, or an oxide thereof. Or it is preferable to form in the layer containing any 1 or more types of organic substance.
- the intermediate layer may be a plurality of layers.
- the intermediate layer is a single metal layer made of any one of elements of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn from the carrier side, or Cr, Ni , Co, Fe, Mo, Ti, W, P, Cu, Al, Zn from the carrier side, or Cr, Ni , Co, Fe, Mo, Ti, W, P, Cu, Al, an alloy layer made of one or more elements selected from the element group, and then Cr, Ni, Co, Fe, Mo, Ti, W , P, Cu, Al, Zn A layer composed of a hydrate or oxide of one or more elements selected from the element group.
- the intermediate layer can be composed of two layers of Ni and Cr.
- the Ni layer is laminated in contact with the interface with the copper foil carrier and the Cr layer is in contact with the interface with the ultrathin copper layer.
- Ni deposition amount of Cr in the intermediate layer can be set to 1000 ⁇ 40000 ⁇ g / dm 2.
- the intermediate layer may contain Zn.
- An ultrathin copper layer is provided on the intermediate layer. Before that, strike plating with a copper-phosphorus alloy may be performed to reduce pinholes in the ultrathin copper layer.
- strike plating include a copper pyrophosphate plating solution.
- the ultrathin copper layer of the copper foil with a carrier of the present invention can be formed by electroplating using an electrolytic bath such as copper sulfate, copper pyrophosphate, copper sulfamate, copper cyanide, etc.
- a copper sulfate bath is preferred because it is possible to form a copper foil at a high current density.
- the thickness of the ultrathin copper layer is not particularly limited, but is generally thinner than the carrier, for example, 12 ⁇ m or less. Typically, it is 0.1 to 12 ⁇ m, more typically 0.5 to 12 ⁇ m, and still more typically 2 to 5 ⁇ m.
- a carrier-attached copper foil including a carrier and an intermediate layer laminated on the carrier and an ultrathin copper layer laminated on the intermediate layer is manufactured.
- the method of using the copper foil with carrier itself is well known to those skilled in the art.
- the surface of the ultra-thin copper layer is made of paper base phenol resin, paper base epoxy resin, synthetic fiber cloth base epoxy resin, glass cloth / paper composite. Ultra-thin bonded to an insulating substrate, bonded to an insulating substrate such as a base epoxy resin, glass cloth / glass nonwoven fabric composite epoxy resin and glass cloth base epoxy resin, polyester film, polyimide film, etc.
- the copper layer can be etched into the intended conductor pattern to finally produce a printed wiring board.
- the peeling site is mainly the interface between the carrier and the intermediate layer or the interface between the intermediate layer and the ultrathin copper layer. Further, when the intermediate layer is composed of a plurality of layers, it may be peeled off at the interface between the plurality of layers.
- the copper foil with a carrier of the present invention may include a resin layer on the surface treatment layer.
- the resin layer may be an insulating resin layer. Note that the order of forming the heat-resistant layer, the rust-proofing layer, the chromate-treated layer, and the silane coupling-treated layer is not limited to each other, and in any order on the ultrathin copper layer or the roughened layer. These layers may be formed.
- the resin layer may be an adhesive resin, that is, an adhesive, or may be a semi-cured (B-stage) insulating resin layer for adhesion.
- the semi-cured state (B stage state) is a state in which there is no sticky feeling even if the surface is touched with a finger, the insulating resin layer can be stacked and stored, and a curing reaction occurs when subjected to heat treatment. Including that.
- the resin layer may contain a thermosetting resin or a thermoplastic resin.
- the resin layer may include a thermoplastic resin.
- the resin layer may contain a known resin, resin curing agent, compound, curing accelerator, dielectric, reaction catalyst, crosslinking agent, polymer, prepreg, skeleton material, and the like.
- the resin layer may be, for example, International Publication No. WO2008 / 004399, International Publication No. WO2008 / 053878, International Publication No. WO2009 / 084533, JP-A-11-5828, JP-A-11-140281, Patent 3184485, International Publication. No. WO 97/02728, Japanese Patent No. 3676375, Japanese Patent Application Laid-Open No.
- Japanese Patent No. 3612594 Japanese Patent Application Laid-Open No. 2002-179721, Japanese Patent Application Laid-Open No. 2002-309444, Japanese Patent Application Laid-Open No. 2003-302068, Japanese Patent No. 3992225, Japanese Patent Application Laid-Open No. -249739, Japanese Patent No. 4136509, Japanese Patent Application Laid-Open No. 2004-82687, Japanese Patent No. 4025177, Japanese Patent Application Laid-Open No. 2004-349654, Japanese Patent No. 4286060, Japanese Patent Application Laid-Open No. 2005-262506, Japanese Patent No. 4570070, and Japanese Patent Application Laid-Open No. 4570070. No. 5-53218, Japanese Patent No.
- WO 2008/114858 International Publication Number WO 2009/008471, JP 2011-14727, International Publication Number WO 2009/001850, International Publication Number WO 2009/145179, International Publication Number Nos. WO2011 / 068157 and JP2013-19056 (resins, resin curing agents, compounds, curing accelerators, dielectrics, reaction catalysts, crosslinking agents, polymers, prepregs, skeletal materials, etc.) and / or You may form using the formation method and formation apparatus of a resin layer.
- the type of the resin layer is not particularly limited.
- epoxy resin polyimide resin, polyfunctional cyanate ester compound, maleimide compound, polymaleimide compound, maleimide resin, aromatic maleimide resin , Polyvinyl acetal resin, urethane resin, polyethersulfone (also referred to as polyethersulfone or polyethersulfone), polyethersulfone (also referred to as polyethersulfone or polyethersulfone) resin, aromatic polyamide resin, aromatic Polyamide resin polymer, rubber resin, polyamine, aromatic polyamine, polyamideimide resin, rubber modified epoxy resin, phenoxy resin, carboxyl group-modified acrylonitrile-butadiene resin, polyphenylene oxide, bismaleimide triazine Resins, thermosetting polyphenylene oxide resins, cyanate ester resins, carboxylic acid anhydrides, polyvalent carboxylic acid anhydrides, linear polymers having crosslinkable functional groups, polyphenylene ether resins, 2,2-
- the epoxy resin has two or more epoxy groups in the molecule and can be used without any problem as long as it can be used for electric / electronic materials.
- the epoxy resin is preferably an epoxy resin epoxidized using a compound having two or more glycidyl groups in the molecule.
- bisphenol A type epoxy resin bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, novolac type epoxy resin, cresol novolac type epoxy resin, alicyclic epoxy resin, brominated (brominated) epoxy Resin, phenol novolac type epoxy resin, naphthalene type epoxy resin, brominated bisphenol A type epoxy resin, orthocresol novolac type epoxy resin, rubber modified bisphenol A type epoxy resin, glycidylamine type epoxy resin, triglycidyl isocyanurate, N, N -Glycidyl amine compounds such as diglycidyl aniline, glycidyl ester compounds such as diglycidyl tetrahydrophthalate, phosphorus-containing epoxy resins, biphenyl type epoxy resins, One or two or more types selected from the group of phenyl novolac type epoxy resin, trishydroxyphenylmethane type epoxy resin, tetraphenylethane type epoxy resin can be used, or
- the phosphorus-containing epoxy resin a known epoxy resin containing phosphorus can be used.
- the phosphorus-containing epoxy resin is, for example, an epoxy resin obtained as a derivative from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide having two or more epoxy groups in the molecule. Is preferred.
- the epoxy resin obtained as a derivative from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is converted to 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.
- a compound represented by the following chemical formula 1 (HCA-NQ) or chemical formula 2 (HCA-HQ) an epoxy resin is reacted with the OH group portion to obtain a phosphorus-containing epoxy resin. Is.
- the phosphorus-containing epoxy resin obtained using the above-described compound as a raw material is preferably used by mixing one or two compounds having the structural formula shown in any one of the following chemical formulas 3 to 5. This is because the resin quality in a semi-cured state is excellent in stability, and at the same time, the flame retardant effect is high.
- the brominated (brominated) epoxy resin a known brominated (brominated) epoxy resin can be used.
- the brominated (brominated) epoxy resin is a brominated epoxy resin having the structural formula shown in Chemical Formula 6 obtained as a derivative from tetrabromobisphenol A having two or more epoxy groups in the molecule, Chemical Formula 7 shown below It is preferable to use one or two brominated epoxy resins having the structural formula shown in FIG.
- maleimide resin aromatic maleimide resin, maleimide compound or polymaleimide compound
- known maleimide resins aromatic maleimide resins, maleimide compounds or polymaleimide compounds
- maleimide resin or aromatic maleimide resin or maleimide compound or polymaleimide compound 4,4′-diphenylmethane bismaleimide, polyphenylmethane maleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3′-dimethyl -5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenylsulfone bismaleimide, 1, It is possible to use 3-bis (3-maleimidophenoxy) benzene, 1,3-bis (4-maleimidophenoxy) benzene and a polymer obtained
- the maleimide resin may be an aromatic maleimide resin having two or more maleimide groups in the molecule, and an aromatic maleimide resin having two or more maleimide groups in the molecule and a polyamine or aromatic polyamine. Polymerization adducts obtained by polymerizing and may be used.
- polyamine or aromatic polyamine known polyamines or aromatic polyamines can be used.
- polyamine or aromatic polyamine m-phenylenediamine, p-phenylenediamine, 4,4′-diaminodicyclohexylmethane, 1,4-diaminocyclohexane, 2,6-diaminopyridine, 4,4′-diaminodiphenylmethane, 2,2-bis (4-aminophenyl) propane, 4,4′-diaminodiphenyl ether, 4,4′-diamino-3-methyldiphenyl ether, 4,4′-diaminodiphenyl sulfide, 4,4′-diaminobenzophenone, 4,4'-diaminodiphenylsulfone, bis (4-aminophenyl) phenylamine, m-xylenediamine, p-xylenediamine, 1,3-
- phenoxy resin a known phenoxy resin can be used. Moreover, what is synthesize
- an epoxy resin a well-known epoxy resin and / or the above-mentioned epoxy resin can be used.
- bisphenol known bisphenols can be used, and bisphenol A, bisphenol F, bisphenol S, tetrabromobisphenol A, 4,4′-dihydroxybiphenyl, HCA (9,10-Dihydro-9-Oxa- Bisphenol obtained as an adduct of 10-phosphophenanthrene-10-oxide) and quinones such as hydroquinone and naphthoquinone can be used.
- the linear polymer having a crosslinkable functional group a known linear polymer having a crosslinkable functional group can be used.
- the linear polymer having a crosslinkable functional group preferably has a functional group that contributes to the curing reaction of an epoxy resin such as a hydroxyl group or a carboxyl group.
- the linear polymer having a crosslinkable functional group is preferably soluble in an organic solvent having a boiling point of 50 ° C. to 200 ° C.
- Specific examples of the linear polymer having a functional group mentioned here include polyvinyl acetal resin, phenoxy resin, polyethersulfone resin, polyamideimide resin and the like.
- the resin layer may contain a crosslinking agent.
- a known crosslinking agent can be used as the crosslinking agent.
- a urethane-based resin can be used as the crosslinking agent.
- a known rubber resin can be used as the rubber resin.
- the rubber resin is described as a concept including natural rubber and synthetic rubber.
- the latter synthetic rubber includes styrene-butadiene rubber, butadiene rubber, butyl rubber, ethylene-propylene rubber, acrylonitrile butadiene rubber, acrylic rubber ( Acrylic ester copolymer), polybutadiene rubber, isoprene rubber and the like.
- a synthetic rubber having heat resistance such as nitrile rubber, chloroprene rubber, silicon rubber, urethane rubber or the like.
- a known polyimide amide resin can be used as the polyamide imide resin.
- the polyimide amide resin for example, trimellitic anhydride, benzophenonetetracarboxylic anhydride and vitorylene diisocyanate are heated in a solvent such as N-methyl-2-pyrrolidone and / or N, N-dimethylacetamide.
- trimellitic anhydride, diphenylmethane diisocyanate, and carboxyl group-terminated acrylonitrile-butadiene rubber in a solvent such as N-methyl-2-pyrrolidone and / or N, N-dimethylacetamide. What is obtained can be used.
- the rubber-modified polyamideimide resin a known rubber-modified polyamideimide resin can be used.
- the rubber-modified polyamideimide resin is obtained by reacting a polyamideimide resin and a rubber resin. The reaction of the polyamide-imide resin and the rubber resin is performed for the purpose of improving the flexibility of the polyamide-imide resin itself. That is, the polyamideimide resin and the rubber resin are reacted to replace a part of the acid component (cyclohexanedicarboxylic acid or the like) of the polyamideimide resin with the rubber component.
- a known polyamideimide resin can be used as the polyamideimide resin.
- As the rubber resin a known rubber resin or the aforementioned rubber resin can be used.
- Solvents used for dissolving the polyamideimide resin and the rubbery resin when polymerizing the rubber-modified polyamideimide resin include dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, nitromethane, nitroethane, tetrahydrofuran , Cyclohexanone, methyl ethyl ketone, acetonitrile, ⁇ -butyrolactone and the like are preferably used alone or in combination.
- a known phosphazene resin can be used as the phosphazene resin.
- the phosphazene resin is a resin containing phosphazene having a double bond having phosphorus and nitrogen as constituent elements.
- the phosphazene resin can dramatically improve the flame retardancy due to the synergistic effect of nitrogen and phosphorus in the molecule.
- unlike 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivatives they exist stably in the resin, and an effect of preventing the occurrence of migration can be obtained.
- fluororesin A known fluororesin can be used as the fluororesin.
- fluororesin examples include PTFE (polytetrafluoroethylene (tetrafluoroethylene)), PFA (tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer), FEP (tetrafluoroethylene / hexafluoropropylene copolymer (4.6).
- ETFE tetrafluoroethylene / ethylene copolymer
- PVDF polyvinylidene fluoride (difluoride)
- PCTFE polychlorotrifluoroethylene (trifluoride)
- aromatic A fluororesin composed of at least one thermoplastic resin selected from polysulfide and aromatic polyether and a fluororesin may be used.
- the resin layer may contain a resin curing agent.
- a known resin curing agent can be used as the resin curing agent.
- resin curing agents include amines such as dicyandiamide, imidazoles and aromatic amines, phenols such as bisphenol A and brominated bisphenol A, novolaks such as phenol novolac resins and cresol novolac resins, and acid anhydrides such as phthalic anhydride. Products, biphenyl type phenol resins, phenol aralkyl type phenol resins and the like can be used.
- the resin layer may contain one or more of the aforementioned resin curing agents. These curing agents are particularly effective for epoxy resins.
- a specific example of the biphenyl type phenol resin is shown in Chemical Formula 8.
- imidazoles can be used, such as 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl- 2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5- Hydroxymethylimidazole etc. are mentioned, These can be used individually or in mixture.
- imidazoles having the structural formula shown in Chemical Formula 10 below are preferably used.
- the moisture absorption resistance of the semi-cured resin layer can be remarkably improved, and the long-term storage stability is excellent. This is because imidazoles function as a catalyst during curing of the epoxy resin and contribute as a reaction initiator that causes a self-polymerization reaction of the epoxy resin in the initial stage of the curing reaction.
- amines can be used as the resin curing agent for the amines.
- the amine resin curing agent for example, the above-mentioned polyamines and aromatic polyamines can be used, and aromatic polyamines, polyamides, and these are obtained by polymerizing or condensing with epoxy resins or polyvalent carboxylic acids.
- One or more selected from the group of amine adducts to be used may be used.
- Examples of the resin curing agent for the amines include 4,4′-diaminodiphenylene sulfone, 3,3′-diaminodiphenylene sulfone, 4,4-diaminodiphenylel, 2,2-bis [4 It is preferable to use at least one of-(4-aminophenoxy) phenyl] propane and bis [4- (4-aminophenoxy) phenyl] sulfone.
- the resin layer may contain a curing accelerator.
- a known curing accelerator can be used as the curing accelerator.
- the curing accelerator tertiary amine, imidazole, urea curing accelerator and the like can be used.
- the resin layer may contain a reaction catalyst.
- a known reaction catalyst can be used as the reaction catalyst.
- finely pulverized silica or antimony trioxide can be used as a reaction catalyst.
- the anhydride of the polyvalent carboxylic acid is preferably a component that contributes as a curing agent for the epoxy resin.
- the anhydride of the polyvalent carboxylic acid is phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, tetrahydroxyphthalic anhydride, hexahydroxyphthalic anhydride, methylhexahydroxyphthalic anhydride, nadine. Acid and methyl nadic acid are preferred.
- the thermoplastic resin may be a thermoplastic resin having a functional group other than an alcoholic hydroxyl group polymerizable with an epoxy resin.
- the polyvinyl acetal resin may have a functional group polymerizable with an epoxy resin or a maleimide compound other than an acid group and a hydroxyl group.
- the polyvinyl acetal resin may have a carboxyl group, an amino group or an unsaturated double bond introduced into the molecule.
- the aromatic polyamide resin polymer examples include those obtained by reacting an aromatic polyamide resin and a rubber resin.
- the aromatic polyamide resin is synthesized by condensation polymerization of an aromatic diamine and a dicarboxylic acid.
- the aromatic diamine at this time, 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylsulfone, m-xylenediamine, 3,3′-oxydianiline and the like are used.
- dicarboxylic acid phthalic acid, isophthalic acid, terephthalic acid, fumaric acid or the like is used.
- the rubber resin to be reacted with the aromatic polyamide resin a known rubber resin or the aforementioned rubber resin can be used.
- This aromatic polyamide resin polymer is used for the purpose of not being damaged by under-etching by an etchant when etching a copper foil after being processed into a copper-clad laminate.
- the resin layer is a cured resin layer (the “cured resin layer” means a cured resin layer) and a half in order from the copper foil side (that is, the ultrathin copper layer side of the copper foil with carrier).
- the resin layer which formed the cured resin layer sequentially may be sufficient.
- the cured resin layer may be composed of a resin component of any one of a polyimide resin, a polyamideimide resin, and a composite resin having a thermal expansion coefficient of 0 ppm / ° C. to 25 ppm / ° C.
- a semi-cured resin layer having a coefficient of thermal expansion after curing of 0 ppm / ° C. to 50 ppm / ° C. may be provided on the cured resin layer.
- the thermal expansion coefficient of the entire resin layer after the cured resin layer and the semi-cured resin layer are cured may be 40 ppm / ° C. or less.
- the cured resin layer may have a glass transition temperature of 300 ° C. or higher.
- the semi-cured resin layer may be formed using a maleimide resin or an aromatic maleimide resin.
- the resin composition for forming the semi-cured resin layer preferably contains a maleimide resin, an epoxy resin, and a linear polymer having a crosslinkable functional group.
- epoxy resin a known epoxy resin or an epoxy resin described in this specification can be used.
- maleimide resins aromatic maleimide resins, linear polymers having crosslinkable functional groups, known maleimide resins, aromatic maleimide resins, linear polymers having crosslinkable functional groups, or the aforementioned maleimide resins.
- An aromatic maleimide resin or a linear polymer having a crosslinkable functional group can be used.
- the cured resin layer is preferably a cured polymer polymer layer having flexibility.
- the polymer layer is preferably made of a resin having a glass transition temperature of 150 ° C. or higher so that it can withstand the solder mounting process.
- the polymer polymer layer is preferably made of one or a mixture of two or more of a polyamide resin, a polyether sulfone resin, an aramid resin, a phenoxy resin, a polyimide resin, a polyvinyl acetal resin, and a polyamideimide resin.
- the thickness of the polymer layer is preferably 3 ⁇ m to 10 ⁇ m.
- the polymer layer preferably contains one or more of epoxy resin, maleimide resin, phenol resin, and urethane resin.
- the semi-cured resin layer is preferably composed of an epoxy resin composition having a thickness of 10 ⁇ m to 50 ⁇ m.
- the epoxy resin composition preferably contains the following components A to E.
- Component A An epoxy resin having one or more selected from the group consisting of a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a bisphenol AD type epoxy resin that have an epoxy equivalent of 200 or less and are liquid at room temperature.
- B component High heat-resistant epoxy resin.
- Component C Phosphorus-containing flame-retardant resin, which is any one of phosphorus-containing epoxy resin and phosphazene-based resin, or a mixture of these.
- Component D A rubber-modified polyamideimide resin modified with a liquid rubber component having a property of being soluble in a solvent having a boiling point in the range of 50 ° C. to 200 ° C.
- E component Resin curing agent.
- the B component is a “high heat resistant epoxy resin” having a high so-called glass transition point Tg.
- the “high heat-resistant epoxy resin” referred to here is preferably a polyfunctional epoxy resin such as a novolac-type epoxy resin, a cresol novolac-type epoxy resin, a phenol novolac-type epoxy resin, or a naphthalene-type epoxy resin.
- the phosphorus-containing epoxy resin of component C the aforementioned phosphorus-containing epoxy resin can be used.
- the phosphazene resin described above can be used as the C component phosphazene resin.
- the rubber-modified polyamide-imide resin described above can be used as the rubber-modified polyamide-imide resin of component D.
- the resin curing agent described above can be used as the E component resin curing agent.
- a solvent is added to the resin composition shown above and used as a resin varnish to form a thermosetting resin layer as an adhesive layer of a printed wiring board.
- the resin varnish is prepared by adding a solvent to the resin composition described above so that the resin solid content is in the range of 30 wt% to 70 wt%, and the resin flow when measured in accordance with MIL-P-13949G in the MIL standard.
- a semi-cured resin film in the range of 5% to 35% can be formed.
- the solvent a known solvent or the aforementioned solvent can be used.
- the resin layer is a resin layer having a first thermosetting resin layer and a second thermosetting resin layer located on the surface of the first thermosetting resin layer in order from the copper foil side
- the curable resin layer is formed of a resin component that does not dissolve in chemicals during desmear processing in the wiring board manufacturing process, and the second thermosetting resin layer dissolves in chemicals during desmear processing in the wiring board manufacturing process. Then, it may be formed using a resin that can be washed and removed.
- the first thermosetting resin layer may be formed using a resin component obtained by mixing one or more of polyimide resin, polyethersulfone, and polyphenylene oxide.
- the second thermosetting resin layer may be formed using an epoxy resin component.
- the thickness t1 ( ⁇ m) of the first thermosetting resin layer is Rz ( ⁇ m) of the roughened surface roughness of the copper foil with carrier, and the thickness of the second thermosetting resin layer is t2 ( ⁇ m). Then, t1 is preferably a thickness that satisfies the condition of Rz ⁇ t1 ⁇ t2.
- the resin layer may be a prepreg in which a skeleton material is impregnated with a resin.
- the resin impregnated in the skeleton material is preferably a thermosetting resin.
- the prepreg may be a known prepreg or a prepreg used for manufacturing a printed wiring board.
- the skeleton material may include aramid fiber, glass fiber, or wholly aromatic polyester fiber.
- the skeleton material is preferably an aramid fiber, a glass fiber, or a non-woven fabric or a woven fabric of wholly aromatic polyester fibers.
- the wholly aromatic polyester fiber is preferably a wholly aromatic polyester fiber having a melting point of 300 ° C. or higher.
- the wholly aromatic polyester fiber having a melting point of 300 ° C. or higher is a fiber produced using a resin called a so-called liquid crystal polymer, and the liquid crystal polymer includes 2-hydroxyl-6-naphthoic acid and p-hydroxybenzoic acid.
- the main component is an acid polymer. Since this wholly aromatic polyester fiber has a low dielectric constant and low dielectric loss tangent, it has excellent performance as a constituent material of an electrically insulating layer and can be used in the same manner as glass fiber and aramid fiber. is there.
- the fibers constituting the nonwoven fabric and woven fabric are preferably subjected to a silane coupling agent treatment in order to improve the wettability with the resin on the surface.
- a silane coupling agent As the silane coupling agent at this time, a known amino-based or epoxy-based silane coupling agent or the aforementioned silane coupling agent can be used depending on the purpose of use.
- the prepreg is a prepreg obtained by impregnating a thermosetting resin into a nonwoven fabric using an aramid fiber or glass fiber having a nominal thickness of 70 ⁇ m or less, or a skeleton material made of glass cloth having a nominal thickness of 30 ⁇ m or less. Also good.
- the resin layer may include a dielectric (dielectric filler).
- a dielectric (dielectric filler) is included in any of the above resin layers or resin compositions, it can be used for the purpose of forming the capacitor layer and increase the capacitance of the capacitor circuit.
- the dielectric (dielectric filler) includes a composite oxide having a perovskite structure such as BaTiO3, SrTiO3, Pb (Zr-Ti) O3 (commonly called PZT), PbLaTiO3 / PbLaZrO (commonly known as PLZT), SrBi2Ta2O9 (commonly known as SBT), and the like.
- Dielectric powder is used.
- the dielectric (dielectric filler) may be in powder form.
- the powder characteristics of the dielectric (dielectric filler) are as follows. First, the particle size is 0.01 ⁇ m to 3.0 ⁇ m, preferably 0.02 ⁇ m to 2.0 ⁇ m. Must be in range.
- the particle size referred to here is indirect in which the average particle size is estimated from the measured values of the laser diffraction scattering type particle size distribution measurement method and the BET method because the particles form a certain secondary aggregation state.
- the accuracy is inferior in measurement, and it refers to the average particle diameter obtained by directly observing a dielectric (dielectric filler) with a scanning electron microscope (SEM) and image analysis of the SEM image. It is. In this specification, the particle size at this time is indicated as DIA.
- the image analysis of the dielectric (dielectric filler) powder observed using a scanning electron microscope (SEM) in this specification is performed using an IP-1000PC manufactured by Asahi Engineering Co., Ltd. Circular particle analysis was performed with a threshold value of 10 and an overlapping degree of 20, and the average particle diameter DIA was obtained.
- the resin layer containing the dielectric for forming the capacitor circuit layer having a low dielectric loss tangent is improved by improving the adhesion between the inner layer circuit surface of the inner layer core material and the resin layer containing the dielectric.
- the copper foil with a carrier which has can be provided.
- Examples of the resin and / or resin composition and / or compound contained in the resin layer include methyl ethyl ketone (MEK), cyclopentanone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, toluene, methanol, ethanol, propylene glycol monomethyl ether , Dimethylformamide, dimethylacetamide, cyclohexanone, ethyl cellosolve, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide and the like to obtain a resin liquid (resin varnish).
- MEK methyl ethyl ketone
- cyclopentanone dimethylformamide, dimethylacetamide, N-methylpyrrolidone, toluene
- methanol ethanol
- propylene glycol monomethyl ether Dimethylformamide, dimethylacetamide, cyclohexanone, ethyl cellosolve
- the ultrathin copper layer or on the heat-resistant layer, rust-preventing layer, chromate-treated layer, or silane coupling agent layer, for example, by a roll coater method, and then heated and dried as necessary.
- a hot air drying furnace may be used for drying, and the drying temperature may be 100 to 250 ° C., preferably 130 to 200 ° C.
- the resin layer composition is dissolved using a solvent, and the resin solid content is 3 wt% to 70 wt%, preferably 3 wt% to 60 wt%, preferably 10 wt% to 40 wt%, more preferably 25 wt% to 40 wt%. It is good also as a resin liquid.
- the resin layer is preferably a semi-cured resin film having a resin flow in the range of 5% to 35% when measured according to MIL-P-13949G in the MIL standard.
- the resin flow is based on MIL-P-13949G in the MIL standard.
- Four 10 cm square samples were sampled from a resin-coated copper foil with a resin thickness of 55 ⁇ m. It is a value calculated based on Formula 1 from the result of measuring the resin outflow weight at the time of lamination in a stacked state (laminate) under the conditions of a press temperature of 171 ° C., a press pressure of 14 kgf / cm 2, and a press time of 10 minutes.
- the copper foil with a carrier provided with the resin layer (copper foil with a carrier with resin) is superposed on the base material, and the whole is thermocompression bonded to thermally cure the resin layer, and then the carrier is peeled off.
- the ultrathin copper layer is exposed (which is naturally the surface on the intermediate layer side of the ultrathin copper layer), and a predetermined wiring pattern is formed thereon.
- this resin-attached copper foil with a carrier can reduce the number of prepreg materials used when manufacturing a multilayer printed wiring board.
- the copper-clad laminate can be manufactured even if the resin layer is made thick enough to ensure interlayer insulation or no prepreg material is used. At this time, the surface smoothness can be further improved by undercoating the surface of the substrate with an insulating resin.
- the material cost of the prepreg material is saved and the laminating process is simplified, which is economically advantageous.
- the multilayer printed wiring board manufactured by the thickness of the prepreg material is used. The thickness is reduced, and there is an advantage that an extremely thin multilayer printed wiring board in which the thickness of one layer is 100 ⁇ m or less can be manufactured.
- the thickness of this resin layer is preferably 0.1 to 120 ⁇ m.
- the thickness of the resin layer is less than 0.1 ⁇ m, the adhesive strength is reduced, and when the copper foil with a carrier with the resin is laminated on the base material provided with the inner layer material without interposing the prepreg material, the circuit of the inner layer material It may be difficult to ensure interlayer insulation between the two.
- the thickness of the resin layer is greater than 120 ⁇ m, it is difficult to form a resin layer having a target thickness in a single coating process, which may be economically disadvantageous because of extra material costs and man-hours.
- the thickness of the resin layer is 0.1 ⁇ m to 5 ⁇ m, more preferably 0.5 ⁇ m to 5 ⁇ m, More preferably, the thickness is 1 ⁇ m to 5 ⁇ m in order to reduce the thickness of the multilayer printed wiring board.
- the thickness of the resin layer is preferably 0.1 to 50 ⁇ m, more preferably 0.5 ⁇ m to 25 ⁇ m, and more preferably 1.0 ⁇ m to 15 ⁇ m. preferable.
- the total resin layer thickness of the cured resin layer and the semi-cured resin layer is preferably 0.1 ⁇ m to 120 ⁇ m, preferably 5 ⁇ m to 120 ⁇ m, preferably 10 ⁇ m to 120 ⁇ m, and 10 ⁇ m to 60 ⁇ m. Are more preferred.
- the thickness of the cured resin layer is preferably 2 ⁇ m to 30 ⁇ m, preferably 3 ⁇ m to 30 ⁇ m, and more preferably 5 to 20 ⁇ m.
- the thickness of the semi-cured resin layer is preferably 3 ⁇ m to 55 ⁇ m, more preferably 7 ⁇ m to 55 ⁇ m, and even more preferably 15 to 115 ⁇ m. If the total resin layer thickness exceeds 120 ⁇ m, it may be difficult to produce a thin multilayer printed wiring board.
- the total resin layer thickness is less than 5 ⁇ m, it is easy to form a thin multilayer printed wiring board, but an insulating layer between inner layer circuits This is because the resin layer may become too thin and the insulation between the circuits of the inner layer tends to become unstable. Moreover, when the cured resin layer thickness is less than 2 ⁇ m, it may be necessary to consider the surface roughness of the roughened copper foil surface. Conversely, if the cured resin layer thickness exceeds 20 ⁇ m, the effect of the cured resin layer may not be particularly improved, and the total insulating layer thickness becomes thick.
- the thickness of the resin layer is 0.1 ⁇ m to 5 ⁇ m, in order to improve the adhesion between the resin layer and the copper foil with carrier, a heat-resistant layer and / or a rust-proof layer is formed on the ultrathin copper layer.
- a heat-resistant layer and / or a rust-proof layer is formed on the ultrathin copper layer.
- the thickness of the above-mentioned resin layer says the average value of the thickness measured by cross-sectional observation in arbitrary 10 points
- this copper foil with a carrier with a resin, on the ultra-thin copper layer, or on the heat-resistant layer, rust-preventing layer, chromate-treated layer, or silane coupling-treated layer
- the carrier can then be peeled off and manufactured in the form of a copper foil with resin without the carrier.
- a step of preparing a copper foil with a carrier and an insulating substrate according to the present invention a step of laminating the copper foil with a carrier and an insulating substrate, and with the carrier
- a copper-clad laminate is formed through a step of peeling the carrier of the copper foil with carrier, and then a semi-additive method, a modified semi-conductor
- the semi-additive method refers to a method in which a thin electroless plating is performed on an insulating substrate or a copper foil seed layer, a pattern is formed, and then a conductive pattern is formed using electroplating and etching.
- a method for manufacturing a printed wiring board according to the present invention using a semi-additive method Preparing a copper foil with a carrier and an insulating substrate according to the present invention, Laminating the copper foil with carrier and an insulating substrate; A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate; Removing all of the ultrathin copper layer exposed by peeling the carrier by a method such as etching or plasma using a corrosive solution such as acid, Providing a through hole or / and a blind via in the resin exposed by removing the ultrathin copper layer by etching; Performing a desmear process on the region including the through hole or / and the blind via, Providing an electroless plating layer for the region including the resin and the through hole or / and the blind via; Providing a plating resist on the electroless plating layer; Exposing the plating resist, and then removing the plating resist in a region where
- the modified semi-additive method is a method in which a metal foil is laminated on an insulating layer, a non-circuit forming portion is protected by a plating resist, and the copper is thickened in the circuit forming portion by electrolytic plating, and then the resist is removed. Then, a method of forming a circuit on the insulating layer by removing the metal foil other than the circuit forming portion by (flash) etching is indicated.
- Preparing a copper foil with a carrier and an insulating substrate according to the present invention Laminating the copper foil with carrier and an insulating substrate; A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate; Providing a through hole or / and a blind via on the insulating substrate and the ultrathin copper layer exposed by peeling the carrier; Performing a desmear process on the region including the through hole or / and the blind via, Providing an electroless plating layer for the region including the through hole or / and the blind via; Providing a plating resist on the surface of the ultrathin copper layer exposed by peeling the carrier, Forming a circuit by electrolytic plating after providing the plating resist; Removing the plating resist; Removing the ultra-thin copper layer exposed by removing the plating resist by flash etching; including.
- Preparing a copper foil with a carrier and an insulating substrate according to the present invention Laminating the copper foil with carrier and an insulating substrate; A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate; Providing a plating resist on the exposed ultrathin copper layer by peeling off the carrier; Exposing the plating resist, and then removing the plating resist in a region where a circuit is formed; Providing an electrolytic plating layer in a region where the circuit from which the plating resist has been removed is formed; Removing the plating resist; Removing the electroless plating layer and the ultrathin copper layer in a region other than the region where the circuit is formed by flash etching or the like; including.
- the partial additive method means that a catalyst circuit is formed on a substrate provided with a conductor layer, and if necessary, a substrate provided with holes for through holes or via holes, and etched to form a conductor circuit. Then, after providing a solder resist or a plating resist as necessary, it refers to a method of manufacturing a printed wiring board by thickening through holes, via holes, etc. on the conductor circuit by electroless plating.
- a method for manufacturing a printed wiring board according to the present invention using a partly additive method Preparing a copper foil with a carrier and an insulating substrate according to the present invention, Laminating the copper foil with carrier and an insulating substrate; A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate; Providing a through hole or / and a blind via on the insulating substrate and the ultrathin copper layer exposed by peeling the carrier; Performing a desmear process on the region including the through hole or / and the blind via, Applying catalyst nuclei to the region containing the through-holes and / or blind vias; Providing an etching resist on the surface of the ultrathin copper layer exposed by peeling the carrier, Exposing the etching resist to form a circuit pattern; Removing the ultrathin copper layer and the catalyst nucleus by a method such as etching or plasma using a corrosive solution such as an acid to form
- the subtractive method refers to a method of selectively removing unnecessary portions of the copper foil on the copper clad laminate by etching or the like to form a conductor pattern.
- Preparing a copper foil with a carrier and an insulating substrate according to the present invention Laminating the copper foil with carrier and an insulating substrate; A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate; Providing a through hole or / and a blind via on the insulating substrate and the ultrathin copper layer exposed by peeling the carrier; Performing a desmear process on the region including the through hole or / and the blind via, Providing an electroless plating layer for the region including the through hole or / and the blind via; Providing an electroplating layer on the surface of the electroless plating layer; A step of providing an etching resist on the surface of the electrolytic plating layer or / and the ultrathin copper layer; Exposing the etching resist to form a circuit pattern; Removing the ultrathin copper layer and the electroless plating layer and the electrolytic plating
- Preparing a copper foil with a carrier and an insulating substrate according to the present invention Laminating the copper foil with carrier and an insulating substrate; A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate; Providing a through hole or / and a blind via on the insulating substrate and the ultrathin copper layer exposed by peeling the carrier; Performing a desmear process on the region including the through hole or / and the blind via, Providing an electroless plating layer for the region including the through hole or / and the blind via; Forming a mask on the surface of the electroless plating layer; Providing an electroplating layer on the surface of the electroless plating layer on which no mask is formed; A step of providing an etching resist on the surface of the electrolytic plating layer or / and the ultrathin copper layer; Exposing the etching resist to form a circuit pattern; Remov
- ⁇ Through holes and / or blind vias and subsequent desmear steps may not be performed.
- the specific example of the manufacturing method of the printed wiring board using the copper foil with a carrier of this invention is demonstrated in detail using drawing.
- the carrier-attached copper foil having an ultrathin copper layer on which a roughened layer is formed will be described as an example.
- the present invention is not limited thereto, and the carrier has an ultrathin copper layer on which a roughened layer is not formed.
- the following method for producing a printed wiring board can be similarly performed using an attached copper foil.
- a copper foil with a carrier (first layer) having an ultrathin copper layer having a roughened layer formed on the surface is prepared.
- FIG. 3-A a copper foil with a carrier (first layer) having an ultrathin copper layer having a roughened layer formed on the surface is prepared.
- a resist is applied on the roughened layer of the ultrathin copper layer, exposed and developed, and etched into a predetermined shape.
- the resist is removed to form a circuit plating having a predetermined shape.
- an embedded resin is provided on the ultrathin copper layer so as to cover the circuit plating (so that the circuit plating is buried), and then the resin layer is laminated, followed by another carrier attachment.
- a copper foil (second layer) is bonded from the ultrathin copper layer side.
- the carrier is peeled off from the second layer copper foil with carrier.
- the other carrier-attached copper foil may be the carrier-attached copper foil of the present invention, a conventional carrier-attached copper foil, or a normal copper foil.
- one or more circuits may be formed on the second layer circuit shown in FIG. 5-H, and these circuits may be formed by a semi-additive method, a subtractive method, a partial additive method, or a modified semi-conductor method. You may carry out by any method of an additive method.
- the carrier-attached copper foil used for the first layer may have a substrate on the carrier-side surface of the carrier-attached copper foil.
- substrate or resin layer since the copper foil with a carrier used for the 1st layer is supported and it becomes difficult to wrinkle, there exists an advantage that productivity improves.
- the substrate any substrate can be used as long as it has an effect of supporting the carrier-attached copper foil used in the first layer.
- the carrier, prepreg, resin layer or known carrier, prepreg, resin layer, metal plate, metal foil, inorganic compound plate, inorganic compound foil, organic compound plate, organic compound A foil can be used.
- the timing for forming the substrate on the carrier side surface is not particularly limited, but it is necessary to form the substrate before peeling off the carrier.
- it is preferably formed before the step of forming a resin layer on the ultrathin copper layer side surface of the copper foil with carrier, and the step of forming a circuit on the ultrathin copper layer side surface of the copper foil with carrier More preferably, it is formed before.
- the copper foil with a carrier according to the present invention is preferably controlled so that the color difference on the surface of the ultrathin copper layer satisfies the following (1).
- the “color difference on the surface of the ultrathin copper layer” means the color difference on the surface of the ultrathin copper layer, or the color difference on the surface of the surface treatment layer when various surface treatments such as roughening treatment are applied. . That is, in the copper foil with a carrier according to the present invention, the color difference of the surface of the ultrathin copper layer, the roughening treatment layer, the heat resistance layer, the rust prevention layer, the chromate treatment layer or the silane coupling layer satisfies the following (1). It is preferably controlled. (1)
- the color difference ⁇ E * ab based on JISZ8730 on the surface of the ultrathin copper layer, the roughened layer, the heat resistant layer, the rust preventive layer, the chromate layer or the silane coupling layer is 45 or more.
- the color differences ⁇ L, ⁇ a, and ⁇ b are respectively measured with a color difference meter, and are shown using the L * a * b color system based on JIS Z8730, taking into account black / white / red / green / yellow / blue. It is a comprehensive index and is expressed as ⁇ L: black and white, ⁇ a: reddish green, ⁇ b: yellow blue.
- ⁇ E * ab is expressed by the following formula 2 using these color differences.
- the above-described color difference can be adjusted by increasing the current density when forming the ultrathin copper layer, decreasing the copper concentration in the plating solution, and increasing the linear flow rate of the plating solution.
- the above-mentioned color difference can also be adjusted by performing a roughening process on the surface of an ultra-thin copper layer and providing a roughening process layer.
- the current density is higher than that of the prior art (for example, 40 to 60 A) using an electrolytic solution containing copper and one or more elements selected from the group consisting of nickel, cobalt, tungsten, and molybdenum. / Dm2), and can be adjusted by shortening the processing time (for example, 0.1 to 1.3 seconds).
- Ni alloy plating (for example, Ni—W alloy plating, Ni—Co—P alloy plating, Ni—Zn alloy plating) is applied to the surface of the treatment layer or the silane coupling treatment layer at a lower current density (0.1 to 1.. 3A / dm 2 ), and the processing time can be set long (20 to 40 seconds).
- the contrast between the ultrathin copper layer and the circuit is As a result, the visibility is improved and the circuit can be accurately aligned.
- the color difference ⁇ E * ab based on JISZ8730 on the surface of the ultrathin copper layer is preferably 50 or more, more preferably 55 or more, and even more preferably 60 or more.
- the contrast with the circuit plating becomes clear. , Visibility becomes good. Accordingly, in the manufacturing process of the printed wiring board as described above, for example, as shown in FIG. 3C, the circuit plating can be formed at a predetermined position with high accuracy. Further, according to the printed wiring board manufacturing method as described above, since the circuit plating is embedded in the resin layer, the ultrathin copper layer is removed by flash etching as shown in FIG. 6-J, for example.
- the circuit plating is protected by the resin layer and the shape thereof is maintained, thereby facilitating the formation of a fine circuit. Further, since the circuit plating is protected by the resin layer, the migration resistance is improved, and the continuity of the circuit wiring is satisfactorily suppressed. For this reason, formation of a fine circuit becomes easy. Also, as shown in FIGS. 6-J and 6-K, when the ultrathin copper layer is removed by flash etching, the exposed surface of the circuit plating has a shape recessed from the resin layer, so that bumps are formed on the circuit plating. In addition, copper pillars can be easily formed thereon, and the production efficiency is improved.
- a known resin or prepreg can be used as the embedding resin (resin).
- a prepreg that is a glass cloth impregnated with BT (bismaleimide triazine) resin or BT resin, an ABF film or ABF manufactured by Ajinomoto Fine Techno Co., Ltd. can be used.
- the resin layer and / or resin and / or prepreg as described in this specification can be used for the embedding resin (resin).
- a long electrolytic copper foil (JTC made by JX Nippon Mining & Metals) having a thickness of 35 ⁇ m was prepared as a carrier.
- a Ni layer having an adhesion amount of 4000 ⁇ m / dm 2 was formed on the shiny surface of the copper foil by electroplating using a roll-to-roll type continuous plating line under the following conditions.
- Nickel sulfate 250-300 g / L Nickel chloride: 35 to 45 g / L Nickel acetate: 10-20g / L Trisodium citrate: 15-30 g / L Brightener: Saccharin, butynediol, etc.
- Sodium dodecyl sulfate 30 to 100 ppm pH: 4-6 Bath temperature: 50-70 ° C Current density: 3 to 15 A / dm 2
- Electrolytic chromate treatment Liquid composition: potassium dichromate 1-10 g / L, zinc 0-5 g / L pH: 3-4 Liquid temperature: 50-60 ° C Current density: 0.1 to 2.6 A / dm 2 Coulomb amount: 0.5-30 As / dm 2
- an ultrathin copper layer having a thickness of 2 to 10 ⁇ m was formed on the Cr layer on the roll-to-roll-type continuous plating line by electroplating under the following conditions to produce a copper foil with a carrier.
- the thickness and type of the copper foil were known copper foil and copper alloy foil thickness, known copper foil and copper alloy. Applicable to all foils.
- the known copper foil and copper alloy foil may be electrolytic copper foil or rolled copper foil.
- a primary particle layer of Cu having an average particle diameter of 0.25 to 0.45 ⁇ m and Cu, Co, and Ni having an average particle diameter of 0.05 to 0.25 ⁇ m formed thereon are formed.
- a secondary particle layer made of a ternary alloy was formed.
- the roughened particle size (particle diameter) is evaluated by observing the roughened particles of the surface-treated copper foil at a magnification of 30000 times that of an electron microscope (SEM (scanning electron microscope)). did.
- SEM scanning electron microscope
- Example 1 The heat-resistant layer composed of the Ni—Co layer, the weather-resistant layer containing Zn, Ni, and Cr, the rust-preventing layer, and the silane coupling treatment were performed within the range of the above conditions.
- the conditions for forming the heat-resistant layer, weather-resistant layer and rust-proof layer are shown below.
- the thickness of the ultrathin copper layer was 2 ⁇ m.
- the plating treatment was performed so that the Ni adhesion amount (total Ni amount) in all of the roughening layer, the heat-resistant layer, the weathering layer, and the rust-preventing layer was 1093 ⁇ g / dm 2 as a whole.
- the amount of Ni deposited, Zn deposited, Co deposited, and Cr deposited in the case of laminating two or more layers of a roughened layer, a heat resistant layer, a weather resistant layer, and a rust preventive layer are the amount of each element deposited. It shows the total amount.
- Table 1 and Table 2 these were written together as needed about the location corresponding to an Example and a comparative example.
- a polyamic acid (U varnish A manufactured by Ube Industries) was applied onto the surface-treated copper foil produced as described above, dried at 100 ° C. and cured at 315 ° C. to form a copper-clad laminate composed of a polyimide resin substrate.
- a fine pattern circuit was formed on this copper clad laminate with a general copper chloride-hydrochloric acid etching solution.
- the fine pattern circuit board was immersed in an aqueous solution of 10 wt% sulfuric acid and 2 wt% hydrogen peroxide for 5 minutes, and then the interface between the resin substrate and the copper foil circuit was observed with an optical microscope to evaluate the penetration.
- the soaking width was ⁇ 3 ⁇ m and good ( ⁇ ).
- the normal state from the epoxy resin plate of the ultrathin copper layer (Room temperature) After measuring peel strength (kg / cm), the hydrochloric acid resistance deterioration rate was measured with a 0.2 mm width circuit after being immersed in an 18% aqueous hydrochloric acid solution for 1 hour.
- the normal peel strength was 0.99 kg / cm, and the hydrochloric acid degradation resistance was 8 (Loss%) or less ( ⁇ ), both of which were good.
- the Cr adhesion amount (total Cr amount) is 89 ⁇ g / dm 2 as a whole
- the Co adhesion amount (total Co amount) is 2010 ⁇ g / dm 2 as a whole
- the Zn adhesion amount (total Zn amount) is 163 ⁇ g / dm 2 as a whole.
- measurement of each said metal adhesion amount Ni adhesion amount of a roughening process stage, total Ni amount, total Co amount, total Zn amount, total Cr amount
- the amount of Ni deposited in the roughening treatment stage was determined by producing a copper foil with a carrier under the same conditions as in each example and each comparative example, and after providing only the roughening treatment layer, collecting a sample, In the same manner as above, the amount of Ni adhesion was measured.
- Example 2 The amount of Ni deposited at the roughening stage was 50 to 250 ⁇ g / dm 2 as described above.
- the heat-resistant layer composed of the Ni—Co layer, the weather-resistant layer containing Zn, Ni, and Cr, the rust-preventing layer, and the silane coupling treatment were performed within the range of the above conditions.
- the conditions for forming the heat-resistant layer, weather-resistant layer and rust-proof layer are shown below.
- the thickness of the ultrathin copper layer was 10 ⁇ m.
- the soaking width ⁇ 3 ⁇ m was good ( ⁇ ).
- Example 3 The amount of Ni deposited at the roughening stage was 50 to 250 ⁇ g / dm 2 as described above.
- the heat-resistant layer composed of the Ni—Co layer, the weather-resistant layer containing Zn, Ni, and Cr, the rust-preventing layer, and the silane coupling treatment were performed within the range of the above conditions.
- the conditions for forming the heat-resistant layer, weather-resistant layer and rust-proof layer are shown below.
- the thickness of the ultrathin copper layer was 5 ⁇ m.
- the soaking width was good at ⁇ 3 ⁇ m.
- Example 4 The amount of Ni deposited at the roughening stage was 50 to 250 ⁇ g / dm 2 as described above.
- the heat-resistant layer composed of the Ni—Co layer, the weather-resistant layer containing Zn, Ni, and Cr, the rust-preventing layer, and the silane coupling treatment were performed within the range of the above conditions.
- the conditions for forming the heat-resistant layer, weather-resistant layer and rust-proof layer are shown below.
- the thickness of the ultrathin copper layer was 3 ⁇ m.
- the soaking width was 0 ⁇ m, which was very good.
- the normal peel strength was 0.99 kg / cm
- the hydrochloric acid degradation resistance was 22 (Loss%)
- Alkali etching property was also good ( ⁇ ).
- the results are shown in Table 1.
- the Cr adhesion amount is 90 ⁇ g / dm 2 as a whole (total Cr amount)
- the Co adhesion amount is 1774 ⁇ g / dm 2 as a whole
- the Zn adhesion amount (total Zn amount) is 223 ⁇ g / dm 2 as a whole. Met.
- Example 5 The amount of Ni deposited at the roughening stage was 50 to 250 ⁇ g / dm 2 as described above.
- the heat-resistant layer composed of the Ni—Co layer, the weather-resistant layer containing Zn, Ni, and Cr, the rust-preventing layer, and the silane coupling treatment were performed within the range of the above conditions.
- the conditions for forming the heat-resistant layer, weather-resistant layer and rust-proof layer are shown below.
- the thickness of the ultrathin copper layer was 7 ⁇ m.
- the soaking width was 0 ⁇ m, which was very good.
- Example 6 The copper foil with a carrier described above was subjected to a roughening treatment under the following conditions.
- the thickness of the ultrathin copper layer was 3 ⁇ m.
- Liquid composition Cu 10-20 g / liter, Co 5-10 g / liter, Ni 5-15 g / liter pH: 2-4 Temperature: 30-50 ° C Current density (D k ): 20 to 60 A / dm 2 Time: 0.5-5 seconds
- an aggregate of finely roughened particles of a ternary alloy composed of Cu, Co, and Ni having an average particle diameter of 0.10 to 0.60 ⁇ m was formed.
- the roughened particle size was evaluated by observing the roughened particles of the copper foil with surface treatment at a magnification of 30000 times with an electron microscope (SEM).
- SEM electron microscope
- the amount of Ni deposited in the roughening stage was 200 to 400 ⁇ g / dm 2 .
- the heat-resistant layer composed of the Ni—Co layer, the weather-resistant layer containing Zn, Ni, and Cr, the rust-preventing layer, and the silane coupling treatment were performed within the range of the above conditions.
- the conditions for forming the heat-resistant layer, weather-resistant layer and rust-proof layer are shown below.
- the soaking width was 0 ⁇ m, which was very good.
- Example 7 The above-mentioned copper foil with a carrier was roughened under the conditions shown below. The thickness of the ultrathin copper layer was 3 ⁇ m.
- Liquid composition Cu 10-20 g / liter, Co 5-10 g / liter, Ni 8-20 g / liter pH: 2-4 Temperature: 30-50 ° C Current density (D k ): 20 to 60 A / dm 2 Time: 0.5-5 seconds
- an aggregate of finely roughened particles of a ternary alloy composed of Cu, Co, and Ni having an average particle diameter of 0.05 to 0.35 ⁇ m was formed.
- the roughened particle size was evaluated by observing the roughened particles of the copper foil with surface treatment at a magnification of 30000 times with an electron microscope (SEM).
- SEM electron microscope
- the amount of Ni deposited in the roughening stage was 300 to 550 ⁇ g / dm 2 .
- the heat-resistant layer composed of the Ni—Co layer, the weather-resistant layer containing Zn, Ni, and Cr, the rust-preventing layer, and the silane coupling treatment were performed within the range of the above conditions.
- the conditions for forming the heat-resistant layer, weather-resistant layer and rust-proof layer are shown below.
- Example 8 In the same roughening treatment as in Example 1, a primary particle layer of Cu having an average particle size of 0.25 to 0.45 ⁇ m, and Cu and Co having an average particle size of 0.05 to 0.25 ⁇ m formed thereon. Then, a secondary particle layer made of a ternary alloy made of Ni was formed. The roughened particle size was evaluated by observing the roughened particles of the copper foil with surface treatment at a magnification of 30000 times with an electron microscope (SEM). The amount of Ni deposited at the roughening treatment stage was 50 to 250 ⁇ g / dm 2 .
- the conditions for forming the heat-resistant layer, weather-resistant layer and rust-proof layer are shown below.
- the thickness of the ultrathin copper layer was 3 ⁇ m.
- Heat-resistant layer Ni-Co layer
- Weather resistant layer Zn—Ni layer
- Rust prevention layer Cr-Zn layer
- the plating treatment was performed so that the Ni adhesion amount in all of the roughening layer, the heat-resistant layer, the weathering layer, and the rust-preventing layer was 741 ⁇ g / dm 2 in total (total Ni amount).
- the surface-treated copper foil was laminated on the following resins, and then the penetration was evaluated by the above-described penetration evaluation method.
- GHPL-830NX Mitsubishi Gas Chemical Co., Ltd. Type A
- GHPL-830NX Mitsubishi Gas Chemical Co., Ltd. Type A
- a fine pattern circuit was formed on this copper clad laminate with a general copper chloride-hydrochloric acid etching solution.
- the fine pattern circuit board was immersed in an aqueous solution of 10 wt% sulfuric acid and 2 wt% hydrogen peroxide for 5 minutes, and then the interface between the resin substrate and the copper foil circuit was observed with an optical microscope to evaluate the penetration.
- the soaking width was 0 ⁇ m, which was very good.
- Example 9 In the same roughening treatment as in Example 1, a primary particle layer of Cu having an average particle size of 0.25 to 0.45 ⁇ m, and Cu and Co having an average particle size of 0.05 to 0.25 ⁇ m formed thereon. Then, a secondary particle layer made of a ternary alloy made of Ni was formed. The roughened particle size was evaluated by observing the roughened particles of the copper foil with surface treatment at a magnification of 30000 times with an electron microscope (SEM). The amount of Ni deposited at the roughening treatment stage was 50 to 250 ⁇ g / dm 2 .
- SEM electron microscope
- the conditions for forming the heat-resistant layer, weather-resistant layer and rust-proof layer are shown below.
- the thickness of the ultrathin copper layer was 3 ⁇ m.
- Heat-resistant layer Ni-Co layer
- Weather resistant layer Zn—Ni layer
- Rust prevention layer Cr-Zn layer
- the plating treatment was performed so that the Ni adhesion amount in all of the roughening layer, the heat resistant layer, the weather resistant layer, and the rust preventive layer was 771 ⁇ g / dm 2 in total (total Ni amount).
- the total Zn content / (total Ni content + total Zn content) 0.06 from the Zn adhesion amount (total Zn content) in all of the roughened layer, heat resistant layer, weather resistant layer, and rust prevention layer.
- the total amount of Co / (total Ni amount) + total Zn amount) 1.8 from the Co adhesion amount (total Co amount) in all of the roughening layer, heat-resistant layer, weathering layer, and rust prevention layer.
- Example 10 A roughening layer was formed on the above-described copper foil with a carrier under the same conditions as in Example 6. By performing the roughening treatment under the above conditions, an aggregate of finely roughened particles of a ternary alloy composed of Cu, Co, and Ni having an average particle diameter of 0.10 to 0.60 ⁇ m was formed. The amount of Ni deposited in the roughening stage was 200 to 400 ⁇ g / dm 2 .
- the heat-resistant layer composed of the Ni—Co layer, the weather-resistant layer containing Zn, Ni, and Cr, the rust-preventing layer, and the silane coupling treatment were performed within the range of the above conditions. The conditions for forming the heat-resistant layer, weather-resistant layer and rust-proof layer are shown below. The thickness of the ultrathin copper layer was 3 ⁇ m.
- Heat-resistant layer Liquid composition: Co 1-10 g / liter, Ni 1-10 g / liter pH: 2-3 Temperature: 40-60 ° C Current density (D k ): 6 to 8 A / dm 2 Time: 0.05 to 3.0 seconds 2) Weather resistant layer (Zn—Ni layer) Current density (D k ): 1.0 to 3.0 A / dm 2 Time: 0.05 to 3.0 seconds 3) Rust prevention layer (Cr-Zn layer) Current density (D k ): 0 A / dm 2 Time: 0.05-3 seconds (immersion chromate treatment)
- the soaking width was good at ⁇ 5 ⁇ m.
- Example 11 In the same roughening treatment as in Example 1, a primary particle layer of Cu having an average particle diameter of 0.2 to 0.45 ⁇ m, and Cu, Co having an average particle diameter of 0.05 to 0.25 ⁇ m formed thereon. Then, a secondary particle layer made of a ternary alloy made of Ni was formed. The roughened particle size was evaluated by observing the roughened particles of the copper foil with surface treatment at a magnification of 30000 times with an electron microscope (SEM). The amount of Ni deposited at the roughening stage was 300 to 550 ⁇ g / dm 2 .
- the conditions for forming the heat-resistant layer, weather-resistant layer and rust-proof layer are shown below.
- the thickness of the ultrathin copper layer was 3 ⁇ m.
- Heat-resistant layer Ni-Co layer
- Weather resistant layer Zn—Ni layer
- Rust prevention layer Cr-Zn layer
- the plating treatment was performed so that the Ni adhesion amount in all of the roughening layer, the heat-resistant layer, the weather-resistant layer, and the rust-preventing layer was 1590 ⁇ g / dm 2 in total (total Ni amount).
- the total Zn amount / (total Ni amount + total Zn amount) 0.10.
- the total amount of Co / (total Ni amount) + total Zn amount) 1.6 from the Co adhesion amount (total Co amount) in all of the roughening layer, heat-resistant layer, weathering layer, and rust prevention layer.
- Example 12 In the same roughening treatment as in Example 1, a primary particle layer of Cu having an average particle diameter of 0.2 to 0.45 ⁇ m, and Cu, Co having an average particle diameter of 0.05 to 0.25 ⁇ m formed thereon. Then, a secondary particle layer made of a ternary alloy made of Ni was formed. The roughened particle size was evaluated by observing the roughened particles of the copper foil with surface treatment at a magnification of 30000 times with an electron microscope (SEM). The amount of Ni deposited at the roughening treatment stage was 50 to 250 ⁇ g / dm 2 .
- the conditions for forming the heat-resistant layer, weather-resistant layer and rust-proof layer are shown below.
- the thickness of the ultrathin copper layer was 3 ⁇ m.
- Heat-resistant layer Ni-Co layer
- Weather resistant layer Zn—Ni layer
- Rust prevention layer Cr-Zn layer
- the plating treatment was performed so that the Ni adhesion amount in all of the roughening layer, the heat-resistant layer, the weathering layer, and the rust-preventing layer was 360 ⁇ g / dm 2 in total (total Ni amount).
- the total Zn content / (total Ni content + total Zn content) 0.35 from the Zn adhesion amount (total Zn content) in all of the roughened layer, heat resistant layer, weather resistant layer, and rust prevention layer.
- the total Co amount / (total Ni amount) + total Zn amount) 1.4.
- Example 1 A roughened layer was formed on the above-described copper foil with a carrier under the same conditions as in Example 1-5.
- the amount of Ni deposited in the roughening stage was 50 to 250 ⁇ g / dm 2 .
- the heat-resistant layer composed of the Ni—Co layer, the weather-resistant layer containing Zn, Ni, and Cr, the rust-preventing layer, and the silane coupling treatment were performed within the range of the above conditions.
- the conditions for forming the heat-resistant layer, weather-resistant layer and rust-proof layer are shown below.
- the thickness of the ultrathin copper layer was 3 ⁇ m.
- the soaking width was poor at> 5 ⁇ m.
- Example 2 A roughened layer was formed on the above-described copper foil with a carrier under the same conditions as in Example 1-5.
- the amount of Ni deposited in the roughening stage was 50 to 250 ⁇ g / dm 2 .
- the heat-resistant layer composed of the Ni—Co layer, the weather-resistant layer containing Zn, Ni, and Cr, the rust-preventing layer, and the silane coupling treatment were performed within the range of the above conditions.
- the conditions for forming the heat-resistant layer, weather-resistant layer and rust-proof layer are shown below.
- the thickness of the ultrathin copper layer was 3 ⁇ m.
- the soaking width was good at ⁇ 3 ⁇ m.
- Example 3 A roughened layer was formed on the above-described copper foil with a carrier under the same conditions as in Example 1-5.
- the amount of Ni deposited in the roughening stage was 50 to 250 ⁇ g / dm 2 .
- the heat-resistant layer composed of the Ni—Co layer, the weather-resistant layer containing Zn, Ni, and Cr, the rust-preventing layer, and the silane coupling treatment were performed within the range of the above conditions.
- the conditions for forming the heat-resistant layer, weather-resistant layer and rust-proof layer are shown below.
- the thickness of the ultrathin copper layer was 3 ⁇ m.
- the total amount of Ni (total Ni amount) in the roughened layer, heat-resistant layer, weather-resistant layer, and rust-preventing layer is 310 ⁇ g / dm 2 , and all of the roughened layer, heat-resistant layer, weather-resistant layer, and rust-proof layer
- Zn amount the amount of Zn deposited (total Zn amount)
- Amount / (total Ni amount + total Zn amount) 1.4.
- the soaking width was good at ⁇ 3 ⁇ m.
- Example 4 A roughened layer was formed on the above-described copper foil with a carrier under the same conditions as in Example 1-5.
- the amount of Ni deposited in the roughening stage was 50 to 250 ⁇ g / dm 2 .
- the heat-resistant layer composed of the Ni—Co layer, the weather-resistant layer containing Zn, Ni, and Cr, the rust-preventing layer, and the silane coupling treatment were performed within the range of the above conditions.
- the conditions for forming the heat-resistant layer, weather-resistant layer and rust-proof layer are shown below.
- the thickness of the ultrathin copper layer was 3 ⁇ m.
- the soaking width was good at 0 ⁇ m.
- Example 21 a copper foil with a carrier was formed under the same conditions as in Example 1 except that a CoMo alloy was formed as an intermediate layer between the carrier and the copper foil.
- the CoMo alloy intermediate layer was produced by plating in a plating solution having the following liquid composition.
- the thickness of the ultrathin copper layer was 2 ⁇ m.
- the soaking width was good at ⁇ 3 ⁇ m.
- Example 22 a copper foil with a carrier was formed under the same conditions as in Example 2 except that Cr was formed as an intermediate layer between the carrier and the copper foil.
- the Cr intermediate layer was produced by plating in a plating solution having the following liquid composition.
- the thickness of the ultrathin copper layer was 10 ⁇ m.
- the soaking width was good at ⁇ 3 ⁇ m.
- Example 23 a copper foil with a carrier was formed under the same conditions as in Example 1 except that Cr / CuP was formed as an intermediate layer between the carrier and the copper foil.
- the Cr / CuP intermediate layer was produced by plating in a plating solution having the following liquid composition.
- the thickness of the ultrathin copper layer was 2 ⁇ m.
- the soaking width was good at ⁇ 3 ⁇ m.
- Example 24 a copper foil with a carrier was formed under the same conditions as in Example 2 except that Ni / Cr was formed as an intermediate layer between the carrier and the copper foil.
- the Ni / Cr intermediate layer was produced by plating in a plating solution having the following liquid composition.
- the thickness of the ultrathin copper layer was 10 ⁇ m.
- NiSO 4 ⁇ 6H 2 O 250 ⁇ 300g / l NiCl 2 ⁇ 6H 2 O: 35 to 45 g / l Boric acid: 10-50 g / l (PH): 2 to 6 (Bath temperature): 30-70 ° C (Current density): 0.1 to 50 A / dm 2
- Example 25 a copper foil with a carrier was formed under the same conditions as in Example 1 except that a Co / chromate-treated layer was formed as an intermediate layer between the carrier and the copper foil.
- the Co / chromate intermediate layer was prepared by plating in a plating solution having the following liquid composition.
- the thickness of the ultrathin copper layer was 2 ⁇ m.
- the soaking width was good at ⁇ 3 ⁇ m.
- Example 26 a copper foil with a carrier was formed under the same conditions as in Example 4 except that an organic layer was formed as an intermediate layer between the carrier and the copper foil.
- the thickness of the ultrathin copper layer was 10 ⁇ m.
- an intermediate layer of the organic layer was prepared by spraying an aqueous carboxybenzotriazole solution having a liquid temperature of 40 ° C., pH 5, and a concentration of 1 to 10 g / l for 10 to 60 seconds.
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Abstract
Description
最終的に、所要の素子が半田付けされて、エレクトロニクスデバイス用の種々の印刷回路板を形成する。印刷回路板用銅箔は、樹脂基材と接着される面(粗化面)と非接着面(光沢面)とで異なるが、それぞれ多くの方法が提唱されている。 Copper and copper alloy foils (hereinafter referred to as copper foils) have greatly contributed to the development of electrical and electronic industries, and are indispensable particularly as printed circuit materials. Copper foils for printed circuits are generally laminated and bonded to substrates such as synthetic resin boards and polyimide films via adhesives, or without using adhesives at high temperature and high pressure, or by applying polyimide precursors. In order to produce a copper-clad laminate by drying and curing, and then forming the desired circuit, the necessary circuit is printed through a resist coating and exposure process, and then an etching process is performed to remove unnecessary portions. Is done.
Finally, the required elements are soldered to form various printed circuit boards for the electronic device. Although the copper foil for printed circuit boards differs in the surface (roughening surface) adhere | attached with a resin base material, and a non-adhesion surface (glossy surface), many methods are each proposed.
銅箔の粗化処理は、銅箔と基材との接着性を決定するものとして、大きな役割を担っている。この粗化処理としては、当初銅を電着する銅粗化処理が採用されていたが、その後、様々な技術が提唱され、耐熱剥離強度、耐塩酸性及び耐酸化性の改善を目的として銅-ニッケル粗化処理が一つの代表的処理方法として定着するようになっている。 For example, the requirements for the roughened surface formed on the copper foil are as follows: 1) No oxidation discoloration during storage, 2) High peel strength with substrate, high temperature heating, wet processing, soldering, chemicals It is sufficient even after treatment or the like, and 3) that there is no so-called lamination stain that occurs after lamination with the substrate and etching.
The roughening treatment of the copper foil plays a major role as determining the adhesiveness between the copper foil and the base material. As this roughening treatment, a copper roughening treatment in which electrodeposition of copper was initially employed was adopted, but various techniques were proposed thereafter, and copper--for the purpose of improving the heat-resistant peel strength, hydrochloric acid resistance and oxidation resistance. Nickel roughening is established as one typical processing method.
そこで、ファインパターン用処理として、本件出願人は、先にCu-Co処理(特許文献2及び特許文献3参照)及びCu-Co-Ni処理(特許文献4参照)を開発した。 However, while the copper-nickel roughening treatment is excellent in heat-resistant peel strength, oxidation resistance, and hydrochloric acid resistance, it is difficult to etch with an alkaline etchant that has recently become important as a fine pattern treatment, and has a pitch of 150 μm. When forming a fine pattern having a circuit width or less, the processing layer becomes an etching residue.
Therefore, the present applicant has previously developed a Cu—Co treatment (see Patent Documents 2 and 3) and a Cu—Co—Ni treatment (see Patent Document 4) as fine pattern treatments.
さらにZnは亜鉛-ニッケル合金層だけでなく、耐候層、防錆層全てに含有させることが可能であるため、耐候層、防錆層全ての全Zn量について、さらには上記全Ni量との比率について検討する必要があることが分かった。 Although this technology is effective, Ni can be contained not only in the zinc-nickel alloy layer but also in the roughened layer, heat-resistant layer, and weather-resistant layer. In order to obtain a copper foil for printed circuit that can exert a very excellent effect on the FPC characteristics, it is found that it is necessary to further examine the total amount of Ni in the roughened layer, the heat-resistant layer, and the weather-resistant layer. It was.
Furthermore, since Zn can be contained not only in the zinc-nickel alloy layer but also in the weather resistant layer and the rust preventive layer, the total Zn content in all of the weather resistant layer and the rust preventive layer is further compared with the above total Ni content. It turns out that the ratio needs to be considered.
極薄銅層と樹脂基材の間の剥離強度を高める方法としては、一般的に、表面のプロファイル(凹凸、粗さ)を大きくした極薄銅層の上に多量の粗化粒子を付着させる方法が代表的である。 Here, with respect to the surface of the ultrathin copper layer of the copper foil with a carrier that becomes the adhesive surface with the resin, the peel strength between the ultrathin copper layer and the resin substrate is mainly sufficient, and the peel strength Is required to be sufficiently retained after high-temperature heating, wet processing, soldering, chemical processing, and the like.
As a method of increasing the peel strength between the ultrathin copper layer and the resin base material, generally, a large amount of roughened particles are adhered on the ultrathin copper layer having a large surface profile (unevenness, roughness). The method is representative.
そのため、キャリア付銅箔について更なる改善が求められている。 For this reason, as a copper foil with a carrier for use in a fine circuit including a semiconductor package substrate, an attempt has been made to use a copper foil with a carrier in which the surface of an ultrathin copper layer is not roughened. The adhesion (peeling strength) between the ultrathin copper layer not subjected to such roughening treatment and the resin is affected by the low profile (unevenness, roughness, roughness) of the general copper foil for printed wiring boards. There is a tendency to decrease when compared. (Patent Document 8)
Therefore, the further improvement is calculated | required about copper foil with a carrier.
電子機器の発展が進む中で、半導体デバイスの小型化、高集積化が更に進み、これらの印刷回路の製造工程で行われる処理が一段と厳しい要求がなされている。本願発明をこれらの要求にこたえる技術を提供することを課題とする。 The present invention relates to a carrier-attached copper foil and a copper-clad laminate, and in particular, after a roughening treatment is formed on the surface of the copper foil, a heat-resistant layer, a weather-resistant layer, and a rust-proof layer are formed thereon, and then a silane cup In copper-clad laminates using ring-treated copper foil with carrier, when the substrate is subjected to acid treatment or chemical etching after fine pattern printed circuit formation, the acid to the interface between the copper foil circuit and the substrate resin It is related with copper foil with a carrier which can improve the suppression of the adhesive fall by "dipping" of this, is excellent in acid-proof adhesion strength, and was excellent in alkali etching property.
Along with the development of electronic devices, the miniaturization and high integration of semiconductor devices have further advanced, and the processing performed in the manufacturing process of these printed circuits has become more severe. It is an object of the present invention to provide a technique that meets these requirements.
1)銅箔または銅合金箔の上に、粗化(トリート)処理を施すことにより形成された粗化処理層、この粗化処理層の上に形成されたNi-Co層からなる耐熱層、及びこの耐熱層の上に形成されたZn、Ni、Crを含有する耐候層及び防錆層を有する表面処理層を有し、前記表面処理層中の全Zn量/(全Zn量+全Ni量)が0.02以上0.35以下であり、前記表面処理層中の全Ni量が1600μg/dm2以下であることを特徴とするキャリア付銅箔。
2)前記表面処理層中の全Zn量/(全Zn量+全Ni量)が0.02以上0.23以下であり、前記表面処理層中の全Ni量が1150μg/dm2以下であることを特徴とする、1)に記載のキャリア付銅箔。
3)前記表面処理層中の全Ni量が、350~1350μg/dm2であることを特徴とする1)又は2)に記載のキャリア付銅箔。
4)前記表面処理層中の全Ni量が、450~1100μg/dm2であることを特徴とする上記1)~3)のいずれか一項に記載のキャリア付銅箔。
5)前記表面処理層中の全Co量が770~3200μg/dm2であり、全Co量/(全Zn量+全Ni量)が3.4以下であることを特徴とする1)~4)のいずれか一項に記載のキャリア付銅箔。
6)前記表面処理層中の全Co量が770~2500μg/dm2であり、全Co/(全Zn+全Ni)が3.0以下であることを特徴とする上記1)~5)のいずれか一項に記載のキャリア付銅箔。
7)前記表面処理層中の全Cr量が50~120μg/dm2であることを特徴とする上記1)~6)のいずれか一項に記載のキャリア付銅箔。 As described above, the present application provides the following invention.
1) A roughening treatment layer formed by subjecting a copper foil or a copper alloy foil to a roughening (treating) treatment, a heat-resistant layer comprising a Ni—Co layer formed on the roughening treatment layer, And a surface treatment layer having a weather resistance layer and a rust prevention layer containing Zn, Ni, Cr formed on the heat-resistant layer, and the total Zn content in the surface treatment layer / (total Zn content + total Ni Amount) is 0.02 or more and 0.35 or less, and the total amount of Ni in the surface treatment layer is 1600 μg / dm 2 or less.
2) The total Zn amount in the surface treatment layer / (total Zn amount + total Ni amount) is 0.02 or more and 0.23 or less, and the total Ni amount in the surface treatment layer is 1150 μg / dm 2 or less. The copper foil with a carrier as described in 1), wherein
3) The copper foil with carrier according to 1) or 2), wherein the total amount of Ni in the surface treatment layer is 350 to 1350 μg / dm 2 .
4) The copper foil with a carrier according to any one of 1) to 3) above, wherein the total amount of Ni in the surface treatment layer is 450 to 1100 μg / dm 2 .
5) The total amount of Co in the surface treatment layer is 770 to 3200 μg / dm 2 , and the total Co amount / (total Zn amount + total Ni amount) is 3.4 or less. The copper foil with a carrier as described in any one of 1).
6) Any one of 1) to 5) above, wherein the total amount of Co in the surface treatment layer is 770 to 2500 μg / dm 2 and total Co / (total Zn + total Ni) is 3.0 or less. A copper foil with a carrier according to claim 1.
7) The copper foil with a carrier according to any one of 1) to 6) above, wherein the total amount of Cr in the surface treatment layer is 50 to 120 μg / dm 2 .
8)前記粗化処理層のNiが50~550μg/dm2であることを特徴とする上記1)~7)のいずれか一項に記載のキャリア付銅箔。
9)前記粗化処理層が、Co、Cu、Niの元素からなる粗化処理層であることを特徴とする上記1)~8)のいずれかに記載のキャリア付銅箔。
10)前記粗化処理層が平均粒子径0.05~0.60μmの微細粒子からなることを特徴とする1)~9)のいずれか一項に記載のキャリア付銅箔。
11)前記粗化処理層が平均粒子径0.05~0.60μmのCu、Co、Niからなる3元系合金の微細粒子からなることを特徴とする上記1)~10)のいずれか一項に記載のキャリア付銅箔。
12)前記粗化処理層が、平均粒子径0.25~0.45μmの一次粒子層と、その上に形成された平均粒子径が0.05~0.25μmの二次粒子層からなることを特徴とする1)~11)のいずれか一項に記載のキャリア付銅箔。
13)前記粗化処理層が、平均粒子径0.25~0.45μmのCuの一次粒子層と、その上に形成された平均粒子径が0.05~0.25μmのCu、Co、Niからなる3元系合金からなる二次粒子層からなることを特徴とする上記1)~12)のいずれかに一項に記載のキャリア付銅箔。 The present application also provides the following invention.
8) The copper foil with a carrier according to any one of 1) to 7) above, wherein Ni in the roughened layer is 50 to 550 μg / dm 2 .
9) The copper foil with carrier according to any one of 1) to 8) above, wherein the roughened layer is a roughened layer made of Co, Cu, or Ni.
10) The copper foil with a carrier according to any one of 1) to 9), wherein the roughened layer comprises fine particles having an average particle diameter of 0.05 to 0.60 μm.
11) Any one of the above 1) to 10), wherein the roughened layer is made of fine particles of a ternary alloy composed of Cu, Co, and Ni having an average particle size of 0.05 to 0.60 μm. The copper foil with a carrier according to the item.
12) The roughening layer is composed of a primary particle layer having an average particle diameter of 0.25 to 0.45 μm and a secondary particle layer having an average particle diameter of 0.05 to 0.25 μm formed thereon. The copper foil with a carrier according to any one of 1) to 11), characterized in that:
13) The roughening layer comprises a primary particle layer of Cu having an average particle diameter of 0.25 to 0.45 μm, and Cu, Co, Ni having an average particle diameter of 0.05 to 0.25 μm formed thereon. The copper foil with a carrier according to any one of 1) to 12) above, wherein the copper foil is a secondary particle layer made of a ternary alloy made of
15)前記表面処理層上に樹脂層を備える1)~13)のいずれか一項に記載のキャリア付銅箔。
16)上記14)記載の印刷回路用銅箔を樹脂基板に積層接着した銅張積層板。
17)上記1)~13)のいずれか一項に記載のキャリア付銅箔を用いて製造したプリント配線板。
18)上記1)~13)のいずれか一項に記載のキャリア付銅箔を用いて製造したプリント回路板。
19)上記1)~13)のいずれか一項に記載のキャリア付銅箔を用いて製造した銅張積層板。
20)上記1)~13)のいずれか一項に記載のキャリア付銅箔と絶縁基板とを準備する工程、
前記キャリア付銅箔と絶縁基板とを積層する工程、
前記キャリア付銅箔と絶縁基板とを積層した後に、前記キャリア付銅箔のキャリアを剥がす工程を経て銅張積層板を形成し、
その後、セミアディティブ法、サブトラクティブ法、パートリーアディティブ法又はモディファイドセミアディティブ法のいずれかの方法によって、回路を形成する工程
を含むプリント配線板の製造方法。
21)上記1)~13)のいずれか一項に記載のキャリア付銅箔の前記極薄銅層側表面に回路を形成する工程、
前記回路が埋没するように前記キャリア付銅箔の前記極薄銅層側表面に樹脂層を形成する工程、
前記樹脂層上に回路を形成する工程、
前記樹脂層上に回路を形成した後に、前記キャリアを剥離させる工程、及び、
前記キャリアを剥離させた後に、前記極薄銅層を除去することで、前記極薄銅層側表面に形成した、前記樹脂層に埋没している回路を露出させる工程
を含むプリント配線板の製造方法。
22)前記樹脂層上に回路を形成する工程が、
前記樹脂層上に別のキャリア付銅箔を極薄銅層側から貼り合わせ、前記樹脂層に貼り合わせたキャリア付銅箔を用いて前記回路を形成する工程である、請求項21に記載のプリント配線板の製造方法。
23)前記樹脂層上に貼り合わせる別のキャリア付銅箔が、1)~13)のいずれか一項に記載のキャリア付銅箔である、22)に記載のプリント配線板の製造方法。
24)前記樹脂層上に回路を形成する工程が、セミアディティブ法、サブトラクティブ法、パートリーアディティブ法又はモディファイドセミアディティブ法のいずれかの方法によって行われる、21)~23)のいずれか一項に記載のプリント配線板の製造方法。
25)キャリアを剥離する前に、キャリア付銅箔のキャリア側表面に基板を形成する工程を更に含む21)~24)の何れか一項に記載のプリント配線板の製造方法。 14) A copper foil for a printed circuit comprising the ultrathin copper layer of the copper foil with a carrier according to any one of 1) to 13) above.
15) The copper foil with a carrier according to any one of 1) to 13), wherein a resin layer is provided on the surface treatment layer.
16) A copper-clad laminate obtained by laminating and bonding a printed circuit copper foil according to 14) above to a resin substrate.
17) A printed wiring board produced using the carrier-attached copper foil according to any one of 1) to 13) above.
18) A printed circuit board produced using the carrier-attached copper foil according to any one of 1) to 13) above.
19) A copper-clad laminate produced using the carrier-attached copper foil according to any one of 1) to 13) above.
20) A step of preparing the carrier-attached copper foil according to any one of 1) to 13) above and an insulating substrate;
Laminating the copper foil with carrier and an insulating substrate;
After laminating the carrier-attached copper foil and the insulating substrate, a copper-clad laminate is formed through a step of peeling the carrier of the carrier-attached copper foil,
Then, the manufacturing method of a printed wiring board including the process of forming a circuit by any method of a semi-additive method, a subtractive method, a partly additive method, or a modified semi-additive method.
21) A step of forming a circuit on the surface of the ultrathin copper layer side of the carrier-attached copper foil according to any one of 1) to 13) above,
Forming a resin layer on the ultrathin copper layer side surface of the carrier-attached copper foil so that the circuit is buried;
Forming a circuit on the resin layer;
Forming the circuit on the resin layer, and then peeling the carrier; and
After the carrier is peeled off, the printed wiring board includes a step of exposing the circuit embedded in the resin layer formed on the surface of the ultrathin copper layer by removing the ultrathin copper layer Method.
22) forming a circuit on the resin layer,
It is the process of bonding another copper foil with a carrier on the said resin layer from the ultra-thin copper layer side, and forming the said circuit using the copper foil with a carrier bonded together to the said resin layer. Manufacturing method of printed wiring board.
23) The method for producing a printed wiring board according to 22), wherein another copper foil with a carrier to be bonded onto the resin layer is the copper foil with a carrier according to any one of 1) to 13).
24) The step of forming a circuit on the resin layer is performed by any one of a semi-additive method, a subtractive method, a partly additive method, or a modified semi-additive method, 21) to 23) The manufacturing method of the printed wiring board of description.
25) The method for producing a printed wiring board according to any one of 21) to 24), further comprising a step of forming a substrate on the carrier-side surface of the carrier-attached copper foil before peeling off the carrier.
電子機器の発展が進む中で、半導体デバイスの小型化、高集積化が更に進み、これらの印刷回路の製造工程で行われる処理が一段と厳しい要求がなされている。本願発明をこれらの要求にこたえる優れた技術である。 The present invention relates to a copper foil for a printed circuit and a copper foil with a carrier for a copper-clad laminate, and in particular, the ultra-thin copper foil with a carrier in which a carrier, an intermediate layer, and an ultra-thin copper layer are laminated in this order. After forming a roughening treatment on the surface of the copper layer, forming a heat-resistant layer, a weather-resistant layer, and a rust-preventing layer on the copper layer, and then using a copper foil with a carrier with a silane coupling treatment, an ultrathin copper layer In the tension laminate, when the substrate is subjected to acid treatment or chemical etching after the fine pattern printed circuit is formed, it improves the suppression of deterioration in adhesion due to acid "soaking" into the interface between the copper foil circuit and the substrate resin. The present invention relates to a copper foil with a carrier, which has excellent acid-resistant adhesion strength and excellent alkali etching properties.
Along with the development of electronic devices, the miniaturization and high integration of semiconductor devices have further advanced, and the processing performed in the manufacturing process of these printed circuits has become more severe. The present invention is an excellent technique that meets these requirements.
本願発明のキャリア付銅箔は、銅箔または銅合金箔の上に、粗化(トリート)処理を施すことにより形成された粗化処理層、この粗化処理層の上に形成されたNi-Co層からなる耐熱層、及びこの耐熱層の上に形成されたZn、Ni、Crを含有する耐候層及び防錆層からなる複数の表面処理層を有する。そして、前記表面処理層中の全Zn量/(全Zn量+全Ni量)が0.02以上0.35以下とする。 The main object of the present invention is to prevent circuit erosion that occurs during surface etching in the pretreatment process in the manufacturing process of the FPC multilayer substrate.
The copper foil with a carrier of the present invention is a roughened layer formed by subjecting a copper foil or a copper alloy foil to a roughening (treat) treatment, and a Ni-- formed on the roughened layer. It has a heat-resistant layer made of a Co layer, and a plurality of surface treatment layers made of a weather-resistant layer containing Zn, Ni, and Cr and a rust-proof layer formed on the heat-resistant layer. The total Zn content / (total Zn content + total Ni content) in the surface treatment layer is set to 0.02 or more and 0.35 or less.
しかしながら、Znは耐候性に効果のある成分であるが、ファインパターン回路形成工程での耐薬品特性には好ましくない成分であり、回路形成のエッチングにおいて「染込み」が起こり易くなる。
一方、Niは「染込み」には効果のある成分であるが、多すぎるとアルカリエッチング性を低下させ、印刷回路用としては不適となる。 This is the main condition that can effectively prevent “soaking” that occurs during surface etching. Zn is a component of a weathering layer and a rust prevention layer in the surface treatment layer of copper foil, Ni is a component of a roughening treatment layer, a heat-resistant layer, and a weathering layer, and Zn and Ni are the surfaces of the copper foil It is an important component as a constituent component of the treatment layer.
However, Zn is a component having an effect on weather resistance, but it is an unfavorable component for chemical resistance characteristics in the fine pattern circuit forming process, and “soaking” easily occurs in etching for circuit formation.
On the other hand, Ni is an effective component for “soaking”, but if it is too much, the alkaline etching property is lowered and it is not suitable for printed circuit.
0.02未満の場合には、Znが少な過ぎるケースとNiが多過ぎるケースがあり、Znが少な過ぎるケースでは耐候性が悪くなり、Niが多過ぎるケースではエッチング性が問題となり、いずれのケースも好ましくない。一方、0.35を越える場合は耐酸性が悪化し易くなるので、エッチング時に「染込み」が起こり易くなり、好ましくない。 Thus, the present invention has found that the balance between Zn and Ni is important. That is, the total Zn amount / (total Zn amount + total Ni amount) in the surface treatment layer is 0.02 or more and 0.35 or less. In a preferred embodiment, the total Zn content / (total Zn content + total Ni content) in the surface treatment layer can be 0.02 or more and 0.23 or less, more preferably 0.04 or more and 0.03 or less. 23 or less.
If it is less than 0.02, there are cases where Zn is too little and cases where Ni is too much. In cases where Zn is too little, the weather resistance deteriorates. In cases where Ni is too much, etching properties become a problem. Is also not preferred. On the other hand, if it exceeds 0.35, the acid resistance tends to be deteriorated, so that “soaking” tends to occur during etching, which is not preferable.
なお、粗化処理段階のNi付着量の定義は、「銅箔(キャリア付銅箔の極薄銅層)上の粗化処理層の中に含まれるNi量」である。粗化処理段階のNi付着量は各実施例、各比較例と同一の条件でキャリア付銅箔を製造した後、各実施例、各比較例と同一の条件で粗化処理層のみを設けた後、サンプルを採取し、全Ni量と同様にNi付着量の測定を行うことで測定した。 Similarly, the definition of the total amount of Ni is “the amount of Ni contained in the roughened layer, the heat-resistant layer, the weather-resistant layer, and the rust-proof layer on the copper foil (the ultra-thin copper layer of the copper foil with carrier)”. . When Ni is not contained in the rust prevention layer, the total amount of Ni is the sum of the amounts of Ni in the roughening treatment layer, the heat resistant layer, and the weather resistant layer. When Ni is contained in the intermediate layer, the ultrathin copper layer is peeled from the carrier. Then, after masking the surface of the ultrathin copper layer on the roughened layer side with a resin, etc., pickle the surface of the ultrathin copper layer on the intermediate layer side, and include it in the surface of the ultrathin copper layer on the intermediate layer side Ni is removed. Thereafter, the amount of Ni may be measured for the ultrathin copper layer. In addition, it is good to perform the pickling of the surface by the side of the intermediate | middle layer of an ultra-thin copper layer with the nitric acid aqueous solution mixed by the ratio of nitric acid: water = 1: 2 (volume).
The definition of the Ni adhesion amount at the roughening treatment stage is “the amount of Ni contained in the roughening treatment layer on the copper foil (the ultrathin copper layer of the copper foil with carrier)”. The amount of Ni deposited in the roughening treatment stage was the same as that of each example and each comparative example, and after manufacturing a copper foil with a carrier, only the roughening layer was provided under the same conditions as each example and each comparative example. Thereafter, a sample was taken and measured by measuring the Ni adhesion amount in the same manner as the total Ni amount.
図1の左側は、樹脂層と表面処理層付銅箔の回路面が密着している様子(▼部)を示す概念図である。図1の右側は、回路の両縁に染込みが発生し、やや密着が少なくなっている様子(▼部)を示す概念図である。 The “soaking” is shown in FIG. 1, but when the surface is etched using a solution of hydrogen peroxide and sulfuric acid, or the circuit is formed using an etching solution made of a cupric chloride solution, a ferric chloride solution, or the like. This refers to a phenomenon in which an etchant penetrates into the interface between a copper foil and a resin when the formation is etched.
The left side of FIG. 1 is a conceptual diagram showing a state (▼ portion) in which the circuit surfaces of the resin layer and the copper foil with a surface treatment layer are in close contact with each other. The right side of FIG. 1 is a conceptual diagram showing a state (▼ portion) in which permeation occurs on both edges of the circuit and adhesion is slightly reduced.
従って、本願発明の キャリア付銅箔は、前記表面処理層中の全Ni量は、1600μg/dm2以下であり、好ましくは1150μg/dm2以下である。また、前記表面処理層中の全Ni量は350~1350μg/dm2とすることが望ましく、450~1100μg/dm2とすることがより望ましい。 Ni is a component contained in the roughened layer, heat resistant layer, weather resistant layer, and rust preventive layer of the surface treatment layer as described above, and is an extremely important component in the surface treatment layer of the ultrathin copper layer. And it is a component effective in "sinking" which is a problem to be solved by the present invention.
Thus, a copper foil with a carrier of the present invention, the total Ni content of the surface treatment layer is at 1600μg / dm 2 or less, preferably 1150μg / dm 2 or less. The total amount of Ni in the surface treatment layer is preferably 350 to 1350 μg / dm 2 , more preferably 450 to 1100 μg / dm 2 .
さらにNiは、耐熱層、耐候層にも含まれるため、全Ni量として350μg/dm2以上が必要である場合があり、更には450μg/dm2以上が必要である場合がある。但し、全Ni量が1350μg/dm2あるいは1100μg/dm2を超えると、アルカリエッチング性の低下や、回路エッチングの際に粗化粒子が基板樹脂表面に残存する問題が発生する場合があるので、Ni量は1350μg/dm2以下が望ましい場合があり、1100μg/dm2以下がより望ましい場合があると言える。 Moreover, since Ni contained in the roughened layer needs to have the surface of the surface-treated copper foil appear black, it may be necessary to contain Ni in an amount of 50 μg / dm 2 or more.
Furthermore, since Ni is also included in the heat-resistant layer and the weather-resistant layer, 350 μg / dm 2 or more may be necessary as the total Ni amount, and 450 μg / dm 2 or more may be necessary. However, if the total amount of Ni exceeds 1350 μg / dm 2 or 1100 μg / dm 2 , there may occur a problem that the alkali etching property deteriorates or the roughened particles remain on the substrate resin surface during circuit etching. Ni amount may desirable 1350μg / dm 2 or less, it can be said that there is a case 1100μg / dm 2 or less is more preferable.
また、前記粗化処理層については、Co、Cu、Niの元素からなる粗化処理層が有効である。前記粗化処理層を、平均粒子径0.05~0.60μmの微細粒子とすることが好ましく、平均粒子径0.05~0.60μmのCu、Co、Niからなる3元系合金の微細粒子の集合体とすることもできる。前記平均粒子径0.05~0.60μmの微細粒子は銅を含む合金めっきの焼けめっき(粗化めっき処理)により形成することができる。
前記粗化処理層については、平均粒子径0.25~0.45μmの一次粒子層と、その上に形成された平均粒子径が0.05~0.25μmの二次粒子層とすることが好ましい。また、前記粗化処理層については、平均粒子径0.25~0.45μmのCuの一次粒子層と、その上に形成された平均粒子径が0.05~0.25μmのCu、Co、Niからなる3元系合金からなる二次粒子層とすることができる。前記一次粒子層は銅めっきの焼けめっき(粗化めっき処理)であることが好ましい。また、前記二次粒子層は銅を含む合金めっきの焼けめっき(粗化めっき処理)により形成することができる。 The effective Ni for the roughened layer of the copper foil with a surface-treated layer of the present invention is 50 to 550 μg / dm 2 .
For the roughened layer, a roughened layer made of Co, Cu, or Ni is effective. The roughening treatment layer is preferably made of fine particles having an average particle size of 0.05 to 0.60 μm, and fine particles of a ternary alloy composed of Cu, Co, Ni having an average particle size of 0.05 to 0.60 μm. It can also be an aggregate of particles. The fine particles having an average particle diameter of 0.05 to 0.60 μm can be formed by burn plating (roughening plating treatment) of alloy plating containing copper.
The roughening treatment layer may be a primary particle layer having an average particle size of 0.25 to 0.45 μm and a secondary particle layer having an average particle size of 0.05 to 0.25 μm formed thereon. preferable. Further, for the roughening treatment layer, a primary particle layer of Cu having an average particle diameter of 0.25 to 0.45 μm, and Cu, Co having an average particle diameter of 0.05 to 0.25 μm formed thereon, A secondary particle layer made of a ternary alloy made of Ni can be formed. The primary particle layer is preferably a copper plating burn plating (roughening plating treatment). Moreover, the said secondary particle layer can be formed by the baking plating (roughening plating process) of the alloy plating containing copper.
平均粒子径0.05~0.60μmのCu、Co、Niからなる3元系合金の微細粗化粒子集合体の粗化処理を施す場合
液組成:Cu10~20g/リットル、Co1~10g/リットル、Ni1~15g/リットル
pH:1~4
温度:30~50℃
電流密度(Dk):20~50A/dm2
時間:1~5秒 (Roughening conditions)
When roughening a finely roughened particle assembly of a ternary alloy composed of Cu, Co, and Ni having an average particle size of 0.05 to 0.60 μm Liquid composition: Cu 10 to 20 g / liter, Co 1 to 10 g / liter , Ni 1-15 g / liter pH: 1-4
Temperature: 30-50 ° C
Current density (D k ): 20 to 50 A / dm 2
Time: 1-5 seconds
液組成:Cu10~20g/リットル、硫酸50~100g/リットル
pH:1~3
温度:25~50℃
電流密度(Dk):1~60A/dm2
時間:1~5秒 (A) Cu primary particle layer formation Liquid composition: Cu 10 to 20 g / liter, sulfuric acid 50 to 100 g / liter pH: 1 to 3
Temperature: 25-50 ° C
Current density (D k ): 1 to 60 A / dm 2
Time: 1-5 seconds
液組成:Cu10~20g/リットル、Co1~15g/リットル、Ni1~15g/リットル
pH:1~3
温度:30~50℃
電流密度(Dk):10~50A/dm2
時間:1~5秒 (B) Formation of secondary particle layer made of ternary alloy consisting of Cu, Co, Ni Liquid composition: Cu 10-20 g / liter, Co 1-15 g / liter, Ni 1-15 g / liter pH: 1-3
Temperature: 30-50 ° C
Current density (D k ): 10 to 50 A / dm 2
Time: 1-5 seconds
液組成:Co1~20g/リットル、Ni1~20g/リットル
pH:1~4
温度:30~60℃
電流密度(Dk):1~20A/dm2
時間:1~5秒 (Conditions for forming a heat-resistant layer)
Liquid composition: Co 1 to 20 g / liter, Ni 1 to 20 g / liter pH: 1 to 4
Temperature: 30-60 ° C
Current density (D k ): 1 to 20 A / dm 2
Time: 1-5 seconds
液組成:Ni1~30g/リットル、Zn1~30g/リットル
pH:2~5
温度:30~50℃
電流密度(Dk):1~3A/dm2
時間:1~5秒 (Condition 1 for forming a weather resistant layer and a rust preventive layer)
Liquid composition: Ni 1-30 g / liter, Zn 1-30 g / liter pH: 2-5
Temperature: 30-50 ° C
Current density (D k ): 1 to 3 A / dm 2
Time: 1-5 seconds
液組成:K2Cr2O7:1~10g/リットル、Zn:0~10g/リットル
pH:2~5
温度:30~50℃
電流密度(Dk):0.01~5A/dm2
時間:0.01~5秒 (Condition 2 for forming a weather resistant layer and a rust preventive layer)
Liquid composition: K 2 Cr 2 O 7 : 1 to 10 g / liter, Zn: 0 to 10 g / liter pH: 2 to 5
Temperature: 30-50 ° C
Current density (D k ): 0.01 to 5 A / dm 2
Time: 0.01-5 seconds
防錆層上の少なくとも粗化面にシランカップリング剤を塗布するシランカップリング処理が施される。
このシランカップリング剤としては、オレフィン系シラン、エポキシ系シラン、アクリル系シラン、アミノ系シラン、メルカプト系シランを挙げることができるが、これらを適宜選択して使用することができる。 (Silane coupling treatment)
A silane coupling treatment for applying a silane coupling agent to at least the roughened surface on the anticorrosive layer is performed.
Examples of the silane coupling agent include olefin silanes, epoxy silanes, acrylic silanes, amino silanes, and mercapto silanes, which can be appropriately selected and used.
本発明のキャリア付銅箔のキャリアには銅箔、アルミ箔、アルミ合金箔または鉄合金、ステンレス、ニッケル、ニッケル合金等の箔を用いることができる。なお、キャリア上への中間層の積層し易さを考慮すると、キャリアは銅箔であることが好ましい。キャリアに用いられる銅箔は典型的には圧延銅箔や電解銅箔の形態で提供される。 (Career)
For the carrier of the copper foil with a carrier of the present invention, a foil of copper foil, aluminum foil, aluminum alloy foil or iron alloy, stainless steel, nickel, nickel alloy or the like can be used. In consideration of the ease of stacking the intermediate layer on the carrier, the carrier is preferably a copper foil. The copper foil used for the carrier is typically provided in the form of a rolled copper foil or an electrolytic copper foil.
キャリアの上には中間層を設ける。キャリアと中間層との間に他の層を設けてもよい。本発明のキャリア付銅箔の中間層はCr、Ni、Co、Fe、Mo、Ti、W、P、Cu、Al、Znまたはこれらの合金、またはこれらの水和物、またはこれらの酸化物、あるいは有機物の何れか一種以上を含む層で形成することが好ましい。中間層は複数の層であっても良い。 (Middle layer)
An intermediate layer is provided on the carrier. Another layer may be provided between the carrier and the intermediate layer. The intermediate layer of the carrier-attached copper foil of the present invention is made of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, or an alloy thereof, or a hydrate thereof, or an oxide thereof. Or it is preferable to form in the layer containing any 1 or more types of organic substance. The intermediate layer may be a plurality of layers.
中間層の上には極薄銅層を設ける。その前に極薄銅層のピンホールを低減させるために銅-リン合金によるストライクめっきを行ってもよい。ストライクめっきにはピロリン酸銅めっき液などが挙げられる。 (Strike plating)
An ultrathin copper layer is provided on the intermediate layer. Before that, strike plating with a copper-phosphorus alloy may be performed to reduce pinholes in the ultrathin copper layer. Examples of the strike plating include a copper pyrophosphate plating solution.
中間層の上には極薄銅層を設ける。中間層と極薄銅層との間には他の層を設けてもよい。本発明のキャリア付銅箔の極薄銅層は、硫酸銅、ピロリン酸銅、スルファミン酸銅、シアン化銅等の電解浴を利用した電気めっきにより形成することができ、一般的な電解銅箔で使用され、高電流密度での銅箔形成が可能であることから硫酸銅浴が好ましい。
極薄銅層の厚みは特に制限はないが、一般的にはキャリアよりも薄く、例えば12μm以下である。典型的には0.1~12μmであり、より典型的には0.5~12μmであり、更に典型的には2~5μmである。 (Ultra-thin copper layer)
An ultrathin copper layer is provided on the intermediate layer. Another layer may be provided between the intermediate layer and the ultrathin copper layer. The ultrathin copper layer of the copper foil with a carrier of the present invention can be formed by electroplating using an electrolytic bath such as copper sulfate, copper pyrophosphate, copper sulfamate, copper cyanide, etc. A copper sulfate bath is preferred because it is possible to form a copper foil at a high current density.
The thickness of the ultrathin copper layer is not particularly limited, but is generally thinner than the carrier, for example, 12 μm or less. Typically, it is 0.1 to 12 μm, more typically 0.5 to 12 μm, and still more typically 2 to 5 μm.
このようにして、キャリアと、キャリア上に中間層が積層され、中間層の上に積層された極薄銅層とを備えたキャリア付銅箔が製造される。キャリア付銅箔自体の使用方法は当業者に周知であるが、例えば極薄銅層の表面を紙基材フェノール樹脂、紙基材エポキシ樹脂、合成繊維布基材エポキシ樹脂、ガラス布・紙複合基材エポキシ樹脂、ガラス布・ガラス不織布複合基材エポキシ樹脂及びガラス布基材エポキシ樹脂、ポリエステルフィルム、ポリイミドフィルム等の絶縁基板に貼り合わせて熱圧着後にキャリアを剥がし、絶縁基板に接着した極薄銅層を目的とする導体パターンにエッチングし、最終的にプリント配線板を製造することができる。
本発明に係るキャリア付銅箔の場合、剥離箇所は主としてキャリアと中間層の界面または中間層と極薄銅層の界面である。また、中間層が複数の層からなる場合には、当該複数の層の界面で剥離する場合がある。 (Copper foil with carrier)
In this way, a carrier-attached copper foil including a carrier and an intermediate layer laminated on the carrier and an ultrathin copper layer laminated on the intermediate layer is manufactured. The method of using the copper foil with carrier itself is well known to those skilled in the art. For example, the surface of the ultra-thin copper layer is made of paper base phenol resin, paper base epoxy resin, synthetic fiber cloth base epoxy resin, glass cloth / paper composite. Ultra-thin bonded to an insulating substrate, bonded to an insulating substrate such as a base epoxy resin, glass cloth / glass nonwoven fabric composite epoxy resin and glass cloth base epoxy resin, polyester film, polyimide film, etc. The copper layer can be etched into the intended conductor pattern to finally produce a printed wiring board.
In the case of the copper foil with a carrier according to the present invention, the peeling site is mainly the interface between the carrier and the intermediate layer or the interface between the intermediate layer and the ultrathin copper layer. Further, when the intermediate layer is composed of a plurality of layers, it may be peeled off at the interface between the plurality of layers.
また、本発明のキャリア付銅箔は、表面処理層の上に樹脂層を備えても良い。前記樹脂層は絶縁樹脂層であってもよい。
なお、前記耐熱層、防錆層、クロメート処理層、シランカップリング処理層を形成する順番は互いに限定されず、極薄銅層上、或いは、粗化処理層上に、どのような順序でこれらの層を形成してもよい。 (Resin layer)
Moreover, the copper foil with a carrier of the present invention may include a resin layer on the surface treatment layer. The resin layer may be an insulating resin layer.
Note that the order of forming the heat-resistant layer, the rust-proofing layer, the chromate-treated layer, and the silane coupling-treated layer is not limited to each other, and in any order on the ultrathin copper layer or the roughened layer. These layers may be formed.
前記リン含有エポキシ樹脂として公知のリンを含有するエポキシ樹脂を用いることができる。また、前記リン含有エポキシ樹脂は例えば、分子内に2以上のエポキシ基を備える9,10-ジヒドロ-9-オキサ-10-ホスファフェナントレン-10-オキサイドからの誘導体として得られるエポキシ樹脂であることが好ましい。 The epoxy resin has two or more epoxy groups in the molecule and can be used without any problem as long as it can be used for electric / electronic materials. The epoxy resin is preferably an epoxy resin epoxidized using a compound having two or more glycidyl groups in the molecule. Also, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, novolac type epoxy resin, cresol novolac type epoxy resin, alicyclic epoxy resin, brominated (brominated) epoxy Resin, phenol novolac type epoxy resin, naphthalene type epoxy resin, brominated bisphenol A type epoxy resin, orthocresol novolac type epoxy resin, rubber modified bisphenol A type epoxy resin, glycidylamine type epoxy resin, triglycidyl isocyanurate, N, N -Glycidyl amine compounds such as diglycidyl aniline, glycidyl ester compounds such as diglycidyl tetrahydrophthalate, phosphorus-containing epoxy resins, biphenyl type epoxy resins, One or two or more types selected from the group of phenyl novolac type epoxy resin, trishydroxyphenylmethane type epoxy resin, tetraphenylethane type epoxy resin can be used, or a hydrogenated product of the epoxy resin or Halogenated substances can be used.
As the phosphorus-containing epoxy resin, a known epoxy resin containing phosphorus can be used. The phosphorus-containing epoxy resin is, for example, an epoxy resin obtained as a derivative from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide having two or more epoxy groups in the molecule. Is preferred.
前記ビフェニル型フェノール樹脂の具体例を化学式8に示す。 The resin layer may contain a resin curing agent. A known resin curing agent can be used as the resin curing agent. For example, resin curing agents include amines such as dicyandiamide, imidazoles and aromatic amines, phenols such as bisphenol A and brominated bisphenol A, novolaks such as phenol novolac resins and cresol novolac resins, and acid anhydrides such as phthalic anhydride. Products, biphenyl type phenol resins, phenol aralkyl type phenol resins and the like can be used. The resin layer may contain one or more of the aforementioned resin curing agents. These curing agents are particularly effective for epoxy resins.
A specific example of the biphenyl type phenol resin is shown in Chemical Formula 8.
前記芳香族ポリアミド樹脂と反応させる前記ゴム性樹脂とは、公知のゴム性樹脂または前述のゴム性樹脂を用いることができる。
この芳香族ポリアミド樹脂ポリマーは、銅張積層板に加工した後の銅箔をエッチング加工する際に、エッチング液によりアンダーエッチングによる損傷を受けないことを目的に用いたものである。 Examples of the aromatic polyamide resin polymer include those obtained by reacting an aromatic polyamide resin and a rubber resin. Here, the aromatic polyamide resin is synthesized by condensation polymerization of an aromatic diamine and a dicarboxylic acid. As the aromatic diamine at this time, 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylsulfone, m-xylenediamine, 3,3′-oxydianiline and the like are used. As the dicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, fumaric acid or the like is used.
As the rubber resin to be reacted with the aromatic polyamide resin, a known rubber resin or the aforementioned rubber resin can be used.
This aromatic polyamide resin polymer is used for the purpose of not being damaged by under-etching by an etchant when etching a copper foil after being processed into a copper-clad laminate.
A成分: エポキシ当量が200以下で、室温で液状のビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、ビスフェノールAD型エポキシ樹脂の群から選ばれる1種又は2種以上からなるエポキシ樹脂。
B成分: 高耐熱性エポキシ樹脂。
C成分: リン含有エポキシ系樹脂、フォスファゼン系樹脂のいずれか1種又はこれらを混合した樹脂であるリン含有難燃性樹脂。
D成分: 沸点が50℃~200℃の範囲にある溶剤に可溶な性質を備える液状ゴム成分で変成したゴム変成ポリアミドイミド樹脂。
E成分: 樹脂硬化剤。 The epoxy resin composition preferably contains the following components A to E.
Component A: An epoxy resin having one or more selected from the group consisting of a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a bisphenol AD type epoxy resin that have an epoxy equivalent of 200 or less and are liquid at room temperature.
B component: High heat-resistant epoxy resin.
Component C: Phosphorus-containing flame-retardant resin, which is any one of phosphorus-containing epoxy resin and phosphazene-based resin, or a mixture of these.
Component D: A rubber-modified polyamideimide resin modified with a liquid rubber component having a property of being soluble in a solvent having a boiling point in the range of 50 ° C. to 200 ° C.
E component: Resin curing agent.
C成分のリン含有エポキシ樹脂として、前述のリン含有エポキシ樹脂を用いることができる。また、C成分のフォスファゼン系樹脂として前述のフォスファゼン系樹脂を用いることができる。
D成分のゴム変成ポリアミドイミド樹脂として、前述のゴム変成ポリアミドイミド樹脂を用いることができる。E成分の樹脂硬化剤として、前述の樹脂硬化剤を用いることができる。 The B component is a “high heat resistant epoxy resin” having a high so-called glass transition point Tg. The “high heat-resistant epoxy resin” referred to here is preferably a polyfunctional epoxy resin such as a novolac-type epoxy resin, a cresol novolac-type epoxy resin, a phenol novolac-type epoxy resin, or a naphthalene-type epoxy resin.
As the phosphorus-containing epoxy resin of component C, the aforementioned phosphorus-containing epoxy resin can be used. The phosphazene resin described above can be used as the C component phosphazene resin.
The rubber-modified polyamide-imide resin described above can be used as the rubber-modified polyamide-imide resin of component D. The resin curing agent described above can be used as the E component resin curing agent.
前記樹脂層は誘電体(誘電体フィラー)を含んでもよい。
上記いずれかの樹脂層または樹脂組成物に誘電体(誘電体フィラー)を含ませる場合には、キャパシタ層を形成する用途に用い、キャパシタ回路の電気容量を増大させることができるのである。この誘電体(誘電体フィラー)には、BaTiO3、SrTiO3、Pb(Zr-Ti)O3(通称PZT)、PbLaTiO3・PbLaZrO(通称PLZT)、SrBi2Ta2O9(通称SBT)等のペブロスカイト構造を持つ複合酸化物の誘電体粉を用いる。 (When the resin layer contains a dielectric (dielectric filler))
The resin layer may include a dielectric (dielectric filler).
In the case where a dielectric (dielectric filler) is included in any of the above resin layers or resin compositions, it can be used for the purpose of forming the capacitor layer and increase the capacitance of the capacitor circuit. The dielectric (dielectric filler) includes a composite oxide having a perovskite structure such as BaTiO3, SrTiO3, Pb (Zr-Ti) O3 (commonly called PZT), PbLaTiO3 / PbLaZrO (commonly known as PLZT), SrBi2Ta2O9 (commonly known as SBT), and the like. Dielectric powder is used.
本件明細書において、レジンフローとは、MIL規格におけるMIL-P-13949Gに準拠して、樹脂厚さを55μmとした樹脂付銅箔から10cm角試料を4枚サンプリングし、この4枚の試料を重ねた状態(積層体)でプレス温度171℃、プレス圧14kgf/cm2、プレス時間10分の条件で張り合わせ、そのときの樹脂流出重量を測定した結果から数式1に基づいて算出した値である。 The resin layer is preferably a semi-cured resin film having a resin flow in the range of 5% to 35% when measured according to MIL-P-13949G in the MIL standard.
In this specification, the resin flow is based on MIL-P-13949G in the MIL standard. Four 10 cm square samples were sampled from a resin-coated copper foil with a resin thickness of 55 μm. It is a value calculated based on Formula 1 from the result of measuring the resin outflow weight at the time of lamination in a stacked state (laminate) under the conditions of a press temperature of 171 ° C., a press pressure of 14 kgf / cm 2, and a press time of 10 minutes.
この樹脂層の厚みは0.1~120μmであることが好ましい。 In addition, when the prepreg material is not used, the material cost of the prepreg material is saved and the laminating process is simplified, which is economically advantageous. Moreover, the multilayer printed wiring board manufactured by the thickness of the prepreg material is used. The thickness is reduced, and there is an advantage that an extremely thin multilayer printed wiring board in which the thickness of one layer is 100 μm or less can be manufactured.
The thickness of this resin layer is preferably 0.1 to 120 μm.
また、樹脂層が誘電体を含む場合には、樹脂層の厚みは0.1~50μmであることが好ましく、0.5μm~25μmであることが好ましく、1.0μm~15μmであることがより好ましい。
また、前記硬化樹脂層、半硬化樹脂層との総樹脂層厚みは0.1μm~120μmであるものが好ましく、5μm~120μmであるものが好ましく、10μm~120μmであるものが好ましく、10μm~60μmのものがより好ましい。そして、硬化樹脂層の厚みは2μm~30μmであることが好ましく、3μm~30μmであることが好ましく、5~20μmであることがより好ましい。また、半硬化樹脂層の厚みは3μm~55μmであることが好ましく、7μm~55μmであることが好ましく、15~115μmであることがより望ましい。総樹脂層厚みが120μmを超えると、薄厚の多層プリント配線板を製造することが難しくなる場合があり、5μm未満では薄厚の多層プリント配線板を形成し易くなるものの、内層の回路間における絶縁層である樹脂層が薄くなりすぎ、内層の回路間の絶縁性を不安定にする傾向が生じる場合があるためである。また、硬化樹脂層厚みが2μm未満であると、銅箔粗化面の表面粗度を考慮する必要が生じる場合がある。逆に硬化樹脂層厚みが20μmを超えると硬化済み樹脂層による効果は特に向上することがなくなる場合があり、総絶縁層厚は厚くなる。 When the copper foil with a carrier having a resin layer is used for producing an extremely thin multilayer printed wiring board, the thickness of the resin layer is 0.1 μm to 5 μm, more preferably 0.5 μm to 5 μm, More preferably, the thickness is 1 μm to 5 μm in order to reduce the thickness of the multilayer printed wiring board.
When the resin layer contains a dielectric, the thickness of the resin layer is preferably 0.1 to 50 μm, more preferably 0.5 μm to 25 μm, and more preferably 1.0 μm to 15 μm. preferable.
The total resin layer thickness of the cured resin layer and the semi-cured resin layer is preferably 0.1 μm to 120 μm, preferably 5 μm to 120 μm, preferably 10 μm to 120 μm, and 10 μm to 60 μm. Are more preferred. The thickness of the cured resin layer is preferably 2 μm to 30 μm, preferably 3 μm to 30 μm, and more preferably 5 to 20 μm. The thickness of the semi-cured resin layer is preferably 3 μm to 55 μm, more preferably 7 μm to 55 μm, and even more preferably 15 to 115 μm. If the total resin layer thickness exceeds 120 μm, it may be difficult to produce a thin multilayer printed wiring board. If the total resin layer thickness is less than 5 μm, it is easy to form a thin multilayer printed wiring board, but an insulating layer between inner layer circuits This is because the resin layer may become too thin and the insulation between the circuits of the inner layer tends to become unstable. Moreover, when the cured resin layer thickness is less than 2 μm, it may be necessary to consider the surface roughness of the roughened copper foil surface. Conversely, if the cured resin layer thickness exceeds 20 μm, the effect of the cured resin layer may not be particularly improved, and the total insulating layer thickness becomes thick.
なお、前述の樹脂層の厚みは、任意の10点において断面観察により測定した厚みの平均値をいう。 When the thickness of the resin layer is 0.1 μm to 5 μm, in order to improve the adhesion between the resin layer and the copper foil with carrier, a heat-resistant layer and / or a rust-proof layer is formed on the ultrathin copper layer. After providing the chromate treatment layer and / or the silane coupling treatment layer, it is preferable to form a resin layer on the heat-resistant layer, rust prevention layer, chromate treatment layer or silane coupling treatment layer.
In addition, the thickness of the above-mentioned resin layer says the average value of the thickness measured by cross-sectional observation in arbitrary 10 points | pieces.
本発明に係るキャリア付銅箔と絶縁基板とを準備する工程、
前記キャリア付銅箔と絶縁基板を積層する工程、
前記キャリア付銅箔と絶縁基板を積層した後に、前記キャリア付銅箔のキャリアを剥がす工程、
前記キャリアを剥がして露出した極薄銅層を酸などの腐食溶液を用いたエッチングやプラズマなどの方法によりすべて除去する工程、
前記極薄銅層をエッチングにより除去することにより露出した前記樹脂にスルーホールまたは/およびブラインドビアを設ける工程、
前記スルーホールまたは/およびブラインドビアを含む領域についてデスミア処理を行う工程、
前記樹脂および前記スルーホールまたは/およびブラインドビアを含む領域について無電解めっき層を設ける工程、
前記無電解めっき層の上にめっきレジストを設ける工程、
前記めっきレジストに対して露光し、その後、回路が形成される領域のめっきレジストを除去する工程、
前記めっきレジストが除去された前記回路が形成される領域に、電解めっき層を設ける工程、
前記めっきレジストを除去する工程、
前記回路が形成される領域以外の領域にある無電解めっき層をフラッシュエッチングなどにより除去する工程、
を含む。 Therefore, in one embodiment of a method for manufacturing a printed wiring board according to the present invention using a semi-additive method,
Preparing a copper foil with a carrier and an insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Removing all of the ultrathin copper layer exposed by peeling the carrier by a method such as etching or plasma using a corrosive solution such as acid,
Providing a through hole or / and a blind via in the resin exposed by removing the ultrathin copper layer by etching;
Performing a desmear process on the region including the through hole or / and the blind via,
Providing an electroless plating layer for the region including the resin and the through hole or / and the blind via;
Providing a plating resist on the electroless plating layer;
Exposing the plating resist, and then removing the plating resist in a region where a circuit is formed;
Providing an electrolytic plating layer in a region where the circuit from which the plating resist has been removed is formed;
Removing the plating resist;
Removing the electroless plating layer in a region other than the region where the circuit is formed by flash etching or the like;
including.
本発明に係るキャリア付銅箔と絶縁基板とを準備する工程、
前記キャリア付銅箔と絶縁基板を積層する工程、
前記キャリア付銅箔と絶縁基板を積層した後に、前記キャリア付銅箔のキャリアを剥がす工程、
前記キャリアを剥がして露出した極薄銅層を酸などの腐食溶液を用いたエッチングやプラズマなどの方法によりすべて除去する工程、
前記極薄銅層をエッチングにより除去することにより露出した前記樹脂の表面について無電解めっき層を設ける工程、
前記無電解めっき層の上にめっきレジストを設ける工程、
前記めっきレジストに対して露光し、その後、回路が形成される領域のめっきレジストを除去する工程、
前記めっきレジストが除去された前記回路が形成される領域に、電解めっき層を設ける工程、
前記めっきレジストを除去する工程、
前記回路が形成される領域以外の領域にある無電解めっき層及び極薄銅層をフラッシュエッチングなどにより除去する工程、
を含む。 In another embodiment of the method for producing a printed wiring board according to the present invention using a semi-additive method,
Preparing a copper foil with a carrier and an insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Removing all of the ultrathin copper layer exposed by peeling the carrier by a method such as etching or plasma using a corrosive solution such as acid,
Providing an electroless plating layer on the surface of the resin exposed by removing the ultrathin copper layer by etching;
Providing a plating resist on the electroless plating layer;
Exposing the plating resist, and then removing the plating resist in a region where a circuit is formed;
Providing an electrolytic plating layer in a region where the circuit from which the plating resist has been removed is formed;
Removing the plating resist;
Removing the electroless plating layer and the ultrathin copper layer in a region other than the region where the circuit is formed by flash etching or the like;
including.
本発明に係るキャリア付銅箔と絶縁基板とを準備する工程、
前記キャリア付銅箔と絶縁基板を積層する工程、
前記キャリア付銅箔と絶縁基板を積層した後に、前記キャリア付銅箔のキャリアを剥がす工程、
前記キャリアを剥がして露出した極薄銅層と絶縁基板にスルーホールまたは/およびブラインドビアを設ける工程、
前記スルーホールまたは/およびブラインドビアを含む領域についてデスミア処理を行う工程、
前記スルーホールまたは/およびブラインドビアを含む領域について無電解めっき層を設ける工程、
前記キャリアを剥がして露出した極薄銅層表面にめっきレジストを設ける工程、
前記めっきレジストを設けた後に、電解めっきにより回路を形成する工程、
前記めっきレジストを除去する工程、
前記めっきレジストを除去することにより露出した極薄銅層をフラッシュエッチングにより除去する工程、
を含む。 Therefore, in one embodiment of the method for manufacturing a printed wiring board according to the present invention using the modified semi-additive method,
Preparing a copper foil with a carrier and an insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Providing a through hole or / and a blind via on the insulating substrate and the ultrathin copper layer exposed by peeling the carrier;
Performing a desmear process on the region including the through hole or / and the blind via,
Providing an electroless plating layer for the region including the through hole or / and the blind via;
Providing a plating resist on the surface of the ultrathin copper layer exposed by peeling the carrier,
Forming a circuit by electrolytic plating after providing the plating resist;
Removing the plating resist;
Removing the ultra-thin copper layer exposed by removing the plating resist by flash etching;
including.
本発明に係るキャリア付銅箔と絶縁基板とを準備する工程、
前記キャリア付銅箔と絶縁基板を積層する工程、
前記キャリア付銅箔と絶縁基板を積層した後に、前記キャリア付銅箔のキャリアを剥がす工程、
前記キャリアを剥がして露出した極薄銅層の上にめっきレジストを設ける工程、
前記めっきレジストに対して露光し、その後、回路が形成される領域のめっきレジストを除去する工程、
前記めっきレジストが除去された前記回路が形成される領域に、電解めっき層を設ける工程、
前記めっきレジストを除去する工程、
前記回路が形成される領域以外の領域にある無電解めっき層及び極薄銅層をフラッシュエッチングなどにより除去する工程、
を含む。 In another embodiment of the method for producing a printed wiring board according to the present invention using the modified semi-additive method,
Preparing a copper foil with a carrier and an insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Providing a plating resist on the exposed ultrathin copper layer by peeling off the carrier;
Exposing the plating resist, and then removing the plating resist in a region where a circuit is formed;
Providing an electrolytic plating layer in a region where the circuit from which the plating resist has been removed is formed;
Removing the plating resist;
Removing the electroless plating layer and the ultrathin copper layer in a region other than the region where the circuit is formed by flash etching or the like;
including.
本発明に係るキャリア付銅箔と絶縁基板とを準備する工程、
前記キャリア付銅箔と絶縁基板を積層する工程、
前記キャリア付銅箔と絶縁基板を積層した後に、前記キャリア付銅箔のキャリアを剥がす工程、
前記キャリアを剥がして露出した極薄銅層と絶縁基板にスルーホールまたは/およびブラインドビアを設ける工程、
前記スルーホールまたは/およびブラインドビアを含む領域についてデスミア処理を行う工程、
前記スルーホールまたは/およびブラインドビアを含む領域について触媒核を付与する工程、
前記キャリアを剥がして露出した極薄銅層表面にエッチングレジストを設ける工程、
前記エッチングレジストに対して露光し、回路パターンを形成する工程、
前記極薄銅層および前記触媒核を酸などの腐食溶液を用いたエッチングやプラズマなどの方法により除去して、回路を形成する工程、
前記エッチングレジストを除去する工程、
前記極薄銅層および前記触媒核を酸などの腐食溶液を用いたエッチングやプラズマなどの方法により除去して露出した前記絶縁基板表面に、ソルダレジストまたはメッキレジストを設ける工程、
前記ソルダレジストまたはメッキレジストが設けられていない領域に無電解めっき層を設ける工程、
を含む。 Therefore, in one embodiment of a method for manufacturing a printed wiring board according to the present invention using a partly additive method,
Preparing a copper foil with a carrier and an insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Providing a through hole or / and a blind via on the insulating substrate and the ultrathin copper layer exposed by peeling the carrier;
Performing a desmear process on the region including the through hole or / and the blind via,
Applying catalyst nuclei to the region containing the through-holes and / or blind vias;
Providing an etching resist on the surface of the ultrathin copper layer exposed by peeling the carrier,
Exposing the etching resist to form a circuit pattern;
Removing the ultrathin copper layer and the catalyst nucleus by a method such as etching or plasma using a corrosive solution such as an acid to form a circuit;
Removing the etching resist;
A step of providing a solder resist or a plating resist on the surface of the insulating substrate exposed by removing the ultrathin copper layer and the catalyst core by a method such as etching or plasma using a corrosive solution such as an acid;
Providing an electroless plating layer in a region where the solder resist or plating resist is not provided,
including.
本発明に係るキャリア付銅箔と絶縁基板とを準備する工程、
前記キャリア付銅箔と絶縁基板を積層する工程、
前記キャリア付銅箔と絶縁基板を積層した後に、前記キャリア付銅箔のキャリアを剥がす工程、
前記キャリアを剥がして露出した極薄銅層と絶縁基板にスルーホールまたは/およびブラインドビアを設ける工程、
前記スルーホールまたは/およびブラインドビアを含む領域についてデスミア処理を行う工程、
前記スルーホールまたは/およびブラインドビアを含む領域について無電解めっき層を設ける工程、
前記無電解めっき層の表面に、電解めっき層を設ける工程、
前記電解めっき層または/および前記極薄銅層の表面にエッチングレジストを設ける工程、
前記エッチングレジストに対して露光し、回路パターンを形成する工程、
前記極薄銅層および前記無電解めっき層および前記電解めっき層を酸などの腐食溶液を用いたエッチングやプラズマなどの方法により除去して、回路を形成する工程、
前記エッチングレジストを除去する工程、
を含む。 Therefore, in one embodiment of the printed wiring board manufacturing method according to the present invention using the subtractive method,
Preparing a copper foil with a carrier and an insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Providing a through hole or / and a blind via on the insulating substrate and the ultrathin copper layer exposed by peeling the carrier;
Performing a desmear process on the region including the through hole or / and the blind via,
Providing an electroless plating layer for the region including the through hole or / and the blind via;
Providing an electroplating layer on the surface of the electroless plating layer;
A step of providing an etching resist on the surface of the electrolytic plating layer or / and the ultrathin copper layer;
Exposing the etching resist to form a circuit pattern;
Removing the ultrathin copper layer and the electroless plating layer and the electrolytic plating layer by a method such as etching or plasma using a corrosive solution such as an acid to form a circuit;
Removing the etching resist;
including.
本発明に係るキャリア付銅箔と絶縁基板とを準備する工程、
前記キャリア付銅箔と絶縁基板を積層する工程、
前記キャリア付銅箔と絶縁基板を積層した後に、前記キャリア付銅箔のキャリアを剥がす工程、
前記キャリアを剥がして露出した極薄銅層と絶縁基板にスルーホールまたは/およびブラインドビアを設ける工程、
前記スルーホールまたは/およびブラインドビアを含む領域についてデスミア処理を行う工程、
前記スルーホールまたは/およびブラインドビアを含む領域について無電解めっき層を設ける工程、
前記無電解めっき層の表面にマスクを形成する工程、
マスクが形成されいない前記無電解めっき層の表面に電解めっき層を設ける工程、
前記電解めっき層または/および前記極薄銅層の表面にエッチングレジストを設ける工程、
前記エッチングレジストに対して露光し、回路パターンを形成する工程、
前記極薄銅層および前記無電解めっき層を酸などの腐食溶液を用いたエッチングやプラズマなどの方法により除去して、回路を形成する工程、
前記エッチングレジストを除去する工程、
を含む。 In another embodiment of the printed wiring board manufacturing method according to the present invention using the subtractive method,
Preparing a copper foil with a carrier and an insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Providing a through hole or / and a blind via on the insulating substrate and the ultrathin copper layer exposed by peeling the carrier;
Performing a desmear process on the region including the through hole or / and the blind via,
Providing an electroless plating layer for the region including the through hole or / and the blind via;
Forming a mask on the surface of the electroless plating layer;
Providing an electroplating layer on the surface of the electroless plating layer on which no mask is formed;
A step of providing an etching resist on the surface of the electrolytic plating layer or / and the ultrathin copper layer;
Exposing the etching resist to form a circuit pattern;
Removing the ultra-thin copper layer and the electroless plating layer by a method such as etching or plasma using a corrosive solution such as an acid to form a circuit;
Removing the etching resist;
including.
まず、図3-Aに示すように、表面に粗化処理層が形成された極薄銅層を有するキャリア付銅箔(1層目)を準備する。
次に、図3-Bに示すように、極薄銅層の粗化処理層上にレジストを塗布し、露光・現像を行い、レジストを所定の形状にエッチングする。
次に、図3-Cに示すように、回路用のめっきを形成した後、レジストを除去することで、所定の形状の回路めっきを形成する。
次に、図4-Dに示すように、回路めっきを覆うように(回路めっきが埋没するように)極薄銅層上に埋め込み樹脂を設けて樹脂層を積層し、続いて別のキャリア付銅箔(2層目)を極薄銅層側から接着させる。
次に、図4-Eに示すように、2層目のキャリア付銅箔からキャリアを剥がす。
次に、図4-Fに示すように、樹脂層の所定位置にレーザー穴あけを行い、回路めっきを露出させてブラインドビアを形成する。
次に、図5-Gに示すように、ブラインドビアに銅を埋め込みビアフィルを形成する。
次に、図5-Hに示すように、ビアフィル上に、上記図3-B及び図3-Cのようにして回路めっきを形成する。
次に、図5-Iに示すように、1層目のキャリア付銅箔からキャリアを剥がす。
次に、図6-Jに示すように、フラッシュエッチングにより両表面の極薄銅層を除去し、樹脂層内の回路めっきの表面を露出させる。
次に、図6-Kに示すように、樹脂層内の回路めっき上にはんだなどによりバンプを形成し、当該バンプ上に銅ピラーを形成する。このようにして本発明のキャリア付銅箔を用いたプリント配線板を作製する。 Here, the specific example of the manufacturing method of the printed wiring board using the copper foil with a carrier of this invention is demonstrated in detail using drawing. Here, the carrier-attached copper foil having an ultrathin copper layer on which a roughened layer is formed will be described as an example. However, the present invention is not limited thereto, and the carrier has an ultrathin copper layer on which a roughened layer is not formed. The following method for producing a printed wiring board can be similarly performed using an attached copper foil.
First, as shown in FIG. 3-A, a copper foil with a carrier (first layer) having an ultrathin copper layer having a roughened layer formed on the surface is prepared.
Next, as shown in FIG. 3B, a resist is applied on the roughened layer of the ultrathin copper layer, exposed and developed, and etched into a predetermined shape.
Next, as shown in FIG. 3C, after forming a plating for a circuit, the resist is removed to form a circuit plating having a predetermined shape.
Next, as shown in FIG. 4-D, an embedded resin is provided on the ultrathin copper layer so as to cover the circuit plating (so that the circuit plating is buried), and then the resin layer is laminated, followed by another carrier attachment. A copper foil (second layer) is bonded from the ultrathin copper layer side.
Next, as shown in FIG. 4-E, the carrier is peeled off from the second layer copper foil with carrier.
Next, as shown in FIG. 4-F, laser drilling is performed at a predetermined position of the resin layer to expose the circuit plating and form a blind via.
Next, as shown in FIG. 5G, copper is buried in the blind via to form a via fill.
Next, as shown in FIG. 5-H, circuit plating is formed on the via fill as shown in FIGS. 3-B and 3-C.
Next, as shown in FIG. 5-I, the carrier is peeled off from the first-layer copper foil with carrier.
Next, as shown in FIG. 6-J, the ultrathin copper layers on both surfaces are removed by flash etching to expose the surface of the circuit plating in the resin layer.
Next, as shown in FIG. 6K, bumps are formed on the circuit plating in the resin layer with solder or the like, and copper pillars are formed on the bumps. Thus, the printed wiring board using the copper foil with a carrier of this invention is produced.
(1)極薄銅層または粗化処理層または耐熱層または防錆層またはクロメート処理層またはシランカップリング処理層の表面のJISZ8730に基づく色差ΔE*abが45以上である。 The copper foil with a carrier according to the present invention is preferably controlled so that the color difference on the surface of the ultrathin copper layer satisfies the following (1). In the present invention, the “color difference on the surface of the ultrathin copper layer” means the color difference on the surface of the ultrathin copper layer, or the color difference on the surface of the surface treatment layer when various surface treatments such as roughening treatment are applied. . That is, in the copper foil with a carrier according to the present invention, the color difference of the surface of the ultrathin copper layer, the roughening treatment layer, the heat resistance layer, the rust prevention layer, the chromate treatment layer or the silane coupling layer satisfies the following (1). It is preferably controlled.
(1) The color difference ΔE * ab based on JISZ8730 on the surface of the ultrathin copper layer, the roughened layer, the heat resistant layer, the rust preventive layer, the chromate layer or the silane coupling layer is 45 or more.
また上述の色差は、極薄銅層の表面に粗化処理を施して粗化処理層を設けることで調整することもできる。粗化処理層を設ける場合には銅およびニッケル、コバルト、タングステン、モリブデンからなる群から選択される一種以上の元素とを含む電界液を用いて、従来よりも電流密度を高く(例えば40~60A/dm2)し、処理時間を短く(例えば0.1~1.3秒)することで調整することができる。極薄銅層の表面に粗化処理層を設けない場合には、Niの濃度をその他の元素の2倍以上としたメッキ浴を用いて、極薄銅層または耐熱層または防錆層またはクロメート処理層またはシランカップリング処理層の表面にNi合金メッキ(例えばNi-W合金メッキ、Ni-Co-P合金メッキ、Ni-Zn合金めっき)を従来よりも低電流密度(0.1~1.3A/dm2)で処理時間を長く(20秒~40秒)設定して処理することで達成できる。 The above-described color difference can be adjusted by increasing the current density when forming the ultrathin copper layer, decreasing the copper concentration in the plating solution, and increasing the linear flow rate of the plating solution.
Moreover, the above-mentioned color difference can also be adjusted by performing a roughening process on the surface of an ultra-thin copper layer and providing a roughening process layer. In the case of providing the roughened layer, the current density is higher than that of the prior art (for example, 40 to 60 A) using an electrolytic solution containing copper and one or more elements selected from the group consisting of nickel, cobalt, tungsten, and molybdenum. / Dm2), and can be adjusted by shortening the processing time (for example, 0.1 to 1.3 seconds). When a roughening layer is not provided on the surface of the ultrathin copper layer, use a plating bath in which the concentration of Ni is twice or more that of other elements, and use an ultrathin copper layer, heat resistant layer, rust preventive layer or chromate. Ni alloy plating (for example, Ni—W alloy plating, Ni—Co—P alloy plating, Ni—Zn alloy plating) is applied to the surface of the treatment layer or the silane coupling treatment layer at a lower current density (0.1 to 1.. 3A / dm 2 ), and the processing time can be set long (20 to 40 seconds).
硫酸ニッケル:250~300g/L
塩化ニッケル:35~45g/L
酢酸ニッケル:10~20g/L
クエン酸三ナトリウム:15~30g/L
光沢剤:サッカリン、ブチンジオール等
ドデシル硫酸ナトリウム:30~100ppm
pH:4~6
浴温:50~70℃
電流密度:3~15A/dm2 ・ Ni layer Nickel sulfate: 250-300 g / L
Nickel chloride: 35 to 45 g / L
Nickel acetate: 10-20g / L
Trisodium citrate: 15-30 g / L
Brightener: Saccharin, butynediol, etc. Sodium dodecyl sulfate: 30 to 100 ppm
pH: 4-6
Bath temperature: 50-70 ° C
Current density: 3 to 15 A / dm 2
・電解クロメート処理
液組成:重クロム酸カリウム1~10g/L、亜鉛0~5g/L
pH:3~4
液温:50~60℃
電流密度:0.1~2.6A/dm2
クーロン量:0.5~30As/dm2 After washing with water and pickling, a Cr layer having an adhesion amount of 11 μg / dm 2 was deposited on the Ni layer by electrolytic chromate treatment under the following conditions on a roll-to-roll type continuous plating line. .
Electrolytic chromate treatment Liquid composition: potassium dichromate 1-10 g / L, zinc 0-5 g / L
pH: 3-4
Liquid temperature: 50-60 ° C
Current density: 0.1 to 2.6 A / dm 2
Coulomb amount: 0.5-30 As / dm 2
・極薄銅層
銅濃度:30~120g/L
H2SO4濃度:20~120g/L
電解液温度:20~80℃
電流密度:10~100A/dm2 Subsequently, an ultrathin copper layer having a thickness of 2 to 10 μm was formed on the Cr layer on the roll-to-roll-type continuous plating line by electroplating under the following conditions to produce a copper foil with a carrier.
・ Ultra-thin copper layer Copper concentration: 30-120 g / L
H 2 SO 4 concentration: 20 to 120 g / L
Electrolyte temperature: 20-80 ° C
Current density: 10 to 100 A / dm 2
前述のキャリア付銅箔の極薄銅層の表面に下記に示す条件で粗化処理を施した。
(A)Cuの一次粒子層形成
液組成:Cu15g/リットル、硫酸75g/リットル
pH:1~3
温度:35℃
電流密度(Dk):40~60A/dm2
時間:0.05~3秒 (Example 1-common items of Examples 5, 8, 9, and 12)
The surface of the ultrathin copper layer of the copper foil with a carrier described above was subjected to a roughening treatment under the following conditions.
(A) Cu primary particle layer formation Liquid composition: Cu 15 g / liter, sulfuric acid 75 g / liter pH: 1 to 3
Temperature: 35 ° C
Current density (D k ): 40-60 A / dm 2
Time: 0.05-3 seconds
液組成:Cu15g/リットル、Co8g/リットル、Ni8g/リットル
pH:1~3
温度:40℃
電流密度(Dk):20~40A/dm2
時間:0.05~3秒 (B) Composition for forming a secondary particle layer composed of a ternary alloy composed of Cu, Co and Ni: Cu 15 g / liter, Co 8 g / liter, Ni 8 g / liter pH: 1 to 3
Temperature: 40 ° C
Current density (D k ): 20 to 40 A / dm 2
Time: 0.05-3 seconds
粗化粒子サイズ(粒子径)は表面処理付銅箔の粗化粒子を電子顕微鏡(SEM(走査型電子顕微鏡))の30000倍の倍率で観察を行い、粗化粒子サイズ(粒子径)を評価した。なお、本願では走査型電子顕微鏡写真の粒子の上に直線を引いた場合に、粒子を横切る直線の長さが最も長い部分の粒子の長さをその粒子の粒子径とした。そして、観察視野内の測定した各粒子の粒子径の算術平均の値を算出し、当該算術平均の値を平均粒子径とした。
粗化処理段階のNi付着量は50~250μg/dm2であった。この結果を、下記表1に示す。 In the above roughening treatment, a primary particle layer of Cu having an average particle diameter of 0.25 to 0.45 μm and Cu, Co, and Ni having an average particle diameter of 0.05 to 0.25 μm formed thereon are formed. A secondary particle layer made of a ternary alloy was formed.
The roughened particle size (particle diameter) is evaluated by observing the roughened particles of the surface-treated copper foil at a magnification of 30000 times that of an electron microscope (SEM (scanning electron microscope)). did. In the present application, when a straight line is drawn on the particle of the scanning electron micrograph, the length of the particle having the longest length of the straight line across the particle is defined as the particle diameter of the particle. And the value of the arithmetic mean of the particle diameter of each particle | grain measured within the observation visual field was computed, and the value of the said arithmetic mean was made into the average particle diameter.
The amount of Ni deposited at the roughening treatment stage was 50 to 250 μg / dm 2 . The results are shown in Table 1 below.
Ni-Co層からなる耐熱層、Zn、Ni、Crを含有する耐候層及び防錆層およびシランカップリング処理は、上記に示す条件の範囲で実施した。耐熱層、耐候層及び防錆層を形成する条件を下記に示す。なお、極薄銅層の厚みは2μmとした。
1)耐熱層(Ni-Co層)
液組成:Co1~8g/リットル、Ni10~20g/リットル
pH:2~3
温度:40~60℃
電流密度(Dk):8~10A/dm2
時間:0.05~3.0秒
2)耐候層(Zn-Ni層)
液組成:Ni15~30g/リットル、Zn1~10g/リットル
pH:2~4
温度:30~50℃
電流密度(Dk):0.5~1.5A/dm2
時間:0.05~3.0秒
3)防錆層(Cr-Zn層)
液組成:K2Cr2O7:1~10g/リットル、Zn:0~5g/リットル
pH:2~4
温度:40~50℃
電流密度(Dk):1~3A/dm2
時間:0.05~3.0秒 (Conditions of Example 1)
The heat-resistant layer composed of the Ni—Co layer, the weather-resistant layer containing Zn, Ni, and Cr, the rust-preventing layer, and the silane coupling treatment were performed within the range of the above conditions. The conditions for forming the heat-resistant layer, weather-resistant layer and rust-proof layer are shown below. The thickness of the ultrathin copper layer was 2 μm.
1) Heat-resistant layer (Ni-Co layer)
Liquid composition: Co 1-8 g / liter, Ni 10-20 g / liter pH: 2-3
Temperature: 40-60 ° C
Current density (D k ): 8 to 10 A / dm 2
Time: 0.05 to 3.0 seconds 2) Weather resistant layer (Zn—Ni layer)
Liquid composition: Ni 15-30 g / liter, Zn 1-10 g / liter pH: 2-4
Temperature: 30-50 ° C
Current density (D k ): 0.5 to 1.5 A / dm 2
Time: 0.05 to 3.0 seconds 3) Rust prevention layer (Cr-Zn layer)
Liquid composition: K 2 Cr 2 O 7 : 1 to 10 g / liter, Zn: 0 to 5 g / liter pH: 2 to 4
Temperature: 40-50 ° C
Current density (D k ): 1 to 3 A / dm 2
Time: 0.05 to 3.0 seconds
粗化処理層、耐熱層、耐候層、防錆層全てにおけるCo付着量(全Co量)から、全Co量/(全Ni量+全Zn量)=1.6であった。
上記の通り、粗化処理層、耐熱層、耐候層、防錆層の二層以上を積層する場合のNi付着量、Zn付着量、Co付着量、Cr付着量はそれぞれの元素の付着量の総量を示すものである。
表1及び表2については、実施例及び比較例の対応する箇所について、これらを必要に応じ、併記した。 The plating treatment was performed so that the Ni adhesion amount (total Ni amount) in all of the roughening layer, the heat-resistant layer, the weathering layer, and the rust-preventing layer was 1093 μg / dm 2 as a whole. The total Zn content / (total Ni content + total Zn content) = 0.13 from the Zn adhesion amount (total Zn content) in all of the roughened layer, heat resistant layer, weather resistant layer, and rust prevention layer.
From the Co adhesion amount (total Co amount) in all of the roughening layer, heat-resistant layer, weathering layer, and rust prevention layer, the total Co amount / (total Ni amount + total Zn amount) = 1.6.
As described above, the amount of Ni deposited, Zn deposited, Co deposited, and Cr deposited in the case of laminating two or more layers of a roughened layer, a heat resistant layer, a weather resistant layer, and a rust preventive layer are the amount of each element deposited. It shows the total amount.
About Table 1 and Table 2, these were written together as needed about the location corresponding to an Example and a comparative example.
次に、この銅張積層板を一般的な塩化銅-塩酸エッチング溶液によりファインパターン回路を形成した。このファインパターン回路基板を硫酸10wt%、過酸化水素2wt%からなる水溶液に5分間浸漬させた後、樹脂基板と銅箔回路の界面を光学顕微鏡にて観察して、染込み評価をおこなった。
染込み評価の結果、染みこみ幅:≦3μmで、良好(〇)であった。 A polyamic acid (U varnish A manufactured by Ube Industries) was applied onto the surface-treated copper foil produced as described above, dried at 100 ° C. and cured at 315 ° C. to form a copper-clad laminate composed of a polyimide resin substrate.
Next, a fine pattern circuit was formed on this copper clad laminate with a general copper chloride-hydrochloric acid etching solution. The fine pattern circuit board was immersed in an aqueous solution of 10 wt% sulfuric acid and 2 wt% hydrogen peroxide for 5 minutes, and then the interface between the resin substrate and the copper foil circuit was observed with an optical microscope to evaluate the penetration.
As a result of the soaking evaluation, the soaking width was ≦ 3 μm and good (◯).
常態ピール強度は0.99kg/cm、耐塩酸劣化性は8(Loss%)以下(〇)であり、ともに良好であった。 After laminating and bonding the ultrathin copper layer side of the copper foil with carrier to the glass cloth base epoxy resin plate, and then peeling off the ultrathin copper layer from the carrier, the normal state from the epoxy resin plate of the ultrathin copper layer (Room temperature) After measuring peel strength (kg / cm), the hydrochloric acid resistance deterioration rate was measured with a 0.2 mm width circuit after being immersed in an 18% aqueous hydrochloric acid solution for 1 hour.
The normal peel strength was 0.99 kg / cm, and the hydrochloric acid degradation resistance was 8 (Loss%) or less (◯), both of which were good.
アルカリエッチング評価の結果、粗化粒子の残存は観察されず、アルカリエッチング性も良好(○)であった。 In order to investigate the alkali etching property, after preparing a sample in which the roughened surface of the copper foil with surface treatment was covered with a vinyl tape, NH 4 OH: 6 mol / liter, NH 4 Cl: 5 mol / liter, CuCl 2 · 2H 2 O: 2 moles / liter, after immersion for 7 minutes in an alkaline etching solution consisting of temperature 50 ° C., was confirmed remaining conditions of the roughening particles on the plastic tape.
As a result of the alkali etching evaluation, the remaining coarse particles were not observed, and the alkali etching property was good (◯).
なお、上記の各金属付着量(粗化処理段階のNi付着量、全Ni量、全Co量、全Zn量、全Cr量)の測定は、表面処理付銅箔の表面処理面を酸溶液に溶解させて、原子吸光分析(VARIAN製、AA240FS)にて評価を行ったものである。なお、粗化処理段階のNi付着量は、各実施例、各比較例と同一の条件でキャリア付銅箔を製造した後、粗化処理層のみ設けた後、サンプルを採取し、全Ni量と同様にNi付着量の測定を行った。 The results are shown in Table 1. In addition, the Cr adhesion amount (total Cr amount) is 89 μg / dm 2 as a whole, the Co adhesion amount (total Co amount) is 2010 μg / dm 2 as a whole, and the Zn adhesion amount (total Zn amount) is 163 μg / dm 2 as a whole. Met.
In addition, measurement of each said metal adhesion amount (Ni adhesion amount of a roughening process stage, total Ni amount, total Co amount, total Zn amount, total Cr amount) measured the surface treatment surface of surface-treated copper foil with an acid solution. And was evaluated by atomic absorption analysis (manufactured by VARIAN, AA240FS). Note that the amount of Ni deposited in the roughening treatment stage was determined by producing a copper foil with a carrier under the same conditions as in each example and each comparative example, and after providing only the roughening treatment layer, collecting a sample, In the same manner as above, the amount of Ni adhesion was measured.
粗化段階のNi付着量は、上記の通り50~250μg/dm2であった。
Ni-Co層からなる耐熱層、Zn、Ni、Crを含有する耐候層及び防錆層およびシランカップリング処理は、上記に示す条件の範囲で実施した。耐熱層、耐候層及び防錆層を形成する条件を下記に示す。なお、極薄銅層の厚みは10μmとした。 (Example 2)
The amount of Ni deposited at the roughening stage was 50 to 250 μg / dm 2 as described above.
The heat-resistant layer composed of the Ni—Co layer, the weather-resistant layer containing Zn, Ni, and Cr, the rust-preventing layer, and the silane coupling treatment were performed within the range of the above conditions. The conditions for forming the heat-resistant layer, weather-resistant layer and rust-proof layer are shown below. The thickness of the ultrathin copper layer was 10 μm.
電流密度(Dk):4~6A/dm2
時間:0.05~3.0秒
2)耐候層(Zn-Ni層)
電流密度(Dk):0.05~0.7A/dm2
時間:0.05~3.0秒
3)防錆層(Cr-Zn層)
電流密度(Dk):1~3A/dm2
時間:0.05~3.0秒 1) Heat-resistant layer (Ni-Co layer)
Current density (D k ): 4 to 6 A / dm 2
Time: 0.05 to 3.0 seconds 2) Weather resistant layer (Zn—Ni layer)
Current density (D k ): 0.05 to 0.7 A / dm 2
Time: 0.05 to 3.0 seconds 3) Rust prevention layer (Cr-Zn layer)
Current density (D k ): 1 to 3 A / dm 2
Time: 0.05 to 3.0 seconds
染込み評価の結果、染みこみ幅:≦3μmで良好(〇)であった。 The total amount of Ni (total Ni amount) in the roughening layer, heat-resistant layer, weathering layer, and rust-preventing layer is 451 μg / dm 2 , and all of the roughening layer, heat-resistant layer, weathering layer, and rust-preventing layer From the amount of Zn deposited (total Zn amount), the total Zn amount / (total Ni amount + total Zn amount) = 0.18, Co adhesion amount in all of the roughened layer, heat resistant layer, weather resistant layer, and rust preventive layer (total From the (Co amount), the total Co amount / (total Ni amount + total Zn amount) = 2.7.
As a result of the soaking evaluation, the soaking width: ≦ 3 μm was good (◯).
以上の結果を表1に示す。この他、Cr付着量は全体(全Cr量)で84μg/dm2、Co付着量(全Co量)は全体で1487μg/dm2、Zn付着量(全Zn量)は全体で100μg/dm2であった。 As a result of the adhesion strength evaluation, the normal peel strength was 1.00 kg / cm, and the hydrochloric acid degradation resistance was 11 (Loss%), which was good (◯). Residual particles were not observed even in the alkali etching evaluation, and it was good (◯).
The results are shown in Table 1. In addition, Cr coating weight total 84μg / dm 2 at (total Cr content), Co deposition amount (total Co content) 1487μg / dm 2, Zn deposition amount in overall (total amount of Zn) are total 100 [mu] g / dm 2 Met.
粗化段階のNi付着量は、上記の通り50~250μg/dm2であった。
Ni-Co層からなる耐熱層、Zn、Ni、Crを含有する耐候層及び防錆層およびシランカップリング処理は、上記に示す条件の範囲で実施した。耐熱層、耐候層及び防錆層を形成する条件を下記に示す。なお、極薄銅層の厚みは5μmとした。 (Example 3)
The amount of Ni deposited at the roughening stage was 50 to 250 μg / dm 2 as described above.
The heat-resistant layer composed of the Ni—Co layer, the weather-resistant layer containing Zn, Ni, and Cr, the rust-preventing layer, and the silane coupling treatment were performed within the range of the above conditions. The conditions for forming the heat-resistant layer, weather-resistant layer and rust-proof layer are shown below. The thickness of the ultrathin copper layer was 5 μm.
電流密度(Dk):6~8A/dm2
時間:0.05~3.0秒
2)耐候層(Zn-Ni層)
電流密度(Dk):0.05~0.7A/dm2
時間:0.05~3.0秒
3)防錆層(Cr-Zn層)
電流密度(Dk):2~4A/dm2
時間:0.05~3.0秒 1) Heat-resistant layer (Ni-Co layer)
Current density (D k ): 6 to 8 A / dm 2
Time: 0.05 to 3.0 seconds 2) Weather resistant layer (Zn—Ni layer)
Current density (D k ): 0.05 to 0.7 A / dm 2
Time: 0.05 to 3.0 seconds 3) Rust prevention layer (Cr-Zn layer)
Current density (D k ): 2 to 4 A / dm 2
Time: 0.05 to 3.0 seconds
以上の結果を表1に示す。この他、Cr付着量は全体(全Cr量)で89μg/dm2、Co付着量は全体(全Co量)で1763μg/dm2、Zn付着量(全Zn量)は全体で157μg/dm2であった。 As a result of the adhesion strength evaluation, the normal peel strength was 0.99 kg / cm, and the hydrochloric acid resistance against degradation was 25 (Loss%), indicating that there was no problem. Residual particles were not observed and the alkali etching property was good (◯).
The results are shown in Table 1. In addition, whole Cr adhesion amount (total Cr content) across 89μg / dm 2, Co deposition amount in (total Co content) at 1763μg / dm 2, Zn deposition amount (total amount of Zn) is total 157μg / dm 2 Met.
粗化段階のNi付着量は、上記の通り50~250μg/dm2であった。
Ni-Co層からなる耐熱層、Zn、Ni、Crを含有する耐候層及び防錆層およびシランカップリング処理は、上記に示す条件の範囲で実施した。耐熱層、耐候層及び防錆層を形成する条件を下記に示す。なお、極薄銅層の厚みは3μmとした。 Example 4
The amount of Ni deposited at the roughening stage was 50 to 250 μg / dm 2 as described above.
The heat-resistant layer composed of the Ni—Co layer, the weather-resistant layer containing Zn, Ni, and Cr, the rust-preventing layer, and the silane coupling treatment were performed within the range of the above conditions. The conditions for forming the heat-resistant layer, weather-resistant layer and rust-proof layer are shown below. The thickness of the ultrathin copper layer was 3 μm.
電流密度(Dk):6~8A/dm2
時間:0.05~3.0秒
2)耐候層(Zn-Ni層)
電流密度(Dk):1~3A/dm2
時間:0.05~3.0秒
3)防錆層(Cr-Zn層)
電流密度(Dk):0.05~1.0A/dm2
時間:0.05~3.0秒 1) Heat-resistant layer (Ni-Co layer)
Current density (D k ): 6 to 8 A / dm 2
Time: 0.05 to 3.0 seconds 2) Weather resistant layer (Zn—Ni layer)
Current density (D k ): 1 to 3 A / dm 2
Time: 0.05 to 3.0 seconds 3) Rust prevention layer (Cr-Zn layer)
Current density (D k ): 0.05 to 1.0 A / dm 2
Time: 0.05 to 3.0 seconds
以上の結果を表1に示す。この他、Cr付着量は全体(全Cr量)で90μg/dm2、Co付着量(全Co量)は全体で1774μg/dm2、Zn付着量(全Zn量)は全体で223μg/dm2であった。 As a result of the evaluation of the adhesion strength, the normal peel strength was 0.99 kg / cm, and the hydrochloric acid degradation resistance was 22 (Loss%). Alkali etching property was also good (◯).
The results are shown in Table 1. In addition, the Cr adhesion amount is 90 μg / dm 2 as a whole (total Cr amount), the Co adhesion amount (total Co amount) is 1774 μg / dm 2 as a whole, and the Zn adhesion amount (total Zn amount) is 223 μg / dm 2 as a whole. Met.
粗化段階のNi付着量は、上記の通り50~250μg/dm2であった。
Ni-Co層からなる耐熱層、Zn、Ni、Crを含有する耐候層及び防錆層およびシランカップリング処理は、上記に示す条件の範囲で実施した。耐熱層、耐候層及び防錆層を形成する条件を下記に示す。なお、極薄銅層の厚みは7μmとした。 (Example 5)
The amount of Ni deposited at the roughening stage was 50 to 250 μg / dm 2 as described above.
The heat-resistant layer composed of the Ni—Co layer, the weather-resistant layer containing Zn, Ni, and Cr, the rust-preventing layer, and the silane coupling treatment were performed within the range of the above conditions. The conditions for forming the heat-resistant layer, weather-resistant layer and rust-proof layer are shown below. The thickness of the ultrathin copper layer was 7 μm.
電流密度(Dk):6~8A/dm2
時間:0.05~3.0秒
2)耐候層(Zn-Ni層)
電流密度(Dk):0.6~1.5A/dm2
時間:0.05~3.0秒
3)防錆層(Cr-Zn層)
電流密度(Dk):1.0~3.0A/dm2
時間:0.05~3.0秒 1) Heat-resistant layer (Ni-Co layer)
Current density (D k ): 6 to 8 A / dm 2
Time: 0.05 to 3.0 seconds 2) Weather resistant layer (Zn—Ni layer)
Current density (D k ): 0.6 to 1.5 A / dm 2
Time: 0.05 to 3.0 seconds 3) Rust prevention layer (Cr-Zn layer)
Current density (D k ): 1.0 to 3.0 A / dm 2
Time: 0.05 to 3.0 seconds
以上の結果を表1に示す。この他、Cr付着量は全体(全Cr量)で115μg/dm2、Co付着量は全体(全Co量)で1857μg/dm2、Zn付着量(全Zn量)は全体で235μg/dm2であった。 As a result of the adhesion strength evaluation, the normal peel strength was 0.99 kg / cm, and the hydrochloric acid degradation resistance was 12 (Loss%), which was good. Alkali etching property was also good (◯).
The results are shown in Table 1. In addition, whole Cr adhesion amount (total Cr content) across 115μg / dm 2, Co deposition amount in (total Co content) at 1857μg / dm 2, Zn deposition amount (total amount of Zn) is total 235μg / dm 2 Met.
前述のキャリア付銅箔に、下記に示す条件で粗化処理を施した。なお、極薄銅層の厚みは3μmとした。
液組成:Cu10~20g/リットル、Co5~10g/リットル、Ni5~15g/リットル
pH:2~4
温度:30~50℃
電流密度(Dk):20~60A/dm2
時間:0.5~5秒 (Example 6)
The copper foil with a carrier described above was subjected to a roughening treatment under the following conditions. The thickness of the ultrathin copper layer was 3 μm.
Liquid composition: Cu 10-20 g / liter, Co 5-10 g / liter, Ni 5-15 g / liter pH: 2-4
Temperature: 30-50 ° C
Current density (D k ): 20 to 60 A / dm 2
Time: 0.5-5 seconds
粗化段階のNi付着量は200~400μg/dm2であった。 By performing the roughening treatment under the above conditions, an aggregate of finely roughened particles of a ternary alloy composed of Cu, Co, and Ni having an average particle diameter of 0.10 to 0.60 μm was formed. The roughened particle size was evaluated by observing the roughened particles of the copper foil with surface treatment at a magnification of 30000 times with an electron microscope (SEM).
The amount of Ni deposited in the roughening stage was 200 to 400 μg / dm 2 .
1)耐熱層(Ni-Co層)
電流密度(Dk):6~8A/dm2
時間:0.05~3.0秒
2)耐候層(Zn-Ni層)
電流密度(Dk):2.0~4.0A/dm2
時間:0.05~3.0秒
3)防錆層(Cr-Zn層)
電流密度(Dk):0A/dm2
時間:0.05~3秒(浸漬クロメート処理) The heat-resistant layer composed of the Ni—Co layer, the weather-resistant layer containing Zn, Ni, and Cr, the rust-preventing layer, and the silane coupling treatment were performed within the range of the above conditions. The conditions for forming the heat-resistant layer, weather-resistant layer and rust-proof layer are shown below.
1) Heat-resistant layer (Ni-Co layer)
Current density (D k ): 6 to 8 A / dm 2
Time: 0.05 to 3.0 seconds 2) Weather resistant layer (Zn—Ni layer)
Current density (D k ): 2.0 to 4.0 A / dm 2
Time: 0.05 to 3.0 seconds 3) Rust prevention layer (Cr-Zn layer)
Current density (D k ): 0 A / dm 2
Time: 0.05-3 seconds (immersion chromate treatment)
以上の結果を、表1に示す。この他、Cr付着量は全体(全Cr量)で110μg/dm2、Co付着量は全体(全Co量)で2475μg/dm2、Zn付着量は全体(全Zn量)で240μg/dm2であった。 As a result of the evaluation of the adhesion strength, the normal peel strength was 0.97 kg / cm, hydrochloric acid deterioration resistance: ≦ 10 (Loss%) or less, which was very good. Alkali etching property was also good (◯).
The results are shown in Table 1. In addition, Cr coating weight total (total Cr amount) at 110μg / dm 2, Co coating weight across the entire 2475μg / dm 2, Zn deposition amount is (total Co content) (total amount of Zn) at 240 [mu] g / dm 2 Met.
前述のキャリア付銅箔に下記に示す条件で粗化処理を施した。なお、極薄銅層の厚みは3μmとした。
液組成:Cu10~20g/リットル、Co5~10g/リットル、Ni8~20g/リットル
pH:2~4
温度:30~50℃
電流密度(Dk):20~60A/dm2
時間:0.5~5秒 (Example 7)
The above-mentioned copper foil with a carrier was roughened under the conditions shown below. The thickness of the ultrathin copper layer was 3 μm.
Liquid composition: Cu 10-20 g / liter, Co 5-10 g / liter, Ni 8-20 g / liter pH: 2-4
Temperature: 30-50 ° C
Current density (D k ): 20 to 60 A / dm 2
Time: 0.5-5 seconds
粗化段階のNi付着量は300~550μg/dm2であった。 By performing the roughening treatment under the above conditions, an aggregate of finely roughened particles of a ternary alloy composed of Cu, Co, and Ni having an average particle diameter of 0.05 to 0.35 μm was formed. The roughened particle size was evaluated by observing the roughened particles of the copper foil with surface treatment at a magnification of 30000 times with an electron microscope (SEM).
The amount of Ni deposited in the roughening stage was 300 to 550 μg / dm 2 .
1)耐熱層(Ni-Co層)
電流密度(Dk):4~6A/dm2
時間:0.05~3.0秒
2)耐候層(Zn-Ni層)
電流密度(Dk):1.5~3.5A/dm2
時間:0.05~3.0秒
3)防錆層(Cr-Zn層)
電流密度(Dk):0A/dm2
時間:0.05~3秒(浸漬クロメート処理) The heat-resistant layer composed of the Ni—Co layer, the weather-resistant layer containing Zn, Ni, and Cr, the rust-preventing layer, and the silane coupling treatment were performed within the range of the above conditions. The conditions for forming the heat-resistant layer, weather-resistant layer and rust-proof layer are shown below.
1) Heat-resistant layer (Ni-Co layer)
Current density (D k ): 4 to 6 A / dm 2
Time: 0.05 to 3.0 seconds 2) Weather resistant layer (Zn—Ni layer)
Current density (D k ): 1.5 to 3.5 A / dm 2
Time: 0.05 to 3.0 seconds 3) Rust prevention layer (Cr-Zn layer)
Current density (D k ): 0 A / dm 2
Time: 0.05-3 seconds (immersion chromate treatment)
以上の結果を、表1に示す。この他、Cr付着量は全体(全Cr量)で55μg/dm2、Co付着量は全体(全Co量)で2167μg/dm2、Zn付着量は全体(全Zn量)で217μg/dm2であった。 As a result of the evaluation of the adhesion strength, the normal peel strength was 0.94 kg / cm, hydrochloric acid deterioration resistance: ≦ 10 (Loss%) or less, which was very good. Alkali etching property was also good (◯).
The results are shown in Table 1. In addition, Cr coating weight total (total amount of Cr) in 55 [mu] g / dm 2, Co coating weight across the entire 2167μg / dm 2, Zn deposition amount is (total Co content) (total amount of Zn) at 217μg / dm 2 Met.
実施例1と同様の粗化処理において、平均粒子径0.25~0.45μmのCuの一次粒子層と、その上に形成された平均粒子径が0.05~0.25μmのCu、Co、Niからなる3元系合金からなる二次粒子層を形成した。
粗化粒子サイズは表面処理付銅箔の粗化粒子を電子顕微鏡(SEM)の30000倍の倍率で観察を行い、粗化粒子サイズを評価した。
粗化処理段階のNi付着量は50~250μg/dm2であった。 (Example 8)
In the same roughening treatment as in Example 1, a primary particle layer of Cu having an average particle size of 0.25 to 0.45 μm, and Cu and Co having an average particle size of 0.05 to 0.25 μm formed thereon. Then, a secondary particle layer made of a ternary alloy made of Ni was formed.
The roughened particle size was evaluated by observing the roughened particles of the copper foil with surface treatment at a magnification of 30000 times with an electron microscope (SEM).
The amount of Ni deposited at the roughening treatment stage was 50 to 250 μg / dm 2 .
1)耐熱層(Ni-Co層)
電流密度(Dk):6~8A/dm2
時間:0.05~3.0秒
2)耐候層(Zn-Ni層)
電流密度(Dk):0~1.0A/dm2
時間:0~2.0秒
3)防錆層(Cr-Zn層)
電流密度(Dk):1~3A/dm2
時間:0.05~3.0秒 The conditions for forming the heat-resistant layer, weather-resistant layer and rust-proof layer are shown below. The thickness of the ultrathin copper layer was 3 μm.
1) Heat-resistant layer (Ni-Co layer)
Current density (D k ): 6 to 8 A / dm 2
Time: 0.05 to 3.0 seconds 2) Weather resistant layer (Zn—Ni layer)
Current density (D k ): 0 to 1.0 A / dm 2
Time: 0 to 2.0 seconds 3) Rust prevention layer (Cr-Zn layer)
Current density (D k ): 1 to 3 A / dm 2
Time: 0.05 to 3.0 seconds
粗化処理層、耐熱層、耐候層、防錆層全てにおけるCo付着量(全Co量)から、全Co量/(全Ni量+全Zn量)=1.9であった。
以下の実施例8、9、21~26については表面処理銅箔を以下の樹脂に積層させた後、上記の染み込み評価方法で染み込みを評価した。
表面処理付銅箔上にGHPL-830NX(三菱ガス化学株式会社製タイプA)を220℃、2時間の熱プレス条件で積層させ、銅張積層板を形成した。 The plating treatment was performed so that the Ni adhesion amount in all of the roughening layer, the heat-resistant layer, the weathering layer, and the rust-preventing layer was 741 μg / dm 2 in total (total Ni amount). The total Zn content / (total Ni content + total Zn content) = 0.02 from the Zn adhesion amount (total Zn content) in all of the roughened layer, heat resistant layer, weather resistant layer, and rust prevention layer.
From the Co adhesion amount (total Co amount) in all of the roughening layer, the heat-resistant layer, the weathering layer, and the rust prevention layer, the total Co amount / (total Ni amount + total Zn amount) = 1.9.
In the following Examples 8, 9, and 21 to 26, the surface-treated copper foil was laminated on the following resins, and then the penetration was evaluated by the above-described penetration evaluation method.
On the surface-treated copper foil, GHPL-830NX (Mitsubishi Gas Chemical Co., Ltd. Type A) was laminated at 220 ° C. under hot pressing conditions for 2 hours to form a copper clad laminate.
染込み評価の結果、染みこみ幅:0μmで非常に良好であった。 Next, a fine pattern circuit was formed on this copper clad laminate with a general copper chloride-hydrochloric acid etching solution. The fine pattern circuit board was immersed in an aqueous solution of 10 wt% sulfuric acid and 2 wt% hydrogen peroxide for 5 minutes, and then the interface between the resin substrate and the copper foil circuit was observed with an optical microscope to evaluate the penetration.
As a result of the soaking evaluation, the soaking width was 0 μm, which was very good.
以上の結果を、表1に示す。この他、Cr付着量は全体(全Cr量)で90μg/dm2、Co付着量は全体(全Co量)で1437μg/dm2、Zn付着量(全Zn量)は全体で15μg/dm2であった。 As a result of the evaluation of the adhesion strength, the normal peel strength was 0.99 kg / cm, and the hydrochloric acid resistance was 5 (Loss%), which was very good. Alkali etching property was also good (◯).
The results are shown in Table 1. In addition, whole Cr adhesion amount (total Cr content) total 90 [mu] g / dm 2, Co deposition amount in (total Co content) at 1437μg / dm 2, Zn deposition amount (total amount of Zn) is total 15 [mu] g / dm 2 Met.
実施例1と同様の粗化処理において、平均粒子径0.25~0.45μmのCuの一次粒子層と、その上に形成された平均粒子径が0.05~0.25μmのCu、Co、Niからなる3元系合金からなる二次粒子層を形成した。
粗化粒子サイズは表面処理付銅箔の粗化粒子を電子顕微鏡(SEM)の30000倍の倍率で観察を行い、粗化粒子サイズを評価した。
粗化処理段階のNi付着量は50~250μg/dm2であった。 Example 9
In the same roughening treatment as in Example 1, a primary particle layer of Cu having an average particle size of 0.25 to 0.45 μm, and Cu and Co having an average particle size of 0.05 to 0.25 μm formed thereon. Then, a secondary particle layer made of a ternary alloy made of Ni was formed.
The roughened particle size was evaluated by observing the roughened particles of the copper foil with surface treatment at a magnification of 30000 times with an electron microscope (SEM).
The amount of Ni deposited at the roughening treatment stage was 50 to 250 μg / dm 2 .
1)耐熱層(Ni-Co層)
電流密度(Dk):6~8A/dm2
時間:0.05~3.0秒
2)耐候層(Zn-Ni層)
電流密度(Dk):0.5~1.0A/dm2
時間:0~2.0秒
3)防錆層(Cr-Zn層)
電流密度(Dk):1~3A/dm2
時間:0.05~3.0秒 The conditions for forming the heat-resistant layer, weather-resistant layer and rust-proof layer are shown below. The thickness of the ultrathin copper layer was 3 μm.
1) Heat-resistant layer (Ni-Co layer)
Current density (D k ): 6 to 8 A / dm 2
Time: 0.05 to 3.0 seconds 2) Weather resistant layer (Zn—Ni layer)
Current density (D k ): 0.5 to 1.0 A / dm 2
Time: 0 to 2.0 seconds 3) Rust prevention layer (Cr-Zn layer)
Current density (D k ): 1 to 3 A / dm 2
Time: 0.05 to 3.0 seconds
粗化処理層、耐熱層、耐候層、防錆層全てにおけるCo付着量(全Co量)から、全Co量/(全Ni量)+全Zn量)=1.8であった。 The plating treatment was performed so that the Ni adhesion amount in all of the roughening layer, the heat resistant layer, the weather resistant layer, and the rust preventive layer was 771 μg / dm 2 in total (total Ni amount). The total Zn content / (total Ni content + total Zn content) = 0.06 from the Zn adhesion amount (total Zn content) in all of the roughened layer, heat resistant layer, weather resistant layer, and rust prevention layer.
The total amount of Co / (total Ni amount) + total Zn amount) = 1.8 from the Co adhesion amount (total Co amount) in all of the roughening layer, heat-resistant layer, weathering layer, and rust prevention layer.
以上の結果を、表1に示す。この他、Cr付着量は全体(全Cr量)で90μg/dm2、Co付着量は全体(全Co量)で1476μg/dm2、Zn付着量(全Zn量)は全体で49μg/dm2であった。 As a result of the penetration evaluation similar to that of Example 8, the penetration width was 0 μm, which was very good. As a result of the adhesion strength evaluation, the normal peel strength was 1.01 kg / cm, hydrochloric acid deterioration resistance: 6 (Loss%), which was very good. Alkali etching property was also good (◯).
The results are shown in Table 1. In addition, whole Cr adhesion amount (total Cr content) total 90 [mu] g / dm 2, Co deposition amount in (total Co content) at 1476μg / dm 2, Zn deposition amount (total amount of Zn) is total 49μg / dm 2 Met.
前述のキャリア付銅箔に実施例6と同様の条件で粗化処理層を形成した。上記の条件で粗化処理を施すことで、平均粒子径0.10~0.60μmからなるCu、Co、Niからなる3元系合金の微細粗化粒子の集合体を形成した。
粗化段階のNi付着量は200~400μg/dm2であった。
Ni-Co層からなる耐熱層、Zn、Ni、Crを含有する耐候層及び防錆層およびシランカップリング処理は、上記に示す条件の範囲で実施した。耐熱層、耐候層及び防錆層を形成する条件を下記に示す。なお、極薄銅層の厚みは3μmとした。 (Example 10)
A roughening layer was formed on the above-described copper foil with a carrier under the same conditions as in Example 6. By performing the roughening treatment under the above conditions, an aggregate of finely roughened particles of a ternary alloy composed of Cu, Co, and Ni having an average particle diameter of 0.10 to 0.60 μm was formed.
The amount of Ni deposited in the roughening stage was 200 to 400 μg / dm 2 .
The heat-resistant layer composed of the Ni—Co layer, the weather-resistant layer containing Zn, Ni, and Cr, the rust-preventing layer, and the silane coupling treatment were performed within the range of the above conditions. The conditions for forming the heat-resistant layer, weather-resistant layer and rust-proof layer are shown below. The thickness of the ultrathin copper layer was 3 μm.
液組成:Co1~10g/リットル、Ni1~10g/リットル
pH:2~3
温度:40~60℃
電流密度(Dk):6~8A/dm2
時間:0.05~3.0秒
2)耐候層(Zn-Ni層)
電流密度(Dk):1.0~3.0A/dm2
時間:0.05~3.0秒
3)防錆層(Cr-Zn層)
電流密度(Dk):0A/dm2
時間:0.05~3秒(浸漬クロメート処理) 1) Heat-resistant layer (Ni-Co layer)
Liquid composition: Co 1-10 g / liter, Ni 1-10 g / liter pH: 2-3
Temperature: 40-60 ° C
Current density (D k ): 6 to 8 A / dm 2
Time: 0.05 to 3.0 seconds 2) Weather resistant layer (Zn—Ni layer)
Current density (D k ): 1.0 to 3.0 A / dm 2
Time: 0.05 to 3.0 seconds 3) Rust prevention layer (Cr-Zn layer)
Current density (D k ): 0 A / dm 2
Time: 0.05-3 seconds (immersion chromate treatment)
実施例1と同様の粗化処理において、平均粒子径0.2~0.45μmのCuの一次粒子層と、その上に形成された平均粒子径が0.05~0.25μmのCu、Co、Niからなる3元系合金からなる二次粒子層を形成した。
粗化粒子サイズは表面処理付銅箔の粗化粒子を電子顕微鏡(SEM)の30000倍の倍率で観察を行い、粗化粒子サイズを評価した。
粗化処理段階のNi付着量は300~550μg/dm2であった。 (Example 11)
In the same roughening treatment as in Example 1, a primary particle layer of Cu having an average particle diameter of 0.2 to 0.45 μm, and Cu, Co having an average particle diameter of 0.05 to 0.25 μm formed thereon. Then, a secondary particle layer made of a ternary alloy made of Ni was formed.
The roughened particle size was evaluated by observing the roughened particles of the copper foil with surface treatment at a magnification of 30000 times with an electron microscope (SEM).
The amount of Ni deposited at the roughening stage was 300 to 550 μg / dm 2 .
1)耐熱層(Ni-Co層)
電流密度(Dk):6~8A/dm2
時間:0.05~3.0秒
2)耐候層(Zn-Ni層)
電流密度(Dk):0.5~1.0A/dm2
時間:0~2.0秒
3)防錆層(Cr-Zn層)
電流密度(Dk):1~3A/dm2
時間:0.05~3.0秒 The conditions for forming the heat-resistant layer, weather-resistant layer and rust-proof layer are shown below. The thickness of the ultrathin copper layer was 3 μm.
1) Heat-resistant layer (Ni-Co layer)
Current density (D k ): 6 to 8 A / dm 2
Time: 0.05 to 3.0 seconds 2) Weather resistant layer (Zn—Ni layer)
Current density (D k ): 0.5 to 1.0 A / dm 2
Time: 0 to 2.0 seconds 3) Rust prevention layer (Cr-Zn layer)
Current density (D k ): 1 to 3 A / dm 2
Time: 0.05 to 3.0 seconds
粗化処理層、耐熱層、耐候層、防錆層全てにおけるCo付着量(全Co量)から、全Co量/(全Ni量)+全Zn量)=1.6であった。 The plating treatment was performed so that the Ni adhesion amount in all of the roughening layer, the heat-resistant layer, the weather-resistant layer, and the rust-preventing layer was 1590 μg / dm 2 in total (total Ni amount). From the Zn adhesion amount (total Zn amount) in all of the roughened layer, heat-resistant layer, weathering layer, and rust prevention layer, the total Zn amount / (total Ni amount + total Zn amount) = 0.10.
The total amount of Co / (total Ni amount) + total Zn amount) = 1.6 from the Co adhesion amount (total Co amount) in all of the roughening layer, heat-resistant layer, weathering layer, and rust prevention layer.
以上の結果を、表1に示す。この他、Cr付着量は全体(全Cr量)で90μg/dm2、Co付着量は全体(全Co量)で2762μg/dm2、Zn付着量(全Zn量)は全体で177μg/dm2であった。 As a result of the infiltration evaluation similar to that in Example 1, the infiltration width was good at 5 μm or less. As a result of the evaluation of the adhesion strength, the normal peel strength was 1.02 kg / cm and the hydrochloric acid resistance against deterioration: 18 (Loss%), which was good. Alkali etching property was also good (◯).
The results are shown in Table 1. In addition, whole Cr adhesion amount (total Cr content) total 90 [mu] g / dm 2, Co deposition amount in (total Co content) at 2762μg / dm 2, Zn deposition amount (total amount of Zn) is total 177μg / dm 2 Met.
実施例1と同様の粗化処理において、平均粒子径0.2~0.45μmのCuの一次粒子層と、その上に形成された平均粒子径が0.05~0.25μmのCu、Co、Niからなる3元系合金からなる二次粒子層を形成した。
粗化粒子サイズは表面処理付銅箔の粗化粒子を電子顕微鏡(SEM)の30000倍の倍率で観察を行い、粗化粒子サイズを評価した。
粗化処理段階のNi付着量は50~250μg/dm2であった。 Example 12
In the same roughening treatment as in Example 1, a primary particle layer of Cu having an average particle diameter of 0.2 to 0.45 μm, and Cu, Co having an average particle diameter of 0.05 to 0.25 μm formed thereon. Then, a secondary particle layer made of a ternary alloy made of Ni was formed.
The roughened particle size was evaluated by observing the roughened particles of the copper foil with surface treatment at a magnification of 30000 times with an electron microscope (SEM).
The amount of Ni deposited at the roughening treatment stage was 50 to 250 μg / dm 2 .
1)耐熱層(Ni-Co層)
電流密度(Dk):6~8A/dm2
時間:0.05~3.0秒
2)耐候層(Zn-Ni層)
電流密度(Dk):0.5~1.0A/dm2
時間:0~2.0秒
3)防錆層(Cr-Zn層)
電流密度(Dk):1~3A/dm2
時間:0.05~3.0秒 The conditions for forming the heat-resistant layer, weather-resistant layer and rust-proof layer are shown below. The thickness of the ultrathin copper layer was 3 μm.
1) Heat-resistant layer (Ni-Co layer)
Current density (D k ): 6 to 8 A / dm 2
Time: 0.05 to 3.0 seconds 2) Weather resistant layer (Zn—Ni layer)
Current density (D k ): 0.5 to 1.0 A / dm 2
Time: 0 to 2.0 seconds 3) Rust prevention layer (Cr-Zn layer)
Current density (D k ): 1 to 3 A / dm 2
Time: 0.05 to 3.0 seconds
粗化処理層、耐熱層、耐候層、防錆層全てにおけるCo付着量(全Co量)から、全Co量/(全Ni量)+全Zn量)=1.4であった。 The plating treatment was performed so that the Ni adhesion amount in all of the roughening layer, the heat-resistant layer, the weathering layer, and the rust-preventing layer was 360 μg / dm 2 in total (total Ni amount). The total Zn content / (total Ni content + total Zn content) = 0.35 from the Zn adhesion amount (total Zn content) in all of the roughened layer, heat resistant layer, weather resistant layer, and rust prevention layer.
From the Co adhesion amount (total Co amount) in all of the roughening layer, the heat resistant layer, the weathering layer, and the rust prevention layer, the total Co amount / (total Ni amount) + total Zn amount) = 1.4.
以上の結果を、表1に示す。この他、Cr付着量は全体(全Cr量)で90μg/dm2、Co付着量は全体(全Co量)で790μg/dm2、Zn付着量(全Zn量)は全体で194μg/dm2であった。 As a result of the penetration evaluation similar to that of Example 1, the penetration width was 0 μm, which was very good. As a result of the evaluation of the adhesion strength, the normal peel strength was 0.96 kg / cm, and the hydrochloric acid degradation resistance was 5 (Loss%), which was favorable. Alkali etching property was also good (◯).
The results are shown in Table 1. In addition, whole Cr adhesion amount (total Cr content) total 90 [mu] g / dm 2, Co deposition amount in (total Co content) at 790μg / dm 2, Zn deposition amount (total amount of Zn) is total 194μg / dm 2 Met.
前述のキャリア付銅箔に実施例1-5と同様の条件で粗化処理層を形成した。粗化段階のNi付着量は50~250μg/dm2であった。
Ni-Co層からなる耐熱層、Zn、Ni、Crを含有する耐候層及び防錆層およびシランカップリング処理は、上記に示す条件の範囲で実施した。耐熱層、耐候層及び防錆層を形成する条件を下記に示す。なお、極薄銅層の厚みは3μmとした。 (Comparative Example 1)
A roughened layer was formed on the above-described copper foil with a carrier under the same conditions as in Example 1-5. The amount of Ni deposited in the roughening stage was 50 to 250 μg / dm 2 .
The heat-resistant layer composed of the Ni—Co layer, the weather-resistant layer containing Zn, Ni, and Cr, the rust-preventing layer, and the silane coupling treatment were performed within the range of the above conditions. The conditions for forming the heat-resistant layer, weather-resistant layer and rust-proof layer are shown below. The thickness of the ultrathin copper layer was 3 μm.
電流密度(Dk):10~15A/dm2
時間:0.05~3.0秒
2)耐候層(Zn-Ni層)
電流密度(Dk):0.05~0.7A/dm2
時間:0.05~3.0秒
3)防錆層(Cr-Zn層)
電流密度(Dk):0.5~1.5A/dm2
時間:0.05~3.0秒 1) Heat-resistant layer (Ni-Co layer)
Current density (D k ): 10 to 15 A / dm 2
Time: 0.05 to 3.0 seconds 2) Weather resistant layer (Zn—Ni layer)
Current density (D k ): 0.05 to 0.7 A / dm 2
Time: 0.05 to 3.0 seconds 3) Rust prevention layer (Cr-Zn layer)
Current density (D k ): 0.5 to 1.5 A / dm 2
Time: 0.05 to 3.0 seconds
以上の結果を、表1に示す。この他、Cr付着量は全体(全Cr量)で81μg/dm2、Co付着量は全体(全Co量)で5444μg/dm2、Zn付着量は全体(全Zn量)で10μg/dm2であった。 As a result of the adhesion strength evaluation, the normal peel strength was 0.98 kg / cm, and the hydrochloric acid degradation resistance was 6 (Loss%), which was good. However, the alkali etching property was poor (x) because residual particles were observed. As a result, the overall evaluation was poor. This is considered due to the fact that the total Zn amount / (total Ni amount + total Zn amount) is small.
The results are shown in Table 1. In addition, Cr coating weight total (total Cr amount) at 81μg / dm 2, Co coating weight across the entire 5444μg / dm 2, Zn deposition amount is (total Co content) (total amount of Zn) at 10 [mu] g / dm 2 Met.
前述のキャリア付銅箔に実施例1-5と同様の条件で粗化処理層を形成した。粗化段階のNi付着量は50~250μg/dm2であった。
Ni-Co層からなる耐熱層、Zn、Ni、Crを含有する耐候層及び防錆層およびシランカップリング処理は、上記に示す条件の範囲で実施した。耐熱層、耐候層及び防錆層を形成する条件を下記に示す。なお、極薄銅層の厚みは3μmとした。 (Comparative Example 2)
A roughened layer was formed on the above-described copper foil with a carrier under the same conditions as in Example 1-5. The amount of Ni deposited in the roughening stage was 50 to 250 μg / dm 2 .
The heat-resistant layer composed of the Ni—Co layer, the weather-resistant layer containing Zn, Ni, and Cr, the rust-preventing layer, and the silane coupling treatment were performed within the range of the above conditions. The conditions for forming the heat-resistant layer, weather-resistant layer and rust-proof layer are shown below. The thickness of the ultrathin copper layer was 3 μm.
電流密度(Dk):10~15A/dm2
時間:0.05~3.0秒
2)耐候層(Zn-Ni層)
電流密度(Dk):0.1~1.0A/dm2
時間:0.05~3.0秒
3)防錆層(Cr-Zn層)
電流密度(Dk):0.5~1.5A/dm2
時間:0.05~3.0秒 1) Heat-resistant layer (Ni-Co layer)
Current density (D k ): 10 to 15 A / dm 2
Time: 0.05 to 3.0 seconds 2) Weather resistant layer (Zn—Ni layer)
Current density (D k ): 0.1 to 1.0 A / dm 2
Time: 0.05 to 3.0 seconds 3) Rust prevention layer (Cr-Zn layer)
Current density (D k ): 0.5 to 1.5 A / dm 2
Time: 0.05 to 3.0 seconds
以上の結果を、表1に示す。この他、Cr付着量は全体(全Cr量)で84μg/dm2、Co付着量は全体(全Co量)で3058μg/dm2、Zn付着量は全体(全Zn量)で199μg/dm2であった。 As a result of the adhesion strength evaluation, the normal peel strength was 0.99 kg / cm, and the hydrochloric acid degradation resistance was 7 (Loss%) or less, which was good. However, the alkali etching property was poor (x) because residual particles were observed. As a result, the overall evaluation was poor. This is considered due to the fact that the total amount of deposited Ni is too large.
The results are shown in Table 1. In addition, Cr coating weight total (total Cr amount) at 84μg / dm 2, Co coating weight across the entire 3058μg / dm 2, Zn deposition amount is (total Co content) (total amount of Zn) at 199μg / dm 2 Met.
前述のキャリア付銅箔に実施例1-5と同様の条件で粗化処理層を形成した。粗化段階のNi付着量は50~250μg/dm2であった。
Ni-Co層からなる耐熱層、Zn、Ni、Crを含有する耐候層及び防錆層およびシランカップリング処理は、上記に示す条件の範囲で実施した。耐熱層、耐候層及び防錆層を形成する条件を下記に示す。なお、極薄銅層の厚みは3μmとした。 (Comparative Example 3)
A roughened layer was formed on the above-described copper foil with a carrier under the same conditions as in Example 1-5. The amount of Ni deposited in the roughening stage was 50 to 250 μg / dm 2 .
The heat-resistant layer composed of the Ni—Co layer, the weather-resistant layer containing Zn, Ni, and Cr, the rust-preventing layer, and the silane coupling treatment were performed within the range of the above conditions. The conditions for forming the heat-resistant layer, weather-resistant layer and rust-proof layer are shown below. The thickness of the ultrathin copper layer was 3 μm.
電流密度(Dk):1.0~3.0A/dm2
時間:0.05~3.0秒
2)耐候層(Zn-Ni層)
電流密度(Dk):0.05~0.7A/dm2
時間:0.05~3.0秒
3)防錆層(Cr-Zn層)
電流密度(Dk):0.5~1.5A/dm2
時間:0.05~3.0秒 1) Heat-resistant layer (Ni-Co layer)
Current density (D k ): 1.0 to 3.0 A / dm 2
Time: 0.05 to 3.0 seconds 2) Weather resistant layer (Zn—Ni layer)
Current density (D k ): 0.05 to 0.7 A / dm 2
Time: 0.05 to 3.0 seconds 3) Rust prevention layer (Cr-Zn layer)
Current density (D k ): 0.5 to 1.5 A / dm 2
Time: 0.05 to 3.0 seconds
以上の結果を、表1に示す。この他、Cr付着量は全体(全Cr量)で82μg/dm2、Co付着量は全体(全Co量)で723μg/dm2、Zn付着量は全体(全Zn量)で207μg/dm2であった。 As a result of the adhesion strength evaluation, the normal peel strength was as good as 0.97 kg / cm, but the hydrochloric acid degradation resistance was 35 (Loss%), which was poor. The alkali etching property was good, but the overall evaluation was poor. This is considered to be caused by a large Zn ratio.
The results are shown in Table 1. In addition, Cr coating weight total (total Cr amount) at 82μg / dm 2, Co coating weight across the entire 723μg / dm 2, Zn deposition amount is (total Co content) (total amount of Zn) at 207μg / dm 2 Met.
前述のキャリア付銅箔に実施例1-5と同様の条件で粗化処理層を形成した。粗化段階のNi付着量は50~250μg/dm2であった。
Ni-Co層からなる耐熱層、Zn、Ni、Crを含有する耐候層及び防錆層およびシランカップリング処理は、上記に示す条件の範囲で実施した。耐熱層、耐候層及び防錆層を形成する条件を下記に示す。なお、極薄銅層の厚みは3μmとした。 (Comparative Example 4)
A roughened layer was formed on the above-described copper foil with a carrier under the same conditions as in Example 1-5. The amount of Ni deposited in the roughening stage was 50 to 250 μg / dm 2 .
The heat-resistant layer composed of the Ni—Co layer, the weather-resistant layer containing Zn, Ni, and Cr, the rust-preventing layer, and the silane coupling treatment were performed within the range of the above conditions. The conditions for forming the heat-resistant layer, weather-resistant layer and rust-proof layer are shown below. The thickness of the ultrathin copper layer was 3 μm.
電流密度(Dk):1.0~3.0A/dm2
時間:0.05~3.0秒
2)耐候層(Zn-Ni層)
電流密度(Dk):0.7~2.0A/dm2
時間:0.05~3.0秒
3)防錆層(Cr-Zn層)
電流密度(Dk):0.8~2.5A/dm2
時間:0.05~3.0秒 1) Heat-resistant layer (Ni-Co layer)
Current density (D k ): 1.0 to 3.0 A / dm 2
Time: 0.05 to 3.0 seconds 2) Weather resistant layer (Zn—Ni layer)
Current density (D k ): 0.7 to 2.0 A / dm 2
Time: 0.05 to 3.0 seconds 3) Rust prevention layer (Cr-Zn layer)
Current density (D k ): 0.8 to 2.5 A / dm 2
Time: 0.05 to 3.0 seconds
以上の結果を、表1に示す。この他、Cr付着量は全体(全Cr量)で122μg/dm2、Co付着量は全体(全Co量)で1546μg/dm2、Zn付着量は全体(全Zn量)で361μg/dm2であった。 As a result of the adhesion strength evaluation, the normal peel strength was as good as 0.99 kg / cm, but the hydrochloric acid resistance against deterioration with hydrochloric acid: 40 (Loss%) was poor. The alkali etching property was good (◯). However, the overall evaluation was poor. This is considered to be caused by a large Zn ratio.
The results are shown in Table 1. In addition, Cr coating weight total (total Cr amount) at 122μg / dm 2, Co coating weight across the entire 1546μg / dm 2, Zn deposition amount is (total Co content) (total amount of Zn) at 361μg / dm 2 Met.
(実施例21)
次に、キャリアと銅箔との間に、中間層としてCoMo合金を形成した以外は、実施例1と同様の条件で、キャリア付銅箔を形成した。この場合の、CoMo合金中間層は、以下の液組成のめっき液中でめっきすることにより作製した。なお、極薄銅層の厚みは2μmとした。 (Example when the composition of the intermediate layer is changed)
(Example 21)
Next, a copper foil with a carrier was formed under the same conditions as in Example 1 except that a CoMo alloy was formed as an intermediate layer between the carrier and the copper foil. In this case, the CoMo alloy intermediate layer was produced by plating in a plating solution having the following liquid composition. The thickness of the ultrathin copper layer was 2 μm.
Na2MoO4・2H2O : 0.5~100g/l
クエン酸ナトリウム二水和物 :20~300g/l
(温度) 10~70℃
(pH) 3~5
(電流密度) 0.1~60A/dm2 (Liquid composition) CoSO 4 · 7H 2 O: 0.5 ~ 100g / l
Na 2 MoO 4 .2H 2 O: 0.5 to 100 g / l
Sodium citrate dihydrate: 20-300 g / l
(Temperature) 10 ~ 70 ℃
(PH) 3-5
(Current density) 0.1 to 60 A / dm 2
以上の結果を、表2に示す。この他、Ni付着量(粗化段階)50~250μg/dm2、Co付着量は全体(全Co量)で2005μg/dm2、Zn付着量は全体(全Zn量)で163μg/dm2であった。 As a result of the evaluation of the adhesion strength, the normal peel strength was 0.90 kg / cm, and the resistance to hydrochloric acid degradation was 10 (Loss%) or less, which was very good. Alkali etching property was also good (◯).
The results are shown in Table 2. In addition, Ni deposition amount (roughening step) 50 ~ 250μg / dm 2, Co coating weight across the entire 2005μg / dm 2, Zn deposition amount is (total Co content) (total amount of Zn) at 163μg / dm 2 there were.
次に、キャリアと銅箔との間に、中間層としてCrを形成した以外は、実施例2と同様の条件で、キャリア付銅箔を形成した。この場合の、Cr中間層は以下の液組成のめっき液中でめっきすることにより作製した。なお、極薄銅層の厚みは10μmとした。 (Example 22)
Next, a copper foil with a carrier was formed under the same conditions as in Example 2 except that Cr was formed as an intermediate layer between the carrier and the copper foil. In this case, the Cr intermediate layer was produced by plating in a plating solution having the following liquid composition. The thickness of the ultrathin copper layer was 10 μm.
CrO3: 200~400g/l
H2SO4: 1.5~4g/l
(pH) 1~4
(液温) 45~60℃
(電流密度)10~40A/dm2 (Liquid composition)
CrO 3 : 200 to 400 g / l
H 2 SO 4 : 1.5 to 4 g / l
(PH) 1-4
(Liquid temperature) 45-60 ℃
(Current density) 10 to 40 A / dm 2
以上の結果を、表2に示す。この他、Ni付着量(粗化段階)50~250μg/dm2、Co付着量は全体(全Co量)で1481μg/dm2、Zn付着量は全体(全Zn量)で99μg/dm2であった。 As a result of the evaluation of the adhesion strength, the normal peel strength was 0.91 kg / cm, hydrochloric acid resistance against degradation: 11 (Loss%), and was very good. Alkali etching property was also good (◯).
The results are shown in Table 2. In addition, Ni deposition amount (roughening step) 50 ~ 250μg / dm 2, Co coating weight across the entire 1481μg / dm 2, Zn deposition amount is (total Co content) (total amount of Zn) at 99 ug / dm 2 there were.
次に、キャリアと銅箔との間に、中間層としてCr/CuPを形成した以外は、実施例1と同様の条件で、キャリア付銅箔を形成した。この場合の、Cr/CuP中間層は以下の液組成のめっき液中でめっきすることにより作製した。なお、極薄銅層の厚みは2μmとした。 (Example 23)
Next, a copper foil with a carrier was formed under the same conditions as in Example 1 except that Cr / CuP was formed as an intermediate layer between the carrier and the copper foil. In this case, the Cr / CuP intermediate layer was produced by plating in a plating solution having the following liquid composition. The thickness of the ultrathin copper layer was 2 μm.
CrO3 :200~400g/l
H2SO4 :1.5~4g/l
(pH) :1~4
(液温) :45~60℃
(電流密度) :10~40A/dm2 (Liquid composition 1)
CrO 3 : 200 to 400 g / l
H 2 SO 4 : 1.5 to 4 g / l
(PH): 1 to 4
(Liquid temperature): 45-60 ° C
(Current density): 10 to 40 A / dm 2
Cu2P2O7 :3H2O :5~50g/l
K4P2O7 :50~300g/l
(温度) :30~60℃
(pH) :8~10
(電流密度) :0.1~1.0A/dm2 (Liquid composition 2)
Cu 2 P 2 O 7 : 3H 2 O: 5 to 50 g / l
K 4 P 2 O 7 : 50 to 300 g / l
(Temperature): 30-60 ° C
(PH): 8 to 10
(Current density): 0.1 to 1.0 A / dm 2
以上の結果を、表2に示す。この他、Ni付着量(粗化段階)50~250μg/dm2、Co付着量は全体(全Co量)で2003μg/dm2、Zn付着量は全体(全Zn量)で163μg/dm2であった。 As a result of the evaluation of the adhesion strength, the normal peel strength was 0.90 kg / cm, and the resistance to hydrochloric acid degradation was 10 (Loss%) or less, which was very good. Alkali etching property was also good (◯).
The results are shown in Table 2. In addition, Ni deposition amount (roughening step) 50 ~ 250μg / dm 2, Co coating weight across the entire 2003μg / dm 2, Zn deposition amount is (total Co content) (total amount of Zn) at 163μg / dm 2 there were.
次に、キャリアと銅箔との間に、中間層としてNi/Crを形成した以外は、実施例2と同様の条件で、キャリア付銅箔を形成した。この場合の、Ni/Cr中間層は以下の液組成のめっき液中でめっきすることにより作製した。なお、極薄銅層の厚みは10μmとした。 (Example 24)
Next, a copper foil with a carrier was formed under the same conditions as in Example 2 except that Ni / Cr was formed as an intermediate layer between the carrier and the copper foil. In this case, the Ni / Cr intermediate layer was produced by plating in a plating solution having the following liquid composition. The thickness of the ultrathin copper layer was 10 μm.
NiSO4・6H2O:250~300g/l
NiCl2・6H2O:35~45g/l
ホウ酸:10~50g/l
(pH):2~6
(浴温):30~70℃
(電流密度):0.1~50A/dm2 (Liquid composition 1)
NiSO 4 · 6H 2 O: 250 ~ 300g / l
NiCl 2 · 6H 2 O: 35 to 45 g / l
Boric acid: 10-50 g / l
(PH): 2 to 6
(Bath temperature): 30-70 ° C
(Current density): 0.1 to 50 A / dm 2
CrO3 :200~400g/l
H2SO4 :1.5~4g/l
(pH) :1~4
(液温) :45~60℃
(電流密度):10~40A/dm2 (Liquid composition 2)
CrO 3 : 200 to 400 g / l
H 2 SO 4 : 1.5 to 4 g / l
(PH): 1 to 4
(Liquid temperature): 45-60 ° C
(Current density): 10 to 40 A / dm 2
次に、キャリアと銅箔との間に、中間層としてCo/クロメート処理の層を形成した以外は、実施例1と同様の条件で、キャリア付銅箔を形成した。
この場合の、Co/クロメート処理の中間層は以下の液組成のめっき液中でめっきすることにより作製した。なお、極薄銅層の厚みは2μmとした。 (Example 25)
Next, a copper foil with a carrier was formed under the same conditions as in Example 1 except that a Co / chromate-treated layer was formed as an intermediate layer between the carrier and the copper foil.
In this case, the Co / chromate intermediate layer was prepared by plating in a plating solution having the following liquid composition. The thickness of the ultrathin copper layer was 2 μm.
クエン酸ナトリウム二水和物 :30~200g/l
(温度) : 10~70℃
(pH) : 3~5
(電流密度): 0.1~60A/dm2 (Liquid composition 1) CoSO 4 · 7H 2 O: 10 to 100 g / l
Sodium citrate dihydrate: 30-200 g / l
(Temperature): 10 ~ 70 ℃
(pH): 3-5
(Current density): 0.1 to 60 A / dm 2
(温度) ;10~70℃
(pH) :10~12
(電流密度) :0.1~1.0A/dm2 (Liquid composition 2): CrO 3 : 1 to 10 g / L
(Temperature); 10 ~ 70 ℃
(pH): 10-12
(Current density): 0.1 to 1.0 A / dm 2
以上の結果を、表2に示す。この他、Ni付着量(粗化段階)50~250μg/dm2、Co付着量は全体(全Co量)で2014μg/dm2、Zn付着量は全体(全Zn量)で164μg/dm2であった。 As a result of the evaluation of the adhesion strength, the normal peel strength was 0.90 kg / cm, and the resistance to hydrochloric acid degradation was 10 (Loss%) or less, which was very good. Alkali etching property was also good (◯).
The results are shown in Table 2. In addition, Ni adhesion amount (roughening stage) 50 to 250 μg / dm 2 , Co adhesion amount as a whole (total Co amount) is 2014 μg / dm 2 , Zn adhesion amount as a whole (total Zn amount) is 164 μg / dm 2 . there were.
次に、キャリアと銅箔との間に、中間層として有機物層を形成した以外は、実施例4と同様の条件で、キャリア付銅箔を形成した。なお、極薄銅層の厚みは10μmとした。この場合の、有機物層の中間層は液温40℃、pH5、濃度1~10g/lのカルボキシベンゾトリアゾール水溶液を、10~60秒間噴霧という条件で作製した。 (Example 26)
Next, a copper foil with a carrier was formed under the same conditions as in Example 4 except that an organic layer was formed as an intermediate layer between the carrier and the copper foil. The thickness of the ultrathin copper layer was 10 μm. In this case, an intermediate layer of the organic layer was prepared by spraying an aqueous carboxybenzotriazole solution having a liquid temperature of 40 ° C., pH 5, and a concentration of 1 to 10 g / l for 10 to 60 seconds.
以上の結果を、表2に示す。この他、Ni付着量(粗化段階)50~250μg/dm2、Co付着量は全体(全Co量)で1484μg/dm2、Zn付着量は全体(全Zn量)で99μg/dm2であった。 As a result of the evaluation of the adhesion strength, the normal peel strength was 0.91 kg / cm, hydrochloric acid resistance against degradation: 11 (Loss%), and was very good. Alkali etching property was also good (◯).
The results are shown in Table 2. In addition, Ni deposition amount (roughening step) 50 ~ 250μg / dm 2, Co coating weight across the entire 1484μg / dm 2, Zn deposition amount is (total Co content) (total amount of Zn) at 99 ug / dm 2 there were.
Claims (25)
- キャリア、中間層、極薄銅層がこの順に積層されているキャリア付銅箔の前記極薄銅層の表面に、粗化(トリート)処理を施すことにより形成された粗化処理層、この粗化処理層の上に形成されたNi-Co層からなる耐熱層、及びこの耐熱層の上に形成されたZn、Ni、Crを含有する耐候層及び防錆層を有する表面処理層を有し、前記表面処理層中の全Zn量/(全Zn量+全Ni量)が0.02以上0.35以下であり、前記表面処理層中の全Ni量が1600μg/dm2以下であることを特徴とするキャリア付銅箔。 A roughening treatment layer formed by subjecting the surface of the ultrathin copper layer of the copper foil with carrier, in which the carrier, the intermediate layer, and the ultrathin copper layer are laminated in this order, to the roughening (treat) treatment, A heat-resistant layer made of a Ni—Co layer formed on the heat treatment layer, and a surface-treated layer having a weather-resistant layer and a rust-proof layer containing Zn, Ni, Cr formed on the heat-resistant layer The total Zn content in the surface treatment layer / (total Zn content + total Ni content) is 0.02 or more and 0.35 or less, and the total Ni content in the surface treatment layer is 1600 μg / dm 2 or less. Copper foil with carrier.
- 前記表面処理層中の全Zn量/(全Zn量+全Ni量)が0.02以上0.23以下であり、前記表面処理層中の全Ni量が1150μg/dm2以下であることを特徴とする、請求項1に記載のキャリア付銅箔。 The total Zn amount in the surface treatment layer / (total Zn amount + total Ni amount) is 0.02 or more and 0.23 or less, and the total Ni amount in the surface treatment layer is 1150 μg / dm 2 or less. The copper foil with a carrier according to claim 1, wherein
- 前記表面処理層中の全Ni量が、350~1350μg/dm2であることを特徴とする請求項1又は請求項2に記載のキャリア付銅箔。 The copper foil with a carrier according to claim 1 or 2 , wherein the total amount of Ni in the surface treatment layer is 350 to 1350 µg / dm 2 .
- 前記表面処理層中の全Ni量が、450~1100μg/dm2であることを特徴とする請求項1~3のいずれか一項に記載のキャリア付銅箔。 The copper foil with a carrier according to any one of claims 1 to 3, wherein the total amount of Ni in the surface treatment layer is 450 to 1100 μg / dm 2 .
- 前記表面処理層中の全Co量が770~3200μg/dm2であり、全Co量/(全Zn量+全Ni量)が3.4以下であることを特徴とする請求項1~4のいずれか一項に記載のキャリア付銅箔。 5. The total amount of Co in the surface treatment layer is 770 to 3200 μg / dm 2 , and the total amount of Co / (total Zn amount + total Ni amount) is 3.4 or less. The copper foil with a carrier as described in any one of Claims.
- 前記表面処理層中の全Co量が770~2500μg/dm2であり、全Co量/(全Zn量+全Ni量)が3.0以下であることを特徴とする請求項1~5のいずれか一項に記載のキャリア付銅箔。 6. The total Co amount in the surface treatment layer is 770 to 2500 μg / dm 2 , and the total Co amount / (total Zn amount + total Ni amount) is 3.0 or less. The copper foil with a carrier as described in any one of Claims.
- 前記表面処理層中の全Cr量が50~130μg/dm2であることを特徴とする請求項1~6のいずれか一項に記載のキャリア付銅箔。 The copper foil with a carrier according to any one of claims 1 to 6, wherein the total amount of Cr in the surface treatment layer is 50 to 130 µg / dm 2 .
- 前記粗化処理層のNi量が50~550μg/dm2であることを特徴とする請求項1~7のいずれか一項に記載のキャリア付銅箔。 The copper foil with a carrier according to any one of claims 1 to 7, wherein the amount of Ni in the roughened layer is 50 to 550 µg / dm 2 .
- 前記粗化処理層が、Co、Cu、Niの元素からなる粗化処理層であることを特徴とする請求項1~8のいずれかに記載のキャリア付銅箔。 The copper foil with a carrier according to any one of claims 1 to 8, wherein the roughening treatment layer is a roughening treatment layer composed of elements of Co, Cu, and Ni.
- 前記粗化処理層が平均粒子径0.05~0.60μmの微細粒子からなることを特徴とする請求項1~9のいずれか一項に記載のキャリア付銅箔。 The copper foil with a carrier according to any one of claims 1 to 9, wherein the roughened layer comprises fine particles having an average particle diameter of 0.05 to 0.60 µm.
- 前記粗化処理層が平均粒子径0.05~0.60μmのCu、Co、Niからなる3元系合金の微細粒子からなることを特徴とする請求項1~10のいずれか一項に記載のキャリア付銅箔。 11. The roughening treatment layer is formed of fine particles of a ternary alloy composed of Cu, Co, and Ni having an average particle diameter of 0.05 to 0.60 μm. Copper foil with carrier.
- 前記粗化処理層が、平均粒子径0.25~0.45μmの一次粒子層と、その上に形成された平均粒子径が0.05~0.25μmの二次粒子層からなることを特徴とする請求項1~11のいずれか一項に記載のキャリア付銅箔。 The roughening treatment layer comprises a primary particle layer having an average particle diameter of 0.25 to 0.45 μm and a secondary particle layer having an average particle diameter of 0.05 to 0.25 μm formed thereon. The copper foil with a carrier according to any one of claims 1 to 11.
- 前記粗化処理層が、平均粒子径0.25~0.45μmのCuの一次粒子層と、その上に形成された平均粒子径が0.05~0.25μmのCu、Co、Niからなる3元系合金からなる二次粒子層からなることを特徴とする請求項1~12のいずれか一項に記載のキャリア付銅箔。 The roughening layer comprises a primary particle layer of Cu having an average particle size of 0.25 to 0.45 μm, and Cu, Co, and Ni having an average particle size of 0.05 to 0.25 μm formed thereon. The copper foil with a carrier according to any one of claims 1 to 12, which comprises a secondary particle layer made of a ternary alloy.
- 上記請求項1~13のいずれか一項に記載のキャリア付銅箔の前記極薄銅層からなる印刷回路用銅箔。 A printed circuit copper foil comprising the ultrathin copper layer of the carrier-attached copper foil according to any one of claims 1 to 13.
- 前記表面処理層上に樹脂層を備える請求項1~13のいずれか一項に記載のキャリア付銅箔。 The carrier-attached copper foil according to any one of claims 1 to 13, further comprising a resin layer on the surface treatment layer.
- 上記請求項14に記載の印刷回路用銅箔を樹脂基板に積層接着した銅張積層板。 A copper-clad laminate obtained by laminating and bonding the printed circuit copper foil according to claim 14 to a resin substrate.
- 請求項1~13のいずれか一項に記載のキャリア付銅箔を用いて製造したプリント配線板。 A printed wiring board manufactured using the carrier-attached copper foil according to any one of claims 1 to 13.
- 請求項1~13のいずれか一項に記載のキャリア付銅箔を用いて製造したプリント回路板。 A printed circuit board manufactured using the carrier-attached copper foil according to any one of claims 1 to 13.
- 請求項1~13のいずれか一項に記載のキャリア付銅箔を用いて製造した銅張積層板。 A copper-clad laminate produced using the carrier-attached copper foil according to any one of claims 1 to 13.
- 請求項1~13のいずれか一項に記載のキャリア付銅箔と絶縁基板とを準備する工程、
前記キャリア付銅箔と絶縁基板とを積層する工程、
前記キャリア付銅箔と絶縁基板とを積層した後に、前記キャリア付銅箔のキャリアを剥がす工程を経て銅張積層板を形成し、
その後、セミアディティブ法、サブトラクティブ法、パートリーアディティブ法又はモディファイドセミアディティブ法のいずれかの方法によって、回路を形成する工程
を含むプリント配線板の製造方法。 Preparing a carrier-attached copper foil according to any one of claims 1 to 13 and an insulating substrate;
Laminating the copper foil with carrier and an insulating substrate;
After laminating the carrier-attached copper foil and the insulating substrate, a copper-clad laminate is formed through a step of peeling the carrier of the carrier-attached copper foil,
Then, the manufacturing method of a printed wiring board including the process of forming a circuit by any method of a semi-additive method, a subtractive method, a partly additive method, or a modified semi-additive method. - 請求項1~13のいずれか一項に記載のキャリア付銅箔の前記極薄銅層側表面に回路を形成する工程、
前記回路が埋没するように前記キャリア付銅箔の前記極薄銅層側表面に樹脂層を形成する工程、
前記樹脂層上に回路を形成する工程、
前記樹脂層上に回路を形成した後に、前記キャリアを剥離させる工程、及び、
前記キャリアを剥離させた後に、前記極薄銅層を除去することで、前記極薄銅層側表面に形成した、前記樹脂層に埋没している回路を露出させる工程
を含むプリント配線板の製造方法。 Forming a circuit on the ultrathin copper layer side surface of the carrier-attached copper foil according to any one of claims 1 to 13,
Forming a resin layer on the ultrathin copper layer side surface of the carrier-attached copper foil so that the circuit is buried;
Forming a circuit on the resin layer;
Forming the circuit on the resin layer, and then peeling the carrier; and
After the carrier is peeled off, the printed wiring board includes a step of exposing the circuit embedded in the resin layer formed on the surface of the ultrathin copper layer by removing the ultrathin copper layer Method. - 前記樹脂層上に回路を形成する工程が、
前記樹脂層上に別のキャリア付銅箔を極薄銅層側から貼り合わせ、前記樹脂層に貼り合わせたキャリア付銅箔を用いて前記回路を形成する工程である、請求項21に記載のプリント配線板の製造方法。 Forming a circuit on the resin layer,
It is the process of bonding another copper foil with a carrier on the said resin layer from the ultra-thin copper layer side, and forming the said circuit using the copper foil with a carrier bonded together to the said resin layer. Manufacturing method of printed wiring board. - 前記樹脂層上に貼り合わせる別のキャリア付銅箔が、請求項1~13のいずれか一項に記載のキャリア付銅箔である、請求項22に記載のプリント配線板の製造方法。 The method for producing a printed wiring board according to claim 22, wherein the copper foil with carrier attached to the resin layer is the copper foil with carrier according to any one of claims 1 to 13.
- 前記樹脂層上に回路を形成する工程が、セミアディティブ法、サブトラクティブ法、パートリーアディティブ法又はモディファイドセミアディティブ法のいずれかの方法によって行われる、請求項21~23のいずれか一項に記載のプリント配線板の製造方法。 The step of forming a circuit on the resin layer is performed by any one of a semi-additive method, a subtractive method, a partly additive method, or a modified semi-additive method. Manufacturing method of printed wiring board.
- キャリアを剥離する前に、キャリア付銅箔のキャリア側表面に基板を形成する工程を更に含む請求項21~24の何れか一項に記載のプリント配線板の製造方法。 The method for producing a printed wiring board according to any one of claims 21 to 24, further comprising a step of forming a substrate on the carrier side surface of the carrier-attached copper foil before peeling off the carrier.
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KR1020177017436A KR102030911B1 (en) | 2012-09-28 | 2013-09-27 | Copper foil provided with carrier, and copper-clad laminate using said copper foil provided with carrier |
JP2014538664A JP6236009B2 (en) | 2012-09-28 | 2013-09-27 | Copper foil with carrier and copper clad laminate using copper foil with carrier |
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