WO2017099093A1 - プリント配線板用表面処理銅箔、プリント配線板用銅張積層板及びプリント配線板 - Google Patents

プリント配線板用表面処理銅箔、プリント配線板用銅張積層板及びプリント配線板 Download PDF

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Publication number
WO2017099093A1
WO2017099093A1 PCT/JP2016/086281 JP2016086281W WO2017099093A1 WO 2017099093 A1 WO2017099093 A1 WO 2017099093A1 JP 2016086281 W JP2016086281 W JP 2016086281W WO 2017099093 A1 WO2017099093 A1 WO 2017099093A1
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WO
WIPO (PCT)
Prior art keywords
copper foil
printed wiring
wiring board
coupling agent
silane coupling
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PCT/JP2016/086281
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English (en)
French (fr)
Japanese (ja)
Inventor
貴広 齋藤
健 繪面
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古河電気工業株式会社
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Application filed by 古河電気工業株式会社 filed Critical 古河電気工業株式会社
Priority to KR1020177027515A priority Critical patent/KR102054281B1/ko
Priority to CN201680004945.8A priority patent/CN107109679B/zh
Publication of WO2017099093A1 publication Critical patent/WO2017099093A1/ja

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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
    • C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • C25D5/48—After-treatment of electroplated surfaces
    • 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
    • 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
    • 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • 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
    • 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
    • H05K3/384—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by plating

Definitions

  • the present invention relates to a surface-treated copper foil for a printed wiring board. Moreover, this invention relates to the copper clad laminated board for printed wiring boards and the printed wiring board using the said surface treatment copper foil for said printed wiring boards.
  • Conductor loss is due to the skin resistance of the conductor circuit.
  • a skin effect phenomenon occurs. That is, when an alternating current is passed through the conductor circuit, the magnetic flux changes and a back electromotive force is generated at the center of the conductor circuit. As a result, it is difficult for current to flow through the center of the conductor. The phenomenon that increases. This skin effect phenomenon causes so-called skin resistance to reduce the effective cross-sectional area of the conductor.
  • the thickness (skin depth) of the skin portion through which current flows is inversely proportional to the square root of the frequency.
  • copper foil used for printed wiring boards generally forms a roughened layer (layer on which roughened particles are formed) on the surface using a technique such as electroplating or etching, and has a physical effect (The adhesive force with the resin base material is enhanced by the anchor effect).
  • a technique such as electroplating or etching
  • the adhesive force with the resin base material is enhanced by the anchor effect.
  • the roughened particles formed on the surface of the copper foil are increased in order to effectively increase the adhesive strength with the resin base material, the transmission loss increases as described above.
  • the dielectric loss is caused by the dielectric constant and dielectric loss tangent of the resin base material.
  • a pulse signal is passed through a conductor circuit, the electric field around the conductor circuit changes.
  • the period (frequency) at which the electric field changes approaches the relaxation time of polarization of the resin base material (the moving time of the charged body that generates polarization) (that is, when the frequency is increased)
  • the electric field change is delayed. In such a state, molecular friction occurs inside the resin, heat is generated, and transmission loss occurs.
  • the resin base of the copper-clad laminate In order to suppress this dielectric loss, a resin with a small amount of a large polar substituent or a resin without a large polar substituent is adopted as the resin base of the copper-clad laminate, and the resin base is polarized due to a change in electric field. It is necessary to make it difficult to produce.
  • the copper foil used for the printed wiring board increases the chemical adhesive force with the resin base material by treating the copper foil surface with a silane coupling agent in addition to the formation of the roughening treatment layer. Is also done.
  • the resin base material In order to improve the chemical adhesion between the silane coupling agent and the resin base material, it is necessary that the resin base material has a substituent having a certain degree of polarity. When a low dielectric substrate with a reduced amount of groups is used, the chemical adhesive strength is reduced, and it is difficult to ensure sufficient adhesion between the copper foil and the resin substrate.
  • a flexible printed wiring board (hereinafter referred to as FPC) is adopted because of easy wiring and light weight.
  • FPC flexible printed wiring board
  • the speed of signal transmission has increased, and impedance matching (matching of output resistance and input resistance) of FPC has become important.
  • a resin base material typically polyimide
  • the FPC is subjected to predetermined processing such as being bonded to a liquid crystal substrate or mounting an IC chip.
  • the alignment at the time of this processing is performed using a positioning pattern that is visible through the portion of the resin base material from which the copper foil has been removed by etching as an index. Therefore, in the above alignment, the permeability (visibility) of the resin base material is important.
  • the transparency of this resin substrate is usually evaluated and managed using the total light transmittance in the visible light region and haze (haze value).
  • the thickness of the resin base material and the alignment process have been diversified, and the level of permeability required for the resin base material after etching has increased.
  • the surface shape of the copper foil bonded to the resin substrate greatly affects the permeability of the resin substrate after etching.
  • a resin base material having flexibility such as polyimide and liquid crystal polymer is laminated with a copper foil under high temperature and high pressure conditions. At that time, since the resin enters the base of the roughened particles formed on the roughened surface of the copper foil, the larger the roughened particles, the deeper the unevenness transferred to the resin. The transmitted light tends to be scattered and tends to be inferior in transparency.
  • Patent Document 2 relating to FPC includes a rust-proofing layer made of a nickel-zinc alloy on an adhesive surface bonded to an insulating layer, and the surface roughness (Rz) of the adhesive surface is 0.05 to 1.5 ⁇ m.
  • An FPC suitable for a chip-on-film (COF) type having an electrolytic copper foil having a specular gloss of 250 or more at an incident angle of 60 ° is described, and the FPC exhibits excellent light transmittance, and the copper foil and the resin It is described that the adhesion to the substrate is also good.
  • COF chip-on-film
  • Patent Document 3 discloses that roughened particles are formed by roughening treatment, the average roughness Rz of the roughened surface is 0.5 to 1.3 ⁇ m, the glossiness is 4.8 to 68, and roughened particles.
  • a surface-treated copper foil having a ratio A / B of 2.00 to 2.45 between the surface area A and the area B obtained when the roughened particles are viewed in plan from the copper foil surface side is described.
  • the copper clad laminate formed by laminating the treated copper foil and the resin substrate has good resin transparency after the copper foil is removed by etching, and good adhesion between the copper foil and the resin. Are listed.
  • the surface-treated copper foil described in Patent Document 1 is excellent in adhesion with a high-frequency resin substrate, but the copper-clad laminate using this surface-treated copper foil has a high transmission loss in the high-frequency band of the GHz band, The advanced requirements for high frequency printed circuit boards have not been fully met.
  • the electrolytic copper foil used in the FPC described in Patent Document 2 is not roughened, and achieves a high degree of adhesion with a resin substrate required for printed wiring boards other than COF. It has not been done.
  • the present invention provides a printed wiring board that has a high transmission loss even when transmitting a high frequency signal in the GHz band, has high adhesion to a resin base material, is excellent in durability, and has excellent visibility. It is an object to provide a surface-treated copper foil for a printed wiring board that can be obtained. Moreover, this invention makes it a subject to provide the copper clad laminated board for printed wiring boards and the printed wiring board (circuit board) using the said surface-treated copper foil for printed wiring boards.
  • a surface-treated copper foil for a printed wiring board having a silane coupling agent layer on the surface on which roughened particles are formed On the surface of the silane coupling agent layer, the average height of the roughened particles is 0.05 ⁇ m or more and less than 0.5 ⁇ m
  • the surface on which the roughened particles are formed has a metal treatment layer having at least one metal selected from chromium, iron, cobalt, nickel, copper, zinc, molybdenum, and tin, or chromium, iron
  • the silane coupling agent is at least one functional group selected from an epoxy group, an amino group, a vinyl group, a (meth) acryloyl group, a styryl group, a ureido group, an isocyanurate group, a mercapto group, a sulfide group, and an isocyanate group.
  • the surface-treated copper foil for a printed wiring board according to the present invention is used for a conductor circuit of a printed wiring board, so that transmission loss when transmitting a high-frequency signal in the GHz band is suppressed to a high level. It is possible to obtain a printed wiring board having high adhesion to the substrate, excellent durability, and excellent visibility.
  • the copper-clad laminate for a printed wiring board according to the present invention is used as a substrate for a printed wiring board, so that transmission loss when transmitting a high-frequency signal in the GHz band is suppressed to a high level. It is possible to obtain a printed wiring board having high adhesion and excellent durability and excellent visibility.
  • the printed wiring board of the present invention is highly suppressed in transmission loss when transmitting a high frequency signal in the GHz band, has high adhesion between the copper foil and the resin base material, is excellent in durability, and is also visible. Excellent.
  • the surface-treated copper foil for printed wiring boards of the present invention (hereinafter referred to as “surface-treated copper foil of the present invention”) has a surface on which roughened particles are formed (a surface on which an antiseptic metal is further adhered if necessary).
  • the average height of the activated particles is 0.05 ⁇ m or more and less than 0.5 ⁇ m, the BET surface area ratio of the silane coupling agent layer surface is 1.2 or more, and the fine surface area coefficient of the silane coupling agent layer surface (Cms) is 2.0 or more and less than 8.0.
  • the average height of the roughened particles measured on the surface of the silane coupling agent layer is 0.05 ⁇ m or more and less than 0.5 ⁇ m, and the BET surface area ratio of the surface Is 1.2 or more and the surface Cms is 2.0 or more and less than 8.0 is simply referred to as “roughening surface”.
  • the roughened surface is preferably entirely covered with a silane coupling agent, but as long as the effects of the present invention are achieved, a portion of the roughened surface may not be covered with the silane coupling agent.
  • a film defect may be generated in a part of the silane coupling agent layer on the roughened surface, and such a form also has “a silane coupling agent layer” in the present invention. Included in the form).
  • the surface-treated copper foil of the present invention only needs to have at least one roughened surface, and both surfaces may be roughened surfaces.
  • the surface-treated copper foil of the present invention is usually in a form in which only one surface is a roughened surface.
  • the roughened surface has a large BET surface area ratio of 1.2 or more although the average height of the roughened particles is as low as less than 0.5 ⁇ m. Therefore, when the surface-treated copper foil and the resin layer are laminated through the roughened surface, and the copper-clad laminate is produced, the anchor effect of the roughened particles and the large surface area are combined, Adhesion between the copper foil and the resin layer is highly enhanced, and a copper-clad laminate having excellent heat resistance can be obtained. Further, the roughened surface has an average height of roughened particles as low as less than 0.5 ⁇ m, and the influence of the presence of roughened particles on the length of the transmission path can be reduced.
  • the average height of the roughened particles on the roughened surface is preferably 0.05 ⁇ m or more and less than 0.5 ⁇ m. 0.05 ⁇ m or more and less than 0.3 ⁇ m is more preferable.
  • the roughened particles are preferably formed uniformly (homogeneously) on the entire roughened surface. The average height of the roughened particles is measured by the method described in Examples described later.
  • the BET surface area ratio is calculated based on the surface area measurement method by the BET method. That is, the BET surface area ratio is obtained by adsorbing a gas molecule whose adsorption occupation area is known on the sample surface, obtaining the surface area of the sample (BET measurement surface area) based on the adsorption amount, and unevenness on the sample surface from the BET measurement surface area. This is the ratio of the value obtained by subtracting the surface area (sample cut-out area) when it is assumed to be absent to the sample cut-out area, and is measured by the method described in the examples described later. In the surface-treated copper foil of the present invention, the larger the value of the BET surface area ratio of the roughened surface, the larger the surface area.
  • the BET surface area ratio of the roughened surface is preferably 1.2 or more and 10 or less, more preferably 4 or more and 8 or less.
  • the surface area of the sample on which the roughened particles are formed can usually be measured with higher accuracy than when a laser microscope is used.
  • the present inventors have succeeded in further increasing the ratio of the surface area of “shadows” and fine irregularities that cannot be measured with a laser microscope by applying a specific roughening plating process described later.
  • the Cms is the ratio of the surface area ratio measured by the BET method to the surface area ratio measured by the laser microscope, and the ratio of the surface area of the “shadow” portion and the fine uneven portion that cannot be measured by the laser microscope is quantified. Is. Details of the calculation method of Cms are as described in the examples described later.
  • Cms of the roughened surface is 2.0 or more and less than 8.0.
  • the average height of the roughened particles on the roughened surface and the BET surface area ratio of the roughened surface are within the range defined by the present invention, and the Cms of the roughened surface is 2.0 or more and less than 8.0.
  • Cms is preferably 2.5 or more and less than 5.0.
  • the surface area measured by the laser microscope and the surface area measured by the BET method have different surface area measurement principles, and Cms may be less than 1 depending on the shape of the roughened surface.
  • the lightness index L * (Lightness) of the roughened surface is preferably 40 or more and less than 60, and more preferably 40 or more and less than 55.
  • L * is small and transmission loss tends to increase.
  • L * increases and the adhesion to the resin base material tends to decrease. L * is measured by the method described in Examples described later.
  • the surface on which the roughened particles are formed before the silane coupling agent treatment is chromium (Cr), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu ), Zinc (Zn), molybdenum (Mo), and tin (Sn), or a metal treatment layer having at least one metal selected from chromium, iron, cobalt, nickel, copper, zinc, molybdenum, And a metal treatment layer having an alloy composed of two or more metals selected from tin.
  • This metal treatment layer has a metal treatment layer having at least one metal selected from nickel, zinc, and chromium, or an alloy made of two or more metals selected from nickel, zinc, and chromium.
  • the copper clad laminate or printed wiring board in which the surface-treated copper foil of the present invention is used is often subjected to heat in the production process, such as an adhesion process between a resin and a copper foil, or a solder process. Due to this heat, copper may diffuse to the resin side and reduce the adhesion between copper and resin, but by providing the metal treatment layer, copper diffusion is prevented and high adhesion to the resin substrate is achieved. Sex can be maintained more stably.
  • the metal which comprises a metal processing layer functions also as a rust prevention metal which prevents the rust of copper.
  • the amount of nickel as a rust preventive metal on the surface on which the roughened particles are formed before the silane coupling agent treatment is also important to control the amount of nickel as a rust preventive metal on the surface on which the roughened particles are formed before the silane coupling agent treatment. That is, when there is a large amount of nickel adhered, copper rust is less likely to occur, and the adhesiveness to the resin at high temperatures tends to improve, but nickel tends to remain after etching, and sufficient insulation reliability is difficult to obtain.
  • the amount of nickel element on the roughened surface is 0.1 mg / dm 2 or more and 0.3 mg / dm from the viewpoint of achieving both adhesion and etching at high temperatures. It is preferable to be less than 2 .
  • ⁇ Copper foil> As copper foil used for manufacture of the surface-treated copper foil of this invention, it can select according to uses and other objectives, such as rolled copper foil and electrolytic copper foil. There is no restriction
  • the foil thickness is usually 4 to 120 ⁇ m, preferably 5 to 50 ⁇ m, and more preferably 6 to 18 ⁇ m.
  • the roughened surface can be formed by applying specific roughened plating conditions. That is, according to the present invention, it is possible for the present inventors to form the roughened surface by performing electroplating treatment within a specific range of molybdenum concentration and under specific conditions described later. It is an invention based on finding out.
  • the inter-electrode flow velocity In order to make it possible to form the roughened surface, it is necessary to set the inter-electrode flow velocity to 0.15 m / second or more and 0.4 m / second or less in the roughening plating treatment.
  • the inter-electrode flow rate is less than 0.15 m / sec, the desorption of hydrogen gas generated on the copper foil does not proceed and the effect of molybdenum is difficult to obtain, and problems such as powder falling are likely to occur.
  • the inter-electrode flow rate exceeds 0.4 m / sec, the supply of copper ions to fine recesses proceeds excessively, and the recesses are filled with plating, and the BET surface area ratio of the surface after the silane coupling agent treatment is 1.2. It becomes difficult to raise more.
  • the value obtained by multiplying the current density by the treatment time in the roughing plating process is 20 (A / dm 2 ) ⁇ second or more and 250 (A / dm 2 ) ⁇ second. It is necessary to: When this value is less than 20 (A / dm 2 ) ⁇ sec, it becomes difficult to make the average height of the roughened particles on the roughened surface after the silane coupling agent treatment 0.05 ⁇ m or more. It becomes difficult to ensure sufficient adhesion with the resin to be laminated.
  • a value obtained by multiplying the current density by the treatment time is preferably 20 (A / dm 2 ) ⁇ second or more and less than 160 (A / dm 2 ) ⁇ second.
  • the value obtained by multiplying the current density multiplied by the processing time by the Mo concentration in the roughing plating process is 1.0 ⁇ (A / dm 2 ) ⁇ sec. ⁇ / (Mg / L) to 3.0 ⁇ (A / dm 2 ) ⁇ second ⁇ / (mg / L) or less.
  • this value is less than 1.0 ⁇ (A / dm 2 ) ⁇ sec ⁇ / (mg / L), it is difficult to obtain a sufficient BET surface area ratio while satisfying other characteristics.
  • the preferable roughening plating process conditions for enabling the formation of the roughened surface are shown below.
  • -Roughening plating conditions Cu: 10 to 30 g / L H 2 SO 4 : 100 to 200 g / L
  • Treatment time 0.1 to 10 seconds
  • molybdenum in addition, is a form in which molybdenum dissolves as ions, and it must change the pH of the copper sulfate plating solution or contain metal impurities that are incorporated into the copper plating film.
  • an aqueous solution of molybdate for example, sodium molybdate or potassium molybdate
  • molybdate for example, sodium molybdate or potassium molybdate
  • ⁇ Metal treatment layer> When the surface-treated copper foil of this invention has a metal treatment layer, there is no restriction
  • Ni plating Ni: 10 to 100 g / L H 3 BO 3 : 1 to 50 g / L PO 2 : 0 to 10 g / L Bath temperature: 10-70 ° C
  • Current density 1 to 50 A / dm 2
  • Treatment time 1 second to 2 minutes pH: 2.0 to 4.0
  • Zn plating Zn: 1-30 g / L NaOH: 10 to 300 g / L Bath temperature: 5-60 ° C
  • Processing time 1 second to 2 minutes (Cr plating) Cr: 0.5 to 40 g / L Bath temperature: 20-70 ° C
  • Current density 0.1 to 10 A / dm 2
  • Treatment time 1 second to 2 minutes pH: 3.0 or less
  • the amount of Si element existing on the roughened surface (that is, the amount of Si element contained in the silane coupling agent layer) is 0.5 ⁇ g / dm 2 or more and less than 15 ⁇ g / dm 2. It is preferable. By setting the amount of Si element to 0.5 ⁇ g / dm 2 or more and less than 15 ⁇ g / dm 2 , it is possible to effectively improve the adhesion to the resin while suppressing the amount of the silane coupling agent used.
  • the amount of Si element contained in the silane coupling agent layer is more preferably 3 ⁇ g / dm 2 or more and less than 15 ⁇ g / dm 2 , and further preferably 5 ⁇ g / dm 2 or more and less than 15 ⁇ g / dm 2 .
  • the said silane coupling agent is suitably selected according to the molecular structure (kind of functional group etc.) of the resin which comprises the resin layer laminated
  • the silane coupling agent is at least one selected from an epoxy group, an amino group, a vinyl group, a (meth) acryloyl group, a styryl group, a ureido group, an isocyanurate group, a mercapto group, a sulfide group, and an isocyanate group. It preferably has a functional group.
  • (Meth) acryloyl group means “acryloyl group and / or methacryloyl group”.
  • the treatment with the silane coupling agent on the surface of the copper foil on which the roughened particles are formed can be performed by a conventional method.
  • a silane coupling agent solution (coating solution) is prepared, and this coating solution is applied to the surface of the copper foil on which the roughened particles are formed and dried, so that the silane cup is formed on the surface of the copper foil on which the roughened particles are formed.
  • a ring agent can be adsorbed or bound.
  • the coating solution for example, a solution containing pure silane coupling agent at a concentration of 0.05 wt% to 1 wt% can be used. There is no particular limitation on the coating method of the coating solution.
  • the coating solution is uniformly flowed on the surface on which the roughened particles are formed, and after being drained using a roll, it is dried by heating.
  • it can be applied by spraying a coating solution on a copper foil stretched with the surface on which the roughened particles are formed facing down between the rolls, and then drying by heating after draining with a roll.
  • the coating temperature There is no particular limitation on the coating temperature, and it is usually carried out at 10 to 40 ° C.
  • the copper-clad laminate for printed wiring boards of the present invention (hereinafter referred to as “the copper-clad laminate of the present invention”) has a resin layer (resin substrate) on the roughened surface of the surface-treated copper foil of the present invention. It has a laminated structure. There is no restriction
  • the resin layer normally used for the copper clad laminated board for producing a printed wiring board is employable. For example, a halogen-free low dielectric base material used for a rigid substrate or a low dielectric polyimide widely used for a flexible substrate can be used.
  • the press temperature in the above-mentioned hot pressing method is preferably about 150 to 400 ° C.
  • the pressing pressure is preferably about 1 to 50 MPa.
  • the thickness of the copper clad laminate is preferably 10 to 1000 ⁇ m.
  • the printed wiring board of the present invention is produced using the copper clad laminate of the present invention. That is, the copper-clad laminate of the present invention can be processed by etching or the like to form a conductor circuit pattern, and other components can be formed or mounted by a conventional method as required.
  • Electrolytic copper foil or rolled copper foil was used as the copper foil serving as the base material for the roughening treatment.
  • an electrolytic copper foil having a thickness of 12 ⁇ m manufactured under the following conditions was used.
  • Examples 3 and 6 and Comparative Examples 5 and 6 a commercially available 12 ⁇ m tough pitch copper rolled foil (manufactured by UACJ Co., Ltd.) subjected to degreasing treatment under the following conditions was used.
  • ⁇ Degreasing conditions> Degreasing solution: Aqueous solution of cleaner 160S (Meltex Co., Ltd.) Concentration: 60 g / L aqueous solution Bath temperature: 60 ° C Current density: 3 A / dm 2 Energizing time: 10 seconds
  • a roughened plated surface was formed on one side of the copper foil by electroplating.
  • the roughening plating treatment surface uses the following rough plating solution basic bath composition, the molybdenum concentration is as shown in Table 1 below, and the interelectrode flow velocity, current density, and treatment time are as shown in Table 1 below. Formed as.
  • the molybdenum concentration was adjusted by adding an aqueous solution of sodium molybdate dissolved in pure water to the basic bath.
  • 3-Glycidoxypropylmethyldimethoxysilane (KBM-402 manufactured by Shin-Etsu Chemical Co., Ltd.): A 0.3 wt% solution was prepared with pure water.
  • 3-aminopropyltrimethoxysilane (KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.): A 0.25 wt% solution was prepared with pure water.
  • 3-Methacryloxypropylmethyldimethoxysilane (KBM-502 manufactured by Shin-Etsu Chemical Co., Ltd.): A 0.25 wt% solution was prepared with a solution adjusted to pH 3 by adding sulfuric acid to pure water.
  • 3-Isocyanatopropyltriethoxysilane (KBE-9007 manufactured by Shin-Etsu Chemical Co., Ltd.): A 0.2 wt% solution was prepared with a solution adjusted to pH 3 by adding sulfuric acid to pure water.
  • 3-Ureidopropyltriethoxysilane (KBE-585, manufactured by Shin-Etsu Chemical Co., Ltd.): A 0.3 wt% solution was prepared with a 1: 1 mixture of ethanol and pure water.
  • FIG. 1 is a SEM image of a cross section parallel to the thickness direction of the roughened surface (surface after silane coupling agent treatment) of the surface-treated copper foil produced in Comparative Example 6. Similarly, in the cross section of each copper foil, the top and bottom of the roughened particles can be confirmed within the field of view, and SEM observation is performed for five different fields of view at a magnification that includes about 10 roughened particles. did.
  • the height of the roughened particles having the highest height is measured, and the average of the five measured values (maximum values) obtained is the roughened surface of the copper foil.
  • the average height of roughened particles in A method for measuring the height of the roughened particles will be described in detail with reference to the drawings.
  • the rough particle to be measured has the longest shortest distance from the straight line connecting the left and right bottoms (the straight line connecting points a and b) of the rough particle to be measured.
  • the shortest distance between the top (point c) and the straight line connecting points a and b was defined as the height H of the roughened particles.
  • FIG. 2 is an SEM image of a cross section parallel to the thickness direction of the roughened surface (surface after silane coupling treatment) of the surface-treated copper foil produced in Example 2.
  • FIG. When the roughened particles are branched and formed in this way, the whole including the branched structure is regarded as one roughened particle. That is, the top of the roughened particles (point f) having the longest shortest distance from the straight line connecting the left and right bottoms of the roughened particles formed in a dendritic shape (straight line connecting points d and e) The shortest distance between the point d and the straight line connecting the points e was defined as the height H of the roughened particles. The results are shown in Table 3 below.
  • the BET surface area ratio A is calculated by dividing the surface area of the roughened surface (BET measurement surface area) measured by the BET method by the sample cut-out area that is the planar view area.
  • the BET measurement surface area was measured by a krypton gas adsorption BET multipoint method using a gas adsorption pore distribution measuring device ASAP2020 manufactured by Micromeritics. Prior to measurement, vacuum drying was performed at 150 ° C. for 6 hours as a pretreatment. A sample (copper foil) used for the measurement was cut into 3 dm 2 to be approximately 3 g, cut into 5 mm squares, and then introduced into the measuring apparatus.
  • the BET surface area ratio A was actually calculated by the following formula.
  • BET surface area ratio A [(BET measurement surface area) ⁇ (sample cutout area)] / (sample cutout area)
  • the surface area measurement of the BET method a surface other than the roughened surface and the surface that has not been roughened ( The surface area of the side surface is also measured, but at the foil thickness assumed by the present invention (for example, about 120 ⁇ m at the maximum), the ratio of the side surface to the total planar view area is very small and can be ignored in practice.
  • the BET measurement surface area may be smaller than the cut-out area due to the measurement principle of the BET method (that is, the BET surface area ratio A is less than 1). Sometimes).
  • the BET surface area ratio A is 1 It will be over.
  • the laser surface area ratio B was calculated based on the measured surface area using a laser microscope VK8500 (manufactured by Keyence Corporation). More particularly, the roughening treated surface of the sample (copper foil), and observed at a magnification 1000 times, to measure the three-dimensional surface area of the plan view area 6550Myuemu 2 portions, dividing the three-dimensional surface area 6550Myuemu 2 Thus, the laser surface area ratio B was determined. The measurement pitch was 0.01 ⁇ m. The results are shown in Table 3.
  • Fine surface coefficient Cms BET surface area ratio A / laser surface area ratio B
  • the amount of Si element ( ⁇ g / dm 2 ) on the roughened surface (that is, the amount of Si element contained in the silane coupling agent layer) is obtained after masking the surface of the sample that has not been subjected to roughening plating with a paint.
  • a mixed acid nitric acid 2: hydrochloric acid 1: pure water 5 (volume ratio)
  • the Si mass in the resulting solution was determined by Hitachi High-Tech Science Corporation. This was determined by quantitative analysis by atomic absorption spectrometry using an atomic absorption spectrophotometer (model: Z-2300). The results are shown in Table 3 below as the amount of Si element.
  • Lightness index L * is L * in JIS-Z8729 color system as defined in L * a * b *.
  • V-660 ultraviolet-visible spectrophotometer
  • the total light spectral reflectance of the roughened surface was measured at a wavelength between 870 and 200 nm. From the obtained spectrum, the lightness index L * value was calculated by the software attached to the measuring instrument and is shown in Table 3.
  • the roughened surface (surface treated with a silane coupling agent) of the surface-treated copper foil having a roughened surface produced in each of the above examples and comparative examples is a polyphenylene ether-based low dielectric constant manufactured by Panasonic Corporation.
  • a copper-clad laminate was prepared by pressing the resin base material MEGRON 6 (thickness 50 to 100 ⁇ m) for 2 hours under conditions of a surface pressure of 3 MPa and 200 ° C. Circuit processing was performed on the obtained laminated plate, and MEGRON 6 was further laminated thereon to finally form a three-layer copper-clad laminate.
  • the transmission line was a microstrip line having a width of 100 ⁇ m and a length of 40 mm.
  • a high frequency signal up to 100 GHz was transmitted to this transmission line using a network analyzer, and the transmission loss was measured.
  • the characteristic impedance was 50 ⁇ .
  • the measured value of transmission loss means that the smaller the absolute value, the smaller the transmission loss and the better the high frequency characteristics.
  • Table 4 lists the evaluation results of transmission loss at 20 GHz and 70 GHz. The evaluation criteria are as follows.
  • ⁇ 20 GHz transmission loss evaluation criteria> A: Transmission loss is -6.2 dB or more B: Transmission loss is less than -6.2 dB to -6.5 dB or more X: Transmission loss is less than -6.5 dB ⁇ 70 GHz transmission loss evaluation criteria> ⁇ : Transmission loss is ⁇ 20.6 dB or more ⁇ : Transmission loss is less than ⁇ 20.6 dB to ⁇ 24.0 dB or more X: Less than ⁇ 24.0 dB
  • Adhesion was evaluated by a peel test.
  • a copper-clad laminate was produced in the same manner as the copper-clad laminate produced in [Evaluation of high-frequency characteristics], and the copper foil part of the obtained copper-clad laminate was masked with a 10 mm width tape.
  • the copper-clad laminate was etched with copper chloride, and then the tape was removed to prepare a circuit wiring board having a width of 10 mm.
  • peel strength when peeling a 10 mm wide circuit wiring portion (copper foil portion) of this circuit wiring board from a resin base material at a speed of 50 mm / min in a 90 degree direction.
  • a copper-clad laminate was produced in the same manner as the copper-clad laminate produced in the above [Evaluation of visibility], and the copper foil part of the obtained copper-clad laminate was masked with a 10 mm width tape.
  • the copper-clad laminate was etched with copper chloride, and then the tape was removed to prepare a circuit wiring board having a width of 10 mm.
  • peel strength when peeling a 10 mm wide circuit wiring portion (copper foil portion) of this circuit wiring board from a resin base material at a speed of 50 mm / min in a 90 degree direction. It was measured.
  • Comparative Example 1 is an example in which the average height of the roughened particles present on the roughened surface of the surface-treated copper foil is smaller than that defined in the present invention.
  • Comparative Examples 2, 3 and 7 are examples in which both the BET surface area ratio and Cms of the roughened surface of the surface-treated copper foil are smaller than those defined in the present invention.
  • the adhesion between the copper foil and the resin base material was inferior.
  • Comparative Examples 4 and 5 are examples in which the average height of the roughened particles existing on the roughened surface of the surface-treated copper foil is larger than that defined in the present invention.
  • Comparative Example 6 is an example in which Cms is smaller than that defined in the present invention.
  • Reference Example 1 is an example in which the copper foil is not subjected to a roughening treatment, and further, neither a metal treatment layer is formed nor a silane coupling agent treatment is performed.
  • the copper clad laminated board was produced using the copper foil of the reference example 1, it became a result inferior to the adhesiveness of copper foil and a resin base material greatly.
  • the average height of the roughened particles formed on the roughened surface of the surface-treated copper foil is within the range defined by the present invention, and the BET surface area ratio and Cms of the roughened surface are also present.
  • the surface-treated copper foils of Examples 1 to 8 satisfying the requirements of the invention were excellent in adhesion between the copper foil and the resin base material when a copper-clad laminate was produced using this.
  • the conductor circuit formed from the copper clad laminate using the surface-treated copper foil of Examples 1 to 8 can effectively suppress transmission loss even when a high-frequency signal is transmitted.
  • the surface treatment of Examples 1 to 8 The resin base material on which the copper foil was laminated and adhered showed good visibility when the copper foil was removed by etching thereafter.

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  • Electrochemistry (AREA)
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PCT/JP2016/086281 2015-12-09 2016-12-06 プリント配線板用表面処理銅箔、プリント配線板用銅張積層板及びプリント配線板 WO2017099093A1 (ja)

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JP7251928B2 (ja) * 2018-06-05 2023-04-04 Ｊｘ金属株式会社 表面処理銅箔、銅張積層板及びプリント配線板
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