WO2011105318A1 - 印刷回路基板用銅箔及び印刷回路基板用銅張積層板 - Google Patents

印刷回路基板用銅箔及び印刷回路基板用銅張積層板 Download PDF

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WO2011105318A1
WO2011105318A1 PCT/JP2011/053646 JP2011053646W WO2011105318A1 WO 2011105318 A1 WO2011105318 A1 WO 2011105318A1 JP 2011053646 W JP2011053646 W JP 2011053646W WO 2011105318 A1 WO2011105318 A1 WO 2011105318A1
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Prior art keywords
copper
copper foil
mass
zinc
printed circuit
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PCT/JP2011/053646
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English (en)
French (fr)
Japanese (ja)
Inventor
晃正 森山
雅史 石井
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Jx日鉱日石金属株式会社
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Application filed by Jx日鉱日石金属株式会社 filed Critical Jx日鉱日石金属株式会社
Priority to KR1020127019538A priority Critical patent/KR101344176B1/ko
Priority to JP2012501763A priority patent/JP5254491B2/ja
Priority to CN201180010771.3A priority patent/CN102783255B/zh
Publication of WO2011105318A1 publication Critical patent/WO2011105318A1/ja

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    • 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
    • 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
    • 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

Definitions

  • the present invention relates to a copper foil for printed circuit boards and a copper clad laminate for printed circuit boards excellent in heat resistance and chemical resistance, in particular, a layer containing nickel, zinc and copper on at least an adhesive surface of the copper foil with a resin ( Hereinafter referred to as “copper nickel zinc layer”), a chromate film layer on the same layer, and a copper foil for a printed circuit board having a silane coupling agent layer if necessary, and the copper foil.
  • copper nickel zinc layer a layer containing nickel, zinc and copper on at least an adhesive surface of the copper foil with a resin
  • copper nickel zinc layer a resin
  • chromate film layer on the same layer
  • the present invention relates to the produced copper-clad laminate for printed circuit boards.
  • a semiconductor package substrate which is a kind of printed circuit board, is a printed circuit board used for mounting a semiconductor IC chip and other semiconductor elements. Since the circuit formed on the semiconductor package substrate is finer than a normal printed circuit board, a resin base material different from a general printed circuit board is used as the substrate material.
  • the semiconductor package substrate is usually manufactured by the following process. First, a copper foil is laminated and bonded to a base material such as a synthetic resin under high temperature and high pressure. This is called a copper clad laminate or simply a laminate. Next, in order to form a target conductive circuit on the laminate, a pattern equivalent to the circuit is printed on the copper foil with a material such as an etching resistant resin. Then, unnecessary portions of the exposed copper foil are removed by an etching process.
  • the printed part is removed and a conductive circuit is formed on the substrate.
  • a predetermined element is finally soldered to the formed conductive circuit to form various printed circuit boards for electronic devices. Finally, it is joined to a resist or a build-up resin substrate.
  • quality requirements for copper foil for printed circuit boards differ between an adhesive surface (so-called roughened surface) to be bonded to a resin base material and a non-adhesive surface (so-called glossy surface) and satisfy both at the same time. is necessary.
  • the requirements for the glossy surface are: (1) good appearance and no oxidation discoloration during storage, (2) good solder wettability, (3) no oxidation discoloration when heated at high temperature, (4 ) Good adhesion to the resist is required.
  • the roughened surface mainly (1) no oxidation discoloration during storage, (2) the peel strength from the base material is high temperature heating, wet treatment, soldering, chemical treatment, etc. It is sufficient that (3) there is no so-called lamination stain that occurs after lamination with the substrate and etching. In recent years, with the miniaturization of circuit print patterns, it has been required to reduce the roughness of the copper foil surface.
  • the frequency of electrical signals has been increased with the increase in communication speed and capacity, and printed circuit boards and copper foils that can cope with this have been demanded.
  • the frequency of the electric signal is 1 GHz or more
  • the influence of the skin effect in which the current flows only on the surface of the conductor becomes significant, and the influence that the current transmission path changes due to the unevenness of the surface and the impedance increases cannot be ignored.
  • the surface roughness of the copper foil is small.
  • many surface treatment methods have been proposed for printed circuit board copper foils.
  • an example of the surface treatment method for the electrolytic copper foil includes the method described below. That is, first, in order to increase the adhesive strength (peel strength) between copper and the resin base material, in general, after applying fine particles of copper and copper oxide to the surface of the copper foil (roughening treatment), brass is imparted to have heat resistance characteristics. Alternatively, a heat-resistant layer (barrier layer) such as zinc is formed. Finally, in order to prevent surface oxidation or the like during transportation or storage, the product is subjected to rust prevention treatment such as immersion or electrolysis chromate treatment or electrolytic zinc chromate treatment.
  • the surface treatment method for forming the heat-resistant layer is particularly important as determining the surface properties of the copper foil. For this reason, many copper foils in which a coating layer such as Zn, Cu—Ni alloy, Cu—Co alloy and Cu—Zn alloy is formed as a metal or alloy for forming a heat-resistant layer have been put into practical use (for example, patents) Reference 1).
  • the copper foil formed with a heat-resistant layer made of Cu—Zn alloy (brass) has no stain on the resin layer when used for a printed circuit board made of epoxy resin, etc. Since the copper foil has excellent properties such as little deterioration of peel strength of the copper foil after being held in, it is widely used industrially.
  • the method for forming the heat-resistant layer made of brass is described in detail in Patent Document 2.
  • This circuit erosion phenomenon is a phenomenon in which the adhesive boundary layer between the copper foil circuit and the resin base material is eroded by the mixed solution of sulfuric acid and hydrogen peroxide, and the peel strength of the copper foil in that portion is significantly deteriorated. Say. If this phenomenon occurs on the entire surface of the circuit pattern, the circuit pattern is peeled off from the substrate, which becomes a serious problem.
  • a nickel-zinc-copper layer in which nickel is added to brass is effective as a surface treatment layer excellent in preventing the circuit erosion phenomenon.
  • the circuit erosion phenomenon can be prevented by adding nickel, depending on the amount of nickel added, the heat resistance (heat-resistant peel strength) may be reduced, or a foot residue may be generated during circuit formation.
  • the inventors have found that they may be inferior to the surface layer comprising.
  • the object of the present invention is to obtain various characteristics of a surface layer made of a Cu—Zn alloy (brass) (normal peel strength of a copper foil of a printed circuit board produced by laminating a copper foil and a resin base material, Copper foil suitable for a semiconductor package substrate in which the above circuit erosion phenomenon is reduced without deteriorating the peel strength (hereinafter referred to as heat-resistant peel strength) and chemical resistance (hydrochloric acid) after being held for a predetermined time at Is to develop.
  • heat-resistant peel strength heat-resistant peel strength
  • chemical resistance hydrochloric acid
  • the present inventors diligently studied the conditions for performing surface treatment on copper foil. As a result, the following heat resistance and chemical resistance of copper foil were improved, that is, sulfuric acid-hydrogen peroxide etching. It was found that this was effective for erosion resistance (circuit erosion resistance) of the roughened surface during soft etching of the glossy surface of the copper foil.
  • the present invention is 1) A copper foil for a printed circuit board provided with a layer containing nickel, zinc and copper (hereinafter referred to as “copper nickel zinc layer”) on the surface of the copper foil, wherein the copper nickel zinc layer per unit area zinc deposition weight 200 [mu] g / dm 2 or more and 2000 [mu] g / dm 2 or less, the copper nickel zinc layer, Ni is from 1 to 50% by weight, (zinc deposition amount (mass%)) / ⁇ 100- (copper deposition amount (Mass%)) ⁇ is 0.3 or more, and (copper adhesion amount (mass%)) / ⁇ 100- (zinc adhesion quantity (mass%)) ⁇ is 0.3 or more.
  • copper foil For copper foil.
  • the present invention also provides: 2) The copper foil for a printed circuit board according to 1 above, wherein a chromate film layer is provided on the copper nickel zinc layer. 3) In the chromate film layer, the chromium adhesion weight is 30 ⁇ g / dm 2 per unit area.
  • the printed circuit board copper foil according to 3 above which is 100 ⁇ g / dm 2 or less as described above 4) A silane coupling agent layer is further provided on the chromate film layer.
  • the copper foil for printed circuit boards according to any one of 1 to 5 above 6) The copper foil for a printed circuit board according to any one of 1 to 5 above, wherein the copper foil is a rolled copper foil. 7) The printed circuit board according to any one of 1 to 7 above.
  • the copper foil for a printed circuit board uses a copper nickel zinc layer so as not to deteriorate the peel strength of the copper foil after the printed circuit board is held at a high temperature.
  • the heat-resistant peel strength of the copper foil can be dramatically improved.
  • this can effectively prevent the circuit erosion phenomenon due to chemicals, and in particular has been given a new property of improving the sulfuric acid-hydrogen peroxide resistance, and copper foil for printed circuit boards (especially, This is extremely effective as a copper clad laminate for a semiconductor package substrate) and a copper clad laminate produced by bonding a copper foil and a resin base material (particularly, a copper clad laminate for a semiconductor package substrate).
  • it can be used as a general copper foil for a printed circuit board.
  • the copper foil of the present invention either an electrolytic copper foil or a rolled copper foil can be used.
  • an electrolytic copper foil it can be applied to a rough surface during electrolytic plating or a glossy surface of the electrolytic copper foil. Further, these surfaces may be further subjected to a roughening treatment.
  • a roughening treatment is performed on the surface of the copper foil after degreasing, for example, “fist-knot” -shaped electrodeposition of copper Is an electrolytic copper foil that can be used as it is.
  • one side is a glossy surface and the opposite side is a rough surface.
  • the electrolytic copper foil has a rough surface and a glossy surface, but in the case of a rough surface, it can be used as it is.
  • the glossy surface of the electrolytic copper foil can be roughened by applying a roughening treatment to further increase the peel strength.
  • a roughening treatment is similarly applied to the rolled copper foil.
  • any known roughening treatment can be used in any case, and there is no particular limitation.
  • the roughened surface of the present invention means an electrolytic copper foil having a rough surface at the time of electrolytic plating or an electrolytic copper foil and a rolled copper foil subjected to a roughening treatment, and can be applied to any copper foil.
  • the copper foil for a semiconductor package substrate of the present invention is composed of a copper nickel zinc layer, a chromate film layer, and a silane coupling agent layer as required, which are formed on the surface of the copper foil to be an adhesive surface with the resin.
  • the copper foil the above rolled copper foil or electrolytic copper foil can be used.
  • the chromate film layer an electrolytic chromate film layer or an immersion chromate film layer can be used.
  • the present invention forms a layer containing nickel, zinc and copper (hereinafter referred to as “copper nickel zinc layer”) on the surface of a copper foil, for example.
  • the zinc adhesion amount per unit area of the copper foil in the copper nickel zinc layer needs to be 200 ⁇ g / dm 2 or more. This is because, regardless of the composition of the copper nickel zinc layer, if the zinc adhesion weight is less than 200 ⁇ g / dm 2 , there is no effect of layer formation and the deterioration of the peel strength after high-temperature heating becomes large.
  • zinc adhesion weight exceeds 2000 ⁇ g / dm 2 , the erosion of the circuit edge by the sulfuric acid-hydrogen peroxide etching solution becomes significant. Therefore zinc coating weight per unit area of the copper foil in the copper-nickel zinc layer is 200 [mu] g / dm 2 or more 2000 [mu] g / dm 2 or less is preferable.
  • the inventors have an important balance of the composition of each metal in the copper nickel zinc layer.
  • the copper nickel zinc layer By forming the copper nickel zinc layer in the region X shown in the composition region of the Cu—Ni—Zn ternary alloy in FIG. They found that they were excellent in peel strength and chemical resistance (hydrochloric acid resistance, sulfuric acid-hydrogen peroxide resistance) after high-temperature heating. The details will be described below.
  • the nickel ratio in the copper nickel zinc layer should be 1% or more. If it is less than 1%, the circuit erosion phenomenon cannot be effectively prevented. However, it is preferable that the nickel ratio in the copper nickel zinc layer exceeds 50% because the balance of zinc and copper in the copper nickel zinc layer described later is lost, the heat-resistant peel strength is lowered, and the foot residue during circuit formation frequently occurs. Absent. Therefore, the nickel ratio in the copper nickel zinc layer is preferably 1% or more and 50% or less.
  • the ratio of the adhesion amount of zinc and copper in the copper nickel zinc layer affects the heat-resistant peel strength or the chemical resistance (hydrochloric acid). Specifically, it is necessary to satisfy the following formula. That is, (Zinc adhesion amount (% by mass)) / ⁇ 100- (Copper adhesion amount (% by mass)) ⁇ (Formula 1) is 0.3 or more, (Copper adhesion amount (% by mass)) / ⁇ 100- (Zinc Adhesion amount (mass%)) ⁇ (Formula 2) must be 0.3 or more (region X in FIG. 1). In order to facilitate understanding, (Expression 1) and (Expression 2) are added to the above expressions, respectively.
  • the ratio of zinc and copper adhesion in the copper nickel zinc layer (zinc adhesion (mass%)) / ⁇ 100- (copper adhesion (mass%)) ⁇ is 0.3 or more, It is preferable that (copper adhesion amount (mass%)) / ⁇ 100- (zinc adhesion quantity (mass%)) ⁇ (Formula 2) satisfies both formulas of 0.3 or more (region X in FIG. 1).
  • the copper nickel zinc layer is usually formed under the following conditions. However, zinc deposition weight per unit area of the copper nickel zinc layer, 200 [mu] g / dm 2 or more and 2000 [mu] g / dm 2 or less, the copper nickel zinc layer, Ni is 1-50 wt%, (zinc deposition amount ( Mass%)) / ⁇ 100- (copper adhesion amount (mass%)) ⁇ (Formula 1) is 0.3 or more, (copper adhesion amount (mass%)) / ⁇ 100- (zinc adhesion amount (mass%)) ⁇ (Equation 2) is not particularly limited as long as the electroplating conditions can achieve 0.3 or more, and other electroplating conditions can also be used.
  • Ni 0.1 g / L to 30 g / L
  • Zn 0.1 g / L to 12 g / L
  • Cu 0.1 g / L to 2 g / L
  • other inorganic acids or organic carboxylic acids citric acid, malic acid, etc.
  • Current density 3-25 A / dm 2
  • any of an electrolytic chromate treatment, an immersion chromate treatment, and a zinc chromate treatment containing zinc in a chromate bath can be applied to produce the chromate film layer.
  • the chromium adhesion weight is less than 30 ⁇ g / dm 2 , the effect of increasing acid resistance and heat resistance is small, so the chromium adhesion weight is 30 ⁇ g / dm 2 or more.
  • the chromium adhesion weight exceeds 100 ⁇ g / dm 2 , the effect of chromate treatment is saturated and the chromium adhesion weight does not increase any more.
  • the chromium adhesion weight per unit area in the chromate treatment layer is desirably 30 to 100 ⁇ g / dm 2 .
  • silane coupling agent used for the copper foil for printed circuit boards of this invention it is desirable to contain 1 or more types of alkoxysilane provided with the functional group which has the reactivity of at least tetraalkoxysilane and resin, for example. .
  • this silane coupling agent is arbitrary, the selection considering the adhesiveness with the resin is desirable.
  • the present invention provides a copper clad produced by laminating a printed circuit board copper foil according to any one of 1) to 7) above and a printed circuit board copper foil according to 8) and a resin base material. Provide a laminate.
  • silane coupling agent treatment (after application and drying) was performed on the rust preventive layer.
  • the conditions for the silane coupling agent treatment are as follows. An aqueous solution containing 0.5% by volume of epoxysilane was applied after adjusting to pH 7 and then dried.
  • FR-4 resin glass cloth base epoxy resin
  • BT resin triazine-bismaleimide resin, trade name: GHPL-830 manufactured by Mitsubishi Gas Chemical
  • the BT resin is a material having high heat resistance and being used for a printed circuit board for a semiconductor package.
  • the copper foil circuit on the laminate was immersed in an etching solution containing 5 to 20% by volume of sulfuric acid and 1 to 10% by volume of hydrogen peroxide, and the thickness of the copper foil circuit was etched by 2 ⁇ m.
  • the relative deterioration rate (loss%) from the peel strength and its normal peel strength is measured.
  • the measurement of the peel strength in this case can be said to be in a harsh environment, and is a harsher condition than the chemical resistance evaluation generally performed when the FR-4 substrate is used. Accordingly, if the BT substrate has good sulfuric acid-hydrogen peroxide resistance, the FR-4 substrate also has sufficient chemical resistance (particularly sulfuric acid-hydrogen peroxide resistance).
  • a laminate is prepared by laminating with a FR-4 resin base material such that the surface of the copper foil on which the copper nickel zinc layer is formed is exposed. Next, measure the adhesion weight of zinc per unit area by dissolving the copper nickel zinc layer exposed on the laminate surface and the copper of its mother layer with hydrochloric acid or nitric acid and conducting chemical analysis of the zinc concentration in the solution. did.
  • the abundance ratio of nickel, zinc and copper contained in the copper nickel zinc layer was measured.
  • the measurement is performed intermittently from the outermost surface to the copper layer which is the base of the copper nickel zinc layer while etching the copper foil thickness by argon ion sputtering, and the abundance ratio of nickel, zinc and copper obtained at each depth was integrated with the depth from the outermost surface, and the average abundance ratio of nickel, zinc and copper in the entire copper nickel zinc layer was calculated.
  • the instrument used for the measurement was AXIS-HS manufactured by KRATOS, and the output of argon ion sputtering was 52.5W. Under this condition, the copper foil thickness is etched by about 20 mm per minute. The sputtering time was 15 to 100 minutes.
  • Example 1 Using an electrolytic copper foil having a thickness of 12 ⁇ m, a copper nickel zinc layer was formed by electroplating on the roughened surface (surface average roughness: 3.8 ⁇ m) of this copper foil under the conditions shown below. Table 1 shows the abundance ratios of nickel, zinc, and copper.
  • chromate treatment was performed on the copper nickel zinc layer to form a rust preventive layer.
  • the processing conditions are shown below. CrO 3 : 4.0 g / L, ZnSO 4 ⁇ 7H 2 O: 2.0 g / L, Na 2 SO 4 : 15 g / L, pH: 4.2, temperature: 45 ° C, current density 3.0A / dm 2 , time: 1.5 seconds
  • Example 1 the adhesion amount of zinc (Zn) in the plating film was 924 ⁇ g / dm 2 , and in the plating film, Ni: 9 mass%, Zn: 42 mass%, Cu: 49 mass%, and the formula 1 ( Zinc adhesion (mass%)) / ⁇ 100- (copper adhesion (mass%)) ⁇ is 0.83, Formula 2 (copper adhesion (mass%)) / ⁇ 100- (zinc adhesion (mass%)) ) ⁇ was 0.85, and both were within the range of the conditions of the present invention.
  • Example 1 the peel strength of the normal BT substrate in the FR substrate was 1.47 kN / m, the peel strength after aging for 2 days was 1.20 kN / m, and the deterioration rate was 18%.
  • the normal peel strength on a normal BT substrate (in a harsh environment) is 1.05 kN / m
  • the peel strength after hydrochloric acid treatment is 0.85 kN / m
  • the deterioration rate is 20%
  • sulfuric acid-hydrogen peroxide resistance The peel strength was 0.98 kN / m and the deterioration rate was 7%, both of which were good results.
  • Table 1 The results are shown in Table 1.
  • Example 2 In Example 2, the zinc (Zn) adhesion amount in the plating film was 320 ⁇ g / dm 2 , and in the plating film, Ni: 31 mass%, Zn: 34 mass%, Cu: 36 mass%, and the formula 1 ( Zinc adhesion (mass%)) / ⁇ 100- (copper adhesion (mass%)) ⁇ is 0.52, Formula 2 (copper adhesion (mass%)) / ⁇ 100- (zinc adhesion (mass%) ) ⁇ was 0.54, both of which were within the range of the present invention.
  • Example 2 the peel strength of the normal BT substrate in the FR substrate was 1.56 kN / m, the peel strength after aging for 2 days was 1.42 kN / m, and the deterioration rate was 9%.
  • the normal peel strength on a normal BT substrate (in a harsh environment) is 0.99 kN / m
  • the peel strength after hydrochloric acid treatment is 0.89 kN / m
  • the deterioration rate is 10%
  • sulfuric acid-hydrogen peroxide resistance The peel strength was 0.86 kN / m and the deterioration rate was 14%, both of which were good results.
  • Table 1 The above results are similarly shown in Table 1.
  • Example 3 In Example 3, the zinc (Zn) adhesion amount in the plating film was 465 ⁇ g / dm 2 , and in the plating film, Ni: 18 mass%, Zn: 12 mass%, Cu: 70 mass%, and the formula 1 ( Zinc adhesion (mass%)) / ⁇ 100- (copper adhesion (mass%)) ⁇ is 0.39, Formula 2 (copper adhesion (mass%)) / ⁇ 100- (zinc adhesion (mass%) ) ⁇ was 0.79, both of which were within the range of the present invention.
  • Example 3 the peel strength of the normal BT substrate in the FR substrate was 1.55 kN / m, the peel strength after aging for 2 days was 1.53 kN / m, and the deterioration rate was 2%.
  • the normal peel strength on a normal BT substrate (in a harsh environment) is 0.99 kN / m
  • the peel strength after hydrochloric acid treatment is 0.93 kN / m
  • the deterioration rate is 6%
  • sulfuric acid-hydrogen peroxide resistance The peel strength was 0.88 kN / m and the deterioration rate was 11%, both of which were good results.
  • Table 1 The above results are similarly shown in Table 1.
  • Example 4 the adhesion amount of zinc (Zn) in the plating film was 390 ⁇ g / dm 2 , and in the plating film, Ni: 2 mass%, Zn: 93 mass%, Cu: 5 mass%, and Formula 1 ( Zinc adhesion (mass%)) / ⁇ 100- (copper adhesion (mass%)) ⁇ is 0.98, Formula 2 (copper adhesion (mass%)) / ⁇ 100- (zinc adhesion (mass%) ) ⁇ Was 0.77, both of which were within the range of the present invention.
  • Example 4 the peel strength of the normal BT substrate in the FR substrate was 1.46 kN / m, the peel strength after aging for 2 days was 1.28 kN / m, and the deterioration rate was 12%.
  • the normal peel strength on a normal BT substrate (in a harsh environment) is 1.01 kN / m
  • the peel strength after hydrochloric acid treatment is 0.86 kN / m
  • the deterioration rate is 15%
  • sulfuric acid-hydrogen peroxide resistance The peel strength was 0.92 kN / m and the deterioration rate was 9%, both of which were good results.
  • Table 1 The above results are similarly shown in Table 1.
  • Example 5 In Example 5, the zinc (Zn) adhesion amount in the plating film was 378 ⁇ g / dm 2 , and in the plating film, Ni: 40 mass%, Zn: 36 mass%, Cu: 24 mass%, and the formula 1 ( Zinc adhesion (mass%)) / ⁇ 100- (copper adhesion (mass%)) ⁇ is 0.47, Formula 2 (copper adhesion (mass%)) / ⁇ 100- (zinc adhesion (mass%)) ) ⁇ Was 0.37, both of which were within the range of the present invention.
  • Example 5 the peel strength of the normal BT substrate in the FR substrate was 1.48 kN / m, the peel strength after aging for 2 days was 1.43 kN / m, and the deterioration rate was 3%. Further, the normal peel strength on a normal BT substrate (harsh environment) is 1.04 kN / m, the peel strength after hydrochloric acid treatment is 0.91 kN / m, the deterioration rate is 13%, and the sulfuric acid-hydrogen peroxide resistant The peel strength was 0.93 kN / m and the deterioration rate was 11%, both of which were good results. The results are shown in Table 1.
  • Example 6 In Example 6, the zinc (Zn) adhesion amount in the plating film was 617 ⁇ g / dm 2 , and in the plating film, Ni: 18 mass%, Zn: 12 mass%, Cu: 70 mass%, and the formula 1 ( Zinc adhesion (mass%)) / ⁇ 100- (copper adhesion (mass%)) ⁇ is 0.39, Formula 2 (copper adhesion (mass%)) / ⁇ 100- (zinc adhesion (mass%) ) ⁇ was 0.79, both of which were within the range of the present invention.
  • Example 6 the peel strength of the normal BT substrate in the FR substrate was 1.45 kN / m, the peel strength after aging for 2 days was 1.42 kN / m, and the deterioration rate was 2%.
  • the normal peel strength on a normal BT substrate (in a harsh environment) is 1.10 kN / m
  • the peel strength after hydrochloric acid treatment is 0.87 kN / m
  • the deterioration rate is 21%
  • sulfuric acid-hydrogen peroxide resistance The peel strength was 0.98 kN / m and the deterioration rate was 11%, both of which were good results.
  • Table 1 The above results are similarly shown in Table 1.
  • Example 7 In Example 7, the zinc (Zn) adhesion amount in the plating film was 1860 ⁇ g / dm 2 , and in the plating film, Ni: 7 mass%, Zn: 9 mass%, Cu: 84 mass%, and the formula 1 ( Zinc adhesion (mass%)) / ⁇ 100- (copper adhesion (mass%)) ⁇ is 0.56, Formula 2 (copper adhesion (mass%)) / ⁇ 100- (zinc adhesion (mass%)) ) ⁇ Was 0.92, and both were within the range of the conditions of the present invention.
  • Example 7 the peel strength of the normal BT substrate in the FR substrate was 1.48 kN / m, the peel strength after aging for 2 days was 1.40 kN / m, and the deterioration rate was 5%.
  • the normal peel strength on a normal BT substrate (in a harsh environment) is 1.02 kN / m
  • the peel strength after hydrochloric acid treatment is 0.98 kN / m
  • the deterioration rate is 4%
  • Table 1 The above results are similarly shown in Table 1.
  • Example 8 In Example 8, the zinc (Zn) adhesion amount in the plating film was 746 ⁇ g / dm 2 , and in the plating film, Ni: 47 mass%, Zn: 30 mass%, Cu: 23 mass%, and the formula 1 ( Zinc adhesion (mass%)) / ⁇ 100- (copper adhesion (mass%)) ⁇ is 0.39, Formula 2 (copper adhesion (mass%)) / ⁇ 100- (zinc adhesion (mass%) ) ⁇ was 0.33, both of which were within the range of the present invention.
  • the peel strength of the normal BT substrate in the FR substrate was 1.47 kN / m
  • the peel strength after aging for 2 days was 1.46 kN / m
  • the deterioration rate was 1%.
  • the normal peel strength on a normal BT substrate (in a harsh environment) is 1.03 kN / m
  • the peel strength after hydrochloric acid treatment is 0.95 kN / m
  • the deterioration rate is 8%
  • sulfuric acid-hydrogen peroxide resistance was 0.95 kN / m and the deterioration rate was 0%, both of which were good results.
  • the results are shown in Table 1.
  • Example 9 the zinc (Zn) adhesion amount in the plating film was 220 ⁇ g / dm 2 , and in the plating film, Ni: 20 mass%, Zn: 69 mass%, Cu: 11 mass%, and the formula 1 ( Zinc adhesion (mass%)) / ⁇ 100- (copper adhesion (mass%)) ⁇ is 0.78, Formula 2 (copper adhesion (mass%)) / ⁇ 100- (zinc adhesion (mass%)) ) ⁇ Was 0.35, and both were within the range of the conditions of the present invention.
  • Example 9 the peel strength of the normal BT substrate in the FR substrate was 1.45 kN / m, the peel strength after aging for 2 days was 1.42 kN / m, and the deterioration rate was 2%. Further, the normal peel strength on a normal BT substrate (harsh environment) is 1.06 kN / m, the peel strength after hydrochloric acid treatment is 0.92 kN / m, the deterioration rate is 13%, and sulfuric acid-hydrogen peroxide resistance The peel strength was 0.98 kN / m and the deterioration rate was 11%, both of which were good results. The above results are similarly shown in Table 1.
  • the plating layers of Examples adhesion weight of zinc per unit area 220 ⁇ g / dm 2 ⁇ 1860 ⁇ g / dm 2 , and the normal peel strength at FR-4 substrate is 1.45kN / m ⁇ 1.56kN / M
  • heat peel strength was 1.20 kN / m to 1.53 kN / m
  • the deterioration rate was in the range of 18% or less
  • the normal peel strength on the BT substrate was in the range of 0.99 kN / m to 1.10 kN / m.
  • the peel strength after treatment with hydrochloric acid / sulfuric acid / hydrogen peroxide solution is 0.85 kN / m to 0.93 kN / m and 0.86 kN / m to 0.98 kN / m, respectively, and the deterioration rate is 4% to 21%, respectively. 0% to 14%, showing good properties.
  • Comparative Example 1 In Comparative Example 1, copper does not exist in the plating film, and the abundance ratio of nickel in the plating film exceeds 50% by mass, thus deviating from the present invention. Further, formula 1 (zinc adhesion amount (mass%)) / ⁇ 100- (copper adhesion quantity (mass%)) ⁇ is 0.49, but formula 2 (copper adhesion quantity (mass%)) / ⁇ 100- (Zinc adhesion amount (mass%)) ⁇ is 0.00, which is not within the range of the present invention. In Comparative Example 1, the peel strength of the normal BT substrate of the FR substrate was 1.50 kN / m, the peel strength after aging for 2.
  • Comparative Example 2 In Comparative Example 2, zinc does not exist in the plating film, and the abundance ratio of nickel in the plating film exceeds 50% by mass, thus deviating from the present invention. Further, formula 2 (copper adhesion amount (mass%)) / ⁇ 100- (zinc adhesion quantity (mass%)) ⁇ is 0.45, but formula 1 (zinc adhesion quantity (mass%)) / ⁇ 100- (Copper adhesion amount (mass%)) ⁇ is 0.00, which is not within the range of the present invention. In Comparative Example 2, the peel strength of the normal BT substrate in the FR substrate was 1.51 kN / m, the peel strength after aging for 2 days was 1.06 kN / m, and the degradation rate was 30%. The heat peel strength of the steel was greatly reduced. The above results are similarly shown in Table 2.
  • Comparative Example 3 In Comparative Example 3, the adhesion amount of zinc (Zn) in the plating film is 620 ⁇ g / dm 2 , but nickel does not exist in the plating film and deviates from the present invention.
  • Formula 1 Zinc adhesion amount (% by mass)) / ⁇ 100- (Copper adhesion amount (% by mass)) ⁇ is 1.00
  • Formula 2 Copper adhesion amount (% by mass)) / ⁇ 100- (Zinc adhesion amount ( Mass%)) ⁇ is 1.00.
  • Comparative Example 4 In Comparative Example 4, the adhesion amount of zinc per unit area is 2564 ⁇ g / dm 2 , which is a departure from the present invention.
  • the normal peel strength on a normal BT substrate in a harsh environment was 1.02 kN / m, but the peel strength after hydrochloric acid treatment was 0.20 kN / m and the deterioration rate was 80%. Further, the peel strength with sulfuric acid-hydrogen peroxide was 0.62 kN / m, the deterioration rate was 39%, and the chemical resistance was greatly reduced in all cases. The above results are similarly shown in Table 2.
  • Comparative Example 5 In Comparative Example 5, the amount of copper present in the plating film was as high as 80% by mass, zinc was 4% by mass, and nickel was 16% by mass. (Zinc adhesion amount (% by mass)) / ⁇ 100- (copper adhesion amount ( Mass%)) ⁇ is 0.2, which is out of the scope of the present invention.
  • the normal peel strength on the FR-4 substrate was 1.12 kN / m, but the peel strength after hydrochloric acid treatment was 1.12 kN / m, the degradation rate was 25%, and FR-4 The heat-resistant peel strength on the substrate was greatly reduced. The above results are similarly shown in Table 2.
  • Comparative Example 6 In Comparative Example 6, since the zinc present in the plating film is as large as 70% by mass and the copper is as small as 6% by mass, (copper adhesion amount (mass%)) / ⁇ 100- (zinc adhesion amount (mass%) ⁇ is In Comparative Example 6, the normal peel strength on the BT substrate was 1.04 kN / m, but the peel strength after hydrochloric acid treatment was 0.16 kN / m. The deterioration rate was as high as 85%, and the chemical resistance (hydrochloric acid) was greatly reduced.
  • Comparative Example 7 In Comparative Example 7, the adhesion amount of zinc per unit area is as small as 150 ⁇ g / dm 2, which deviates from the present invention. In Comparative Example 7, the peel strength after aging for 2 days on the FR-4 substrate was 1.01 kN / m, the deterioration rate was as large as 31%, and the heat resistance was greatly reduced. The above results are similarly shown in Table 2.
  • Comparative Example 8 In Comparative Example 8, the abundance ratio of nickel in the plating film exceeds 50% by mass, and (Zinc adhesion amount (% by mass)) / ⁇ 100- (Copper adhesion amount (% by mass)) ⁇ is 0.27. It deviates from the scope of the present invention. In Comparative Example 8, the peel strength after aging for 2 days on the FR-4 substrate was 1.10 kN / m, the deterioration rate increased to 23%, and the heat-resistant peel strength on the FR-4 substrate was greatly reduced. The above results are similarly shown in Table 2.
  • the copper adhesion amount (% by mass)) / ⁇ 100- (Zinc adhesion amount (% by mass)) is 0.28, which is out of the scope of the present invention.
  • the normal peel strength on the substrate was 1.01 kN / m, but the peel strength after hydrochloric acid treatment was 0.71 kN / m, the deterioration rate was as high as 30%, and the chemical resistance (hydrochloric acid) was greatly reduced.
  • the above results are similarly shown in Table 2.
  • the plating bath conditions for producing the copper nickel zinc layer of the present invention are as follows: Ni: 0.1 g / L to 30 g / L, Zn: 0.1 g / L to 12 g / L, Cu: 0.00.
  • the basic bath is preferably 1 g / L to 2 g / L and sulfuric acid (H 2 SO 4 ): 0.1 g / L to 10 g / L.
  • the case of applying to the roughened surface of the electrolytic copper foil has been described, but it goes without saying that the same applies to the electrolytic copper foil in which the roughened surface is roughened.
  • the absolute value of normal peel strength may differ depending on the shape of the roughening treatment and the surface roughness, but the heat-resistant peel strength and sulfuric acid -The relative deterioration rate from the normal peel of the peel strength after the hydrogen peroxide treatment can be reduced.
  • the copper foil for printed circuit boards it is a central subject of the invention to select the optimum conditions for the copper nickel zinc layer.
  • the heat-resistant peel strength of the copper foil is drastically improved, the circuit erosion phenomenon is effectively prevented, and the sulfuric acid / hydrogen peroxide resistance is constantly and stably exerted. Therefore, it should be easily understood that the selection of the electrolytic copper foil and the rolled copper foil or the selection of the roughened surface can be arbitrarily selected according to the purpose.
  • the copper foil for printed circuit boards of the present invention uses a copper nickel zinc layer so as not to deteriorate the peel strength with the resin after high-temperature heating, and the heat-resistant peel strength of the copper foil is reduced. It can be improved dramatically. In addition, this has provided new properties that can effectively prevent the circuit erosion phenomenon and can stably and effectively exert chemical resistance (sulfuric acid-hydrogen peroxide system resistance) in recent years.
  • printed circuit board copper foil especially copper foil for semiconductor package board
  • printed circuit board especially semiconductor package board

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Laminated Bodies (AREA)
  • Parts Printed On Printed Circuit Boards (AREA)
  • Manufacturing Of Printed Wiring (AREA)
  • Electroplating Methods And Accessories (AREA)
PCT/JP2011/053646 2010-02-24 2011-02-21 印刷回路基板用銅箔及び印刷回路基板用銅張積層板 WO2011105318A1 (ja)

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JP2012501763A JP5254491B2 (ja) 2010-02-24 2011-02-21 印刷回路基板用銅箔及び印刷回路基板用銅張積層板
CN201180010771.3A CN102783255B (zh) 2010-02-24 2011-02-21 印刷电路基板用铜箔及印刷电路基板用覆铜层压板

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CN111971420A (zh) * 2018-04-27 2020-11-20 Ｊｘ金属株式会社 表面处理铜箔、覆铜积层板及印刷配线板
US20210267052A1 (en) * 2018-07-18 2021-08-26 Showa Denko Materials Co., Ltd. Copper-clad laminate, printed wiring board, semiconductor package and method for producing copper-clad laminate

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JP5497808B2 (ja) * 2012-01-18 2014-05-21 Ｊｘ日鉱日石金属株式会社 表面処理銅箔及びそれを用いた銅張積層板
CN104755220B (zh) * 2013-10-18 2016-11-16 三菱电机株式会社 加工工作台用工装件、加工工作台用工装件的制造方法及激光加工方法

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CN111971420B (zh) * 2018-04-27 2023-12-22 Ｊｘ金属株式会社 表面处理铜箔、覆铜积层板及印刷配线板
US20210267052A1 (en) * 2018-07-18 2021-08-26 Showa Denko Materials Co., Ltd. Copper-clad laminate, printed wiring board, semiconductor package and method for producing copper-clad laminate

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KR20120115339A (ko) 2012-10-17
TW201137183A (en) 2011-11-01
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