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WO2009084533A1 - Feuille de cuivre avec résine et processus de production d'une feuille de cuivre avec résine - Google Patents

Feuille de cuivre avec résine et processus de production d'une feuille de cuivre avec résine Download PDF

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Publication number
WO2009084533A1
WO2009084533A1 PCT/JP2008/073412 JP2008073412W WO2009084533A1 WO 2009084533 A1 WO2009084533 A1 WO 2009084533A1 JP 2008073412 W JP2008073412 W JP 2008073412W WO 2009084533 A1 WO2009084533 A1 WO 2009084533A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin
copper foil
resin layer
cured resin
cured
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2008/073412
Other languages
English (en)
Japanese (ja)
Inventor
Tetsuro Sato
Toshifumi Matsushima
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsui Kinzoku Co Ltd
Original Assignee
Mitsui Mining and Smelting Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2008325025A external-priority patent/JP5636159B2/ja
Application filed by Mitsui Mining and Smelting Co Ltd filed Critical Mitsui Mining and Smelting Co Ltd
Priority to KR1020107014604A priority Critical patent/KR101357230B1/ko
Priority to CN2008801233016A priority patent/CN101909878A/zh
Publication of WO2009084533A1 publication Critical patent/WO2009084533A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • 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
    • H05K3/4655—Adding a circuit layer by laminating a metal foil or a preformed metal foil pattern by using a laminate characterized by the insulating layer
    • 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
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/0154—Polyimide
    • 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
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0183—Dielectric layers
    • H05K2201/0195—Dielectric or adhesive layers comprising a plurality of layers, e.g. in a multilayer structure
    • 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
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/06—Thermal details
    • H05K2201/068—Thermal details wherein the coefficient of thermal expansion is important
    • 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
    • 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

Definitions

  • the present invention relates to a resin-coated copper foil used as a printed wiring board material and a method for producing the resin-coated copper foil.
  • the resin-attached copper foil is obtained by laminating and arranging a resin layer as an insulating layer on a copper foil as a conductor.
  • a multilayer printed wiring board manufactured by a build-up method (hereinafter simply referred to as “build-up printed wiring board”). Have been used for various purposes such as manufacturing field.
  • build-up printed wiring board a multilayer printed wiring board manufactured by a build-up method
  • a via hole is formed by drilling an insulating layer formed of a resin layer of a resin-coated copper foil laminated to an inner core material by laser processing or the like.
  • the outer layer copper foil is subjected to pattern etching to form an outer layer circuit.
  • the copper foil with resin is further laminated
  • the build-up printed wiring board is manufactured by repeating the same outer layer circuit formation.
  • Patent Document 1 discloses a product that improves the dimensional stability of printed wiring board products by adding an inorganic filler such as silica to the resin layer to lower the thermal expansion coefficient. ing.
  • an inorganic filler such as silica
  • Patent Document 1 in addition, in order to reduce the thermal expansion coefficient, a resin having a high glass transition temperature such as a bismaleimide resin or a cyanoester resin is frequently used.
  • JP 2005-322682 A Japanese Patent Laid-Open No. 11-10794
  • the peel strength comparable to that when using a roughened copper foil is used.
  • the copper for copper clad laminates is provided with two or more adhesive layers on a non-roughened copper foil for the purpose of providing a copper foil for copper clad laminate excellent in circuit formation in which copper particles do not remain in the resin after etching treatment There is a foil.
  • the non-roughened copper foil provided with two or more adhesive layers that can be grasped from the contents disclosed in Patent Document 2 lacks the adhesive stability between the non-roughened copper foil and the resin layer, and has solder heat resistance and thermal shock. The characteristics such as the property are not at a level that can cope with the fine pitch of recent circuits, and the thermal expansion performance equivalent to the resin-coated copper foil disclosed in Patent Document 1 cannot be obtained. It was not possible to improve the dimensional stability.
  • the resin-coated copper foil according to the present invention includes a resin layer having a low coefficient of thermal expansion, and is excellent in dimensional stability when processed into a printed wiring board.
  • the resin-coated copper foil according to the present invention described below is excellent in adhesion stability with a resin layer even when a low-roughness non-roughened copper foil is used, and is suitable as a high-density printed wiring board material. Become.
  • an outline of the present invention will be described.
  • the resin-coated copper foil according to the present invention is a resin-coated copper foil in which a cured resin layer and a semi-cured resin layer are sequentially formed on the surface of the copper foil, and the copper on the side in contact with the cured resin layer
  • the surface roughness (Rzjis) of the foil is 0.5 ⁇ m to 2.5 ⁇ m
  • the cured resin layer is made of any one of polyimide resin, polyamideimide resin, and these composite resins 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. is provided on the cured resin layer.
  • the resin-coated copper foil according to the present invention has a thermal expansion coefficient of 40 ppm / ° C. or less of the entire resin layer after the cured resin layer and the semi-cured resin layer formed on the surface of the copper foil are cured. .
  • the cured resin layer has a glass transition temperature of 300 ° C. or higher.
  • the semi-cured resin layer is formed using a maleimide resin.
  • the maleimide resin is an aromatic maleimide resin having two or more maleimide groups in the molecule.
  • the maleimide resin is a polymerization adduct obtained by polymerizing an aromatic maleimide resin having two or more maleimide groups in the molecule and an aromatic polyamine.
  • the semi-cured resin layer contains 20 to 70 parts by weight of a maleimide resin when the semi-cured resin layer is 100 parts by weight. .
  • the cured resin layer has a thickness of 3 ⁇ m to 30 ⁇ m.
  • the semi-cured resin layer has a thickness of 7 ⁇ m to 55 ⁇ m.
  • the total thickness of the cured resin layer and the semi-cured resin layer is more preferably 10 ⁇ m to 60 ⁇ m.
  • the resin-coated copper foil according to the present invention it is more preferable to use a non-roughened copper foil as the copper foil.
  • Manufacturing method of resin-coated copper foil A method of manufacturing the above-described resin-coated copper foil, which is characterized by passing through the following step A and step B.
  • Step A On the surface of a copper foil having a surface roughness (Rzjis) of 0.5 ⁇ m to 2.5 ⁇ m, any one of polyimide resin, polyamideimide resin, and composite resin having a thermal expansion coefficient of 0 ppm / ° C. to 25 ppm / ° C.
  • a cured resin layer is formed using the resin component.
  • Step B A resin-coated copper foil is obtained by providing a semi-cured resin layer having a thermal expansion coefficient of 0 ppm / ° C. to 50 ppm / ° C. after curing on the cured resin layer.
  • the thermal expansion coefficient is 0 ppm / ° C. on the surface of the copper foil having a surface roughness (Rzjis) of 0.5 ⁇ m to 2.5 ⁇ m.
  • a casting method or a laminating method is used.
  • step B when the amount of the resin composition containing a maleimide resin used for forming the semi-cured resin layer is 100 parts by weight, A resin composition containing 20 to 70 parts by weight of a maleimide resin is used.
  • a surface modification step for plasma treatment or corona treatment of the surface of the cured resin layer is provided between the step A and the step B.
  • the resin-coated copper foil according to the present invention includes a resin layer having excellent adhesion between the metal foil and the resin layer, the copper foil (circuit) after being processed into a printed wiring board and the cured resin layer Excellent adhesion stability.
  • the build-up printed wiring board using the resin-coated copper foil according to the present invention has a small thermal expansion coefficient of the resin layer after the resin-coated copper foil is cured, so that the thermal history during processing to the printed wiring board On the other hand, good dimensional stability can be maintained.
  • the resin-coated copper foil according to the present invention provides good adhesion between the copper foil and the resin layer without roughening the surface of the copper foil on the resin layer side, and the printed wiring board. Even after being processed, the adhesive strength is excellent between the copper foil constituting the resin-coated copper foil and the cured resin layer.
  • the resin-coated copper foil according to the present invention is composed of a cured resin layer and a semi-cured resin layer, even if the copper foil alone is of a thickness that cannot be handled, a hard cured resin layer is present. By being present, it is possible to effectively prevent the occurrence of damage such as wrinkles or creases in the copper foil during handling, and the handleability is excellent. Further, the resin-coated copper foil according to the present invention can be used as a non-roughened copper foil, and is therefore suitable for forming a fine pitch circuit.
  • the resin-coated copper foil according to the present invention has a low coefficient of thermal expansion after the resin layer is cured, the positional accuracy between the interlayer circuits of the build-up printed wiring board is improved, and the circuit height is easily increased. Densification becomes possible.
  • the method for producing a resin-coated copper foil according to the present invention does not require special special equipment when laminating a copper foil, a cured resin layer, and a semi-cured resin layer, without making a new capital investment, It is possible to manufacture excellent copper foil with resin.
  • the resin-attached copper foil according to the present invention is a resin-attached copper foil formed in a state in which a cured resin layer and a semi-cured resin layer are sequentially laminated on the surface of the copper foil.
  • the copper foil with resin according to the present invention is a copper foil having a surface roughness (Rzjis) on the side in contact with the cured resin layer of 0.5 ⁇ m to 2.5 ⁇ m, a very low roughness copper foil or a non-roughened copper foil.
  • Rzjis surface roughness
  • the resin-coated copper foil according to the present invention can use a copper foil having a surface roughness of 0.5 ⁇ m to 2.0 ⁇ m on the side in contact with the cured resin layer, and has recently been demanded. It is possible to cope with the low profile. Conventionally, in order to improve the adhesion between the resin layer and the copper foil, the surface of the copper foil is roughened.
  • the resin-attached copper foil according to the present invention has good adhesion between the copper foil and the resin layer without subjecting the copper foil to a roughening treatment. That is, in the resin-coated copper foil according to the present invention, the cured resin layer is laminated on the copper foil surface, but even if the surface of the copper foil on the side where the cured resin layer is laminated is low roughness, Excellent adhesion to the cured resin layer. In particular, when a non-roughened copper foil is used as the copper foil constituting the resin-coated copper foil according to the present invention, not only the manufacturing cost as the copper foil can be reduced, but also the low profile as the copper foil can be achieved.
  • the thickness of the copper foil is not particularly limited, but when an electrolytic copper foil is used, the thickness is preferably 7 ⁇ m to 18 ⁇ m. Moreover, when using copper foil of 5 micrometers or less, it is preferable to use copper foil with a carrier.
  • the “cured resin layer” is a layer composed of a resin that does not reflow by heating.
  • the cured resin layer is preferably composed of a resin having a coefficient of thermal expansion after curing of 0 ppm / ° C. to 25 ppm / ° C.
  • the thermal expansion coefficient of the cured resin layer exceeds 25 ppm / ° C.
  • significant thermal expansion occurs in the cured resin layer, resulting in heat that is higher than that of the cured resin layer.
  • Adhesion at the interface with the copper foil with small expansion is reduced, and it becomes impossible to prevent circuit peeling due to thermal history of the printed wiring board manufacturing process or expansion / contraction behavior due to thermal shock, and dimensional accuracy of the resulting build-up printed wiring board Is difficult to obtain.
  • the lower the thermal expansion coefficient of the cured resin layer the better the dimensional accuracy of the build-up printed wiring board using the resin-coated copper foil, so the lower limit value of the thermal expansion coefficient is 0 ppm / ° C.
  • the coefficient of thermal expansion of the cured resin layer is 0 ppm / ° C. or more depending on the selection and combination of the acid component, amine component, and isocyanate component, which are raw materials for the polyimide resin and polyamideimide resin, and the molecular weight during the addition reaction. It can be adjusted to 25 ppm / ° C.
  • the thermal expansion coefficient is more preferably 20 ppm / ° C. or less.
  • the resin component can be used for the resin-coated copper foil of the present invention as long as it has such a thermal expansion coefficient and exhibits sufficient insulation in electrical and electronic material applications.
  • a resin component of any one of a polyimide resin, a polyamideimide resin, and a composite resin thereof are preferable to use. These resins have extremely good electrical insulation performance, mechanical strength, and flexibility performance, and are suitable for electronic material applications. Therefore, since this cured resin layer functions as a support layer for the copper foil, even if the used copper foil layer is thin and lacks handling properties, good handling performance can be obtained when viewed as a resin-coated copper foil.
  • the cured resin layer has a required amount of maleimide resin, epoxy resin, polyethersulfone resin, cyanoester when the thermal expansion coefficient is included in the above range and appropriate fluidity adjustment is required. A resin or the like may be added.
  • the polyimide resin adds two carboxylic dianhydrides in the molecule such as pyromellitic anhydride and a polyamine compound having two amino groups in the molecule such as 4,4′-diaminodiphenylmethane. After the reaction, it is obtained by causing dehydration and ring closure by heating.
  • the polyamideimide resin is obtained by reacting a compound having both a carboxyl group and a carboxylic acid anhydride in the molecule, such as trimellitic anhydride, and an isocyanate compound such as methylene diisocyanate.
  • the composite resin of the polyimide resin and the polyamideimide resin is a polyimide-modified polyamideimide resin in which a part of the acid component of the polyamideimide resin is replaced with a substance having two carboxylic dianhydrides in the molecule. Say something.
  • the cured resin layer having a glass transition temperature of 300 ° C. or higher improves the heat resistance characteristics required for various printed wiring boards such as solder heat resistance, thermal shock resistance, and high temperature durability. It is preferable from the viewpoint.
  • the glass transition temperature of this cured resin layer is less than 300 ° C., the process of manufacturing a resin-coated copper foil, the thermal shock due to solder reflow applied in the process of manufacturing a build-up printed wiring board, the high temperature heating by pressing, etc.
  • a peeling phenomenon at the interface between the “copper foil or circuit” and the “cured resin layer” occurs at a temperature, which increases the risk of delamination and circuit peeling.
  • the preferred thickness of the cured resin layer described above is 3 ⁇ m to 30 ⁇ m.
  • the thickness of the cured resin layer is less than 3 ⁇ m, it is not preferable because the effect of improving the dimensional stability of the multilayer printed wiring board manufactured by the build-up method cannot be obtained sufficiently.
  • the thickness of the cured resin layer exceeds 30 ⁇ m, in the process of forming the cured resin layer on the copper foil, a deformation called curl is strongly generated by heating when the resin composition is applied and dried.
  • the handling property as a resin-added copper foil is lowered, and automatic layup using an automatic piling apparatus cannot be performed, which is not preferable.
  • the thickness of the cured resin layer is more preferably 5 ⁇ m to 30 ⁇ m.
  • the “thickness” is a calculated thickness of a resin film obtained by applying a certain amount of resin on the assumption that the surface of the copper foil is a perfect plane.
  • the cured resin layer using the polyimide resin or polyamideimide resin described above has excellent adhesion with non-roughened copper foil and is generally used as a resin layer for resin-coated copper foil. Compared to resin-based resin compositions, it exhibits a significantly lower coefficient of thermal expansion. However, since such a cured resin layer has high heat resistance and does not reflow, an attempt is made to embed the resin in the gap between the circuits of the inner layer circuit on the surface of the inner layer core material by press molding of the build-up method. However, it is in a cured state in which it is difficult to embed resin in the gap between circuits. Therefore, in the present invention, a semi-cured resin layer is further laminated on the cured resin layer so that the resin in the gap between the circuits of the inner layer circuit can be embedded.
  • This semi-cured resin layer is a resin layer provided on the cured resin layer, and is formed of a thermosetting resin that reflows by heating and causes a curing reaction.
  • the semi-cured resin layer preferably has a coefficient of thermal expansion after curing of 0 ppm / ° C. to 50 ppm / ° C. By setting the thermal expansion coefficient after curing in such a range, the difference from the thermal expansion coefficient of the cured resin layer is suppressed, and delamination or the like occurs due to the difference in shrinkage behavior with respect to the heat received by the entire cured resin layer. Can be prevented.
  • a more preferable range of the coefficient of thermal expansion after curing of the semi-cured resin layer is 0 ppm / ° C. to 30 ppm / ° C.
  • cures shall be 40 ppm / degrees C or less.
  • Such a semi-cured resin layer is preferably formed using a maleimide resin.
  • the maleimide resin exhibits high fluidity before curing, but has excellent heat resistance and low thermal expansion coefficient after curing. In addition, the thermal expansion coefficient of the maleimide resin is lower than that of the epoxy resin.
  • this maleimide resin exhibits a property of being hard and brittle once cured, it has low adhesion to a metal foil such as a copper foil, and even if used in combination with a non-roughened copper foil, it is practical. Adhesive strength cannot be obtained. Therefore, a semi-cured resin layer formed of a maleimide resin can be used for forming a resin layer of a resin-coated copper foil for the first time in combination with the above-described cured resin layer.
  • the maleimide resin referred to here is preferably an aromatic maleimide resin having two or more maleimide groups in the molecule.
  • the above aromatic maleimide resin may be used as it is, but it is used as a polymerization adduct obtained by polymerizing an aromatic maleimide resin having two or more maleimide groups in the molecule and an aromatic polyamine. May be.
  • the aromatic polyamine also acts as a curing agent for the epoxy resin, the addition of the aromatic polyamine is useful as a means for cross-linking both when the maleimide resin and the epoxy resin are used in combination.
  • the semi-cured resin layer preferably contains 20 to 70 parts by weight of maleimide resin when the formed semi-cured resin layer is 100 parts by weight.
  • blending maleimide-type resin with content of this range it becomes possible to make compatible the effect
  • the content of the maleimide resin is less than 20 parts by weight, the effect of lowering the thermal expansion coefficient of the cured semi-cured resin layer cannot be obtained, which is not preferable.
  • the semi-cured resin layer becomes a brittle resin layer when cured, and the resin layer is likely to crack, and the reliability as an insulating layer of the printed wiring board is increased. Since it falls, it is not preferable.
  • the preferred thickness of the semi-cured resin layer mentioned here is 7 ⁇ m to 55 ⁇ m.
  • the thickness of the semi-cured resin layer is less than 7 ⁇ m, it is difficult to embed the resin in the inter-circuit gap even if the resin is embedded in the inter-circuit gap of the inner layer circuit on the surface of the inner layer core material.
  • the thickness of the semi-cured resin exceeds 55 ⁇ m, the variation in the thickness of the resin layer of the resin-coated copper foil cured during the press processing by the build-up method increases, and the thickness in the plane of the printed wiring board increases. This is not preferable because it promotes variation.
  • the thickness of the semi-cured resin layer is more preferably 15 ⁇ m to 55 ⁇ m.
  • the total thickness of the cured resin layer and the semi-cured resin layer is preferably 10 ⁇ m to 60 ⁇ m.
  • the total thickness of the resin layers of the resin-attached copper foil is less than 10 ⁇ m, the thickness of the above-described cured resin layer is increased, and the thickness of the semi-cured resin layer is decreased from an appropriate range. As a result, it becomes difficult to embed the inner layer circuit, and the resin-attached copper foil is not suitable for practical use.
  • via holes having a diameter of about 50 ⁇ m have been formed by laser processing.
  • the total thickness of the cured resin layer and the semi-cured resin layer of the resin-coated copper foil according to the present invention exceeds 60 ⁇ m, the hole shape by laser processing can be improved, It becomes difficult to make the inner peripheral wall surface of the hole smooth. As a result, there is a problem in the interlayer conductive plating process after forming the via hole, which is not preferable.
  • the total thickness of the cured resin layer and the semi-cured resin layer is more preferably 20 ⁇ m to 60 ⁇ m.
  • the resin-coated copper foil according to the present invention includes a semi-cured resin layer that enables bonding to the inner core material, and further includes a cured resin layer to suppress thermal expansion and is suitable for a build-up method. It is.
  • the resin layer of the resin-coated copper foil is composed of the cured resin layer and the semi-cured resin layer, at the interface between the cured resin layer and the semi-cured resin layer, from the viewpoint of the resin composition,
  • the resin composition is compatible, and adhesion at the interface between the two resin layers is ensured, and a change in dimensions due to thermal history and thermal shock received in the processing process after lamination can be suppressed.
  • the resin-coated copper foil according to the present invention can be used not only as a printed wiring board but also as a capacitor circuit forming material having a cured resin layer as a dielectric layer.
  • a resin-coated copper foil according to the present invention by laminating a resin-coated copper foil according to the present invention on a copper circuit pattern and hot pressing, the resin-coated copper foil is pushed so that the semi-cured resin layer is located between the copper circuit patterns, and the cured resin layer is By striking the copper circuit pattern, the cured resin layer can be a dielectric layer.
  • Step A Any of polyimide resin, polyamideimide resin, and these composite resins having a thermal expansion coefficient of 0 ppm / ° C. to 25 ppm / ° C. on the surface of a copper foil having a surface roughness (Rzjis) of 0.5 ⁇ m to 2.5 ⁇ m
  • a cured resin layer is formed using the resin component.
  • copper foil will be described.
  • the copper foil is described as a concept including all copper foils manufactured by a rolling method and an electrolytic method. However, in consideration of product cost, it is preferable to use electrolytic copper foil.
  • the rust prevention treatment layer is formed to prevent the surface of the electrolytic copper foil from being oxidatively corroded so as not to hinder the manufacturing process of the copper clad laminate and the printed wiring board.
  • the method used for the rust prevention treatment may be any of organic rust prevention using benzotriazole, imidazole or the like, or inorganic rust prevention using zinc, chromate, zinc alloy or the like. Techniques such as electrolytic copper foil showering and electrodeposition can be employed.
  • a rust-preventing element is deposited on the surface of the electrolytic copper foil by electrolysis or other so-called substitution deposition methods.
  • a zinc pyrophosphate plating bath, a zinc cyanide plating bath, a zinc sulfate plating bath, or the like can be used for the zinc rust prevention treatment.
  • the concentration is 5 g / l to 30 g / l zinc, 50 g / l to 500 g / l potassium pyrophosphate
  • the liquid temperature is 20 ° C. to 50 ° C.
  • the pH is 9 to 12
  • the current density is 0.3 A. / Dm 2 to 10 A / dm 2 .
  • the type of rust prevention treatment is not limited as described above, but when the electrolytic copper foil used in the present invention is used without performing a roughening treatment, the resin film and the copper foil surface are wetted.
  • a nickel-zinc alloy constituting the rust-preventing layer having a composition containing 50 wt% to 99 wt% nickel and 50 wt% to 1 wt% zinc, excluding inevitable impurities.
  • the anti-corrosion treatment layer formed of this nickel-zinc alloy cannot be expected to improve the adhesion to various substrates.
  • nickel content exceeds 99 wt%, the tendency to remain after etching becomes strong, which is not preferable.
  • the total adhesion amount of nickel and zinc is in the range of 20 mg / m 2 to 100 mg / m 2 . It is desirable to make it.
  • this anticorrosive layer when it adheres to a special substrate where adhesion strength is difficult to ensure, the electrolytic copper foil does not easily peel off from the adhesive interface, and chemical resistance characteristics It is excellent in moisture resistance or solder heat resistance. If the total adhesion amount is less than 20 mg / m 2 , a rust preventive treatment layer having a uniform thickness cannot be obtained, and the variation in adhesion strength increases. On the other hand, if the total adhesion amount exceeds 100 mg / m 2 , there is a tendency that an etching residue of a nickel component is generated during etching for forming a conductor circuit, which is not preferable.
  • the one with more nickel tends to improve the adhesion strength, chemical resistance, moisture resistance and solder heat resistance, and the tendency to decrease chemical resistance and solder heat resistance when the amount of zinc increases. is doing.
  • the anticorrosive layer is composed of a nickel-zinc alloy layer and a chromate layer.
  • the presence of the chromate layer tends to improve the corrosion resistance and at the same time improve the adhesion to the resin layer.
  • a substitution method or an electrolysis method may be employed according to a conventional method.
  • the silane coupling agent treatment is a treatment for chemically improving the adhesion with the insulating layer constituent material after the roughening treatment, the rust prevention treatment and the like are completed.
  • the silane coupling agent used for the silane coupling agent treatment is not particularly limited. In consideration of the properties of the insulating layer constituent material used, the plating solution used in the printed wiring board manufacturing process, etc.
  • a silane coupling agent, an amino silane coupling agent, a mercapto silane coupling agent and the like can be arbitrarily selected and used.
  • vinyl trimethoxy silane, vinyl phenyl trimethoxy silane, ⁇ -methacryloxypropyl trimethoxy silane, ⁇ -glycol are mainly used for the same coupling agent as used for prepreg glass cloth for printed wiring boards.
  • a method for forming a cured resin layer on the surface of the copper foil will be described.
  • a method of depositing copper on the cured resin layer by an electroless method and growing it by an electrolytic method to obtain a laminated state, laminating a resin film on the surface of the copper foil Any known technique such as a method of pressing and pasting, a coating method in which a resin varnish is applied to the surface of a copper foil and then dried by heating is applicable.
  • a casting method or a laminating method it is preferable to use a casting method or a laminating method.
  • the polyimide precursor varnish is applied to the surface of the metal foil, the imidization reaction is caused by heating, and the process of curing to form a polyimide resin is repeated several times.
  • a resin varnish obtained by dissolving a reaction product of an acid component of trimellitic anhydride and an isocyanate such as methylene diisocyanate in an organic solvent such as N-methylpyrrolidone is used. It forms by apply
  • This casting method has an advantage that it is easy to form a polyimide resin layer or a polyamideimide resin layer having a desired thickness.
  • a polyimide film, a polyamideimide film or the like may be laminated by a laminating method after applying an adhesive.
  • the copper foil with an adhesive layer which the present applicant has already proposed in Japanese Patent No. 3949676 is adopted, and a commercially available polyimide film or the like is used for the adhesive layer (ultra-thin primer resin layer) of the copper foil with an adhesive layer.
  • Step B In this step, a resin-coated copper foil is obtained by providing a semi-cured resin layer having a thermal expansion coefficient of 0 ppm / ° C. to 50 ppm / ° C. after curing on the cured resin layer.
  • the semi-cured resin layer is formed using a resin composition containing 20 to 70 parts by weight of a maleimide resin when the amount of the resin composition containing a maleimide resin is 100 parts by weight.
  • the content of the maleimide resin in the resin composition is defined as a range showing preferable characteristics as a semi-cured resin layer of the resin-coated copper foil.
  • the resin composition for forming the semi-cured resin layer will be described.
  • the resin composition used here contains a maleimide resin, an epoxy resin, and a linear polymer having a crosslinkable functional group as essential components.
  • the maleimide resin may be a polymerization adduct obtained by polymerizing an aromatic maleimide resin and an aromatic polyamine.
  • maleimide resins examples include 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, 1,3-bis (3-maleimidophenoxy) Benzene, 1,3-bis (4-maleimidophenoxy) benzene and the like can be used.
  • the content of the maleimide resin is less than 20 parts by weight, the effect of lowering the thermal expansion coefficient of the cured semi-cured resin layer cannot be obtained, which is not preferable.
  • the content of the maleimide resin exceeds 70 parts by weight, the semi-cured resin layer becomes a brittle resin layer when cured, and the resin layer is likely to crack, and the reliability as an insulating layer of the printed wiring board is increased. Since it falls, it is not preferable.
  • the epoxy resin used here is a so-called bisphenol-based epoxy resin. And it is preferable to mix and use 1 type, or 2 or more types chosen from the group of bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol AD type epoxy resin.
  • the bisphenol-based epoxy resin is selectively used as a liquid epoxy resin at 25 ° C.
  • the liquid epoxy resin When the liquid epoxy is highly pure, if it is supercooled, the crystallized state is maintained even when the liquid epoxy is returned to room temperature, and the appearance may be solid. In this case, since it can be used after returning to a liquid state, it is included in the liquid epoxy resin referred to herein. Furthermore, the temperature of 25 ° C. is specified here in order to clarify the meaning of around room temperature.
  • the epoxy equivalent exceeds 200, it becomes semi-solid or solid at 25 ° C., so it is difficult to prepare a resin composition, and it becomes impossible to contribute to suppression of curling phenomenon when a resin-coated copper foil is produced. It is not preferable.
  • the epoxy equivalent said here is the gram number (g / eq) of resin containing 1 gram equivalent of epoxy groups.
  • it is the above-mentioned bisphenol-type epoxy resin, it may be used individually by 1 type, or 2 or more types may be mixed and used for it. In addition, when two or more kinds are mixed and used, there is no particular limitation with respect to the mixing ratio.
  • This bisphenol-based epoxy resin is used in a blending ratio of 3 to 20 parts by weight when the resin composition is 100 parts by weight.
  • the epoxy resin is less than 3 parts by weight, the cured resin layer becomes brittle and easily cracks.
  • the amount exceeds 20 parts by weight, the resin surface becomes sticky at 25 ° C., so that the handling property is lacking.
  • 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 linear polymer having a crosslinkable functional group is used in a blending ratio of 3 to 30 parts by weight when the resin composition is 100 parts by weight. When the epoxy resin is less than 3 parts by weight, the resin flow becomes large.
  • aromatic polyamine examples include 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'-diaminodiphenyl sulfone, bis (4-aminophenyl) Phenylamine, m-xylenediamine, p- Phenylenediamine, 4,4'-diaminodicyclohexylmethane, 1,4-diamino
  • epoxy resin curing agent When an epoxy resin curing agent is required, amines such as dicyandiamide, imidazoles and aromatic amines, phenols such as bisphenol A and brominated bisphenol A, novolacs such as phenol novolac resin and cresol novolac resin Acid anhydrides such as phthalic anhydride are used. Since the addition amount of the epoxy resin curing agent with respect to the epoxy resin at this time is naturally derived from the respective equivalents, no special addition amount limitation is performed.
  • amines such as dicyandiamide, imidazoles and aromatic amines
  • phenols such as bisphenol A and brominated bisphenol A
  • novolacs such as phenol novolac resin and cresol novolac resin
  • Acid anhydrides such as phthalic anhydride
  • the resin composition composed of the resin components described above is preferably a resin varnish using an organic solvent having a boiling point of 50 ° C. to 200 ° C.
  • the solvent is greatly diffused by heating, and it is difficult to obtain a good semi-cured state when the resin varnish is changed to a semi-cured resin.
  • the boiling point exceeds 200 ° C., the solvent tends to remain in a semi-cured state. That is, the normally required volatilization rate is not satisfied, and industrial productivity is not satisfied.
  • organic solvent mentioned here include one single solvent or two or more selected from the group of methanol, ethanol, methyl ethyl ketone, toluene, propylene glycol monomethyl ether, dimethylformamide, dimethylacetamide, cyclohexanone, ethyl cellosolve, and the like. It is a mixed solvent.
  • the resin varnish is applied onto a cured resin layer of copper foil and dried to form a semi-cured resin layer.
  • the coating method and drying method at this time There are no particular limitations on the coating method and drying method at this time.
  • a surface modification step of the cured resin layer between the step A and the step B by plasma treatment or corona treatment as an additional step.
  • the surface modification step the surface of the cured resin layer is modified and adhesion with the semi-cured resin is improved. That is, the cured resin layer and the semi-cured resin layer are formed of different resin compositions, and one of the resin layers is already cured, so the adhesion between the two resin layers may be reduced, Even in such a case, the adhesion between the cured resin layer and the semi-cured resin layer is improved by performing plasma treatment or corona treatment on the surface of the cured resin layer.
  • the plasma treatment referred to here is a treatment performed by bringing a plasma air flow generated by applying a generally used high voltage into contact with the surface of the hard resin layer.
  • a copper foil provided with a cured resin layer is disposed between electrodes, and a high-frequency, high voltage is applied to perform corona discharge to perform surface modification of the hard resin layer. Any known method can be applied to the plasma treatment or the corona treatment.
  • Example 1 shows an example of a resin-coated copper foil in which a polyimide resin layer is formed as a cured resin layer on the surface of an electrolytic copper foil and a maleimide resin is used to form a semi-cured resin layer.
  • the nickel-zinc alloy plating was performed under the conditions of a pyrophosphoric acid bath (nickel 2.5 g / l, zinc 0.5 g / l, liquid temperature 40 ° C., current density 0.6 A / dm 2 , 8 seconds).
  • the electrolytic chromate treatment was performed using chromic acid having a concentration of 1.0 g / l, pH 12, liquid temperature 30 ° C., current density 1.8 A / dm 2 , and electrolysis time 8 seconds.
  • the silane coupling agent treatment uses a solution in which ⁇ -aminopropyltrimethoxysilane is added to a concentration of 5.0 g / l using ion-exchanged water as a solvent, and this solution is prevented by showering. Adsorption treatment was performed by spraying on the surface of the rust treatment layer, and a silane coupling agent layer was formed on the rust prevention treatment layer.
  • the foil temperature is adjusted to 140 ° C. with an electric heater to be dried by passing through an oven with the atmosphere temperature adjusted and heated for 4 seconds to condense the silane coupling agent.
  • the reaction was promoted to obtain a finished electrolytic copper foil.
  • a cured resin layer was formed by a casting method using the obtained polyamic acid varnish.
  • a polyamic acid varnish was applied to the glossy surface of the above-mentioned electrolytic copper foil with a multi coater (manufactured by Hirano Techseed Co., Ltd .: M-400) and dried in a hot air dryer under conditions of 110 ° C. ⁇ 6 minutes.
  • the resin thickness of the cured resin layer after drying was 35 ⁇ m, and the solvent remaining rate at this stage was 32 wt% with respect to the total amount of the resin layer.
  • the composite of electrolytic copper foil coated with this polyamic acid varnish was placed in a hot air oven substituted with nitrogen, heated from room temperature to 400 ° C.
  • a material was used.
  • the solvent residual ratio of the copper-clad polyimide resin base material obtained by this final heat treatment was 0.5 wt% with respect to the total amount of the resin adhered to the electrolytic copper foil.
  • the copper foil (copper-clad polyimide resin base material) on which the cured resin layer was laminated was subjected to corona treatment to modify the surface of the cured resin layer.
  • the corona treatment was performed in air under the conditions of power 210 W, speed 2 m / min, discharge amount 300 W ⁇ min / m 2 , and irradiation distance 1.5 mm from the electrode.
  • the electrolytic copper foil is removed by etching from the copper foil (corona-treated copper-clad polyimide resin base material) on which the cured resin layer after the surface modification treatment is laminated. did.
  • the resin thickness of the cured resin layer (polyimide film) obtained by removing the electrolytic copper foil was 27 ⁇ m, and the thermal expansion coefficient was 25 ppm / ° C.
  • a semi-cured resin layer is formed on the cured resin layer of the corona-treated copper-clad polyimide resin substrate.
  • the following resin composition was dissolved using N, N′-dimethylacetamide as a solvent to prepare a resin varnish having a resin solid content of 30 wt%.
  • the above-mentioned resin varnish is applied to the polyimide resin surface of a corona-treated copper-clad polyimide resin substrate, air-dried at room temperature for 5 minutes, and heat-dried at 160 ° C. for 5 minutes to form a semi-cured resin layer. Laminated and formed. The resin thickness of the semi-cured resin layer at this time was 20 ⁇ m.
  • the above-mentioned resin varnish used for formation of a semi-hardened resin layer is apply
  • the thermal expansion coefficient of the test cured resin layer was 45 ppm / ° C.
  • the thickness of the entire resin layer of the resin-attached copper foil obtained as described above was 47 ⁇ m. Then, the copper foil is etched away from the resin-coated copper foil by a method described later, and this is subjected to curing heating at 200 ° C. ⁇ 2 hours using a resin layer composed of a cured resin layer and a semi-cured resin layer. The thermal expansion coefficient of the entire resin layer after the semi-cured resin layer was cured was measured. As a result, the thermal expansion coefficient was 35 ppm / ° C. Further, the peel strength was 1.0 kgf / cm.
  • Example 2 is different in thickness from the cured resin layer of Example 1. That is, in the formation of the cured resin layer of Example 1, the resin thickness after drying at 110 ° C. ⁇ 6 minutes was set to 35 ⁇ m, whereas in Example 2, the resin after drying at 110 ° C. ⁇ 6 minutes was used. The thickness was 8 ⁇ m. Others produced the resin-coated copper foil by the same method as in Example 1. In the cured resin layer of Example 2, the resin thickness after drying at 400 ° C. for 8 minutes was 5 ⁇ m, and the residual solvent ratio was 0.1 wt%. The thermal expansion coefficient of the entire resin layer after completely curing the semi-cured resin was 38 ppm / ° C., and the peel strength of the copper foil was 0.95 kgf / cm.
  • Example 3 differs from Example 1 in the configuration of the cured resin layer. That is, in the formation of the cured resin layer, the resin used was Viromax HR16NN (trade name, manufactured by Toyobo Co., Ltd.), and the thickness of the cured resin layer after drying at 110 ° C. for 6 minutes was 28 ⁇ m. The maximum temperature was 380 ° C. Otherwise, a resin-coated copper foil was prepared in the same manner as in Example 1. At this time, the thickness of the cured resin layer after drying at 380 ° C. ⁇ 8 minutes was 24 ⁇ m, the residual solvent rate was 0.8 wt%, and the thermal expansion coefficient of the cured resin layer was 23 ppm / ° C. Further, the thermal expansion coefficient of the entire resin layer of the resin-coated copper foil after completely curing the semi-cured resin was 34 ppm / ° C., and the peel strength of the copper foil was 0.80 kgf / cm.
  • the resin used was Viromax HR16NN (trade name, manufactured
  • Example 4 produced a resin-coated copper foil in the same manner as in Example 1 except that the resin used was changed to the following composition in forming the semi-cured resin layer.
  • Maleimide resin Bisphenol A diphenyl ether bismaleimide (Brand name: BMI-4000, manufactured by Daiwa Kasei Kogyo Co., Ltd.) / 25 parts by weight
  • Epoxy resin Cresol novolac type epoxy resin (Brand name: Epototo YDCN-703, manufactured by Toto Kasei Co., Ltd.) / 25 wt
  • Linear polymer having partially crosslinkable functional group polyvinyl acetal resin (trade name: Denkabutyral 5000A, manufactured by Denki Kagaku Kogyo Co., Ltd.) / 10 parts by weight
  • epoxy resin curing agent cyanate ester resin (trade name: Primaset PT-30, Lonza Ltd) / 40 parts by weight
  • the resin composition was dissolved using dimethylacetamide as a solvent to prepare a resin solid content of 40 wt%. Then, further, as an curing catalyst, an imidazole compound (trade name: Curesol 2P4MHZ, manufactured by Shikoku Kasei Kogyo Co., Ltd.) / 0.5 part by weight and acetylacetone zinc (reagent 0.01 part by weight) are added, and the resin varnish is added. Obtained.
  • This resin varnish was applied, dried and cured in the same manner as in Example 1 to form a semi-cured resin layer. The resin thickness of the semi-cured resin layer at this time was 20 ⁇ m.
  • the thermal expansion coefficient after curing of the semi-cured resin layer was measured by the same method as in Example 1.
  • the thermal expansion coefficient was 48 ppm / ° C.
  • the thermal expansion coefficient is 38 ppm / ° C.
  • the peel strength of the copper foil was 1.0 kgf / cm.
  • Comparative Example 1 In Comparative Example 1, an example of a resin-coated copper foil in which only the same semi-cured resin layer as in Example 1 is formed on the same electrolytic copper foil as used in Example 1 is shown.
  • the resin composition for the semi-cured resin layer prepared under the same conditions as in Example 1 was applied to the glossy surface side of the same electrolytic copper foil as used in Example 1, and air-dried at room temperature for 5 minutes, 160 ° C. X Heat drying under conditions of 5 minutes to form a semi-cured resin layer. At this time, the thickness of the semi-cured resin layer was 20 ⁇ m.
  • Example 1 the coefficient of thermal expansion after curing of the semi-cured resin layer was measured. At this time, the thickness of the semi-cured resin layer after curing was 20 ⁇ m, and the thermal expansion coefficient was 45 ppm / ° C. And the peeling strength after hardening a semi-hardened resin layer by the same method as Example 1 was measured. As a result, the peel strength was 0.3 kgf / cm.
  • the comparative example 2 shows the example which manufactured the structure of copper foil and the cured resin layer on the same conditions as Example 1 except the composition of Example 1 and a semi-hardened resin layer differing. In order to avoid repeated descriptions, descriptions of the configurations of the copper foil and the cured resin layer are omitted.
  • the semi-cured resin layer formed in Comparative Example 2 was prepared by dissolving the following resin composition using N, N′-dimethylacetamide as a solvent to form a resin varnish having a resin solid content of 30 wt%.
  • Heat-resistant epoxy resin Naphthalene-type heat-resistant epoxy resin (trade name: HP-4700, manufactured by Dainippon Ink and Chemicals) / 40 parts by weight aromatic polyamine: 1,3-bis [4-aminophenoxy] benzene (trade name: TPE -R, manufactured by Wakayama Seika Kogyo Co., Ltd.) / 25 parts by weight epoxy resin: bisphenol A type epoxy resin (trade name: Epicron 850S, manufactured by Dainippon Ink & Chemicals, Inc.) / 20 parts by weight linear having functional groups capable of crosslinking Polymer: Polyvinyl acetal resin (trade name: Denka Butyral 5000A, manufactured by Denki Kagaku Kogyo Co., Ltd.) / 15 parts by weight
  • the resin varnish was applied, air-dried at room temperature for 5 minutes, and 160 ° C. ⁇ 5 minutes.
  • a semi-cured resin layer was formed by heating and drying under conditions. The resin thickness of the semi-cured resin layer at this time was 20 ⁇ m.
  • Example 2 the coefficient of thermal expansion after curing of the semi-cured resin layer was measured. At this time, the thickness of the semi-cured resin layer after curing was 20 ⁇ m, and the thermal expansion coefficient was 70 ppm / ° C. Moreover, the thickness of the whole resin layer of the resin-coated copper foil obtained in Comparative Example 2 was 47 ⁇ m. And the thermal expansion coefficient of the whole resin layer which consists of a cured resin layer and a semi-hardened resin layer, and the peeling strength were measured by the same method as Example 1 after hardening a semi-hardened resin layer. As a result, the thermal expansion coefficient was 62 ppm / ° C., and the peel strength was 1.0 kgf / cm. These values are summarized in Table 1 so that they can be compared with the examples.
  • Example 1 With respect to the resin-coated copper foils obtained in the examples and comparative examples, the measurement results of solder heat resistance, peel strength, and thermal expansion coefficient are shown in Table 1. With reference to Table 1, Examples and Comparative Examples Contrast. First, in the case of Example 1 to Example 4, all of the characteristics show a significantly excellent value. On the other hand, Comparative Example 1 is an example in which only the semi-cured resin layer of Example 1 was formed, but the thermal expansion coefficient, the peel strength, and the solder heat resistance all showed values sufficient for practical use. Absent. From this, it can be said that even if only a semi-cured resin layer is formed on the surface of the copper foil, a practical copper foil with resin cannot be obtained.
  • a printed wiring board was prepared for evaluation of solder heat resistance and peel strength.
  • the resin-coated copper foil obtained in the example or comparative example was vacuum applied to both surfaces of a 0.5 mm thick FR-4 grade copper clad laminate with a blackened 12 ⁇ m inner layer circuit on the surface.
  • the laminate was pressed under the conditions of a pressure of 20 kgf / cm 2 and a temperature of 170 ° C. ⁇ 60 minutes.
  • a multilayer printed wiring board provided with the obtained four copper layers was manufactured.
  • the peeling strength is formed by etching the outer layer copper foil of the multilayer printed wiring board to form a 10 mm-width linear circuit for measuring the peeling strength. The peel strength was measured by peeling it off.
  • the thermal expansion coefficient is prepared by two pieces each of the resin-coated copper foils obtained in each example or comparative example, laminated so that the resin surfaces of the resin-coated copper foils are in contact with each other, and cured by hot press I let you.
  • the curing conditions at this time were 170 ° C. ⁇ 60 minutes at a pressure of 20 kgf / cm 2 .
  • the copper foil was removed by an etching method, the above-mentioned copper foil with resin was laminated again, and the copper foil was removed by etching. By repeating this, a resin plate having a thickness of about 0.2 mm was prepared. And the thermal expansion coefficient of this resin board was measured based on JISC6481.
  • the resin-coated copper foil according to the present invention is a low profile copper foil having a low roughness on the surface of the copper foil on which the resin layer is provided by configuring the resin layer with two layers of a cured resin layer and a semi-cured resin layer. In addition, it becomes possible to obtain good adhesion between the resin layer and the copper foil. Moreover, since the resin-coated copper foil according to the present invention includes a resin layer having a low thermal expansion coefficient as compared with a conventional resin-coated copper foil, when used as a raw material for producing a multilayer printed wiring board in a build-up method, Since it has excellent dimensional stability against high temperature thermal history and thermal shock applied in the manufacturing process of the wiring board, it is possible to provide a high-quality multilayer printed wiring board.
  • the resin-coated copper foil according to the present invention can be used as a capacitor circuit forming material having a cured resin layer as a dielectric layer.

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  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention se rapporte à une feuille de cuivre contenant une résine qui peut réaliser une amélioration de la stabilité dimensionnelle d'une carte de circuit imprimé constituée et peut réaliser la formation circuit de pas fin. L'invention décrit également un processus de production de la feuille de cuivre contenant une résine. La feuille de cuivre contenant une résine comprend une feuille de cuivre, et une couche de résine durcie et couche de résine semi-durcie disposées dans cet ordre sur une surface de la feuille de cuivre. La rugosité de surface (Rzjis) d'un côté, de la feuille de cuivre, en contact avec la couche de résine durcie est de 0,5 μm à 2,5 μm. La couche de résine durcie comprend tout composant de résine sélectionné parmi des résines polyimides et polyamides-imides ayant un coefficient de dilatation thermique de 0 ppm/°C à 25 ppm/°C ou des résines composites des résines polyimides et des résines polyamides-imides. La couche de résine semi-durcie est placée sur la couche de résine durcie et a un coefficient de dilatation thermique de 0 ppm/°C à 50 ppm/°C après durcissement.
PCT/JP2008/073412 2007-12-28 2008-12-24 Feuille de cuivre avec résine et processus de production d'une feuille de cuivre avec résine Ceased WO2009084533A1 (fr)

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CN2008801233016A CN101909878A (zh) 2007-12-28 2008-12-24 带树脂铜箔以及带树脂铜箔的制造方法

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WO2012017909A1 (fr) * 2010-08-03 2012-02-09 三井金属鉱業株式会社 Procédé de production de carte de câblage imprimé, et carte de câblage imprimé
CN103155724A (zh) * 2010-10-08 2013-06-12 三井金属矿业株式会社 印刷线路板的制造方法以及用该印刷线路板的制造方法得到的印刷线路板
WO2015012327A1 (fr) 2013-07-23 2015-01-29 Jx日鉱日石金属株式会社 Feuille de cuivre traitée en surface, feuille de cuivre avec support, substrat, substrat de résine, carte à circuit imprimé, stratifié cuivré, et procédé de fabrication d'une carte à circuit imprimé
WO2015012376A1 (fr) 2013-07-24 2015-01-29 Jx日鉱日石金属株式会社 Feuille de cuivre traitée en surface, feuille de cuivre comprenant un transporteur, substrat, substrat de résine, carte de circuit imprimé, stratifié plaqué cuivre, et procédé de production de carte de circuit imprimé
EP3046400A2 (fr) 2015-01-16 2016-07-20 JX Nippon Mining & Metals Corporation Feuille de cuivre comportant support, stratifié, carte de câblage imprimé, dispositif électronique et procédé de fabrication de carte de câblage imprimée
EP3048864A2 (fr) 2015-01-21 2016-07-27 JX Nippon Mining & Metals Corporation Feuille de cuivre avec support, stratifié, carte de circuit imprimé et procédé de fabrication d'une carte de circuit imprimé
EP3054751A2 (fr) 2015-02-06 2016-08-10 JX Nippon Mining & Metals Corporation Feuille de cuivre comportant support, stratifié, carte de câblage imprimé, dispositif électronique et procédé de fabrication de carte de câblage imprimée
EP3232747A1 (fr) 2016-04-15 2017-10-18 JX Nippon Mining & Metals Corp. Feuille de cuivre, feuille de cuivre pour circuit haute fréquence, feuille de cuivre fixée à un support, feuille de cuivre fixée à un support pour circuit haute fréquence, stratifié, procédé de fabrication de carte de circuit imprimé et procédé de fabrication d'un dispositif électronique

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CN103155724A (zh) * 2010-10-08 2013-06-12 三井金属矿业株式会社 印刷线路板的制造方法以及用该印刷线路板的制造方法得到的印刷线路板
WO2015012327A1 (fr) 2013-07-23 2015-01-29 Jx日鉱日石金属株式会社 Feuille de cuivre traitée en surface, feuille de cuivre avec support, substrat, substrat de résine, carte à circuit imprimé, stratifié cuivré, et procédé de fabrication d'une carte à circuit imprimé
WO2015012376A1 (fr) 2013-07-24 2015-01-29 Jx日鉱日石金属株式会社 Feuille de cuivre traitée en surface, feuille de cuivre comprenant un transporteur, substrat, substrat de résine, carte de circuit imprimé, stratifié plaqué cuivre, et procédé de production de carte de circuit imprimé
EP3046400A2 (fr) 2015-01-16 2016-07-20 JX Nippon Mining & Metals Corporation Feuille de cuivre comportant support, stratifié, carte de câblage imprimé, dispositif électronique et procédé de fabrication de carte de câblage imprimée
EP3048864A2 (fr) 2015-01-21 2016-07-27 JX Nippon Mining & Metals Corporation Feuille de cuivre avec support, stratifié, carte de circuit imprimé et procédé de fabrication d'une carte de circuit imprimé
EP3054751A2 (fr) 2015-02-06 2016-08-10 JX Nippon Mining & Metals Corporation Feuille de cuivre comportant support, stratifié, carte de câblage imprimé, dispositif électronique et procédé de fabrication de carte de câblage imprimée
US9839124B2 (en) 2015-02-06 2017-12-05 Jx Nippon Mining & Metals Corporation Copper foil provided with carrier, laminate, printed wiring board, electronic device and method for fabricating printed wiring board
EP3232747A1 (fr) 2016-04-15 2017-10-18 JX Nippon Mining & Metals Corp. Feuille de cuivre, feuille de cuivre pour circuit haute fréquence, feuille de cuivre fixée à un support, feuille de cuivre fixée à un support pour circuit haute fréquence, stratifié, procédé de fabrication de carte de circuit imprimé et procédé de fabrication d'un dispositif électronique

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