WO2011068157A1 - Composition de résine destinée à être utilisée dans la formation d'une couche de collage dans une carte de circuit imprimé souple multicouche, vernis de résine, feuille de cuivre revêtue de résine, procédé de fabrication pour la feuille de cuivre revêtue de résine destinée à être utilisée dans la fabrication d'une carte de circuit imprimé souple multicouche et carte de circuit imprimé souple multicouche - Google Patents

Composition de résine destinée à être utilisée dans la formation d'une couche de collage dans une carte de circuit imprimé souple multicouche, vernis de résine, feuille de cuivre revêtue de résine, procédé de fabrication pour la feuille de cuivre revêtue de résine destinée à être utilisée dans la fabrication d'une carte de circuit imprimé souple multicouche et carte de circuit imprimé souple multicouche Download PDF

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Publication number
WO2011068157A1
WO2011068157A1 PCT/JP2010/071570 JP2010071570W WO2011068157A1 WO 2011068157 A1 WO2011068157 A1 WO 2011068157A1 JP 2010071570 W JP2010071570 W JP 2010071570W WO 2011068157 A1 WO2011068157 A1 WO 2011068157A1
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WIPO (PCT)
Prior art keywords
resin
component
flexible printed
weight
copper foil
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Application number
PCT/JP2010/071570
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English (en)
Japanese (ja)
Inventor
武志 白井
敏文 松島
佐藤　哲朗
Original Assignee
三井金属鉱業株式会社
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Filing date
Publication date
Application filed by 三井金属鉱業株式会社 filed Critical 三井金属鉱業株式会社
Priority to CN201080054803.5A priority Critical patent/CN102640576B/zh
Priority to JP2011544285A priority patent/JP5750049B2/ja
Priority to KR1020127012372A priority patent/KR101757411B1/ko
Publication of WO2011068157A1 publication Critical patent/WO2011068157A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • 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
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4246—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof polymers with carboxylic terminal groups
    • C08G59/4261—Macromolecular compounds obtained by reactions involving only unsaturated carbon-to-carbon bindings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/44—Amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C08G59/621—Phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/14—Polyamide-imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
    • C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09J179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/28—Metal sheet
    • 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
    • H05K1/03—Use of materials for the substrate
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
    • C08L2666/22—Macromolecular compounds not provided for in C08L2666/16 - C08L2666/20
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/304—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being heat-activatable, i.e. not tacky at temperatures inferior to 30°C
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2463/00—Presence of epoxy resin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2479/00—Presence of polyamine or polyimide
    • C09J2479/08—Presence of polyamine or polyimide 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0393—Flexible materials
    • 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
    • H05K2201/0104—Properties and characteristics in general
    • H05K2201/012—Flame-retardant; Preventing of inflammation
    • 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
    • H05K2201/03—Conductive materials
    • H05K2201/0332—Structure of the conductor
    • H05K2201/0335—Layered conductors or foils
    • H05K2201/0358—Resin coated copper [RCC]

Definitions

  • the present invention relates to a resin composition for forming an adhesive layer of a multilayer flexible printed wiring board, a resin-coated copper foil in which a resin layer is formed with the resin varnish, a method for producing the resin-coated copper foil, and a multilayer flexible printed wiring board.
  • a flexible printed wiring board having bendability is used as a printed wiring board used for supplying electronic signals of electronic devices.
  • the flexible wiring board disclosed in Patent Document 1 has a structure in which an adhesive layer I, a conductor layer on which a circuit pattern is formed, an adhesive layer II, and a coverlay film are sequentially laminated on a base film.
  • an adhesive composition intended to obtain a sufficient bending life even when used at a high temperature is employed.
  • flex resistance is important for flexible printed wiring boards because of the product characteristics with bendability.
  • heat is applied in a reflow process or the like, and therefore, folding resistance is required not to deteriorate even when used at a high temperature. Therefore, folding resistance and heat resistance are also desired for adhesives used for flexible printed wiring boards.
  • Patent Document 2 discloses a resin composition for the purpose of non-halogenation for flame retardancy, flex resistance, and environmental friendliness.
  • Patent Document 1 and Patent Document 2 all contain an inorganic filler (inorganic filler) for improving heat resistance, elastic modulus, flame retardancy, and the like. Therefore, when used as an adhesive for multilayer flexible printed wiring boards, there is a limit to the flexibility and the thinning of the adhesive layer.
  • an inorganic filler when included, the laser workability is lowered and the formation accuracy of the via hole is lowered.
  • punching the adhesive layer of the B stage the adhesive layer is likely to fall off or crack. As a result, the adhesive layer powder adheres to the conductor layer, and the connection reliability is lowered.
  • insulation performance will fall.
  • An object of the present invention is to provide a resin composition for forming an adhesive layer of a multilayer flexible printed wiring board, a resin varnish, a resin-coated copper foil, a method for producing the resin-coated copper foil, and a multilayer flexible printed wiring board.
  • the resin composition for forming an adhesive layer of a multilayer flexible printed wiring board according to the present invention is a resin composition used for forming an adhesive layer for multilayering an inner flexible printed wiring board.
  • Each component of the component is included.
  • a component Solid high heat-resistant epoxy resin having a softening point of 50 ° C. or higher (excluding biphenyl type epoxy resin).
  • Component B An epoxy resin curing agent comprising one or more of a biphenyl type phenol resin and a phenol aralkyl type phenol resin.
  • Component C A rubber-modified polyamide-imide resin soluble in a solvent having a boiling point in the range of 50 ° C. to 200 ° C.
  • D component An organic phosphorus-containing flame retardant.
  • E component Biphenyl type epoxy resin.
  • the resin varnish according to the present invention is a resin varnish prepared by adding a solvent to the resin composition described above to have a resin solid content in the range of 30 wt% to 70 wt%.
  • the resin flow when measured at a resin thickness of 55 ⁇ m is in the range of 0% to 10%.
  • the resin-coated copper foil according to the present invention is a resin-coated copper foil provided with a resin layer on the surface of the copper foil, and the resin layer is formed using the above-described resin composition for forming an adhesive layer of a multilayer flexible printed wiring board. It is formed.
  • a method for producing a resin-coated copper foil for producing a multilayer flexible printed wiring board according to the present invention is a method for producing a resin-coated copper foil for producing the above-mentioned multilayer flexible printed wiring board, comprising the following steps a and b:
  • the resin varnish used for forming the resin layer is prepared by the procedure, and the resin varnish is applied to the surface of the copper foil and dried to obtain a resin-coated copper foil as a semi-cured resin layer having a thickness of 10 ⁇ m to 80 ⁇ m.
  • Step a When the weight of the resin composition is 100 parts by weight, the A component is 3 to 30 parts by weight, the B component is 13 to 35 parts by weight, the C component is 10 to 50 parts by weight, and the D component Is a resin composition containing the respective components in the range of 3 to 16 parts by weight and the E component in the range of 5 to 35 parts by weight.
  • Step b The resin composition is dissolved using an organic solvent to obtain a resin varnish having a resin solid content of 30 wt% to 70 wt%.
  • the multilayer flexible printed wiring board according to the present invention is obtained by using a resin composition for forming an adhesive layer of a multilayer flexible printed wiring board.
  • the resin composition according to the present invention can prevent a decrease in folding resistance due to thermal deterioration, and can improve cracking at the B stage.
  • the resin-coated copper foil obtained using the resin composition according to the present invention does not require an inorganic filler when used as a constituent material of a flexible printed wiring board, and thus has excellent flexibility and a laser. Processing and punching can be performed with high accuracy, and occurrence of powder falling and cracking can be prevented.
  • the resin-coated copper foil according to the present invention does not contain an inorganic filler, it is suitable for forming a via hole in a multilayer flexible printed wiring board and can improve the reliability of interlayer connection.
  • Resin composition The resin composition according to the present invention is used to form an adhesive layer for multilayering an inner flexible printed wiring board.
  • Each of the following components A to E is included.
  • a component Solid high heat-resistant epoxy resin having a softening point of 50 ° C. or higher (excluding biphenyl type epoxy resin).
  • Component B An epoxy resin curing agent comprising one or more of a biphenyl type phenol resin and a phenol aralkyl type phenol resin.
  • Component C A rubber-modified polyamide-imide resin soluble in a solvent having a boiling point in the range of 50 ° C. to 200 ° C.
  • D component An organic phosphorus-containing flame retardant.
  • E component Biphenyl type epoxy resin.
  • the A component is a solid high heat resistant epoxy resin having a softening point of 50 ° C. or higher.
  • the component A is an epoxy resin having a high so-called glass transition temperature Tg.
  • the reason why a solid high heat resistant epoxy resin having a softening point of 50 ° C. or higher among the epoxy resins is used is that the glass transition temperature Tg is high, and a high heat resistance effect can be obtained by adding a small amount.
  • the “solid high heat resistant epoxy resin having a softening point of 50 ° C. or higher” mentioned here is one or more of cresol novolac type epoxy resin, phenol novolac type epoxy resin, and naphthalene type epoxy resin. It is preferable.
  • the component A further includes a novolac type epoxy resin, a cresol novolac type epoxy resin, a phenol novolak type epoxy resin, and a naphthalene type. It is good also as what contains the highly heat-resistant epoxy resin which consists of any 1 type or 2 types or more of an epoxy resin.
  • a high heat-resistant epoxy composed of one or more of a novolak type epoxy resin, a cresol novolak type epoxy resin, a phenol novolak type epoxy resin, and a naphthalene type epoxy resin that is liquid at room temperature. If the resin is contained, the effect of further improving the glass transition temperature Tg and improving the B stage cracking can be enhanced.
  • the component A is preferably used in the range of 3 to 30 parts by weight when the resin composition is 100 parts by weight. When the component A is less than 3 parts by weight, it is difficult to increase the Tg of the resin composition. On the other hand, when the component A exceeds 30 parts by weight, the cured resin layer becomes brittle and the flexibility is completely impaired, which is not preferable for use as a flexible printed wiring board. More preferably, the component A is used in the range of 10 to 25 parts by weight, and thus it is possible to stably achieve both high Tg of the resin composition and good flexibility of the resin layer after curing.
  • the B component is an epoxy resin curing agent composed of one or more of a biphenyl type phenol resin and a phenol aralkyl type phenol resin.
  • the addition amount of the epoxy resin curing agent is naturally derived from the reaction equivalent to the resin to be cured, and does not require any particular quantitative limitation.
  • the component B is preferably used in the range of 13 to 35 parts by weight when the resin composition is 100 parts by weight.
  • this B component is less than 13 parts by weight, considering the resin composition of the present invention, it becomes impossible to obtain a sufficiently cured state, and it becomes impossible to obtain the flexibility of the cured resin layer.
  • the component B exceeds 35 parts by weight, the moisture absorption resistance of the cured resin layer tends to deteriorate, which is not preferable.
  • C component is a rubber-modified polyamideimide resin soluble in a solvent having a boiling point in the range of 50 ° C to 200 ° C.
  • This rubber-modified polyamideimide resin is obtained by reacting a polyamideimide resin and a rubber resin, and is performed for the purpose of improving the flexibility of the polyamideimide resin itself. That is, the polyamideimide resin and the rubber resin are reacted to replace a part of the acid component (cyclohexanedicarboxylic acid or the like) of the polyamideimide resin with the rubber component.
  • the rubber component is described as a concept including natural rubber and synthetic rubber, and the latter synthetic rubber includes styrene-butadiene rubber, butadiene rubber, butyl rubber, ethylene-propylene rubber, acrylonitrile butadiene rubber and the like. Furthermore, from the viewpoint of ensuring heat resistance, it is also useful to selectively use a synthetic rubber having heat resistance such as nitrile rubber, chloroprene rubber, silicon rubber, urethane rubber and the like. Since these rubber-like resins react with the polyamide-imide resin to produce a copolymer, it is desirable to have various functional groups at both ends.
  • CTBN carboxy group-terminated butadiene nitrile rubber
  • the said rubber component may copolymerize only 1 type or may copolymerize 2 or more types.
  • a rubber component it is preferable to use a rubber component having a number average molecular weight of 1000 or more from the viewpoint of stabilization of flexibility.
  • Solvents used for dissolving the polyamideimide resin and the rubbery resin when polymerizing the rubber-modified polyamideimide resin include dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, nitromethane, nitroethane, tetrahydrofuran , Cyclohexanone, methyl ethyl ketone, acetonitrile, ⁇ -butyrolactone and the like are preferably used alone or in combination.
  • a polymerization temperature in the range of 80 ° C. to 200 ° C.
  • a solvent having a boiling point of more than 200 ° C. is used for these polymerizations, it is preferable that the solvent is subsequently replaced with a solvent having a boiling point in the range of 50 ° C. to 200 ° C. depending on the application.
  • examples of the solvent having a boiling point in the range of 50 ° C. to 200 ° C. include one single solvent selected from the group of methyl ethyl ketone, dimethylacetamide, dimethylformamide, and two or more mixed solvents.
  • 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., when the semi-cured resin is used from the state of the resin varnish, it is difficult to obtain a good semi-cured resin layer because the solvent is difficult to dry.
  • the copolymerization amount of the rubber component when the weight of the rubber-modified polyamideimide resin is 100% by weight, the copolymerization amount of the rubber component may be 0.8% by weight or more. preferable. When the copolymerization amount is less than 0.8% by weight, the rubber-modified polyamide-imide resin lacks flexibility when the resin layer formed using the resin composition according to the present invention is cured, Since the adhesiveness with copper foil also falls, it is not preferable. More preferably, the copolymerization amount of the rubber component is 3% by weight or more, more preferably 5% by weight or more. Empirically, there is no particular problem even if the copolymerization amount exceeds 40% by weight. However, since the effect of improving the flexibility of the cured resin layer is saturated, resources are wasted, which is not preferable.
  • the rubber-modified polyamide-imide resin described above is required to be soluble in a solvent. This is because preparation as a resin varnish is difficult unless it is soluble in a solvent.
  • the rubber-modified polyamideimide resin is used in a blending ratio of 10 parts by weight to 50 parts by weight when the weight of the resin composition is 100 parts by weight. When the rubber-modified polyamideimide resin is less than 10 parts by weight, the resin flow suppressing effect is hardly exhibited. In addition, the cured resin layer becomes brittle and it is difficult to improve flexibility. As a result, there is an effect that microcracks of the resin layer are likely to occur. On the other hand, when the rubber-modified polyamide-imide resin is added in an amount exceeding 50 parts by weight, the embedding property in the inner layer circuit is lowered, and as a result, voids are easily generated, which is not preferable.
  • D component is an organic phosphorus-containing flame retardant and is used to improve flame retardancy.
  • organic phosphorus-containing flame retardants include phosphorus-containing flame retardants composed of phosphate esters and / or phosphazene compounds.
  • the component D is preferably used in the range of 3 to 16 parts by weight when the resin composition is 100 parts by weight. When the content of the D component is less than 3 parts by weight, the flame retardancy effect cannot be obtained. On the other hand, even if the content of the D component exceeds 16 parts by weight, improvement in flame retardancy cannot be expected. A more preferable content of component D is 5 to 14 parts by weight.
  • the resin composition according to the present invention is flame retardant when added so that the total phosphorus content is in the range of 0.5 to 5% by weight when the weight of the resin composition is 100% by weight. Is preferable.
  • the E component is a biphenyl type epoxy resin.
  • the biphenyl type epoxy resin contributes to improvement of so-called glass transition temperature Tg and flexibility.
  • Examples of the biphenyl type epoxy resin include a biphenyl aralkyl type epoxy resin.
  • the component E is preferably used in the range of 5 to 35 parts by weight when the resin composition is 100 parts by weight. When the content of the E component is less than 5 parts by weight, the effect of increasing the glass transition temperature Tg and the flexibility cannot be obtained. On the other hand, even if the content of the E component exceeds 35 parts by weight, it is not possible to expect a high Tg and an improvement in flexibility. A more preferable content of the E component is 7 to 25 parts by weight.
  • the flame retardancy can be further improved by using a resin composition containing a phosphorus-containing flame-retardant epoxy resin as the F component.
  • the phosphorus-containing flame-retardant epoxy resin is a general term for epoxy resins containing phosphorus in an epoxy skeleton, and is a so-called halogen-free flame-retardant epoxy resin. Then, when the phosphorus atom content of the resin composition according to the present application is 100% by weight of the resin composition, the phosphorus content can be in the range of 0.1% to 5% by weight of phosphorus atoms derived from the F component Any flame retardant epoxy resin can be used.
  • a phosphorus-containing flame-retardant epoxy resin having two or more epoxy groups in the molecule which is a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative
  • the structural formula of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is shown in Chemical Formula 3.
  • This 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative, a phosphorus-containing flame-retardant epoxy resin having two or more epoxy groups in the molecule, is 9,10-dihydro-9.
  • -Oxa-10-phosphaphenanthrene-10-oxide is reacted with naphthoquinone or hydroquinone to give the compound shown in the following chemical formula 4 or chemical formula 5, and then the epoxy resin is reacted with the OH group portion to make it difficult to contain phosphorus. What was made into the flammable epoxy resin is preferable.
  • a specific example of a phosphorus-containing flame-retardant epoxy resin having two or more epoxy groups in the molecule which is a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative
  • the use of a compound having the structural formula shown in Chemical Formula 6, Chemical Formula 7 or Chemical Formula 8 is preferred.
  • the resin composition may be one of the phosphorus-containing flame-retardant epoxy resins as the F component, or two or more phosphorus-containing flame-retardant epoxy resins. May be used in combination.
  • the phosphorus atom derived from the F component is in the range of 0.1% to 5% by weight. It is preferable to add so that it becomes.
  • the phosphorus-containing flame-retardant epoxy resin has different amounts of phosphorus atoms contained in the epoxy skeleton depending on the type.
  • the component F is usually used in the range of 5 to 50 parts by weight when the resin composition is 100 parts by weight. In the case where the F component is less than 5 parts by weight, it becomes difficult to make the phosphorus atom derived from the F component 0.1% by weight or more in consideration of the blending ratio of the other resin components. Can not get. On the other hand, even if the F component exceeds 50 parts by weight, the effect of improving flame retardancy is saturated, and at the same time, the cured resin layer becomes brittle.
  • “High Tg” and “flexibility” of the cured resin layer described above are generally inversely proportional characteristics.
  • By mixing and using in a well-balanced manner it is possible to obtain a resin composition suitable for flexible printed wiring board applications.
  • the resin composition according to the present invention is further selected from the group consisting of bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol AD type epoxy resin having an epoxy equivalent of 200 or less and being liquid at room temperature as the G component. Or it is good also as what contains the epoxy resin which consists of 2 or more types.
  • the reason why the bisphenol-based epoxy resin is selectively used is that the compatibility with the component C (rubber-modified polyamideimide resin) is good, and it is easy to impart appropriate flexibility to the semi-cured resin layer. If the epoxy equivalent exceeds 200, the resin becomes semi-solid at room temperature, and the flexibility in the semi-cured state decreases, which is not preferable.
  • 1 type may be used independently or 2 or more types may be used in mixture. In addition, when two or more kinds are mixed and used, there is no particular limitation with respect to the mixing ratio.
  • the epoxy resin of component G when the resin composition is 100 parts by weight, exhibits a sufficient thermosetting property when used in a blending ratio of 2 to 15 parts by weight. It is preferable because the occurrence of a so-called warp phenomenon can be reduced, and the flexibility of the resin layer in a semi-cured state can be further improved.
  • the said epoxy resin exceeds 15 weight part, there exists a tendency for a flame retardance to fall from the balance with another resin component, or for the resin layer after hardening to become hard.
  • component C rubber-modified polyamideimide resin
  • the resin composition according to the present invention may further include a low elastic substance made of a thermoplastic resin and / or a synthetic rubber as the H component.
  • a low elastic substance made of a thermoplastic resin and / or a synthetic rubber as the H component.
  • the low-elasticity material as the H component include acrylonitrile butadiene rubber, acrylic rubber (acrylic ester copolymer), polybutadiene rubber, isoprene, hydrogenated polybutadiene, polyvinyl butyral, polyethersulfone, phenoxy, and polymer epoxy.
  • aromatic polyamides One of these may be used alone, or two or more may be used in combination.
  • acrylonitrile butadiene rubber is preferably used.
  • a carboxyl-modified product can take a crosslinked structure with an epoxy resin and improve the flexibility of the cured resin layer.
  • the carboxyl-modified product it is preferable to use carboxy group-terminated nitrile butadiene rubber (CTBN), carboxy group-terminated butadiene rubber (CTB), or carboxy-modified nitrile butadiene rubber (C-NBR).
  • CBN carboxy group-terminated nitrile butadiene rubber
  • C-NBR carboxy-modified nitrile butadiene rubber
  • the H component is preferably used at a blending ratio of 25 parts by weight or less when the resin composition is 100 parts by weight. If an H component in an amount exceeding 25 parts by weight is added, problems such as a decrease in glass transition temperature Tg, a decrease in solder heat resistance, a decrease in peel strength, and an increase in thermal expansion coefficient are undesirable.
  • the resin composition according to the present invention can improve the flame retardancy and the glass transition temperature Tg by combining the above components A to E, and can prevent the heat resistance of the folding resistance. And sufficient flexibility can be obtained, without adding an inorganic filler like the conventional resin composition for adhesive agents. Furthermore, it is possible to prevent cracking in a semi-cured state and powder falling off during punching.
  • Resin varnish according to the present invention is prepared by adding a solvent to the above resin composition so that the resin solid content is in the range of 30 wt% to 70 wt%.
  • the semi-cured resin layer formed by this resin varnish has a resin flow in the range of 0% to 10% when measured with a resin thickness of 55 ⁇ m in accordance with MIL-P-13949G in the MIL standard.
  • the solvent mentioned here one single solvent selected from the group of methyl ethyl ketone, dimethylacetamide, dimethylformamide, etc., which is a solvent having a boiling point in the range of 50 ° C. to 200 ° C., or a mixed solvent of two or more types is used. It is preferable.
  • the range of the resin solid content shown here is a range in which the film thickness can be controlled to the most accurate one when applied to the surface of the copper foil.
  • the resin solid content is less than 30% by weight, the viscosity is too low and it flows immediately after application to the copper foil surface, making it difficult to ensure film thickness uniformity.
  • the resin solid content exceeds 70% by weight, the viscosity increases and it becomes difficult to form a thin film on the surface of the copper foil.
  • the resin varnish preferably has a measured resin flow in the range of 0% to 10% when a semi-cured resin layer is formed using the resin varnish.
  • the resin flow is high, the thickness of the insulating layer formed using the resin layer of the resin-coated copper foil becomes nonuniform.
  • the resin varnish according to the present invention can suppress the resin flow to a low value of 10% or less.
  • the resin varnish which concerns on this invention can implement
  • a more preferable range of the resin flow of the resin varnish according to the present invention is 0% to 5%.
  • the resin flow is based on MIL-P-13949G in the MIL standard.
  • Four 10 cm square samples were sampled from a resin-coated copper foil with a resin thickness of 55 ⁇ m. It is a value calculated based on Equation 1 from the result of measuring the resin outflow weight at the time of laminating under the conditions of a press temperature of 171 ° C., a press pressure of 14 kgf / cm 2 , and a press time of 10 minutes in a stacked state (laminate). .
  • the resin-coated copper foil according to the present invention is a resin-coated copper foil for producing a multilayer flexible printed wiring board having a resin layer on the surface of the copper foil. And in the said copper foil with resin, the resin layer was formed using the resin composition for contact bonding layer formation of the above-mentioned multilayer flexible printed wiring board, It is characterized by the above-mentioned.
  • the copper foil is not particularly limited, and the thickness is not particularly limited.
  • the manufacturing method of copper foil is not restricted, and what was obtained by all the manufacturing methods, such as an electrolytic method or a rolling method, can be used.
  • the surface on which the resin layer of the copper foil is formed may or may not be roughened. If there exists a roughening process, the adhesiveness of copper foil and a resin layer will improve. And if it does not perform a roughening process, since it will become a flat surface, the formation capability of a fine pitch circuit will improve. Furthermore, the surface of the copper foil may be subjected to rust prevention treatment.
  • rust prevention treatment it is possible to employ inorganic rust prevention using known zinc, zinc-based alloys, or the like, or organic rust prevention using an organic monomolecular film such as benzimidazole or triazole. Furthermore, it is preferable to provide a silane coupling agent treatment layer on the surface on which the resin layer of the copper foil is formed.
  • the silane coupling agent layer plays a role as an auxiliary agent for improving the wettability between the surface of the copper foil not particularly roughened and the resin layer and improving the adhesion.
  • silane coupling agent treatment is epoxy functional silane coupling agent, olefin functional silane, acrylic functional silane, amino functional silane coupling
  • agents such as an agent or a mercapto-functional silane coupling agent can be used, and the peel strength exceeds 0.8 kgf / cm by selecting and using a suitable silane coupling agent according to the application become.
  • silane coupling agent that can be used here will be described more specifically.
  • the formation of the silane coupling agent layer is not particularly limited, such as a commonly used dipping method, showering method, spraying method, or the like.
  • a method that can contact and adsorb the solution containing the copper foil and the silane coupling agent most uniformly can be arbitrarily employed.
  • These silane coupling agents are used at a temperature of room temperature by dissolving 0.5 to 10 g / l in water as a solvent. Since the silane coupling agent forms a film by condensation bonding with OH groups protruding on the surface of the copper foil, the effect is not significantly increased even if a solution having a very high concentration is used. Therefore, it should be originally determined according to the processing speed of the process.
  • the adsorption rate of the silane coupling agent is slow, which is not suitable for general commercial profit, and the adsorption is not uniform. Moreover, even if the concentration exceeds 10 g / l, the adsorption rate is not particularly increased, which is uneconomical.
  • the copper foil with resin described above is one kind of polyimide resin, polyamide resin, polyether sulfone resin, phenoxy resin, aramid resin, polyvinyl acetal resin between the copper foil to be used and the semi-cured resin layer. It is also possible to form an auxiliary resin layer made of two or more kinds of mixed resins. This auxiliary resin layer is formed before the semi-cured resin layer is formed. By adopting such a two-layer structure of an auxiliary resin layer and a semi-cured resin layer, it is possible to further improve the flexibility as a resin-coated copper foil and to be suitable for flexible printed wiring board applications. it can. These auxiliary resin layers can be formed by a method generally called a casting method.
  • a resin varnish for forming either a polyimide resin, a polyamide resin, or a mixed resin of these two types is applied to the copper foil surface, a part of the solvent is removed by a drying process, and the temperature is further increased. It can be formed by removing the solvent and / or dehydrating condensation reaction in the drying step.
  • the thickness of the auxiliary resin layer is desirably 10 ⁇ m or less. If it exceeds 10 ⁇ m, the total thickness will increase when combined with the semi-cured resin layer referred to in the present invention, so it is difficult to reduce the total thickness when processed into a flexible printed wiring board. At the same time, the curling phenomenon is likely to occur in the resin-coated copper foil due to heating when forming the semi-cured resin layer, which is not preferable.
  • the manufacturing method of resin-coated copper foil according to the present invention is a manufacturing method of the resin-coated copper foil for manufacturing the multilayer flexible printed wiring board, comprising the following steps a, A resin varnish used for forming the resin layer is prepared in the procedure of step b, and the resin varnish is applied to the surface of the copper foil and dried to form a semi-cured resin layer having a thickness of 10 ⁇ m to 80 ⁇ m. It is characterized by doing.
  • the thickness of the semi-cured resin layer is less than 10 ⁇ m, the adhesion with the inner-layer flexible printed wiring board tends to vary.
  • Step a When the weight of the resin composition is 100 parts by weight, the A component is 3 to 30 parts by weight, the B component is 13 to 35 parts by weight, the C component is 10 to 50 parts by weight, and the D component Is a resin composition containing the respective components in the range of 3 to 16 parts by weight and the E component in the range of 5 to 35 parts by weight. Since the description about each component and the mixture ratio described here is as above-mentioned, description here is abbreviate
  • Step b The resin composition is dissolved using an organic solvent to obtain a resin varnish.
  • the organic solvent at this time is a solvent having a boiling point in the range of 50 ° C. to 200 ° C. as described above, one kind of single solvent selected from the group of methyl ethyl ketone, dimethylacetamide, dimethylformamide, etc. It is preferable to use a mixed solvent. This is because of the same reason as described above.
  • a resin varnish having a resin solid content of 30 wt% to 70 wt% is used. The reason for determining the range of the resin solid content is the same as described above.
  • the application method is not particularly limited. However, considering that the target thickness must be applied with high accuracy, a coating method and a coating apparatus corresponding to the film thickness to be formed may be appropriately selected and used. Moreover, what is necessary is just to employ
  • Multilayer flexible printed wiring board according to the present invention is obtained by using the above-described resin composition for forming an adhesive layer of a multilayer flexible printed wiring board. . That is, using the resin composition according to the present invention as a resin varnish, a resin-coated copper foil is produced using the resin varnish. And it is set as the multilayer flexible printed wiring board using this copper foil with resin. At this time, there is no special limitation regarding a manufacturing process until it is set as a multilayer flexible printed wiring board using copper foil with resin. Any known manufacturing technique can be used.
  • the multilayer flexible printed wiring board said to this invention says what is provided with the conductor layer containing the circuit shape of three or more layers. Examples are shown below.
  • Component A Solid high heat resistant epoxy resin (cresol novolac type epoxy resin YDCN-704, softening point 90 ° C. manufactured by Toto Kasei Co., Ltd.), Liquid heat-resistant epoxy resin (Naphthalene-type epoxy resin DIC Corporation HP4032-D)
  • Component B Epoxy resin curing agent (MEH-7851M manufactured by Meiwa Kasei Co., Ltd.)
  • Component C Rubber-modified polyamideimide resin
  • Component D Phosphorus-containing flame retardant (Aromatic condensed phosphate ester PX-200 manufactured by Daihachi Chemical Co., Ltd.)
  • E component biphenyl type epoxy resin (NC-3000 manufactured by Nippon Kayaku Co., Ltd.)
  • F component phosphorus-containing flame-retardant epoxy resin
  • G component bisphenol A type liquid epoxy resin (Epiclon 850S manufactured by DIC Corporation)
  • H component low elasticity material (acrylonitrile butadiene rubber JSR
  • polyamideimide resin had a logarithmic viscosity of 0.65 dl / g and a glass transition temperature of 160 ° C.
  • Example of synthesis of phosphorus-containing flame-retardant epoxy resin To a 4-necked glass separable flask equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet, 10- (2,5-dihydroxyphenyl) -10H 324 parts by weight of -9-oxa-10-phosphaphenanthrene-10-oxide (manufactured by Sanko Co., Ltd., HCA-HQ) and 300 parts by weight of ethyl cellosolve were charged and dissolved by heating. 680 parts by weight of YDF-170 (Bisphenol F type epoxy resin manufactured by Toto Kasei Co., Ltd.) was charged, stirred while introducing nitrogen gas, heated to 120 ° C. and mixed.
  • YDF-170 Bisphenol F type epoxy resin manufactured by Toto Kasei Co., Ltd.
  • Example 1 uses a phosphorus-containing flame-retardant epoxy resin, a rubber-modified polyamide-imide resin, and the like obtained by the synthesis method described above, and a resin composition having a blending ratio shown in Table 1, and further uses dimethyl as a solvent.
  • the resin varnish was applied to a roughened surface of a commercially available electrolytic copper foil (18 ⁇ m thick) using an edge coater so that the thickness after drying was 50 ⁇ m, and the heating conditions were 150 ° C. for 3 minutes. Then, the solvent was diffused to obtain a resin-coated copper foil. Using this resin-coated copper foil, the glass transition temperature Tg, the flexibility evaluation of the cured resin layer, and the punching performance were evaluated. Moreover, the multilayer printed wiring board was produced using this copper foil with resin, and the peeling strength and the normal-state solder heat resistance test, the boiling solder heat resistance test, and the moisture absorption solder heat resistance test were done. Further, a resin-coated copper foil provided with a resin layer having a thickness of 55 ⁇ m was prepared by the same method as that for the resin-coated copper foil, and the resin flow was evaluated. These evaluations and test results are summarized in Table 2.
  • the bending resistance test by the MIT method uses a film folding fatigue tester with a tank (product number: 549) manufactured by Toyo Seiki Seisakusho as the MIT folding resistance device, with a bending radius of 0.8 mm and a load of 0.5 kgf. Repeated bending test of the bending resistance test film was performed. In Table 2 showing the results, a flex resistance test film that was able to measure the number of repeated bendings of 2000 times or more was evaluated as acceptable. In addition, the number of repeated bendings was measured with one reciprocation of the drive head of the MIT folding apparatus as one time (one cycle).
  • the punching performance of B-stage resin-coated copper foil is as follows: B-stage resin-coated copper foil is placed with the copper foil surface facing up, and punched from the bottom surface (resin surface) to the top surface (copper foil surface) with a punch. Processing was performed. When punching with a punch, if the resin powder is generated as x rejected, no resin powder is produced, but if the B stage resin is cracked, pass B, and if the B stage resin is neither resin powder nor cracked Evaluated as excellent ⁇ . The evaluation results are shown in Table 2.
  • Boiled solder heat resistance test After removing the copper foil layer of the outer layer of the solder heat resistance measurement sample cut out to a size of 50 mm ⁇ 50 mm from the above four-layer multilayer printed wiring board, it was immersed in boiling ion exchange water. Then, a boiling treatment for 3 hours was performed. And from the sample which boiled, the water
  • Moisture-absorbing solder heat resistance test In the production of the above-described four-layer multilayer printed wiring board, the resin-coated copper foil was held in a constant temperature and humidity chamber at a temperature of 30 ° C. and a relative humidity of 65% for 15 hours to absorb moisture. A thing was used. The other production conditions of the four-layer multilayer printed wiring board are as described above. Then, a solder heat resistance measurement sample cut out to a size of 50 mm ⁇ 50 mm from this four-layer multilayer printed wiring board was floated on a 260 ° C. solder bath, and the time until blistering was measured. The results are shown in Table 2. The time until blistering was evaluated as ⁇ for 300 seconds or more and x for less than 300 seconds.
  • Example 2 to Example 7 In Examples 2 to 7, instead of the resin composition of Example 1, the resin components described above were used to obtain the resin compositions having the blending ratios listed in Table 1, and dimethylacetamide was used as the solvent. A resin varnish was prepared. Others are the same as in the first embodiment.
  • the resin-coated copper foils shown in Examples 1 to 7 had good evaluation results in terms of peel strength, solder heat resistance, flexible performance, and punching performance.
  • the resin flow was extremely low, with 1% in Examples 1 and 5 and less than 1% in Examples 2 to 4, 4, and 7.
  • the punching performance was very good.
  • the resin flow in the holes formed by punching was small, and good results were obtained.
  • the glass transition temperature Tg could be sufficiently high.
  • Comparative Example 1 resulted in inferior punching performance
  • Comparative Example 2 resulted in inferior normal solder heat resistance and hygroscopic solder heat resistance.
  • the resin composition according to the present invention is compatible with high-density mounting of flexible printed wiring boards, and in particular, has the flexibility and heat resistance of multilayer flexible printed wiring boards, and has high connection reliability and high performance.
  • the present invention can be used for manufacturing a multilayer flexible printed wiring board.

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Abstract

L'invention porte sur une composition de résine qui empêche les craquelures à l'état B et qui empêche la chute de poudre qui peut survenir, par exemple, pendant le procédé de fabrication de cartes de circuit imprimé souples, et qui présente un bon équilibre entre la résistance au pliage, la résistance à la chaleur et la performance d'écoulement de résine et similaire. La composition de résine, qui est utilisée pour former la couche de collage pour la formation de plusieurs couches d'une carte de circuit imprimé souple interne, est caractérisée en ce qu'elle contient comme composants : (A) : une résine époxyde solide ayant une résistance à la chaleur élevée et un point de flexibilité d'au moins 50°C ; (B) : un agent durcisseur de résine époxyde comprenant au moins une résine biphényl-phénolique et/ou une résine phénol-aralkylphénolique ; (C) : un polyamide-imide modifié par du caoutchouc qui est soluble dans un solvant ayant un point d'ébullition dans la plage comprise entre 50°C et 200°C ; (D) un ignifugeant organique contenant du phosphore ; et (E) : une résine époxyde biphénylique.
PCT/JP2010/071570 2009-12-02 2010-12-02 Composition de résine destinée à être utilisée dans la formation d'une couche de collage dans une carte de circuit imprimé souple multicouche, vernis de résine, feuille de cuivre revêtue de résine, procédé de fabrication pour la feuille de cuivre revêtue de résine destinée à être utilisée dans la fabrication d'une carte de circuit imprimé souple multicouche et carte de circuit imprimé souple multicouche WO2011068157A1 (fr)

Priority Applications (3)

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CN201080054803.5A CN102640576B (zh) 2009-12-02 2010-12-02 多层柔性印刷电路板的粘合层形成用的树脂组合物、树脂清漆、带树脂铜箔，多层柔性印刷电路板制造用的带树脂铜箔的制造方法以及多层柔性印刷电路板
JP2011544285A JP5750049B2 (ja) 2009-12-02 2010-12-02 多層フレキシブルプリント配線板の接着層形成用の樹脂組成物、樹脂ワニス、樹脂付銅箔、多層フレキシブルプリント配線板製造用の樹脂付銅箔の製造方法及び多層フレキシブルプリント配線板
KR1020127012372A KR101757411B1 (ko) 2009-12-02 2010-12-02 다층 플렉서블 프린트 배선판의 접착층 형성용 수지 조성물, 수지 바니시, 수지 부착 동박, 다층 플렉서블 프린트 배선판 제조용 수지 부착 동박의 제조 방법 및 다층 플렉서블 프린트 배선판

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102295740A (zh) * 2011-07-11 2011-12-28 复旦大学 聚酰胺酰亚胺固化的环氧树脂复合材料及其制备方法
CN103450836A (zh) * 2013-09-04 2013-12-18 九江福莱克斯有限公司 一种环保挠性导热环氧树脂胶黏剂及使用该胶黏剂制作的高导热挠性基材
CN103834342A (zh) * 2014-03-19 2014-06-04 天津科技大学 一种用于柔性印刷电路板的耐高温无卤阻燃胶粘剂
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
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
WO2015182161A1 (fr) * 2014-05-28 2015-12-03 東洋紡株式会社 Composition adhésive utilisant de la résine de polyamide-imide
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WO2015182161A1 (fr) * 2014-05-28 2015-12-03 東洋紡株式会社 Composition adhésive utilisant de la résine de polyamide-imide
TWI688314B (zh) * 2014-07-10 2020-03-11 南韓商三星電機股份有限公司 製造印刷電路板用的鍍樹脂金屬箔、印刷電路板以及製造上述的方法
JP2016016672A (ja) * 2014-07-10 2016-02-01 サムソン エレクトロ−メカニックス カンパニーリミテッド． 印刷回路基板の製造用樹脂付き金属箔、印刷回路基板及びその製造方法
JP2016113556A (ja) * 2014-12-16 2016-06-23 リンテック株式会社 ダイ接着用接着剤
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
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JP2019196473A (ja) * 2018-05-11 2019-11-14 サムスン エレクトロニクス カンパニー リミテッド プリント回路基板及びｉｃパッケージ用樹脂組成物、並びにこれを用いた製品
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TW201130909A (en) 2011-09-16
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