[go: up one dir, main page]

WO2008004399A1 - Composition de résine de liaison pour des substrats de résine fluorée et stratifiés à placage de métal obtenus à l'aide de la composition - Google Patents

Composition de résine de liaison pour des substrats de résine fluorée et stratifiés à placage de métal obtenus à l'aide de la composition Download PDF

Info

Publication number
WO2008004399A1
WO2008004399A1 PCT/JP2007/061562 JP2007061562W WO2008004399A1 WO 2008004399 A1 WO2008004399 A1 WO 2008004399A1 JP 2007061562 W JP2007061562 W JP 2007061562W WO 2008004399 A1 WO2008004399 A1 WO 2008004399A1
Authority
WO
WIPO (PCT)
Prior art keywords
fluororesin
metal
foil
metal foil
adhesive layer
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/JP2007/061562
Other languages
English (en)
Japanese (ja)
Inventor
Tetsuro Sato
Toshifumi Matsushima
Tetsuhiro Matsunaga
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
Application filed by Mitsui Mining and Smelting Co Ltd filed Critical Mitsui Mining and Smelting Co Ltd
Publication of WO2008004399A1 publication Critical patent/WO2008004399A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/386—Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • 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
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/034—Organic insulating material consisting of one material containing halogen
    • 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
    • H05K2201/015—Fluoropolymer, e.g. polytetrafluoroethylene [PTFE]
    • 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
    • H05K2201/0355—Metal foils

Definitions

  • Fluororesin substrate adhesive resin composition and metal-clad laminate obtained using the fluororesin substrate adhesive resin composition are fluororesin substrate adhesive resin composition and metal-clad laminate obtained using the fluororesin substrate adhesive resin composition
  • the present invention relates to a fluororesin substrate adhesive resin composition, a fluororesin substrate adhesive using the fluororesin substrate adhesive resin, and the fluororesin substrate adhesive.
  • the present invention relates to a metal-clad laminate, a printed wiring board, and a method for producing the metal-clad laminate.
  • a fluororesin substrate-adhesive resin composition which is an adhesive raw material having excellent adhesion to a fluororesin substrate, which is said to be difficult to obtain good adhesion even when bonded to a metal foil
  • the present invention relates to an adhesive for a fluororesin substrate using the fluororesin substrate-adhesive resin composition.
  • Patent Document 1 describes a dielectric obtained by combining a glass cloth having a low dielectric constant and a low dielectric loss tangent and a fluororesin, and an electrolytic copper foil formed on at least one principal surface of the dielectric.
  • a fluororesin copper-clad laminate having a characteristic of 1 (12 GHz) or less is disclosed. From this document, it can be understood that the fluororesin base material has excellent dielectric properties and is extremely useful as a material for constituting an insulating layer of a printed wiring board in a high frequency region.
  • Patent Document 2 In order to improve the adhesion between the fluororesin substrate and the metal foil, Patent Document 2 describes that a fluororesin adhesive impregnation is performed between the fluororesin-impregnated layer in which the fluororesin is impregnated and held in a glass cloth and the metal foil. A printed wiring board provided with a layer is disclosed. The fluororesin adhesion impregnated layer at this time is used to improve the adhesion between the metal foil and the fluororesin impregnated layer immediately below the metal foil by the anchor effect due to the resin characteristics, and to enhance the peel strength. .
  • the fluororesin adhesion impregnation layer preferably uses PTFE as the fluororesin of the fluororesin impregnation layer and PFA as the fluororesin of the fluororesin adhesion impregnation layer. That is, the fluororesin is combined with both the base material and the adhesive layer.
  • Patent Document 3 any one selected from polyallylsulfone, aromatic polysulfide, and aromatic polyether is used for the purpose of providing a wiring board that can be used with high reliability even under high-temperature and high-humidity conditions. Also disclosed is the use of a fluororesin composition comprising at least one thermoplastic resin and a fluororesin as an insulating layer constituting material of a printed wiring board.
  • Patent Document 4 does not improve the adhesion between the fluororesin substrate and the metal foil, but improves the adhesion between the fluororesin substrate and the conductor formed by the screen printing method.
  • the surface of the substrate on which the conductor wiring is to be formed is subjected to a roughening treatment, a plasma treatment, a roughening treatment, a plasma treatment, or a roughening treatment followed by a metal film coating by sputtering.
  • a printed wiring board characterized in that one of the treatments is subjected to one surface treatment.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2002-307611
  • Patent Document 2 WO01 / 003478
  • Patent Document 3 Japanese Patent Laid-Open No. 11 199738
  • Patent Document 4 WO2003 / 103352 Disclosure of the invention
  • copper foils manufactured by an electrolytic method or a rolling method have been widely used for the circuit formation.
  • This copper foil is usually subjected to a roughening treatment, an antifungal treatment, and a silane coupling agent treatment on the bonding surface.
  • a roughening treatment an antifungal treatment, and a silane coupling agent treatment on the bonding surface.
  • the adhesion between the fluororesin substrate and the copper foil is low, the chemical resistance and moisture absorption resistance against the etching solution and the like are remarkably deteriorated, making it impossible to form a fine pitch circuit.
  • the inventors of the present invention as a result of earnest research, formed an adhesive interface between the fluororesin base material and the metal foil using the resin composition described below, thereby producing a fluororesin-based printed wiring board. This greatly improved the peel strength of the circuit and made it possible to use a non-roughened metal foil. Therefore, the metal foil described below mainly means a non-roughened metal foil. The present invention will be described below.
  • Fluororesin substrate adhesive resin composition Fluororesin substrate adhesive resin according to the present invention
  • the composition is a resin composition for forming an adhesive layer for laminating a metal foil to a fluororesin substrate.
  • the resin composition is soluble in a solvent and has a hydroxyl group as a functional group in the molecule. 2 to 50 parts by weight of a polymer component having one or more of a carboxyl group and an amino group, and an epoxy resin having a boiling point of 200 ° C or higher and an amine epoxy resin curing agent having a boiling point of 200 ° C or higher. It is characterized by containing 50 parts by weight or more of an epoxy resin compound.
  • the polymer component is selected from the group consisting of a polybulassal resin, a phenoxy resin, an aromatic polyamide resin, a polyether sulfone resin, and a polyamideimide resin. It is preferable to use one or a mixture of two or more.
  • the epoxy resin having a boiling point of 200 ° C or higher is bisphenol A type epoxy resin, bisphenol F type epoxy resin, rubber-modified bis. It is preferable to use one or a mixture of two or more selected from the group of phenol A type epoxy resins and biphenyl type epoxy resins.
  • the amine-based epoxy resin curing agent may be an aromatic polyamine, a polyamide, or an epoxy resin or polyvalent rubonic acid that is polymerized or condensed. It is preferable to use one or more selected from the group of amine adducts obtained by the above method.
  • Adhesive for fluororesin base material is a resin adhesive used for bonding a metal foil to a fluororesin substrate, and the fluororesin base material It is obtained by adding an organic solvent to the adhesive resin composition and mixing it.
  • the adhesive for a fluororesin substrate according to the present invention is one solvent selected from the group consisting of methyl ethyl ketone, cyclopentanone, dimethylformamide, dimethylacetamide, and N-methylbivinylidone. Alternatively, it is preferable to use a mixed solvent thereof.
  • Metal foil with adhesive layer is a metal foil with an adhesive layer provided on the surface of the metal foil with an adhesive layer to the substrate, the adhesive layer comprising the fluororesin. It is formed using a resin adhesive for substrates.
  • the adhesive layer has a thickness of 0. ⁇ ⁇ ⁇ ⁇
  • the adhesive layer of the metal foil with an adhesive layer has a resin flow when measured according to MIL-P-13949G in the MIL standard.
  • the metal foil is copper foil, nickel foil, tin foil, gold foil, silver foil, platinum foil, iron foil, cobalt foil, copper alloy foil, nickel alloy foil. It is preferable to use any of the following strengths: a soot alloy foil, a gold alloy foil, a silver alloy foil, a platinum alloy foil, an iron alloy foil, and a cobalt alloy foil.
  • Metal-clad laminate is a metal-clad laminate obtained by adhering a metal layer to the surface of a fluororesin substrate via an adhesive layer, and the adhesive layer includes: It contains the said resin composition, It is characterized by the above-mentioned.
  • the metal-clad laminate according to the present invention is a metal-clad laminate obtained by attaching a metal layer to the surface of a fluororesin substrate via an adhesive layer, and the adhesive layer includes the fluororesin It is formed using the adhesive agent for base materials.
  • the printed wiring board according to the present invention is obtained by etching and etching the metal foil of the metal-clad laminate.
  • Method for producing metal-clad laminate The method for producing a metal-clad laminate according to the present invention is characterized by the following steps A-1 to C1, and for convenience of explanation, Hereinafter referred to as “first manufacturing method”.
  • Step A1 A step of applying an activation treatment to the bonding surface of the fluororesin base material to the metal foil.
  • Process C 1 A process for forming a metal-clad laminate by hot-pressing the adhesive layer surface of the metal foil with an adhesive layer in contact with the laminated surface subjected to the activation treatment of the fluororesin base material .
  • the method for producing a metal-clad laminate according to the present invention includes the following steps A-2 to C: It is also possible to adopt one characterized by going through 2. For convenience of explanation, it is hereinafter referred to as “second manufacturing method”.
  • Step A-2 A step of applying an activation treatment to the bonding surface of the fluororesin base material to the metal foil.
  • Step B-2 Prepare a fluororesin substrate adhesive, apply this fluororesin substrate adhesive to the surface of the releasable plastic film, and dry it.
  • Step C2 The semi-cured resin layer of the adhesive layer with a releaseable plastic film is brought into contact with the laminated surface subjected to the activation treatment of the fluororesin base material, and is temporarily bonded to each other, and the releaseable plastic film The step of peeling off and leaving the semi-cured resin layer on the surface of the fluororesin substrate.
  • Step D-2 A step of forming a metal-clad laminate by laminating a metal foil on the surface of the semi-cured resin layer provided on the surface of the fluororesin substrate in Step C2 and hot pressing it.
  • the method for producing a metal-clad laminate according to the present invention includes the following steps A-3 to C:
  • Step A—3 A step of applying an activation treatment to the bonding surface of the metal foil of the fluororesin substrate.
  • Step B-3 Step of preparing an adhesive for a fluororesin substrate.
  • Step C3 Applying the adhesive for the fluororesin base material prepared in Step B-3 to the activated surface of the fluororesin base material and drying it, 0.5 111 to 3111 half thickness A step of forming a cured resin layer.
  • Step D-3 A step of forming a metal-clad laminate by laminating a metal foil on the surface of the semi-cured resin layer provided on the surface of the fluororesin substrate in Step C3 and hot pressing it.
  • the fluororesin substrate-adhesive resin composition according to the present invention has no roughening relative to the fluororesin substrate. It is suitable for forming an adhesive layer when laminating metal foil, and it significantly improves the adhesion between the fluororesin base material and non-roughened metal foil, and the circuit when subjected to a heat shock. The delamination phenomenon can be effectively prevented.
  • an adhesive layer is to be formed with this fluororesin substrate adhesive resin composition
  • an organic solvent is added to the fluororesin substrate resin composition to provide an optimal resin flow suitable for layer formation.
  • the resin solid content can be obtained and can be used as an adhesive for a fluororesin substrate.
  • the metal foil it is easy to form an adhesive layer on the surface of the metal foil using the resin adhesive for a fluororesin substrate, and it is possible to provide a metal foil with an adhesive layer for a fluororesin substrate.
  • the best adhesion to the fluororesin substrate can be obtained by setting the thickness of the adhesive layer to a semi-cured resin layer of 0.5 m to 3 m.
  • various non-roughened metal foils can be used as the metal foil, and the metal foil can be widely used without being limited to printed wiring board applications.
  • the adhesive layer is interposed, the press temperature during hot pressing can be lowered, and the production cost can be reduced.
  • the adhesion between the fluororesin base material and the metal layer can be more stably improved by applying an activation treatment to the bonded surface of the metal foil of the fluororesin base material in advance.
  • the resin composition for adhesion of a fluororesin substrate according to the present invention is (1) soluble in a solvent and has a hydroxyl group or a carboxyl group in the molecule as a functional group. 2 to 50 parts by weight of a polymer component having one or more amino groups, (2) an epoxy resin having a boiling point of 200 ° C or higher and an amine epoxy resin curing agent having a boiling point of 200 ° C or higher It contains 50 parts by weight or more of a resin blend. here Then, it is a case where the sum total of the said polymer component and an epoxy resin compound is 100 weight part.
  • a polymer component that is soluble in a solvent and has one or more of a hydroxyl group, a carboxyl group, and an amino group in a molecule as a functional group (hereinafter simply referred to as “polymer component”). Is preferably a mixture of one or two or more selected from the group consisting of a polybulacetal resin, a phenoxy resin, an aromatic polyamide resin, a polyethersulfone resin, and a polyamideimide resin.
  • the polymer component here is required to have the property of being soluble in a solvent. If not possible, it will be difficult to adjust the solid content using a solvent.
  • the polymer component strength is less than 3 parts by weight, the hardness after press molding of the copper clad laminate becomes high and brittle, so that toughness cannot be obtained.
  • the polymer component exceeds 50 parts by weight, the heat resistance is lowered, and it becomes impossible to withstand the press molding temperature of the copper clad laminate, thereby causing resin deterioration. More preferably, the polymer component is 2 to 30 parts by weight. The heat resistance and flexibility as the cured resin are the best.
  • Epoxy resin having a boiling point of 200 ° C or higher is selected from the group of bisphenol A type epoxy resin, bisphenol F type epoxy resin, rubber-modified bisphenol A type epoxy resin, and biphenyl type epoxy resin. It is preferable to use one kind or a mixture of two or more kinds.
  • a linear (bifunctional) epoxy resin By using a linear (bifunctional) epoxy resin, the adhesion between the fluororesin substrate and the metal foil can be increased. Therefore, the total of the “epoxy resin having a boiling point of 200 ° C or higher” and the “amine-based epoxy resin curing agent having a boiling point of 200 ° C or higher”, which is the main component of this resin composition, is called an epoxy resin compound, and this is 50 weight.
  • epoxy resin curing agent if it is only intended to be cured, amines such as dicyandiamide, imidazoles and aromatic amines, phenols such as bisphenol A and bisphenol A bromide A, etc. All kinds of curing agents such as phenols, phenolic nopolac resins and cresol novolac resins, etc. and acid anhydrides such as phthalic anhydride That power S. However, it is most preferable to use an amine epoxy resin curing agent having a boiling point of 200 ° C. or higher from the viewpoint of significantly improving the adhesion between the fluororesin substrate and the metal foil.
  • the epoxy resin curing agent will boil due to the press molding, and bubbles are likely to be generated in the cured insulating resin layer. .
  • the most stable adhesion can be obtained when an amine epoxy resin curing agent is used to form an adhesive layer between the fluororesin substrate and the metal foil. That is, the “amine-based epoxy resin curing agent having a boiling point of 200 ° C. or higher” is selected from the group of aromatic polyamines, polyamides, and amine adducts obtained by polymerizing or condensing these with epoxy resins or polyvalent carboxylic acids. The case where one kind or two or more kinds are used.
  • the curing accelerator is a tertiary amine, imidazole, urea curing accelerator or the like.
  • the mixing ratio of the curing accelerator is not particularly limited. This is because the curing accelerator is a good one that the manufacturer arbitrarily determines the amount of addition in consideration of the heating conditions during the press working.
  • a rubbery resin to the resin composition referred to in the present invention.
  • the rubbery resin mentioned here 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 and the like.
  • heat resistance it is also useful to selectively use heat-resistant synthetic rubbers such as nitrile rubber, chloroprene rubber, silicon rubber and urethane rubber.
  • the above-mentioned polymer polymer crosslinking agent is added as necessary.
  • the urethane resin is used as a cross-linking material.
  • the epoxy resin is 50 parts by weight to 80 parts by weight
  • the curing agent is 1 part by weight.
  • curing accelerator 0.01 parts by weight 1.0 parts by weight
  • cross-linking agent 1 part by weight to 5 parts by weight rubber resin 1 part by weight
  • Form of Fluororesin Substrate Adhesive Generally, it is difficult to use the resin composition for adhering a fluororesin base as it is to form an adhesive layer. Therefore, an organic solvent is added to and mixed with the fluororesin substrate adhesive resin composition and used as an adhesive for a fluororesin substrate.
  • the resin solid content is preferably adjusted to 10 wt% to 40 wt%. When the resin solid content is less than 10 wt%, the viscosity is too low, and even if a resin film for forming an adhesive layer is formed, it flows immediately after coating and it is difficult to ensure film thickness uniformity. On the other hand, when the resin solid content exceeds 40 wt%, it becomes difficult to form a thin resin film with high viscosity.
  • any one of methyl ethyl ketone, cyclopentanone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, one solvent or a mixed solvent thereof should be used.
  • a solvent that can dissolve the resin composition is selected.
  • methyl ethyl ketone and / or cyclopentanone is used as a solvent, it is easy to efficiently volatilize and remove by heat at the time of press working in the production of a metal laminate, and also easy to purify volatile gas.
  • the mixing ratio is not particularly limited. However, when methyl ethyl ketone is used as a co-solvent for cyclopentanone, the rate of volatilization removal is preferred. Les.
  • the resin solid content of the resin solution is preferably 10 wt% to 40 wt% for the same reason.
  • the metal foil with an adhesive layer according to the present invention has a metal foil 4 with an adhesive layer provided with an adhesive layer 3 for a substrate on the surface of the metal foil 2.
  • the adhesive layer is formed by using the resin adhesive for a fluororesin substrate. This forming method will be described later.
  • the adhesive layer is a semi-cured resin layer having a thickness of 0.
  • it if it is not a semi-cured resin layer, it will not be reflowed by hot pressing, so that the fluororesin substrate and the metal foil cannot be bonded together.
  • the reason why the thin resin layer is formed in this way is to reliably create a state in which the resin flow described below hardly occurs at the time of pressing.
  • the thickness of this adhesive layer is less than 0. ⁇ ⁇ , it is difficult to make the thickness uniform, and it is difficult to leave a resin layer having a uniform thickness between the fluororesin substrate and the metal foil.
  • the peel strength varies greatly.
  • the thickness of the adhesive layer exceeds, the good electrical properties of the fluororesin substrate are deteriorated. Note that the thickness of the adhesive layer is a converted thickness when it is assumed that the resin is applied to a completely flat surface per lm 2 .
  • the adhesive layer of the metal foil with an adhesive layer has a resin flow of 5% or less when measured according to MIL-P-13949G in the MIL standard. It is preferable to have characteristics. Unless the resin flow force is within this range, good adhesion between the fluororesin substrate and the metal foil cannot be obtained. The lower limit is not specified, but it is about 1%. Regarding the resin flow, the thickness of the adhesive layer and the resin solid content of the resin adhesive for the fluororesin substrate used when forming the adhesive layer are factors that determine the characteristics. Of course, resin flow is important. Usually, when laminating a metal foil and a fluororesin substrate, air stagnation may occur at the interface.
  • the copper clad laminate Taking the case of manufacturing as an example, a resin flow of about 5mm to 5mm from the end is intentionally caused by an lm 2 size copper clad laminate that also serves as an air vent.
  • the fact that this resin flow hardly occurs is an important factor for ensuring good adhesion between the fluororesin base material and the metal foil.
  • the resin flow is determined by the value measured according to MIL-P-13949G of the MIL standard.
  • the adhesive layer is intentionally formed on the surface of the electrolytic copper foil with a thickness of 40 m, and four 10 cm square samples are manufactured.
  • the four 10cm square samples are stacked and bonded together under the conditions of a press temperature of 171 ° C, a press pressure of 14kgf / cm 2 and a press time of 10 minutes, and the resin flow at that time is calculated and calculated according to Equation 1. It was. Note that the resin flow of a normal resin-prepared copper foil (40 11 m thick resin layer) is about 20% when using a normal pre-preda.
  • the metal foil is a copper foil, a nickel foil, a tin foil, a gold foil, a silver foil, a platinum foil, an iron foil, a cobalt foil, a copper alloy foil, or a nickel alloy foil. It is preferable to use any of the following strengths: a soot alloy foil, a gold alloy foil, a silver alloy foil, a platinum alloy foil, an iron alloy foil, and a cobalt alloy foil. That is, it is described with the concept of all metal foils that can be used for electronic materials. All of the metal foils may be obtained by an electrolytic method, obtained by a rolling method, or obtained by a physical vapor deposition method, regardless of the production method. Moreover, there is no special limitation regarding the thickness.
  • adhesion can be further improved by subjecting the surface of the metal foil to an antifouling treatment, a silane coupling agent treatment, or the like.
  • the metal foil used in the present invention is intended for the one that omits the roughening treatment.
  • the roughening treatment means that the surface of the metal foil is fine.
  • the generally known roughening treatment is a roughening treatment performed by depositing and forming fine copper grains applied to the electrolytic copper foil and the rolled copper foil.
  • the antifungal treatment referred to here is appropriately selected according to the type of the fluororesin substrate and is not particularly limited.
  • As the antifouling treatment either an organic antifouling using benzotriazole, imidazole or the like, or an inorganic fender using zinc, chromate, zinc alloy, nickel alloy or the like may be adopted.
  • organic fenders techniques such as dip coating, showering and electrodeposition of organic fenders can be employed.
  • an inorganic barrier it is possible to use a method in which the barrier element is deposited on the surface of the copper foil by electrolysis, or a so-called substitution deposition method.
  • the anti-bacterial treatment layer is not particularly described and omitted.
  • the silane coupling agent treatment is carried out using one or two or more of amino-based silane coupling agent, epoxy-based silane coupling agent, and mercapto-based silane coupling agent. It is common.
  • various types such as the most common epoxy functional silane coupling agent, olefin functional silane, acrylic functional silane, etc. can be used as the silane coupling agent.
  • an amino functional silane coupling agent or a mercapto functional silane coupling agent because the adhesion between the fluorine resin substrate and the metal foil can be further improved. It has been said that the higher the peel strength of printed circuit boards, the better.
  • silane coupling agents will be described more specifically. Mainly coupling agents similar to those used for prepreda glass cloth for printed wiring boards, buttrimethoxysilane, butenyltrimethoxylane, ⁇ -methacryloxyprovir trimethoxy Silane, ⁇ -Aminopropyltriethoxysilane, ⁇ — ⁇ (aminoethyl) ⁇ —Aminopropyltrimethoxysilane, ⁇ —3— (4- (3-Aminopropoxy) ptoxy) propyl 3-aminopropyl trimethoxy Silane, imidazole silane, triazine silane, ⁇ mercaptopropyltrimethoxysilane, and the like can be used.
  • the method for treating the silane coupling agent is not particularly limited, such as a commonly used dipping method, showering method, spraying method or the like.
  • a method that allows the metal foil and the solution containing the silane coupling agent to be brought into contact and adsorbed most uniformly can be arbitrarily adopted.
  • the silane coupling agent is used at a temperature of room temperature by dissolving 0.5 to 10 g / l in water as a solvent.
  • the silane coupling agent concentration is less than 0.5 g / l, the adsorption rate of the silane coupling agent is not suitable for the general commercial basis, and the adsorption is not uniform. Even if the concentration exceeds lOg / 1, the adsorption rate is not particularly high, which is uneconomical.
  • the silane coupling agent-treated layer is not particularly described and is omitted.
  • the metal-clad laminate according to the present invention is a metal-clad laminate obtained by attaching a metal layer to the surface of a fluororesin substrate via an adhesive layer, and the adhesive layer Includes the above resin composition. Further, the adhesive layer is formed using the fluororesin substrate adhesive.
  • Fig. 2 shows the cross-sectional configuration of the metal-clad laminate according to the present invention.
  • Fig. 2 (a) shows a single-sided metal-clad laminate la
  • Fig. 2 (b) shows a double-sided metal-clad laminate lb
  • Fig. 2 (c) shows a 4-layer metal-clad laminate with an inner circuit 9 inside. lc is shown.
  • the metal-clad laminate according to the present invention is a state in which the metal foil 2 is bonded to the outer layer that is not related to the layer structure, and the inner layer includes the fluororesin base layer 5 and includes the metal foil.
  • a laminate having an adhesive layer 3 between 2 and a fluororesin substrate layer 5 is referred to.
  • FIG. 2 (c) briefly describes a method of manufacturing the four-layer metal-clad laminate lc provided with the inner layer circuit 9 therein.
  • the double-sided printed wiring board 21 is formed by etching the metal layers on both sides of the double-sided metal-clad laminate lb shown in FIG. Then, using a double-sided printed wiring board 21 and a pre-preda 22 such as FR-4, etc., the four-layer metal-clad laminate lc is obtained by laminating as shown in FIG. 3 and hot pressing.
  • the fluororesin base material referred to here is PTFE (polytetrafluoroethylene (tetrafluoride)), PFA (tetrafluoroethylene 'perfluoroalkyl butyl ether copolymer), FEP (tetrafluoroethylene.hexafluoropropylene copolymer (4.6 hexafluoride)), ETFE (tetrafluoroethylene.ethylene copolymer), PVDF (polyvinylidene fluoride (2 fluorine)) )), PCTFE (polychlorinated trifluoroethylene (trifluoride)), and at least any one selected from polyallylsulfone, aromatic polysulfide and aromatic polyether as disclosed in Patent Document 3.
  • PTFE polytetrafluoroethylene
  • PFA tetrafluoroethylene 'perfluoroalkyl butyl ether copolymer
  • FEP tetrafluoroethylene.hexafluoropropylene
  • the printed wiring board according to the present invention is obtained by etching the metal foil of the metal-clad laminate.
  • the etching process at this time is not particularly limited, an etching resist layer is provided on the surface of the metal foil, the etching pattern is exposed and developed, the resist pattern is formed, and an etching solution capable of dissolving the constituent metal components of the metal foil.
  • the circuit etching is performed.
  • Step A-1 In this step, an activation treatment is applied to the bonding surface of the metal foil of the fluororesin substrate.
  • the activation treatment referred to here is performed to improve the adhesion between the fluororesin substrate and the adhesive layer, and as a result, improve the adhesion of the metal foil to the surface of the fluororesin substrate.
  • this activation treatment is roughening treatment, plasma treatment, or a combination treatment combining them.
  • a wet or dry blast method, a wet etching method, a dry etching method, or the like can be used.
  • a wet etching roughening process using a chemical technique often employs a technique called sodium etching.
  • the roughened surface formed by this roughening treatment preferably has an average roughness (Ra) of 20 nm to 100 nm! /.
  • This average roughness (Ra) is less than 20nm In this case, the adhesion between the fluororesin substrate and the adhesive layer cannot be improved.
  • the average roughness (Ra) exceeds lOOnm, the effect of improving the adhesion between the fluororesin substrate and the adhesive layer due to the roughening does not increase further.
  • the plasma treatment is a treatment in which a plasma stream is generated with an inert gas such as nitrogen gas or argon gas, and the surface of the fluororesin substrate is brought into contact with the plasma stream.
  • the inert gas is decompressed and introduced into the atmosphere, a pair of flat plate electrodes are arranged in parallel, a voltage is applied between the electrodes to generate a plasma stream, and a fluororesin substrate is placed in the plasma stream. Put in and process for a certain time.
  • a plasma stream is generated between the high-frequency electrodes and the like, and a fluororesin substrate is placed in the plasma stream and processed for a certain period of time.
  • the input power (W) and the electrode area (cm 2) power density is calculated from the (W / cm 2) is 0. 05W / cm 2 ⁇ ; IW / If cm 2 is used, a processing time of 30 seconds to 1 minute is adopted. This plasma treatment time does not significantly improve the adhesion between the fluororesin substrate and the metal foil even if it is unnecessarily long.
  • FIG. 5 (a) conceptually shows the activated fluororesin substrate 5.
  • Step B-1 In this step, an adhesive for a fluororesin substrate is prepared, and this adhesive for a fluororesin substrate is applied to the surface of the metal foil and dried, so that the surface of the metal foil is coated.
  • a metal foil with an adhesive layer is produced by forming a semi-cured resin layer having a thickness of 0.5 to 111 m. The preparation of the fluororesin substrate adhesive is as described above.
  • the adhesive for a fluororesin base material is applied to the surface of the metal foil 2 and dried, so that a 0.5 m to 3 m thick semi-cured resin layer (drawing) is formed on the surface of the metal foil 2.
  • the metal foil 4 with an adhesive layer shown in FIG. 5 (b) is manufactured by forming the “simply shown as“ adhesive layer 3 ””.
  • Step C 1 In this step, as shown in FIG. 5 (c), the bonded surface subjected to the activation treatment of the fluororesin substrate in Step A-1 is obtained in Step B-1.
  • the metal-laminated laminate la shown in FIG. 5 (d) is obtained by laminating the adhesive layer 3 of the metal foil 4 with the adhesive layer in contact with each other and performing hot press molding. There is no particular limitation on the hot pressing conditions at this time. However, in the case of the manufacturing method according to the present invention, in the press working using a conventional fluororesin substrate
  • Pressing force of 260 ° C to 400 ° C or so has been adopted, and press working at a low temperature of around 200 ° C (190 ° C to 220 ° C) is possible. Therefore, there is an advantage that the manufacturing cost can be reduced because the heat energy required for press working is low. The same applies hereinafter.
  • the second method for producing a metal-clad laminate according to the present invention is characterized by going through the following steps A-2 to C2.
  • Step IV-2 In this step, activation treatment is performed on the bonding surface of the metal foil of the fluororesin substrate, which is the same as in the case of the first manufacturing method. Therefore, the description is omitted.
  • FIG. 6 (a) conceptually shows the activated fluororesin substrate 5.
  • Step B-2 In this step, the fluororesin base material adhesive is prepared by the above-described method, and the fluororesin base material adhesive is applied to the surface of the releasable plastic film 7 and dried.
  • the releasable plastic film and a semi-cured resin layer having a thickness of 0 ⁇ 5 111 to 3 111 shown simply as “adhesive layer 3” in the drawing)
  • An adhesive layer 8 with a releasable plastic film is produced in a laminated state.
  • the releasable plastic film is used in the sense of selectively using a film having releasability, and there is no particular limitation on the material, thickness, and the like. Specifically, it is preferable to use a PET film, a thermoplastic fluororesin film, a polyimide resin film, or the like. At this time, with respect to the method of applying the adhesive for the fluororesin base material to the releasable plastic film, an edge coater, a comma coater, a Daravia coater, etc. that are not particularly limited can be used.
  • Step C 2 In this step, as shown in FIG. 6 (c), the semi-cured resin of the adhesive layer 8 with the releasable plastic film is applied to the bonded surface on which the fluororesin substrate 5 has been activated.
  • the layers shown simply as “adhesive layer 3” in the drawing) are brought into contact with each other and are temporarily bonded together, and the releasable plastic film 7 is peeled and removed.
  • Step D-2 In this step, the metal foil 2 is laminated on the surface of the semi-cured resin layer provided on the surface of the fluororesin substrate in Step C2, as shown in FIG.
  • the metal-clad laminate la shown in Fig. 6 (e) is formed by press forming.
  • the third method for producing a metal-clad laminate according to the present invention includes the following steps A-3 to It is characterized by passing C3.
  • Step A-3 In this step, an activation treatment is performed on the bonding surface of the metal foil of the fluororesin substrate, which is the same as in the case of the first manufacturing method. Therefore, the description is omitted.
  • FIG. 7 (a) conceptually shows the activated fluororesin substrate 5.
  • Step B-3 In this step, an adhesive for a fluororesin substrate is prepared. Therefore, since the explanation about this adjustment is as described above, the duplicate explanation here is omitted.
  • Step C 3 In this step, the fluororesin base material adhesive prepared in Step B is applied to the activated surface of the fluororesin base material 5 and dried, so that FIG. )
  • a semi-cured resin layer (shown simply as “adhesive layer 3” in the drawing) having a thickness of 0.5 m to 3 m is formed.
  • an edge coater, a comma coater, a gravure coater, or the like that has special limitations can be used.
  • Step D-3 In this step, a metal foil is formed on the surface of the semi-cured resin layer (shown as "adhesive layer 3" in the drawing) provided on the surface of the fluororesin substrate 5 in Step C3.
  • the metal-clad laminate la shown in Fig. 7 (c) is obtained.
  • Step A1 In this step, an activation treatment was performed on the laminated surface of the metal foil of a PTFE fluororesin base material (manufactured by Yodogawa Hitec Co., Ltd.) having a thickness of 0.6 mm.
  • a PTFE fluororesin base material manufactured by Yodogawa Hitec Co., Ltd.
  • the metal sodium treatment at this time is performed by extracting fluorine atoms from the surface of the fluororesin substrate by the action of metal sodium or a sodium complex, and generating hydroxyl groups, carbonyl groups, or force loxyl groups on the surface. This is intended to activate the surface of the material.
  • a tetra-etch treatment solution manufactured by Junye Co., Ltd. was used.
  • Step B-1 Here, 69 parts by weight of epoxy resin, 11 parts by weight of curing agent, 0.2 part by weight of curing accelerator, 15 parts by weight of polymer component, 3 parts by weight of crosslinking agent, 3 parts by weight of rubbery resin A resin composition for adhering a part of the fluorine resin substrate was prepared. Specifically, it is shown in Table 1 below.
  • the resin composition shown in Table 1 was adjusted to a resin solid content of 30% by weight using methyl ethyl ketone and dimethylacetamide to obtain an adhesive for a fluororesin substrate. Then, using a gravure coater, this non-roughened electrolytic copper foil (thickness: 18 m, flaw-proofing treatment layer: zinc-nickel alloy layer, silane-bonding agent treatment: ( ⁇ -aminopropyltriethoxysilane) was applied to the bonding surface. Then air-dry for 5 minutes and then dry for 3 minutes in a heated atmosphere at 140 ° C to form a semi-cured 1.5 ⁇ 111 thick semi-cured resin layer (adhesive layer).
  • a metal foil 4 with an adhesive layer shown in FIG. 5 (b) was produced.
  • the resin flow of the semi-cured resin layer (adhesive layer) obtained at this time was measured with the above-mentioned adhesive for a fluororesin base material.
  • a copper foil provided on one side was manufactured and used as a resin flow measurement sample.
  • four 10 cm square samples were collected from the resin flow measurement sample, and the resin flow was measured in accordance with the above-mentioned MIL-P-13949G. As a result, the resin flow was 1.5%.
  • Step C 1 In this step, as shown in FIG. 5 (c), the three samples obtained in Step A-1
  • the adhesive layer 3 of the metal foil 4 with the adhesive layer obtained in Step B-1 is brought into contact with the bonded surface of the fluororesin base material (Sample 1, Sample 2, Sample 3) that has been activated.
  • the peel strength between the fluororesin substrate and the copper foil circuit was measured.
  • Table 2 shows the results.
  • the peel strength referred to in this specification is the strength when the copper foil circuit is peeled from the base material in the 90 ° direction (perpendicular to the substrate).
  • the normal peel strength is the peel strength measured without any treatment immediately after manufacturing the circuit by etching as described above.
  • the peel strength after heating is the peel strength measured after floating in a solder bath at 260 ° C for 20 seconds and then cooled to room temperature.
  • Step A-2 Since this step is the same as that of Example 1, it is omitted. Therefore, three types of fluororesin base material, sample: [, sample 2 and sample 3 were also produced here.
  • Fig. 6 (a) conceptually shows the activated fluororesin base material 5.
  • Step B-2 This step uses the same fluororesin substrate adhesive prepared in Example 1, and uses this fluororesin substrate adhesive as a releasable plastic film 7.
  • Fig. 6 (b) shows that the coating is applied to the surface using a nolem using a gravure coater, air-dried for 5 minutes, and then dried in a heated atmosphere at 140 ° C for 3 minutes.
  • an adhesive layer 8 with a release plastic film in which the release plastic film and a 1.5 ⁇ semi-cured resin layer (in the drawing, simply indicated as “adhesion layer 3”) are laminated is manufactured. did.
  • Step C 2 In this step, the semi-cured resin of the adhesive layer 8 with a releasable plastic film as shown in FIG. 6 (c) is applied to the bonded surface of the fluororesin substrate 5 that has been activated. layer (In the drawing, it is simply indicated as “adhesive layer 3”). The layers were brought into contact with each other and temporarily bonded by applying moderate pressure, and the releasable plastic film 7 was peeled and removed.
  • Step D-2 In this step, the same roughened copper foil (metal foil) as used in Example 1 was formed on the surface of the semi-cured resin layer provided on the surface of the fluororesin substrate in Step C2. As shown in Fig. 6 (d), two layers are laminated and hot press-molded at 200 ° CX for 60 minutes at a pressure of 32 kgf / cm 2 , resulting in three types of layer structure (Fig. 6 (e)) ( CL2-1, CL2 2, CL2 3) metal-clad laminate la.
  • Step A-3 Since this step is the same as that of Example 1, it is omitted. Therefore, three types of fluororesin base material, sample: [, sample 2 and sample 3 were also produced here.
  • FIG. 7 (a) conceptually shows the fluororesin substrate 5 that has been activated.
  • Step B-3 In this step, the same adhesive for a fluororesin substrate as that prepared in Example 1 was prepared.
  • Step C 3 In this step, the fluororesin substrate adhesive prepared in Step B 3 is applied to the activated surface of the fluororesin substrate 5, air-dried for 5 minutes, and then 140 By drying for 3 minutes in a heated atmosphere at ° C, as shown in Fig. 7 (b), a 1.5-thickness semi-cured resin layer (shown as "adhesive layer 3" in the drawing) .) was formed. Application of the adhesive for the fluororesin substrate at this time was performed using an edge coater.
  • Step D-3 Here, on the surface of the semi-cured resin layer (shown simply as "adhesive layer 3" in the drawing) provided on the surface of the fluororesin substrate 5 in Step C3, 18 111 By laminating the same copper foil (metal foil) 2 as used in Example 1 of thickness and hot press forming at a pressure of 32 kgf / cm 2 at 200 ° C for 60 minutes, Fig. 7 (c) Three types (CL3-1, CL3-2, CL3-3) of metal-clad laminate la having the layer structure shown were used.
  • the hydrochloric acid resistance deterioration rate is within 5%, and the moisture resistance deterioration rate is within 10%.
  • the hydrochloric acid resistance deterioration rate is around 10% and the moisture resistance deterioration rate is 15% or more, even if unroughened metal foil is used, In addition, it can be said that the adhesion between the fluororesin substrate and the metal foil is improved.
  • the non-roughened metal foil and the fluororesin base material show very high adhesion, and the circuit delamination phenomenon when subjected to heat shock, etc. It can be effectively prevented and a fluororesin copper-clad laminate and a fluororesin printed wiring board can be provided.
  • a non-roughened metal foil can be used, a fine pitch pattern can be easily formed even when a circuit is formed by an etching method. Therefore, low dielectric loss It has excellent high frequency characteristics related to dielectric properties such as loss and low dielectric constant, crosstalk characteristics, etc., other heat resistance and durability, excellent adhesion between the circuit and the substrate, and high fine pitch pattern.
  • the method for producing a metal-clad laminate according to the present invention does not require a new device, can use conventional equipment, and can be pressed at a low temperature. Inexpensive.
  • FIG. 1 is a schematic cross-sectional view showing a layer structure of a metal foil with an adhesive layer according to the present invention.
  • FIG. 2 is a schematic cross-sectional view showing an example of a layered composition of a metal-clad laminate according to the present invention.
  • FIG. 3 is a schematic diagram showing an image of manufacturing a multilayer printed wiring board.
  • FIG. 4 is a schematic view showing an image of manufacturing a multilayer printed wiring board.
  • FIG. 5 is a flowchart for explaining a manufacturing process of a metal-clad laminate according to the present invention.
  • FIG. 6 is a flowchart for explaining a manufacturing process of a metal-clad laminate according to the present invention.
  • FIG. 7 is a flowchart for explaining a manufacturing process of a metal-clad laminate according to the present invention.

Landscapes

  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention vise à proposer une technique qui apporte un perfectionnement remarquable, par l'utilisation de moyens plus faciles, dans l'adhésion étroite d'un substrat de résine fluorée et d'une feuille de métal qui n'en est pas rendue plus grossière, et qui permet la formation de circuits à fins écartements. L'objectif peut être atteint par l'utilisation, comme composition de résine pour former la couche de liaison pour une liaison adhésive d'une feuille de métal à un substrat de résine fluorée, d'une composition de résine de liaison pour substrats de résine fluorée qui est caractérisée par le fait qu'elle comprend 2 à 20 parties en poids d'un composant polymère soluble dans un solvant, portant une ou plusieurs sortes de groupes fonctionnels choisis parmi l'hydroxyle, le carboxyle et l'amino dans la molécule et au moins 50 parties en poids d'un composé de résine époxy consistant en une résine époxy ayant un point d'ébullition de 200 °C ou au-dessus et un agent de durcissement de type amine pour des résines époxy qui a un point d'ébullition de 200 °C ou au-dessus. L'invention concerne également des adhésifs pour substrats de résine fluorée qui contiennent la composition de résine ; une feuille de métal recouvert d'adhésif (4) qui est un stratifié constitué d'une feuille de métal (2) et d'une couche de liaison (3) ; des stratifiés à placage de cuivre obtenus par l'utilisation de la composition ; et un procédé pour la fabrication de stratifiés.
PCT/JP2007/061562 2006-06-07 2007-06-07 Composition de résine de liaison pour des substrats de résine fluorée et stratifiés à placage de métal obtenus à l'aide de la composition Ceased WO2008004399A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2006-158092 2006-06-07
JP2006158092A JP2007326923A (ja) 2006-06-07 2006-06-07 フッ素樹脂基材接着用樹脂組成物及びそのフッ素樹脂基材接着用樹脂組成物を用いて得られる金属張積層板

Publications (1)

Publication Number Publication Date
WO2008004399A1 true WO2008004399A1 (fr) 2008-01-10

Family

ID=38894372

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2007/061562 Ceased WO2008004399A1 (fr) 2006-06-07 2007-06-07 Composition de résine de liaison pour des substrats de résine fluorée et stratifiés à placage de métal obtenus à l'aide de la composition

Country Status (2)

Country Link
JP (1) JP2007326923A (fr)
WO (1) WO2008004399A1 (fr)

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010194930A (ja) * 2009-02-26 2010-09-09 Sumitomo Bakelite Co Ltd 絶縁層付支持材料の製造方法、絶縁層付支持材料、プリント配線板および絶縁層付支持材料の製造装置
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
EP3339016A4 (fr) * 2015-08-20 2019-05-01 AGC Inc. Base multicouche et procédé de production de corps moulé associé
CN112048249A (zh) * 2020-09-02 2020-12-08 江西省信合新材料科技有限公司 一种柔性线路板用多层保护膜
US11549035B2 (en) 2020-12-16 2023-01-10 Saint-Gobain Performance Plastics Corporation Dielectric substrate and method of forming the same
US11596064B2 (en) 2020-07-28 2023-02-28 Saint-Gobain Performance Plastics Corporation Dielectric substrate and method of forming the same
WO2023100499A1 (fr) * 2021-12-03 2023-06-08 ニッカン工業株式会社 Composition de résine, coverlay l'utilisant, feuille adhésive, feuille métallique fixée à une résine, stratifié plaqué de métal ou carte imprimée
US12173201B2 (en) 2020-12-16 2024-12-24 Versiv Composites Limited Copper-clad laminate and method of forming the same
US12262468B2 (en) 2020-07-28 2025-03-25 Versiv Composites Limited Copper-clad laminate and method of forming the same
TWI879482B (zh) * 2024-03-07 2025-04-01 國立清華大學 帶載體超薄銅箔及其製造方法
US12391850B2 (en) 2020-12-16 2025-08-19 Versiv Composites Limited Dielectric substrate and method of forming the same

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014192718A1 (fr) * 2013-05-31 2014-12-04 住友電気工業株式会社 Corps composite métal et résine, matériau de câblage, et procédé de production de corps composite métal et résine
JP6332787B2 (ja) * 2014-02-17 2018-05-30 住友電工プリントサーキット株式会社 カバーレイ及びプリント配線板
KR102122938B1 (ko) * 2019-12-30 2020-06-15 (주)아이피아이테크 연성동박적층필름용 본드 플라이층 및 그 제조 방법

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07286155A (ja) * 1994-02-22 1995-10-31 Japan Energy Corp 金属箔張積層板用接着剤及びそれを用いた金属箔張積層板
WO2001003478A1 (fr) * 1999-07-05 2001-01-11 Nippon Pillar Packing Co., Ltd. Circuit imprimé et son pré-imprégné
JP2001089734A (ja) * 1999-09-24 2001-04-03 Sumitomo Bakelite Co Ltd 多層プリント配線板用層間絶縁接着剤
JP2001098027A (ja) * 1999-07-29 2001-04-10 Mitsubishi Chemicals Corp 変性ポリビニルアセタール系樹脂
JP2002307611A (ja) * 2001-04-12 2002-10-23 Chuko Kasei Kogyo Kk フッ素樹脂銅張積層板
JP2003342350A (ja) * 2002-05-30 2003-12-03 Japan Epoxy Resin Kk 高分子量エポキシ樹脂、電気積層板用樹脂組成物及び電気積層板
JP2005029710A (ja) * 2003-07-08 2005-02-03 Nippon Kayaku Co Ltd 接着剤組成物
JP2006052318A (ja) * 2004-08-11 2006-02-23 Hitachi Chem Co Ltd 熱硬化性樹脂組成物及びそれを用いた樹脂ワニス

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07286155A (ja) * 1994-02-22 1995-10-31 Japan Energy Corp 金属箔張積層板用接着剤及びそれを用いた金属箔張積層板
WO2001003478A1 (fr) * 1999-07-05 2001-01-11 Nippon Pillar Packing Co., Ltd. Circuit imprimé et son pré-imprégné
JP2001098027A (ja) * 1999-07-29 2001-04-10 Mitsubishi Chemicals Corp 変性ポリビニルアセタール系樹脂
JP2001089734A (ja) * 1999-09-24 2001-04-03 Sumitomo Bakelite Co Ltd 多層プリント配線板用層間絶縁接着剤
JP2002307611A (ja) * 2001-04-12 2002-10-23 Chuko Kasei Kogyo Kk フッ素樹脂銅張積層板
JP2003342350A (ja) * 2002-05-30 2003-12-03 Japan Epoxy Resin Kk 高分子量エポキシ樹脂、電気積層板用樹脂組成物及び電気積層板
JP2005029710A (ja) * 2003-07-08 2005-02-03 Nippon Kayaku Co Ltd 接着剤組成物
JP2006052318A (ja) * 2004-08-11 2006-02-23 Hitachi Chem Co Ltd 熱硬化性樹脂組成物及びそれを用いた樹脂ワニス

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010194930A (ja) * 2009-02-26 2010-09-09 Sumitomo Bakelite Co Ltd 絶縁層付支持材料の製造方法、絶縁層付支持材料、プリント配線板および絶縁層付支持材料の製造装置
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
EP3339016A4 (fr) * 2015-08-20 2019-05-01 AGC Inc. Base multicouche et procédé de production de corps moulé associé
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
US11805600B2 (en) 2020-07-28 2023-10-31 Saint-Gobain Performance Plastics Corporation Dielectric substrate and method of forming the same
US11596064B2 (en) 2020-07-28 2023-02-28 Saint-Gobain Performance Plastics Corporation Dielectric substrate and method of forming the same
US12250767B2 (en) 2020-07-28 2025-03-11 Versiv Composites Limited Dielectric substrate and method of forming the same
US12262468B2 (en) 2020-07-28 2025-03-25 Versiv Composites Limited Copper-clad laminate and method of forming the same
CN112048249A (zh) * 2020-09-02 2020-12-08 江西省信合新材料科技有限公司 一种柔性线路板用多层保护膜
US11549035B2 (en) 2020-12-16 2023-01-10 Saint-Gobain Performance Plastics Corporation Dielectric substrate and method of forming the same
US12049577B2 (en) 2020-12-16 2024-07-30 Versiv Composites Limited Dielectric substrate and method of forming the same
US12173201B2 (en) 2020-12-16 2024-12-24 Versiv Composites Limited Copper-clad laminate and method of forming the same
US12391850B2 (en) 2020-12-16 2025-08-19 Versiv Composites Limited Dielectric substrate and method of forming the same
WO2023100499A1 (fr) * 2021-12-03 2023-06-08 ニッカン工業株式会社 Composition de résine, coverlay l'utilisant, feuille adhésive, feuille métallique fixée à une résine, stratifié plaqué de métal ou carte imprimée
JP2023083121A (ja) * 2021-12-03 2023-06-15 ニッカン工業株式会社 樹脂組成物、及び、これを用いたカバーレイフィルム、接着剤シート、樹脂付き金属箔、金属張積層板またはプリント配線板
JP7348673B2 (ja) 2021-12-03 2023-09-21 ニッカン工業株式会社 樹脂組成物、及び、これを用いたカバーレイフィルム、接着剤シート、樹脂付き金属箔、金属張積層板またはプリント配線板
TWI879482B (zh) * 2024-03-07 2025-04-01 國立清華大學 帶載體超薄銅箔及其製造方法

Also Published As

Publication number Publication date
JP2007326923A (ja) 2007-12-20

Similar Documents

Publication Publication Date Title
WO2008004399A1 (fr) Composition de résine de liaison pour des substrats de résine fluorée et stratifiés à placage de métal obtenus à l'aide de la composition
CN102047774B (zh) 多层柔性印刷电路板的粘合层形成用的树脂组合物
CN101223015B (zh) 带有载体的预浸料及其制造工艺、薄双面板及其制造工艺和多层印刷电路板的制造工艺
TWI466970B (zh) 用於製造電路板之氰酸酯系黏著劑樹脂組成物及包含其之可撓性覆金屬層合物
JP5636159B2 (ja) 樹脂付銅箔および樹脂付銅箔の製造方法
TWI678396B (zh) 印刷配線板用樹脂組成物、附樹脂銅箔、覆銅積層板及印刷配線板
TWI490266B (zh) A resin composition for forming a bonding layer of a multilayer flexible printed circuit board, a resin varnish, a resin copper foil having a resin copper foil, a multilayer flexible printed circuit board, and a multilayer flexible printed circuit board
TWI609043B (zh) Resin copper foil, copper-clad laminate and printed wiring board
WO2019188087A1 (fr) Stratifié cuivré
KR101464140B1 (ko) 수지 조성물
WO2005009093A1 (fr) Feuille en cuivre a couche adhesive extremement fine et procede de production de ladite feuille
TWI713610B (zh) 配線基板之製造方法、配線基板及天線
WO2009084533A1 (fr) Feuille de cuivre avec résine et processus de production d'une feuille de cuivre avec résine
Noh et al. Effect of laminating parameters on the adhesion property of flexible copper clad laminate with adhesive layer
TWI821399B (zh) 積層體、印刷基板及其製造方法
JP4992514B2 (ja) プリント配線板の製造方法
JP5074882B2 (ja) 多層プリント配線板の製造方法及びその製造方法で得られた多層プリント配線板
KR101362288B1 (ko) 프라이머 수지층 부착 동박, 상기 동박을 포함하는 프린트 배선판용 동부착적층판, 상기 동박의 제조방법, 및 상기 동박의 제조에 사용되는 프라이머 수지 조성물
EP1218178B1 (fr) Couche favorisant l'adhesion utilisee avec des preimpregnes epoxy
KR101469614B1 (ko) 양면 연성회로기판의 금속회로패턴 형성방법
JP6816566B2 (ja) 樹脂組成物、接着フィルム、プリプレグ、多層プリント配線板及び半導体装置
JP7666240B2 (ja) インダクタ内蔵基板の製造方法
JP4370926B2 (ja) 薄葉配線板材料とその製造方法
CN113801537A (zh) 附底漆铜箔及铜箔层叠板

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 07828132

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: RU

122 Ep: pct application non-entry in european phase

Ref document number: 07828132

Country of ref document: EP

Kind code of ref document: A1