[go: up one dir, main page]

WO2020158604A1 - Stratifié, procédé de production de celui-ci, procédé de production de stratifié composite, et procédé de production de film polymère - Google Patents

Stratifié, procédé de production de celui-ci, procédé de production de stratifié composite, et procédé de production de film polymère Download PDF

Info

Publication number
WO2020158604A1
WO2020158604A1 PCT/JP2020/002517 JP2020002517W WO2020158604A1 WO 2020158604 A1 WO2020158604 A1 WO 2020158604A1 JP 2020002517 W JP2020002517 W JP 2020002517W WO 2020158604 A1 WO2020158604 A1 WO 2020158604A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
metal foil
polymer
laminate
foil 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/JP2020/002517
Other languages
English (en)
Japanese (ja)
Inventor
渉 笠井
敦美 山邊
達也 寺田
細田　朋也
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.)
AGC Inc
Original Assignee
Asahi Glass 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 Asahi Glass Co Ltd filed Critical Asahi Glass Co Ltd
Priority to KR1020217023787A priority Critical patent/KR102865559B1/ko
Priority to JP2020569583A priority patent/JP7230932B2/ja
Priority to CN202080011655.2A priority patent/CN113365804A/zh
Publication of WO2020158604A1 publication Critical patent/WO2020158604A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • 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
    • B32B15/082—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 comprising vinyl resins; comprising acrylic resins
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • 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
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/10—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer characterised by a fibrous or filamentary layer reinforced with filaments
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/16—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer formed of particles, e.g. chips, powder or granules
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/16—Electroplating with layers of varying thickness
    • 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
    • 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
    • H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
    • 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
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/285—Permanent coating compositions
    • 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
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/07—Parts immersed or impregnated in a matrix
    • B32B2305/076—Prepregs
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards

Definitions

  • the present invention relates to a laminate having a predetermined polymer layer, which is provided in direct contact with the surface of a predetermined metal foil layer, a method for producing the same, a method for producing a composite laminate, and a method for producing a polymer film.
  • the surface roughness of copper foil is reduced and a polymer layer using a low dielectric constant polymer is formed for the purpose of lowering the dielectric constant.
  • low dielectric constant polymers are generally less polar and have poorer adhesion to other materials.
  • the copper foil having a reduced surface roughness has an excessively high surface smoothness, so that the anchor effect of the polymer layer is unlikely to occur and the adhesiveness is poor. Therefore, it is difficult to firmly bond the polymer layer containing the low dielectric constant polymer and the low-roughness copper foil.
  • the surface of the copper foil is treated with a surface treatment agent containing a silicon atom such as a silane coupling agent. It is no exaggeration to say that the surface of copper foil used in commercial printed wiring boards is treated with a silane coupling agent.
  • a silane coupling agent etrafluoroethylene-based polymers (TFE-based polymers) have been attracting attention as low-dielectric-constant polymers, but TFE-based polymers are particularly poor in adhesiveness with other materials. Therefore, the surface of the copper foil is also treated with a silane coupling agent to enhance the adhesiveness with the copper foil (see Patent Document 1).
  • Nickel is excellent as a barrier layer, but its resistivity is higher than that of copper. Therefore, a printed wiring board containing a large amount of nickel has a large transmission loss. Further, since nickel itself is easily denatured at a high temperature, the adhesiveness between the polymer layer and the copper foil is apt to be deteriorated after the high temperature exposure in the manufacturing process of the printed wiring board. In order to solve such a problem, it has been proposed to provide an antioxidant treatment layer containing cobalt and molybdenum on the surface of the copper foil (see Patent Document 4).
  • a prepreg is adhered to the TFE polymer layer so as to cover the entire circuit pattern and laminated.
  • the adhesive force between the TFE polymer layer and the prepreg is low, and delamination between them tends to occur. Therefore, before adhering the prepreg, the surface of the TFE polymer layer is surface-treated (silane coupling agent treatment, plasma treatment, etc.) to improve the adhesiveness (see Patent Documents 5 and 6).
  • the TFE-based polymer is poor in the interaction with the silane coupling agent, the effect of improving the adhesiveness between the TFE-based polymer and the copper foil by the silane coupling agent is not sufficient. It was limited. Further, the silane coupling agent tends to cause variations in its reactivity and variations in the amount attached to the surface of the copper foil, which is an unstable factor in the adhesiveness of the TFE polymer to the copper foil.
  • the present inventors have found that the use of a predetermined TFE-based polymer and metal foil makes it possible to eliminate unstable elements by using a silane coupling agent.
  • the present inventors when the TFE polymer is used as the low dielectric constant polymer, the initial adhesive strength between the layer containing cobalt and molybdenum and the TFE polymer is extremely low, and the TFE polymer is not easily exposed after exposure to high temperature. The adhesive strength was still not enough. Therefore, as a result of diligent studies to improve the initial adhesive strength, the present inventors have used a metal foil having a surface on which nickel is present in a predetermined trace amount, and a predetermined TFE-based polymer on the surface of the metal foil. It has been found that when a polymer layer containing the same is provided, a laminate having excellent initial adhesive strength and adhesive strength after high temperature exposure and excellent electrical characteristics can be obtained.
  • a polymer layer containing a TFE-based polymer that exhibits high adhesiveness to a prepreg can be obtained by using a metal foil having a predetermined surface texture, and completed the present invention. did.
  • the present invention provides a laminate in which uniform and high adhesion is obtained between a polymer layer and a metal foil layer, and a method for producing the same.
  • the present invention also provides a laminate having excellent electrical properties, which has a high initial adhesive force between the polymer layer and the metal foil layer and maintains a high adhesive force even after a high temperature heat history, and a method for producing the same.
  • the present invention provides a method for producing a polymer film that exhibits high adhesion to a prepreg or the like even if surface treatment is omitted, and a method for producing a composite laminate in which peeling between the polymer layer and the prepreg layer is unlikely to occur. For the purpose of providing.
  • the present invention has the following aspects.
  • a metal foil layer in which no silicon atoms are present on the surface, or a nickel atom ratio detected when fluorescent X-ray analysis is performed on the surface is 0.03 to
  • a laminate which is a metal foil layer containing 0.25% by mass.
  • the metal foil layer includes a base material layer and a roughening treatment layer having metal particles and having the surface.
  • the metal foil layer includes a base material layer and a roughening treatment layer having metal particles and having the surface, and the metal particles are copper, nickel, phosphorus, tungsten, arsenic, molybdenum, or chromium.
  • the metal foil layer includes a base material layer and a roughening treatment layer having metal particles and having the surface, and the metal particles include needle-shaped metal particles.
  • ⁇ 5> The laminate according to any one of ⁇ 1> to ⁇ 4>, wherein the ten-point average roughness of the surface of the metal foil layer is 0.1 ⁇ m or more.
  • the tetrafluoroethylene-based polymer is a tetrafluoroethylene-based polymer containing a unit based on a unit based on perfluoro(alkyl vinyl ether), or polytetrafluoroethylene having a number average molecular weight of 200,000 or less.
  • the tetrafluoroethylene-based polymer contains a unit based on perfluoro(alkyl vinyl ether), and a tetrafluoroethylene-based polymer having an oxygen-containing polar group, or a unit based on perfluoro(alkyl vinyl ether) based on all units.
  • ⁇ 8> The laminate according to any one of ⁇ 1> to ⁇ 7>, wherein the polymer layer has a peel strength of 10 N/cm or more with respect to the metal foil layer.
  • a method for producing a laminated body comprising: forming a polymer layer containing the above in a direct contact, and obtaining a laminated body having the polymer layer provided in direct contact with a surface of a metal foil layer composed of the metal foil.
  • the melt viscosity at 380° C. is 1 ⁇ 10 2 to 1 ⁇ 10 6 on the surface of a metal foil in which the proportion of nickel atoms detected by fluorescent X-ray analysis is 0.03 to 0.25 mass %.
  • a polymer layer containing a tetrafluoroethylene-based polymer of Pa ⁇ s is formed in direct contact, and a laminate having the polymer layer provided in direct contact with the surface of the metal foil layer composed of the metal foil is obtained. And a method for manufacturing a laminate.
  • a method for producing a composite laminate comprising: obtaining a composite laminate in which a solder mask layer and a solder mask layer are laminated. ⁇ 14> The method according to ⁇ 13>, wherein the exposed surface of the polymer layer is treated with an acid solution, and a solder resist is directly applied as it is and cured to form a solder mask layer.
  • the laminated body which can obtain uniform and high adhesiveness between a polymer layer and a metal foil, and its manufacturing method are provided. Further, according to the present invention, between the polymer layer and the metal foil, there is a high initial adhesive force, and the high adhesive force is maintained even after a high temperature heat history, and a laminate excellent in electrical characteristics, and the production thereof. A method is provided. Further, according to the present invention, there is provided a polymer film exhibiting a high adhesive force to a prepreg and the like, and a composite laminate in which peeling between the polymer layer and the prepreg layer does not easily occur.
  • D50 of powder is a particle size distribution of powder measured by a laser diffraction/scattering method, and a cumulative curve is calculated by setting the total volume of particles constituting the powder (hereinafter, also referred to as "powder particles") as 100%. , The particle diameter at the point where the cumulative volume becomes 50% on the cumulative curve (volume-based cumulative 50% diameter).
  • Powder D90 is a point where the particle size distribution of powder is measured by a laser diffraction/scattering method, a cumulative curve is calculated with the total volume of the powder particle group as 100%, and the cumulative volume becomes 90% on the cumulative curve. Is the particle size (volume-based cumulative 90% size).
  • D50 and D90 of the powder are the volume-based cumulative 50% diameter and the volume-based cumulative 90% diameter of the powder particles, respectively.
  • the “melt viscosity of the polymer” is based on ASTM D 1238, and a sample of the polymer (2 g) which had been heated at the measurement temperature for 5 minutes in advance was loaded with 0.7 MPa using a flow tester and a 2 ⁇ -8L die. It is the value measured by holding at the measurement temperature at.
  • the "melting temperature (melting point) of the polymer” is a temperature corresponding to the maximum value of the melting peak of the polymer measured by the differential scanning calorimetry (DSC) method.
  • “Viscosity” is a value measured with a B-type viscometer at room temperature (25° C.) under a rotation speed of 30 rpm. The measurement is repeated three times, and the average value of the three measured values is used.
  • “Ten-point average roughness (Rzjis)” is a value defined in Annex JA of JIS B 0601:2013.
  • “Peeling strength” means fixing a position 50 mm from one end in the length direction of a laminate cut out in a rectangular shape (length 100 mm, width 10 mm), pulling speed 50 mm/min, laminate from one end in the length direction. Is the maximum load (N/cm) applied when the metal foil and the polymer layer are separated from each other at 90°.
  • the “unit” in a polymer may be an atomic group formed directly from a monomer by a polymerization reaction, and the polymer obtained by the polymerization reaction is treated by a predetermined method to convert an atomic group in which a part of the structure is converted. May be The unit based on the monomer A contained in the polymer is also simply referred to as “monomer A unit”.
  • the laminate of the present invention (this laminate) is provided in direct contact with the metal foil layer and the surface of the metal foil layer, and has a melt viscosity at 380° C. of 1 ⁇ 10 2 to 1 ⁇ 10 6 Pa ⁇ s.
  • a polymer layer (hereinafter, also referred to as “F layer”) containing a fluoroethylene polymer (hereinafter, also referred to as “F polymer”).
  • the metal foil layer in the present laminate is a metal foil layer having no silicon atom on the surface (hereinafter, also referred to as “metal foil layer 1”), or a nickel atom detected when the surface is subjected to fluorescent X-ray analysis.
  • metal foil layer 2 Is 0.03 to 0.25% by mass (hereinafter, also referred to as "metal foil layer 2").
  • the present laminate having the metal foil layer 1 will be referred to as the present laminate 1
  • the present laminate having the metal foil layer 2 will be referred to as the present laminate 2.
  • the laminate 1 has a metal foil layer 1 and an F layer provided in direct contact with the surface of the metal foil layer 1.
  • the F layer may be provided on only one surface of the metal foil layer 1 or on both surfaces.
  • no silicon atom is present on the surface of the metal foil layer 1 (surface on the F layer side).
  • the manufacturing method of the present laminate 1 is a method of forming the F layer by directly contacting the surface of the metal foil layer 1 without treating the surface with the silane coupling agent.
  • XRF fluorescent X-ray analysis
  • the metal foil constituting the metal foil layer 1 has an oxide (hydroxide or the like) generated by oxidation on its surface.
  • an F polymer having a predetermined melt viscosity is likely to interact with an oxide and/or a metal atom present on the surface of the metal foil, and particularly when the F polymer contains an oxygen-containing polar group, the oxygen-containing polar group Is believed to interact strongly with oxides and/or metal atoms present on the surface of the metal foil.
  • the F layer containing the F polymer exhibited high adhesiveness with the metal foil.
  • the treatment with the silane coupling agent is performed by utilizing the wetting and spreading of the solution containing the silane coupling agent on the surface of the metal foil. Therefore, in the initial stage, the solution is likely to collect in the portion where the silane coupling agent is bound, and the portion where the silane coupling agent is bound and the portion where the silane coupling agent is not bound are scattered like islands, and are present on the surface of the metal foil. It is considered that the amount of the silane coupling agent varies. Moreover, the degree is greatly influenced by the surface properties of the metal foil. Therefore, when the F layer is formed on the surface of the metal foil in such a state, uniform adhesiveness between the F layer and the metal foil is unlikely to be exhibited.
  • the present laminate 1 since the surface of the metal foil is not treated with the silane coupling agent, it is possible to prevent the above inconvenience from occurring, and to prevent the occurrence of the above-mentioned inconvenience between the F layer and the metal foil (metal foil layer 1). It is presumed that uniform adhesiveness was obtained.
  • This laminate 2 has a metal foil layer 2 and an F layer provided in direct contact with the surface of the metal foil layer 2.
  • the F layer may be provided on only one surface of the metal foil layer 2 or on both surfaces.
  • a predetermined amount (trace amount) of nickel atoms is present on the surface of the metal foil layer 2 (surface on the F layer side).
  • the manufacturing method of the present laminate 2 is a method of forming the F layer by directly contacting the surface of the metal foil on which nickel atoms are present in a predetermined amount.
  • the proportion of nickel atoms present on the surface of the metal foil can be measured by analyzing the surface of the metal foil by a fluorescent X-ray analysis (XRF) method.
  • XRF fluorescent X-ray analysis
  • the metal foil forming the metal foil layer 2 has nickel oxide (hydroxide or the like) formed on the surface thereof by oxidation.
  • nickel oxide hydrogen oxide or the like
  • an F polymer having a predetermined melt viscosity is likely to interact strongly with the oxide or nickel atom present on the surface of the metal foil, and particularly when the F polymer contains an oxygen-containing polar group, the oxygen-containing polar group It is considered that the group strongly interacts with this oxide or nickel atom.
  • the F layer containing the F polymer exhibited high initial adhesiveness with the metal foil (metal foil layer 2).
  • the presence of nickel atoms exerts an effect of preventing deterioration (corrosion) of the surface of the metal foil due to the F polymer. For this reason, it is presumed that the present laminate 2 maintained a high adhesive force between the F layer and the metal foil (metal foil layer 2) even after the thermal history at high temperature.
  • the F polymer in the present invention is a polymer containing a unit based on tetrafluoroethylene (TFE) (TFE unit), and is preferably a hot melt processable polymer.
  • the melt viscosity of the F polymer at 380° C. is 1 ⁇ 10 2 to 1 ⁇ 10 6 Pa ⁇ s, preferably 1 ⁇ 10 3 to 1 ⁇ 10 6 Pa ⁇ s.
  • the melting temperature of the F polymer is preferably 140 to 320°C, more preferably 200 to 320°C, and further preferably 260 to 320°C. In this case, it is easy to further improve the adhesiveness of the F layer to the metal foil (metal foil layers 1 and 2).
  • the F polymer preferably has an oxygen-containing polar group.
  • the oxygen-containing polar group possessed by the F polymer may be contained in a unit based on the monomer having the oxygen-containing polar group, may be contained in the terminal portion of the polymer main chain, and may be subjected to surface treatment (radiation treatment, electron beam treatment). , Corona treatment, plasma treatment, etc.), and the former is preferable.
  • the oxygen-containing polar group contained in the F polymer may be a group prepared by modifying a polymer having a group capable of forming an oxygen-containing polar group.
  • the oxygen-containing polar group contained in the polymer terminal group can be obtained by adjusting the components (polymerization initiator, chain transfer agent, etc.) used in the polymerization of the polymer.
  • the oxygen-containing polar group is a polar atomic group containing an oxygen atom.
  • the oxygen-containing polar group in the present invention does not include the ester bond itself and the ether bond itself, but includes an atomic group containing these bonds as a characteristic group.
  • the oxygen-containing polar group is preferably at least one group selected from the group consisting of a hydroxyl group-containing group, a carbonyl group-containing group, an acetal group and an oxycycloalkane group, more preferably a hydroxyl group-containing group or a carbonyl group-containing group, and -CF 2 CH 2 OH, —C(CF 3 ) 2 OH, 1,2-glycol group (—CH(OH)CH 2 OH), —CF 2 C(O)OH, >CFC(O)OH, carboxamide group (-C(O)NH 2, etc.), acid anhydride residue (-C(O)OC(O)-), imide residue (-C(O)NHC(O)-, etc.), dicarboxylic acid residue (—CH(C(O)OH)CH 2 C(O)OH) or a carbonate group (—OC(O)O—) is more preferable.
  • the oxygen-containing polar group is a polar group and is a cyclic group or a ring-opening group thereof, a cyclic acid anhydride residue, a cyclic imide residue, A cyclic carbonate group, a cyclic acetal group, a 1,2-dicarboxylic acid residue or a 1,2-glycol group is particularly preferred, and a cyclic acid anhydride residue is most preferred.
  • the oxycycloalkane group is preferably an epoxy group or an oxetanyl group.
  • the F polymer includes a TFE unit, a unit based on hexafluoropropylene (HFP), perfluoro(alkyl vinyl ether) (PAVE) or fluoroalkyl ethylene (FAE) (hereinafter, also referred to as “PAE unit”), and an oxygen-containing polar group.
  • a polymer containing a unit based on a monomer having (hereinafter, also referred to as “polar unit”) is preferable.
  • the proportion of TFE units is preferably 50 to 99 mol%, and particularly preferably 90 to 99 mol%, based on all units constituting the F polymer.
  • the PAE units are preferably units based on PAVE or units based on HFP, particularly preferably units based on PAVE. Two or more types of PAE units may be used.
  • the proportion of PAE units is preferably 0.5 to 9.97 mol%, and more preferably 0.5 to 9.97 mol%, based on all units constituting the F polymer.
  • the polar unit is preferably a unit based on a monomer having an acid anhydride residue, a carbonate group, a cyclic acetal group, a 1,2-dicarboxylic acid residue, a 1,2-diol residue, or a 1,3-diol residue.
  • a monomer unit having a cyclic acid anhydride residue or a cyclic carbonate group is more preferable, and a monomer unit having a cyclic acid anhydride residue is more preferable.
  • the polarity unit may be one type or two or more types.
  • Examples of the monomer having a cyclic acid anhydride residue include itaconic anhydride, citraconic anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride (also called hymic acid anhydride; hereinafter also referred to as “NAH”) or maleic anhydride. Acids are preferred and NAH is more preferred.
  • the proportion of polar units is preferably 0.01 to 3 mol% based on all units constituting the F polymer.
  • the F polymer in this case may further include units other than TFE units, PAE units, and polar units (hereinafter, also referred to as “other units”).
  • the other unit may be one type or two or more types.
  • Examples of the monomer that forms another unit include ethylene, propylene, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride (VDF), and chlorotrifluoroethylene (CTFE).
  • Other units are preferably ethylene, VDF or CTFE, more preferably ethylene.
  • the proportion of the other units in the F polymer is preferably 0 to 50 mol %, more preferably 0 to 40 mol% based on all the units constituting the F polymer.
  • Preferable embodiments of the F polymer include F polymers containing units based on PAVE (PAVE units), or PTFE having a number average molecular weight of 200,000 or less.
  • the number average molecular weight of PTFE is a value calculated based on the following formula (1).
  • Mn 2.1 ⁇ 10 10 ⁇ Hc ⁇ 5.16 ...
  • Mn represents the number average molecular weight of the above PTFE
  • ⁇ Hc represents the heat of crystallization (cal/g) of the above PTFE measured by the differential scanning calorimetry.
  • the Mn of PTFE is preferably 10 or less, more preferably 50,000 or less.
  • the Mn of PTFE is preferably 10,000 or more.
  • a more preferable embodiment of the F polymer is a F polymer containing units based on PAVE and having an oxygen-containing polar group, or an F polymer containing 2.0 to 5.0 mol% of units based on PAVE, and oxygen.
  • An F polymer having no contained polar group may be mentioned.
  • the F polymer of this embodiment is likely to form fine spherulites in the F layer and is likely to have high adhesion with other components.
  • the former polymer preferably contains 90 to 99 mol% of TFE units, 0.5 to 9.97 mol% of PAVE units and 0.01 to 3 mol% of polar units based on all units. ..
  • the content of PAVE units in the latter polymer is preferably 2.1 mol% or more, and more preferably 2.2 mol% or more, based on all units.
  • the latter polymer is composed of only TFE units and PAVE units, and preferably contains 95.0 to 98.0 mol% of TFE units and 2.0 to 5.0 mol% of PAVE units based on the total units. ..
  • the latter polymer does not have an oxygen-containing polar group means that the polymer has less than 500 oxygen-containing polar groups per 1 ⁇ 10 6 carbon atoms constituting the polymer main chain. Means there is.
  • the number of oxygen-containing polar groups is preferably 100 or less, more preferably 50 or less.
  • the lower limit of the number of oxygen-containing polar groups is usually 0.
  • the latter polymer may be produced by using a polymerization initiator, a chain transfer agent, or the like that does not generate an oxygen-containing polar group as a terminal group of the polymer chain. It may be produced by fluorinating an F polymer or the like having an oxygen-containing polar group derived from it as an end group of the polymer main chain. Examples of the fluorination treatment method include a method using fluorine gas (see JP-A-2019-194314, etc.).
  • the metal constituting the metal foils to be the metal foil layers 1 and 2 copper, iron, nickel, aluminum, zinc, alloys thereof (copper alloy, stainless steel, nickel alloy (including 42 alloy), aluminum alloy). Etc.) can be mentioned.
  • a copper foil is preferable, a rolled copper foil having no distinction between front and back and a copper foil such as an electrolytic copper foil having distinction between front and back are more preferable, and a rolled copper foil is further preferable. Since the rolled copper foil has a small surface roughness, the transmission loss can be reduced even when the laminated body is processed into a printed wiring board.
  • the rolled copper foil is preferably used after being immersed in a hydrocarbon-based organic solvent to remove the rolling oil.
  • the surface on which the F layer is formed may be any surface in the rolled copper foil, and may be either the deposition surface or the glossy surface in the electrolytic copper foil.
  • the metal foil may be a metal foil with a carrier that is laminated on the carrier via an intermediate layer.
  • the metal foil may have a laminated structure including a base material layer (for example, copper foil) made of the above metal, and a roughening treatment layer made of metal particles (roughening particles).
  • the surface of the roughening treatment layer constitutes the surface of the metal foil.
  • the roughening treatment layer include a roughening treatment layer composed of nickel-containing metal particles (roughening particles).
  • the metal particles are preferably formed of copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, cobalt, zinc or an alloy containing one or more of these, and copper, nickel, cobalt or one or more of these is used. More preferably, it is formed of an alloy containing.
  • the metal particles are more preferably formed of nickel alone or an alloy of nickel and at least one of copper, phosphorus, tungsten, arsenic, molybdenum, chromium, cobalt and zinc, and at least nickel, at least copper and cobalt. Most preferably, it is formed of an alloy containing one type. Such metal particles have excellent adhesion to the metal (especially copper) that constitutes the base material layer.
  • the roughening treatment layer containing nickel forms a wiring having a narrow width and a short distance (for example, 30 ⁇ m or less) from the metal foil (metal foil layers 1 and 2) when the laminate is processed into a printed wiring board. Even in this case, however, it is possible to preferably prevent the migration from occurring between the wirings. Further, the nickel-containing metal particles are likely to be deposited on the base material layer so as to include needle-shaped metal particles. With the roughening treatment layer containing acicular metal particles, the anchoring effect of the F layer on the surface thereof is further improved, and the adhesiveness of the F layer to the metal foil can be sufficiently enhanced.
  • the proportion of nickel atoms present on the surface of the metal foil (metal foil layer 2) is 0.03 to 0.25 mass%, preferably 0.04 to 0.2 mass%, and 0.05 to 0.15. Mass% is more preferable.
  • the proportion of nickel atoms present on the surface of the metal foil (metal foil layer 2) is 0.03 to 0.25 mass%, preferably 0.04 to 0.2 mass%, and 0.05 to 0.15. Mass% is more preferable.
  • the anchor effect to the surface of the F layer metal foil (metal foil layers 1 and 2) is suitably exhibited, and as a result, the adhesiveness (adhesion) of the F layer to the metal foil (metal foil layers 1 and 2).
  • the average particle size of the metal particles is preferably 0.1 to 0.25 ⁇ m.
  • the ten-point average roughness of the surface of the metal foil (the surface on the F layer side) is preferably 0.1 to 1.5 ⁇ m.
  • 0.3 to 1.3 ⁇ m is more preferable. Further, if the ten-point average roughness is in the above range, the degree of unevenness on the surface of the metal foil is not too large, so that even if the laminate is processed into a printed wiring board, an increase in transmission loss can be suppressed.
  • the ten-point average roughness of the surface of the roughening treatment layer can be adjusted by setting the size of metal particles, the number of metal particles, and the like.
  • the roughening treatment layer is preferably formed by depositing (electrodeposition) metal particles on the base material layer by an electroplating method using the base material layer as a cathode.
  • the electrodeposition amount such as the size of the metal particles and the number of metal particles can be controlled mainly by adjusting the current density and the electrodeposition time.
  • the following plating conditions (1) or (2) are suitably used for electroplating.
  • the surface of the metal foil may be subjected to a roughening treatment such as dry etching or wet etching to adjust the ten-point average roughness of the surface to the above range. Further, depending on the combination of the F polymer and the metal forming the metal foil, high adhesion between the F layer and the metal foil (metal foil layers 1 and 2) can be obtained even if the roughening treatment is omitted. Further, the metal foil may include at least one layer of a heat-resistant treatment layer, a rust-prevention treatment layer and a chromate treatment layer from the viewpoint of improving various properties.
  • the metal foil has a laminated structure
  • these layers are provided on the surface of the roughening treatment layer opposite to the base material layer or between the roughening treatment layer and the metal foil.
  • a publicly known method can be adopted for forming the heat-resistant treatment layer, the rust-prevention treatment layer or the chromate treatment layer.
  • the heat-resistant treatment layer, the rust-prevention treatment layer or the chromate treatment layer constitutes the outermost layer of the metal foil, the surface thereof constitutes the surface of the metal foil.
  • the thickness of the metal foil is appropriately determined according to the application of the laminate, and when the laminate is processed into a printed wiring board and used, it is preferably 1 to 100 ⁇ m, more preferably 6 to 30 ⁇ m.
  • the thickness of the ultrathin metal foil is preferably 2 to 5 ⁇ m.
  • the surface of the metal foil layer 1 is formed by directly contacting the F layer on the surface of the metal foil without treating the surface of the metal foil with the silane coupling agent and forming the surface of the metal foil layer 1.
  • the present laminated body 2 having the F layer provided in direct contact with the surface of the metal foil layer 2 is manufactured.
  • it is preferable that the surface of the metal foil is roughened as described above, if necessary, before forming the F layer on the surface of the metal foil.
  • the F layer is formed by a method of applying a dispersion liquid in which a powder of F polymer is dispersed in a solvent to the surface of the metal foil and heating, or a method of thermocompression-bonding a film containing the F polymer on the surface of the metal foil. Is preferred.
  • the dispersion liquid is applied to the surface of the metal foil, and when the metal foil to which the dispersion liquid is applied is heated, the solvent is removed from the dispersion liquid and powder.
  • the F layer is formed by firing and the main laminates 1 and 2 are obtained.
  • the method of applying the dispersion liquid to the surface of the metal foil may be any method as long as it forms a stable liquid film (wet film) of the dispersion liquid on the surface of the metal foil, such as coating method, droplet discharge method, and dipping method.
  • the coating method is preferable. By using the coating method, a liquid film can be efficiently formed on the surface of the metal foil with simple equipment.
  • a coating method As a coating method, a spray method, a roll coating method, a spin coating method, a gravure coating method, a micro gravure coating method, a gravure offset method, a knife coating method, a kiss coating method, a bar coating method, a die coating method, a fountain Mayer bar method, a slot die coating.
  • a spray method As a coating method, a spray method, a roll coating method, a spin coating method, a gravure coating method, a micro gravure coating method, a gravure offset method, a knife coating method, a kiss coating method, a bar coating method, a die coating method, a fountain Mayer bar method, a slot die coating.
  • the metal foil to which the dispersion is applied is held at the volatilization temperature of the solvent, the dispersion is dried, and then the dried film is held at a temperature above the volatilization temperature of the solvent to bake the powder.
  • the “solvent volatilization temperature” is preferably the boiling point of the solvent ⁇ 50° C., more preferably the temperature above the boiling point of the solvent, and even more preferably the temperature above the boiling point of the solvent+50° C.
  • the drying temperature means the temperature of the drying atmosphere.
  • the solvent does not necessarily have to be completely volatilized, and may be volatilized to such an extent that the layer shape after holding is stable.
  • the amount of the solvent to be volatilized is preferably 50% by mass or more of the solvent contained in the dispersion liquid.
  • the drying may be carried out in one step at a constant temperature, or in two or more steps at different temperatures.
  • Examples of the drying method include a method using an oven, a method using a ventilation drying furnace, and a method of irradiating heat rays such as infrared rays. Drying may be performed under either normal pressure or reduced pressure.
  • the dry atmosphere may be any of oxidizing gas atmosphere (oxygen gas etc.), reducing gas atmosphere (hydrogen gas etc.) and inert gas atmosphere (helium gas, neon gas, argon gas, nitrogen gas etc.). ..
  • the drying temperature is preferably 50 to 280°C, more preferably 120 to 260°C.
  • the drying time is preferably 0.1 to 30 minutes, more preferably 0.5 to 20 minutes. If the dispersion liquid is dried under the above conditions, the present laminates 1 and 2 can be preferably produced while maintaining high productivity.
  • the firing method examples include a method using an oven, a method using a ventilation drying furnace, and a method of irradiating heat rays such as infrared rays.
  • a firing method a method of irradiating far infrared rays is preferable because the powder can be fired in a short time and has a relatively compact size.
  • the firing method may be a method combining infrared heating and hot air heating.
  • the effective wavelength band of far infrared rays is preferably 2 to 20 ⁇ m, more preferably 3 to 7 ⁇ m in order to promote the uniform firing of the powder.
  • the dried product of the dispersion liquid may be pressed with a heating plate, a heating roll or the like.
  • the firing atmosphere may be any of an oxidizing gas atmosphere, a reducing gas atmosphere and an inert gas atmosphere. However, the firing atmosphere is preferably a reducing gas atmosphere or an inert gas atmosphere from the viewpoint of suppressing the oxidative deterioration of the metal foil and the F layer to be formed.
  • the firing temperature is set according to the type of F polymer, and is preferably 180°C to 400°C, more preferably 200 to 380°C, even more preferably 220°C to 370°C.
  • the firing temperature means the temperature of the firing atmosphere.
  • the firing time is preferably 30 seconds to 30 minutes, more preferably 1 to 15 minutes. If the powder is fired under such conditions, the firing of the powder is promoted, the productivity of the present laminates 1 and 2 is increased, and the generation of hydrofluoric acid due to the decomposition of the F polymer is easily suppressed.
  • B/A is preferably 0.1 to 1.5, more preferably 0.3 to 1.3. ..
  • the specific value of D50 of the powder is preferably 0.05 to 6 ⁇ m, more preferably 0.2 to 3 ⁇ m. Within this range, the fluidity and dispersibility of the powder will be good, and the electrical properties (low dielectric constant, etc.) and heat resistance of the F layer will be most easily exhibited.
  • D90 of the powder is preferably 8 ⁇ m or less, more preferably 5 ⁇ m or less.
  • the loosely packed bulk density of the powder is preferably 0.05 g/mL or more, more preferably 0.08 to 0.5 g/mL.
  • the dense packing bulk density of the powder is preferably 0.05 g/mL or more, more preferably 0.1 to 0.8 g/mL.
  • the powder particles of the F polymer preferably consist of the F polymer. 80 mass% or more is preferable and, as for content of F polymer in a powder particle, 100 mass% is more preferable.
  • Other components that may be included in the powder particles include aromatic polyester, polyamideimide, thermoplastic polyimide, polyphenylene ether, and polyphenylene oxide.
  • the solvent in the dispersion liquid is a compound that is liquid at 25° C., and may be an aqueous solvent or a non-aqueous solvent.
  • the solvent is preferably water, amide, alcohol, sulfoxide, ester, ketone or glycol ether, more preferably water, ketone or amide, still more preferably ketone or amide.
  • As the solvent one type may be used alone, or two or more types may be used in combination.
  • the solvent include water, methanol, ethanol, isopropanol, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, diethyl ether, dioxane, ethyl lactate, ethyl acetate. , Butyl acetate, methyl ethyl ketone, methyl isopropyl ketone, cyclopentanone, cyclohexanone, ethylene glycol monoisopropyl ether, cellosolve (methyl cellosolve, ethyl cellosolve, etc.).
  • the solvent is a polar solvent from the viewpoint of increasing the wettability between the surface of the metal foil and the F polymer and allowing the hydroxyl group and/or the metal atom on the surface of the metal foil and the oxygen-containing polar group of the F polymer to interact better.
  • a polar solvent from the viewpoint of increasing the wettability between the surface of the metal foil and the F polymer and allowing the hydroxyl group and/or the metal atom on the surface of the metal foil and the oxygen-containing polar group of the F polymer to interact better.
  • water, amide or ketone is preferred, and water, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, cyclohexanone or methyl ethyl ketone is more preferred.
  • the dispersion preferably further contains a fluorine-based dispersant.
  • the fluorinated dispersant is a compound having a function of chemically and/or physically adsorbing on the surface of the powder particles to stably disperse the powder particles in a solvent.
  • the dispersibility of the powder is further improved, the wettability between the surface of the metal foil and the F polymer is increased, and the oxide and/or metal atom and the F polymer on the surface of the metal foil are dispersed. Highly likely to interact with the oxygen-containing polar group possessed.
  • the fluorine-based dispersant is preferably a compound (surfactant) having a hydrophobic moiety containing a fluorine atom and a hydrophilic moiety, more preferably fluoropolyol, fluorosilicone or fluoropolyether, and further preferably fluoropolyol.
  • the fluorine-based dispersant is preferably a nonionic polymeric compound. Such a fluorine-based dispersant has a high interaction with the above-mentioned solvent, and thus the coating film-forming properties (thixo ratio, adhesiveness, transparency, etc.) of the dispersion liquid are easily improved.
  • Fluoropolyol unlike F polymer, is a polymeric polyol having a hydroxyl group and a fluorine atom. Further, in the polymeric polyol, a part of hydroxyl groups may be chemically modified and modified. Examples of the fluoropolyol include compounds having a main chain composed of a carbon chain derived from an ethylenically unsaturated monomer and a side chain branched from the main chain having a fluorine-containing hydrocarbon group and a hydroxyl group.
  • the decomposition product of the fluoropolyol when the dispersion is applied and heated easily forms an oxide on the surface of the metal foil, and the metal foil (metal foil layers 1 and 2) And the polymer layer can be more firmly adhered.
  • Fluoropolyol is a copolymer containing a unit based on a fluorine-containing (meth)acrylate having a polyfluoroalkyl group or a polyfluoroalkenyl group and a unit based on a hydrophilic (meth)acrylate having a polyoxyalkylene group or a hydroxyalkyl group.
  • (meth)acrylate is a general term for acrylate derivatives in which the hydrogen atom at the ⁇ -position of acrylate, methacrylate and acrylate is substituted with another atom or atomic group.
  • fluorine-containing (meth)acrylate examples include CH 2 ⁇ CHCOO(CH 2 ) 2 (CF 2 ) 4 F, CH 2 ⁇ C(CH 3 )COO(CH 2 ) 2 (CF 2 ) 4 F, CH.
  • the fluoropolyol may contain only a unit based on a fluorine-containing (meth)acrylate and a unit based on a hydrophilic (meth)acrylate, and may further contain another unit.
  • the fluorine content of the fluoropolyol is preferably 10 to 45% by mass, more preferably 15 to 40% by mass.
  • the weight average molecular weight of the fluoropolyol is preferably 2,000 to 80,000, more preferably 6,000 to 20,000.
  • fluorosilicone examples include polyorganosiloxane containing a C—F bond in a part of the side chain.
  • fluoropolyether examples include compounds in which a part of hydrogen atoms of polyoxyalkylene alkyl ether is substituted with fluorine atoms.
  • the fluoropolyether also includes monool compounds of the above compounds.
  • the dispersion may contain other materials. Other materials may or may not dissolve in the dispersion. Such other material may be a non-curable resin or a curable resin.
  • the non-curable resin include a heat-meltable resin and a non-meltable resin.
  • the heat-meltable resin include thermoplastic polyimide.
  • the non-melting resin include a cured product of a curable resin.
  • the curable resin examples include a polymer having a reactive group, an oligomer having a reactive group, a low molecular compound, and a low molecular compound having a reactive group.
  • the reactive group include a carbonyl group-containing group, a hydroxy group, an amino group and an epoxy group.
  • the curable resin is an epoxy resin, a thermosetting polyimide, a polyimide precursor polyamic acid, an acrylic resin, a phenol resin, a polyester resin, a polyolefin resin, a modified polyphenylene ether resin, a polyfunctional cyanate ester resin, a polyfunctional maleimide-cyan.
  • Examples thereof include acid ester resins, polyfunctional maleimide resins, vinyl ester resins, urea resins, diallyl phthalate resins, melanin resins, guanamine resins, and melamine-urea co-condensation resins.
  • epoxy resin examples include various types of epoxy resins (naphthalene type, cresol novolac type, bisphenol A type, bisphenol F type, bisphenol S type, alicyclic type, aliphatic chain type, cresol novolac type, phenol novolac type). Type, alkylphenol novolac type, aralkyl type, biphenol type, etc.).
  • bismaleimide resin examples include the resin composition (BT resin) described in JP-A-7-70315 and the resin described in International Publication No. 2013/008667.
  • the polyamic acid usually has a reactive group capable of reacting with the oxygen-containing polar group of the F polymer.
  • Examples of diamines and polycarboxylic acid dianhydrides that form polyamic acids include [0020] in Japanese Patent No. 5766125, [0019] in Japanese Patent No. 5766125, and [0055] in Japanese Patent Application Laid-Open No. 2012-145676, [0057] and the like.
  • thermoplastic resins such as thermoplastic polyimide and heat-curable cured products of curable resins.
  • thermoplastic resin polyester resin, polyolefin resin, styrene resin, polycarbonate, thermoplastic polyimide, polyarylate, polysulfone, polyallylsulfone, aromatic polyamide, aromatic polyetheramide, polyphenylene sulfide, polyallyl ether ketone, polyamide
  • imide liquid crystalline polyester and polyphenylene ether
  • thermoplastic polyimide liquid crystalline polyester or polyphenylene ether are preferable.
  • Such other materials include thixotropic agents, antifoaming agents, inorganic fillers, reactive alkoxysilanes, dehydrating agents, plasticizers, weathering agents, antioxidants, heat stabilizers, lubricants, antistatic agents, and additives.
  • a whitening agent, a coloring agent, a conductive agent, a release agent, a surface treatment agent, a viscosity modifier, and a flame retardant are also included.
  • the viscosity of the dispersion liquid is preferably 50 to 10000 mPa ⁇ s, more preferably 75 to 1000 mPa ⁇ s, and further preferably 100 to 500 mPa ⁇ s. In this case, not only is the dispersibility of the dispersion liquid excellent, but also its coatability and compatibility with varnishes of different resin materials are excellent.
  • the thixo ratio of the dispersion is preferably 1.0 to 2.2, more preferably 1.4 to 2.2, and even more preferably 1.5 to 2.0. In this case, not only the dispersibility of the dispersion liquid is excellent, but also the homogeneity of the F layer is likely to be improved.
  • the thixo ratio is calculated by dividing the viscosity of the dispersion liquid measured under the condition of the rotation speed of 30 rpm by the viscosity of the dispersion liquid measured under the condition of the rotation speed of 60 rpm.
  • the film containing the F polymer in the method of thermocompression-bonding the film containing the F polymer on the surface of the metal foil, when the film containing the F polymer is thermocompression bonded to the surface of the metal foil, the F layer is formed, and the metal foil layer 1 and the metal foil layer 1 composed of the metal foil are formed.
  • the main laminates 1 and 2 having the F layer provided in direct contact with the surface of 2 are obtained.
  • the film can be produced by a method of molding the F polymer itself or a composition containing the F polymer into a film by an extrusion molding method, an inflation molding method, or the like.
  • the laminated body is manufactured by a preliminary heating step in which a temporary laminated body in which a film is laminated on the surface of a metal foil is heated without being pressed in the thickness direction (laminating direction) while being transported, and a temporary laminated body. It is performed through a thermocompression bonding step in which the body is heated and pressed in the thickness direction (laminating direction) to be bonded.
  • the temporary laminate the metal foil and the film are in close contact with each other, but are in a state where they are not yet adhered (pressed).
  • the film Before forming the temporary laminate, the film may be preliminarily heat-treated at a temperature of 100°C or higher and lower than 250°C (preferably 180°C or higher and lower than 250°C). If heat treatment is performed in advance, the shrinkage of the film in the preheating step and the thermocompression bonding step can be reduced, and as a result, the warpage of the laminate can be reduced.
  • the surface of the film (the surface on the metal foil side) may be subjected to surface treatment such as corona discharge treatment and plasma treatment. If the surface treatment is performed in advance, the number of oxygen-containing polar groups existing on the surface of the film can be increased, and in the resulting laminate, the adhesive strength of the F layer to the metal foil layers 1 and 2 can be further increased.
  • the temporary laminate is heated by the preliminary heating means without being pressed in the laminating direction (thickness direction) before being pressure-bonded in the subsequent thermocompression bonding step.
  • the preheating means may be a contact method in which a heat source is brought into contact with the temporary laminate or a non-contact method in which the temporary laminate is heated in a non-contact manner.
  • the contact method is preferable as the preheating means because the metal foil and the film are easily attached to each other. Specifically, a method of transporting the temporary laminated body in contact with a heated metal roll is preferable.
  • the temperature (temporary heating temperature) of the temporary laminate immediately before being pressed in the thermocompression bonding step is preferably 20° C.
  • the preheating temperature is preferably equal to or lower than the thermocompression bonding temperature. When the preheating temperature is within the above range, shrinkage and breakage of the film can be favorably prevented.
  • the temporary laminate may be heated continuously or intermittently.
  • the transportation time (preheating time) from the position where preheating is started to the temporary laminate being transported to immediately before the temporary lamination is pressed in the thermocompression bonding step is preferably 10 to 30 seconds.
  • the preheating time is within the above range, the adhesive force of the F layer to the metal foil layers 1 and 2 is increased in the obtained laminate while satisfactorily preventing the film from shrinking or breaking.
  • the preheating step is performed by the contact type preheating means, if the preheating time is in the above range, the temperature of the temporary laminate becomes the same temperature as the surface temperature of the heat source brought into contact with the temporary laminate.
  • thermocompression bonding process is preferably performed continuously using a thermocompression bonding device or the like equipped with one or more thermocompression bonding means.
  • the thermocompression bonding means means that press-bonds by pressing the temporary laminate while heating it.
  • a heat roll pressure bonding device having a pair of metal rolls is preferably used as the heat pressure bonding means.
  • the temporary laminate is heated by contact with the metal roll when passing between the pair of metal rolls heated to a predetermined temperature, and receives a pressing force in the thickness direction.
  • the film is crimped to the metal foil.
  • the temporary laminated body may pass through a plurality of pairs of metal rolls in order.
  • the surface temperature (temperature of thermocompression bonding) of the metal roll that pressurizes the temporary laminate is preferably the melting temperature of the F polymer or higher, and more preferably 400° C. or higher. In this case, good adhesive strength of the F layer to the metal foil layers 1 and 2 is obtained, and peeling is less likely to occur.
  • the pressure between the pair of metal rolls (pressure for thermocompression bonding) that pressurizes the temporary laminate is a roll linear pressure represented by a load applied per 1 cm width of the roll, and is preferably 98 to 1470 N/cm. In this case, the film does not easily break during thermocompression bonding, good adhesive strength of the F layer to the metal foil layers 1 and 2 is obtained, and peeling hardly occurs.
  • the traveling speed (speed of thermocompression bonding) when the temporary laminate passes between a pair of metal rolls is preferably 0.5 m/min or more, more preferably 1 m/min or more. In this case, thermocompression bonding can be sufficiently performed, and the productivity of the main laminates 1 and 2 can be further improved.
  • the speed of thermocompression bonding is preferably 8 m/min or less. In this case, the F layer and the metal foil layers 1 and 2 can be easily adhered firmly.
  • the film may be a laminated film having a heat resistant resin film on the surface of the film (base film) containing the F polymer opposite to the metal foil.
  • the heat resistant resin film contains a heat resistant resin, and may contain additives and the like as necessary. From the viewpoint of increasing the heat resistance of the heat-resistant resin film, the content of the heat-resistant resin in the heat-resistant resin film is preferably 50% by mass or more, more preferably 80% by mass or more.
  • thermosetting resin As the heat resistant resin, polyimide (aromatic polyimide etc.), polyarylate, polysulfone, polyallyl sulfone (polyether sulfone etc.), aromatic polyamide, aromatic polyether amide, polyphenylene sulfide, polyallyl ether ketone, polyamide imide , And liquid crystal polyester.
  • the heat-resistant resin is preferably a thermosetting resin because it is easy to obtain higher heat resistance.
  • thermosetting resin include thermosetting polyimide, epoxy resin, and acrylic resin. From the viewpoint of improving the electrical characteristics of the laminate, the thermosetting resin is preferably thermosetting polyimide.
  • aromatic polyimide is preferable, and wholly aromatic polyimide produced by polycondensation of aromatic dicarboxylic acid and aromatic diamine is more preferable.
  • an inorganic filler having a low relative dielectric constant and a low dielectric loss tangent is preferable.
  • Such inorganic fillers include silica, clay, talc, calcium carbonate, mica, diatomaceous earth, alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, calcium hydroxide, magnesium hydroxide, Aluminum hydroxide, basic magnesium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dawsonite, hydrotalcite, calcium sulfate, barium sulfate, calcium silicate, montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, glass fiber, Examples thereof include glass beads, silica-based balloons, carbon black, carbon nanotubes, carbon nanohorns, graphite, carbon fibers, glass balloons, carbon burns, wood powder, and zinc borate.
  • the inorganic fillers may be used alone or in combination of two or more.
  • the peel strength of the F layer from the metal foil layers 1 and 2 is preferably 10 N/cm or more, more preferably 15 N/cm or more.
  • the upper limit of the peel strength is usually 20 N/cm.
  • the warpage rate of the present laminates 1 and 2 is preferably 25% or less, more preferably 7% or less. In this case, the handleability when processing the laminated bodies 1 and 2 into a printed wiring board and the transmission characteristics of the obtained printed wiring board are excellent.
  • the dimensional change rate of the laminates 1 and 2 is preferably ⁇ 1% or less, more preferably ⁇ 0.2% or less. In this case, it is easy to process the laminated bodies 1 and 2 into a printed wiring board and further form a multilayered structure.
  • the water contact angle of the surface of the F layer is preferably 70 to 100°, more preferably 70 to 90°. In this case, the adhesiveness between the F layer and another substrate is more excellent.
  • the thickness of the F layer is preferably 1 to 50 ⁇ m, more preferably 5 to 15 ⁇ m. Within this range, it is easy to balance the electrical characteristics and the warp suppressing effect of the laminate when the laminates 1 and 2 are processed into a printed wiring board.
  • the composition and thickness of each F layer are, respectively, from the viewpoint of suppressing warpage of the laminates 1 and 2. It is preferably the same.
  • the relative permittivity of the F layer is preferably 1.98 or less, more preferably 1.95 or less.
  • the lower limit of the relative dielectric constant of the F layer is usually 1.50.
  • the dielectric loss tangent of the F layer is preferably 0.0024 or less, more preferably 0.0019 or less.
  • the lower limit of the relative dielectric constant of the F layer is usually 0.0005.
  • the present laminates 1 and 2 can be preferably used for a printed wiring board or the like which is required to have a low dielectric constant.
  • the relative dielectric constant and dielectric loss tangent of the F layer are values measured at a measurement frequency of 10 GHz by a cavity resonator perturbation method using a network analyzer as a measuring instrument.
  • the laminates 1 and 2 can be processed into a printed wiring board.
  • an interlayer insulating film may be formed on the pattern circuit, and a conductor circuit may be further formed on the interlayer insulating film.
  • the interlayer insulating film may be formed from the above dispersion liquid.
  • a solder resist may be laminated on the pattern circuit.
  • the solder resist may be formed from the above dispersion liquid.
  • a coverlay film may be laminated on the pattern circuit.
  • the coverlay film may be formed from the above dispersion liquid.
  • the method for producing a composite laminate (present composite) of the present invention comprises removing at least a part of a metal foil layer of a predetermined laminate (metal layer with F layer), adhering a prepreg to an exposed polymer layer, It is a method for obtaining a composite laminate in which at least a polymer layer and a prepreg layer are laminated.
  • a two-layer composite laminate having a polymer layer and a prepreg layer can be obtained.
  • a part of the metal foil layer to form a circuit pattern a three-layer composite laminate having a polymer layer, a prepreg layer, and a circuit pattern sandwiched between them can be obtained.
  • the latter composite laminate can be suitably used as a printed wiring board.
  • the laminate used for producing the composite laminate includes a metal foil layer having a surface having a ten-point average roughness of 0.1 ⁇ m or more, and an F layer laminated on the surface.
  • the surface of the metal foil layer has a ten-point average roughness of 0.1 ⁇ m or more, and minute irregularities are irregularly present.
  • the F layer formed on this surface has the surface shape of the metal foil layer transferred to the contact surface with the metal foil layer. Therefore, on the contact surface of the F layer exposed by the removal of the metal foil layer, minute irregularities corresponding to the surface shape of the metal foil layer are irregularly present.
  • a prepreg is adhered to the contact surface having such a surface texture to obtain a composite laminate, it is considered that a high anchoring effect for the contact surface of the F layer of the prepreg is produced. As a result, it is presumed that a high adhesive force (peeling strength) was developed between the F layer and the prepreg layer. The effects as described above are remarkably exhibited in a preferred embodiment of the present invention described later.
  • the aspect of the F polymer in the method for producing the present composite body is the same as that of the F polymer in the present laminate body including the preferable aspect.
  • Aspects of the metal constituting the metal foil layer in the method for producing the present composite body are the same as those of the metal constituting the metal foil layer in the present laminate including suitable aspects.
  • the ten-point average roughness of the surface of the metal foil layer in the method for producing this composite is 0.1 ⁇ m or more, preferably 0.3 ⁇ m or more.
  • the ten-point average roughness is preferably 7 ⁇ m or less, more preferably 2.5 ⁇ m or less, still more preferably 2 ⁇ m or less. Further, if the ten-point average roughness is in the above range, the degree of unevenness on the surface of the metal foil layer is not too large, so that even if the present composite is processed into a printed wiring board, an increase in transmission loss can be suppressed.
  • the matrix resin of the prepreg and the F polymer are compatibilized, and the adhesive force between the layers is more likely to be improved.
  • the ten-point average roughness of the surface can be adjusted by setting the size of metal particles, the number of metal particles, and the like.
  • the roughening treatment layer is preferably formed by depositing (electrodeposition) metal particles on the base material layer by an electroplating method using the base material layer as a cathode.
  • the electrodeposition amount such as the size of the metal particles and the number of metal particles can be controlled mainly by adjusting the current density and the electrodeposition time.
  • the conditions for electroplating can be the same as the conditions for electroplating in the laminate.
  • the surface of the metal foil layer may be subjected to a roughening treatment such as dry etching or wet etching to adjust the ten-point average roughness of the surface within the above range.
  • the metal foil layer may include at least one layer selected from a heat-resistant treatment layer, a rust-prevention treatment layer and a chromate treatment layer from the viewpoint of improving various properties.
  • these layers are provided on the surface of the roughening treatment layer opposite to the base material layer or between the roughening treatment layer and the metal foil.
  • a publicly known method can be adopted for forming the heat-resistant treatment layer, the rust-prevention treatment layer or the chromate treatment layer.
  • the heat-resistant treatment layer, the rust-prevention treatment layer or the chromate treatment layer constitutes the outermost layer of the metal foil layer
  • the surface thereof constitutes the surface of the metal foil layer.
  • the thickness of the metal foil layer the same conditions as the thickness of the metal foil layer of the present laminate can be adopted.
  • the aspect of the F layer in the method for producing the present composite body is the same as that in the present laminate body, including its preferable aspect and its forming method.
  • the removal of the metal foil layer in the method for producing the present composite body is preferably performed by wet etching.
  • wet etching unnecessary portions of the metal foil layer can be accurately and sufficiently removed while preventing damage to the minute uneven shape transferred to the contact surface of the F layer.
  • wet etching is preferably performed using an acid solution.
  • the F polymer has a hydrolyzable acid anhydride residue as the oxygen-containing polar group
  • the oxygen-containing polar group is activated by the acid solution, the adhesive force of the F layer with the prepreg layer is likely to be further increased.
  • activation of the oxygen-containing polar group conversion of an acid anhydride group into a 1,2-dicarboxylic acid group can be mentioned.
  • the acid solution an aqueous solution of an inorganic acid such as hydrochloric acid, dilute nitric acid or hydrofluoric acid can be used.
  • a prepreg is a sheet-shaped substrate in which a matrix resin is impregnated into a base material (tow, woven cloth, etc.) of reinforcing fibers (glass fiber, carbon fiber, etc.).
  • the matrix resin may be a thermoplastic resin or a thermosetting resin. That is, the prepreg layer is a layer formed from the prepreg.
  • the prepreg layer is a layer containing a cured product of the matrix resin if the matrix resin is curable, and a layer containing a melted and solidified product of the matrix resin if the matrix resin is thermoplastic.
  • thermosetting resin examples include the resins described in the description of the above-mentioned dispersion liquid, and an epoxy resin, polyphenylene oxide, polyphenylene ether, or polybutadiene is preferable.
  • the polyphenylene ether is preferably a modified polyphenylene ether, more preferably a vinyl group-containing polyphenylene ether.
  • thermoplastic resin examples include the resins mentioned in the description of the dispersion liquid.
  • the matrix resin one type may be used alone, or two or more types may be used in combination.
  • the matrix resin of the prepreg is preferably an epoxy resin, polyphenylene oxide, polyphenylene ether or polybutadiene from the viewpoint of workability.
  • the prepreg preferably contains a curing agent, and contains a curing agent having three or more curable groups (isocyanate group, blocked isocyanate group, etc.) in one molecule. Hardeners are more preferred.
  • a resin having a fluorine atom may be used as the matrix resin. Examples of such resin include F polymer, polyimide having a fluorine atom, and epoxy resin having a fluorine atom.
  • Preferable embodiments of the matrix resin include an embodiment composed only of a matrix resin having no fluorine atom, and an embodiment composed of a matrix resin having no fluorine atom and a matrix resin having a fluorine atom.
  • the reinforcing fiber sheet includes a reinforcing fiber bundle composed of a plurality of reinforcing fibers, a cloth woven from the reinforcing fiber bundle, a unidirectional reinforcing fiber bundle in which a plurality of reinforcing fibers are aligned in one direction, and the unidirectional reinforcing fiber.
  • a unidirectional cloth composed of a bundle or a combination of these, and a laminate of a plurality of reinforcing fiber bundles.
  • the reinforcing fibers continuous long fibers having a length of 10 mm or more are preferable.
  • the reinforcing fibers do not need to be continuous over the entire length of the reinforcing fiber sheet in the length direction or the entire width in the width direction, and may be divided in the middle.
  • the reinforcing fiber may be subjected to a surface treatment such as a silane coupling agent treatment.
  • Examples of the reinforcing fiber include inorganic fiber, metal fiber, organic fiber and the like.
  • Examples of the inorganic fiber include carbon fiber, graphite fiber, glass fiber, silicon carbide fiber, silicon nitride fiber, alumina fiber, silicon carbide fiber, boron fiber and the like.
  • Examples of the metal fibers include aluminum fibers, brass fibers, stainless fibers and the like.
  • Examples of the organic fibers include aromatic polyamide fibers, polyaramid fibers, polyparaphenylenebenzoxazole (PBO) fibers, polyphenylene sulfide fibers, polyester fibers, acrylic fibers, nylon fibers, polyethylene fibers and the like.
  • the reinforcing fibers may be used alone or in combination of two or more.
  • the glass fiber is preferable as the reinforcing fiber in the printed circuit board material application.
  • the method of adhering the prepreg to the F layer is preferably a method of bringing the prepreg into contact with the contact surface of the F layer in which at least a part of the laminate is exposed, and thermocompression bonding.
  • the temperature for thermocompression bonding is preferably not higher than the melting temperature of the F polymer, more preferably 120 to 300°C, and even more preferably 160 to 220°C. Within this range, the polymer layer and the prepreg layer can be firmly bonded while suppressing the thermal deterioration of the prepreg.
  • the pressure for thermocompression bonding is preferably 0.2 MPa or more.
  • the pressure is preferably 10 MPa or less, more preferably 4 MPa or less.
  • the F layer and the prepreg layer can be more firmly bonded while suppressing damage to the prepreg. Furthermore, when the prepreg is thermocompression bonded to the contact surface of the F layer at such heat temperature or pressure bonding, the prepreg layer that has entered the F layer due to the anchor effect and the F polymer are more compatible and integrated, The adhesive strength is easier to improve.
  • thermocompression bonding is preferably performed in a reduced pressure atmosphere, more preferably at a vacuum degree of 20 kPa or less. Within this range, it is possible to prevent bubbles from being mixed into the interface between the F layer and the prepreg layer, and suppress deterioration of the present composite due to oxidation. Further, during hot pressing, it is preferable to raise the temperature after reaching the above vacuum degree. In this way, since the F layer is pressure-bonded before being softened, that is, before a certain degree of fluidity and adhesiveness is developed, it is possible to prevent the generation of bubbles.
  • the exposed surface of the F layer is subjected to a hydrophilic treatment.
  • the F layer can be directly adhered to the prepreg layer without doing so.
  • the hydrophilic treatment is a treatment for reducing the contact angle of water with respect to the exposed surface of the F layer, and specific examples thereof include plasma treatment, ionizing radiation treatment, and treatment with a silane coupling agent.
  • the peel strength of the F layer from the prepreg layer is preferably 10 N/cm or more, more preferably 15 N/cm or more.
  • the upper limit of the peel strength is usually 20 N/cm.
  • the warpage rate of the present composite body is preferably 25% or less, more preferably 7% or less. In this case, the transmission characteristics of this composite (printed wiring board) are excellent.
  • the dimensional change rate of the composite is preferably ⁇ 1% or less, more preferably ⁇ 0.2% or less. In this case, it is easy to make the composite into multiple layers.
  • a processed laminate obtained by removing a part of the metal foil layer of the laminate and forming a metal circuit layer (circuit pattern) from the metal foil layer is a printed circuit having excellent solder reflow resistance. It is useful as a substrate.
  • a multilayer printed circuit board having such a multilayer structure of the printed circuit board and having an F layer as the outermost layer is excellent in heat resistance, and specifically, even at 288° C., the prepreg layer has an interface at the interface. Swelling and peeling at the interface of the metal circuit layer are less likely to occur.
  • the F layer has a predetermined thickness (1 to 15 ⁇ m, particularly 3 to 9 ⁇ m), this tendency tends to be remarkable.
  • a multilayer printed circuit board having such a multilayer structure of the printed circuit board and having a prepreg layer as the outermost layer is also excellent in heat resistance, and specifically, even at 300° C., the prepreg layer has an interface at the interface. Swelling and peeling at the interface of the metal circuit layer are less likely to occur.
  • the F layer has a predetermined thickness (1 to 15 ⁇ m, particularly 3 to 9 ⁇ m), this tendency tends to be remarkable.
  • the metal of a laminate having a metal foil layer having a surface having a ten-point average roughness of 0.1 ⁇ m or more and an F layer laminated on the surface.
  • a method for producing a laminate in which at least a part of a foil is removed, a solder resist is applied to the exposed F layer and cured to form a solder mask layer, and at least the F layer and the solder mask layer are laminated. It The mode of removing at least a part of the metal foil (metal foil layer), the F polymer, the F layer, the laminated body, and the metallic foil layer of the laminated body in this manufacturing method includes the preferable range of the present composite body. It is similar to those of the manufacturing method.
  • solder resist A publicly known solder resist can be used as the solder resist. Further, the application and curing of the solder resist may be appropriately determined according to the type of solder resist used. In this manufacturing method, it is preferable that the surface of the exposed F layer is treated with an acid solution and the solder resist is directly applied and cured as it is. In this case, in the formation of the solder mask layer, it is easier to form the solder mask layer having more excellent adhesion as compared with the case where the surface treatment (buffing) is performed after the acid treatment.
  • all the metal foil layers of the above-mentioned laminate can be removed and the remaining single F layer can be used as a polymer film.
  • a polymer film can be used as an adhesive layer for adhering two substrates, an interlayer insulating film, a solder resist layer, a coverlay film, or the like.
  • the laminate and the method for producing the same, the method for producing the composite laminate, and the method for producing the polymer film of the present invention have been described above, but the present invention is not limited to the configurations of the above-described embodiments.
  • the laminate of the present invention may have any other configuration added to the configuration of the above-described embodiment, or may be replaced with any configuration exhibiting the same function.
  • the method for producing a laminate of the present invention, the method for producing a composite laminate, and the method for producing a polymer film, respectively, in the configuration of the above-described embodiment, other optional steps may be added, the same. It may be replaced with any step that exerts the function of.
  • F polymer 1 a copolymer containing 98.0 mol%, 0.1 mol% and 1.9 mol% of units based on TFE, units based on NAH and units based on PPVE in this order (melting temperature: 300° C., 380° C.
  • F polymer 2 a copolymer containing 98.0 mol% and 2.0 mol% of units based on TFE and units based on PPVE in this order and having no oxygen-containing polar group (melting temperature: melting at 305° C., 380° C. Viscosity: 3 ⁇ 10 5 Pa ⁇ s)
  • F polymer 3 a copolymer having no functional group, containing 97.5 mol% and 2.5 mol% of units based on TFE and units based on PPVE in this order (melting temperature: 305° C., melt viscosity at 380° C.: 3 ⁇ 10 5 Pa ⁇ s)
  • Powder 1 Powder composed of F polymer 1 (D50: 2.6 ⁇ m, D90: 7.1 ⁇ m)
  • Powder 2 Powder composed of F polymer 2 (D50: 3.5 ⁇ m, D90: 9.2 ⁇ m)
  • Powder 3 Powder composed of F polymer 2 (D50: 1.8 ⁇ m, D90: 4.9 ⁇ m)
  • Powder 4 Powder composed of F polymer 1 (D50: 1.8 ⁇ m, D90: 5.2 ⁇ m)
  • Powder 5 Powder composed of F polymer 3 (D50: 1.9 ⁇ m, D90: 5.5 ⁇ m)
  • D50 and D90 were measured by dispersing the powder in water using a laser diffraction/scattering type particle size distribution measuring device (LA-920 measuring device manufactured by Horiba Ltd.).
  • [Fluorine-based dispersant] FP1 CH 2 ⁇ CHCOO(CH 2 ) 4 OCF(CF 3 )(C(CF(CF 3 ) 2 )( ⁇ C(CF 3 ) 2 ) and CH 2 ⁇ CHCOO(CH), which are nonionic fluoropolyols. 2 ) 4 (OCH 2 CH 2 ) 10 OH copolymer [sheet] Sheet 1: Sheet made of F polymer 1 (thickness: 10 ⁇ m) Sheet 2: Sheet made of F polymer 3 (thickness: 10 ⁇ m) [Prepreg] Prepreg 1: Thermosetting resin composition containing polyphenylene ether resin, glass fiber and silica filler
  • Dispersion 1 After 47 parts by mass of N-methyl-2-pyrrolidone (NMP), 2.5 parts by mass of FP1 and 50 parts by mass of powder 1 were put into a pot, zirconia balls were put into the pot. Then, the pot was rolled at 150 rpm for 1 hour to disperse the powder 1 in NMP to prepare a dispersion 1. (Dispersion liquid 2) Dispersion 2 was prepared in the same manner as Dispersion 1 except that Powder 1 was changed to Powder 2.
  • NMP N-methyl-2-pyrrolidone
  • Dispersion liquid 2 Dispersion 2 was prepared in the same manner as Dispersion 1 except that Powder 1 was changed to Powder 2.
  • Dispersion 3 Dispersion 3 was prepared in the same manner as Dispersion 1 except that Powder 1 was changed to Powder 3.
  • Dispersion liquid 4 was prepared in the same manner as dispersion liquid 1 except that powder 1 was changed to powder 4 and the amount of FP1 was changed to 3 parts by mass.
  • Dispersion 5 was prepared in the same manner as Dispersion 1 except that Powder 1 was changed to Powder 5 and the amount of FP1 was changed to 3 parts by mass.
  • metal foil 1 Using a rolled copper foil (base material layer) having a thickness of 12 ⁇ m as a cathode, electroplating was performed under the following conditions to form a roughening treatment layer on the surface of the rolled copper foil. Thereby, the metal foil 1 was produced. Then, a heat-resistant treatment layer and a chromate layer were sequentially formed on the surface of the roughening treatment layer.
  • the thickness of the metal foil 1 was 15 ⁇ m, and the ten-point average roughness of the surface was 0.6 ⁇ m.
  • ⁇ Primary particle plating (1)> Liquid composition: Copper sulfate pentahydrate 11 g/L, sulfuric acid 52 g/L Liquid temperature: 22°C Current density: 40 A/dm 2 Electrodeposition time: 1 second ⁇ Primary particle plating (2)> Liquid composition: Copper sulfate pentahydrate 19 g/L, sulfuric acid 101 g/L Liquid temperature: 42°C Current density: 4 A/dm 2 Electrodeposition time: 3 seconds ⁇ Secondary particle plating> Liquid composition: Copper sulfate pentahydrate 15 g/L, nickel sulfate hexahydrate 10 g/L , Cobalt sulfate heptahydrate 7g/L Liquid temperature: 37°C Current density: 30 A/dm 2 Electrodeposition time: 1 second
  • Metal foil 2 On the surface of the metal foil 1, a solution containing a silane coupling agent (“KBM series” manufactured by Shin-Etsu Chemical Co., Ltd.) in an amount of 1% by volume was used and subjected to surface treatment under the following conditions to prepare a metal foil 2.
  • the thickness of the metal foil 2 was 15 ⁇ m, and the ten-point average roughness of the surface was 0.6 ⁇ m.
  • Metal foil 3 Using titanium coated with a white metal oxide as an anode, and using an electrolytic copper foil having a ten-point average roughness (Rzjis) of 0.75 ⁇ m and a thickness of 12 ⁇ m as a cathode, electroplating was performed under the following conditions. A roughening treatment layer was formed on the surface of the electrolytic copper foil to prepare a metal foil 3.
  • Rzjis ten-point average roughness
  • Metal foil 4 was produced in the same manner as the metal foil 3 except that the liquid composition shown below was changed.
  • Liquid composition copper sulfate pentahydrate 15 g/L, cobalt sulfate heptahydrate 8.5 g/L
  • the ten-point average roughness of the surface of the metal foil 4 was 1.0 ⁇ m.
  • the proportion of nickel atoms existing on the surface of the metal foil 4 (roughening treatment layer) measured in the same manner as above was 0.00% by mass.
  • Metal foil 5 A metal foil 5 was produced in the same manner as the metal foil 3 except that the liquid composition shown below was changed.
  • Liquid composition copper sulfate pentahydrate 15 g/L, cobalt sulfate heptahydrate 8.5 g/L , Nickel sulfate hexahydrate 8.6 g/L
  • the ten-point average roughness of the surface of the metal foil 5 was 1.0 ⁇ m. Further, the proportion of nickel atoms present on the surface of the metal foil 5 (roughening treatment layer) measured in the same manner as above was 0.30 mass %.
  • Metal foil 6 After electroplating the electrolytic copper foil to form a roughening treatment layer, a heat-resistant treatment layer and a chromate layer were sequentially formed on the roughening treatment layer to produce a metal foil 6.
  • the ten-point average roughness of the surface of the metal foil 6 was 0.2 ⁇ m, and the thickness was 12 ⁇ m.
  • Metal foil 7 A metal foil 7 was manufactured in the same manner as the metal foil 6.
  • the ten-point average roughness of the surface of the metal foil 7 was 1.2 ⁇ m, and the thickness was 18 ⁇ m.
  • Metal foil 8 A metal foil 8 was manufactured in the same manner as the metal foil 6.
  • the ten-point average roughness of the surface of the metal foil 8 was 7.7 ⁇ m, and the thickness was 18 ⁇ m.
  • the liquid dispersion 1 was formed by coating the surface of the metal foil 1 with the dispersion liquid 1 by roll-to-roll by die coating.
  • the metal foil 1 on which this liquid film was formed was passed through a drying oven at 120° C. for 30 minutes and dried by heating. The dry coating was then heated at 380°C for 15 minutes in a nitrogen oven. In this way, the laminated body 1 in which the F layer was formed on the surface of the metal foil 1 was manufactured.
  • Example 2 (comparative example) A laminate 2 was produced in the same manner as in Example 1 except that the metal foil 1 was changed to the metal foil 2.
  • Example 3 (comparative example) A laminate 3 was produced in the same manner as in Example 1 except that the dispersion liquid 1 was changed to the dispersion liquid 2.
  • Example 4 A laminate 4 having an F layer thickness of 12 ⁇ m was produced in the same manner as in Example 1 except that the metal foil 1 was changed to the metal foil 3. Using two sheets of this laminate 4 and one sheet of a polyimide film (thickness: 25 ⁇ m; Ube Industries, Ltd., “Upilex 25S”), apply the F layer of each laminate 1 to both sides of the polyimide film. And laminated by heating at 360° C. to further produce a laminate 41 having metal foil layers on both outermost surfaces.
  • Example 5 A laminate 5 and a laminate 51 each having an F layer thickness of 12 ⁇ m were manufactured in the same manner as in Example 4 except that the metal foil 3 was changed to the metal foil 4.
  • Example 6 A laminate 6 and a laminate 61 each having an F layer thickness of 12 ⁇ m were manufactured in the same manner as in Example 4 except that the metal foil 3 was changed to the metal foil 5.
  • Example 7 A laminate 7 having an F layer thickness of 12 ⁇ m was produced in the same manner as in Example 4 except that the dispersion liquid 1 was changed to the dispersion liquid 3.
  • Example 8 First, the liquid dispersion 4 was applied onto the surface of the metal foil 7 by roll-to-roll coating by the gravure reverse method. Next, the metal foil 7 on which this liquid film was formed was passed through a drying oven at 100° C., 120° C. and 140° C. for a total of 5 minutes, and dried by heating. Then, the dry film was heated at 380° C. for 3 minutes in a far infrared oven under a nitrogen atmosphere. Thereby, the laminated body 8 in which the F layer was formed on the surface of the metal foil layer was manufactured. The thickness of the F layer was 5 ⁇ m.
  • the F layer of the laminate 8 and the prepreg 1 were laminated and thermocompression bonded under the conditions of a temperature of 200° C., a pressure of 3 MPa, and a time of 15 minutes.
  • all the metal foil layers of the laminated body 8 are removed with an acid solution, and the prepreg 1 is laminated on the contact surface (exposed surface) as it is, and heated at a temperature of 200° C., a pressure of 3 MPa, and a time of 15 minutes. Crimped.
  • a composite laminate 8 in which the exposed F layer and the prepreg layer were laminated was obtained.
  • Example 9 A composite laminate 9 was produced in the same manner as in Example 8 except that the metal foil 7 was changed to the metal foil 6 and the dispersion liquid 4 was changed to the dispersion liquid 5.
  • Example 10 A composite laminate 10 was produced in the same manner as in Example 8 except that the dispersion liquid 4 was changed to the dispersion liquid 5.
  • Example 11 comparative example
  • a composite laminate 11 was produced in the same manner as in Example 10 except that the metal foil 7 was changed to the metal foil 8 and the thickness of the F layer was 15 ⁇ m.
  • Example 12 First, the sheet 1 was laminated on the surface of the metal foil 7 and thermocompression bonded for 3 minutes at 380° C. in an oven under a nitrogen atmosphere. This produced the laminated body in which the F layer was formed on the surface of the metal foil layer. Next, after the F layer side of the laminate was subjected to vacuum plasma treatment, the F layer of the laminate and the prepreg 1 were laminated and thermocompression bonded under the conditions of a temperature of 200° C., a pressure of 3 MPa, and a time of 15 minutes.
  • Example 13 A composite laminate 13 was produced in the same manner as in Example 12 except that the sheet 1 was changed to the sheet 2.
  • the laminate 1 since the surface of the metal foil was not treated with the silane coupling agent, high peel strength was obtained, and variation in peel strength between samples was small. On the other hand, in the laminate 2, since the surface of the metal foil was treated with the silane coupling agent, not only sufficient peel strength could not be obtained, but also variation in peel strength between samples was large. Further, in the laminate 3, since the F polymer 2 having no oxygen-containing polar group was used, a metal foil whose surface was not treated with a silane coupling agent was used, but the peel strength was low.
  • Retention rate (%) (Peeling strength after heating)/(Initial peeling strength) ⁇ 100 The results are summarized in Table 2.
  • the laminated body 41 was used to form a sample circuit of a microstrip line.
  • the line width of the signal layer was 120 ⁇ m, the line length was 50 mm, and the back surface was a solid ground layer.
  • the sample circuit was sandwiched by UTF (Universal Test Fixture), and the transmission loss at 40 GHz was measured using a network analyzer.
  • the transmission loss of each of the laminated body 51 and the laminated body 61 was measured in the same manner as the laminated body 41. The results are summarized in Table 3.
  • solder resist was dried at 80° C. for 3 minutes, exposed to UV light of 400 mJ/cm 2 , and then immersed in a 1 mass% sodium carbonate aqueous solution for 60 seconds to develop. After that, the solder resist is post-cured at 150° C. for 60 minutes, further exposed to UV light of 1000 mJ/cm 2 to form a solder mask layer, and a composite laminate in which the exposed F layer and the solder mask layer are laminated. I got 14.
  • Example 15 A composite laminate 15 was obtained in the same manner as in Example 14 except that the metal foil 8 was used.
  • Example 16 A composite laminate 16 was obtained in the same manner as in Example 14 except that the contact surface (exposed surface) of the F layer was treated with a soft etching agent, buffed, and then solder resist was applied.
  • the laminate of the present invention and the composite laminate produced by the present invention have excellent electrical properties and adhesiveness, and have a polymer layer firmly fixed to a metal foil layer. Therefore, the antenna component, the printed wiring board, and the power semiconductor It can be used after being processed into insulating layers, aircraft parts, automobile parts, etc.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Electrochemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention aborde le problème de la fourniture d'un stratifié qui a atteint une adhérence uniforme et élevée entre une couche de polymère et une couche de feuille métallique ; et d'un procédé de production de ce stratifié. La solution selon la présente invention porte sur un stratifié qui comprend une couche de feuille métallique et une couche de polymère qui est disposée sur la surface de la couche de feuille métallique de façon à être en contact direct avec celle-ci, et qui contient un polymère à base de tétrafluoroéthylène ayant une viscosité à l'état fondu allant de 1 × 102 à 1 × 106 Pa∙s at 380°C. Ce stratifié est configuré de telle sorte que : aucun atome de silicium n'est présent dans la surface de la couche de feuille métallique ; ou le taux d'atomes de nickel détectés dans la surface de la couche de feuille métallique au moyen d'une analyse de fluorescence par rayons X va de 0,03 % massique à 0,25 % massique.
PCT/JP2020/002517 2019-01-30 2020-01-24 Stratifié, procédé de production de celui-ci, procédé de production de stratifié composite, et procédé de production de film polymère Ceased WO2020158604A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020217023787A KR102865559B1 (ko) 2019-01-30 2020-01-24 적층체 및 그 제조 방법, 복합 적층체의 제조 방법, 그리고 폴리머 필름의 제조 방법
JP2020569583A JP7230932B2 (ja) 2019-01-30 2020-01-24 積層体及びその製造方法、複合積層体の製造方法、並びにポリマーフィルムの製造方法
CN202080011655.2A CN113365804A (zh) 2019-01-30 2020-01-24 层叠体及其制造方法、复合层叠体的制造方法以及聚合物膜的制造方法

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
JP2019014510 2019-01-30
JP2019-014510 2019-01-30
JP2019014509 2019-01-30
JP2019-044625 2019-03-12
JP2019044625 2019-03-12
JP2019-014509 2019-06-28
JP2019-192671 2019-10-23
JP2019192671 2019-10-23

Publications (1)

Publication Number Publication Date
WO2020158604A1 true WO2020158604A1 (fr) 2020-08-06

Family

ID=71839973

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2020/002517 Ceased WO2020158604A1 (fr) 2019-01-30 2020-01-24 Stratifié, procédé de production de celui-ci, procédé de production de stratifié composite, et procédé de production de film polymère

Country Status (5)

Country Link
JP (1) JP7230932B2 (fr)
KR (1) KR102865559B1 (fr)
CN (1) CN113365804A (fr)
TW (1) TWI850322B (fr)
WO (1) WO2020158604A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022145352A1 (fr) * 2020-12-28 2022-07-07 株式会社ダイセル Composé, agent de liaison, corps assemblé, substrat imprimé et procédé de fabrication de corps lié
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
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
US12391850B2 (en) 2020-12-16 2025-08-19 Versiv Composites Limited Dielectric substrate and method of forming the same

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116406078B (zh) * 2023-03-30 2025-07-22 广州方邦电子股份有限公司 金属箔的承载体、金属箔及其应用
CN116321700A (zh) * 2023-03-30 2023-06-23 广州方邦电子股份有限公司 金属箔的承载体、金属箔及其应用

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013042781A1 (fr) * 2011-09-22 2013-03-28 ダイキン工業株式会社 Corps stratifié et son procédé de production
WO2014126193A1 (fr) * 2013-02-14 2014-08-21 三井金属鉱業株式会社 Feuille de cuivre à surface traitée, et stratifié plaqué par du cuivre obtenu à l'aide de la feuille de cuivre à surface traitée
WO2016159102A1 (fr) * 2015-04-01 2016-10-06 三菱鉛筆株式会社 Dispersion non aqueuse contenant une résine à base de fluor ; composition du type solution de précurseur de polyimide contenant une résine à base de fluor ; polyimide, film de polyimide et composition adhésive pour cartes à circuits imprimés, utilisant chacun ladite composition du type solution de précurseur de polyimide contenant une résine à base de fluor ; et procédés de production de ces derniers
WO2017222027A1 (fr) * 2016-06-23 2017-12-28 旭硝子株式会社 Procédé de fabrication de composition liquide contenant une poudre de résine fluorée
JP2018090903A (ja) * 2016-12-05 2018-06-14 Ｊｘ金属株式会社 表面処理銅箔、キャリア付銅箔、積層体、プリント配線板の製造方法及び電子機器の製造方法
WO2018212285A1 (fr) * 2017-05-18 2018-11-22 Ａｇｃ株式会社 Film et stratifié de résine d'hydrocarbure fluoré, et procédé de production d'un stratifié thermiquement pressé

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4295800B2 (ja) 2002-05-13 2009-07-15 三井金属鉱業株式会社 電解銅箔
JP4958045B2 (ja) 2006-10-27 2012-06-20 三井金属鉱業株式会社 フレキシブル銅張積層板製造用の表面処理銅箔及びその表面処理銅箔を用いて得られるフレキシブル銅張積層板
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
JP6687409B2 (ja) 2016-02-09 2020-04-22 福田金属箔粉工業株式会社 高彩度処理銅箔及び該処理銅箔を用いた銅張積層板並びに該処理銅箔の製造方法
JP6728529B2 (ja) 2016-07-15 2020-07-22 住友電工ファインポリマー株式会社 プリプレグ及び多層基板
US10820414B2 (en) * 2016-12-05 2020-10-27 Jx Nippon Mining & Metals Corporation Surface treated copper foil, copper foil with carrier, laminate, method for manufacturing printed wiring board, and method for manufacturing electronic device

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013042781A1 (fr) * 2011-09-22 2013-03-28 ダイキン工業株式会社 Corps stratifié et son procédé de production
WO2014126193A1 (fr) * 2013-02-14 2014-08-21 三井金属鉱業株式会社 Feuille de cuivre à surface traitée, et stratifié plaqué par du cuivre obtenu à l'aide de la feuille de cuivre à surface traitée
WO2016159102A1 (fr) * 2015-04-01 2016-10-06 三菱鉛筆株式会社 Dispersion non aqueuse contenant une résine à base de fluor ; composition du type solution de précurseur de polyimide contenant une résine à base de fluor ; polyimide, film de polyimide et composition adhésive pour cartes à circuits imprimés, utilisant chacun ladite composition du type solution de précurseur de polyimide contenant une résine à base de fluor ; et procédés de production de ces derniers
WO2017222027A1 (fr) * 2016-06-23 2017-12-28 旭硝子株式会社 Procédé de fabrication de composition liquide contenant une poudre de résine fluorée
JP2018090903A (ja) * 2016-12-05 2018-06-14 Ｊｘ金属株式会社 表面処理銅箔、キャリア付銅箔、積層体、プリント配線板の製造方法及び電子機器の製造方法
WO2018212285A1 (fr) * 2017-05-18 2018-11-22 Ａｇｃ株式会社 Film et stratifié de résine d'hydrocarbure fluoré, et procédé de production d'un stratifié thermiquement pressé

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11596064B2 (en) 2020-07-28 2023-02-28 Saint-Gobain Performance Plastics Corporation Dielectric substrate and method of forming the same
US11805600B2 (en) 2020-07-28 2023-10-31 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
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
WO2022145352A1 (fr) * 2020-12-28 2022-07-07 株式会社ダイセル Composé, agent de liaison, corps assemblé, substrat imprimé et procédé de fabrication de corps lié
JPWO2022145352A1 (fr) * 2020-12-28 2022-07-07

Also Published As

Publication number Publication date
JP7230932B2 (ja) 2023-03-01
CN113365804A (zh) 2021-09-07
TW202037488A (zh) 2020-10-16
KR20210121048A (ko) 2021-10-07
KR102865559B1 (ko) 2025-09-26
TWI850322B (zh) 2024-08-01
JPWO2020158604A1 (ja) 2021-12-02

Similar Documents

Publication Publication Date Title
JP7230932B2 (ja) 積層体及びその製造方法、複合積層体の製造方法、並びにポリマーフィルムの製造方法
JPWO2018212285A1 (ja) フッ素樹脂フィルムおよび積層体、ならびに、熱プレス積層体の製造方法
TWI824049B (zh) 分散液
CN112236302B (zh) 带树脂的金属箔的制造方法、带树脂的金属箔、层叠体及印刷基板
JP2020180245A (ja) パウダー分散液、積層体の製造方法、積層体及びプリント基板の製造方法
KR20210016327A (ko) 수지 부착 금속박의 제조 방법 및 수지 부착 금속박
JP2020158720A (ja) 複合粒子、分散液、積層体の製造方法、膜の製造方法及び被覆織布の製造方法
WO2021075504A1 (fr) Liquide de dispersion non aqueux et son procédé de production
TWI814836B (zh) 分散液、附樹脂之金屬箔之製造方法、及印刷基板之製造方法
JP2021075030A (ja) 積層体、積層体の製造方法、シート、及びプリント回路基板
CN112004610A (zh) 层叠体的制造方法及层叠体
WO2020059606A1 (fr) Stratifié, carte imprimée et procédé de fabrication de celle-ci
WO2020004338A1 (fr) Feuille métallique fixée à une résine
WO2020241607A1 (fr) Composition liquide
JP2020070401A (ja) 分散液
JP2020055241A (ja) 樹脂付金属箔及び樹脂付金属箔の製造方法
KR102787276B1 (ko) 적층체 및 적층체의 제조 방법
JP7452534B2 (ja) パウダー分散液、パウダー分散液の製造方法及び樹脂付基板の製造方法
JP2020083990A (ja) 複合体の製造方法及び複合体
KR102897538B1 (ko) 액상 조성물

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: 20748570

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2020569583

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20748570

Country of ref document: EP

Kind code of ref document: A1