WO2020255871A1 - 金属張積層体の製造方法 - Google Patents

金属張積層体の製造方法 Download PDF

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Publication number
WO2020255871A1
WO2020255871A1 PCT/JP2020/023194 JP2020023194W WO2020255871A1 WO 2020255871 A1 WO2020255871 A1 WO 2020255871A1 JP 2020023194 W JP2020023194 W JP 2020023194W WO 2020255871 A1 WO2020255871 A1 WO 2020255871A1
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Prior art keywords
metal
clad laminate
manufacturing
liquid crystal
sided
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PCT/JP2020/023194
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English (en)
French (fr)
Japanese (ja)
Inventor
健 ▲高▼橋
崇裕 中島
翔真 佐々木
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株式会社クラレ
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Priority to JP2021528172A priority Critical patent/JP7458396B2/ja
Priority to CN202080043587.8A priority patent/CN114007832B/zh
Priority to KR1020217040426A priority patent/KR20220020270A/ko
Publication of WO2020255871A1 publication Critical patent/WO2020255871A1/ja

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    • 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
    • B29C63/00—Lining or sheathing, i.e. applying preformed layers or sheathings of plastics; Apparatus therefor
    • B29C63/02—Lining or sheathing, i.e. applying preformed layers or sheathings of plastics; Apparatus therefor using sheet or web-like material
    • 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
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/22—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of indefinite length
    • B29C43/24—Calendering
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D17/00—Forming single grooves in sheet metal or tubular or hollow articles
    • B21D17/04—Forming single grooves in sheet metal or tubular or hollow articles by rolling
    • 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
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/003—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor characterised by the choice of material
    • 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
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/32—Component parts, details or accessories; Auxiliary operations
    • 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
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/32—Component parts, details or accessories; Auxiliary operations
    • B29C43/52—Heating or cooling
    • 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
    • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
    • B29C59/04—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing using rollers or endless belts
    • 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
    • B29C63/00—Lining or sheathing, i.e. applying preformed layers or sheathings of plastics; Apparatus therefor
    • B29C63/0004—Component parts, details or accessories; Auxiliary operations
    • 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
    • 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
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/40—General aspects of joining substantially flat articles, e.g. plates, sheets or web-like materials; Making flat seams in tubular or hollow articles; Joining single elements to substantially flat surfaces
    • B29C66/41—Joining substantially flat articles ; Making flat seams in tubular or hollow articles
    • 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
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/74—Joining plastics material to non-plastics material
    • B29C66/742—Joining plastics material to non-plastics material to metals or their alloys
    • 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
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/80—General aspects of machine operations or constructions and parts thereof
    • B29C66/83—General aspects of machine operations or constructions and parts thereof characterised by the movement of the joining or pressing tools
    • B29C66/834—General aspects of machine operations or constructions and parts thereof characterised by the movement of the joining or pressing tools moving with the parts to be joined
    • B29C66/8341—Roller, cylinder or drum types; Band or belt types; Ball types
    • B29C66/83411—Roller, cylinder or drum types
    • B29C66/83413—Roller, cylinder or drum types cooperating rollers, cylinders or drums
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • 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
    • B32B43/00—Operations specially adapted for layered products and not otherwise provided for, e.g. repairing; Apparatus therefor
    • B32B43/006—Delaminating
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2009/00—Layered products
    • B29L2009/003—Layered products comprising a metal layer

Definitions

  • thermoplastic liquid crystal polymer film a film made of a thermoplastic polymer capable of forming an optically anisotropic molten phase (hereinafter, this may be referred to as a thermoplastic liquid crystal polymer) (hereinafter, this is referred to as a thermoplastic liquid crystal polymer film).
  • a metal-clad laminate or a metal-clad laminate in which a metal layer is laminated on one surface (which may be), and a metal shaping sheet is laminated on the other surface, the surface of the thermoplastic liquid crystal polymer film side being a shaping surface.
  • the present invention relates to a method for producing a metal-clad laminate) from which the metal shaping sheet on the other surface is peeled off.
  • Thermoplastic liquid crystal polymer film is known as a material having excellent heat resistance, low hygroscopicity, high frequency characteristics, etc., and has been attracting attention as an electronic circuit material for high-speed transmission in recent years.
  • a metal-clad laminate of a thermoplastic liquid crystal polymer film and a metal foil is used, but in the bonding process in the circuit processing process, the thermoplastic liquid crystal polymer film provided in the metal-clad laminate is provided.
  • the interlayer adhesiveness between the metal and the bonding sheet may not be sufficient.
  • thermoplastic liquid crystal polymer film Conventionally, in a single-sided metal-clad laminate having a metal layer on one surface of a thermoplastic liquid crystal polymer film in order to improve the interlayer adhesiveness with a bonding sheet, an uneven shape is formed on the surface of the thermoplastic liquid crystal polymer film on the other side.
  • the shaping process to be given was being performed.
  • Patent Document 1 Japanese Unexamined Patent Publication No. 2016-10967 includes a step of stacking a first metal foil, a liquid crystal polymer film, and a second metal foil in this order and heating and pressurizing the second metal foil.
  • the surface to be laminated on the liquid crystal polymer film is a matte surface, and a method for producing a liquid crystal polymer film with a metal foil in which the matte surface is subjected to a mold release treatment is disclosed.
  • Patent Document 2 Japanese Unexamined Patent Publication No. 2006-179609
  • a method for producing a laminated wiring board which comprises superimposing a laminate on the surface of another unit substrate to form a laminated plate having two or more layers, and heating and pressurizing the laminated plate. Is disclosed as a liquid crystal polymer.
  • the metal layer serving as a transmission line has a skin effect, so that the high-frequency characteristics of the metal layer, that is, the transmission loss depends on its surface roughness. Therefore, it is desirable to use a low-roughness metal layer having a small surface roughness because the transmission loss is small, that is, the high-frequency characteristics are improved.
  • Patent Document 1 when the first metal foil, the liquid crystal polymer film, and the second metal foil to be peeled off later for the shaping treatment are laminated and heated and pressed to be laminated and integrated at once. If a low-roughness material is used for the first metal foil, it is necessary to heat the first metal foil to near the melting point (or above the melting point) in order to improve the interlayer adhesiveness between the first metal foil and the liquid crystal polymer film. .. In that case, high-temperature heat is applied even at the interface between the second metal leaf and the liquid crystal polymer film, which will be peeled off later, and even if the second metal leaf is subjected to the mold release treatment, the interlayer adhesion is caused by the anchor effect due to the unevenness of the surface. Since the property is high, it becomes difficult to peel off the second metal foil.
  • liquid crystal polymer molecules of the thermoplastic liquid crystal polymer film are easily oriented by heating and pressurizing, the orientation changes significantly when heated and pressed at a high temperature as described above, and the resulting metal-clad laminate warps. Is large, and the dimensional change is large, which makes it difficult to form a circuit board.
  • an object of the present invention is to provide a method for producing a metal-clad laminate having a small dimensional change and being efficiently shaped.
  • the inventors of the present invention have independently performed the production of the single-sided metal-clad laminate and the shaping treatment of the single-sided metal-clad laminate, thereby performing the shaping treatment. It has been found that the dimensional change of the metal-clad laminate can be suppressed because the heating and pressurizing at a high temperature can be avoided. Then, a single-sided metal-clad laminate in which a metal layer is adhered to one surface of the thermoplastic liquid crystal polymer film is prepared, and the single-sided metal-clad laminate and the metal shaping sheet are continuously thermocompression bonded to be efficiently applied. It was found that the shape processing can be performed, and the present invention has been completed.
  • a longer release cushion material (C) is prepared, In the thermocompression bonding step, the release cushion material (C) is arranged on at least one of the non-contact side of the single-sided metal-clad laminate (A) and the metal shaping sheet (B), and a pair of pressure rolls (r). 1, is introduced into the r 2), method for producing a metal clad laminate.
  • the peel strength between the release cushion material (C) and the single-sided metal-clad laminate (A) or the metal shaping sheet (B) is 0.
  • a method for producing a metal-clad laminate which is 1 N / mm or less (preferably 0.05 N / mm or less, more preferably 0.03 N / mm or less).
  • the release cushioning material (C) is a heat-resistant resin film, a heat-resistant composite film, a heat-resistant non-woven fabric, and a mold release material on at least one surface.
  • the single-sided metal-clad laminate (A), the metal shaping sheet (B), and the release cushion material (C) are stacked in the order of (C) / (A) / (B) / (r 2 ).
  • a method for manufacturing a metal-clad laminate to be introduced [Aspect 11] The method for producing a metal-clad laminate according to the tenth aspect, wherein in the thermocompression bonding step, the pressure roll (r 2 ) has a higher heating temperature than the pressure roll (r 1 ). Method.
  • Aspect 12 The method for producing a metal-clad laminate according to any one of aspects 1 to 11, wherein a plurality of long single-sided metal-clad laminates (A) and elongated metal shaping sheets (B) are provided.
  • a method for manufacturing a metal-clad laminate which prepares and manufactures a plurality of metal-clad laminates.
  • Aspect 13 The method for manufacturing a metal-clad laminate according to aspect 11, which is subordinate to any one of aspects 6 to 9, wherein a plurality of sets of single-sided metal-clad laminate (A) and metal addition are formed in the thermocompression bonding step.
  • the single-sided metal-clad laminate (A), the metal shaping sheet (B), and the release cushion material (C) are stacked in the order of / (C) / (A) / (B) / (r 2 ).
  • a method for manufacturing a metal-clad laminate in which a single-sided metal-clad laminate (A), a metal shaping sheet (B), and a release cushioning material (C) are stacked and introduced. ..
  • a single-sided metal-clad laminate and a metal shaping sheet are prepared and arranged so that the thermoplastic liquid crystal polymer film surface of the single-sided metal-clad laminate and the shaping surface of the metal shaping sheet are in contact with each other.
  • a metal-clad laminate in which a metal shaping sheet is laminated on a thermoplastic liquid crystal polymer film surface of a single-sided metal-clad laminate, or a metal-clad laminate that has been shaped-treated is continuously connected.
  • the metal-clad laminate is a metal-clad laminate having a metal layer on one surface of a thermoplastic liquid crystal polymer film and a metal shaping sheet on the other surface, or a thermoplastic liquid crystal polymer film. It may be a metal-clad laminate having a metal layer on one surface and the other surface being shaped, and may be appropriately provided with other accessories (for example, a release cushioning material).
  • thermoplastic liquid crystal polymer film used in the production method of the present invention is formed from a liquid crystal polymer that can be melt-molded.
  • the thermoplastic liquid crystal polymer is a polymer capable of forming an optically anisotropic molten phase, and the chemical composition thereof is not particularly limited as long as it is a liquid crystal polymer that can be melt-molded. , Thermoplastic liquid crystal polyester, or thermoplastic liquid crystal polyester amide in which an amide bond is introduced therein.
  • thermoplastic liquid crystal polymer may be a polymer in which an imide bond, a carbonate bond, an isocyanate-derived bond such as a carbodiimide bond or an isocyanurate bond is further introduced into an aromatic polyester or an aromatic polyester amide.
  • thermoplastic liquid crystal polymer used in the present invention include known thermoplastic liquid crystal polyesters and thermoplastic liquid crystal polyesteramides derived from the compounds classified into (1) to (4) and derivatives thereof exemplified below. Can be mentioned. However, it goes without saying that the combination of various raw material compounds has an appropriate range in order to form a polymer capable of forming an optically anisotropic molten phase.
  • Aromatic or aliphatic diols (see Table 1 for typical examples)
  • Aromatic diamine, aromatic hydroxyamine or aromatic aminocarboxylic acid (see Table 4 for typical examples)
  • thermoplastic liquid crystal polymers obtained from these raw material compounds include copolymers having structural units shown in Tables 5 and 6.
  • a copolymer containing p-hydroxybenzoic acid and / or 6-hydroxy-2-naphthoic acid as at least a repeating unit is preferable, and (i) p-hydroxybenzoic acid and 6-hydroxy- A copolymer containing a repeating unit with 2-naphthoic acid, or at least one aromatic hydroxycarboxylic acid selected from the group consisting of (ii) p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, and at least one.
  • a copolymer containing a repeating unit of the aromatic diol of the above and at least one aromatic dicarboxylic acid is preferable.
  • the p-hydroxybenzoic acid of the repeating unit (A) if the thermoplastic liquid crystal polymer contains at least a repeating unit of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, the p-hydroxybenzoic acid of the repeating unit (A).
  • At least one aromatic hydroxycarboxylic acid (C) selected from the group consisting of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid and 4,4'-.
  • aromatic diol (D) selected from the group consisting of dihydroxybiphenyl, hydroquinone, phenylhydroquinone, and 4,4'-dihydroxydiphenyl ether, and the group consisting of terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid.
  • the molar ratio of the repeating unit derived from 6-hydroshiki-2-naphthoic acid in the aromatic hydroxycarboxylic acid (C) may be, for example, 85 mol% or more, preferably 90 mol% or more. It may be preferably 95 mol% or more.
  • the molar ratio of the repeating unit derived from 2,6-naphthalenedicarboxylic acid in the aromatic dicarboxylic acid (E) may be, for example, 85 mol% or more, preferably 90 mol% or more, and more preferably 95 mol%. It may be% or more.
  • optically anisotropic molten phase referred to in the present invention can be formed can be determined by, for example, placing the sample on a hot stage, heating the sample in a nitrogen atmosphere, and observing the transmitted light of the sample. ..
  • a preferred thermoplastic liquid crystal polymer has a melting point (hereinafter referred to as Tm 0 ) having, for example, a melting point in the range of 200 to 360 ° C., preferably in the range of 240 to 350 ° C., and more preferably Tm 0.
  • the temperature is 260 to 330 ° C.
  • the melting point can be obtained by observing the thermal behavior of the thermoplastic liquid crystal polymer sample using a differential scanning calorimeter. That is, after the thermoplastic liquid crystal polymer sample was heated at a rate of 10 ° C./min to completely melt it, the melt was cooled to 50 ° C. at a rate of 10 ° C./min and again at a rate of 10 ° C./min. The position of the endothermic peak that appears after the temperature is raised is determined as the melting point of the thermoplastic liquid crystal polymer sample.
  • the thermoplastic liquid crystal polymer may have a melt viscosity of 30 to 120 Pa ⁇ s at a shear rate of 1000 / s at (Tm 0 + 20) ° C., preferably a melt viscosity of 50. It may have ⁇ 100 Pa ⁇ s.
  • thermoplastic liquid crystal polymer includes thermoplastic polymers such as polyethylene terephthalate, modified polyethylene terephthalate, polyolefin, polycarbonate, polyarylate, polyamide, polyphenylene sulfide, polyetheretherketone, and fluororesin, as long as the effects of the present invention are not impaired. , Various additives, fillers and the like may be added.
  • thermoplastic liquid crystal polymer film used in the production method of the present invention is obtained, for example, by extrusion molding the melt-kneaded product of the thermoplastic liquid crystal polymer.
  • Any method is used as the extrusion molding method, but the well-known T-die method, inflation method and the like are industrially advantageous.
  • the inflation method stress is applied not only in the mechanical axis direction (hereinafter abbreviated as MD direction) of the thermoplastic liquid crystal polymer film but also in the direction orthogonal to this (hereinafter abbreviated as TD direction), and the MD direction and TD direction are applied. Since it can be uniformly stretched in the direction, a thermoplastic liquid crystal polymer film having controlled molecular orientation, dielectric properties, etc. in the MD direction and the TD direction can be obtained.
  • MD direction mechanical axis direction
  • TD direction direction orthogonal to this
  • the melt sheet extruded from the T-die may be stretched not only in the MD direction of the thermoplastic liquid crystal polymer film but also in both the MD direction and the TD direction at the same time to form a film.
  • the melt sheet extruded from the T die may be once stretched in the MD direction and then stretched in the TD direction to form a film.
  • a predetermined draw ratio corresponding to the stretching ratio in the MD direction
  • a blow ratio corresponding to the stretching ratio in the TD direction
  • the draw ratio of such extrusion molding may be, for example, about 1.0 to 10 as the draw ratio (or draw ratio) in the MD direction, preferably about 1.2 to 7, and more preferably 1. It may be about 3 to 7. Further, the stretching ratio (or blow ratio) in the TD direction may be, for example, about 1.5 to 20, preferably about 2 to 15, and more preferably about 2.5 to 14.
  • thermoplastic liquid crystal polymer film may be adjusted by heating at about ° C., preferably (Tm 0 ) to (Tm 0 +20) ° C.) for several hours.
  • the melting point (Tm) of the thermoplastic liquid crystal polymer film can be obtained by observing the thermal behavior of the thermoplastic liquid crystal polymer film sample using a differential scanning calorimeter. That is, the position of the endothermic peak that appears when the temperature of the thermoplastic liquid crystal polymer film sample is raised at a rate of 10 ° C./min can be determined as the melting point (Tm) of the thermoplastic liquid crystal polymer film.
  • the single-sided metal-clad laminate used in the production method of the present invention is one in which a metal layer is arranged on one surface of the thermoplastic liquid crystal polymer film.
  • a commercially available product may be used as the single-sided metal-clad laminate.
  • a metal foil is bonded to a thermoplastic liquid crystal polymer film by thermocompression bonding as a metal layer.
  • the metal layer may be formed by sputtering, vapor deposition, electroless plating or the like. From the viewpoint of production efficiency and convenience, a method of adhering a metal foil to a thermoplastic liquid crystal polymer film by thermocompression bonding is preferable.
  • a long one-sided metal-clad laminate is used.
  • the long object may have a roll shape wound on a roll, or may have a non-roll shape not wound on a roll.
  • the length of the long object is not particularly limited as long as it can be continuously conveyed, but it may be 100 m or more (for example, 100 to 500 m).
  • a method of adhering the metal foil to the thermoplastic liquid crystal polymer film a method of superimposing the thermoplastic liquid crystal polymer film and the metal leaf and continuously thermocompression bonding by a roll press or a double belt press by a roll-to-roll method is preferable. ..
  • the peel strength between the thermoplastic liquid crystal polymer film and the metal layer of the single-sided metal-clad laminate may be 0.6 N / mm or more, preferably 0.8 N / mm or more, and more preferably 1.0 N / mm or more. It may be. Further, the upper limit of the peel strength between the thermoplastic liquid crystal polymer film of the single-sided metal-clad laminate and the metal layer is not particularly limited, but may be, for example, 2.0 N / mm or less.
  • the peel strength is the peel strength (peeling strength) measured with reference to JIS C 5016-1994 (peeling in the 90 ° direction).
  • preparation of a single-sided metal-clad laminate for example, production of a single-sided metal-clad laminate by thermocompression bonding of a thermoplastic liquid crystal polymer film and metal leaf
  • shaping treatment of the single-sided metal-clad laminate that is, Thermocompression bonding with the metal shaping sheet
  • the metal forming the metal layer is not particularly limited, and may be, for example, gold, silver, copper, iron, tin, nickel, aluminum, chromium, or an alloy metal thereof.
  • the metal foil formed of the metal may be used, and a copper foil or a stainless steel foil is preferable from the viewpoint of conductivity, handleability, cost and the like.
  • the copper foil those produced by a rolling method or an electrolytic method can be used.
  • the metal foil may be subjected to surface treatment such as roughening treatment, which is usually performed, as long as the high frequency characteristics of the metal-clad laminate of the present invention are not impaired.
  • the thickness of the metal layer can be appropriately set as needed, and may be, for example, about 1 to 50 ⁇ m, more preferably in the range of 9 to 35 ⁇ m.
  • the metal shaping sheet used in the production method of the present invention is a sheet made of metal, and at least one surface is a shaping surface.
  • a long metal shaping sheet is used.
  • the elongated object may have a roll shape wound on a roll, or may have a non-roll shape not wound on a roll.
  • the length of the long object is not particularly limited as long as it can be continuously conveyed, but it may be 100 m or more (for example, 100 to 500 m).
  • the metal shaping sheet is preferably a metal foil having at least one surface having a shaping surface.
  • the metal forming the metal shaping sheet is not particularly limited, and may be, for example, gold, silver, copper, iron, tin, nickel, aluminum, chromium or an alloy metal thereof, and when a metal foil is used.
  • a metal foil formed of the metal may be used, and a copper foil or a stainless steel foil is preferable from the viewpoint of handleability, cost, and the like.
  • these metal foils those produced by a rolling method or an electrolytic method can be used, and surface treatment such as roughening treatment may be performed in order to obtain a desired shaped surface.
  • the metal forming the metal shaping sheet is a material having a coefficient of thermal expansion similar to that of the metal forming the metal layer of the single-sided metal-clad laminate (for example). , The same type of metal). In particular, it is preferable that both the metal layer and the metal shaping sheet are copper foils.
  • the shaped surface of the metal shaped sheet may have, for example, a surface roughness (Rz) of 1.0 to 7.0 ⁇ m from the viewpoint of improving the interlayer adhesiveness with the bonding sheet in circuit processing.
  • the surface roughness (Rz) of the shaped surface of the metal shaping sheet is transferred, and the surface roughness (Rz) of the surface roughness (Rz) similar to that of the metal shaping sheet is transferred to the surface of the thermoplastic liquid crystal polymer film.
  • the surface roughness (Rz) of the shaping surface of the metal shaping sheet may be preferably 1.5 to 5.5 ⁇ m, more preferably 2.0 to 4.5 ⁇ m.
  • the surface roughness (Rz) indicates the ten-point average roughness measured with reference to JIS B 0601-1994 using a contact-type surface roughness meter, and is the roughness of the reference length. In the curve, it represents the sum of the average of the mountain heights from the highest peak to the fifth in the highest order and the average of the valley depths from the deepest valley bottom to the fifth.
  • the shaping surface of the metal shaping sheet may be subjected to a mold release treatment from the viewpoint of facilitating peeling of the metal shaping sheet after thermocompression bonding.
  • a method of the mold release treatment for example, a method of applying a mold release agent to the shape surface of the metal shape sheet to provide a mold release layer may be used.
  • the release agent include silicone-based resins and fluororesins.
  • the thickness of the metal shaping sheet can be appropriately set as needed, and may be, for example, about 5 to 50 ⁇ m, more preferably in the range of 9 to 35 ⁇ m.
  • a release cushion material may be used in the production method of the present invention, if necessary.
  • a long material may be used as the release cushion material.
  • the elongated object may have a roll shape wound on a roll, or may have a non-roll shape not wound on a roll.
  • the length of the long object is not particularly limited as long as it can be continuously conveyed, but it may be 100 m or more (for example, 100 to 500 m).
  • the release cushioning material is not particularly limited as long as it can be peeled off from the adjacent adherend after thermal pressure bonding, has heat resistance, and has cushioning properties, and is a non-thermoplastic polyimide film, aramid film, or Teflon ( Heat-resistant resin film such as a film (registered trademark); heat-resistant composite film (for example, composite film composed of a plurality of heat-resistant resin films, composite film composed of metal foil and heat-resistant resin film); heat-resistant fiber (for example, heat resistance) A heat-resistant non-woven film composed of resin fibers (resin fibers, metal fibers); and a metal foil (for example, a coating layer of a release agent such as a silicone-based resin or a fluorine-based resin) on at least one surface.
  • Heat-resistant resin film such as a film (registered trademark)
  • heat-resistant composite film for example, composite film composed of a plurality of heat-resistant resin films, composite film composed of metal foil and heat-resistant resin film
  • release cushioning materials may be used alone or in combination of two or more.
  • the release cushion material (for example, a heat-resistant resin film, a heat-resistant composite film, or a heat-resistant non-woven fabric) is subjected to a mold release treatment from the viewpoint of facilitating peeling from the adherend after thermocompression bonding. May be.
  • the mold release processing method include the above-mentioned methods.
  • a heat-resistant resin film, a heat-resistant composite film, and a heat-resistant non-woven fabric are preferable from the viewpoint of excellent heat resistance and cushioning property (repulsive elasticity).
  • the thickness of the release cushion material can be appropriately set as needed, and may be, for example, about 5 to 300 ⁇ m, preferably 10 to 150 ⁇ m, and more preferably 25 to 75 ⁇ m. ..
  • the surface roughness (Rz) of at least one surface of the release cushion material is 2.0 ⁇ m from the viewpoint of facilitating peeling from the adherend (single-sided metal-clad laminate or metal shaping sheet) after thermocompression bonding. It may be less than or equal to, preferably 1.8 ⁇ m or less, and more preferably 1.5 ⁇ m or less. Further, the lower limit of the surface roughness (Rz) of at least one surface of the release cushion material is not particularly limited, but may be, for example, 0.05 ⁇ m or more, preferably 0.10 ⁇ m or more, and more preferably 0. It may be 15 ⁇ m or more.
  • the method for producing a metal-clad laminate of the present invention is: A long single-sided metal-clad laminate (A) in which a metal layer is adhered to one surface of a thermoplastic liquid crystal polymer film, and a long metal shaping sheet (B) in which at least one surface is a shaping surface. ) And the process of preparing A pair of pressure rolls (r 1 , r 2 ) are arranged so that the thermoplastic liquid crystal polymer film surface of the single-sided metal-clad laminate (A) and the shaping surface of the metal shaping sheet (B) are in contact with each other. The thermocompression bonding process to be introduced into At least prepare.
  • the single-sided metal-clad laminate (A) and the metal shaping sheet (B) are not particularly limited as long as they can be introduced into the pressure roll as a long product, and for example, a long product manufactured upstream of the thermocompression bonding step can be used. It may be transported as it is and used, or an unwinding roll may be prepared.
  • a long product manufactured upstream is used as it is, for example, a single-sided metal-clad laminate (A) is manufactured by superimposing a thermoplastic liquid crystal polymer film and a metal foil and continuously thermocompression bonding, and winding the product. Instead, it may be overlapped with the separately prepared metal shaping sheet (B) downstream of the transport direction as it is.
  • thermoplastic liquid crystal polymer film surface of the single-sided metal-clad laminate (A) and the shaping surface of the metal shaping sheet (B) are arranged and overlapped so as to be in contact with each other.
  • each unwinding roll is a thermoplastic liquid crystal polymer film in which the single-sided metal-clad laminate (A) and the metal shaping sheet (B) are adjacent to each other and the single-sided metal-clad laminate (A) is adjacent to each other. It is arranged so that the surface and the shaping surface of the metal shaping sheet (B) are in contact with each other.
  • the method for producing a metal-clad laminate of the present invention is: In the preparatory process, a longer release cushion material (C) is prepared, In the thermocompression bonding step, the release cushion material (C) is arranged on at least one of the non-contact side of the single-sided metal-clad laminate (A) and the metal shaping sheet (B), and a pair of pressure rolls (r). 1, it may be introduced to r 2).
  • the release cushion material (C) acts as a cushion, so that pressure is applied in thermocompression bonding between the single-sided metal-clad laminate (A) and the metal shaping sheet (B).
  • the pressure from the roll can be dispersed, and the transferability of the shaped surface of the metal shaping sheet (B) to the surface of the thermoplastic liquid crystal polymer film can be improved.
  • the heating temperature in the pressure roll (r 1, r 2) is high, pressure if pressure pressure is low, when the short pressing time is uniform pressure due to the presence of the releasing cushion material (C) Highly effective in improving sex.
  • the release cushion material (C) is a single-sided metal-clad laminate (A) on the non-contact surfaces of the single-sided metal-clad laminate (A) and the metal shaping sheet (B). ) And / or may be arranged adjacent to the metal shaping sheet (B).
  • the release cushion material (C) is arranged adjacent to the metal layer of the single-sided metal-clad laminate (A), and the metal-clad laminate is formed in the order of at least (C) / (A) / (B). It may be thermocompression bonded as described above.
  • the release cushion material (C) By adjoining the release cushion material (C) to the metal layer side of the single-sided metal-clad laminate (A), heat is suppressed from the release cushion material (C) being transferred from the single-sided metal-clad laminate (A) side. Since it acts as a heat insulating material, it is possible to prevent the thermoplastic liquid crystal polymer film from being heated more than necessary from the metal layer side, and to prevent the liquid crystal polymer molecules from being easily oriented.
  • At least one of the pressure rolls (r 1 , r 2 ) is a heated pressure roll (hr), and the heated pressure roll (hr) is changed to (hr) / (B). ) / (A), or when the release cushion material (C) is used, (hr) / (B) / (A) / (C) or (hr) / (C) / (B) It may be introduced in the order of / (A).
  • the heating and pressurizing conditions can be adjusted so as to prevent the thermoplastic liquid crystal polymer film from being heated more than necessary, and the shaping process can be performed efficiently.
  • a plurality of long single-sided metal-clad laminates (A) and a plurality of elongated metal shaping sheets (B) are prepared, and a plurality of metal-clad laminates are prepared. It may be manufactured.
  • a release cushion material is provided between a plurality of sets of single-sided metal-clad laminates (A) and laminates including a metal shaping sheet (B) in a thermocompression bonding step. It may be introduced in layers.
  • thermocompression bonding step a pair of pressure rolls (r 1, r 2) at least one release cushion material in contact with the pressure roll of the (C) May be introduced.
  • the plurality of single-sided metal-clad laminates (A) may be the same or different.
  • the plurality of metal shaping sheets (B) may be the same or different.
  • the obtained plurality of metal-clad laminates may be the same or different.
  • the obtained metal-clad laminate (a metal-clad laminate in which a metal layer is laminated on one surface of a thermoplastic liquid crystal polymer film and a metal shaping sheet is provided on the other surface) is a thermoplastic liquid crystal polymer film and metal shaping.
  • the peel strength (P1) between the sheet and the sheet may be 0.5 N / mm or less, preferably 0.2 N / mm or less, and more preferably 0.1 N / mm or less.
  • the peel strength (P2) between the thermoplastic liquid crystal polymer film and the metal layer may be, for example, 0.6 N / mm or more, preferably 0.8 N / mm. It may be mm or more, more preferably 1.0 N / mm or more.
  • the upper limit of the peel strength between the thermoplastic liquid crystal polymer film and the metal layer is not particularly limited, but may be 2.0 N / mm or less.
  • the obtained metal-clad laminate has a peel strength (P1) between the thermoplastic liquid crystal polymer film and the metal shaping sheet, and a peel strength (P2) between the thermoplastic liquid crystal polymer film and the metal layer.
  • the divided value (P1 / P2) may be 0.6 or less, preferably 0.4 or less, and more preferably 0.2 or less.
  • the orientation degree f (f1) on the metal layer side in the thickness direction of the thermoplastic liquid crystal polymer film is set to the orientation degree f (or the shaping treatment surface side) on the metal shaping sheet side (or shaping treatment surface side).
  • the value (f1 / f2) divided by f2) may be 1.05 to 1.40, preferably 1.10 to 1.35, and more preferably 1.15 to 1.30.
  • the degree of orientation on the metal layer side in the thickness direction of the thermoplastic liquid crystal polymer film is the degree of orientation on the side in contact with the metal layer when the thermoplastic liquid crystal polymer film is divided into two equal parts in the thickness direction.
  • the degree of orientation on the metal shaping sheet side (shape processing surface side) in the thickness direction of the thermoplastic liquid crystal polymer film is the same as the metal shaping sheet when the thermoplastic liquid crystal polymer film is divided into two equal parts in the thickness direction.
  • the degree of orientation of the part on the contact side (the surface side that has been shaped).
  • the degree of orientation f is an index that gives the degree of orientation of the crystal region of the polymer, and is calculated as follows.
  • the change in crystal orientation can be obtained from a wide-angle X-ray photograph.
  • the metal shaping sheet of the metal-clad laminate is peeled off, the metal layer is etched and removed, and the obtained film is cut out in the MD direction, attached to the sample holder, and X-rays are incident from the Edge direction for imaging.
  • the diffraction image is exposed on the plate.
  • H is the half price range.
  • the degree of orientation f is measured on both the metal layer side and the metal shaping sheet side (shape processing surface side) of the thermoplastic liquid crystal polymer film.
  • FIG. 1 is a schematic side view for explaining a method for manufacturing a metal-clad laminate according to the first embodiment.
  • a method for manufacturing a metal-clad laminate according to the first embodiment As shown in FIG. 1, in the first embodiment, on the upstream side of the pair of pressure rolls (r 1, r 2), unwinding sided metal-clad laminate unwound sided metal-clad laminate (A) roll 11 and the metal shaping sheet unwinding roll 12 for unwinding the metal shaping sheet (B) are prepared.
  • the single-sided metal-clad laminate (A) and the metal shaping sheet (B) are placed between the pair of pressure rolls (r 1 , r 2 ) (r 1 ) / (A). ) / (B) / (r 2 ), each unwinding roll is arranged in this order.
  • the single-sided metal-clad laminate unwinding roll 11 and the metal shaping sheet unwinding roll 12 are arranged so as to be in contact with each other.
  • thermoplastic liquid crystal polymer film of the single-sided metal-clad laminate (A) As a result, it is possible to suppress the dimensional change of the metal-clad laminate, the occurrence of wrinkles due to the difference in thermal expansion of each material, and further, the thermoplastic liquid crystal polymer film of the single-sided metal-clad laminate (A). The peelability between the surface and the shaped surface of the metal shaping sheet (B) can be improved.
  • the pressurizing roll a known heating and pressurizing device can be used, and examples thereof include a metal roll, a rubber roll, and a resin-coated metal roll.
  • the pressure roll (r 1 ) may be a metal roll from the viewpoint of increasing the heating efficiency
  • the pressure roll (r 2 ) is a metal roll like the pressure roll (r 1 ). It may be a rubber roll or a resin-coated metal roll.
  • the pair of pressure rolls (r 1, r 2) is to be heated only one may be heated both.
  • the heating temperature of the pressure roll (r 1, r 2) may be identical to one another or may be different.
  • the pressure roll disposed on the metal shaping sheet (B) side has a higher temperature, and in the case of the first embodiment as shown in FIG. 1, the metal shaping sheet (B) side.
  • the heating temperature of the pressure roll (r 2 ) disposed in may be higher than that of the pressure roll (r 1 ).
  • the heating temperature is from the pressure roll (r 1) towards the pressure roll (r 2) is high, for example, the temperature difference between the heating temperature of the heating temperature and the pressure roller (r 1) of the pressure roll (r 2) May be 20 to 200 ° C., preferably 25 to 150 ° C., and more preferably 30 to 100 ° C.
  • thermocompression bonding temperature and the pressure condition of the pressure roll are not particularly limited, but from the viewpoint of improving the transferability of the unevenness of the shaping surface of the metal shaping sheet (B), for example, a thermoplastic liquid crystal polymer film.
  • the thermocompression bonding temperature may be, for example, (Tm-150) ° C. or higher, preferably (Tm-130) ° C. or higher (for example, (Tm-100) ° C. or higher) with respect to the melting point (Tm). It may be preferably (Tm-110) ° C. or higher (for example, (Tm-90) ° C. or higher).
  • the temperature may be lower than (Tm) ° C., preferably (Tm-5) ° C. or lower. It may be preferably (Tm-10) ° C. or lower.
  • the thermocompression bonding temperature may be the heating temperature of the pressurizing rolls (r 1 , r 2 ), and when the heating temperatures of the pair of pressurizing rolls (r 1 , r 2 ) are different from each other, pressurization is performed.
  • the thermocompression bonding temperature may be the higher of the heating temperatures of the rolls (r 1 , r 2 ).
  • the pressurizing pressure may be in the range of 16.0 t / m (156.8 kN / m) or less, preferably 8.0 t / m (78.4 kN / m) or less.
  • the lower limit of the pressurizing pressure is not particularly limited, but may be 0.5 t / m (4.9 kN / m) or more.
  • the pressurizing pressure is a value obtained by dividing the force applied to the pressurizing roll (crimping load) by the maximum width of the material passing between the pressurizing rolls.
  • a cooling roll may be provided on the downstream side of the pressure roll, if necessary.
  • the cooling roll is preferably provided between the pressure roll and the first release roll.
  • the cooling roll may be composed of a pair of rolls or one single roll.
  • the manufacturing method of the present invention may further include a peeling step of peeling the metal shaping sheet (B) from the thermoplastic liquid crystal polymer film surface of the single-sided metal-clad laminate (A) after the thermocompression bonding step.
  • the stripping step for example, after passing through the pair of pressure rolls (r 1, r 2), by using the pair of pressure rolls (r 1, r 2) as a release roll immediately sided metal-clad laminate (A).
  • the metal shaping sheet (B) may be peeled from (), or the metal shaping sheet (A) may be peeled from the single-sided metal-clad laminate (A) by using at least one peeling roll arranged separately from the pressure roll. B) may be peeled off.
  • the metal-clad laminates (D) ((A) / (B)) obtained by the thermocompression bonding step are passed through the release rolls 21 and 21.
  • the metal-clad laminate (E) is produced by being peeled off between (A) and (B), and is wound on the metal-clad laminate take-up roll 31.
  • the metal-clad laminate (E) obtained by peeling the metal shaping sheet (B) is laminated in the order of metal layer / thermoplastic liquid crystal polymer film, and the metal layer of the thermoplastic liquid crystal polymer film is not adhered. The unevenness of the shaping surface of the metal shaping sheet (B) is transferred to the surface on the side.
  • the surface roughness (Rz) of the metal-clad laminate (E) on the side where the metal layer of the thermoplastic liquid crystal polymer film is not adhered may be 1.0 to 7.0 ⁇ m, preferably 1.5. It may be ⁇ 5.5 ⁇ m, more preferably 2.0 ⁇ 4.5 ⁇ m.
  • the peel strength between the single-sided metal-clad laminate (A) and the metal shaping sheet (B) may be appropriately set as long as the peeling step can be performed.
  • the peel strength between the single-sided metal-clad laminate (A) and the metal shaping sheet (B) is preferably 0.5 N / mm or less, and more preferably 0.2 N / mm or less. , 0.1 N / mm or less, more preferably.
  • the lower limit is not particularly limited, but may be 0 N / mm.
  • thermocompression bonding step a shaping process is performed by heating and pressurizing at a lower temperature while maintaining a low interlayer adhesiveness between the single-sided metal-clad laminate (A) and the metal shaping sheet (B). Can be applied.
  • the peeled metal shaping sheet (B) is wound by the metal shaping sheet winding roll 32.
  • the peeled metal shaping sheet (B) may be reused if necessary.
  • FIG. 2 is a schematic side view for explaining a method for manufacturing the metal-clad laminate according to the second embodiment.
  • Members having the same role as those in FIG. 1 are designated by the same reference numerals, and the description thereof will be omitted.
  • A unwinding sided metal-clad laminate unwound sided metal-clad laminate
  • A unwinding sided metal-clad laminate unwound sided metal-clad laminate
  • A unwinding sided metal-clad laminate unwound sided metal-clad laminate
  • C release cushion material
  • single-sided metal-clad laminate (A), a metal shaped sheet (B) and release the cushion material (C) is a pair of pressure rolls (r 1, r 2) between at , (R 1 ) / (C) / (A) / (B) / (r 2 ), and each unwinding roll is arranged in this order.
  • the upstream side of the pair of pressure rolls (r 1, r 2), the thermoplastic liquid crystal polymer film surface and the vehicle surface of the metal shaped sheet (B) of the single-sided metal-clad laminate (A) The single-sided metal-clad laminate unwinding roll 11 and the metal shaping sheet unwinding roll 12 are arranged so as to be in contact with each other, and the metal layer surface of the single-sided metal-clad laminate (A) and the release cushion material (C) are further arranged.
  • the release cushion material unwinding roll 13 is arranged so as to come into contact with each other.
  • the use of release packing cushion (C), dispersing the pressure from the pair of pressure rolls (r 1, r 2) by the cushioning It is possible to improve the transferability of the metal shaping sheet (B) to the thermoplastic liquid crystal polymer film having the uneven shape of the shaping surface. Further, since the overlapping release cushion material and (C) the metal layer side of the single-sided metal-clad laminate (A), the role of releasing the cushion material (C) is to insulate the heat from the pressure roll (r 1) Further, it is possible to suppress heat transfer more than necessary to the surface of the thermoplastic liquid crystal polymer film on the metal layer side, and it is possible to suppress dimensional change.
  • a metal-clad laminate obtained by a thermal pressure bonding step using at least one peeling roll (a metal-clad laminate comprising a single-sided metal-clad laminate (A) and a metal shaping sheet (B)).
  • the single-sided metal-clad laminate (A) is a metal-clad laminate in which the surface of the thermoplastic liquid crystal polymer film is shaped, and the metal-clad laminate is provided with the release cushion material (C).
  • the cushion material (C) may be peeled off.
  • the pair of pressure rolls (r 1, r 2) is used as the peeling rolls, the release cushion material immediately from the metal-clad laminate (C ) May be peeled off, or the release cushion material (C) may be peeled off from the metal-clad laminate by using at least one peeling roll arranged separately from the pressure roll.
  • the order of peeling of the metal shaping sheet (B) and peeling of the release cushion material (C) can be appropriately set according to the mode of the metal-clad laminate.
  • the metal-clad laminate (F) ((C) / (A) / (B)) obtained by the thermocompression bonding step is the first peeling roll 21, By passing through 21, the metal-clad laminate (D) is produced by peeling between (C) / (A).
  • the metal-clad laminate (D) obtained by peeling the release cushion material (C) is the metal layer of the single-sided metal-clad laminate (A) / the thermoplastic liquid crystal polymer film / metal of the single-sided metal-clad laminate (A).
  • the shaping sheets (B) are laminated in this order.
  • the peel strength between the release cushion material (C) and the single-sided metal-clad laminate (A) or the metal shaping sheet (B) is appropriately set as long as the peeling step can be performed. May be done.
  • the peel strength between the release cushion material (C) and the single-sided metal-clad laminate (A) or the metal shaping sheet (B) is preferably 0.1 N / mm or less, preferably 0.05 N / mm. It is more preferably mm or less, and further preferably 0.03 N / mm or less.
  • the lower limit is not particularly limited, but may be 0 N / mm.
  • the release cushion material (C) that has been peeled off is wound by the release cushion material winding roll 33.
  • the peeled release cushion material (C) can be reused as needed.
  • the metal-clad laminate (D) from which the release cushion material (C) has been peeled off is peeled between (A) / (B) by passing through the second peeling rolls 22 and 22, and the metal-clad laminate (D) is peeled off.
  • (E) is manufactured and wound on a metal-clad laminate winding roll 31.
  • FIG. 3 is a schematic side view for explaining a method for manufacturing the metal-clad laminate according to the third embodiment.
  • the single-sided metal-clad laminate (A), the metal shaping sheet (B) and the release cushion material (C) are made of a pair of pressure rolls (r 1 , r). 2 ), each unwinding roll is arranged in the order of (r 1 ) / (C) / (A) / (B) / (C) / (r 2 ).
  • the members having the same role as those in FIG. 2 are designated by the same reference numerals, and the description thereof will be omitted.
  • metal tensioning is performed between the pair of pressure rolls (r 1 , r 2 ) so as to form (C) / (A) / (B) / (C).
  • the release cushion material (C) is peeled off between (C) / (A) and (B) / (C) to produce a metal-clad laminate (D), and then the laminated body (D) is manufactured.
  • the metal shaping sheet (B) is peeled off from the metal-clad laminate (D) to produce the metal-clad laminate (E).
  • the heating temperature of the pair of pressure rolls (r 1, r 2) which may be the same as each other or different, for example, the first
  • the heating temperature of the pressure roll (r 2 ) on the metal shaping sheet (B) side may be higher than that of the pressure roll (r 1 ).
  • the heating temperature of the metal shaped sheet (B) and the adjacent release cushion material (C) in contact with pressure roll (r 2) single-sided metal-clad laminate of metal shaped sheet (B) ( Heat can be efficiently transferred to the thermoplastic liquid crystal polymer film surface (surface to be subjected to the shaping treatment) side of A).
  • FIG. 4 is a schematic side view for explaining a method for manufacturing the metal-clad laminate according to the fourth embodiment.
  • the single-sided metal-clad laminate (A), the metal shaping sheet (B), and the release cushion material (C) are made of a pair of pressure rolls (r 1 , r). 2 ), each unwinding roll is arranged in the order of (r 1 ) / (B) / (A) / (C) / (A) / (B) / (r 2 ).
  • the members having the same role as those in FIG. 2 are designated by the same reference numerals, and the description thereof will be omitted.
  • the pair of pressure rolls (r 1 , r 2 ) are overlapped so as to be (B) / (A) / (C) / (A) / (B).
  • the release cushion material (C) is peeled off from the metal-clad laminate (F) to produce two metal-clad laminates (D), and then a metal shaping sheet (a metal shaping sheet (D) is produced from the metal-clad laminate (D).
  • B) is peeled off to produce two metal-clad laminates (E).
  • a plurality of metal-clad laminates can be manufactured, and the production efficiency is high.
  • the two metal-clad laminates (D) may be the same or different from each other.
  • the two metal-clad laminates (E) may be the same as or different from each other.
  • the release cushion material (C) is overlapped with the single-sided metal-clad laminate (A) on both sides, so that the release layers are arranged on both sides. preferable.
  • a pair of pressure rolls (r 1 , 1 ,) are used from the viewpoint of suppressing the occurrence of wrinkles due to the difference in thermal expansion in the thermocompression bonding step.
  • r 2 may be the same, and the heating temperature may be the same.
  • FIG. 5 is a schematic side view for explaining a method for manufacturing the metal-clad laminate according to the fifth embodiment.
  • the single-sided metal-clad laminate (A), the metal shaping sheet (B) and the release cushion material (C) are made of a pair of pressure rolls (r 1 , r). Between 2 ), each unwinding roll is in the order of (r 1 ) / (C) / (B) / (A) / (A) / (B) / (C) / (r 2 ). Be placed.
  • the members having the same role as those in FIG. 2 are designated by the same reference numerals, and the description thereof will be omitted.
  • a plurality of metal-clad laminates can be manufactured, and the production efficiency is high.
  • the two metal-clad laminates (D) may be the same or different from each other.
  • the two metal-clad laminates (E) may be the same as or different from each other.
  • FIG. 6 is a schematic side view for explaining a method for manufacturing the metal-clad laminate according to the sixth embodiment.
  • the single-sided metal-clad laminate (A), the metal shaping sheet (B) and the release cushion material (C) are made of a pair of pressure rolls (r 1 , r). Between 2 ), each unwinding roll is in the order of (r 1 ) / (C) / (A) / (B) / (B) / (A) / (C) / (r 2 ). Be placed.
  • the members having the same role as those in FIG. 2 are designated by the same reference numerals, and the description thereof will be omitted.
  • a plurality of metal-clad laminates can be manufactured, and the production efficiency is high.
  • the two metal-clad laminates (D) may be the same or different from each other.
  • the two metal-clad laminates (E) may be the same as or different from each other.
  • a sample with a width of 250 mm and a length of 250 mm is taken from a single-sided metal-clad laminate, the sample is placed on a horizontal table, and the height of the part of the four corners of the sample that floats most from the table is measured on a scale. , This was a warp. Those with a warp of less than 5 mm were evaluated as A, and those with a warp of 5 mm or more were evaluated as B.
  • Example 1 Single-sided metal-clad laminate (A) obtained in Production Example 1, electrolytic copper foil as metal shaping sheet (B) ("JX-EFL-V2" manufactured by JX Nippon Mining & Metals Co., Ltd., thickness 12 ⁇ m, surface roughness of shaped surface is (Rz) 2.0 .mu.m), and the protective material (C) as a polyimide film (manufactured by Kaneka Corporation, "apical NPI", prepared as a roll unwinding thickness 75 [mu] m), respectively, a pair of pressure rolls (r 1, r Introduced in the order of r 1 / C / A / B / r 2 between 2 ).
  • the surface temperature of the metal rolls is set to 200 ° C.
  • the pressure pressure is set to 8 t / m
  • the speed is 3.0 m / min. by passing through a pair of pressure rolls (r 1, r 2) were thermocompression bonding.
  • thermocompression bonding as shown in FIG. 2, after passing through a pair of pressure rolls (r 1, r 2), using a pair of peeling rolls (21), separating the polyimide film (C), followed by a pair
  • the single-sided metal-clad laminate (E) and the metal shaping sheet (B) are separated by the peeling roll (22) of the above, and the surface shape of the metal shaping sheet (B) is transferred to the surface of the thermoplastic liquid crystal polymer film.
  • a metal-clad laminate (E) was obtained.
  • Table 7 shows the peelability of the metal shaping sheet (B) and the warp measurement results of the obtained single-sided metal-clad laminate (E).
  • the peel strength between the single-sided metal-clad laminate (E) and the metal shaping sheet (B) was 0.05 N / mm or less. Further, the peel strength between the single-sided metal-clad laminate (E) and the polyimide film (C) was not adhered at all and could not be measured.
  • Example 2 A single-sided metal-clad laminate (E) was produced in the same manner as in Example 1 except that the surface temperature of the metal roll was set to 240 ° C.
  • Table 7 shows the peelability of the metal shaping sheet (B) and the warp measurement results of the obtained single-sided metal-clad laminate (E).
  • the peel strength between the single-sided metal-clad laminate (E) and the metal shaping sheet (B) was 0.08 N / mm or less. Further, the peel strength between the single-sided metal-clad laminate (E) and the polyimide film (C) was not adhered at all and could not be measured.
  • thermoplastic liquid crystal polymer film (L) ("Vexter” (registered trademark) manufactured by Kuraray Co., Ltd., melting point 310 ° C., thickness 50 ⁇ m) and copper foil (M) (Fukuda metal foil)
  • L thermoplastic liquid crystal polymer film
  • M copper foil
  • C CF-H9A-DS-HD2
  • thermoplastic liquid crystal polymer film When the single-sided metal-clad laminate (E) is produced by introducing in the order of r 1 / C / M / L / B / r 2 between (r 1 , r 2 ), a thermoplastic liquid crystal polymer film ( The peeling strength between the L) and the copper foil (M) is low, and when the metal shaping sheet (B) is peeled off, the peeling occurs partially between the thermoplastic liquid crystal polymer film (L) and the copper foil (M). It is thought that.
  • the surface temperature of the metal roll can be set to a relatively low temperature, whereby the single-sided metal-clad laminate (A) can be set to a relatively low temperature.
  • the body and the metal shaping sheet did not adhere firmly to each other, and the molecular orientation of the thermoplastic liquid crystal polymer film did not change, resulting in good peelability and warpage.
  • the shape-treated metal-clad laminate can be efficiently produced, and the obtained metal-clad laminate has irregularities transferred to it, so that the metal-clad laminate is bonded to the bonding sheet. It has excellent properties and good circuit workability. Therefore, the obtained metal-clad laminate can be effectively used as a component used in the fields of electricity / electronics, office equipment / precision equipment, power semiconductors, etc., for example, a circuit board (particularly a substrate for millimeter-wave radar). Can be done.
PCT/JP2020/023194 2019-06-17 2020-06-12 金属張積層体の製造方法 WO2020255871A1 (ja)

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