WO2021193194A1 - 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
WO2021193194A1
WO2021193194A1 PCT/JP2021/010347 JP2021010347W WO2021193194A1 WO 2021193194 A1 WO2021193194 A1 WO 2021193194A1 JP 2021010347 W JP2021010347 W JP 2021010347W WO 2021193194 A1 WO2021193194 A1 WO 2021193194A1
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pair
liquid crystal
crystal polymer
metal
thermoplastic liquid
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PCT/JP2021/010347
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English (en)
French (fr)
Japanese (ja)
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健 ▲高▼橋
崇裕 中島
小野寺　稔
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株式会社クラレ
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Priority to KR1020227033022A priority Critical patent/KR20220156004A/ko
Priority to CN202180021663.XA priority patent/CN115279586B/zh
Priority to JP2022509949A priority patent/JP7182030B2/ja
Publication of WO2021193194A1 publication Critical patent/WO2021193194A1/ja

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    • 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
    • B32B38/0036—Heat treatment
    • B32B38/004—Heat treatment by physically contacting the layers, e.g. by the use of heated platens or rollers
    • 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
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/02—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by a sequence of laminating steps, e.g. by adding new layers at consecutive laminating stations
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/027—Thermal properties
    • 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
    • B32B2305/55—Liquid crystals

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).
  • the present invention relates to a method for producing a metal-clad laminate in which a metal foil is laminated on at least one surface (or a metal-clad laminate having a metal layer on at least one surface of a thermoplastic liquid crystal polymer film).
  • 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 laminate of a thermoplastic liquid crystal polymer film and a metal foil typified by copper foil is used, and a laminate composed of such a thermoplastic liquid crystal polymer film and a metal foil is manufactured.
  • a technique there is a method in which a thermoplastic liquid crystal polymer film cut to a predetermined size and a metal foil are placed on top of each other between the upper and lower hot plates by using a hot press device, and heat-pressed in a vacuum state.
  • this method is a batch method, there is a problem that the production efficiency is poor.
  • Patent Document 1 Japanese Patent No. 5661051 describes the roll-to-roll method on both the front and back sides.
  • spacing film (C) is also the surface roughness (Rz) 2.0 .mu.m or less, a pair of pressure rolls (r 1, r 2) between (r 1) / (B) / (a) / ( The insulating film (A), the metal foil (B), and the separating film (C) are laminated and heat-bonded in the order of C) / (A) / (B) / (r 2), and the separating film is heat-bonded.
  • a method for manufacturing a single-sided metal-clad laminate obtained by peeling from (C) to obtain two single-sided metal-clad laminates is disclosed.
  • Patent Document 1 is characterized in that two metal-clad laminates are vertically symmetrically arranged so as to be in contact with each other with the separation film as the center, and thermocompression bonding is performed by a roll-to-roll method. At the same time as being introduced into the pressure roll, it comes into direct contact with the insulating film.
  • thermoplastic liquid crystal polymer film when used as the insulating film, since the thermoplastic liquid crystal polymer film is a thermoplastic resin, the thermoplastic liquid crystal polymer film is slightly softened by heat immediately before being introduced between the pressure rolls. Since slackening occurs in the film, partial contact with a separating film having a different thermal expansion coefficient and elastic coefficient causes an appearance defect such as wrinkles in that portion.
  • an object of the present invention is to provide a method for efficiently producing a metal-clad laminate by a roll-to-roll method without causing appearance defects such as wrinkles.
  • the inventors of the present invention arrange a protective material in the outermost layer so as to sandwich the laminate material to be introduced into the pair of pressure rolls, and use the protective material as the protective material.
  • the protective material does not come into contact with the thermoplastic liquid crystal polymer film, so that it is possible to suppress the occurrence of appearance defects due to their partial contact, and it is surprising.
  • the adhesiveness between the films can be suppressed, and as a result, the occurrence of appearance defects such as wrinkles can be suppressed. The finding has led to the completion of the present invention.
  • [Aspect 1] It is a method of manufacturing a plurality of metal-clad laminates. In the step of introducing the laminate material via the pair of protective materials (C 1 , C 2 ) in contact with the pair of pressure rolls (r 1 , r 2 ) and thermocompression bonding the laminate material with the pressure roll.
  • the laminate material is a pair of outermost metal foils (M 1 , M 2 ) in contact with the pair of protective materials (C 1 , C 2 ), and at least a pair of thermoplastic liquid crystal polymer films (F,).
  • thermocompression bonding step of thermocompression bonding the laminate material with at least one pair of thermoplastic liquid crystal polymer films (F, F) in contact with each other in the laminate material.
  • a thermoplastic liquid crystal polymer film separation step of separating at least a pair of thermoplastic liquid crystal polymer films (F, F) after the thermocompression bonding step.
  • a method for manufacturing a metal-clad laminate comprising at least. [Aspect 2] The method for producing a metal-clad laminate according to the first aspect. In the thermocompression bonding step, the laminate material is thermocompression bonded with at least a pair of metal foils (M, M) in contact with each other in the laminate material.
  • a metal leaf separation step of separating at least a pair of metal foils (M, M) in contact with each other after the thermocompression bonding step is provided.
  • a method for manufacturing a metal-clad laminate [Aspect 3] The method for producing a metal-clad laminate according to aspect 1 or 2, wherein the metal-clad laminate is introduced into the pair of pressure rolls (r 1 , r 2 ) via the pair of protective materials (C 1 , C 2).
  • thermoplastic liquid crystal polymer film having a degree smaller than fv.
  • Tm The melting point (Tm) of the thermoplastic liquid crystal polymer film according to any one of aspects 1 to 4, wherein the thermocompression bonding temperature has the lowest melting point among the thermoplastic liquid crystal polymer films in the laminate material. relative to L), (the Tm L -120) °C ⁇ (Tm L) °C range (preferably (Tm L -100) is ° C. ⁇ (Tm L) range ° C.), method for producing a metal-clad laminate ..
  • a method for producing a metal-clad laminate more preferably in the range of 0 to 50 ° C.
  • the protective material (C 1 ) and / or the protective material (C 2 ) is made of a heat-resistant resin film, a heat-resistant composite film, and a heat-resistant non-woven fabric.
  • the protective material (C 1 ) and the protective material (C 2 ) are selected from the group consisting of a heat-resistant resin film, a heat-resistant composite film, and a heat-resistant non-woven fabric, respectively.
  • It is a protective material), a method of manufacturing a metal-clad laminate.
  • thermoplastic liquid crystal polymer film and the protective material are arranged so as not to be adjacent to each other and introduced into a pressure roll and thermocompression bonded, a metal-clad laminate in which the occurrence of poor appearance is suppressed can be efficiently produced. Can be manufactured well.
  • a plurality of sets of metal-clad laminates in which a metal foil is laminated on at least one surface of a thermoplastic liquid crystal polymer film can be continuously produced.
  • 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 their derivatives exemplified below. Can be mentioned. However, it goes without saying that there is an appropriate range in the combination of various raw material compounds 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 repeating units shown in Tables 5 and 6.
  • a polymer 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-are particularly preferable.
  • a copolymer containing a repeating unit of an aromatic diol and / or an aromatic hydroxyamine of at least one aromatic dicarboxylic acid is preferred.
  • 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 each repeating unit of at least one selected aromatic dicarboxylic acid (E) in the thermoplastic liquid crystal polymer is the aromatic hydroxycarboxylic acid (C): the aromatic diol (D): the aromatic dicarboxylic acid.
  • the molar ratio of the repeating unit derived from 6-hydroxy-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, for example, by 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 ) of, for example, 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, the thermoplastic liquid crystal polymer sample was heated from room temperature (for example, 25 ° C.) at a rate of 10 ° C./min to completely melt, and then the melt was cooled to 50 ° C. at a rate of 10 ° C./min. The position of the endothermic peak that appears after the temperature is raised again at a rate of 10 ° C./min is determined as the melting point of the thermoplastic liquid crystal polymer sample.
  • 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 a 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.
  • thermophysical properties of the thermoplastic liquid crystal polymer, the thickness of the desired thermoplastic liquid crystal polymer film, other production conditions, etc. affect the specific relationship between the draw ratio and the blow ratio, for example, the above draw ratio cannot be shown.
  • the crystal orientation fp in the plane direction can be controlled to be smaller than the crystal orientation fv in the thickness direction by adjusting the blow ratio to be larger than the draw ratio.
  • 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 may be, for example, 270 to 380 ° C., preferably 280 to 370 ° C.
  • 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 from room temperature (for example, 25 ° C.) at a rate of 10 ° C./min can be determined as the melting point (Tm) of the thermoplastic liquid crystal polymer film. can.
  • the thickness of the thermoplastic liquid crystal polymer film can be appropriately set according to the application. For example, considering that it is used as a material for an insulating layer of a multilayer circuit board, it may be 10 to 500 ⁇ m, preferably 15 to. It may be 250 ⁇ m, more preferably 25 to 180 ⁇ m.
  • the metal foil used in the production method of the present invention is not particularly limited, and may be, for example, gold, silver, copper, iron, nickel, aluminum or an alloy metal thereof, and has conductivity, handleability, and handling property. Copper foil or stainless foil is preferable from the viewpoint of cost and the like. As the copper foil, those produced by a rolling method or an electrolytic method can be used.
  • the thickness of the metal foil can be appropriately set as needed, and may be, for example, about 5 to 50 ⁇ m, more preferably in the range of 8 to 35 ⁇ m. Further, the metal foil may be subjected to surface treatment such as roughening treatment which is usually performed.
  • the protective material used in the production method of the present invention is not particularly limited as long as it can be easily peeled off from the adjacent metal foil after thermal pressure bonding and has heat resistance, and is a non-thermoplastic polyimide film, aramid film, or Teflon.
  • Heat-resistant resin film such as (registered trademark) film; 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); Examples thereof include a metal foil; and a heat-resistant non-woven fabric made of heat-resistant fibers (for example, heat-resistant resin fibers and metal fibers).
  • These protective materials may be used alone or in combination of two or more.
  • 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 impact resilience.
  • the thickness of the protective material can be appropriately set as needed, and may be, for example, about 10 to 300 ⁇ m, preferably 15 to 150 ⁇ m, and more preferably 15 to 130 ⁇ m. Further, the protective material may be subjected to a mold release treatment on one side or both sides for the purpose of improving the peelability from the metal foil after thermocompression bonding. Examples of the mold release treatment method include a method of providing a heat-resistant mold release resin film such as a silicone resin or a fluororesin on at least one surface of the protective material.
  • the method for producing a metal-clad laminate of the present invention is: In the step of introducing the laminate material via the pair of protective materials (C 1 , C 2 ) in contact with the pair of pressure rolls (r 1 , r 2 ) and thermocompression bonding the laminate material with the pressure roll.
  • the laminate material is a pair of outermost metal foils (M 1 , M 2 ) in contact with the pair of protective materials (C 1 , C 2 ), and at least a pair of thermoplastic liquid crystal polymer films (F,).
  • thermocompression bonding step which comprises at least F) and thermocompression-bonds the laminate material in a state where the at least pair of thermoplastic liquid crystal polymer films (F, F) are in contact with each other in the laminate material.
  • thermoplastic liquid crystal polymer film separation step of separating at least a pair of thermoplastic liquid crystal polymer films (F, F) after the thermocompression bonding step. At least prepare.
  • thermoplastic liquid crystal polymer film and the metal foil is not particularly limited as long as the laminate material can be formed and the laminate material can be introduced into the pressure roll via the protective material, for example, the laminate material.
  • Unwinding rolls of each constituent material may be prepared and each unwinding roll may be arranged so that a laminate material having a desired configuration can be formed.
  • the laminate material refers to a material for laminating in a predetermined arrangement in order to produce a desired plurality of metal-clad laminates, and the whole is sandwiched between a pair of protective materials (C 1 , C 2). which it is introduced to a pair of pressure rolls (r 1, r 2).
  • thermoplastic liquid crystal polymer film (F) as a constituent material for forming one metal-clad laminate in the laminate material may be singular or plural.
  • the metal foil (M) may be singular or plural. When a plurality of them are included, they may be the same or different.
  • each constituent material of the laminate material may be a simple substance of the thermoplastic liquid crystal polymer film (F), a single body of the metal foil (M), or on one surface of the thermoplastic liquid crystal polymer film (F). It may be a single-sided metal-clad laminate (M / F) on which a metal foil (M) is arranged.
  • a metal-clad laminate is formed as long as the effect of the present invention is not impaired.
  • a material other than the above may be contained, for example, a protective material (C) may be arranged between a pair of metal foils (M, M), and the arrangement in the order of M / C / M may be performed. You may have.
  • each unwinding roll may be arranged so as to satisfy the following conditions, for example.
  • the pair of outermost layer metal foils (M 1 , M 2 ) unwound from the metal foil unwinding roll each form the outermost layer in the laminate material, and the pair of protective materials (C 1 , C 2 ). In contact with each.
  • the pair of thermoplastic liquid crystal polymer films (F, F) unwound from the thermoplastic liquid crystal polymer film unwinding roll has at least a portion in contact with each other in the laminate material.
  • the laminate material may have at least a pair of metal foils (M, M) in contact with each other. Since the portion where the metal foils are in contact with each other can be easily separated after the thermocompression bonding step, when manufacturing a plurality of metal-clad laminates (for example, three or more metal-clad laminates), the laminate material It is preferable that the pair of metal foils (M, M) have a portion in contact with each other.
  • the laminate material is formed into a pair of pressure rolls (r 1 , r 2 ) via a pair of protective materials (C 1 , C 2 ) by arranging in any of the following orders (i) to (vi). It may be introduced.
  • r 1 / C 1 / M 1 / F / F / M 2 / C 2 / r 2 (Ii) r 1 / C 1 / M 1 / F / F / M / M / F / M 2 / C 2 / r 2 (Iii) r 1 / C 1 / M 1 / F / M / M / F / F / M / M / F / M 2 / C 2 / r 2 (Iv) r 1 / C 1 / M 1 / F / F / M / M / F / F / M 2 / C 2 / r 2 (V) r 1 / C 1 / M 1 / F / F
  • At least one of the pair of thermoplastic liquid crystal polymer films (F, F) in contact with each other in the laminate material is a thermoplastic liquid crystal polymer film in which the degree of crystal orientation fp in the plane direction is smaller than the degree of crystal orientation fv in the thickness direction. It may be.
  • the larger the degree of crystal orientation fv in the thickness direction of the thermoplastic liquid crystal polymer film the more difficult it is for the film to adhere to the thermoplastic liquid crystal polymer film in contact with the film, so that it becomes easier to separate after the thermocompression bonding step.
  • the smaller the degree of crystal orientation fp in the plane direction the less likely it is that peeling anisotropy occurs when the film and the thermoplastic liquid crystal polymer film in contact with the film are separated from each other.
  • the crystal orientation degree 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. First, the thermoplastic liquid crystal polymer film is cut out in the MD direction and attached to the sample holder.
  • X-rays are incident on the crystal orientation fp in the plane direction from the Throwh direction, and the crystal orientation fv in the thickness direction is X from the Edge direction.
  • a line is incident and the diffraction image is exposed on the imaging plate.
  • each of the thickness direction and the plane direction (MD direction) is converted into an orientation distribution curve, and the degree of crystal orientation is obtained from the half-value width H of the peak of the curve of the diffraction intensity with respect to the ⁇ angle in the circumferential direction.
  • f crystal orientation degree fp in the plane direction and crystal orientation degree fv in the thickness direction
  • H is the half price range.
  • thermoplastic liquid crystal polymer film (F) has a crystal orientation degree fp in the plane direction of 0.4 to 0.8. It may be, preferably 0.5 to 0.7.
  • the crystal orientation fv in the thickness direction may be 0.7 to 0.9, preferably 0.7 to 0.8.
  • the pair of thermoplastic liquid crystal polymer films (F, F) in contact with each other in the laminate material may be the same or different from each other, for example, the difference in melting point between them is in the range of 0 to 70 ° C. It may be in the range of 0 to 60 ° C, more preferably in the range of 0 to 50 ° C.
  • the melting points of the plurality of thermoplastic liquid crystal polymer films in the laminate material are different, the melting points of the pair of thermoplastic liquid crystal polymer films (F, F) in contact with each other are all the other thermoplastic liquid crystal polymers in the laminate material.
  • film may be greater than the lowest melting point (Tm L) having the.
  • the lowest melting point (Tm L) all of the thermoplastic liquid crystal polymer film included in the multilayer material means the lowest melting point among the melting point (Tm) with respectively.
  • thermoplastic liquid crystal polymer film (F, F) in the laminate material is prior to the thermocompression bonding step.
  • a heating step of softening by heating it is possible to suppress the occurrence of poor appearance of the obtained metal-clad laminate.
  • a protective material heating step for heating the pair of protective materials (C 1 , C 2) may be further provided.
  • the protective material heating step is not particularly limited as long as capable of heating the pair of protective material (C 1, C 2), a pair of protective material by an external heating means such as a heater (C 1, C 2) may be heated Then, the pair of protective materials (C 1 , C 2 ) may be heated by a heating roll provided separately from the pressure rolls (r 1 , r 2). Alternatively, the pair of protective materials (C 1 , C 2 ) may be heated by circumscribing the pair of protective materials (C 1 , C 2 ) to the pair of pressure rolls (r 1 , r 2).
  • the time during which the protective material and the pressure roll are externally contacted is the type of protective material and the state of the protective material. It can be appropriately set depending on various conditions such as the heating temperature of the pressure roll, but from the viewpoint of removing water from the protective material, it is preferably 1.0 second or longer, for example, 1.0 to 200. It may be seconds, or 3.0 to 125 seconds.
  • the protective material heating step may be determined based on the thermocompression bonding temperature.
  • the temperature of the protective material heating step may be, for example, T-30 to T + 30 ° C. It may be, preferably T-15 to T + 15 ° C.
  • the heating time can be appropriately set according to the heating means.
  • the water content of the protective material is within a predetermined range (for example, 1100 ppm or less, 900 ppm or less, 700 ppm or less, or 400 ppm or less). It is preferable to heat in the range that becomes.
  • the obtained plurality of metal-clad laminates may be the same or different.
  • FIG. 1 is a schematic side view for explaining a method for manufacturing a metal-clad laminate according to the first embodiment.
  • the protective material unwinding roll that unwinds the pair of protective materials (C 1 , C 2 ) on the upstream side of the pair of pressure rolls (r 1 , r 2). 11, 11, the metal foil unwinding rolls 12, 12 for unwinding the pair of outermost metal foils (M 1 , M 2 ), and the thermoplastic liquid crystal polymer film for unwinding the pair of thermoplastic liquid crystal polymer films (F, F).
  • Unwinding rolls 13 and 13 are prepared.
  • a pair of protective materials C 1 , C 2
  • a pair of outermost metal foils M 1 , M 2
  • a pair of thermoplastic liquid crystal polymer films F, F
  • Each unwinding roll is arranged between the pair of pressure rolls (r 1 , r 2 ) in the order of r 1 / C 1 / M 1 / F / F / M 2 / C 2 / r 2.
  • the protective material unwinding rolls 11 and 11 for unwinding the pair of protective materials (C 1 , C 2 ) on the upstream side of the pair of pressure rolls (r 1 , r 2) are the outermost layers, respectively.
  • Metal leaf unwinding rolls 12 and 12 for unwinding a pair of outermost layer metal foils (M 1 , M 2 ) are arranged inside the pair of thermoplastic liquid crystal polymer films (F). , F) is unwound, and the thermoplastic liquid crystal polymer film unwinding rolls 13 and 13 are arranged.
  • thermoplastic liquid crystals are arranged from each unwinding roll as shown in the direction of the arrow.
  • a polymer film (F, F), a pair of outermost metal foils (M 1 , M 2 ), and a pair of protective materials (C 1 , C 2 ) are unwound and a pair of pressure rolls (r 1 , r 2). ), It is introduced in the MD direction (or the laminating direction) indicated by the arrow.
  • the laminate material M 1 / F / F / M 2 is passed through the pair of protective materials (C 1 , C 2 ), that is, C 1 / M 1 It is introduced in the order of / F / F / M 2 / C 2 , and pressure is applied to the laminate material at a predetermined heating temperature.
  • the protective material and the thermoplastic liquid crystal polymer film are arranged so as not to come into contact with each other, partial contact between the thermoplastic liquid crystal polymer film and the protective material having a different coefficient of thermal expansion or elastic modulus can be obtained. It is possible to suppress the occurrence of poor appearance of the metal-clad laminate.
  • the pressure from the pressure roll can be dispersed at the time of thermocompression bonding, or wrinkles due to the non-uniformity of the pressure applied to the laminate material. Occurrence can be suppressed.
  • the protective material in the outermost layer so as to sandwich the laminate material, it is possible to suppress unnecessary heat conduction to the inner layer of the laminate material, or the thermoplastic liquid crystal polymer films are thermocompression bonded to each other. As a result, it is possible to efficiently manufacture the metal-clad laminate while suppressing the occurrence of poor appearance of the obtained metal-clad laminate.
  • 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 pair of pressure rolls (r 1 , r 2 ) may be the same or different from each other.
  • 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.
  • each of the heating temperature of the pair of pressure rolls (r 1, r 2) may be identical to one another or may be different.
  • the heating temperature of one pressure roll is set higher than the heating temperature of the other pressure roll in consideration of the melting point of the thermoplastic liquid crystal polymer film and the like. It may have been done.
  • 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 5 to 80 ° C, preferably 10 to 70 ° C, more preferably 20 to 50 ° C.
  • thermocompression bonding temperature and the pressure condition of the pressure roll are not particularly limited, but from the viewpoint of improving the adhesiveness between the thermoplastic liquid crystal polymer film and the metal foil and suppressing the occurrence of wrinkles, for example, heat.
  • the thermocompression bonding temperature may be in the range of (Tm-120) ° C. to (Tm) ° C., preferably (Tm-100) ° C. to (Tm) ° C. with respect to the melting point (Tm) of the thermoplastic liquid crystal polymer film. It may be.
  • the thermocompression temperature is the melting point of the thermoplastic liquid crystal polymer film having the lowest melting point among the thermoplastic liquid crystal polymer films in the laminate material (TmL ).
  • (Tm L -120) °C ⁇ (Tm L) may be in the range of ° C., preferably may be (Tm L -100) °C ⁇ ( Tm L) °C.
  • the heat crimping temperature may be the heating temperature of the pressure rolls (r 1 , r 2 ), and when the heating temperatures of the pair of pressure rolls (r 1 , r 2 ) are different from each other, the pair of pressure rolls (r 1, r 2) may be heated. Any high heating temperatures of the heating temperature of the pressure roll (r 1, r 2) may be a thermocompression bonding temperature.
  • the pressurizing pressure may be in the range of 1.0 t / m (9.8 kN / m) to 15 t / m (147 kN / m), preferably 1.5 t / m (14.7 kN / m) to 12 t / m. It may be in the range of m (117.6 kN / m).
  • the pressurizing pressure is a value obtained by dividing the force (crimping load) applied to the pressurizing roll by the work width.
  • the speed at which the protective material and the laminate material are passed through the pair of pressure rolls (r 1 , r 2 ) is appropriately set according to the thermocompression bonding temperature, the pressure conditions of the pressure rolls, and the size of the pressure rolls. However, it may be, for example, 0.5 to 5.0 m / min, preferably 1.0 to 4.0 m / min.
  • the production method of the present invention includes a thermoplastic liquid crystal polymer film separation step of separating at least a pair of thermoplastic liquid crystal polymer films (F, F) after the thermal pressure bonding step, for example, a pair of pressure rolls (r). Immediately after passing through 1 , r 2 ), the pair of thermoplastic liquid crystal polymer films (F, F) may be separated, or a pair of separation rolls may be provided separately from the pressure roll. The thermoplastic liquid crystal polymer films (F, F) may be separated from each other.
  • the peel strength between the thermoplastic liquid crystal polymer film (F) and the thermoplastic liquid crystal polymer film (F) in the laminate after thermocompression bonding may be 0.3 kN / m or less, preferably 0.2 kN / m. Hereinafter, it may be more preferably 0.1 kN / m or less.
  • the peel strength is the peel strength (peeling strength) measured in accordance with JIS C 6471: 1995 (peeling in the 90 ° direction).
  • the manufacturing method of the present invention may include a protective material separation step for separating at least one of the protective materials in contact with each other and the outermost layer metal foil.
  • the protective material separation step and the thermoplastic liquid crystal polymer film separation step may be performed step by step so that one of the separation steps is performed first and then the other separation step is performed.
  • the thermoplastic liquid crystal polymer film separation step may be performed at the same time.
  • the protective material is arranged in the outermost layer, the protective material can be separated extremely easily. As a result, it is possible to suppress the occurrence of wrinkles that are likely to occur when separation is difficult, and it is possible to produce a high-quality metal-clad laminate with high productivity.
  • separation steps can be performed by a known or conventional method.
  • a pair of pressure rolls r 1 , r 2
  • pressure may be performed. Separation may be performed using at least one separation roll arranged separately from the roll.
  • At least one separation roll may be a pair of separation rolls, a plurality of separation rolls arranged independently, or a combination thereof. Further, the order of the separation rolls may be appropriately set, and any of them may be on the upstream side.
  • the metal-clad laminate obtained after the thermocompression bonding step may be wound together with the protective material in a state where the metal-clad laminate and the protective material are overlapped with each other without performing the protective material separation step. ..
  • the manufacturing method of the present invention may include a cooling step of cooling the laminate after the thermocompression bonding step.
  • the cooling roll may be provided on the downstream side of the pressure roll.
  • the cooling roll is preferably provided between the pressure roll and the first separation roll.
  • the cooling roll may be composed of a pair of rolls or one single roll.
  • the laminate C 1 / M 1 / F / F / M 2 / C 2 obtained by the thermocompression bonding step is a pair of pressure rolls (r 1 , r 2). ), Immediately after passing through, separation is performed simultaneously between C 1 / M 1 , M 2 / C 2 and F / F.
  • the pair of protective materials (C 1 , C 2 ) separated between C 1 / M 1 and M 2 / C 2 are wound by the protective material winding rolls 31 and 31, respectively.
  • the pair of separated protective materials (C 1 , C 2 ) can be reused if necessary.
  • two single-sided metal-clad laminates (M 1 F, M 2 F) are manufactured.
  • the obtained single-sided metal-clad laminate is wound by the metal-clad laminate winding rolls 32 and 32 via the guide rolls 21 and 21, respectively.
  • one or a plurality of guide rolls or the like may be arranged between the pressure roll and the winding by each winding roll, and may be used for induction, tension adjustment, widening, and the like.
  • 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.
  • the thermoplastic liquid crystal polymer film (F) the pair of outermost layer metal foils (M 1 , M 2 ), the metal foil (M), and the pair of protective materials (C).
  • the laminate material M 1 / F / F / M / M / F / M 2 is provided via the pair of protective materials (C 1 , C 2 ), that is, , C 1 / M 1 / F / F / M / M / F / M 2 / C 2 are introduced in this order.
  • C 1 , C 2 the pair of protective materials
  • at least a pair of metal foils (M, M) may be in contact with each other in the laminate material, and at least a pair of metal foils (M, M) are in contact with each other in the laminate material.
  • a metal leaf separation step of separating at least a pair of metal foils (M, M) in contact with each other after the heat-bonding step may be provided.
  • the portion where the metal foils are in contact with each other can be easily separated after the thermocompression bonding step.
  • the peeling strength between the metal foil (M) and the metal foil (M) in the laminated body after the thermocompression bonding is 0.3 kN. It may be less than / m, preferably 0.2 kN / m or less, and more preferably 0.1 kN / m or less.
  • each separation step of the thermoplastic liquid crystal polymer film separation step, the metal foil separation step and the protective material separation step can be performed by a known or conventional method.
  • at least one separation roll is used to (i). Separation of a pair of protective materials (C 1 , C 2 ) and a pair of outermost metal foils (M 1 , M 2 ), (ii) Separation between a pair of thermoplastic liquid crystal polymer films (F, F), (iii) ) At least one of the separations between the pair of metal foils (M, M) may be performed.
  • the order of (i), (ii) and (iii) is not particularly limited, and a plurality of these may be performed simultaneously or stepwise. It is also possible to use a pair of pressure rolls (r 1, r 2) as the separating roll.
  • the above (i), (ii) and (iii) may be performed at once by passing between a pair of separation rolls.
  • one of (i), (ii) and (iii) may be passed between a pair of separation rolls at the same time, and the remaining separation is stepwise by a single separation roll.
  • the separation may be carried out stepwise by a single separation roll, and then passed between a pair of separation rolls to perform the remaining separation.
  • separation between the protective material and the outermost metal foil that is, between C 1 / M 1 and M 2 / C 2 .
  • separation step selected from the metal leaf M / M and the thermoplastic liquid crystal polymer film F / F may be performed.
  • At least one separation step selected from the metal leaf M / M and the thermoplastic liquid crystal polymer film F / F is subsequently or simultaneously performed, and then, if necessary, is performed.
  • a protective material separation step may be performed.
  • the laminate C 1 / M 1 / F / F / M / M / F / M 2 / C 2 obtained by the thermocompression bonding step is a first separation roll.
  • a pair of protective materials (C 1 , C 2 ) are separated between C 1 / M 1 and M 2 / C 2.
  • the pair of separated protective materials (C 1 , C 2 ) are wound by the protective material winding rolls 31 and 31, respectively.
  • the pair of separated protective materials (C 1 , C 2 ) can be reused if necessary.
  • the laminated body M 1 / F / F / M / M / F / M 2 from which the pair of protective materials (C 1 , C 2 ) are separated passes through the second separation rolls 42 and 42, thereby passing through the second separation rolls 42 and 42.
  • a laminate (M 2 FM) is manufactured.
  • the obtained metal-clad laminate is wound by the metal-clad laminate winding rolls 32, 32, 32, respectively.
  • the two single-sided metal-clad laminates (M 1 F, MF) may be the same or different from each other.
  • FIG. 3 is a schematic side view for explaining a method for manufacturing the metal-clad laminate according to the third embodiment.
  • the thermoplastic liquid crystal polymer film (F), the pair of outermost layer metal foils (M 1 , M 2 ), the metal foil (M), and the pair of protective materials (C). 1 , C 2 ) is between a pair of pressure rolls (r 1 , r 2 ), r 1 / C 1 / M 1 / F / F / M / M / F / F / M 2 / C 2 / r as a second order, the upstream side of the pair of pressure rolls (r 1, r 2), each supply roll is arranged.
  • the members having the same roles as those in FIGS. 1 and 2 are designated by the same reference numerals, and the description thereof will be omitted.
  • the laminate material M 1 / F / F / M / M / F / F / M 2 is interposed via a pair of protective materials (C 1 , C 2). That is, they are introduced in the order of C 1 / M 1 / F / F / M / M / F / F / M 2 / C 2.
  • the pair of protective materials (C 1 , C 2 ) unwound from the protective material unwinding rolls 11 and 11 are respectively introduced in the pair of pressure rolls before being introduced in contact with the laminate material. against the heated pair of pressure rolls (r 1, r 2), a predetermined time, the protective member heating process of circumscribing takes place.
  • the pair of protective materials (C 1 , C 2 ) come into contact with the outer circumference of the pair of pressure rolls (r 1 , r 2 ), so that the pair of protective materials (C 1 , C 2 ) It is possible to remove water from the water. Then, by reducing the water content of the pair of protective materials (C 1 , C 2 ) before coming into contact with the pair of outermost metal foils (M 1 , M 2 ), air bubbles, poor stacking, etc. It is possible to suppress the occurrence of problems.
  • the starting point of contact with the outer periphery of the pressure roll can be appropriately set according to the size of the pressure roll and the rotation speed of the pressure roll, and a pair of protective materials (from a predetermined starting point).
  • the protective material heating step may be performed so that C 1 and C 2) follow the pressure roll.
  • the circumscribed circle in the present invention means that the protective material is brought into contact with the protective material along the outer circumference of the pressure roll from a predetermined starting point.
  • the position of the protective material unwinding roll is not particularly limited as long as the pair of protective materials (C 1 , C 2 ) can come into contact with the pair of pressure rolls (r 1 , r 2 ), and the protective material unwinding roll is not particularly limited.
  • the protective material unwound from the roll may be circumscribed directly to the pressure roll, and the protective material unwound from the protective material unwinding roll is once passed through one or more guide rolls and then the pressure roll. May be circumscribed to. For example, it is preferable to provide a pair of guide rolls for circumscribing a pair of protective materials (C 1 , C 2 ) to a pair of pressure rolls (r 1 , r 2).
  • the pair of protective materials (C 1 , C 2 ) are unwound from the protective material unwinding rolls 11 and 11 and then directly connected to the pair of pressure rolls (r 1 , r 2 ). Rather than being introduced into a pair of pressure rolls (r 1 , r 2 ), they pass through guide rolls 21 and 21 arranged in the vicinity of the pair of pressure rolls (r 1, r 2), and then from guide rolls 21 and 21 to a pair of pressure rolls (r 1). , R 2 ) may be circumscribed.
  • the guide rolls 21 and 21 allow the pair of protective materials (C 1 , C 2 ) to be circumscribed to the desired location of the pair of pressure rolls (r 1 , r 2).
  • the installation location of the guide roll is not particularly limited as long as the pair of protective materials (C 1 , C 2 ) can be circumscribed to the pair of pressure rolls (r 1 , r 2). Although the roll is arranged in the vicinity of the pressure roll, it may be in contact with the pressure roll.
  • the protective material (C 1 ) is circumscribed on the pressure roll (r 1 ) and the protective material (C 2 ) is circumscribed on the pressure roll (r 2) before thermocompression bonding.
  • the protective material By circumscribing (or holding) the protective material to the pressure roll in this way, the moisture contained in the protective material can be removed, and the protective material can be preheated to near the thermocompression bonding temperature in advance. ..
  • the distance at which the protective material circumscribes the pressure roll can be appropriately set, but for example, it may be 1/8 or more laps of the pressure roll, 1/4 or more, or 1/2. It may be more than one lap.
  • the pair of protective materials (C 1 , C 2 ) is the laminate material M 1 / F / F / M / M / F / F / after the protective material heating step. While sandwiching M 2 as its outermost layer, the whole is introduced into a pair of pressure rolls (r 1 , r 2).
  • the laminate C 1 / M 1 / F / F / M / M / F / F / M 2 / C 2 obtained by the thermocompression bonding step passes through the first separation rolls 41 and 41.
  • the protective material (C 1 , C 2 ) is separated between C 1 / M 1 and M 2 / C 2.
  • the pair of separated protective materials (C 1 , C 2 ) are wound by the protective material winding rolls 31 and 31, respectively.
  • the pair of separated protective materials (C 1 , C 2 ) can be reused if necessary.
  • the laminate M 1 / F / F / M / M / F / F / M 2 from which the pair of protective materials (C 1 , C 2 ) are separated passes through the second separation rolls 42, 42. Is separated between M / M and F / F, and four single-sided metal-clad laminates (M 1 F, MF, MF, M 2 F) are manufactured. Further, the obtained single-sided metal-clad laminate is wound by the metal-clad laminate winding rolls 32, 32, 32, 32, 32, respectively.
  • the four single-sided metal-clad laminates (M 1 F, MF, MF, M 2 F) may be the same or different from each other.
  • the film thickness was measured using a digital thickness gauge (manufactured by Mitutoyo Co., Ltd.) at 1 cm intervals in the TD direction, and the average value of 10 points arbitrarily selected from the center and edges was used as the film thickness. ..
  • each of the thickness direction and the plane direction (MD direction) is converted into an orientation distribution curve, and the curve of the diffraction intensity with respect to the ⁇ angle in the circumferential direction is about 20 ° ((110) plane).
  • Is calculated from the half-value width H of the peak of the intensity distribution obtained by ring-integrating) from the following equation (1). bottom. f (180-H) / 180 (1)
  • Example 1 Thermoplastic liquid crystal polymer film (manufactured by Kuraray Co., Ltd., “Vexter” (registered trademark), melting point 310 ° C., thickness 25 ⁇ m), electrolytic copper foil as metal leaf (manufactured by Fukuda Metal Foil Powder Industry Co., Ltd., “CF-H9A-DS-” HD2 ”, thickness 12 ⁇ m), and a polyimide film (manufactured by Kaneka Co., Ltd.,“ Apical NPI ”, thickness 75 ⁇ m) as a protective material were prepared as unwinding rolls.
  • Vexter registered trademark
  • electrolytic copper foil as metal leaf manufactured by Fukuda Metal Foil Powder Industry Co., Ltd., “CF-H9A-DS-” HD2 ”, thickness 12 ⁇ m
  • a polyimide film manufactured by Kaneka Co., Ltd.,“ Apical NPI ”, thickness 75 ⁇ m
  • the degree of crystal orientation fp in the plane direction of the thermoplastic liquid crystal polymer film was 0.65, and the degree of crystal orientation fv in the thickness direction was 0.80.
  • these unwinding rolls are a pair of thermoplastic liquid crystal polymer films (F, F), a pair of electrolytic copper foils (M 1 , M 2 ), and a pair of polyimide films (C 1 , C 2). ) Is between the pair of pressure rolls (r 1 , r 2 ) in the order of r 1 / C 1 / M 1 / F / F / M 2 / C 2 / r 2. Placed.
  • the laminate material M 1 / F / F / M 2 was introduced into the pair of pressure rolls (r 1 , r 2 ) via the pair of polyimide films (C 1 , C 2).
  • the surface temperature of the metal rolls was set to 230 ° C. and the pressure pressure was set to 8 t / m, and a pair of polyimide films (C 1).
  • C 2 sandwiched between laminate materials M 1 / F / F / M 2 was thermocompression bonded by passing through a pair of pressure rolls (r 1 , r 2 ) at a speed of 3.0 m / min.
  • thermocompression bonding As shown in FIG. 1, after passing through a pair of pressure rolls (r 1, r 2), by using the pair of pressure rolls (r 1, r 2), a pair of polyimide film (C 1 , C 2 ) are separated, and the pair of thermoplastic liquid crystal polymer films (F, F) are separated to obtain two single-sided copper-clad laminates (M 1 F, M 2 F), and a take-up roll is obtained. I wound up each of them. Table 7 shows the appearance evaluation results of the obtained copper-clad laminate.
  • Example 2 Thermoplastic liquid crystal polymer film (manufactured by Kuraray Co., Ltd., "Vexter” (registered trademark), melting point 310 ° C., thickness 100 ⁇ m), electrolytic copper foil as metal leaf (manufactured by Fukuda Metal Foil Powder Industry Co., Ltd., “CF-H9A-DS-” HD2 ”, thickness 12 ⁇ m), and a polyimide film (manufactured by Kaneka Co., Ltd.,“ Apical NPI ”, thickness 75 ⁇ m) as a protective material were prepared as unwinding rolls.
  • Vexter registered trademark
  • electrolytic copper foil as metal leaf manufactured by Fukuda Metal Foil Powder Industry Co., Ltd., “CF-H9A-DS-” HD2 ”, thickness 12 ⁇ m
  • a polyimide film manufactured by Kaneka Co., Ltd.,“ Apical NPI ”, thickness 75 ⁇ m
  • the degree of crystal orientation fp in the plane direction of the thermoplastic liquid crystal polymer film was 0.60, and the degree of crystal orientation fv in the thickness direction was 0.70.
  • these unwinding rolls are a pair of thermoplastic liquid crystal polymer films (F, F), a pair of electrolytic copper foils (M 1 , M 2 ), and a pair of polyimide films (C 1 , C 2). ) Is between the pair of pressure rolls (r 1 , r 2 ) in the order of r 1 / C 1 / M 1 / F / F / M 2 / C 2 / r 2. Placed.
  • the laminate material M 1 / F / F / M 2 was introduced into the pair of pressure rolls (r 1 , r 2 ) via the pair of polyimide films (C 1 , C 2).
  • the surface temperature of the metal rolls was set to 255 ° C. and the pressure pressure was set to 12 t / m, and a pair of polyimide films (C 1).
  • C 2 sandwiched between laminate materials M 1 / F / F / M 2 was thermocompression bonded by passing through a pair of pressure rolls (r 1 , r 2 ) at a speed of 3.0 m / min.
  • thermocompression bonding As shown in FIG. 1, after passing through a pair of pressure rolls (r 1, r 2), by using the pair of pressure rolls (r 1, r 2), a pair of polyimide film (C 1 , C 2 ) are separated, and the pair of thermoplastic liquid crystal polymer films (F, F) are separated to obtain two single-sided copper-clad laminates (M 1 F, M 2 F), and a take-up roll is obtained. I wound up each of them. Table 7 shows the appearance evaluation results of the obtained copper-clad laminate.
  • thermoplastic liquid crystal polymer film manufactured by Kuraray Co., Ltd., "Vexter” (registered trademark), melting point 310 ° C., thickness 100 ⁇ m
  • electrolytic copper foil and polyimide film is r 1 / M / F / C /. It was arranged in the order of F / M / r 2 and thermocompression-bonded in the same manner as in Example 2 except that it was passed through a pressure roll. ) was separated to prepare two single-sided copper-clad laminates F / M. Table 7 shows the appearance evaluation results of the obtained copper-clad laminate.
  • thermoplastic liquid crystal polymer film manufactured by Kuraray Co., Ltd., "Vexter” (registered trademark), melting point 310 ° C., thickness 100 ⁇ m
  • electrolytic copper foil and polyimide film
  • r 1 / C 1 / F / M Arranged in the order of / M / F / C 2 / r 2 , hot-bonded in the same manner as in Example 2 except that the pressure roll was passed, and a pair of pressure rolls (r 1 , r).
  • the pair of pressure rolls (r 1 , r 2 ) are used to separate the pair of polyimide films (C 1 , C 2 ) and between the pair of electrolytic copper foils (M, M).
  • M, M electrolytic copper foils
  • a polyimide film is arranged as a protective material in the outermost layer so as to sandwich the laminate material, and a pair of the protective materials are arranged so as to be in contact with the copper foil. No appearance defects such as wrinkles were observed in the obtained copper-clad laminate because it was introduced into the pressure roll of.
  • a metal-clad laminate can be efficiently manufactured, and the obtained metal-clad laminate is used in the fields of electricity / electronics, office equipment / precision equipment, power semiconductors, and the like. It can be effectively used as a component to be used, for example, a circuit board (particularly a substrate for a millimeter wave radar).

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JP2014128913A (ja) * 2012-12-28 2014-07-10 Nippon Steel & Sumikin Chemical Co Ltd 両面金属張積層体の製造方法
JP2019135301A (ja) * 2013-10-03 2019-08-15 株式会社クラレ 熱可塑性液晶ポリマーフィルム、回路基板、およびそれらの製造方法
WO2017154811A1 (ja) * 2016-03-08 2017-09-14 株式会社クラレ 金属張積層板の製造方法および金属張積層板

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