WO2021193195A1 - 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
WO2021193195A1
WO2021193195A1 PCT/JP2021/010348 JP2021010348W WO2021193195A1 WO 2021193195 A1 WO2021193195 A1 WO 2021193195A1 JP 2021010348 W JP2021010348 W JP 2021010348W WO 2021193195 A1 WO2021193195 A1 WO 2021193195A1
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Prior art keywords
liquid crystal
crystal polymer
thermoplastic liquid
pair
metal
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PCT/JP2021/010348
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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 JP2022509950A priority Critical patent/JP7182747B2/ja
Priority to CN202180021743.5A priority patent/CN115298024A/zh
Priority to KR1020227033025A priority patent/KR20220154701A/ko
Publication of WO2021193195A1 publication Critical patent/WO2021193195A1/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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • B32B2037/109—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure using a squeegee
    • 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
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat

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 suppressing the occurrence of appearance defects such as wrinkles.
  • thermoplastic liquid crystal polymer films are arranged in contact with each other in producing a plurality of metal-clad laminates.
  • thermoplastic liquid crystal polymer film having a planar crystal orientation fp smaller than a thickness direction crystal orientation fv is used for at least one of the thermoplastic liquid crystal polymer films.
  • heat is generated.
  • thermoplastic liquid crystal polymer films are in contact with each other without using a separating film at the time of pressure bonding, the adhesiveness between the thermoplastic liquid crystal polymer films can be suppressed and the thermoplastic liquid crystal polymer films can be easily separated. Further, it was found that the obtained metal-clad laminate can suppress the occurrence of appearance defects such as wrinkles, and the present invention has been completed.
  • [Aspect 1] It is a method of manufacturing a plurality of metal-clad laminates.
  • a step of continuously thermocompression bonding a laminate material at least a pair of thermoplastic liquid crystal polymer films (F, F) in which the laminate materials are in contact with each other and a pair of thermoplastic liquid crystal polymer films (F, F).
  • thermoplastic liquid crystal polymer film separation step of separating at least a pair of thermoplastic liquid crystal polymer films (F, F) in contact with each other after the thermocompression bonding step.
  • At least The pair of thermoplastic liquid crystal polymer films (F, F) to be separated is a metal, at least one of which 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.
  • a method for manufacturing a stretched laminate [Aspect 2] The method for producing a metal-clad laminate according to the first aspect, wherein the thermoplastic liquid crystal polymer film has a crystal orientation degree fp in the plane direction of 0.4 to 0.7 (preferably 0.5 to 0.6).
  • a method for manufacturing a metal-clad laminate within the range [Aspect 3] The method for producing a metal-clad laminate according to the first or second aspect, wherein the degree of crystal orientation fv in the thickness direction of the thermoplastic liquid crystal polymer film is 0.7 to 0.9 (preferably 0.7 to 0. A method for producing a metal-clad laminate within the range of 8). [Aspect 4] The method for producing a metal-clad laminate according to any one of aspects 1 to 3, wherein the thermocompression bonding step is a continuous isotropic press or a thermal roll press using a pair of pressure rolls (r 1 , r 2). A method for manufacturing a metal-clad laminate, which is carried out in.
  • the protective material (C 1 ) and / or the protective material (C 2 ) is a protection selected from the group consisting of a heat-resistant resin film, a heat-resistant composite film, and a heat-resistant non-woven film.
  • the material (preferably, the protective material (C 1 ) and the protective material (C 2 ) are protective materials selected from the group consisting of a heat-resistant resin film, a heat-resistant composite film, and a heat-resistant non-woven film, respectively).
  • thermocompression bonding temperature the melting point of the thermoplastic liquid crystal polymer film having the lowest melting point among the thermoplastic liquid crystal polymer film of the laminate material in (Tm L ) relative to, (Tm L -120) °C ⁇ (Tm L) °C ( preferably (Tm L -100) in the range of °C ⁇ (Tm L) °C) , method for producing a metal clad laminate.
  • thermoplastic liquid crystal polymer film having a specific crystal orientation by using a thermoplastic liquid crystal polymer film having a specific crystal orientation, the thermoplastic liquid crystal polymer films can be easily separated from each other even after thermocompression bonding, so that the occurrence of poor appearance is suppressed.
  • the metal-clad laminate can be efficiently manufactured.
  • 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.
  • 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. It may have 50 to 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 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.
  • the crystal orientation fp in the plane direction and the crystal orientation fv in the thickness direction can be controlled to a specific relationship 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.
  • a protective material may be used in the production method of the present invention, if necessary.
  • the protective material 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 heat resistant to non-thermoplastic polyimide films, aramid films, Teflon (registered trademark) films, etc.
  • Heat-resistant resin 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); metal foil such as aluminum foil or stainless steel foil; and heat-resistant fiber Examples thereof include heat-resistant non-woven fabrics made of (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 continuously thermocompression bonding the laminate materials, at least a pair of thermoplastic liquid crystal polymer films (F, F) in which the laminate materials are in contact with each other and the pair of thermoplastic liquid crystal polymer films (F, F). ), At least composed of at least a pair of metal foils (M, M) arranged in contact with each other, and at least a pair of thermoplastic liquid crystal polymer films (F, F) 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) in contact with each other 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 continuously thermocompression bonded.
  • an unwinding roll of each material constituting the laminate material is prepared.
  • each unwinding roll may be arranged so that a laminate material having a desired constitution can be formed.
  • the method for producing a metal-clad laminate of the present invention is a roll-to-roll method in which each material unwound from an unwinding roll is superposed and wound up by a winding roll after at least a thermocompression bonding step and a separation step. You may.
  • the laminate material refers to a material for laminating in a predetermined arrangement in order to produce a plurality of desired metal-clad laminates.
  • 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.
  • the laminate material is formed by at least a pair of thermoplastic liquid crystal polymer films (F, F) in contact with each other and at least a pair of metal foils arranged in contact with the outer surfaces of the pair of thermoplastic liquid crystal polymer films (F, F). It suffices if the arrangement is at least composed of (M, M), and when each constituent material is prepared by an unwinding roll in forming the laminate material, each unwinding roll is contained in the laminate material. It may be arranged so as to include the arrangement in the order of M / F / F / M.
  • 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 crystal having a crystal orientation fp in the plane direction in the thickness direction. It is a thermoplastic liquid crystal polymer film having an orientation degree smaller than fv.
  • the crystals are oriented in the thickness direction.
  • thermoplastic liquid crystal polymer films (F, F) in contact with each other can be prevented from adhering to each other after thermal pressure bonding, and can be easily separated, probably because the cage layer structure is developed.
  • Both of the pair of thermoplastic liquid crystal polymer films (F, F) in contact with each other in the laminate material are thermoplastic liquid crystal polymer films in which the crystal orientation fp in the plane direction is smaller than the crystal orientation fv in the thickness direction. It is preferable to have.
  • the crystal orientation degree f is an index that gives the degree of orientation of the crystal region of the polymer, and the closer the crystal orientation degree fp in the plane direction is to 0.5, the more the crystal orientation in the biaxial direction of the film plane is. It means that the crystal orientation is closer to isotropic, and the larger the crystal orientation fv in the thickness direction (for example, the closer to 1.0), the higher the crystal orientation with respect to the film thickness direction.
  • the change in crystal orientation can be obtained from a wide-angle X-ray photograph.
  • 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.
  • 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 used in the production method of the present invention, at least one of the pair of thermoplastic liquid crystal polymer films (F, F) in contact with each other in the laminate material is the thermoplastic liquid crystal polymer film (F).
  • the degree of crystal orientation fp in the plane direction may be 0.4 to 0.7, preferably 0.5 to 0.6. By setting this range, when separating the pair of thermoplastic liquid crystal polymer films (F, F) that are in contact with each other after thermocompression bonding, anisotropy of delamination is less likely to occur in the MD direction and the TD direction. It is possible to suppress the occurrence of appearance defects such as wrinkles. For example, when the degree of crystal orientation fp in the plane direction is too large, delamination tends to occur easily only in the MD direction, which may roughen the surface shape of the peeled surface and cause poor appearance.
  • the degree of crystal orientation fv in the thickness direction may be 0.7 to 0.9, preferably 0.7 to 0.8.
  • the degree of crystal orientation fv in the thickness direction is too small, it tends to be easily adhered between a pair of thermoplastic liquid crystal polymer films (F, F) after thermocompression bonding, and it is difficult to peel off, resulting in wrinkles and the like. It may cause poor appearance.
  • the difference (fv-fp) between the crystal orientation degree fp in the plane direction and the crystal orientation degree fv in the thickness direction may be 0.05 or more, preferably 0.1. As mentioned above, it may be more preferably 0.2 or more.
  • the upper limit of the difference (fv-fp) between the crystal orientation degree fp in the plane direction and the crystal orientation degree fv in the thickness direction is not particularly limited, but may be 0.5 or less, for example.
  • 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.
  • the laminate material at least a pair of inner layer metal foils (M, M) may be 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 Among them, it is preferable that the pair of inner layer metal foils (M, M) have a portion in contact with each other.
  • One of the pair of inner layer metal foils (M, M) is arranged in contact with the outer surface of the above-mentioned pair of thermoplastic liquid crystal polymer films (F, F), respectively. ) May be configured.
  • each constituent material of the laminate material may include a material other than forming the metal-clad laminate, as long as the effect of the present invention is not impaired.
  • the protective material (C) may be arranged between the and, and may have the arrangement in the order of M / C / M.
  • the laminate material may have an outermost layer metal foil (M 1 , M 2 ). Since the outermost layer metal foil (M 1 ) and the outermost layer metal foil (M 2 ) form the outermost layer of the laminate material, they may adhere to a pressure roll or the like in the thermocompression bonding process, resulting in poor appearance. In addition, even when the laminate material is thermocompression bonded via a pair of protective materials (C 1 , C 2 ) described later, the protective material can be prevented from coming into contact with the thermoplastic liquid crystal polymer film, so that wrinkles are formed. It is possible to suppress the occurrence of poor appearance such as.
  • the laminate material may be arranged in any of the following orders (i) to (vi).
  • a protective material (C) may be laminated and thermocompression-bonded, if necessary, at the time of thermocompression bonding.
  • the mode of use of the protective material (C) is not limited as long as it does not impair the effects of the present invention, and may be arranged outside the laminate material or as a constituent material of the laminate material. good.
  • the laminate material may be thermocompression bonded via a pair of protective materials (C 1 , C 2).
  • the protective material (C) may be a protective material selected from the group consisting of a heat-resistant resin film, a heat-resistant composite film, and a heat-resistant non-woven fabric. Further, from the viewpoint of suppressing appearance defects such as wrinkles, the laminate material may be arranged so that the thermoplastic liquid crystal polymer film (F) and the protective material (C) are not adjacent to each other.
  • a protective material heating step of heating a pair of protective materials (C 1 , C 2) may be further provided prior to the thermocompression bonding step.
  • 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 the heating roll. Further, for example, when the thermocompression bonding step is performed by a continuous isotropic press, a pair of protective materials (C 1 , C 2 ) are externally contacted with a preheating drum to form a pair of protective materials (C 1 , C 2 ).
  • thermocompression bonding process is performed by a thermocompression roll press using a pair of pressure rolls (r 1 , r 2 ), a pair of protective materials (C 1 , C 2 ) are applied to the pressure rolls (c 1, C 2).
  • a pair of protective materials (C 1 , C 2 ) may be heated by external contact with 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.
  • a thermal compression bonding process may be performed by hot roll press by continuous isostatic pressing or a pair of pressure rolls (r 1, r 2).
  • a continuous isotropic pressure press for example, a double belt press may be used to press from above and below via a pair of endless belts.
  • a continuous isotropic press when pressing continuously, it may be divided into a single region or a plurality of regions to heat or cool.
  • 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 first embodiment is an embodiment of performing thermocompression bonding with a heat roll press by the pair of press rolls (r 1, r 2), a pair of pressure rolls (r 1, r 2 )
  • the metal foil unwinding rolls 11 and 11 for unwinding the pair of outermost layer metal foils (M 1 , M 2 ), and the thermoplastic for unwinding the pair of thermoplastic liquid crystal polymer films (F, F).
  • Liquid crystal polymer film unwinding rolls 12 and 12 are prepared.
  • a pair of outermost metal foils (M 1 , M 2 ) and a pair of thermoplastic liquid crystal polymer films (F, F) are formed by a pair of pressure rolls (r 1 , r 2 ). Each unwinding roll is arranged in the order of r 1 / M 1 / F / F / M 2 / r 2.
  • the metal leaf unwinding rolls 11 and 11 for unwinding the pair of outermost layer metal foils (M 1 , M 2 ) are the outermost layers on the upstream side of the pair of pressure rolls (r 1 , r 2), respectively.
  • the thermoplastic liquid crystal polymer film unwinding rolls 12 and 12 for unwinding a pair of thermoplastic liquid crystal polymer films (F, F) are arranged inside the thermoplastic liquid crystal polymer films (F, F).
  • thermoplastic liquid crystals are arranged from each unwinding roll as shown in the direction of the arrow.
  • the polymer film (F, F) and the pair of outermost metal foils (M 1 , M 2 ) are unwound and are directed by the arrows in the MD direction ( r 1 , r 2 ) with respect to the pair of pressure rolls (r 1, r 2). Or it is introduced in the laminating direction).
  • the laminate material M 1 / F / F / M 2 is introduced into the pair of pressure rolls (r 1 , r 2 ) in this order, and the pressure is applied to the laminate material at a predetermined heating temperature.
  • the degree of crystal orientation fp in the plane direction of at least one of the pair of thermoplastic liquid crystal polymer films (F, F) in the plane direction is higher than the degree of crystal orientation fv in the thickness direction. Even if they are in contact with each other, the pair of thermoplastic liquid crystal polymer films (F, F) can be easily separated from each other after thermal pressure bonding. Therefore, it is possible to suppress the occurrence of poor appearance, and it is not necessary to use a protective material or a separating material, so that the production cost can be reduced and the metal-clad laminate can be efficiently manufactured.
  • 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 laminate material is passed through the pair of pressure rolls can be appropriately set according to the thermocompression bonding temperature, the pressure conditions of the pressure rolls, and the size of the pressure rolls. However, for example, it may be 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).
  • the thermoplastic liquid crystal polymer films (F, F) may be separated immediately after passing through 1, r 2 ), and a pair of heats may be provided by at least one separation roll disposed separately from the pressure roll.
  • the plastic 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 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 separation roll.
  • the cooling roll may be composed of a pair of rolls or one single roll.
  • the laminate M 1 / F / F / M 2 obtained by the thermocompression bonding step is immediately F after passing through a pair of pressure rolls (r 1 , r 2). Separated between / F, two single-sided metal-clad laminates (M 1 F, M 2 F) are manufactured. Further, the obtained single-sided metal-clad laminate is wound by the metal-clad laminate winding rolls 31 and 31, 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.
  • a metal foil winding that unwinds a pair of outermost layer metal foils (M 1 , M 2 ) on the upstream side of the pair of pressure rolls (r 1 , r 2).
  • Unwinding rolls 13 and 13 are prepared.
  • thermoplastic liquid crystal polymer films F, F
  • M 1 , M 2 outermost metal foils
  • C 1 , C 2 protective materials
  • the protective material unwinding rolls 13 and 13 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 11 and 11 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) unwinding thermoplastic liquid crystal polymer film unwinding rolls 12, 12 are arranged.
  • 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.
  • a protective material is further provided so as to sandwich the laminate material. By arranging it in the outermost layer, adhesion between the thermoplastic liquid crystal polymer films can be suppressed.
  • 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 may be provided.
  • 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 when 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. This can be done with at least one separating roll disposed 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 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 32 and 32, respectively.
  • the pair of separated protective materials (C 1 , C 2 ) can be reused if necessary.
  • FIG. 3 is a schematic side view for explaining a method for manufacturing the metal-clad laminate according to the third embodiment.
  • 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 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.
  • the pair of protective materials (C 1 , C 2 ) unwound from the protective material unwinding rolls 13 and 13 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 pressure rolls (r 1 , r 2 ) to cause moisture from the pair of protective materials (C 1 , C 2). Can be removed. 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 directly unwound from the protective material unwinding rolls 13 and 13 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, the guide roll 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.
  • 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 of at least a pair of thermoplastic liquid crystal polymer films (F, F), ( iii) At least one of the separations between at least a pair of metal foils (M, M) may be separated.
  • 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 32 and 32, 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 31, 31, and 31, respectively.
  • the two single-sided metal-clad laminates (M 1 F, MF) may be the same or different from each other.
  • FIG. 4 is a schematic side view for explaining a method for manufacturing the metal-clad laminate according to the fourth embodiment.
  • the thermocompression bonding step is performed by a continuous isotropic press, and a pair of outermost layer metal foils (M 1 , M 2 ) and a pair of thermoplastic liquid crystal polymer films.
  • Double belt press so that (F, F) is in the order of b 1 / M 1 / F / F / M 2 / b 2 between the pair of endless belts (b 1 , b 2 ) of the double belt press.
  • Each unwinding roll is arranged on the upstream side of 51.
  • thermocompression bonding step is performed by a continuous isotropic press
  • a substantially uniform pressure can be applied over the entire pressure band
  • a known device can be used.
  • the double belt press 51 comprises a pair of endless belts (b 1 , b 2 ), heating drums 61, 61 and cooling drums 62, 62 for passing the pair of endless belts (b 1 , b 2), and a laminate material.
  • Cooling devices 71, 71 that heat a pair of endless belts (b 1 , b 2 ) to heat and pressurize, and cooling to cool a pair of endless belts (b 1 , b 2 ) to cool and pressurize a laminate material.
  • the devices 72 and 72 are provided.
  • the endless belt a known material and shape (for example, thickness) can be used, and examples thereof include a metal belt and a rubber belt, but it is preferable to use a stainless steel endless belt.
  • the pair of endless belts (b 1 , b 2 ) are hung between the heating drums 61, 61 and the cooling drums 62, 62, respectively, and the heating drums 61, 61 and the cooling drums 62, 62 rotate. Moves around.
  • the pair of endless belts (b 1, b 2), the laminate material M 1 / F / F / M 2 is introduced stacked in this order, while being pressed by a pair of endless belts (b 1, b 2) It passes between the heating drums 61, 61 and the cooling drums 62, 62, and pressurization can be performed substantially evenly between them.
  • the double belt press 51 heats a pair of endless belts (b 1 , b 2 ) by the heating drums 61, 61 and the heating devices 71, 71, and heats and pressurizes the region while the laminate material passes through the region. can.
  • thermocompression bonding step can be performed by passing the laminate material through a pair of endless belts (b 1 , b 2 ) and applying heat and pressure, and the thermocompression bonding temperature is not particularly limited, but is described above.
  • the thermocompression bonding temperature may be set in the same manner as in the case of the pressure roll.
  • the laminate material can be pressurized by surface contact with a pair of endless belts (b 1 , b 2 ) for a predetermined time, so that the temperature conditions of the thermocompression bonding temperature are all.
  • the temperature may be set to a constant temperature in the region, or the temperature may be changed step by step.
  • the pressurizing pressure for thermocompression bonding may be in the range of 0.5 to 10 MPa, preferably 1.0 to 5.0 MPa.
  • the thermocompression bonding time can be set by changing the size of the apparatus and the transport speed of the laminate material according to the thermocompression bonding temperature and the thermoplastic liquid crystal polymer film used, and is, for example, 10 to 300 seconds. It may be 30 to 240 seconds.
  • the double belt press 51 cools the pair of endless belts (b 1 , b 2 ) by the cooling devices 72, 72 and the cooling drums 62, 62, and cools and pressurizes the region while the laminated material passes through the region. be able to. Therefore, the cooling step can be performed by passing the laminate material through a pair of endless belts (b 1 , b 2) and applying cooling pressure.
  • a cooling region is provided in addition to the heating region, but the temperature may be changed to a desired temperature setting such as setting the entire region to the heating region.
  • the cooling step may be performed by providing a cooling roll on the downstream side of the double belt press device.
  • the laminate M 1 / F / F / M 2 obtained through the thermocompression bonding step and the cooling step in the double belt press 51 is the first separation rolls 41, 41.
  • the F / F is separated, and 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 31 and 31, respectively.
  • 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)
  • thermoplastic liquid crystal polymer having a melting point of 280 ° C. is melt-extruded with a copolymer of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid (molar ratio: 73/27), and the thermoplastic liquid crystal is subjected to an inflation molding method.
  • a polymer film was produced.
  • a film having a film thickness of 50 ⁇ m and having an fp of 0.5 and an fv of 0.7 is referred to as type A
  • a film having an fp of 0.8 and fv of 0.8 is referred to as type B.
  • thermoplastic liquid crystal polymer film was produced.
  • a film having a film thickness of 100 ⁇ m, fp of 0.6 and fv of 0.8 is type C, a film of fp of 0.5 and fv of 0.7 is type D, fp is 0.5 and fv is 0.
  • the film of 5 be type E.
  • Example 1 Type A thermoplastic liquid crystal polymer film obtained in the reference example, electrolytic copper foil as a metal foil (manufactured by Fukuda Metal Foil Powder Industry Co., Ltd., "CF-H9A-DS-HD2", thickness 12 ⁇ m), and polyimide as a protective material. Films (manufactured by Kaneka Co., Ltd., "Apical NPI", thickness 75 ⁇ m) were prepared as unwinding rolls. As shown in FIG. 2, 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.
  • CF-H9A-DS-HD2 thickness 12 ⁇ m
  • 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 roll is set to 230 ° C. and the pressure pressure is set to 8 t / m, and a pair of polyimide films (C 1 ,
  • the laminate material C 1 / M 1 / F / F / M 2 / C 2 sandwiched between C 2 ) is thermocompression bonded by passing through a pressure roll (r 1 , r 2 ) at a speed of 3.0 m / min. rice field.
  • thermocompression bonding As shown in FIG. 2, after passing through a pair of pressure rolls (r 1, r 2), by using the pair of pressure rolls (r 1, r 2), between the thermoplastic liquid crystal polymer film was successfully separated, and then two single-sided copper-clad laminates were obtained and wound up by winding rolls, respectively.
  • Table 7 shows the appearance evaluation results of the obtained copper-clad laminate.
  • Example 2 Same as Example 1 except that the thermoplastic liquid crystal polymer film was changed to the type C thermoplastic liquid crystal polymer film obtained in the reference example, the surface temperature of the metal roll was set to 255 ° C., and the pressurizing pressure was set to 12 t / m. A copper-clad laminate was prepared. The separation between the thermoplastic liquid crystal polymer films after thermocompression bonding could be facilitated. Table 7 shows the appearance evaluation results of the obtained copper-clad laminate.
  • Example 3 As the type D thermoplastic liquid crystal polymer film obtained in the reference example and the metal foil, an electrolytic copper foil (manufactured by Fukuda Metal Leaf Powder Industry Co., Ltd., “CF-T8”, thickness 35 ⁇ m) was prepared as an unwinding roll. As shown in FIG. 4, a pair of thermoplastic liquid crystal polymer films (F, F) and a pair of electrolytic copper foils (M 1 , M 2 ) are placed between a pair of endless belts (b 1 , b 2 ), b. Each unwinding roll was arranged in the order of 1 / M 1 / F / F / M 2 / b 2.
  • the laminate material M 1 / F / F / M 2 was introduced into the pair of endless belts (b 1 , b 2).
  • a metal drum with a diameter of 0.8 m is used as the heating drum, the surface temperature of the pair of endless belts (b 1 , b 2 ) is set to 230 ° C., the pressurizing pressure is set to 3 MPa, and the laminate material M 1 / F / F. / M 2 was thermocompression bonded by passing through endless belts (b 1 , b 2 ) at a speed of 1 m / min.
  • thermoplastic liquid crystal polymer films can be well separated by the first separation roll, and then two single-sided copper-clad laminates are obtained and each is wound up by a take-up roll. I rolled it up.
  • Table 7 shows the appearance evaluation results of the obtained copper-clad laminate.
  • thermoplastic liquid crystal polymer film was changed to the type B thermoplastic liquid crystal polymer film obtained in the reference example, but after thermocompression bonding, the thermoplastic liquid crystal polymer film was prepared. Since they were adhered to each other, it was difficult to separate the thermoplastic liquid crystal polymer films, and the obtained copper-clad laminate had wrinkles.
  • thermoplastic liquid crystal polymer film was changed to the type E thermoplastic liquid crystal polymer film obtained in the reference example, but after thermocompression bonding, the thermoplastic liquid crystal polymer film was produced. Since they were adhered to each other, it was difficult to separate the thermoplastic liquid crystal polymer films, and the obtained copper-clad laminate had wrinkles.
  • thermoplastic liquid crystal polymer film having a crystal orientation fp in the plane direction smaller than the crystal orientation fv in the thickness direction was used, so that the thermoplastic liquid crystal polymer after thermocompression bonding was used.
  • the peelability between the films was good, and no appearance defects such as wrinkles were observed in the obtained copper-clad laminate.
  • 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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PCT/JP2021/010348 2020-03-24 2021-03-15 金属張積層体の製造方法 WO2021193195A1 (ja)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004358677A (ja) * 2003-06-02 2004-12-24 Nippon Steel Chem Co Ltd 積層体の製造方法
WO2011093427A1 (ja) * 2010-01-29 2011-08-04 新日鐵化学株式会社 片面金属張積層体の製造方法
WO2012020818A1 (ja) * 2010-08-12 2012-02-16 新日鐵化学株式会社 金属張積層板
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
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
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

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100503215C (zh) * 2003-12-26 2009-06-24 株式会社钟化 柔性多层板的制造方法
JP5025186B2 (ja) * 2005-08-19 2012-09-12 宇部日東化成株式会社 フレキシブル金属箔積層体の製造方法
JP5242030B2 (ja) * 2006-07-31 2013-07-24 宇部日東化成株式会社 複数組の金属箔／樹脂フィルム構造の長尺状積層体の製造法
WO2013021893A1 (ja) * 2011-08-09 2013-02-14 宇部日東化成株式会社 積層体製造装置及び積層体の製造方法
EP3608100A4 (en) * 2017-04-07 2020-12-09 Kuraray Co., Ltd. METAL-PLATED LAMINATE SHEET AND ITS MANUFACTURING PROCESS

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004358677A (ja) * 2003-06-02 2004-12-24 Nippon Steel Chem Co Ltd 積層体の製造方法
WO2011093427A1 (ja) * 2010-01-29 2011-08-04 新日鐵化学株式会社 片面金属張積層体の製造方法
WO2012020818A1 (ja) * 2010-08-12 2012-02-16 新日鐵化学株式会社 金属張積層板
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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