WO2023140187A1 - 液晶ポリマーフィルム、並びに、これを用いた回路基板用絶縁材料及び金属箔張積層板 - Google Patents

液晶ポリマーフィルム、並びに、これを用いた回路基板用絶縁材料及び金属箔張積層板 Download PDF

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WO2023140187A1
WO2023140187A1 PCT/JP2023/000768 JP2023000768W WO2023140187A1 WO 2023140187 A1 WO2023140187 A1 WO 2023140187A1 JP 2023000768 W JP2023000768 W JP 2023000768W WO 2023140187 A1 WO2023140187 A1 WO 2023140187A1
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Prior art keywords
liquid crystal
crystal polymer
film
orientation
polymer film
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PCT/JP2023/000768
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English (en)
French (fr)
Japanese (ja)
Inventor
育男 巣山
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Denka Co Ltd
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Denka Co Ltd
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Priority to CN202380015024.1A priority Critical patent/CN118369372A/zh
Priority to JP2023575225A priority patent/JPWO2023140187A1/ja
Priority to KR1020247024800A priority patent/KR20240130109A/ko
Publication of WO2023140187A1 publication Critical patent/WO2023140187A1/ja
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • 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
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
    • B29C55/08—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique transverse to the direction of feed
    • 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
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/20—Edge clamps
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/024—Woven fabric
    • 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
    • B32B7/03—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 with respect to the orientation of features
    • B32B7/035—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 with respect to the orientation of features using arrangements of stretched films, e.g. of mono-axially stretched films arranged alternately
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514—Oriented
    • B32B2307/516—Oriented mono-axially
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers

Definitions

  • the present invention relates to a liquid crystal polymer film, and an insulating material for circuit boards and a metal foil clad laminate using the same.
  • a varnish-impregnated composite material which is obtained by impregnating a glass cloth with a varnish containing a thermosetting resin such as an epoxy resin, an inorganic filler, a solvent, etc., and then heat-press molding the material.
  • a thermosetting resin such as an epoxy resin, an inorganic filler, a solvent, etc.
  • this manufacturing method has a poor process margin during manufacturing and is inferior in productivity from the viewpoint of, for example, resin flowability during varnish impregnation and curability during hot press molding.
  • the thermosetting resin easily absorbs moisture, and its dimensions change as it absorbs moisture, so the resulting varnish-impregnated composite material is inferior in dimensional accuracy (heating dimensional accuracy).
  • a liquid crystal polymer is a polymer that exhibits liquid crystallinity in a molten state or in a solution state.
  • thermotropic liquid crystal polymers that exhibit liquid crystallinity in a molten state can be extruded and have excellent properties such as high gas barrier properties, high film strength, high heat resistance, high insulation, low water absorption, and low dielectric properties in the high frequency range. Therefore, thermoplastic liquid crystal polymer films manufactured by melt extrusion molding such as the inflation method and the T-die method are being studied for practical use in gas barrier film material applications, electronic material applications, electrical insulating material applications, and the like.
  • insulating materials for circuit boards using liquid crystal polymers are excellent in high-frequency characteristics and low dielectric properties
  • flexible printed circuit boards (FPC) flexible printed circuit board laminates, fiber-reinforced flexible laminates, etc. in the fifth generation mobile communication system (5G) and millimeter wave radar, etc., which will be developed in the future.
  • 5G fifth generation mobile communication system
  • millimeter wave radar millimeter wave radar
  • thermoplastic liquid crystal polymer due to the high degree of liquid crystal orientation and relatively rigid molecular chains of the thermoplastic liquid crystal polymer, and further to the shear stress caused by the die and die swell during melt extrusion, the polymer chains are highly molecularly oriented in the flow direction of the film, that is, the machine direction (longitudinal direction).
  • machine direction longitudinal direction
  • significant anisotropy occurs, for example, between the MD direction and the TD direction (transverse direction), making it difficult to obtain a thermoplastic liquid crystal polymer film with high industrial utility value.
  • the stretching process is a technique for stretching the entire liquid crystal polymer film to a large extent in a uniaxial direction or biaxial direction, it is not possible to finely adjust the orientation direction and the degree of orientation. Therefore, at present, the liquid crystal polymer film is stretched mainly to adjust the surface roughness and surface accuracy of the liquid crystal polymer film.
  • Patent Document 1 discloses that a laminate in which a liquid crystal polymer film is sandwiched between a pair of laminate films (a fluororesin porous film having a specific gravity of 1.3 or more and a breaking elongation rate in the stretching direction of 400% or more) is prepared in advance, and the laminate is stretched uniaxially or biaxially under temperature conditions that soften the fluororesin porous film but do not substantially melt the liquid crystal polymer film.
  • a liquid crystal polymer film with low surface roughness and high surface precision is obtained.
  • thermoplastic polymer film As a method of stretching a thermoplastic polymer film alone, for example, in Patent Document 2, a thermoplastic polymer capable of forming an optically anisotropic molten phase having a dielectric constant of 3.25 or less in both the MD and TD directions is heated in a range from a temperature 60° C. lower than the heat deformation temperature (TD) (TD-60° C.) to a temperature 5° C. lower than the TD (TD-5° C.) to obtain a biaxial stretching of 2 times in the MD direction and 2.5 times in the TD direction.
  • TD heat deformation temperature
  • TD-5° C. TD-5° C.
  • Patent Document 1 shows that when a polyimide film having a small elongation at break is used, the laminate film breaks during the stretching process, and the desired stretching process cannot be performed. That is, the technique of Patent Document 1 essentially requires a stretching process using a special laminate film, that is, a fluororesin porous film having a high elongation at break, and is inferior in versatility. Moreover, in such a stretching process, the orientation direction and degree of orientation cannot be precisely adjusted. Moreover, when the stretching treatment is performed at a stretching ratio (MD direction ⁇ TD direction) of 1.5 or more, the resulting thermoplastic polymer film tends to be greatly impaired in flexibility and conformability compared to before the stretching treatment.
  • MD direction ⁇ TD direction a stretching ratio
  • thermoplastic polymer film can be stretched alone by precise temperature control to raise the heat distortion temperature of the thermoplastic polymer film by 40 to 100 ° C above the heat distortion temperature of the raw film, but it requires a complicated and long heat treatment, and is inferior in productivity and versatility. Moreover, in such a stretching process, the orientation direction and degree of orientation cannot be precisely adjusted. Moreover, when the stretching treatment is performed at a stretching ratio (MD direction ⁇ TD direction) of 1.5 or more, the resulting thermoplastic polymer film tends to be greatly impaired in flexibility and conformability compared to before the stretching treatment.
  • Patent Document 1 discloses or suggests that the orientation control of a single-layer liquid crystal polymer film is divided into predetermined depth regions in the thickness direction.
  • An object of the present invention is to provide a novel liquid crystal polymer film having a predetermined orientation direction and degree of orientation for each depth region in the thickness direction, thereby reducing the anisotropy in the MD direction and the TD direction in the entire film, as well as an insulating material for circuit boards and a metal foil clad laminate using the same.
  • the present inventors newly developed a novel liquid crystal polymer film in which the orientation direction and degree of orientation for each depth region in the thickness direction are adjusted to a predetermined state, and found that the liquid crystal polymer film whose orientation was controlled in this way alleviated the anisotropy between the MD direction and the TD direction as a whole film, leading to the completion of the present invention.
  • a liquid crystal polymer film containing at least a thermoplastic liquid crystal polymer and having a thickness T When the film surface is used as a reference plane (0%) of the thickness T, it is divided into three regions: a depth region A corresponding to a position of 0 to 25% of the thickness T from the reference plane, a depth region B corresponding to a position of 25 to 75% of the thickness T, and a depth region C corresponding to a position of 75 to 100% of the thickness T.
  • the orientation direction X of the thermoplastic liquid crystal polymer in the in-plane direction of the film in the depth region A and/or the orientation direction Z of the thermoplastic liquid crystal polymer in the in-plane direction of the film in the depth region C is different from the orientation direction Y of the thermoplastic liquid crystal polymer in the in-plane direction of the film in the depth region B.
  • liquid crystal polymer film according to any one of (1) to (6) having a total thickness of 15 to 300 ⁇ m or less.
  • An insulating material for a circuit board comprising a laminate having at least the liquid crystal polymer film according to any one of (1) to (10) and a woven fabric provided on at least one surface of the liquid crystal polymer film.
  • a metal foil-clad laminate comprising the liquid crystal polymer film according to any one of (1) to (10) and a metal foil provided on one side and/or both sides of the liquid crystal polymer film.
  • a metal foil-clad laminate comprising a laminate having at least the liquid crystal polymer film and the woven fabric according to any one of (1) to (10), and a metal foil provided on one side and/or both sides of the laminate.
  • the alignment direction and degree of alignment in the in-plane direction of the film are controlled for each predetermined depth region, and as a result, the anisotropy between the MD direction and the TD direction of the film as a whole is relaxed. It is possible to realize a novel liquid crystal polymer film, an insulating material for circuit boards, a metal foil-clad laminate, etc. using the same.
  • FIG. 2 is a conceptual diagram for explaining the depth region of the liquid crystal polymer film of one embodiment
  • FIG. 3 is a schematic diagram for explaining the alignment state of the liquid crystal polymer film of one embodiment. 3 is a plan view for explaining alignment directions X, Y, and Z of depth regions A, B, and C
  • FIG. 1 is a schematic diagram showing an embodiment of a method for producing a liquid crystal polymer film
  • FIG. It is a schematic diagram which shows an example of crimping
  • It is a schematic diagram which shows an example of shear shear stress application process S2.
  • FIG. 4 is a schematic diagram showing another embodiment of a method for producing a liquid crystal polymer film;
  • FIG. 4 is a schematic diagram showing another embodiment of a method for producing a liquid crystal polymer film
  • FIG. 4 is a schematic diagram showing another embodiment of a method for producing a liquid crystal polymer film;
  • FIG. 4 is a conceptual diagram showing the principle of calculating the degree of orientation based on the area ratio of orientation peaks.
  • BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic cross section which shows the insulating material for circuit boards of one Embodiment.
  • 1 is a schematic cross-sectional view showing a metal foil-clad laminate of one embodiment
  • FIG. 1 is a schematic cross-sectional view showing a metal foil-clad laminate of one embodiment
  • FIG. 1 is an X-ray diffraction image of a liquid crystal polymer film of Preparation Example 1.
  • FIG. 4 is an azimuth angle distribution curve of the liquid crystal polymer film of Preparation Example 1.
  • FIG. 1 is an X-ray diffraction image of the liquid crystal polymer film of Example 1.
  • FIG. 4 is an azimuth angle distribution curve of the liquid crystal polymer film of Example 1.
  • FIG. 2 is an X-ray diffraction image of depth region A of the liquid crystal polymer film of Example 1.
  • FIG. 4 is an azimuth angle distribution curve of the depth region A of the liquid crystal polymer film of Example 1.
  • FIG. 4 is an X-ray diffraction image of the depth region B of the liquid crystal polymer film of Example 1.
  • FIG. 4 is an azimuth angle distribution curve of the depth region B of the liquid crystal polymer film of Example 1.
  • FIG. 4 is an azimuth angle distribution curve of the depth region B of the liquid crystal polymer film of Example 1.
  • the liquid crystal polymer film 100 of this embodiment is a single-layer liquid crystal polymer (LCP) film having a thickness T and containing at least a thermoplastic liquid crystal polymer.
  • LCP liquid crystal polymer
  • the liquid crystal polymer film 100 of the present embodiment is divided into three regions, depth region A corresponding to a position 0 to 25% from the reference plane (0%) of the thickness T, depth region B corresponding to a position 25 to 75% of the thickness T, and depth region C corresponding to a position 75 to 100% from the reference plane (0%) of the film surface on the upper side of the drawing toward the thickness T direction from one film surface side (upper side in the figure).
  • the orientation direction and the degree of orientation of the thermoplastic liquid crystal polymer in the direction are respectively controlled to a predetermined state, so that the entire film has an orientation degree of 0.0% or more and less than 10.0% in the in-plane direction of the film.
  • FIG. 1 is a conceptual diagram (cross-sectional view) for explaining each depth region of the liquid crystal polymer film 100 of this embodiment.
  • the depth areas A, B, and C are areas divided by a predetermined thickness ratio from one film surface (upper surface in the drawing) of the liquid crystal polymer film 100 toward the other film surface side (lower surface in the drawing). That is, one film surface (upper surface in the figure) is a reference plane (0%) with a thickness T, and a region corresponding to a position of 0 to 25% of the thickness T from this reference plane is the depth region A (surface layer side region). The position of 100% of the thickness T from the reference plane corresponds to the back surface of the liquid crystal polymer film 100 (bottom surface in the drawing).
  • FIG. 2 is a conceptual diagram showing the alignment state of the liquid crystal polymer film 100 of this embodiment.
  • the alignment direction is helically displaced from the depth region B toward the depth region A while maintaining the alignment in the Y direction in the depth region B, thereby aligning in the X direction (the TD direction in this embodiment) on the 0% reference plane that is the film surface, and helically displacing the alignment direction from the depth region B toward the depth region C on the back surface of the film. It is oriented in the Z direction (the TD direction in this embodiment).
  • the liquid crystal polymer film 100 of the present embodiment has a predetermined alignment direction and degree of alignment for each of the depth areas A, B, and C.
  • One of the features of the liquid crystal polymer film 100 of the present embodiment is that the orientation direction X of the depth region A and/or the orientation direction Z of the depth region C described above is different from the orientation direction Y of the thermoplastic liquid crystal polymer in the depth region B.
  • the alignment direction X and/or the alignment direction Z are different from the alignment direction Y in this way, the alignment method and the alignment degree of the entire film of the liquid crystal polymer film 100 (recognized as a so-called vector sum of the alignment directions and the alignment degrees of the depth regions A, B, and C) are greatly reduced.
  • the orientation direction and degree of orientation of the entire liquid crystal polymer film 100, the orientation direction and orientation degree of depth region A alone, the orientation direction and orientation degree of depth region B alone, and the orientation direction and orientation degree of depth region C alone are all determined by performing X-ray diffraction measurement from one surface side of the target sample by a transmission method, and all determine the orientation of the thermoplastic liquid crystal polymer in the in-plane direction of the film of the target sample.
  • FIG. 3 is a plan view (plan view of the liquid crystal polymer film 100) for explaining the orientation directions X, Y, and Z of the depth regions A, B, and C.
  • FIG. Here, the alignment directions X, Y, and Z when viewing the liquid crystal polymer film 100 in plan view are indicated by solid lines, and the MD direction and TD direction are plotted as auxiliary lines.
  • the angle formed by the orientation directions X and Y is ⁇ xy
  • the angle formed by the orientation directions Y and Z is ⁇ yz.
  • the liquid crystal polymer film 100 with low orientation in which the degree of orientation in the film in-plane direction is 0.0% or more and less than 10.0% in the entire film (total of the depth regions A to C) is realized.
  • the orientation directions X, Y, and Z of the depth regions A, B, and C are shown so as not to overlap the MD direction and the TD direction, but the orientation directions X, Y, and Z may coincide with the MD direction or the TD direction.
  • Preferred alignment directions X, Y, Z are described in detail below.
  • the orientation direction X is preferably different from the orientation direction Y.
  • the alignment direction X and the alignment direction Y being different means that the alignment direction X and the alignment direction Y do not overlap, that is, the angle ⁇ xy formed by the alignment direction X and the alignment direction Y is not 0°.
  • the angle ⁇ xy formed by the orientation direction X and the orientation direction Y is preferably 90° ⁇ 60°, more preferably 90° ⁇ 45°, still more preferably 90° ⁇ 30°, particularly preferably 90° ⁇ 15°, and most preferably 90° ⁇ 10°.
  • the orientation direction X preferably coincides with or is close to the TD direction.
  • the orientation direction Z is preferably different from the orientation direction Y.
  • the alignment direction Z and the alignment direction Y being different means that the alignment direction Z and the alignment direction Y do not overlap, that is, the angle ⁇ yz formed by the alignment direction Y and the alignment direction Z is not 0°.
  • the angle ⁇ yz formed by the orientation direction Y and the orientation direction Z is preferably 90° ⁇ 60°, more preferably 90° ⁇ 45°, still more preferably 90° ⁇ 30°, particularly preferably 90° ⁇ 15°, and most preferably 90° ⁇ 10°.
  • the alignment direction Z preferably coincides with or is close to the TD direction.
  • the orientation degree of the depth region A may be set according to the desired orientation direction and orientation degree of the entire film, and is not particularly limited, but is preferably 3.0 to 25.0%, more preferably 4.0 to 25.0%, still more preferably 5.0 to 25.0%, and particularly preferably 5.0 to 20.0%.
  • the orientation degree of the entire film should be small as the sum of the orientation directions X, Y, Z and the orientation degrees of the depth regions A, B, and C, so the orientation degree of the depth region A may be smaller, the same, or larger than the orientation degrees of the depth regions B and C.
  • the degree of orientation of the depth region B may be set according to the desired orientation direction and degree of orientation of the entire film, and is not particularly limited, but is preferably 3.0 to 25.0%, more preferably 4.0 to 25.0%, still more preferably 5.0 to 25.0%, and particularly preferably 5.0 to 20.0%.
  • the orientation degree of the entire film should be small as the sum of the orientation directions X, Y, Z and the orientation degrees of the depth regions A, B, and C, so the orientation degree of the depth region B may be smaller, the same, or larger than the orientation degrees of the depth regions A and C.
  • the orientation degree of the depth region C may be set according to the desired orientation direction and orientation degree of the entire film, and is not particularly limited, but is preferably 3.0 to 25.0%, more preferably 4.0 to 25.0%, still more preferably 5.0 to 25.0%, and particularly preferably 5.0 to 20.0%. Note that the orientation degree of the entire film should be small as the sum of the orientation directions X, Y, Z and the orientation degrees of the depth regions A, B, and C, so the orientation degree of the depth region C may be smaller, the same, or larger than the orientation degrees of the depth regions A and B.
  • the degree of orientation of the entire liquid crystal polymer film 100 of the present embodiment is preferably 0.0% or more and less than 10.0%, more preferably 0.0% or more and less than 9.0%, still more preferably 0.0% or more and less than 8.0%, and particularly preferably 0.0% or more and less than 7.0%.
  • the thickness of the liquid crystal polymer film 100 can be appropriately set according to requirements, and is not particularly limited. Considering the handleability and productivity during extrusion molding, the thickness is preferably 15 ⁇ m or more and 300 ⁇ m or less, more preferably 18 ⁇ m or more and 250 ⁇ m or less, and still more preferably 20 ⁇ m or more and 200 ⁇ m or less.
  • the melting point (melting temperature) of the liquid crystal polymer film 100 is not particularly limited, but from the viewpoint of heat resistance and workability of the film, the melting point (melting temperature) is preferably 200 to 400°C, preferably 250 to 360°C, more preferably 260 to 355°C, further preferably 270 to 350°C, and particularly preferably 275 to 345°C.
  • the melting point of the liquid crystal polymer film 100 is measured using a DSC8500 (manufactured by PerkinElmer) in order to see the value after canceling the heat history. means the melting peak temperature in differential scanning calorimetry (DSC) when d heating).
  • the liquid crystal polymer film 100 of the present embodiment is preferably a melt extruded film (for example, a T-die melt extruded film, an inflation melt extruded film, etc.) obtained by melt extruding a resin composition containing at least a thermoplastic liquid crystal polymer.
  • a melt extruded film for example, a T-die melt extruded film, an inflation melt extruded film, etc.
  • melt-extruded film is a concept that includes not only a melt-extruded film obtained by melt-extrusion molding a resin composition containing at least a thermoplastic liquid crystal polymer (melt-extruded film before orientation control treatment, which will be described later, hereinafter, simply referred to as "pre-treatment melt-extruded film 11"), but also a melt-extruded film obtained after melt-extrusion molding (pre-treatment melt-extruded film 11) subjected to a predetermined orientation control treatment (melt-extruded film after orientation control treatment).
  • T-die melt-extrusion LCP films and inflation melt-extrusion LCP films are generally known to be highly anisotropic LCP films in which the polymer chains of the thermoplastic liquid crystal polymer are highly molecularly oriented in the flow direction of the film, that is, in the MD direction, due to the high degree of liquid crystal orientation and relatively rigid molecular chains of the thermoplastic liquid crystal polymer, and also to the shear stress caused by the die and die swell during melt extrusion (for example, the linear expansion coefficient in the MD direction (CTE, 23 ⁇ 200°C) is about -20 ppm/K, and the coefficient of linear expansion in the TD direction (CTE, 23-200°C) is about 80 ppm/K).
  • melt-extruded film having an orientation state that did not exist in the past i.e., the orientation direction and degree of orientation of the depth regions A, B, and C described above and an orientation degree of 0.0% or more and less than 10.0% in the in-plane direction of the entire film
  • a melt extruded film containing at least a thermoplastic liquid crystal polymer will be described in detail below.
  • thermoplastic liquid crystal polymer contained in the liquid crystal polymer film 100 one known in the art can be used, and the type is not particularly limited.
  • a liquid crystal polymer is a polymer that forms an optically anisotropic molten phase, and typically includes a thermotropic liquid crystal compound.
  • the properties of the anisotropic molten phase can be confirmed by a known method such as polarization inspection using crossed polarizers. More specifically, confirmation of the anisotropic molten phase can be carried out by using a Leitz polarizing microscope and observing a sample placed on a Leitz hot stage under a nitrogen atmosphere at a magnification of 40 times.
  • thermoplastic liquid crystal polymers include, but are not limited to, liquid crystal polymers obtained by polycondensation of aromatic or aliphatic dihydroxy compounds, aromatic or aliphatic dicarboxylic acids, aromatic hydroxycarboxylic acids, aromatic diamines, aromatic hydroxylamines, aromatic aminocarboxylic acids, and the like.
  • thermoplastic liquid crystal polymers include, but are not particularly limited to, aromatic polyamide resins obtained by polycondensing monomers such as aromatic hydroxycarboxylic acids, aromatic diamines, and aromatic hydroxyamines; and (totally) aromatic polyester resins obtained by polycondensing monomers such as aromatic diols, aromatic carboxylic acids, and aromatic hydroxycarboxylic acids. These can be used individually by 1 type or in arbitrary combinations and ratios of 2 or more types.
  • Thermoplastic liquid crystal polymers are generally classified into type I, type II, type III, etc. in terms of heat distortion temperature (TDUL). Any type of thermoplastic liquid crystal polymer can be suitably used for the thermoplastic liquid crystal polymer used in the present embodiment.
  • thermoplastic liquid crystal polymer with a TDUL of about 250 to 350 ° C. and a relatively high heat-resistant type II thermoplastic liquid crystal polymer with a TDUL of about 240 to 250 ° C. are preferably used.
  • (wholly) aromatic polyester resins exhibiting thermotropic liquid crystal-like properties and having a melting point of 250°C or higher, preferably 280°C to 380°C, are preferably used.
  • a (wholly) aromatic polyester resin for example, a (wholly) aromatic polyester resin that exhibits liquid crystallinity when melted and synthesized from monomers such as aromatic diols, aromatic carboxylic acids, and hydroxycarboxylic acids is known.
  • Typical examples thereof include polycondensates of ethylene terephthalate and parahydroxybenzoic acid, polycondensates of phenol, phthalic acid and parahydroxybenzoic acid, and polycondensates of 2,6-hydroxynaphthoic acid and parahydroxybenzoic acid, but are not particularly limited thereto.
  • the (totally) aromatic polyester resin can be used alone or in any combination and ratio of two or more. Depending on the required performance, a highly heat-resistant wholly aromatic polyester resin having a relatively high melting point or high heat distortion temperature may be used, or an aromatic polyester resin having a relatively low melting point or low heat distortion temperature and excellent moldability may be used.
  • the basic structure is 6-hydroxy-2-naphthoic acid and its derivatives (hereinafter sometimes simply referred to as "monomer component A”), and one or more selected from the group consisting of parahydroxybenzoic acid, terephthalic acid, isophthalic acid, 6-naphthalenedicarboxylic acid, 4,4'-biphenol, bisphenol A, hydroquinone, 4,4-dihydroxybiphenol, ethylene terephthalate, and derivatives thereof is used as a monomer component (hereinafter simply referred to as "monomer component (sometimes referred to as "B”).) includes (all) aromatic polyester resins.
  • Such a (wholly) aromatic polyester resin forms an anisotropic molten phase in which linear chains of molecules are regularly arranged in a molten state, typically exhibits thermotropic liquid crystal-like properties, and has excellent basic performance in terms of mechanical properties, electrical properties, high frequency properties, heat resistance, hygroscopicity, and the like.
  • the (wholly) aromatic polyester resin of one preferred embodiment described above can have any configuration as long as it has the monomer component A and the monomer component B as essential units.
  • it may have two or more monomer components A, or three or more monomer components A.
  • the (totally) aromatic polyester resin of one preferred embodiment described above may contain other monomer components (hereinafter sometimes simply referred to as "monomer component C") other than the monomer component A and the monomer component B.
  • the (totally) aromatic polyester resin of one preferred embodiment described above may be a polycondensate of a binary or higher system consisting only of the monomer component A and the monomer component B, or a polycondensate of a ternary or higher monomer component consisting of the monomer component A, the monomer component B and the monomer component C.
  • Examples of other monomer components include those other than the monomer component A and monomer component B described above, specifically aromatic or aliphatic dihydroxy compounds and derivatives thereof; aromatic or aliphatic dicarboxylic acids and derivatives thereof; aromatic hydroxycarboxylic acids and derivatives thereof; aromatic diamines, aromatic hydroxyamines or aromatic aminocarboxylic acids and derivatives thereof; Other monomer components can be used singly or in any combination and ratio of two or more.
  • the "derivative” may be an ester-forming monomer such as an acylated product, an ester derivative, or an acid halide of the monomer components A and B which may have a modifying group as described above.
  • the method for synthesizing the thermoplastic liquid crystal polymer is not particularly limited, and a known method can be applied.
  • a known polycondensation method for forming an ester bond by the monomer components described above such as melt polymerization, melt acidolysis, slurry polymerization, or the like, can be applied.
  • an acylation or acetylation step may be performed according to a conventional method.
  • the content ratio of the thermoplastic liquid crystal polymer in the liquid crystal polymer film 100 of the present embodiment is not particularly limited, and can be appropriately set according to the required performance in consideration of the blending balance with other essential components and optional components.
  • the content of the thermoplastic LCD polymer is preferably 50 % or less, more preferably 60 % to 100 % or less, more preferably, more preferably, more preferably 60 % mass or less. It is 70 % by mass or 100 % by mass or less, especially preferably 80 % by mass to 100 % by mass or less, the most preferably 90 % by mass or 100 % or less.
  • the liquid crystal polymer film 100 may further contain an inorganic filler.
  • an inorganic filler By containing an inorganic filler, the liquid crystal polymer film 100 with a reduced coefficient of linear expansion can be realized. Specifically, the liquid crystal polymer film 100 with reduced anisotropy of the coefficient of linear expansion in the MD direction, the TD direction, and the ZD direction (Z-axis direction; film thickness direction) can be easily obtained.
  • Such a liquid crystal polymer film 100 is particularly useful for applications such as rigid substrates that require multi-layer lamination.
  • any known inorganic filler in the industry can be used, and the type is not particularly limited.
  • examples include kaolin, calcined kaolin, calcined clay, uncalcined clay, silica (e.g., natural silica, fused silica, amorphous silica, hollow silica, wet silica, synthetic silica, aerosil, etc.), aluminum compounds (e.g., boehmite, aluminum hydroxide, alumina, hydrotalcite, aluminum borate, aluminum nitride, etc.), magnesium compounds (e.g., magnesium aluminometasilicate, magnesium carbonate, magnesium oxide, magnesium hydroxide, etc.), calcium compounds (e.g., calcium carbonate, calcium hydroxide, calcium sulfate, calcium sulfite, calcium borate, etc.), molybdenum.
  • silica e.g., natural silica, fused silica, amorphous silica, hollow silic
  • Den compounds e.g., molybdenum oxide, zinc molybdate, etc.
  • talc e.g., natural talc, calcined talc, etc.
  • mica mica
  • These can be used individually by 1 type, and can also be used in combination of 2 or more type.
  • silica is preferable from the viewpoint of dielectric properties and the like.
  • the inorganic filler used here may be subjected to surface treatment known in the art. Moisture resistance, adhesive strength, dispersibility, etc. can be improved by surface treatment.
  • surface treatment agents include silane coupling agents, titanate coupling agents, sulfonic acid esters, carboxylic acid esters, and phosphoric acid esters, but are not particularly limited thereto.
  • the median diameter (d50) of the inorganic filler is preferably 0.01 ⁇ m or more and 50 ⁇ m or less, more preferably 0.03 ⁇ m or more and 50 ⁇ m or less, and still more preferably 0.1 ⁇ m or more and 50 ⁇ m or less, from the viewpoint of the demand reduction effect.
  • the median diameter (d50) of the inorganic filler means a value measured on a volume basis by a laser diffraction/scattering method using a laser diffraction/scattering particle size distribution analyzer (LA-500 manufactured by Horiba, Ltd.).
  • the content of the inorganic filler is not particularly limited, and can be set appropriately according to the required performance, taking into consideration the blending balance with other essential ingredients and optional ingredients. From the viewpoint of kneadability and handleability during preparation, the effect of reducing the linear expansion coefficient, etc., the total content of the inorganic filler in terms of solid content with respect to the total amount of the liquid crystal polymer film 100 is preferably 1% by mass or more and 45% by mass or less.
  • the liquid crystal polymer film 100 may contain resin components other than the above-described thermoplastic liquid crystal polymer (hereinafter sometimes simply referred to as "other resin components"), such as thermoplastic resins other than the thermoplastic liquid crystal polymer, thermosetting resins, thermoplastic elastomers, etc., as long as the effects of the present invention are not excessively impaired.
  • the liquid crystal polymer film 100 may contain additives known in the art, such as release improvers such as higher fatty acids having 10 to 25 carbon atoms, higher fatty acid esters, higher fatty acid amides, higher fatty acid metal salts, polysiloxanes, and fluororesins; coloring agents such as dyes and pigments; organic fillers; Good.
  • additives can be used singly or in combination of two or more. These additives can be included in the molten resin composition prepared when the liquid crystal polymer film 100 is molded.
  • the content of these resin components and additives is not particularly limited, but from the viewpoint of moldability and thermal stability, each is preferably 0.01 to 10% by mass, more preferably each 0.1 to 7% by mass, and still more preferably each 0.5 to 5% by mass, relative to the total amount of the liquid crystal polymer film 100.
  • the liquid crystal polymer film 100 whose orientation is controlled as described above can be obtained by applying a manufacturing method known in the art, and the manufacturing method is not particularly limited.
  • the manufacturing method is not particularly limited.
  • a conventional melt extrusion molding is applied to obtain a melt extruded film (pre-treatment melt extruded film 11) in which the orientation direction and degree of orientation of the depth regions A, B, and C do not satisfy the above conditions, and then the melt extruded film is subjected to a predetermined orientation control treatment to obtain the liquid crystal polymer film 100 whose orientation is controlled as described above.
  • a melt-extruded film such as a T-die extruded film or an inflation film is preferably used.
  • the pre-treatment melt-extruded film 11 can be obtained, for example, by preparing a resin composition containing the above-described thermoplastic liquid crystal polymer and optional components such as inorganic fillers, other resin components, and additives that are blended as necessary, and melt-extrusion molding the resin composition to a predetermined thickness.
  • the preparation of the resin composition is not particularly limited as long as it is carried out according to a conventional method.
  • Each of the components described above can be produced and processed by known methods such as kneading, melt-kneading, granulation, extrusion molding, pressing or injection molding.
  • a kneading device such as a generally used single-screw or twin-screw extruder or various kneaders can be used.
  • the thermoplastic liquid crystal polymer, other resin components, inorganic fillers, additives and the like may be dry-blended in advance using a mixing device such as a tumbler or Henschel mixer.
  • the set temperature of the cylinder of the kneading device may be appropriately set and is not particularly limited, but generally the range of the melting point of the liquid crystal polymer or higher and 360° C. or lower is preferable, and the melting point of the liquid crystal polymer +10° C. or higher and 360° C. or lower is more preferable.
  • the effects of the present invention are not excessively impaired, and it is known in the industry, for example, high -grade fatty acids, high -grade fatty acids, high -grade fatty acids, high -grade fatty acids amide, high -grade fatty acid metal salt, polyciloxan, fluorores, etc.
  • Color agents such as dye, pigments, etc.; organic filling agents; antioxidants; heat stabilizers; optical stabilizers; UV -stabilizers; flame -retardant; surface activity; surfactants; rust prevention agent may contain a fluorescent agent. These additives can be used singly or in combination of two or more.
  • the content of the additive is not particularly limited, but from the viewpoint of molding processability, thermal stability, etc., it is preferably 0.01 to 10% by mass, more preferably 0.1 to 7% by mass, more preferably 0.5 to 5% by mass, based on the total amount of the resin composition in terms of solid content.
  • melt-extruded film 11 As a method for forming the melt-extruded film (pre-treatment melt-extruded film 11), various known methods can be applied, and the type is not particularly limited.
  • a T-die method or an inflation method for example, a multi-manifold type co-extrusion method or a feed block type co-extrusion method; for example, a multilayer co-extrusion method such as a two-layer co-extrusion method or a three-layer co-extrusion method;
  • the above-described resin composition is extruded into a film form from a T-die by a melt-extrusion film-forming method using a T-die (hereinafter sometimes simply referred to as "T-die melt extrusion") to form a film, and then the T-die melt-extruded film is subjected to pressure and heat treatment as necessary, and then cooling treatment, crimping treatment, pressure and heat treatment, etc.
  • pre-treatment melt-extrusion film 11 a predetermined melt-extrusion film
  • pre-treatment melt-extruded film 11 a thermoplastic resin layer, a liquid crystal polymer film layer, and a liquid crystal polymer film layer which is an intermediate layer (core layer) of a three-layer coextruded film having a laminated structure in which at least the thermoplastic resin layer is arranged in this order is also preferably used.
  • the single-layer pre-treatment melt-extruded film 11 can be taken out by removing the thermoplastic resin layers of both outer layers of the three-layer coextruded film.
  • the setting conditions for melt extrusion are not particularly limited, and may be appropriately set according to the type and composition of the resin composition to be used, the desired performance of the target melt-extruded film, and the like.
  • the set temperature of the extruder cylinder is preferably 230-360°C, more preferably 280-350°C.
  • the slit gap of the T-die may be appropriately set according to the type and composition of the resin composition to be used, the desired performance of the target melt-extruded film (pre-treatment melt-extruded film 11), etc., and is not particularly limited.
  • it is preferably 0.1 to 1.5 mm, more preferably 0.1 to 0.5 mm.
  • the thickness of the melt-extruded film can be appropriately set according to requirements and is not particularly limited. Considering the handleability and productivity during T-die melt extrusion molding, the thickness is preferably from 10 ⁇ m to 500 ⁇ m, more preferably from 20 ⁇ m to 300 ⁇ m, and even more preferably from 30 ⁇ m to 250 ⁇ m.
  • the melting point (melting temperature) of the melt-extruded film is not particularly limited, but from the viewpoint of heat resistance and workability of the film, the melting point (melting temperature) is preferably 200 to 400°C. There is.
  • the melting point of the melt-extruded film is measured using a DSC8500 (manufactured by PerkinElmer), in order to see the value after eliminating the heat history, the melt-extruded film is heated in the temperature range of 30 to 400 ° C.
  • the above resin composition is, for example, melt-extruded with a T-die
  • a T-die melt-extruded film having a coefficient of linear expansion (CTE) in the machine direction (machine direction; longitudinal direction) of -40 to 40 ppm/K and a coefficient of linear expansion (CTE) in the transverse direction (transverse direction) of 50 to 120 ppm/K is easily obtained.
  • melt extrusion molding there is a melt phase for anisotropy of liquid crystal polymer.
  • a high degree of orientation (large anisotropy) melt extruded film pre-treatment melt extruded film 11
  • pre-treatment melt extruded film 11 a high degree of orientation melt extruded film
  • the orientation direction and degree of orientation of depth regions A, B, and C can be arbitrarily controlled by the orientation control treatment described later, so that it can be used as it is as the pre-treatment melt extruded film 11, and further described later as necessary.
  • the degree of orientation (anisotropy) can be reduced in advance by performing the pressure heating step.
  • FIG. 4 is a schematic diagram showing a main part of a suitable method for manufacturing the liquid crystal polymer film 100 of this embodiment.
  • a melt-extruded film pre-treatment melt-extruded film 11 obtained by melt-extrusion molding of a resin composition containing at least a thermoplastic liquid crystal polymer and whose orientation direction and degree of orientation in depth regions A, B, and C do not satisfy the conditions described above is subjected to orientation control to obtain a liquid crystal polymer film 100 (melt-extruded film after orientation control treatment) in which a predetermined orientation direction and degree of orientation are imparted to each of depth regions A, B, and C as described above.
  • melt-extruded film highly oriented in the MD direction as the pre-treatment melt-extruded film 11 (a melt-extruded film that does not satisfy the conditions described above in terms of the orientation direction and the degree of orientation of the depth regions A, B, and C) is shown, but the present invention is not particularly limited to this example.
  • this preferred manufacturing method comprises a step of preparing a crimped body 10 comprising a first membrane member 21, a pre-processed melt-extruded film 11 highly oriented in the MD direction, and a second membrane member 31 (crimped body preparation step S1), and pulling the film ears of the first membrane member 21 and/or the second membrane member 31 of the crimped body 10 outward relative to the pre-processed melt-extruded film 11 so that the pre-processed melt-extruded film 11 of the crimped body 10 is and a step of applying shear shear stress ⁇ (shear shear stress application step S2).
  • shear shear stress application step S2 shear shear stress application step
  • the pressure-bonded body 10 is prepared in which the first film member 21, the pre-treatment melt-extruded film 11, and the second film member 31 are laminated in this order in cross-sectional view.
  • one first membrane member 21 is provided on the surface side of the pre-treatment melt-extrusion film 11
  • the other second membrane member 31 is provided on the back side of the pre-treatment melt-extrusion film 11 .
  • These three layers are thermo-compressed to form the compressed body 10, which is a laminate having a three-layer structure.
  • the first membrane member 21 and the second membrane member 31 are provided on the surface side and/or the back side of the pre-treatment melt-extrusion film 11
  • the pressure-bonded body 10 which is a laminated body having a three-layer structure, consists of one side end 21a (film ear) of the first film member 21 that protrudes to one side (right direction in the drawing) in the width direction in a cross-sectional view of the pre-treatment melt-extruded film 11 without being laminated with the pre-treatment melt-extrusion film 11, and one side end 3 of the second film member 31 that protrudes to the other side (the left direction in the drawing) in the cross-sectional view of the pre-treatment melt-extruded film 11 without being laminated with the pre-treatment melt-extrusion film 11. 1a (film ear).
  • the first film member 21 and the second film member 31 are film-like bodies for applying shear shear stress ⁇ to the pre-treatment melt-extrusion film 11 by respectively adhering to the front side and the back side of the pre-treatment melt-extrusion film 11 .
  • the materials that constitute the first film member 21 and the second film member 31 are not particularly limited as long as they can adhere to the pre-treatment melt-extrusion film 11 and have a tensile strength when applying the shear shear stress ⁇ to the pre-treatment melt-extrusion film 11.
  • the impregnated body means a composite material in which a melted or softened resin is impregnated or pressed into paper, woven fabric, nonwoven fabric, foamed sheet, porous material, or the like.
  • a thermosetting resin film such as a polyimide film
  • a metal foil such as an aluminum foil or a copper foil are preferred.
  • the first film member 21 and the second film member 31 may be made of the same constituent material or may be made of different constituent materials.
  • the method for producing the crimped body 10 is not particularly limited, and a known lamination forming method can be applied.
  • the first membrane member 21, the pre-treatment melt-extruded film 11 and the second membrane member 31 are superimposed in this order, and the crimped body 10 can be obtained by crimping or thermally crimping them using known equipment such as a press machine, crimping roll, non-contact heater, oven, blowing device, heat roll, cooling roll, heat press machine, and double belt press.
  • known equipment such as a press machine, crimping roll, non-contact heater, oven, blowing device, heat roll, cooling roll, heat press machine, and double belt press.
  • the pre-treatment melt-extruded film 11 and the first film member 21 and the second film member 31 having a wider width than the pre-treatment melt-extrusion film 11 are supplied to a hot laminator having a thermo-press roll 51, and these three layers are thermo-compressed to obtain the crimped body 10.
  • the supply positions of the pre-treatment melt extruded film 11 and the first membrane member 21 and the second membrane member 31 are adjusted so that the one-side end portion 21a (film ear portion) of the first membrane member 21 and the one-side end portion 31a (film ear portion) of the second membrane member 31 are formed (see FIG. 4).
  • the processing conditions for crimping may be appropriately set according to the material to be used, and are not particularly limited. For example, it can be carried out under the conditions of a surface pressure of 0.3 to 10 MPa and a heating temperature of not less than the thermal deformation temperature of the melt-extruded film 11 before treatment and a melting point +70° C. or less, preferably under a condition of not less than the melting point of the melt-extruded film 11 before treatment and not more than 60° C. higher than the melting point at a surface pressure of 0.6 to 8 MPa.
  • various release agents may be placed between the pre-treatment melt-extrusion film 11 and the first film member 21 of the pressure-bonded body 10 and between the pre-treatment melt-extrusion film 11 and the second film member 31.
  • various primers, adhesive agents, and the like may be used in place of the release agent.
  • shear shear stress application step S2 In this shear shear stress applying step S2, the one-side end 21a and/or the one-side end 31a of the crimped body 10 is pulled outwardly with respect to the pre-processed melt-extruded film 11, thereby applying a shear shear stress ⁇ to the pre-processed melt-extruded film 11 of the crimped body 10 (see FIG. 4).
  • the one-side end 21a and the one-side end 31a are gripped by the first gripper 71a
  • the one-side end 31a is gripped by the second gripper 72a
  • the first gripper 71a and the second gripper 72a are moved in the direction of relatively separating them (see FIG. 4).
  • the first gripper 71a can be moved to the right side of the film, which is one side in the width direction
  • the second gripper 72a can be moved to the left side of the film, which is the other side in the width direction.
  • such a pulling operation can be performed with high efficiency and high precision using a drawing machine provided with clamp mechanisms 71 and 72 having grippers 71a and 72a such as chucks and clips.
  • one side end 21a may be held by a first gripper 71a and one side end 31a may be fixed by a stator 73a, and in this state, the first gripper 71a may be moved away from the stator 73a. Specifically, in FIG. 7, the first gripper 71a can be moved to the outside of the film on the right side of the drawing.
  • the shear shear stress applying step S2 at least one of the one-side end portion 21a and the one-side end portion 31a is pulled outward from the pre-treatment melt-extrusion film 11, so that the shear shear stress ⁇ is applied to the pre-treatment melt-extrusion film 11 from the surface side of the pre-treatment melt-extrusion film 11 (the pressure bonding surface side between the pre-treatment melt-extrusion film 11 and the first film member 21 and the second film member 31).
  • the shear shear stress ⁇ has a large absolute value acting on the surface side (the pressure-bonding surface side between the pre-treatment melt-extrusion film 11 and the first membrane member 21) and the back side (the pressure-bonding surface side between the pre-treatment melt-extrusion film 11 and the second membrane member 31) of the pre-treatment melt-extrusion film 11, and acts with a smaller absolute value toward the center in the thickness direction of the pre-treatment melt-extrusion film 11.
  • This preferred manufacturing method focuses on such an anisotropically generated shear shear stress ⁇ in the film thickness direction, and utilizes the anisotropically generated shear shear stress ⁇ to arbitrarily adjust the direction and degree of orientation of the molecular orientation and polymer chain orientation of the pre-treatment melt extruded film 11.
  • the above-described crimped body 10 is produced using the pre-treatment melt-extrusion film 11 highly oriented in the MD direction, and the one-side end 21a and the one-side end 31a are pulled relative to the pre-treatment melt-extrusion film 11, for example, in the TD direction (90° direction with respect to the MD direction).
  • a large shear shear stress ⁇ is applied to the film surface side and the film back surface side, and the orientation in the MD direction changes to the orientation in the TD direction.
  • the shear shear stress ⁇ decreases toward the center in the thickness direction of the film
  • the degree of orientation change from the MD direction to the TD direction decreases toward the center in the thickness direction
  • the orientation orientation change (change rate) typically transitions in a spiral shape in the thickness direction, and in this example, the orientation in the MD direction is maintained in the central region in the thickness direction.
  • the orientation direction and orientation strength can be arbitrarily adjusted by adjusting the temperature, tensile direction, tensile magnification, tensile speed, etc. of the one-side end portion 21a and/or the one-side end portion 31a.
  • the pulling direction ⁇ of the one-side end portion 21a and/or the one-side end portion 31a is not particularly limited as long as it is the outside of the film, and may be set according to the desired orientation direction.
  • the pulling direction ⁇ can be arbitrarily set between 0° and 180° with respect to the MD direction.
  • first film member 21 and the second film member 31 show an example using the crimping body 10 in which the first film member 21 and the second film member 31 protrude on one side in the width direction (right direction in the drawing) with substantially the same width, and the first film member 21 and the second film member 31 protrude on the other side in the width direction (left direction in the drawing) with substantially the same width.
  • the first film member 21 may be biased to one width direction side (right direction in the drawing) in a cross-sectional view with respect to the unprocessed melt-extruded film 11, and the second film member 31 may be biased to the other width direction side (left direction in the drawing) in a cross-sectional view.
  • the tensile ratio of the pre-treatment melt-extruded film 11 in the shear shear stress application step S2 may be set according to the desired orientation direction and degree of orientation, and is not particularly limited.
  • the draw ratio (MD direction ⁇ TD direction) is set to 1.5 or more and 150 or less, but in the application of the shear shear stress ⁇ in this manufacturing method, the tensile ratio (MD direction ⁇ TD direction) can be adjusted within the range of 1.0005 to 1.1000.
  • the tensile strength (MD direction ⁇ TD direction) is 1.0010 to 1.1000.
  • the tensile ratio in the TD direction is preferably 1.0005 to 1.1000, more preferably 1.0010 to 1.1000.
  • the tensile ratio in the MD direction is preferably 1.0000 to 1.0100, more preferably 1.0000 to 1.0050.
  • the tensile speed of the first membrane member 21 and/or the second membrane member 31 in the shear shear stress application step S2 may be set according to the desired orientation direction and degree of orientation, and is not particularly limited.
  • the pulling speed is preferably 0.1 to 300 mm/min, more preferably 1 to 200 mm/min, still more preferably 5 to 100 mm/min.
  • the treatment temperature in the shear shear stress application step S2 is not particularly limited as long as it is equal to or higher than the glass transition point of the pre-treatment melt-extruded film 11, but from the viewpoint of increasing the degree of freedom in orientation direction and orientation by melting the pre-treatment melt-extrusion film 11, it is preferably at least the melting point of the pre-treatment melt-extrusion film 11, and more preferably at the melting point +10°C or higher of the pre-treatment melt-extrusion film 11.
  • the upper limit temperature is not particularly limited, the melting point of the melt-extruded film 11 before treatment + 70°C or less is a standard.
  • the orientation direction and degree of orientation can be arbitrarily controlled for each of the depth regions A, B, and C, whereby the degree of orientation of the entire liquid crystal polymer film 100 can be adjusted to 0.0% or more and less than 10.0%.
  • the direction and degree of orientation can be arbitrarily adjusted, and the liquid crystal polymer film 100 (melt extruded film after orientation control treatment) having physical property values that did not exist in the past can be realized.
  • the pressure-bonded body 10 After applying a shear shear stress ⁇ to the pre-treatment melt-extruded film 11, the pressure-bonded body 10 is cooled as necessary, and then the first film member 21 and the second film member 31 which are pressure-bonded to both surfaces of the pressure-bonded body 10 are peeled off (removed), whereby the liquid crystal polymer film 100 (melt-extruded film after orientation control) can be obtained.
  • Cooling of the crimping body 10 can be carried out using, for example, a pair of cooling rolls 75 . It can also be carried out by natural cooling. Then, the liquid crystal polymer film 100 can be taken up by a take-up roll, for example, and wound into a roll shape by a take-up roll to form a raw material roll.
  • the liquid crystal polymer film 100 can be used as it is as long as it has a predetermined orientation direction and degree of orientation for each of the depth regions A, B, and C. However, it is possible to further reduce the orientation (anisotropy) or release the internal strain further by performing a pressurization and heating process as necessary. Further, the liquid crystal polymer film 100 may be provided with a predetermined orientation direction and degree of orientation for each of the depth regions A, B, and C as described above by subjecting the pre-treatment melt extruded film 11 to a pressure heating step.
  • the heat and pressure treatment may be performed using methods known in the art, such as contact heat treatment and non-contact heat treatment, and the type is not particularly limited.
  • heat setting can be performed using known equipment such as a non-contact heater, oven, blower, hot roll, cooling roll, heat press, and double belt press.
  • a release film or porous film known in the art can be placed on the surface of the melt-extruded film 11 before treatment or the liquid crystal polymer film 100, and heat treatment can be performed.
  • thermocompression molding method when performing this heat treatment, from the viewpoint of orientation control, a hot compression molding method is preferably used in which a release film or a porous film is placed on the front and back of the pre-treatment melt-extruded film 11 or the liquid crystal polymer film 100, and is sandwiched between endless belt pairs of a double belt press machine while being thermally pressed and then the release film or porous film is removed.
  • the thermocompression molding method may be performed with reference to, for example, JP-A-2010-221694.
  • the processing temperature for thermocompression molding of the unprocessed melt-extruded film 11 and the liquid crystal polymer film 100 between the pair of endless belts of the double belt press is preferably a temperature higher than the melting point of the thermoplastic liquid crystal polymer and a temperature higher than the melting point by 70°C or lower, more preferably a temperature higher than the melting point by +5°C or higher, and a temperature higher than the melting point by 60°C or lower, further preferably a temperature higher than the melting point by +10°C or higher by 50°C in order to control the crystalline state of the melt-extruded film 11 or the liquid crystal polymer film 100 before the treatment. °C high temperature or less.
  • thermocompression bonding conditions at this time can be appropriately set according to the desired performance, and are not particularly limited, but are preferably carried out under the conditions of a surface pressure of 0.5 to 10 MPa and a heating temperature of 250 to 430 ° C., more preferably a surface pressure of 0.6 to 8 MPa and a heating temperature of 260 to 400 ° C., more preferably a surface pressure of 0.7 to 6 MPa and a heating temperature of 270 to 370 ° C..
  • a non-contact heater or oven it is preferable to carry out the treatment under conditions of, for example, 200 to 320° C. for 1 to 20 hours.
  • the degree of orientation of the liquid crystal polymer film 100 and the pre-treatment melt-extruded film 11 means a value calculated from the following formula based on the area ratio of the orientation peak of the diffraction intensity distribution curve obtained by performing X-ray diffraction measurement by a transmission method using an X-ray diffractometer.
  • a measurement target with a small degree of orientation (%) a broad diffraction peak with a small peak intensity is observed in X-ray diffraction measurement, so a calculation method based on the half-value width of the orientation peak cannot guarantee high measurement accuracy.
  • the degree of orientation (%) is calculated by a calculation method based on the area ratio of the orientation peak instead of the half width of the orientation peak.
  • the peak intensity (orientation component) is measured by 2 ⁇ / ⁇ scan, and the intensity in the azimuth direction from 0° to 360° is measured by ⁇ scan to obtain the intensity distribution in the azimuth direction (base intensity (isotropic component)).
  • the ratio to the area of the polar component) is calculated as the degree of orientation (%).
  • the degree of orientation of less than 25% may be referred to as "low orientation”
  • the degree of orientation of 25% or more may be referred to as "high orientation”.
  • the orientation directions of the liquid crystal polymer film 100 and the pre-treatment melt-extruded film 11 were determined based on the angle of the peak top of the orientation peak.
  • the peak intensity (orientation component) is measured by 2 ⁇ / ⁇ scanning, and the intensity is measured from 0° to 360° in the azimuthal direction by ⁇ scanning to obtain the intensity distribution in the azimuthal direction (base intensity (isotropic component)), and it is determined from the position of the peak top of the oriented component excluding the area of the base isotropic component.
  • the position of the peak top is recognized at 90 ° ⁇ 5 ° and 270 ° ⁇ 5 ° as "MD orientation”
  • the position of the peak top is recognized at 180 ° ⁇ 5 ° and 360 ° ⁇ 5 ° as "TD orientation”
  • the position of the peak top is recognized at 0 ° to 360 ° (however, the peak top is recognized at 90 ° ⁇ 5 ° and 270 ° ⁇ 5 ° and 0 ° ⁇ 5 °, 180 ° ⁇ 5 ° and 360 ° ⁇ 5 ° excluding those with peak tops observed.) are sometimes referred to as “oblique orientation", and those in which the orientation component is broad and the peak top is not clearly observed, and those in which the peak top is observed but the degree of orientation is less than 10% are sometimes referred to as "non-orientation”.
  • the applied strength of the shear shear stress ⁇ is different between the surface side and the back side of the pre-treatment melt-extrusion film 11 and the vicinity of the thickness direction center of the pre-treatment melt-extrusion film 11 . Therefore, for example, as shown in FIG. 2, the obtained liquid crystal polymer film 100 may have different alignment directions and degrees of alignment in the thickness T direction. Such a difference can be discriminated by evaluating the orientation direction and degree of orientation of each section of the depth regions A, B, and C, as shown in FIG. For example, the orientation direction and orientation degree of only the depth region A can be evaluated by removing the depth regions B and C from the liquid crystal polymer film 100 by mechanical polishing, chemical polishing, or the like.
  • the orientation direction and degree of orientation of only the depth region B can be evaluated by removing the depth regions A and C from the liquid crystal polymer film 100 by mechanical polishing, chemical polishing, or the like.
  • the processing conditions for extracting each region are not particularly limited and may be, for example, an etching process using an aqueous amine solution or a polishing process using abrasive paper of about #1500. However, from the viewpoint of ensuring the objectivity of the measurement data, the conditions described in Examples described later shall be followed.
  • the orientation direction and orientation degree can be arbitrarily adjusted over the entire thickness T direction, or can be made different for each region (for example, depth regions A, B, and C) divided in the thickness T direction.
  • the alignment control method described above it is possible to obtain the liquid crystal polymer film 100 in which the alignment direction and the degree of alignment are arbitrarily adjusted, and by adjusting the alignment direction and the degree of alignment, it is possible to realize the liquid crystal polymer film 100 having physical property values that did not exist in the past.
  • the film melts at a temperature above its melting point and cannot be stretched because its shape cannot be maintained during stretching.
  • the shear shear stress ⁇ can be applied even at a temperature above the melting point.
  • the draw ratio (MD direction ⁇ TD direction) is 1.5 or more and 150 or less, whereas the above orientation control method can make the tensile ratio (MD direction ⁇ TD direction) extremely small, so the influence of excessive deterioration of flexibility and shape followability can be greatly reduced.
  • the non-oriented liquid crystal polymer film 100 which is excellent in high-frequency characteristics and low dielectric properties, has smaller linear expansion coefficients in the MD and TD directions and anisotropy of the linear expansion coefficients than the conventional technology. Therefore, the liquid crystal polymer film 100 of the present embodiment is not only used for electronic circuit boards, multilayer boards, high heat dissipation boards, flexible printed wiring boards, antenna boards, opto-electronic mixed boards, IC packages, etc., but also becomes a particularly useful material as an insulating material for circuit boards such as flexible printed circuit boards (FPC), flexible printed circuit board laminates, fiber-reinforced flexible laminates, etc., for fifth-generation mobile communication systems (5G) and millimeter-wave radars, which will develop in the future.
  • FPC flexible printed circuit boards
  • 5G fifth-generation mobile communication systems
  • millimeter-wave radars which will develop in the future.
  • the linear expansion coefficient (JIS K7197 compliant) of the liquid crystal polymer film 100 of the present embodiment can be appropriately set according to the desired performance and is not particularly limited, but the linear expansion coefficient in the MD direction is preferably 0 to 30 ppm/K, more preferably 0 to 25 ppm/K, still more preferably 0 to 20 ppm/K, and the linear expansion coefficient in the TD direction is preferably 0 to 30 ppm/K, more preferably 0 to 25 ppm/K, and still more preferably. is between 0 and 20 ppm/K.
  • the linear expansion coefficient is measured by the TMA method in accordance with JIS K7197, and means the average value of the linear expansion coefficients (CTE, 23 to 200°C) at 23 to 200°C measured by the same method.
  • the coefficient of linear expansion measured here means the value obtained when the liquid crystal polymer film 100 is heated (1st heating) at a temperature increase rate of 5°C/min, cooled to the measurement environmental temperature (23°C) (1st cooling), and then heated for the second time (2nd heating) at a temperature increase rate of 5°C/min, in order to see the value in which the thermal history is eliminated.
  • other detailed measurement conditions are in accordance with the conditions described in Examples described later.
  • FIG. 10 is a schematic cross-sectional view showing a main part of the insulating material 200 for circuit boards of this embodiment.
  • the circuit board insulating material 200 of this embodiment comprises a laminate having at least the liquid crystal polymer film 100 and the woven fabric WF provided on one side and/or both sides of the liquid crystal polymer film 100 .
  • the circuit board insulating material 200 includes a laminate having a laminate structure (three-layer structure) in which the liquid crystal polymer film 100, the woven fabric WF, and the liquid crystal polymer film 100 are arranged at least in this order.
  • this laminate one liquid crystal polymer film 100 is provided on the surface side of the woven fabric WF, and the other liquid crystal polymer film 100 is provided on the back side of the woven fabric WF.
  • These three layers are thermo-compressed to form a laminate having a three-layer structure.
  • a laminate having a three-layer structure is exemplified here, it goes without saying that a laminate having a two-layer structure omitting the liquid crystal polymer film 100 on one side, or a laminate having a laminate structure having four or more layers in which the liquid crystal polymer film 100 and the woven fabric WF are further laminated.
  • a woven fabric WF is provided on one side and/or both sides of the liquid crystal polymer film 100
  • a woven fabric WF is a cloth made of woven fibers.
  • the type of fibers of the woven fabric WF is not particularly limited, and any of inorganic fibers, organic fibers, and organic-inorganic hybrid fibers can be used.
  • inorganic fiber woven fabric WF is preferably used.
  • inorganic fibers include, but are not limited to, glass fibers such as E glass, D glass, L glass, M glass, S glass, T glass, Q glass, UN glass, NE glass, spherical glass, inorganic fibers other than glass such as quartz, and ceramic fibers such as silica.
  • a woven fabric subjected to opening treatment or stuffing treatment is suitable from the viewpoint of dimensional stability.
  • glass cloth is preferable from the viewpoint of mechanical strength, dimensional stability, water absorption, and the like.
  • a glass cloth surface-treated with a silane coupling agent such as epoxysilane treatment or aminosilane treatment can also be preferably used.
  • the woven fabric WF can be used singly or in combination of two or more.
  • the thickness of the woven fabric WF can be appropriately set according to the required performance, and is not particularly limited. It is preferably 10 to 300 ⁇ m, more preferably 10 to 200 ⁇ m, still more preferably 15 to 180 ⁇ m, from the viewpoint of lamination property, workability, mechanical strength, and the like.
  • the total thickness of the circuit board insulating material 200 can be appropriately set according to the required performance, and is not particularly limited. It is preferably 30 to 500 ⁇ m, more preferably 50 to 400 ⁇ m, even more preferably 70 to 300 ⁇ m, particularly preferably 90 to 250 ⁇ m, from the viewpoint of lamination property, workability, mechanical strength, and the like.
  • the circuit board insulating material 200 of the present embodiment has a small coefficient of linear expansion in the MD direction and the TD direction by adopting the above-described configuration, and has a small anisotropy.
  • the average coefficient of linear expansion (CTE, 23 to 200° C.) in the MD direction of the insulating material 200 for a circuit board of the present embodiment is not particularly limited, but from the viewpoint of improving the adhesion to the metal foil, it is preferably 5 ppm/K or more and 25 ppm/K or less, more preferably 7 ppm/K or more and 24 ppm/K or less, further preferably 9 ppm/K or more and 23 ppm/K or less.
  • the average linear expansion coefficient in the TD direction (CTE, 23 to 200 ° C.) is preferably 5 ppm/K or more and 25 ppm/K or less, more preferably 7 ppm/K or more and 24 ppm/K or less, and still more preferably 9 ppm/K or more and 23 ppm/K or less.
  • the average linear expansion coefficient in the ZD direction (CTE, 23 to 200 ° C.) is preferably 10 ppm/K or more and 100 ppm/K or less, more preferably 15 ppm/K or more and 98 ppm/K or less, and still more preferably 20 ppm/K or more and 95 ppm/K or less.
  • the dielectric properties of the circuit board insulating material 200 of the present embodiment can be appropriately set according to the desired performance, and are not particularly limited.
  • the dielectric constant ⁇ r (36 GHz) is preferably 3.0 or more and 3.7 or less, more preferably 3.0 to 3.5.
  • the dielectric loss tangent tan ⁇ (36 GHz) is preferably 0.0010 or more and 0.0050 or less, more preferably 0.0010 or more and 0.0045 or less.
  • the relative dielectric constant ⁇ r and the dielectric loss tangent tan ⁇ mean values at 36 GHz measured by the cavity resonator contact motion method according to JIS K6471. Further, other detailed measurement conditions are in accordance with the conditions described in Examples described later.
  • the circuit board insulating material 200 described above can be manufactured by appropriately applying a known manufacturing method, and the manufacturing method is not particularly limited.
  • the insulating material 200 for a circuit board can be obtained by laminating the liquid crystal polymer film 100 and the woven fabric WF, applying heat and pressure, and thermocompression bonding the liquid crystal polymer film 100 and the woven fabric WF. It is also preferable to laminate the liquid crystal polymer film 100, the woven fabric WF, and the liquid crystal polymer film 100 in this order to form a laminate, and apply heat and pressure while sandwiching the laminate using a pressing machine, a double belt press, or the like to form the circuit board insulating material 200 by thermocompression molding.
  • the processing temperature during thermocompression bonding can be appropriately set according to the required performance, and is not particularly limited, but is preferably 200 to 400°C, more preferably 250 to 360°C, and still more preferably 270 to 350°C.
  • the processing temperature during thermocompression bonding is the value measured at the surface temperature of the liquid crystal polymer film 100 of the laminate described above.
  • the pressurization conditions at this time can be appropriately set according to the desired performance, and are not particularly limited.
  • FIG. 11 is a schematic cross-sectional view showing the main part of the metal foil-clad laminate 300 of this embodiment.
  • the metal foil-clad laminate 300 of this embodiment comprises the liquid crystal polymer film 100 and the metal foil MF provided on one side and/or both sides of the liquid crystal polymer film 100 .
  • the metal foil-clad laminate 300 is a double-sided metal foil-clad laminate having a laminate structure (three-layer structure) in which at least the metal foil MF, the liquid crystal polymer film 100, and the metal foil MF are arranged in this order. These three layers are thermo-compressed to form a laminate having a three-layer structure.
  • the double-sided metal foil-clad laminate is shown in this embodiment, the present invention can also be implemented in a mode in which only one surface of the liquid crystal polymer film 100 is provided with the metal foil MF.
  • the present invention can be implemented with a laminate with a two-layer structure in which one of the metal foils MF is omitted, or a laminate with a laminate structure of four or more layers in which the liquid crystal polymer film 100 and the woven fabric WF are further laminated.
  • FIG. 12 is a schematic cross-sectional view showing the main part of the metal foil-clad laminate 400 of this embodiment.
  • the metal foil clad laminate 400 of the present embodiment comprises a laminate having at least the liquid crystal polymer film 100 and the woven fabric WF provided on one side and/or both sides of the liquid crystal polymer film 100, and a metal foil MF provided on one side and/or both sides of the laminate.
  • the metal foil-clad laminate 400 is a double-sided metal foil-clad laminate having a laminated structure (five-layer structure) in which at least the metal foil MF, the liquid crystal polymer film 100, the woven fabric WF, the liquid crystal polymer film 100, and the metal foil MF are arranged in this order. These five layers are thermo-compressed to form a laminate having a five-layer structure.
  • the double-sided metal foil-clad laminate is shown in this embodiment, the present invention can also be implemented as a mode in which the metal foil MF is provided only on one surface.
  • the present invention can be implemented with a laminate with a four-layer structure in which one of the metal foils MF is omitted, or a laminate with a laminate structure of six or more layers in which the liquid crystal polymer film 100, the insulating material for circuit board 200, and the woven fabric WF are further laminated.
  • the material of the metal foil MF is not particularly limited, but gold, silver, copper, copper alloys, nickel, nickel alloys, aluminum, aluminum alloys, iron, iron alloys, and the like can be mentioned.
  • copper foil, aluminum foil, stainless steel foil, and copper-aluminum alloy foil are preferable, and copper foil is more preferable.
  • any one manufactured by a rolling method, an electrolysis method, or the like can be used, but a rolled copper foil with a small surface roughness is preferable.
  • the thickness of the metal foil MF can be appropriately set according to the desired performance, and is not particularly limited. It is usually preferably 1.5 to 1000 ⁇ m, more preferably 2 to 500 ⁇ m, still more preferably 5 to 150 ⁇ m, particularly preferably 7 to 100 ⁇ m.
  • the metal foil MF may be subjected to surface treatment such as chemical surface treatment such as acid cleaning and rust prevention as long as the effects of the present invention are not impaired.
  • the type and thickness of the metal foil MF may be the same or different.
  • the method of providing the metal foil MF on the surfaces of the liquid crystal polymer film 100 and the circuit board insulating material 200 can be carried out according to a conventional method, and is not particularly limited.
  • a method of laminating a metal foil MF on the liquid crystal polymer film 100 or the insulating material 200 for a circuit board and bonding or crimping both layers, a physical method (dry method) such as sputtering or vapor deposition, a chemical method (wet method) such as electroless plating or electroplating after electroless plating, or a method of applying a metal paste may be used.
  • the metal foil-clad laminates 300 and 400 can also be obtained by hot-pressing a laminate obtained by laminating the liquid crystal polymer film 100 or the insulating material 200 for circuit boards and one or more metal foils MF using, for example, a multistage press machine, a multistage vacuum press machine, a continuous molding machine, an autoclave molding machine, or the like.
  • the metal foil-clad laminates 300 and 400 described above can be manufactured by appropriately applying a known manufacturing method, and the manufacturing method is not particularly limited.
  • One example is a method in which the liquid crystal polymer film 100 or the insulating material 200 for circuit boards and the metal foil MF are superimposed to form a laminated body in which the metal foil MF is placed on the liquid crystal polymer film 100, and the laminated body is sandwiched between endless belt pairs of a double-belt press and subjected to thermocompression molding.
  • the liquid crystal polymer film 100 used in the present embodiment has small coefficients of linear thermal expansion in the MD and TD directions, and in a preferred embodiment, has small anisotropy in the MD and TD directions, so high peel strength to the metal foil MF can be obtained.
  • the temperature during thermocompression bonding of the metal foil MF can be appropriately set according to the required performance and is not particularly limited, but is preferably 50°C lower than the melting point of the liquid crystal polymer and 50°C higher than the melting point, more preferably 40°C lower than the melting point and 40°C higher than the melting point, more preferably 30°C lower than the melting point and 30°C higher than the melting point, and particularly preferably 20°C lower than the melting point and 20°C higher than the melting point. Preferred.
  • the temperature at the time of thermocompression bonding of the metal foil MF is the value measured at the surface temperature of the liquid crystal polymer film 100 described above.
  • the crimping conditions at this time can be appropriately set according to the desired performance, and are not particularly limited. For example, when using a double belt press, the surface pressure is 0.5 to 10 MPa and the heating temperature is 200 to 360 ° C. It is preferable to perform under the conditions.
  • the metal foil-clad laminates 300 and 400 of the present embodiment may have another laminated structure or a further laminated structure as long as they have a two-layer thermocompression bonded body of the liquid crystal polymer film 100 and the metal foil MF.
  • a multilayer structure such as a five-layer structure such as polymer film 100/woven fabric WF/liquid crystal polymer film 100/metal foil MF;
  • a plurality of (for example, 2 to 50) metal foil-clad laminates 300 and 400 can be laminated and thermocompressed.
  • the peel strength between the liquid crystal polymer film 100 and the metal foil MF is not particularly limited, but from the viewpoint of providing higher peel strength, it is preferably 0.8 (N/mm) or more, more preferably 1.0 (N/mm) or more, and still more preferably 1.2 (N/mm) or more.
  • the metal foil-clad laminates 300 and 400 of the present embodiment can achieve high peel strength, so that separation between the liquid crystal polymer film 100 and the metal foil MF can be suppressed, for example, in the heating process of manufacturing the substrate.
  • deterioration of the basic performance of liquid crystal polymer can be suppressed while maintaining peel strength at the same level as conventional technology.
  • the metal foil-clad laminates 300 and 400 of the present embodiment can be used as materials for circuit boards such as electronic circuit boards and multilayer boards by pattern-etching at least part of the metal foil MF.
  • the metal foil-clad laminates 300 and 400 of the present embodiment have excellent dielectric properties in a high frequency range, small coefficients of linear thermal expansion in the MD and TD directions, and in a preferred embodiment, small anisotropy in the MD and TD directions, excellent dimensional stability, easy production, and excellent productivity.
  • melt viscosity The melt viscosity [Pa ⁇ sec] of each liquid crystal polymer film was measured under the following conditions. Measuring instrument: Capilograph 1D (manufactured by Toyo Seiki Seisakusho) Equipment used: Cylinder length 10.00mm, cylinder diameter 1.00mm, barrel diameter 9.55mm Measurement conditions: temperature [°C] and shear rate [sec -1 ] during extrusion molding of each liquid crystal polymer film
  • each liquid crystal polymer film was subjected to X-ray diffraction measurement by a transmission method to measure the degree of orientation.
  • X-ray diffraction measurement (2 ⁇ / ⁇ scan, ⁇ scan) was performed using a parallel beam optical system and a transmission method.
  • the degree of orientation was calculated from the above formula based on the area ratio of the orientation peak.
  • the orientation direction was determined from the position of the peak top of the orientation component excluding the area of the base isotropic component.
  • samples of depth regions A, B, and C were prepared from each liquid crystal polymer film, and the orientation direction and degree of orientation of the depth regions A, B, and C of each liquid crystal polymer film were measured in the same manner as described above.
  • Samples of depth regions A, B, and C were obtained by immersing each liquid crystal polymer film in a 70% aqueous solution of monoethylamine (manufactured by Daicel Corporation) for 14 days under an environment of 23° C. and 50% RH. Each was prepared by drying at 0° C. for 1 hour and cooling in an environment of 23° C. and 50% RH for 24 hours.
  • thermoplastic liquid crystal polymer (a copolymer having a monomer composition of 74 mol% p-hydroxybenzoic acid and 26 mol% 6-hydroxy-2-naphthoic acid, a melt viscosity of 80 Pa sec at a temperature of 300°C and a shear rate of 500 sec ⁇ 1 ) was extruded from an extruder at 300°C by a T-die casting method to obtain a liquid crystal polymer film of Preparation Example 1 having a width of 250 mm, a thickness of 50 ⁇ m and a melting point of 280°C.
  • the obtained liquid crystal polymer film of Preparation Example 1 was highly oriented in the MD direction, and the degree of orientation was 43%.
  • the linear thermal expansion coefficient in the MD direction of the entire film of the liquid crystal polymer film of Preparation Example 1 was -19 ppm/°C, and the linear thermal expansion coefficient in the TD direction of the entire film was 81 ppm/°C.
  • thermoplastic liquid crystal polymer (a copolymer having a monomer composition of 74 mol% p-hydroxybenzoic acid and 26 mol% 6-hydroxy-2-naphthoic acid, a melt viscosity of 80 Pa sec at a temperature of 300 ° C. and a shear rate of 500 sec ⁇ 1 ) is extruded from an extruder at 300 ° C. by a T die casting method to form a liquid crystal polymer film of Preparation Example 2 having a width of 250 mm, a thickness of 100 ⁇ m and a melting point of 280 ° C. (pre-treatment melt extrusion film) was obtained.
  • the obtained liquid crystal polymer film of Preparation Example 2 was highly oriented in the MD direction, and the degree of orientation was 44%.
  • the linear thermal expansion coefficient in the MD direction of the liquid crystal polymer film of Preparation Example 2 as a whole was -18 ppm/°C, and the linear thermal expansion coefficient in the TD direction of the entire film was 83 ppm/°C.
  • Example 1 Polyimide films (first film member 21 and second film member 31) having a thickness of 50 ⁇ m and a width of 270 mm coated with a release agent were superimposed on both sides of the liquid crystal polymer film of Preparation Example 1, respectively, and thermocompression was performed using a thermal laminator under conditions of a temperature of 300° C., a pressure of 0.8 MPa, and a speed of 1.0 m/min to produce a crimped body 10 having a structure equivalent to that of FIG. At this time, the width of the one-side end portion 21a (film ear portion) of the first film member 21 and the one-side end portion 31a (film ear portion) of the second film member 31 were both 10 mm.
  • the obtained crimped body 10 is supplied to a uniaxial stretching machine, and under the conditions of a temperature of 316° C., a tensile speed of 15 mm/min, a tensile distance of 1.2 mm, and a tensile ratio of 1.0048, one side ends 21a and 31a of the crimped body 10 are held by chucks 71a and 72b of clamp mechanisms 71 and 72 as shown in FIGS. TD) to apply shear shear stress ⁇ to the liquid crystal polymer film of Preparation Example 1. After that, both polyimide films were peeled off from the compressed body 10 to obtain the liquid crystal polymer film 100 of Example 1 (liquid crystal polymer film after alignment control).
  • the obtained liquid crystal polymer film of Example 1 was non-oriented throughout the film, and the degree of orientation was 5.0%.
  • the linear thermal expansion coefficient in the MD direction of the entire liquid crystal polymer film of Example 1 was 9 ppm/°C, and the linear thermal expansion coefficient in the TD direction of the entire film was 25 ppm/°C.
  • Samples of depth regions A, B, and C of the liquid crystal polymer film of Example 1 were prepared, and the alignment direction and degree of alignment were confirmed.
  • Example 2 The liquid crystal polymer film of Preparation Example 2 was used in place of the liquid crystal polymer film of Preparation Example 1, and the speed during thermocompression bonding was changed to 0.8 m/min. The resulting liquid crystal polymer film of Example 2 was non-oriented throughout the film and had a degree of orientation of 5.3%.
  • the linear thermal expansion coefficient in the MD direction of the entire liquid crystal polymer film of Example 2 was 10 ppm/°C, and the linear thermal expansion coefficient in the TD direction of the entire film was 24 ppm/°C. Samples of depth regions A, B, and C of the liquid crystal polymer film of Example 2 were prepared, and the alignment direction and degree of alignment were confirmed.
  • Example 3 Aluminum foil (first film member 21, second film member 31) having a thickness of 50 ⁇ m and a width of 270 mm was used instead of the polyimide film, the temperature during thermocompression bonding was changed to 295° C., and the temperature during application of the shear shear stress ⁇ was changed to 314° C., and the same procedure as in Example 1 was performed to obtain the liquid crystal polymer film 100 after orientation control of Example 3.
  • the obtained liquid crystal polymer film of Example 3 was non-oriented throughout the film, and the degree of orientation was 5.5%.
  • the linear thermal expansion coefficient in the MD direction of the entire liquid crystal polymer film of Example 3 was 11 ppm/°C, and the linear thermal expansion coefficient in the TD direction of the entire film was 25 ppm/°C. Samples of depth regions A, B, and C of the liquid crystal polymer film of Example 3 were prepared, and the alignment direction and degree of alignment were confirmed.
  • Comparative example 1 A liquid crystal polymer film 100 after alignment control of Comparative Example 1 was obtained in the same manner as in Example 1, except that the tensile distance was changed to 3.0 mm and the tensile magnification was changed to 1.0120 when the shear shear stress ⁇ was applied.
  • the obtained liquid crystal polymer film of Comparative Example 1 was highly oriented in the TD direction throughout the film, and the degree of orientation was 33%.
  • the linear thermal expansion coefficient in the MD direction of the entire liquid crystal polymer film of Comparative Example 1 was 73 ppm/°C, and the linear thermal expansion coefficient in the TD direction of the entire film was -10 ppm/°C. Samples of depth regions A, B, and C of the liquid crystal polymer film of Comparative Example 1 were prepared, and the alignment direction and degree of alignment were confirmed.
  • Comparative example 2 A liquid crystal polymer film 100 after orientation control of Comparative Example 2 was obtained in the same manner as in Example 1 except that the tensile distance was changed to 0.5 mm and the tensile magnification was changed to 1.0020 when the shear shear stress ⁇ was applied.
  • the obtained liquid crystal polymer film of Comparative Example 2 was highly oriented in the MD direction throughout the film, and the degree of orientation was 28%.
  • the linear thermal expansion coefficient in the MD direction of the entire liquid crystal polymer film of Comparative Example 2 was -9 ppm/°C, and the linear thermal expansion coefficient in the TD direction of the entire film was 44 ppm/°C. Samples of depth regions A, B, and C of the liquid crystal polymer film of Comparative Example 2 were prepared and the alignment direction and degree of alignment were confirmed.
  • Table 1 shows the measurement results of each liquid crystal polymer film.
  • 13 and 14 show the X-ray diffraction image and the azimuthal distribution curve of the liquid crystal polymer film (pre-treatment melt extruded film) of Preparation Example 1, respectively.
  • 15 and 16 show the X-ray diffraction image and azimuth angle distribution curve of the liquid crystal polymer film of Example 1, respectively.
  • 17 and 18 show an X-ray diffraction image and an azimuth angle distribution curve of the depth region A of the liquid crystal polymer film of Example 1, respectively.
  • 19 and 20 show an X-ray diffraction image and an azimuth angle distribution curve of the depth region B of the liquid crystal polymer film of Example 1, respectively.

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