LCP extruded film, LCP stretched film, insulating material for circuit boards, and metal foil clad laminate

Abstract

The present invention provides a novel LCP extruded film in which the molecular orientation and internal strain of the thermoplastic liquid crystal polymer are sufficiently reduced, and the anisotropy of the dimensional change rate is significantly reduced compared to conventional films, as well as an LCP stretched film, insulating material for circuit boards, and metal foil-clad laminates using the same. [Solution] An LCP extruded film containing a thermoplastic liquid crystal polymer and having a thickness of 15 μm to 300 μm, wherein the hardness H1 at a point at a depth of 1 μm located 1 μm from the film surface in the thickness direction and the hardness H2 at the thickness center point, measured by nanoindentation on a film cross section parallel to the MD direction, satisfy -10.0 ≤ 100 × (H2 - H1) / H1 ≤ 0.0, and the coefficient of linear expansion in the MD and TD directions at 23 to 200°C, measured by the TMA method in accordance with JIS K7197, is within the range of -30 to 55 ppm / K.

Description

[Technical Field]

[0001] The present invention relates to LCP extruded film, LCP stretched film, insulating material for circuit boards, and metal Regarding foil-clad laminates, etc. [Background technology]

[0002] Conventionally, insulating materials for circuit boards have been made from thermosetting resins such as epoxy resins and inorganic fillers. A varnish-impregnated composite material is made by impregnating glass cloth with varnish containing agents, etc., and then heat-pressing it. This is known. However, this manufacturing method has limitations, for example, in terms of resin flowability during varnish impregnation and heat pressing. In terms of curability during molding, etc., the manufacturing process has little tolerance and is less productive. Also, heat Curable resins readily absorb moisture, and their dimensions change as they absorb moisture, resulting in varnish. The dimensional accuracy (heat-induced dimensional accuracy) of the impregnated composite material is inferior.

[0003] On the other hand, liquid crystal polymers (LCPs) are in a molten or solution state. It is a polymer that exhibits liquid crystalline properties. In particular, it is a thermotropic liquid that exhibits liquid crystalline properties in the molten state. Crystal polymers are extrudeable and possess high gas barrier properties, high film strength, high heat resistance, and high thermal insulation properties. It possesses excellent properties such as a fine edge, low water absorption rate, and low dielectric properties in the high-frequency range. Therefore, it is thermoplastic. Films using liquid crystal polymers are used in gas barrier film materials, electronic materials, and electrical applications. Its practical application is being considered for gas insulating material applications.

[0004] However, when single-layer extrusion molding is actually performed, the high performance of thermoplastic liquid crystal polymers Due to its high degree of liquid crystal alignment, thermoplastic liquid crystal polymer films have high industrial value. In other words, to obtain a thermoplastic liquid crystal polymer film with excellent thickness accuracy, good appearance and surface flatness. It turned out that this was difficult.

[0005] Therefore, for example, Patent Document 1 describes using a three-layer co-extrusion die instead of a single-layer extrusion die, A fully aromatic polyester-based thermotropic liquid crystal polymer is used as the intermediate layer, and polypolymer is used as both outer layers. Olefin resin or polycarbonate resin is simultaneously extruded, and the intermediate layer is thermoplastic liquid crystal poly A three-layer laminated film is formed, in which the outer layers are thermoplastic resin layers, and the thermoplastic resin layers of both outer layers are formed. By peeling off the plastic resin layer and extracting the intermediate layer as a film, it is possible to achieve excellent thickness accuracy and appearance. It has been disclosed that a thermoplastic liquid crystal polymer film with good surface flatness can be obtained.

[0006] Furthermore, for example, Patent Document 2 describes the thermoplastic liquid crystal polymer film described in Patent Document 1. Regarding the MD direction (Machine Direction; longitudinal direction), the TD direction (Transverse Direction) It was discovered that the strength in the lateral direction (n) was not sufficient for practical use, and a multi-manifold system was developed. By using a three-layer co-extrusion die with a feed block system instead of an extrusion die, The thermoplastic liquid crystal polymer film is in the TD direction and MD direction (Machine Direction; longitudinal direction) It is disclosed that the anisotropy of the intensity in the direction is mitigated. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Japanese Patent Application Publication No. 63-31729 [Patent Document 2] Japanese Patent Application Publication No. 2-178016 [Overview of the Initiative]

Problems to be Solved by the Invention

[0008] Insulating materials for circuit boards using liquid crystal polymers are excellent in high-frequency characteristics and low dielectric properties, and are attracting attention in recent years as insulating materials for circuit boards such as flexible printed wiring boards (FPCs), flexible printed wiring board laminates, and fiber-reinforced flexible laminates in the upcoming fifth-generation mobile communication system (5G), millimeter-wave radars, etc.

[0009] In the technologies described in Patent Documents 1 and 2 mentioned above, it is said that a thermoplastic liquid crystal polymer film excellent in thickness accuracy, appearance, and surface flatness can be realized. However, in reality, although the generation of peeling of the skin layer and peeling of fibrillated fibers caused by the highly molecular orientation of the thermoplastic liquid crystal polymer on the film surface can be suppressed, the thermoplastic liquid crystal polymer films described in Patent Documents 1 and 2 are still highly molecularly oriented as a whole film and could not withstand practical use as an insulating material for circuit boards.

[0010] Specifically, in the application of insulating materials for circuit boards, a thermoplastic liquid crystal polymer film may have a metal foil such as copper foil thermocompression-bonded to one side and / or both sides thereof and be used as a metal foil-clad laminate. Then, when this metal foil is pattern-etched or the like to form fine wirings, etc., a metal foil-clad laminate can be used as a material for circuit boards such as electronic circuit boards and multi-layer boards. Therefore, a high degree of dimensional stability is required for the thermoplastic liquid crystal polymer film that supports the metal foil. However, the thermoplastic liquid crystal polymer films described in Patent Documents 1 and 2 ​​​​​​​​​​The difference in dimensional change rates between the TD direction and MD direction after etching is important for liquid crystal polymer films. However, it was too large and could not meet the demands for application in ultra-fine machining in recent years.

[0011] The present invention has been made in view of the above problems. The object of the present invention is thermoplastic liquid crystal polymer The molecular orientation and internal strain of the material are sufficiently reduced, and the anisotropy of the dimensional change rate is significantly lower compared to conventional materials. A novel LCP extruded film with reduced emissions, and an LCP stretched film using the same. The objective is to provide insulating materials for road substrates, metal foil-clad laminates, and the like. [Means for solving the problem]

[0012] The inventors of the present invention have conducted diligent studies to solve the above problems, and as a result, have found that the film surface, as well as the film surface, Even within the film, the molecular orientation and internal strain of the thermoplastic liquid crystal polymer are alleviated, MD method Hardness at a depth of 1 μm measured by nanoindentation method on a film cross-section parallel to the direction. LCP extruded film with a small difference between hardness H1 and hardness H2 at the center of thickness, and a small coefficient of linear expansion. A new film was created, and furthermore, this LCP extruded film exhibits an anisotropic change in dimensional rate compared to conventional films. We discovered that the properties were reduced, and thus completed the present invention.

[0013] In other words, the present invention provides various specific embodiments as shown below. (1) LCP press containing thermoplastic liquid crystal polymer with a thickness of 15 μm to 300 μm For a film, a nanoindentation method is applied to the film cross-section parallel to the MD direction. The hardness H1 and thickness measured at a point located 1 μm deep from the film surface in the thickness direction, and the thickness The hardness H2 at the center point satisfies -10.0 ≤ 100 × (H2 - H1) / H1 ≤ 0.0 Furthermore, measured by the TMA method in accordance with JIS K7197 at temperatures between 23 and 200°C. The linear expansion coefficients in the MD and TD directions are within the range of -30 to 55 ppm / K, LC P extruded film.

[0014] (2) The LC described in (1) wherein the coefficient of linear expansion in the TD direction is 0 to 55 ppm / K. P extruded film. (3) The laminated extruded film having an outer layer, an intermediate layer, and the outer layer with both outer layers removed. An LCP extruded film as described in (1) or (2), which is the intermediate layer. (4) On the surface of the film, by a cross-cut method in accordance with JIS K5600-5-6 In the adhesion test, any one of items (1) to (3) that does not have a peelable skin layer of tape The LCP extruded film described.

[0015] (5) The hardness H2 at the center point of the thickness is 0.240 (GPa) or higher (1)~(4 LCP extruded film as described in any one of the items of ) (6) The hardness H1 at the point with a depth of 1 μm is 0.250 (GPa) or more (1)~( 5) An LCP extruded film as described in any one of the items. (7) LCP extrusion according to any one of (1) to (6) further containing an inorganic filler film. (8) LCP extruded film according to any one of items (1) to (7) which is a T-die extruded film Room.

[0016] (9)(1) to (8) The LCP extruded film and the LCP extruded film A circuit comprising a laminate having at least woven fabric provided on one and / or both sides of a film Insulating material for circuit boards. (10) The LCP extruded film described in any one of the items (1) to (8) and the LCP extruded A metal foil-clad laminate comprising metal foil provided on one and / or both sides of a film. (11)(1)~(8) at least one LCP extruded film and woven fabric described in any one of the above items. A laminate comprising a metal foil provided on one and / or both sides of the laminate, Foil-clad laminate.

[0017] (12) A stretched LCP extruded film as described in any one of items (1) to (8), LCP stretched film. (13) The stretched body has a total stretch ratio of 1.3 to 2.5 times that of the LCP extruded film. The LCP stretched film according to (12) having (MD direction × TD direction).

[0018] (14)(12) or (13) LCP stretched film and the LCP stretched film A laminate comprising a woven fabric provided on at least one side thereof, for use with a circuit board. Insulating material. (15)(12) or (13) LCP stretched film and the LCP stretched film A metal foil-clad laminate having metal foil provided on one side and / or both sides. (16)(12) or (13) comprises at least the LCP stretched film and woven fabric described in (16)(12) or (13). A metal foil laminate comprising a laminate and metal foil provided on one and / or both sides of the laminate, layer plate. [Effects of the Invention]

[0019] According to one aspect of the present invention, a novel LC is provided in which the anisotropy of the dimensional change rate is reduced compared to the conventional. P extruded film, LCP stretched film, insulating material for circuit boards, and metal foil-clad laminates are among the products we manufacture. It can be expressed. Furthermore, according to one aspect of the present invention, dimensional changes in the MD direction and TD direction Novel LCP extruded films, LCP stretched films, and circuit board insulation with low production rates. Materials and metal foil-clad laminates can be realized. Therefore, various embodiments of the present invention Therefore, it is possible to realize highly reliable products that are suitable for the ultra-fine machining processes of recent years. [Brief explanation of the drawing]

[0020] [Figure 1] This is a schematic perspective view showing an LCP extruded film according to one embodiment. [Figure 2] This figure shows the calculation method for hardness measurement using the nanoindentation method. [Figure 3] This is a schematic cross-sectional view showing an LCP extruded film of one embodiment. [Figure 4] This is a conceptual diagram illustrating the principle for calculating the degree of orientation based on the area ratio of the orientation peak. [Figure 5] This figure shows a co-extrusion method for LCP extruded film according to one embodiment. [Figure 6] This figure shows a co-extrusion method for LCP extruded film according to one embodiment. [Figure 7] This figure shows a co-extrusion method for LCP extruded film according to one embodiment. [Figure 8] This is a schematic cross-sectional view showing an insulating material for a circuit board in one embodiment. [Figure 9] This is a schematic cross-sectional view showing a metal foil-clad laminate in one embodiment. [Figure 10] This is a schematic cross-sectional view showing a metal foil-clad laminate in one embodiment. [Modes for carrying out the invention]

[0021] The embodiments of the present invention will be described in detail below with reference to the drawings. Unless otherwise specified, the positional relationships of the elements shall be based on those shown in the drawings. The dimensional ratios of the surfaces are not limited to those shown in the illustration. However, the following embodiments are based on this. These are illustrative examples for illustrating the invention, and the present invention is not limited to these examples. The present invention can be implemented with modifications without departing from its essence. In this specification, for example, the notation of a numerical range "1 to 100" means that its lower limit is "1" and This should include both the upper limit value "100" and the upper limit value. The same applies to the notation of other numerical ranges. .

[0022] (LCP extruded film) Figure 1 is a schematic cross-sectional view showing the main part of the LCP extruded film 100 of this embodiment. The LCP extruded film 100 in the applied form is made of a resin composition containing a thermoplastic liquid crystal polymer with a thickness of 1 It is extruded into a film shape with a thickness of 5 μm to 300 μm.

[0023] As mentioned earlier, conventional LCP extruded films have a skin layer on the film surface. Delamination and peeling of fibrillated fibers occur on the film surface of the thermoplastic liquid crystal polymer. The molecules were extremely oriented in that region. This was due to shear stress from the side of the apparatus during extrusion. As a result, the thermoplastic liquid crystal polymer is highly oriented on the surface of the extruded product. It is presumed that this is the case. And, by improving as in Patent Documents 1 and 2, thermoplastics It was confirmed that the extreme molecular orientation on the film surface of the liquid crystal polymer was alleviated. At the same time, controlling only the molecular orientation of thermoplastic liquid crystal polymers on the film surface is not sufficient. The inventors found that they could not create a material that could withstand the required performance as an insulating material for circuit boards. This was revealed by their findings. In other words, LCP extruded film with reduced anisotropy in dimensional change rate To achieve this, the molecular orientation of the thermoplastic liquid crystal polymer on the film surface must be controlled. Furthermore, it is possible to control the molecular orientation of thermoplastic liquid crystal polymers occurring within the film and internal strain. Reductions of these factors are also necessary.

[0024] Unlike the prior art, the LCP extruded film 100 of this embodiment has only the film surface Furthermore, the molecular orientation and internal strain of the thermoplastic liquid crystal polymer are alleviated even within the film. As a result, the anisotropy of the dimensional change rate is significantly reduced compared to conventional methods. In this embodiment, the LCP extruded film 100 has a film cross-section parallel to the MD direction. Depth measured by the noindentation method, located 1 μm from the film surface in the thickness direction. The hardness H1 at the 1 μm point and the hardness H2 at the center of the thickness are equal to -10.0 ≤ 100 × (H2 - H1). The condition satisfies / H1 ≤ 0.0 and is measured by the TMA method in accordance with JIS K7197. The coefficient of linear expansion in the MD and TD directions at 23-200°C is -30-55 ppm / It is characterized by being within the range of K. Further details are provided below.

[0025] As the LCP extruded film 100, an extruded film such as a T-die extruded film is preferred. It is used. In addition, the LCP extruded film 100 is a thermoplastic resin layer, thermoplastic liquid crystal A three-layer laminate having a polymer layer and a thermoplastic resin layer arranged in at least this order. A thermoplastic liquid crystal polymer layer, which is an intermediate layer (core layer) of the co-extruded film, is also preferably used. In this case, by removing the thermoplastic resin layers of both outer layers of the three-layer co-extruded film, a single layer of thermoplastic resin is obtained. It can be used as a plastic liquid crystal polymer film (LCP extruded film 100). Extruded films of plastic liquid crystal polymers are woven or nonwoven fabrics made from thermoplastic liquid crystal polymer fibers. Compared to cloth, it can be manufactured at a lower cost and produce uniform products.

[0026] The thermoplastic liquid crystal polymer contained in the LCP extruded film 100 is known in the industry. Liquid crystal polymers can be used, and their type is not particularly limited. These are polymers that form a molten phase, and typical examples include thermotropic liquid crystal compounds. Furthermore, the properties of the anisotropic fused phase can be determined by known methods such as polarization testing using orthogonal polarizers. This can be confirmed using a Leitz polarization microscope. More specifically, the anisotropic molten phase can be confirmed using a Leitz polarization microscope. Using a mirror, the sample placed on the Leitz hot stage was observed at 40x magnification under a nitrogen atmosphere. It can be implemented by understanding the situation.

[0027] Specific examples of thermoplastic liquid crystal polymers include aromatic or aliphatic dihydroxy compounds, fragrances Aliphatic or aliphatic dicarboxylic acids, aromatic hydroxycarboxylic acids, aromatic diamines, aromatic hydroxycarboxylic acids Examples include those obtained by polycondensing monomers such as roxyamines and aromatic aminocarboxylic acids. These are not the only examples. Thermoplastic liquid crystal polymers are preferably copolymers. Specifically... These are monomers such as aromatic hydroxycarboxylic acids, aromatic diamines, and aromatic hydroxyamines. Aromatic polyamide resin obtained by polycondensation of aromatic diols, aromatic carboxylic acids, aromatic (Total) aromatic polyester resins obtained by polycondensation of monomers such as hydroxycarboxylic acids; etc. These include, but are not limited to, a single type or two or more types. It can be used in any combination and ratio.

[0028] Thermoplastic liquid crystal polymers are generally classified into Type I and Type II from the perspective of their thermal distortion temperature (TDUL). They are classified into types III, etc. The LCP extruded film 100 of this embodiment is of any type Even thermoplastic liquid crystal polymers of the type can be suitably used, depending on the application. You can select and use it. For example, it is required to be applied to lead-free solder at temperatures of around 230-260°C. For electronic circuit board applications, TDUL is a type I heat-resistant material with a high heat resistance of approximately 250-350°C. Plastic liquid crystal polymer, TDUL is a relatively high heat-resistant type II with a temperature range of approximately 240-250°C. Plastic liquid crystal polymers are preferably used.

[0029] Among these, those exhibiting thermotropic liquid crystal-like properties and having a melting point of 250°C or higher are preferred. Alternatively, a (fully) aromatic polyester resin with a melting point of 280°C to 380°C is preferably used. Examples of such (all) aromatic polyester resins include aromatic diols, aromatic Synthesized from monomers such as hydroxycarboxylic acids and other hydroxycarboxylic acids, exhibiting liquid crystalline properties upon melting. All aromatic polyester resins are known. A typical example is ethylene Polycondensate of terephthalate and parahydroxybenzoic acid, phenol and phthalic acid and para Polycondensation with hydroxybenzoic acid, 2,6-hydroxynaphthoic acid and parahydroxybenzoic acid Examples include polycondensation products with aromatic acids, but are not limited to these. Polyester resins can be used individually or in any combination and ratio of two or more types. This is possible. Depending on the required performance, a relatively high melting point or high heat distortion temperature and high heat resistance can be used. Aromatic polyester resins are used, or materials with a relatively low melting point or low heat distortion temperature are used for molding. Aromatic polyester resins with excellent workability can be used.

[0030] A preferred embodiment is 6-hydroxy-2-naphthoic acid and its derivatives (hereinafter referred to as It is sometimes simply referred to as "monomer component A." ) has as its basic structure, parahydroxy Benzoic acid, terephthalic acid, isophthalic acid, 6-naphthalenedicarboxylic acid, 4,4'-bifluic acid Enol, bisphenol A, hydroquinone, 4,4-dihydroxybiphenol, eth One or more selected from the group consisting of lenterephthalate and its derivatives are used as monomers. There is at least one component (hereinafter sometimes simply referred to as "monomer component B") Examples include (all) aromatic polyester resins. In a molten state, the linear chains of the molecules in the resin are arranged in a regular manner, forming an anisotropic molten phase, typically... It exhibits otropic liquid crystal-like properties, and possesses mechanical properties, electrical properties, high-frequency properties, heat resistance, and absorption properties. It will possess excellent basic performance in terms of moisture resistance and other factors.

[0031] Furthermore, the (all) aromatic polyester resin of the preferred embodiment described above has a minimum essential unit. Any configuration can be adopted as long as it contains monomer component A and monomer component B. For example, even if it has two or more monomer components A, it may have three or more monomer components A. It may also be used. Furthermore, the (all) aromatic polyester resin of the preferred embodiment described above may be mono Other monomer components other than monomer component A and monomer component B (hereinafter simply referred to as "monomer") It may contain the following: -Component C (which may be referred to as "component C"). One embodiment of the (all) aromatic polyester resin is derived solely from monomer component A and monomer component B. Even in polycondensates of two or more elements, monomer component A, monomer component B and monomer component It may also be a polycondensate of three or more monomer components consisting of C. Therefore, other than monomer components A and B mentioned above, specifically aromatic or Aliphatic dihydroxy compounds and their derivatives; aromatic or aliphatic dicarboxylic acids and their derivatives Forms; aromatic hydroxycarboxylic acids and their derivatives; fragrance diamines, aromatic hydroxyamines Examples include ammonium compounds or aromatic aminocarboxylic acids and their derivatives; however, the examples are not limited to these. It is not possible. Other monomer components may be used individually or in any combination and ratio of two or more. It can be used in [location / service].

[0032] In this specification, "derivative" refers to a monomer component that contains halogens. Atoms (e.g., fluorine, chlorine, bromine, iodine), alkyl groups with 1 to 5 carbon atoms. Groups (e.g., methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, iso Aryl groups such as butyl groups, s-butyl groups, t-butyl groups, etc., phenyl groups, hydroxyl groups, carbon 1 to 5 alkoxy groups (e.g., methoxy group, ethoxy group, etc.), carbonyl group, -O-, Those that have modified groups such as -S-, -CH2-, etc. introduced (hereinafter referred to as "having substituents") It is sometimes referred to as a "monomer component." ) Here, "derivative" means the above-mentioned derivative. Acylated compounds, ester derivatives, or acid compounds of monomer components A and B, which may have decorative groups. They may also be ester-forming monomers such as chloromethyl compounds.

[0033] In one particularly preferred embodiment, parahydroxybenzoic acid and its derivatives and 6-hydroxybenzoic acid C-2-naphthoic acid and its derivatives in binary polycondensates; parahydroxybenzoic acid and so A ternary system of derivatives of 6-hydroxy-2-naphthoic acid and its derivatives and monomer component C The above polycondensates; parahydroxybenzoic acid and its derivatives and 6-hydroxy-2-naphtho E acids and their derivatives, terephthalic acid, isophthalic acid, 6-naphthalenedicarboxylic acid, 4, 4'-Biphenol, Bisphenol A, Hydroquinone, 4,4-Dihydroxybiphen One or more selected from the group consisting of ethanol, ethylene terephthalate, and derivatives thereof. A ternary or higher polycondensate consisting of; parahydroxybenzoic acid and its derivatives and 6-hydroxy C-2-naphthoic acid and its derivatives, terephthalic acid, isophthalic acid, 6-naphthalenediacid Rubonic acid, 4,4'-biphenol, bisphenol A, hydroquinone, 4,4-dihydrogen Selected from the group consisting of roxybiphenol, ethylene terephthalate, and derivatives thereof. Examples include polycondensates of quaternary or greater systems consisting of one or more elements and one or more monomer components C; These have relatively low melting points compared to, for example, homopolymers of p-hydroxybenzoic acid. It can be obtained as having these properties, and therefore thermoplastic liquid crystal polymers using these properties are This results in excellent formability when heat-pressed onto the adherend.

[0034] (Total) The melting point of aromatic polyester resin is lowered, and the LCP extruded film 100 is applied to the substrate. To improve the formability during heat-pressing, or to heat-press the LCP extruded film 100 onto a metal foil. From the perspective of obtaining high peel strength, etc., the monomer for (all) aromatic polyester resin - The molar ratio of component A is preferably 10 mol% or more and 90 mol% or less, and 30 mol More preferably % to 85 mol%, and even more preferably 50 mol% to 80 mol%. i. Similarly, the content of monomer component B on a molar ratio basis relative to the (total) aromatic polyester resin. The ratio is preferably 10 mol% to 90 mol%, and preferably 15 mol% to 70 mol%. It is more preferable that the concentration be 20 mol% or more and more preferably 50 mol% or less. Also, (total) aromatic polymer The content of monomer component C, which may be included in the ester resin, is 10 moles in molar ratio. Preferably less than %; more preferably 8 mol% or less; even more preferably 5 mol% or less; particularly Preferably, it is 3 mol% or less.

[0035] Furthermore, known methods can be applied to the synthesis of (whole) aromatic polyester resins. , and not particularly limited. Known polycondensation that forms ester bonds with the monomer components described above. Legal methods such as melt polymerization, melt acidolysis, and slurry polymerization can be applied. When applying these polymerization methods, the acylation or acetylation step is performed according to the conventional method. That's fine.

[0036] The LCP extruded film 100 may further contain an inorganic filler. By including -, it is possible to realize an LCP extruded film 100 with a reduced coefficient of linear expansion. Specifically, the MD direction, TD direction, and ZD direction (Z-axis direction; film thickness direction) An LCP extruded film 100 with reduced anisotropy of the coefficient of linear expansion is easily obtained. The LCP extruded film 100 is used, for example, in rigid substrate applications where multilayer lamination is required. This will be particularly useful.

[0037] Inorganic fillers can be those known in the industry, and their types are not particularly limited. For example, kaolin, calcined kaolin, calcined clay, uncalcined clay, silica (for example, natural silica) Lica, fused silica, amorphous silica, hollow silica, wet silica, synthetic silica, aero Zill, etc.), aluminum compounds (e.g., boehmite, aluminum hydroxide, alumina, etc.) Idrotalcite, aluminum borate, aluminum nitride, etc.), magnesium compounds ( For example, magnesium aluminometasilicate, magnesium carbonate, magnesium oxide, water Magnesium oxide, etc.), calcium compounds (e.g., calcium carbonate, calcium hydroxide, Calcium sulfate, calcium sulfite, calcium borate, etc.), molybdenum compounds (e.g.) Molybdenum oxide, zinc molybdate, etc.), talc (e.g., natural talc, calcined talc, etc.), Mica, titanium dioxide, zinc oxide, zirconium oxide, barium sulfate, zinc borate Barium metaborate, sodium borate, boron nitride, aggregated boron nitride, silicon nitride, Examples include carbon nitride, strontium titanate, barium titanate, zinc stanate, and other stannate salts. However, these are not the only options. One type can be used alone, or two types can be used together. The above can also be used in combination. Among these, from the viewpoint of dielectric properties, etc., silicon Ka is preferable.

[0038] Furthermore, the inorganic fillers used here are those that have undergone surface treatment known in this industry. This is also acceptable. Surface treatment can improve moisture resistance, adhesive strength, dispersibility, etc. The treatment agents include silane coupling agents, titanate coupling agents, and sulfonic acid esters. Examples include, but are not limited to, carboxylates, phosphate esters, etc. .

[0039] The median diameter (d50) of the inorganic filler can be set appropriately according to the required performance, and is not particularly limited It is not done. From the viewpoint of kneadability and handling during preparation, and the effect of reducing the coefficient of linear expansion, inorganic fillers The d50 is preferably 0.01 μm or more and 50 μm or less, and more preferably 0.03 μm or less. The particle size is 50 μm or less, more preferably 0.1 μm or more and 50 μm or less. In this case, the median diameter (d50) of the inorganic filler is determined by the particle size distribution of the laser diffraction / scattering method. Using a measuring device (LA-500 manufactured by Horiba, Ltd.), volume bases were determined by laser diffraction and scattering. It refers to the value measured in a specific order.

[0040] The amount of inorganic filler will be determined considering the balance of other essential and optional components. The settings can be adjusted as appropriate depending on the performance, and are not particularly limited. Factors such as kneadability and handling during preparation, and the coefficient of linear expansion are considered. From the viewpoint of reduction effect, etc., in terms of solid content relative to the total amount of LCP extruded film 100, inorganic f The total content of the film is preferably 1% by mass or more and 45% by mass or less, and more preferably total The amount is 3% by mass or more and 40% by mass or less, and more preferably 5% by mass or more and 35% by mass or less in total. be.

[0041] The LCP extruded film 100 is subjected to the above-mentioned thermoplastic properties, to the extent that it does not excessively impair the effects of the present invention. Resin components other than plastic liquid crystal polymers (hereinafter referred to simply as "other resin components") It may contain, for example, thermosetting resins or thermoplastic resins. The output film 100 contains additives known in the industry, to the extent that they do not excessively impair the effects of the present invention. For example, higher fatty acids with 10 to 25 carbon atoms, higher fatty acid esters, higher fatty acid amides, and higher lipids. Release agents such as metal phosphate salts, polysiloxanes, and fluororesins; colorants such as dyes and pigments; organic Fillers; antioxidants; heat stabilizers; light stabilizers; UV absorbers; flame retardants; antistatic agents; interface agents It may contain properties agents, rust inhibitors, defoamers, fluorescent agents, etc. Only one of each of these additives may be included. These additives can be used individually or in combination of two or more. These can be included in the molten resin composition prepared during the molding of the extruded film 100. The content of resin components and additives is not particularly limited, but from the perspective of moldability and thermal stability, Preferably, each of these amounts is 0.01 to 10% by mass relative to the total amount of LCP extruded film 100. More preferably 0.1 to 7% by mass each, and even more preferably 0.5 to 5% by mass each. It is a percentage.

[0042] The thickness of the LCP extruded film 100 can be set as appropriate according to requirements and is not particularly limited. Considering handling and productivity during extrusion molding, a thickness of 15 μm to 300 μm is preferable. More preferably 18 μm to 250 μm, and even more preferably 20 μm to 200 μm It is less than or equal to m.

[0043] Furthermore, the LCP extruded film 100 of this embodiment is not only film surface but also film Internally, it also alleviates molecular orientation and internal strain of the thermoplastic liquid crystal polymer, thereby achieving the desired dimensions. From the viewpoint of reducing the anisotropy of the rate of change, nano-indices are applied to the film cross-section parallel to the MD direction. A point at a depth of 1 μm, located 1 μm from the film surface in the thickness direction, measured using the puncture method. The hardness H1 and the hardness H2 at the center of the thickness are adjusted to satisfy the following relationship. . Preferably, -10.0 ≤ 100 × (H2 - H1) / H1 ≤ 0.0. More preferably, -7.5 ≤ 100 × (H2 - H1) / H1 ≤ 0.0. More preferably, -5.0 ≤ 100 × (H2 - H1) / H1 ≤ 0.0. The relationship expressed by the above formula, that is, the relationship between the hardness H1 at a depth of 1 μm and the hardness H2 at the center of the thickness. This indicates the orientation of the thermoplastic liquid crystal polymer in the film; the lower its absolute value, the more MD (Metallic Disorder) This means that the orientation in the direction and the orientation in the TD direction are isotropic.

[0044] Here, in the film cross-section parallel to the MD direction, 1 μm from the film surface in the thickness direction A point located at a depth of 1 μm (in a plan view of the film cross-section, in the thickness direction from one film surface) The hardness H1 at the 1 μm position is, near the film surface of the LCP extruded film 100, This is an index indicating molecular orientation and internal strain of thermoplastic liquid crystal polymers. Hardness H at a depth of 1 μm. 1 tends to increase as the orientation of the thermoplastic liquid crystal polymer decreases, The higher the orientation of the rimer, the smaller the tend to be. And the hardness H1 at a depth of 1 μm is, Preferably, it is 0.250 GPa or higher, more preferably 0.255 GPa or higher. On the other hand, The center point of the thickness in the film cross-section parallel to the MD direction (in a plan view of the film cross-section, one side of the film The hardness H2 (at equally spaced positions from one film surface to the other) is measured in LCP extruded film. This shows the molecular orientation and internal strain of the thermoplastic liquid crystal polymer within the film of Mu 100. This is an indicator. The hardness H2 at the center of the thickness is greater the lower the orientation of the thermoplastic liquid crystal polymer. This tends to be the case, and the higher the orientation of the thermoplastic liquid crystal polymer, the smaller the thickness tends to be. The hardness H2 at the center point is preferably 0.240 GPa or higher, more preferably 0.245 GPa. It is greater than or equal to a. Furthermore, the preparation of a film cross-section parallel to the MD direction of the LCP extruded film 100. The method is not particularly limited, but in order to ensure objectivity between measurement data, under freezing conditions The LCP extruded film 100 is processed with an ion beam to obtain a smooth cross-section of the film parallel to the MD direction. The following shall be produced.

[0045] In this specification, hardness measurement by nanoindentation method is performed on diamond. Using a Berkovich-type indenter, LCP extrusion was performed under the condition of an indentation depth hmax = 0.05 μm. For a cross-section of film 100 parallel to the MD direction, the hardness at a point 1 μm from the film surface is This will be done by measuring H1 and the hardness H2 at the center of the thickness. Also, as shown in Figure 2, Furthermore, hardness H1 and hardness H2 are determined by the maximum load Pmax and the contact projected area A (indenter and film cross section). It shall be calculated using the following formula based on the area of ​​contact between the surfaces. Hardness (GPa) = Pmax / A

[0046] On the other hand, the LCP extruded film 100 of this embodiment is a thermoplastic represented by the degree of orientation described above. Thermodynamic properties expressed not only by the molecular orientation of the liquid crystal polymer, but also by the linear expansion coefficients in the MD and TD directions. The molecular orientation of the plastic liquid crystal polymer is also sufficiently reduced. As mentioned earlier, the conventional technology The LCP extruded films described in Patent Documents 1 and 2 are made of thermoplastic resins of both outer layers when three layers are co-extruded. The molecular orientation of the thermoplastic liquid crystal polymer is slightly relaxed by being protected by the layer, and this Therefore, the anisotropy of the strength in the MD direction and TD direction of the resulting thermoplastic liquid crystal polymer film is mild. It appears that they are being harmonized. However, in reality, the LC described in Patent Documents 1 and 2 P-extruded films consistently achieve a linear expansion coefficient in the MD direction of approximately -20 ppm / K. In contrast, the coefficient of linear expansion in the TD direction exceeds 55 ppm, and sometimes reaches 100 ppm. Some reach approximately / K. As is clear from this, prior art Patent Document 1 and The LCP extruded film described in 2 is composed of thermoplastic liquid crystal polymer as a whole. It is easy to see that significant child orientation or internal distortions remain. Therefore, the thermoplasticity of the LCP extruded film 100 as a whole film. The molecular orientation and internal strain of liquid crystal polymers are determined by the hardness obtained by the nanoindentation method described above. It needs to be controlled in combination with the coefficient of linear expansion.

[0047] The LCP extruded film 100 of this embodiment has a coefficient of linear expansion (CT) in the MD direction and the TD direction. E,α2,23~200℃) is in the range of -30~55 ppm / K. The LCP extruded film 100, which has a coefficient of linear expansion, is in a state where internal strain and other factors are sufficiently reduced. Furthermore, compared to those that are not, the anisotropy of the rate of dimensional change is small, and the absolute value of the rate of dimensional change is This can result in a sufficiently small LCP extruded film. LCP extruded film 100 of this embodiment The coefficient of linear expansion in the MD direction (CTE, α2, 23~200℃) is further related to adhesion to the metal foil. From the viewpoint of improving properties, it is preferable that the concentration be within the range of -30 to 10 ppm / K, and -2 It is more preferable that the concentration is within the range of 5 to 5 ppm / K, and within the range of -20 to 0 ppm / K. It is even more preferable that the LCP extruded film 100 of this embodiment has a TD direction The coefficient of linear expansion (CTE, α2, 23~200℃) is used to further improve adhesion to metal foil, etc. From this perspective, it is preferable that the concentration is in the range of 0 to 55 ppm / K, and 0 to 50 ppm / K It is more preferable that it be within the range, and even more preferable that it be within the range of 0 to 45 ppm / K. In this specification, the coefficient of linear expansion (CTE, α2, 23~200℃) is defined as JIS. This refers to values ​​measured by the TMA method in accordance with SK7197, within the temperature range of 23 to 200°C. Furthermore, other detailed measurement conditions shall follow the conditions described in the examples below. do.

[0048] In this specification, the measurement of the coefficient of thermal expansion shall be performed in accordance with JIS K7197 TMA The method is used, and the average coefficient of linear expansion is the average of the coefficients of linear expansion measured in the same method between 23 and 200°C. This refers to the average value. The coefficient of linear expansion measured here is obtained using LC to see the value after eliminating the thermal history. After heating the P extruded film 100 at a heating rate of 5°C / min (1st heating) The temperature is cooled to the ambient temperature (23°C) (1st cooling), and then increased at 5°C / min. This refers to the value obtained when the second heating (2nd heating) is performed, based on the heating rate. Other detailed measurement conditions shall follow those described in the examples below.

[0049] Furthermore, the LCP extruded film 100 of this embodiment is not only on the film surface but also inside the film In this section, the molecular orientation and internal strain of the thermoplastic liquid crystal polymer are alleviated, and the desired dimensional changes are achieved. From the viewpoint of reducing the anisotropy of the chemical ratio, the degree of orientation α1 including the exposed film surface S1, The film surface S1 is exposed by etching it in the thickness direction. The degree of orientation α2, which includes the film surface S2 located at a depth of 5 μm from surface S1, is related to the following: It is desirable to satisfy the requirements. Preferably, -4.0 ≤ [(α2-α1) / α1] × 100 ≤ 0.0. More preferably, -3.0 ≤ [(α2 - α1) / α1] × 100 ≤ 0.0. More preferably, -2.0 ≤ [(α2-α1) / α1] × 100 ≤ 0.0.

[0050] Here, as shown in Figure 3, the film surface S1 is the LCP extruded film 1 of this embodiment. It is the outermost surface of 00, and is an exposed surface that is exposed outward. It includes the film surface S1. The degree of orientation (degree of orientation α1) is preferably 39.0% or less, more preferably 38.5% or less. , more preferably 38.0% or less. On the other hand, the film surface S2 is L of this embodiment. By etching the film surface S1 of the CP extruded film 100 in the thickness direction, a new This is the surface that is exposed, and in Figure 3, it is a virtual surface located at a depth of 5 μm from the film surface S1. This is represented by a dashed line. The degree of orientation (degree of orientation α2) including this film surface S2 is preferably 37. It is 7% or less, more preferably 37.5% or less, and even more preferably 37.3% or less. Furthermore, the depth at which the film surface S2 is located is determined by considering the dissolution error during etching, etc. It does not need to be exactly 5 μm from the surface S1, but 5.0 μm or more from the film surface S1. It would be good if it were present. Also, the etching conditions for creating the film surface S2 are not particularly limited. However, in order to ensure objectivity between measurement data, the conditions described in the examples below will be used. They shall be considered different.

[0051] In this specification, the film surface S1, S2 of the LCP extruded film 100 is included. The degree of orientation α1, α2 (%) was obtained by X-ray diffraction measurement using the transmission method with an X-ray diffractometer. The value calculated from the following formula based on the area ratio of the orientation peak in the diffraction intensity distribution curve. This means that, generally, for objects with a small degree of orientation (%), X-ray diffraction measurements produce a peak. Because low intensity and broad diffraction peaks are observed, calculations based on the full width at half maximum of the oriented peaks are performed. The current method cannot guarantee high measurement accuracy. Therefore, in this specification, half of the orientation peak is used. The calculation method is based on the area ratio of the orientation peak, rather than the value range, for the film surfaces S1 and S2. The degree of orientation α1 and α2 (%) are calculated, respectively. Specifically, this is shown in Figure 4 and Equation 1. As described above, the calculation method is based on the area ratio of the orientation peak, and the peak is calculated using a 2θ / θ scan. The intensity (orientation component) is measured, and the azimuth angle is measured from 0° to 360° using a beta scan. The intensity is measured at the base to obtain the intensity distribution in the azimuthal direction (base intensity (isotropic component)), and the base The area occupied by the orientation component, excluding the area of ​​the isotropic component, is the total area (the area of ​​the orientation component). The degree of orientation (%) is calculated by determining the proportion of the area (product + area of ​​isotropic components) that occupies.

number

[0052] On the other hand, the dielectric properties of the LCP extruded film 100 in this embodiment are appropriately set according to the desired performance. It can be determined and is not particularly limited. From the viewpoint of obtaining higher dielectric properties, the relative permittivity ε r (36GH z) is preferably 3.0 to 3.7, and more preferably 3.0 to 3.5. Furthermore, the dielectric loss tangent tanδ (36 GHz) is preferably 0.0010 or more and 0.0050 or less. More preferably, it is 0.0010 or more and 0.0045 or less. In this specification, ratio Dielectric constant ε r (36GHz) and dielectric loss tangent tanδ(36GHz) are specified in JIS K6471. This refers to the value at 36 GHz measured using the cavity resonator contact method compliant with [specific standard]. Other detailed measurement conditions shall follow those described in the examples below.

[0053] (Manufacturing method for LCP extruded film) The LCP extruded film 100 of this embodiment is made of the thermoplastic liquid crystal polymer described above, and necessary Depending on the circumstances, a resin composition containing optional components such as inorganic fillers or other resin components is extruded to a predetermined thickness. It can be obtained by molding. Various known methods can be applied to the extrusion method. The type is not particularly limited. For example, the T-die method or the inflation method; for example, the multi-die method. Nifold co-extrusion and feedblock co-extrusion; for example, two-layer co-extrusion and three-layer co-extrusion. Multilayer co-extrusion methods, such as layered co-extrusion, can be applied in any combination.

[0054] Among these, the film surface (film surface S1) and the inside of the film (film surface From the viewpoint of ease of controlling the molecular orientation of the thermoplastic liquid crystal polymer in S2), a preferred one In one embodiment, the above-mentioned resin composition is extruded using a T-die (hereinafter, simply This is sometimes called the "T-die extrusion method." ) The material is extruded from a T-die and formed into a film. Then, as necessary, cooling, crimping, pressurizing and heating treatments are performed, followed by the specified LCP extrusion. A method for obtaining film 100 is mentioned. Specifically, a method for the first surface layer containing thermoplastic resin is mentioned. Resin composition A, resin composition B for the intermediate layer containing a thermoplastic liquid crystal polymer, thermoplastic resin Prepare the second surface resin composition C containing the following, and extrude it from the co-extrusion die of the extruder. These are co-extruded to extrude a three-layer co-extruded molten material, and the intermediate layer is a thermoplastic liquid crystal polymer layer. A co-extrusion method is preferred for forming the LCP extruded film 100. According to this, the intermediate layer of thermoplastic liquid crystal polymer is protected by the thermoplastic resin layers on both outer layers. The molecular orientation of the thermoplastic liquid crystal polymer in the mer layer is relaxed. The following describes the LC of this embodiment. A preferred embodiment of the method for manufacturing the P extruded film 100 will be described in detail.

[0055] Figures 5 to 7 show preferred methods for manufacturing the LCP extruded film 100 according to the above-described embodiment. This figure shows one embodiment. Here, the thermoplastic liquid crystal polymer described above, and, if necessary, The above resin composition B, which contains optional components such as machine fillers and other resin components, is applied to the T-die of an extruder. Then it is melt-extruded into a film. At this time, thermoplastic is applied to both sides of the above-mentioned film-like molten extruded material. By co-extruding resin compositions A and C containing a resin, the first outer layer containing a thermoplastic resin (peelable) is produced. A layer, an intermediate layer (LCP layer) containing a thermoplastic liquid crystal polymer, and a second layer containing a thermoplastic resin. A co-extruded molten product (3-layer laminated film) of a predetermined thickness, having a layer (release layer), is produced. The co-extruded molten material is drawn out by the take-up roll and sent to the cooling roll and then the crimping roll. After that, the first outer layer and the second outer layer are peeled off from the intermediate layer, and the thermoplastic resin layers of both outer layers and the intermediate layer The thermoplastic liquid crystal polymer layer (LCP extruded film 100) and the film are each wound onto a winding roll. It will be taken.

[0056] The preparation of resin composition B containing the above-mentioned thermoplastic liquid crystal polymer can be carried out according to a conventional method. The process is not particularly limited. Each of the above components may be processed by, for example, kneading, melt kneading, granulation, extrusion molding, etc. It can be manufactured and processed by known methods such as molding or injection molding. When mixing, a single-screw or twin-screw extruder or various kneaders are commonly used. A kneading device can be used. When supplying each component to these melting and kneading devices, liquid crystal particles can be used. Rimmer, other resin components, inorganic fillers, additives, etc. are pre-mixed in a tumbler or Henschel mixer. Dry blending may be performed using a mixing device such as a siphon. During melt mixing, the syringe of the mixing device The setting temperature can be set as appropriate and is not particularly limited, but generally it is the melting point of the liquid crystal polymer. A range of 360°C or less is preferred, and more preferably 10°C or more above the melting point of the liquid crystal polymer. It is below 60℃.

[0057] The preparation of resin compositions A and C, which contain thermoplastic resins, can also be carried out according to conventional methods, and there are no particular limitations. Not specified. Examples of thermoplastic resins include polyethylene, polypropylene, and polymethyl Lupentene, polyolefin resins such as ethylene-α-olefin copolymers, PMMA, etc. Acrylic resins, polyamide resins, acrylonitrile-butadiene-styrene copolymers (ABS resin), polystyrene (PS), polyvinyl chloride, polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polycarbonate (PC), poly Examples include ether ether ketone (PEEK) and polyphenyl sulfide (PPS). However, it is not limited to these. When it is made into a co-extruded molten product, polycarbonate and the like Whether it is a polar resin or a non-polar resin such as polymethylpentene, it is effective as a release layer. These thermoplastic resins are contained in the LCP extruded film 100 mentioned above. Other resin components or inorganic fillers may be added to the resin composition. Even if A and resin composition C have the same resin composition, or even if they have different resin compositions, Often, a product may contain the same thermoplastic resin or different thermoplastic resins. The resin compositions A and C, which contain thermoplastic resins, can be subjected to processes such as kneading, melt kneading, granulation, and extrusion molding. It can be manufactured and processed by known methods such as pressing or injection molding. When performing melting and mixing, commonly used single-screw or twin-screw extruders and various kneaders are used. A kneading apparatus can be used. When supplying each component to these melting kneading apparatuses, heat Plastic resins, other resin components, inorganic fillers, additives, etc. are pre-treated in a tumbler or Henschel. Dry blending may be done using a mixing device such as a mixer. During melting and kneading, the kneading device The binder temperature should be set appropriately, below the temperature at which the thermoplastic resin does not degrade due to thermal decomposition. While not particularly limited, generally a temperature above the melting point of the thermoplastic resin is preferred, and more preferably a thermoplastic temperature. The melting point of the plastic resin is 10°C or higher.

[0058] The setting conditions for co-extrusion depend on the type and composition of the resin composition used and the target extruded film. The settings can be set appropriately according to the desired performance, etc., and are not particularly limited. For example, the cylinder of an extruder The set temperature depends on the type and composition of the resin composition used, and the desired performance of the extruded film. The temperature can be set appropriately depending on the circumstances, and is not particularly limited, but 230 to 360°C is preferred. Preferably, the temperature is 280-350°C.

[0059] Similarly, the die width (mm) of a T-die also depends on the type and composition of the resin composition used, and the size of the die. The setting can be appropriately determined according to the desired performance of the target extruded film, and is not particularly limited. Generally, 200 to 2000 mm is preferred, and more preferably 400 to 1500 mm. ru.

[0060] Furthermore, for example, the lip opening (mm) of a T-die is similarly affected by the type and combination of resin compositions used. The setting can be appropriately determined according to the desired performance of the extruded film, and is not particularly limited. However, generally, 0.1 to 3.0 (mm) is preferred, and more preferably 0.2 to 2.0 ( It is (mm).

[0061] And, for example, the shear rate of the lip wall of the T-die (sec -1 Similarly, the resin components used The settings should be adjusted appropriately according to the type and composition of the product, the desired performance of the extruded film, etc. While not particularly limited, generally 100-1500 (sec) -1) is preferable, and more preferable 150-1000 (sec) -1 )

[0062] Also, the total discharge volume (mm) of the resin composition of the T-die 3 Similarly, the resin composition used ( / sec) The settings can be adjusted as appropriate depending on the type and composition of the material, the desired performance of the extruded film, etc. While not limited to this range, generally 500-15000 (mm) 3 ( / sec) is preferred, and more preferably The range is 1500-10000 (mm 3 ( / sec)

[0063] On the other hand, the melt viscosity (Pa·sec) of thermoplastic liquid crystal polymers is similarly determined by the resin composition used. The settings can be adjusted as appropriate depending on the type and composition of the material, the desired performance of the extruded film, etc. While not limited to these, generally 10 to 300 (Pa·sec) is preferred, more The melt viscosity of thermoplastic liquid crystal polymers is 20-250 (Pa·sec). The sec) conforms to JIS K7199 and uses a Capillograph 1D (manufactured by Toyo Seiki Seisakusho Co., Ltd.). Using this, the cylinder length is 10.00 mm, the cylinder diameter is 1.00 mm, and the barrel diameter is 9. Under the conditions of 55mm, the conditions used in the manufacture of LCP extruded film 100 (die temperature, and lip This refers to the value measured by the shear rate of the wall.

[0064] Similarly, the take-up speed (mm / sec) of the co-extruded film also depends on the type of resin composition used. The type and composition, the desired performance of the extruded film, etc., can be set appropriately, and there are no particular limitations. Although not specified, generally 15 to 1000 (mm / sec) is preferred, and more preferably 20 It is approximately 500 mm / sec.

[0065] Here, from the perspective of reducing the molecular orientation of the thermoplastic liquid crystal polymer in the MD direction during coextrusion , the shear stress (kPa) during coextrusion is preferably low. When the shear stress during coextrusion is large , the thermoplastic liquid crystal polymer is likely to be highly oriented in the MD direction, and internal strain is likely to remain. When the shear stress during coextrusion is small , in both the film surface and the film interior, the molecular orientation of the thermoplastic liquid crystal polymer is likely to be reduced, and internal strain is less likely to remain . Incidentally, the shear stress (kPa) during coextrusion is a value represented by the product of the shear rate (sec ) of the lip wall surface and -1 the melt viscosity (Pa·sec) of the thermoplastic liquid crystal polymer. The shear rate is a value calculated based on the total discharge amount of the resin composition, the die width , and the lip opening during coextrusion. Therefore, the shear stress during coextrusion can be controlled by adjusting these respective values . Specifically, the shear stress during coextrusion is preferably 40 kPa or less, more preferably 38 kPa or less, and even more preferably 36 kPa or less. The lower limit value thereof is not particularly limited, but considering productivity etc., 5 kPa or more is preferable, and more preferably 10 kPa or more.

[0066] Also, from the perspective of reducing the molecular orientation of the thermoplastic liquid crystal polymer in the MD direction during coextrusion, the drawdown ratio during coextrusion is preferably low. When the drawdown ratio during coextrusion is large , the thermoplastic liquid crystal polymer is likely to be highly oriented in the MD direction, and internal strain is likely to remain. When the drawdown ratio during coextrusion is small , in both the film surface and the film interior, the molecular orientation of the thermoplastic liquid crystal polymer is likely to be reduced, and internal strain is less likely to remain . Incidentally, the drawdown ratio is the take-up speed (mm / sec) / thermoplastic liquid crystal poly mer This value is expressed as the flow velocity (mm / sec) of a polymer, and the flow velocity of thermoplastic liquid crystal polymers is co-extraction. This value is calculated based on the total discharge volume of the resin composition at the time of ejection, the die width, and the lip opening. Therefore, the drawdown ratio during co-extrusion can be controlled by adjusting each of these values. Specifically, the drawdown ratio during co-extrusion is preferably 3.5 or less, and more preferably... Or 3.3 or less, more preferably 3.1 or less. The lower limit is not particularly limited Although not required, considering productivity and other factors, a value of 1.0 or higher is preferable, and more preferably 1.2 or higher. be.

[0067] The thickness of the resulting LCP extruded film 100 can be set as appropriate according to requirements, and is not particularly limited. It will not be done. Considering handling and productivity during extrusion molding, the ideal thickness is 15 μm to 300 μm. Preferably, more preferably 18 μm to 250 μm, and even more preferably 20 μm or more. It is 200 μm or less.

[0068] The melting point (melting temperature) of the resulting LCP extruded film 100 is not particularly limited, however From the perspective of heat resistance and processability of the material, the melting point (melting temperature) should be between 200 and 400°C. Preferably, and especially from the viewpoint of improving thermocompression adhesion to metal foil, a temperature of 250 to 360°C is preferred. , more preferably 260-355°C, even more preferably 270-350°C, particularly preferably The melting point of the LCP extruded film 100 is 275-345°C. The values ​​were obtained using the DSC8500 (manufactured by PerkinElmer) to eliminate the thermal history. To achieve this, the extruded film is heated in the temperature range of 30-400°C at a heating rate of 20°C / min (1 (1st heating) followed by cooling at a rate of 50°C / min (1st cooling) ) and then a second heating (2nd heating) was performed at a heating rate of 20°C / min. This refers to the melting peak temperature in differential scanning calorimetry (DSC). In addition, Therefore, the measurement conditions described in the examples below shall be followed.

[0069] The extruded LCP extruded film 100 can be used as is, Furthermore, by performing a pressurized heating process as needed, its orientation (anisotropy) can be further reduced. This can also release internal strain, thereby reducing the anisotropy of the dimensional change rate. LCP extruded film 100 with reduced absolute value of dimensional change rate It is also possible to achieve a film-to-film ratio of 100.

[0070] The heat and pressure treatment is carried out using methods known in the industry, such as contact heat treatment, non-contact heat treatment, etc. Any type of device can be used, and the type is not particularly limited. For example, a non-contact heater, an oven, Known machines such as blowing machines, hot rolls, cooling rolls, hot presses, and double belt hot presses. It can be heat-set using a container. At this time, if necessary, LCP extruded film 1 A release film or porous film known in the industry is placed on the surface of 00 and heat treatment is performed. This can be done. Also, when performing this heat treatment, from the viewpoint of controlling orientation, LCP extruded fill The front and back of the Mu100 are fitted with release film or porous film for the end of a double belt press machine. The two Resbelts are heat-pressed together while sandwiched between them, and then the release film and porous film are removed. A hot-pressure molding method is preferably used. For example, the hot-pressure molding method is described in Japanese Patent Application Publication No. 2010-22. This can be done by referring to No. 1694, etc. LCP extruded film 10 using the above resin composition 0 is the processing temperature when hot-press forming between the endless belt pair of a double belt press machine. This is to control the crystalline state of the LCP extruded film 100, and the melting point of the liquid crystal polymer is higher than that of the liquid crystal polymer. It is preferable to carry out the process at a temperature above 70°C and 70°C above the melting point, and more preferably at a temperature below the melting point. A temperature of 5°C higher or more, and 60°C higher or less than the melting point, and more preferably 10°C higher than the melting point. The temperature is above a certain level, but no more than 50°C above the melting point. The thermocompression bonding conditions at this time are as follows: The setting can be adjusted as appropriate, and is not particularly limited, but the surface pressure is 0.5 to 10 MPa when heating. It is preferable to carry out the process under conditions of a temperature of 250 to 430°C, and more preferably under a surface pressure of 0.6 to 8 M. Under conditions of heating at a temperature of 260-400°C in Pa, and more preferably at a surface pressure of 0.7-6 MPa, the material is applied. This is under conditions of a heat temperature of 270-370°C. On the other hand, when using non-contact heaters or ovens... In some cases, it is preferable to carry out the process under conditions such as 200-320°C for 1-20 hours.

[0071] (Insulating material for circuit boards) Figure 8 is a schematic cross-sectional view showing the main parts of the insulating material 200 for circuit boards according to this embodiment. The insulating material 200 for circuit boards in the form of the above-mentioned LCP extruded film 100 and this LCP Laminate having at least a woven fabric WF provided on one and / or both sides of the extruded film 100 It is something that possesses a physical body.

[0072] Specifically, the insulating material 200 for circuit boards is LCP extruded film 100, woven fabric WF, and The LCP extruded film 100 is arranged in a laminated structure (3-layer structure) in at least this order. It comprises a laminate. In this laminate, one of the LCP extruded films 100 is woven The other LCP extruded film 100 is provided on the surface side of the cloth WF, and is provided on the back side of the woven cloth WF. These three layers are heat-sealed together, thereby forming a three-layer laminate. Here, a laminated structure with three layers is given as an example, but the present invention relates to one of the LCP extruded fills. Even in a two-layer laminated structure with the 100 layer omitted, LCP extruded film 100 and woven fabric WF Needless to say, this can also be done with laminated structures of four or more layers, which are further stacked. do not have.

[0073] Hereinafter, in this specification, "woven fabric W on one side and / or both sides of LCP extruded film 100" "F is provided" means that, as in this embodiment, an LCP extruded film 100 is provided on the surface of the woven fabric WF. In addition to the embodiment in which it is directly placed, the illustration shows the LCP extruded film 100 and the woven fabric WF being placed between them. Any layer (e.g., primer layer, adhesive layer, etc.) intervenes, and the LCP extruded film 100 This means that it includes configurations in which the elements are positioned at a distance from the woven fabric WF.

[0074] Woven fabric WF is a fabric made by weaving fibers. The type of fiber used in woven fabric WF is not particularly limited. It can be used with any of the following: inorganic fibers, organic fibers, or organic-inorganic hybrid fibers. In particular, inorganic fiber woven fabric WF is preferably used. Inorganic fiber woven fabric WF is LCP By heat-pressing the extruded film 100, the anisotropy of the dimensional change rate in the MD direction and TD direction is reduced. This can be kept small, and in a more preferred embodiment, the dimensional change rates in the MD and TD directions themselves can be It can be made smaller. Commercially available products can be used as woven WF, and in this industry It can be manufactured by known methods.

[0075] Examples of inorganic fibers include E glass, D glass, L glass, M glass, S glass, and T glass. Glass, Q glass, UN glass, NE glass, spherical glass, glass fibers, quartz, etc. Examples include inorganic fibers other than glass, ceramic fibers such as silica, etc., but are not limited to these. It is not fixed. Inorganic fiber woven fabrics WF are woven fabrics that have undergone fiber opening and weave tightening treatments, and dimensional stability It is preferable from the viewpoint of mechanical strength, dimensional stability, water absorption, etc. Glass cloth is preferred. From the viewpoint of improving the heat-pressure bonding with the LCP extruded film 100, Glass cloth that has undergone fiber opening and pore filling treatment is preferred. Also, epoxy silane treatment is preferred. Glass cloths that have been surface-treated with silane coupling agents such as aminosilane treatment are also suitably used. It is possible to use it. Furthermore, woven fabric WF can be used either individually or in appropriate combinations of two or more types. It is possible to be there.

[0076] The thickness of the woven WF can be set appropriately according to the required performance and is not particularly limited. Lamination properties and processing From the viewpoint of properties, mechanical strength, etc., 10 to 300 μm is preferred, and more preferably 10 to 20 The particle size is 0 μm, more preferably 15 to 180 μm.

[0077] The total thickness of the insulating material 200 for circuit boards can be set appropriately according to the required performance, and is not particularly limited. No. From the viewpoint of lamination, processability, mechanical strength, etc., 30 to 500 μm is preferred, and more preferably... The particle size is preferably 50-400 μm, more preferably 70-300 μm, and especially preferably 90- It is 250 μm.

[0078] The insulating material 200 for the circuit board of this embodiment adopts the above-described configuration, in the MD direction Furthermore, the anisotropy of the dimensional change rate in the TD direction is small, and in a more preferred embodiment, the MD direction and the TD direction It can reduce the dimensional change rate itself, and moreover, it has excellent dielectric properties in the high-frequency range. It has the remarkable advantages of being easy to manufacture and having excellent productivity.

[0079] The insulating material 200 for circuit boards described above can be manufactured by appropriately applying known manufacturing methods. The manufacturing method is not particularly limited. For example, LCP extruded film 10 0 and woven fabric WF are laminated, heated and pressurized, and the LCP extruded film 100 and woven fabric WF are By thermocompression bonding, an insulating material 200 for circuit boards can be obtained. In addition, LCP extrusion The lum 100, woven fabric WF, and LCP extruded film 100 are stacked in this order to form a laminate. The laminate is then heated and pressurized while being held between the plates using a press machine or a double belt press machine. Furthermore, a method of thermo-pressing the insulating material 200 for the circuit board is also preferred. Note that the processing temperature during thermocompression bonding The degree can be set appropriately according to the required performance and is not particularly limited, but is between 200 and 400. °C is preferred, more preferably 250-360°C, and even more preferably 270-350°C. Yes. The processing temperature during heat bonding is the surface temperature of the LCP extruded film 100 of the laminate mentioned above. The value measured by temperature shall be used. Furthermore, the pressurization conditions shall be set appropriately according to the desired performance. It is possible, and is not particularly limited, but for example, at a surface pressure of 0.5 to 10 MPa for 1 to 240 minutes, Preferably, the surface pressure is 0.8 to 8 MPa for 1 to 120 minutes.

[0080] (Metal foil-clad laminate) Figure 9 is a schematic cross-sectional view showing the main part of the metal foil-clad laminate 300 of this embodiment. The metal foil laminated board 300 is made of the above LCP extruded film 100 and this LCP extruded film It comprises a metal foil MF provided on one side and / or both sides of the lum 100.

[0081] Specifically, the metal foil laminated board 300 consists of metal foil MF, LCP extruded film 100, and Double-sided metal foil having a laminated structure (3-layer structure) in which metal foil MF is arranged in at least this order. It is a laminated board. These three layers are heat-pressed together, thereby forming a three-layer laminated structure. In this embodiment, a double-sided metal foil laminate is shown, but LCP extruded film is also used. The present invention can also be implemented in a configuration in which the metal foil MF is provided on only one surface of M100. Yes. In other words, although a three-layer laminate is given as an example here, the present invention is one of the metal foil MF Even in a two-layer laminated structure that omits the LCP extruded film 100 or woven fabric WF further Needless to say, this is also possible with laminated structures consisting of four or more layers stacked together.

[0082] Figure 10 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 form is made of the above LCP extruded film 100 and this LCP extruded film The film 100 has at least the above-mentioned woven fabric WF provided on one and / or both sides. It comprises a layered body and metal foil MF provided on one and / or both sides of the laminated body. .

[0083] Specifically, the metal foil laminate 400 consists of metal foil MF, LCP extruded film 100, and woven fabric. WF, LCP extruded film 100, and metal foil MF are arranged in at least this order in a compound This is a double-sided metal foil laminate with a layered structure (5-layer structure). These 5 layers are heat-pressed together. This forms a five-layer laminate. In this embodiment, double-sided metal foil Although a laminated board has been shown, the present invention also applies to a configuration in which the metal foil MF is provided on only one surface. It is feasible. That is, although a five-layer laminate is exemplified here, the present invention is one of the Even in the case of a laminate with a four-layer structure in which the metal foil MF is omitted, it is needless to say that it is also feasible to form a laminate with a six-layer or more structure by further laminating the LCP extrusion film 100, the insulating material 200 for circuit boards, and the woven fabric WF. Even in the case of a laminate with a four-layer structure in which the metal foil MF is omitted, it is needless to say that it is also feasible to form a laminate with a six-layer or more structure by further laminating the LCP extrusion film 100, the insulating material 200 for circuit boards, and the woven fabric WF. も実施可能なことは言うまでもない。

[0084] The material of the metal foil MF is not particularly limited, and examples thereof include gold, silver, copper, copper alloy, nickel, nickel alloy, aluminum, aluminum alloy, iron, iron alloy, etc. Among these, copper foil, aluminum foil, stainless steel foil, and alloy foil of copper and aluminum are preferable, and copper foil is more preferable. Any copper foil produced by methods such as rolling or electrolysis can be used, but electrolytic copper foil or rolled copper foil with a relatively large surface roughness is preferable. ッケル合金、アルミニウム、アルミニウム合金、鉄、鉄合金等が挙げられる。これらの中 のものでも使用できるが、表面粗さが比較的に大きい電解銅箔や圧延銅箔が でも、銅箔、アルミニウム箔、ステンレス箔、及び銅とアルミニウムとの合金箔が好まし く、銅箔がより好ましい。かかる銅箔としては、圧延法或いは電気分解法等によって製造 されるいずれのものでも使用できるが、表面粗さが比較的に大きい電解銅箔や圧延銅箔が 好ましい。

[0085] The thickness of the metal foil MF can be appropriately set according to the desired performance and is not particularly limited. Usually, 1. 5~1000μm is preferable, more preferably 2~500μm, still more preferably 5~1 50μm, and particularly preferably 7~100μm. As long as the effects of the present invention are not impaired, the metal foil MF may be subjected to surface treatment such as chemical surface treatment like pickling. い限り、金属箔MFは、酸洗浄等の化学的表面処理等の表面処理が施されていてもよい。 なお、金属箔MFの種類や厚みは、同一であっても異なっていてもよい。

[0086] The method of providing the metal foil MF on the surface of the LCP extrusion film 100 or the insulating material 200 for circuit boards can be carried out according to a conventional method and is not particularly limited. Methods such as laminating the metal foil MF on the LCP extrusion film 100 or the insulating material 200 for circuit boards and bonding or crimping the two layers, physical methods (dry methods) such as sputtering and vapor deposition, electroless plating, and electroless plating 方法は、常法にしたがって行うことができ、特に限定されない。LCP押出フィルム10 0や回路基板用絶縁材料200の上に金属箔MFを積層して両層を接着ないしは圧着させ る方法、スパッタリングや蒸着等の物理法(乾式法)、無電解めっきや無電解めっき後の This can be done using any of the following methods: chemical methods such as electroplating (wet methods), or methods such as applying metal paste. In addition, LCP extruded film 100 and insulating material for circuit boards 200 and one or more metal foils MF A laminate formed by stacking these materials can be used in, for example, a multi-stage press, a multi-stage vacuum press, a continuous molding machine, or an autoc Metal foil-clad laminates 300 and 400 are obtained by hot pressing using a lath molding machine or the like. It is also possible.

[0087] The metal foil laminates 300 and 400 described above can be manufactured by appropriately applying known manufacturing methods. The manufacturing method is not particularly limited. For example, LCP extruded film 100 and circuit board insulating material 200 and metal foil MF are layered together to form LCP extruded film 1 A laminate is formed by placing metal foil MF on top of 00, and this laminate is used in the double belt press machine One method is to heat-press the material while sandwiching it between a pair of dress belts. As mentioned above, The LCP extruded film 100 used in the embodiment has different dimensional change rates in the MD direction and the TD direction. The directional properties are small, and in a more preferred embodiment, the dimensional change rates in the MD and TD directions themselves are small. Therefore, high peel strength to metal foil MF can be obtained.

[0088] The temperature during the heat-compression bonding of metal foil MF can be set appropriately according to the required performance, and is not limited to It is not done, but the temperature is 50°C lower than the melting point of the liquid crystal polymer and 50°C higher than the melting point. The following is preferable: a temperature 40°C lower than the melting point and 40°C higher than the melting point. Preferably, the temperature is 30°C lower than the melting point and more preferably 30°C higher than the melting point. It is preferable that the temperature be at least 20°C lower than the melting point and at least 20°C higher than the melting point. The temperature during the heat-pressing of the metal foil MF is the same as the surface temperature of the LCP extruded film 100 mentioned above. The value measured in degrees shall be used. Furthermore, the crimping conditions at this time shall be set appropriately according to the desired performance. This is possible, and is not particularly limited, but for example, when using a double belt press machine, the surface pressure is 0.5 It is preferable to perform the procedure under conditions of ~10 MPa and a heating temperature of 200~360°C.

[0089] The metal foil-clad laminates 300 and 400 of this embodiment consist of an LCP extruded film 100 and metal foil M As long as it has a two-layer heat-sealed body with F, it has another laminated structure or further laminated structure It may also be possible. For example, a two-layer structure of metal foil MF / LCP extruded film 100; metal foil MF / LCP extruded film 100 / metal foil MF, LCP extruded film 100 / metal foil MF / LC Three-layer structure such as P extruded film 100; metal foil MF / LCP extruded film 100 / woven fabric 4-layer structure such as WF / LCP extruded film 100; metal foil MF / LCP extruded film 1 00 / Metal foil MF / LCP extruded film 100 / Metal foil MF, Metal foil MF / LCP extruded film Five-layer structure such as film 100 / woven fabric WF / LCP extruded film 100 / metal foil MF; etc. , can be made into a multilayer structure. Also, multiple (for example, 2 to 50) metal foil-clad laminates 3 00 and 400 can also be laminated and heat-pressed together.

[0090] In the metal foil-clad laminates 300 and 400 of this embodiment, the LCP extruded film 100 and gold The peel strength with the attached foil MF is not particularly limited, but from the perspective of achieving higher peel strength Therefore, it is preferable that it is 0.8 (N / mm) or more, and more preferably 1.0 (N / mm). ) or more, more preferably 1.2 (N / mm) or more. As described above, this embodiment In the metal foil-clad laminates 300 and 400, high peel strength can be achieved, for example, in substrate manufacturing In the manufacturing heating process, peeling between the LCP extrusion film 100 and the metal foil MF can be suppressed. Also, when obtaining peel strength equivalent to that of the prior art, manufacturing conditions excellent in process margin and productivity can be applied. Therefore, while maintaining the peel strength comparable to the conventional level, deterioration of the basic performance of the liquid crystal polymer can be suppressed. And the metal foil laminated boards 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 a part of the metal foil MF. Also, the metal foil laminated boards 300 and 400 of the present embodiment have excellent dielectric characteristics in the high-frequency range, small anisotropy in the dimensional change rates in the MD direction and the TD direction, and in a more preferable

[0091] aspect, the dimensional change rates themselves in the MD direction and the TD direction are small, excellent in dimensional stability, easy to manufacture and excellent in productivity. Therefore, it becomes a particularly useful material as an insulating material for flexible printed wiring boards (FPC) etc. in the fifth-generation mobile communication system (5G), millimeter-wave radar, etc. In addition, in each of the above-described embodiments, the LCP extrusion film 100 obtained by extruding a resin composition containing a thermoplastic liquid crystal polymer into a film shape is used. However, if necessary, the LCP extrusion film 100 can be further subjected to uniaxial and / or biaxial stretching treatment and used in the form of an LCP stretched film (a stretched body of the LCP extrusion film 100). And using this LCP stretched film, the above-described insulating material 200 for circuit boards, metal foil laminated boards 300, 400, etc. can be configured. The setting conditions during the stretching treatment include the type and composition of the resin composition used, and the target LCP stretching

[0092] (LCP stretched film)

[0093] ​​​​​​​ The settings can be adjusted as appropriate according to the desired performance of the film, and are not particularly limited. For example, the LCP extruded film 100 is directed in the TD direction (Transverse Direction). It can be stretched to 1.1 to 2.5 times its original length at 90 to 180°C, and then, for example, 100 It is preferable to perform heat treatment (heat setting) at ~240°C for 1 to 600 seconds. Biaxial stretching is performed. In some cases, for example, the LCP extruded film 100 is preferably directed in the MD direction (Machine Direction). The material was stretched 1.1 to 2.5 times in the longitudinal direction at 70 to 180°C to produce a uniaxially oriented film. Furthermore, in the TD direction (Transverse Direction), at 90-180°C, 1.1-2 It can be stretched to 0.5 times its original size, and then heat-treated at, for example, 100-240°C for 1-600 seconds. It is preferable to perform thermal setting. At this time, simultaneous biaxial stretching should be performed rather than sequential stretching. It is also possible to do so. The stretching ratio is not particularly limited, but it improves film transportability, release properties, and thickness. From the perspective of suppressing the occurrence of unevenness and wrinkles, the total stretch ratio in the MD direction × TD direction (stretch in the MD direction) When the elongation ratio is m and the elongation ratio in the TD direction is n, the elongation ratio expressed as m × n is 1 Preferably 0.1 times or more, more preferably 1.2 times or more, and even more preferably 1.3 times or more. Particularly preferable is 1.5 times or more. However, there is no particular upper limit, but it is 3.0 times or less. The following is considered a guideline, preferably 2.7 times or less, more preferably less than 2.5 times, and even more preferably The ratio is less than 2.3 times. Also, when heat setting, methods known in this industry, such as contact type, are used. Heat treatment, non-contact heat treatment, etc. can be performed, and the type is not particularly limited. Non-contact heaters, ovens, blow machines, hot rolls, cooling rolls, hot presses, double Heat setting can be done using known equipment such as a belt heat press. At this time, if necessary Accordingly, a release film or porous film known in the industry is applied to the surface of the LCP stretched film. It can be arranged and subjected to heat and pressure treatment.

[0094] LCP stretched film (stretched form of LCP extruded film 100) LCP extruded film 10 The coefficient of linear expansion (CTE, α2, 23~200℃) in the MD and TD directions of 0 is the desired performance. It can be set appropriately according to the anisotropy of the rate of dimensional change and dimensional change From the perspective of reducing the absolute value of the coloration rate and improving adhesion to the metal foil, the values ​​were set to -20 to 1 respectively. Preferably, the concentration is within the range of 5 ppm / K, and each concentration is within the range of -15 to 10 ppm / K. It is more preferable that the concentrations are within the range of -10 to 5 ppm / K. Preferably, each value is within the range of -10 to 0 ppm / K. [Examples]

[0095] The features of the present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is... However, this is not limited in any way. That is, the materials shown in the following examples, The dosage, proportion, processing content, processing procedure, etc. may be changed as appropriate, as long as they do not deviate from the spirit of the present invention. This can be done. Furthermore, the values ​​of the various manufacturing conditions and evaluation results in the following examples are the actual results of the present invention. This has meaning as a preferred upper limit or preferred lower limit in the method of application, and is preferred The desired numerical range is a combination of the upper or lower limit mentioned above and the values ​​of the following examples or the values ​​of the examples themselves. The range defined by the combination is also clear.

[0096] [Melting viscosity] The melt viscosity [Pa·sec] of each LCP extruded film was measured under the following conditions. . Measuring instrument: Capillograph 1D (manufactured by Toyo Seiki Seisakusho Co., Ltd.) Equipment used: Cylinder length 10.00mm, cylinder diameter 1.00mm, barrel diameter 9.55mm Measurement conditions: Temperature [°C] and shear rate [sec] during extrusion molding of each LCP extruded film. -1 ]

[0097] [Hardness measurement using nanoindentation method] Each LCP extruded fill is processed using a nanoindentation method compliant with ISO 14577. The hardness H1 at a depth of 1 μm and the hardness H2 at the center of the thickness of the material were measured. Measurement equipment: Nanoindenter Hysitron TI 950 TriboIndenter (manufactured by Bruker) Indenter used: Diamond Berkovich type indenter Measurement conditions: Indentation depth hmax 0.05 μm Measurement method: Load-unload test Note that the measurement surface of each LCP extruded film is parallel to the MD direction of each LCP extruded film. The film has a smooth cross-section, and such a smooth cross-section of the film is obtained by freezing each LCP extruded film. It was manufactured by cutting using ion beam processing.

[0098] [Coefficient of linear expansion] Each LCP extruded film and LCP stretched film are processed using the TMA method in accordance with JIS K7197. The coefficient of thermal expansion of Lum was measured. Measuring instrument: TMA 4000SE (manufactured by NETZSCH) Measurement method: Tensile mode Measurement conditions: Sample size 25mm x 4mm x 50μm thickness Chuck spacing: 20mm Temperature range: 23-200℃ (2nd RUN) Heating rate: 5°C / min Atmosphere: Nitrogen (flow rate 50 ml / min) Test load 5gf *The value from 2ndRUN was used to see the value after the thermal history had been eliminated.

[0099] [Orientation degree] Using the Smartlab X-ray diffractometer (manufactured by Rigaku Corporation), the film surface S1 or F1 was measured by transmission. X-ray diffraction measurements were performed on each LCP extruded film, including the film surface S2, and the degree of orientation was measured for each. Here, a copper-filled tube was used as the X-ray source, and X-ray diffraction measurements were performed using a parallel beam optical system and transmission method. (2θ / θ scan, β scan) is performed, and first, the 2θ / θ scan yields 2θ = 19.5°. We confirmed that there is a peak top at 2θ=19.5 using a beta scan. By measuring the intensity from 0° to 360° in the azimuth direction relative to the element, the azimuth direction The intensity distribution was obtained. The base intensity (isotropic component) and peak intensity of the obtained β profile ( The degree of orientation was calculated from the orientation component based on the area ratio of the orientation peak using the above formula. Furthermore, the film surface S2 of each LCP extruded film is subjected to 23°C. Immersed in a 70% monoethylamine aqueous solution (manufactured by Daicel Corporation) for 168 hours under a 50% RH environment. Then, both surfaces of each LCP extruded film were etched to a thickness of 5 μm, and then washed with running water for 5 minutes. Then, wash with distilled water, dry at 80°C for 1 hour, and store in a 23°C and 50% RH environment for 24 hours. Each was adjusted by cooling for a set period of time.

[0100] [Tape peel test] The film surface of each LCP extruded film is coated with a chrome coating in accordance with JIS K5600-5-6. Adhesion tests were conducted using the scat method to confirm the presence or absence of a skin layer in each case. At this time, width Using Nichiban's cellophane tape (registered trademark) measuring 24mm x 50mm in length, peel off the tape. If there is no peeling in the grid pattern afterwards, it is called "no skin layer," and if there is peeling, it is called "skin layer." It was described as having "layers". ○ No skin layer × Skin layer present

[0101] [Dimensional change rate and anisotropy after metal foil etching] Each LCP extruded film has a 12μm thick electrolytic copper foil (TQ-M7VS manufactured by Mitsui Mining & Smelting Co., Ltd.) on both sides. By stacking P) and heat-pressing them together at a temperature of 320°C and a surface pressure of 1 MPa for 1 minute, copper foil A double-sided metal foil laminate was fabricated, each having a three-layer structure of / LCP extruded film / copper foil. And, in accordance with JPCA-UB01 (2017), the same standard's "16.4.4-18 Dimensional changes" The bifacial metal obtained according to the "conversion rate" and "16.4.4-2-2 Sample preparation by copper foil removal" Samples were prepared from foil-clad laminates and measured using a measuring microscope (Mitutoyo MF-A4020C). The dimensional change rate of each sample after copper foil etching was measured using [a specific method], and the anisotropy of the dimensional change rate was evaluated. Here, β1 represents the dimensional change rate in the MD direction, and β2 represents the dimensional change rate in the TD direction. ◎ The anisotropy of the dimensional change rate is very small (|β2-β1|≦0.3%) ○ Small anisotropy in dimensional change rate (0.3% < |β2 - β1| < 0.4%) × The anisotropy of the dimensional change rate is large (0.4% ≤ |β2 - β1|)

[0102] (Examples 1-3) As an intermediate layer, a type II thermoplastic liquid crystal polymer (monomer composition is p-hydroxybenzoic acid 7) A copolymer of 4 mol% and 26 mol% 6-hydroxy-2-naphthoic acid, at a temperature of 300°C and shear rate 500 sec -1 The melt viscosity is 80 Pa·sec), and the surface layers on both sides of the intermediate layer are used. Using polycarbonate PC (Teijin's Panlight L-1225L), see Table 1. Under the molding conditions shown, the machine is equipped with a T-die with a die width of 600 mm and a lip opening of 0.2 to 1.0 mm. Each resin is co-extruded at 300°C from a two-type three-layer extruder using the T-die casting method, and the intermediate layer A 50 μm thick, two-layer, three-part film was formed. From the formed two-layer, three-part film, the two surface layers of the poly The carbonate film was peeled off on the winding line, and the melting point was 280°C and the thickness was 50 μm. LCP extruded films of each of the three examples were obtained. Furthermore, glass cloth is placed between the pair of thermoplastic liquid crystal polymer films obtained in Examples 1 to 3. With (IPC No.#1037) sandwiched inside, use a hot press machine at 300°C for 5 minutes. Examples 1-3, which have a melting point of 280°C and a total thickness of 100 μm, are obtained by performing a heat-sealing process between them. An insulating material for circuit boards was obtained.

[0103] (Comparative Example 1) Type II thermoplastic liquid crystal polymer (monomer composition is p-hydroxybenzoic acid 74 mol%) 6-hydroxy-2-naphthoic acid 26 mol% copolymer, temperature 300°C and shear rate 5 00sec -1 The melt viscosity was 80 Pa·sec), and under the molding conditions shown in Table 1, the die width T-die casting from a single-layer extruder equipped with a 600mm T-die and a lip opening of 0.3mm A liquid crystal polymer is extruded at 300°C using the pulping method, resulting in a ratio with a melting point of 280°C and a thickness of 50 μm. An LCP extruded film for comparative example 1 was obtained.

[0104] (Comparative Examples 2-4) Except for changing the molding conditions as shown in Table 1, the same method as in Example 1 was used to produce a melting point of 28 Comparative Examples 2 to 4 LCP extruded films having a temperature of 0°C and a thickness of 50 μm were obtained.

[0105] [Table 1]

[0106] (Examples 4-6) Type I thermoplastic liquid crystal polymer (monomer composition is p- Hydroxybenzoic acid 79 mol%, 6-hydroxy-2-naphthoic acid 20 mol%, tere 1 mol% phthalic acid copolymer, temperature 330°C and shear rate 500 sec. -1 The melt viscosity is Except for using 70 Pa·sec as an intermediate layer and co-extruding each resin at 330°C, this is the same as Example 1. Similarly, LCP extruded filtrates of Examples 4-6 having a melting point of 315°C and a thickness of 50 μm were obtained. They each obtained Mu. Furthermore, glass cloth is placed between the thermoplastic liquid crystal polymer films of the pair of examples 4-6 obtained. With (IPC No.#1037) sandwiched inside, use a hot press machine at 330°C for 5 minutes. Examples 4-6, which have a melting point of 315°C and a total thickness of 100 μm, are obtained by performing a heat-sealing process between them. An insulating material for circuit boards was obtained.

[0107] (Comparative Example 5) Type I thermoplastic liquid crystal polymer (monomer composition is p- Hydroxybenzoic acid 79 mol%, 6-hydroxy-2-naphthoic acid 20 mol%, tere 1 mol% phthalic acid copolymer, temperature 330°C and shear rate 500 sec. -1 The melt viscosity is The procedure was the same as in Comparative Example 1, except that the liquid crystal polymer was extruded at 330°C using 70 Pa·sec. Using this method, an LCP extruded film of Comparative Example 2 having a melting point of 315°C and a thickness of 50 μm was obtained. .

[0108] (Comparative Examples 6-8) Except for changing the molding conditions as shown in Table 2, the same method as in Example 4 was used to produce a melting point of 31 Comparative Examples 6 to 8 LCP extruded films having a temperature of 5°C and a thickness of 50 μm were obtained.

[0109] [Table 2]

[0110] (Examples 7-9) Instead of polycarbonate, polymethylpentene PMP (TP, manufactured by Mitsui Chemicals) is used for the surface layers on both sides. Except for using X MX004), the same method as in Example 1 was used, with a melting point of 280°C and a thickness of 50 Examples 7-9 yielded LCP extruded films having a μm size. Furthermore, glass cloth is placed between the thermoplastic liquid crystal polymer films of the pair of examples 7-9 obtained. With (IPC No.#1037) sandwiched inside, use a hot press machine at 300°C for 5 minutes. By performing a heat-sealing process between them, Examples 7-9 have a melting point of 280°C and a total thickness of 100 μm. An insulating material for circuit boards was obtained.

[0111] (Comparative Examples 9-11) Except for changing the molding conditions as shown in Table 3, the same method as in Example 7 was used to produce a melting point of 28 Comparative Examples 9 to 11 LCP extruded films having a temperature of 0°C and a thickness of 50 μm were obtained.

[0112] [Table 3]

[0113] Tables 4-6 show the measurement results.

[0114] [Table 4]

[0115] [Table 5]

[0116] [Table 6]

[0117] Table 7 shows the measurement results. [Table 7]

[0118] The LCP extruded films obtained in Examples 1, 4, and 7 were subjected to TD method at 130°C using a uniaxial stretcher. By stretching it 1.5 times in the direction (total stretching ratio: 1.5 times) and heat setting it at 130°C for 2 minutes... LCP stretched films were obtained.

[0119] Table 8 shows the measurement results. [Table 8]

[0120] The LCP extruded films obtained in Examples 1, 4, and 7 were subjected to TD method at 130°C using a uniaxial stretcher. By stretching it 2.0 times in the direction (total stretching ratio: 2.0 times) and heat setting it at 130°C for 2 minutes... LCP stretched films were obtained.

[0121] Table 9 shows the measurement results. [Table 9] [Industrial applicability]

[0122] The LCP extruded film of the present invention is suitable for electronic circuit boards, multilayer substrates, high heat dissipation substrates, and flexible Widely used in applications such as printed circuit boards, antenna substrates, optoelectronic mixed-signal substrates, and IC packages. Furthermore, it is effectively usable, particularly suitable for ultra-fine machining and highly reliable, making it suitable for fifth-generation migration. Flexible printed circuit boards (FP) used in mobile communication systems (5G) and millimeter-wave radar, etc. It can be used particularly widely and effectively as an insulating material such as C) or as a metal foil-clad laminate. [Explanation of symbols]

[0123] 100 ···LCP extruded film 100a... surface 100b...plane H1 ···Hardness at a depth of 1 μm H2 ··Hardness at the center of the thickness S1 ···Film surface S2 ···Film surface with a depth of 5μm 200 ···Insulating material for circuit boards 300 ···Metal foil-clad laminate 400 ··Metal foil-clad laminate WF ···Woven fabric MF ···metal foil

Claims

1. LCP extruded fiber containing thermoplastic liquid crystal polymer with a thickness of 15 μm to 300 μm It is a film, The film cross-section, parallel to the MD direction, was measured using the nanoindentation method. The hardness H1 at a point located 1 μm deep in the thickness direction from the surface and the hardness H2 at the center of the thickness. The following conditions must be met: -10.0 ≤ 100 × (H2 - H1) / H1 ≤ 0.0, and JIS K The MD direction and T in the 23-200°C range are measured by the TMA method in accordance with 7197. The coefficient of linear expansion in direction D is within the range of -30 to 55 ppm / K. LCP extruded film.

2. The coefficient of linear expansion in the TD direction is 0 to 55 ppm / K. The LCP extruded film according to claim 1.

3. An outer layer, an intermediate layer, and the intermediate layer obtained by removing both outer layers from a laminated extruded film having an outer layer. It is a layer. The LCP extruded film according to claim 1 or 2.

4. The surface of the film is densely covered by a cross-cut method in accordance with JIS K5600-5-6. In adhesion tests, the tape does not have a peelable skin layer. The LCP extruded film according to any one of claims 1 to 3.

5. The hardness H2 at the center point of the thickness is 0.240 (GPa) or higher. The LCP extruded film according to any one of claims 1 to 4.

6. The hardness H1 at the point with a depth of 1 μm is 0.250 (GPa) or higher. The LCP extruded film according to any one of claims 1 to 5.

7. Further containing inorganic fillers The LCP extruded film according to any one of claims 1 to 6.

8. It is a T-die extruded film. The LCP extruded film according to any one of claims 1 to 7.

9. LCP extruded film according to any one of claims 1 to 8 and the LCP extruded film A laminate comprising a woven fabric provided on at least one side thereof, Insulating material for circuit boards.

10. LCP extruded film according to any one of claims 1 to 8 and the LCP extruded film It comprises metal foil provided on one side and / or both sides, Metal foil-clad laminate.

11. The present invention comprises at least one LCP extruded film and woven fabric according to any one of claims 1 to 8. The laminate comprises a laminate and metal foil provided on one and / or both sides of the laminate. Metal foil-clad laminate.

12. A stretched LCP extruded film according to any one of claims 1 to 8, comprising LCP stretched film.

13. The stretched body has a stretching ratio of 1.3 to 2.5 times that of the LCP extruded film (MD method). (Having direction × TD direction) The LCP stretched film according to claim 12.

14. The LCP stretched film according to claim 12 or 13 and at least the LCP stretched film It comprises a laminate having at least one woven fabric on one side, Insulating material for circuit boards.

15. The LCP stretched film according to claim 12 or 13 and one side of the LCP stretched film and Equipped with metal foil on both sides, Metal foil-clad laminate.

16. A laminate having at least the LCP stretched film and woven fabric described in claim 12 or 13 , comprising a metal foil provided on one side and / or both sides of the laminate, Metal foil-clad laminate.

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