Method for manufacturing thermoplastic liquid crystal polymer films

Abstract

This invention provides a manufacturing method for producing films with small film thickness tolerances using melt extrusion. [Solution] A method for manufacturing a thermoplastic liquid crystal polymer film using a pair of rolling rolls, wherein the pair of rolling rolls consists of a first roll and a second roll, both of which have metal surfaces, and comprises at least the steps of supplying molten extruded thermoplastic liquid crystal polymer resin between the first roll and the second roll, and a rolling step of passing the supplied thermoplastic liquid crystal polymer resin between the pair of rolling rolls to form a thermoplastic liquid crystal polymer film, wherein the first roll and / or the second roll are metal elastic rolls.

Description

Technical Field

[0001] The present invention relates to a method for producing a thermoplastic liquid crystal polymer film.

Background Art

[0002] Thermoplastic liquid crystal polymer films are widely used as base films for circuit boards in the fields of electric / electronic devices and automotive parts due to their excellent mechanical strength and electrical properties, etc.

[0003] As a method for producing a thermoplastic liquid crystal polymer film, a film-forming method by T-die extrusion has been conventionally studied.

[0004] Patent Document 1 discloses a method for producing an LCP extrusion film in which a resin composition for a first surface layer containing a thermoplastic resin, a resin composition for a central layer containing a thermoplastic liquid crystal polymer, and a resin composition for a second surface layer containing a thermoplastic resin are co-extruded from a two-kind three-layer extruder under specific shear stress and draw-down ratio conditions to form a two-kind three-layer film, and then the first and second surface layers are removed.

[0005] Also, Patent Document 2 describes using a rubber roll or the like for a pressure bonding roll in a production method by melt extrusion. Patent Document 3 has also studied a method of laminating a thermoplastic liquid crystal polymer film onto a metal sheet with a rolling roll including a metal elastic roll.

Prior Art Documents

[0007] However, in the method described in Patent Document 1, the melt-extruded thermoplastic resin is pressed with metal rolls, which causes a heat crown phenomenon where the metal rolls deform into an elliptical shape due to thermal expansion, resulting in a change in the gap between the rolls in the width direction. In particular, when the thickness of the thermoplastic resin layer decreases, there are problems such as the thickness tolerance becoming larger in the center and at the edges in the width direction. Thermoplastic liquid crystal polymers, which are engineering plastics, have a higher molding temperature than general resins, and the metal rolls used also become hot, making them prone to the heat crown phenomenon. Thus, it has been difficult to obtain a film with excellent thickness accuracy and good flatness by single-layer extrusion of thermoplastic liquid crystal polymers using a T-die. In the method described in Patent Document 2, when molten resin is pressed, the rubber roll becomes hot and cannot be separated from the molded film, causing the film to tear. Furthermore, with long-term use, the rubber lining on the surface of the rubber roll and the roll shaft can delaminate due to the high temperature. Although Patent Document 3 shows that metal elastic rolls have higher heat resistance than rubber rolls, the metal sleeve on the surface of the metal elastic roll is harder than the surface of the rubber roll. When a thermoplastic liquid crystal polymer is laminated with other thin films in the form of a molded film, there are problems such as lamination defects occurring due to insufficient film thickness tracking if there are local differences in film thickness.

[0008] The present invention aims to provide a method for producing films of melt-extruded thermoplastic liquid crystal polymer resins that have a small film thickness tolerance and can be produced stably over a long period of time even under high-temperature conditions. [Means for solving the problem]

[0009] The inventors of the present invention, after diligent research to achieve the above objective, discovered that by using a metal elastic roll when forming a film from a melt-extruded thermoplastic liquid crystal polymer resin, it is possible to manufacture a film with a small film thickness tolerance and stable performance over a long period of time even under high-temperature conditions, thus completing the present invention.

[0010] In other words, the present invention may be configured in the following embodiments. [Aspect 1] A method for producing a polymer film capable of forming an optically anisotropic molten phase (hereinafter referred to as a thermoplastic liquid crystal polymer film) using a pair of rolling rolls, wherein the pair of rolling rolls consists of a first roll and a second roll, both of which have metal surfaces. A method for manufacturing a thermoplastic liquid crystal polymer film, comprising at least the steps of: supplying a molten-extruded thermoplastic liquid crystal polymer resin between a first roll and a second roll; and a rolling step of passing the supplied thermoplastic liquid crystal polymer resin between a pair of rolling rolls to form a thermoplastic liquid crystal polymer film, wherein the first roll and / or the second roll are metallic elastic rolls.

[0011] [Aspect 2] A method for manufacturing a thermoplastic liquid crystal polymer film, wherein one of the pair of rolling rolls is a metal heating roll and the other roll is a metal elastic roll.

[0012] [Aspect 3] A method for producing a thermoplastic liquid crystal polymer film, according to embodiment 1 or 2, wherein the pressure between a pair of rolling rolls is 0.1 to 30 kg / mm ​​(preferably 0.1 to 20 kg / mm, more preferably 0.5 to 10 kg / mm, and even more preferably 1 to 5 kg / mm) in terms of linear pressure.

[0013] [Aspect 4] A method for producing a thermoplastic liquid crystal polymer film, comprising the step of cooling the surface of the metal elastic roll, according to any one of the three embodiments.

[0014] [Aspect 5] A method for manufacturing a thermoplastic liquid crystal polymer film, according to any one of embodiments 1 to 4, wherein the thickness of the thermoplastic liquid crystal polymer film is 5 μm or more and 500 μm or less.

[0015] [Aspect 6] The manufacturing method according to any one of Aspects 1 to 5, wherein the step of supplying the thermoplastic liquid crystal polymer resin is performed in a state where a release sheet is supplied to the first roll and / or the second roll. A method for manufacturing a thermoplastic liquid crystal polymer film.

[0016] [Aspect 7] The manufacturing method according to any one of Aspects 1 to 6, wherein the step of supplying the thermoplastic liquid crystal polymer resin is performed in a state where a shaping sheet is supplied to the first roll and / or the second roll. A method for manufacturing a thermoplastic liquid crystal polymer film.

[0017] [Aspect 8] The manufacturing method according to any one of Aspects 1 to 7, wherein the first roll is a metal heating roll, the second roll is a metal elastic roll, the metal heating roll is MR, the metal elastic roll is MER, the release sheet is RS, the shaping sheet is MS, and when the thermoplastic liquid crystal polymer resin is LCP, the arrangement of MR, MER, RS, MS, and LCP is as follows: MR / LCP / MER MR / RS / LCP / MER MR / LCP / RS / MER MR / RS / LCP / RS / MER MR / MS / LCP / MER MR / LCP / MS / MER, or MR / MS / LCP / MS / MER The step of supplying the thermoplastic liquid crystal polymer resin is performed so as to be as above. A method for manufacturing a thermoplastic liquid crystal polymer film.

[0018] [Aspect 9] The manufacturing method according to any one of Aspects 1 to 7, wherein the first roll is a metal elastic roll, the second roll is a metal heating roll, the metal elastic roll is MER, the metal heating roll is MR, the release sheet is RS, the shaping sheet is MS, and when the thermoplastic liquid crystal polymer resin is LCP, the arrangement of MER, MR, RS, MS, and LCP is as follows: MER / LCP / MR MER / RS / LCP / MR MER / LCP / RS / MR MER / RS / LCP / RS / MR MER / MS / LCP / MR MER / LCP / MS / MR, or MER / MS / LCP / MS / MR A method for manufacturing a thermoplastic liquid crystal polymer film, comprising a step of supplying a thermoplastic liquid crystal polymer resin so as to obtain the above.

Advantages of the Invention

[0019] According to the present invention, by shaping the melt-extruded thermoplastic liquid crystal polymer resin while nipping it with a pair of rolling rolls using at least one metal elastic roll, even if a heat crown phenomenon occurs in the metal roll when using the metal roll on the other side, the metal elastic roll follows the deformation and can mitigate the gap change. Therefore, it is possible to reduce the film thickness tolerance of the film, and it is possible to stably manufacture the film over a long period even in the shaping of a high-temperature molten resin.

Brief Description of the Drawings

[0020] [Figure 1] It is a schematic diagram for explaining a rolling device used in a method for manufacturing a thermoplastic liquid crystal polymer film according to a first embodiment of the present invention. [Figure 2] It is a schematic diagram for explaining a rolling device used in a method for manufacturing a thermoplastic liquid crystal polymer film according to a second embodiment of the present invention. [Figure 3] It is a schematic diagram for explaining a rolling device used in a method for manufacturing a thermoplastic liquid crystal polymer film according to a third embodiment of the present invention. [Figure 4] It is a schematic diagram for explaining a rolling device used in a method for manufacturing a thermoplastic liquid crystal polymer film according to a fourth embodiment of the present invention. [Figure 5] It is a schematic diagram for explaining a rolling device used in a method for manufacturing a thermoplastic liquid crystal polymer film according to a fifth embodiment of the present invention. [Figure 6] This is a schematic diagram illustrating a rolling apparatus used in a method for manufacturing a thermoplastic liquid crystal polymer film according to a sixth embodiment of the present invention. [Figure 7] This is a schematic diagram illustrating a rolling apparatus used in a method for manufacturing a thermoplastic liquid crystal polymer film according to a seventh embodiment of the present invention. [Figure 8] This is a schematic diagram illustrating a rolling apparatus used in a method for manufacturing a thermoplastic liquid crystal polymer film according to a modified example of the first embodiment of the present invention. [Modes for carrying out the invention]

[0021] <Method for manufacturing thermoplastic liquid crystal polymer film> The present invention relates to a method for manufacturing a thermoplastic liquid crystal polymer film, which is a method for manufacturing a polymer film capable of forming an optically anisotropic molten phase (hereinafter referred to as a thermoplastic liquid crystal polymer film) using a pair of rolling rolls, wherein the pair of rolling rolls consists of a first roll and a second roll, both of which have metal surfaces, and comprises at least the steps of supplying a molten-extruded thermoplastic liquid crystal polymer resin between the first roll and the second roll, and a rolling step of passing the supplied thermoplastic liquid crystal polymer resin between the pair of rolling rolls to form a thermoplastic liquid crystal polymer film, wherein the first roll and / or the second roll are metallic elastic rolls. Furthermore, supplying thermoplastic liquid crystal polymer resin between the first roll and the second roll includes not only the case where the resin is directly extruded toward the gap between the pair of rolling rolls, but also the case where the resin extruded onto the first roll or the second roll flows into the gap along the outer circumference of the roll. It also includes the case where a release sheet or shaping sheet is placed on the outer circumference of the first roll or the second roll, and the resin is supplied between the pair of rolling rolls via these sheets.

[0022] The above method may include a step of winding the formed thermoplastic liquid crystal polymer film onto a winding roll positioned horizontally away from the rolling rolls (horizontally, the rotation axis positioned horizontally away from the gap between the pair of rolling rolls). In this case, the rolling roll positioned horizontally away from the winding roll may be referred to as the first roll, and the rolling roll positioned closer to the winding roll may be referred to as the second roll.

[0023] (Thermoplastic liquid crystal polymer resin) In the description of the present invention, the thermoplastic liquid crystal polymer resin is a resin containing a thermoplastic liquid crystal polymer. The thermoplastic liquid crystal polymer is composed of a melt-mold liquid crystalline polymer (or a polymer capable of forming an optically anisotropic molten phase), and its chemical composition is not particularly limited as long as it is a melt-mold liquid crystalline polymer, but examples include thermoplastic liquid crystal polyester, or thermoplastic liquid crystal polyesteramide in which an amide bond is introduced thereto.

[0024] Furthermore, the thermoplastic liquid crystal polymer may be a polymer in which an aromatic polyester or aromatic polyesteramide is further modified by introducing isocyanate-derived bonds such as imide bonds, carbonate bonds, carbodiimide bonds, or isocyanurate bonds.

[0025] Specific examples of thermoplastic liquid crystal polymers used in the present invention include known thermoplastic liquid crystal polyesters and thermoplastic liquid crystal polyesteramides derived from compounds classified as (1) to (4) below and their derivatives. However, it goes without saying that there is an appropriate range for the combination of various raw material compounds in order to form a polymer that can form an optically anisotropic molten phase.

[0026] (1) Aromatic or aliphatic diols (see Table 1 for representative examples) [Table 1]

[0027] (2) Aromatic or aliphatic dicarboxylic acids (see Table 2 for representative examples) [Table 2]

[0028] (3) Aromatic hydroxycarboxylic acids (see Table 3 for representative examples) [Table 3]

[0029] (4) Aromatic diamines, aromatic hydroxyamines, or aromatic aminocarboxylic acids (see Table 4 for representative examples) [Table 4]

[0030] Typical examples of thermoplastic liquid crystal polymers obtained from these raw material compounds include copolymers having repeating units, as shown in Tables 5 and 6.

[0031] [Table 5] [Table 6]

[0032] Of these copolymers, copolymers containing p-hydroxybenzoic acid and / or 6-hydroxy-2-naphthoic acid as at least a repeating unit are preferred, and in particular, (i) copolymers containing repeating units of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, or (ii) copolymers containing repeating units of at least one aromatic hydroxycarboxylic acid selected from the group consisting of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, at least one aromatic diol and / or aromatic hydroxyamine, and at least one aromatic dicarboxylic acid are preferred.

[0033] For example, in copolymer (i), if the thermoplastic liquid crystal polymer contains repeating units of at least p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, the molar ratio (A) / (B) of p-hydroxybenzoic acid in repeating unit (A) to 6-hydroxy-2-naphthoic acid in repeating unit (B) is preferably about 10 / 90 to 90 / 10 in the thermoplastic liquid crystal polymer, more preferably about 15 / 85 to 85 / 15, and even more preferably about 20 / 80 to 80 / 20.

[0034] In the case of copolymer (i), in addition to the repeating units of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, repeating units composed of aromatic diols or aromatic dicarboxylic acids (e.g., terephthalic acid) may be included, from the viewpoint of adjusting the molecular weight, etc.

[0035] Furthermore, in the case of copolymer (ii), at least one aromatic hydroxycarboxylic acid (C) selected from the group consisting of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, at least one aromatic diol (D) selected from the group consisting of 4,4'-dihydroxybiphenyl, hydroquinone, phenylhydroquinone, and 4,4'-dihydroxydiphenyl ether, and at least one aromatic dicarb selected from the group consisting of terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid The molar ratio of acid (E) to each repeating unit in the thermoplastic liquid crystal polymer may be approximately (C):(D):(E) = (30~80):(35~10):(35~10), more preferably (C):(D):(E) = (35~75):(32.5~12.5):(32.5~12.5), and even more preferably (C):(D):(E) = (40~70):(30~15):(30~15).

[0036] Furthermore, the molar ratio of repeating units derived from 6-hydroxy-2-naphthoic acid among the aromatic hydroxycarboxylic acid (C) may be, for example, 85 mol% or more, preferably 90 mol% or more, and more preferably 95 mol% or more. The molar ratio of repeating units derived from 2,6-naphthalenedicarboxylic acid among the aromatic dicarboxylic acid (E) may be, for example, 85 mol% or more, preferably 90 mol% or more, and more preferably 95 mol% or more.

[0037] Furthermore, the aromatic diol (D) may be repeating units (D1) and (D2) derived from two different aromatic diols selected from the group consisting of hydroquinone, 4,4'-dihydroxybiphenyl, phenylhydroquinone, and 4,4'-dihydroxydiphenyl ether, in which case the molar ratio of the two aromatic diols may be (D1) / (D2) = 23 / 77 to 77 / 23, more preferably 25 / 75 to 75 / 25, and even more preferably 30 / 70 to 70 / 30.

[0038] Furthermore, the molar ratio of repeating structural units derived from aromatic diols to repeating structural units derived from aromatic dicarboxylic acids is preferably (D) / (E) = 95 / 100 to 100 / 95. If the ratio deviates from this range, the degree of polymerization does not increase and the mechanical strength tends to decrease.

[0039] Furthermore, the ability to form an optically anisotropic molten phase as referred to in this invention can be determined, for example, by placing the sample on a hot stage, heating it in a nitrogen atmosphere, and observing the transmitted light of the sample.

[0040] The melting point (Tm0) of the thermoplastic liquid crystal polymer resin is preferably in the range of 200 to 380°C, more preferably in the range of 260 to 370°C, even more preferably in the range of 300 to 360°C, even more preferably in the range of 305 to 355°C, and particularly preferably in the range of 310 to 350°C. The melting point of the thermoplastic liquid crystal polymer resin can be obtained by observing the thermal behavior of the thermoplastic liquid crystal polymer resin sample using a differential scanning calorimeter. Specifically, the melting point (Tm0) of the thermoplastic liquid crystal polymer resin can be determined by heating the thermoplastic liquid crystal polymer resin sample from room temperature (e.g., 25°C) at a rate of 10°C / min until it is completely melted at 400°C, then cooling the molten material to 50°C at a rate of 10°C / min, and then heating it again at a rate of 10°C / min, at which point the position of the endothermic peak that appears is taken.

[0041] Furthermore, from the viewpoint of melt moldability, the thermoplastic liquid crystal polymer resin may have, for example, a melt viscosity of 30 to 120 Pa·s at a shear rate of 1000 / s at (Tm0+20)°C, and preferably a melt viscosity of 50 to 100 Pa·s.

[0042] The thermoplastic liquid crystal polymer resin may contain thermoplastic polymers such as polyethylene terephthalate, modified polyethylene terephthalate, polyolefin, polycarbonate, polyarylate, polyamide, polyphenylene sulfide, polyether ether ketone, and fluororesin, as well as various additives, to the extent that the effects of the present invention are not impaired. It may also contain fillers such as organic fillers and inorganic fillers as needed. Therefore, the thermoplastic liquid crystal polymer resin includes thermoplastic liquid crystal polymers as the main component, and also includes thermoplastic liquid crystal polymer compositions containing one or more of these different polymers, additives, and fillers.

[0043] The thermoplastic liquid crystal polymer resin may contain 50% by weight or more of thermoplastic liquid crystal polymer, preferably 80% by weight or more, more preferably 90% by weight or more, even more preferably 95% by weight or more, and even more preferably 98% by weight or more.

[0044] (Supplying process for thermoplastic liquid crystal polymer resin) The present invention relates to a method for producing a thermoplastic liquid crystal polymer film using a pair of rolling rolls, wherein the pair of rolling rolls consists of a first roll and a second roll, both of which have metal surfaces, and the method comprises at least a step of supplying a molten-extruded thermoplastic liquid crystal polymer resin between the first roll and the second roll.

[0045] In the present invention, the step of supplying the thermoplastic liquid crystal polymer resin may be performed with a release sheet or shaping sheet supplied to the first roll and / or the second roll. For example, if the first roll is a metal heating roll and the second roll is a metal elastic roll, and the metal heating roll is MR, the metal elastic roll is MER, the release sheet is RS, the shaping sheet is MS, and the thermoplastic liquid crystal polymer resin is LCP, then the arrangement of MR, MER, LCP, and RS and MS (if used) is as follows: MR / LCP / MER MR / RS / LCP / MER MR / LCP / RS / MER MR / RS / LCP / RS / MER MR / MS / LCP / MER MR / LCP / MS / MER, or MR / MS / LCP / MS / MER The process of supplying the thermoplastic liquid crystal polymer resin may be carried out in such a manner.

[0046] In the present invention, the step of supplying the thermoplastic liquid crystal polymer resin may be performed with a release sheet or shaping sheet supplied to the first roll and / or the second roll. For example, if the first roll is a metal elastic roll and the second roll is a metal heated roll, and the metal elastic roll is MER, the metal heated roll is MR, the release sheet is RS, the shaping sheet is MS, and the thermoplastic liquid crystal polymer resin is LCP, then the arrangement of MER, MR, LCP, and RS and MS (if used) is as follows: MER / LCP / MR MER / RS / LCP / MR MER / LCP / RS / MR MER / RS / LCP / RS / MR MER / MS / LCP / MR MER / LCP / MS / MR, or MER / MS / LCP / MS / MR The process of supplying the thermoplastic liquid crystal polymer resin may be carried out in such a manner.

[0047] In the manufacturing method of the present invention, the method of melt-extruding the thermoplastic liquid crystal polymer resin is not particularly limited, and any extruder can be used as long as the orientation of the rigid rod-shaped molecules of the thermoplastic liquid crystal polymer can be controlled, such as a single-screw extruder, twin-screw extruder, or multi-screw extruder.

[0048] It is preferable to then supply the molten resin obtained by a melting means such as an extruder to a die using a gear pump. Using a gear pump reduces fluctuations in the discharge volume in the extruder, improves the stability of the supply speed (supply volume / time), and improves the stability of the film thickness. The molten resin supplied at a stable supply speed by the gear pump, or the molten resin supplied directly from the extruder, is supplied to the die, for example, through a tubular flow path, and discharged from the die in the form of a film.

[0049] As for the die, conventionally known dies can be used to form the molten resin that is extruded in a film-like manner, and dies of various structures can be used. In the manufacturing method of the present invention, it is preferable to use a T-die to supply the thermoplastic liquid crystal polymer resin that has been molten extruded to the first roll.

[0050] The T-die temperature is preferably Tm0 to (Tm0+50)°C, more preferably (Tm0+5) to (Tm0+40)°C, and even more preferably (Tm0+10) to (Tm0+30)°C, based on the melting point (Tm0) of the thermoplastic liquid crystal polymer resin. In this invention, since the surfaces of both the first and second rolls constituting the pair of rolling rolls are formed of metal, long-term stable manufacturing is possible even when molding molten resin discharged from such a high-temperature T-die.

[0051] (Rolling process of thermoplastic liquid crystal polymer resin) The present invention relates to a method for producing a thermoplastic liquid crystal polymer film using a pair of rolling rolls, comprising at least a rolling step of passing a thermoplastic liquid crystal polymer resin between the pair of rolling rolls to form a thermoplastic liquid crystal polymer film.

[0052] The first roll and / or second roll constituting the pair of rolling rolls are metallic elastic rolls. Preferably, one roll of the pair of rolling rolls is a metal heating roll and the other roll is a metallic elastic roll. A metallic elastic roll is a roll composed of an elastic body roll and a metal surface layer formed around it. An elastic body roll is a roll that has the characteristic of being more elastically deformable than a metal roll. The material constituting the elastic body roll is not particularly limited to organic or inorganic materials, but examples of organic materials include preferably rubber rolls, more preferably heat-resistant rubber rolls. Examples of inorganic materials include inorganic nonwoven fabric rolls. Alternatively, a hollow roll made of metal or heat-resistant resin filled with air or an inert gas at a constant pressure may be used. In that case, a hollow roll with a metal layer as its outer shell filled with air or an inert gas may be used as a metallic elastic roll. Alternatively, a roll comprising an axial roll and a thin metal film covering the outer surface of the axial roll, with a fluid sealed between the axial roll and the thin metal film, may be used. The thin metal film is fixed at both ends of the axial roll, and the fluid sealed between the thin metal film and the axial roll can be, for example, water or oil. By controlling the temperature of this fluid, it becomes possible to control the temperature of the metal elastic roll.

[0053] The hardness of the heat-resistant rubber roll used in metal elastic rolls is not particularly limited as long as it is suitable for the molding temperature, but it may be between 60 and 250 degrees, more preferably between 70 and 200 degrees, and more preferably between 80 and 150 degrees. The hardness referred to is the hardness measured according to JIS K 6253-3:2012.

[0054] The thickness of the metal surface layer formed around the elastic roll may be, for example, 100 to 1000 μm, preferably 150 to 800 μm, and more preferably 200 to 500 μm. The metal surface layer is formed from a metal with excellent heat resistance and rigidity (e.g., nickel, stainless steel, etc.), and depending on the thickness and material, it may be a cylindrical plating layer or a metal sheet processed into a cylindrical shape.

[0055] For example, the metal elastic roll may be a heat-resistant rubber roll with a hardness of 90 degrees to which a metal band with a thickness of 380 μm is attached to the outer circumference, and the metal surface of the metal elastic roll may have a ten-point average roughness Rzjis of 0.2 μm or less. The ten-point average roughness Rzjis is measured in accordance with JIS B 0601:2001.

[0056] When metal elastic rolls are used for extended periods, they gradually heat up, and the sleeve (metal band) of the metal elastic roll may expand due to heat and detach. Therefore, it is preferable to have a mechanism for cooling the surface of the metal elastic roll. Examples of cooling methods include cooling the entire roll by passing cooling water through it, or using the roll while cooling the sleeve with cold air. The process of cooling the surface of the metal elastic roll may be performed continuously or intermittently during the rolling process.

[0057] The heating method for the metal heating roll is not particularly limited, but dielectric heating or IR heating is preferable. In addition, to reduce shape changes due to the heat crowning phenomenon, a segmented heating type roll may be used. A segmented heating type is a method in which heating is performed in multiple parts along the rotation axis of the roll, and the heating temperature of each part is controlled individually. Furthermore, to reduce the effects of the heat crowning phenomenon, the surface of the metal heating roll may be machined in advance, for example, so that the diameter of the center is smaller than the diameters of both ends, and the roll is formed into a shape that becomes flat during rolling.

[0058] From the viewpoint of reducing the film thickness tolerance of the thermoplastic liquid crystal polymer film, the surface temperature of the metal heating roll is preferably (Tm0-250) to (Tm0-10)°C, more preferably (Tm0-150) to (Tm0-30)°C, and even more preferably (Tm0-120) to (Tm0-60)°C, based on the melting point (Tm0) of the thermoplastic liquid crystal polymer resin.

[0059] In the manufacturing method of the present invention, the pressure between a pair of rolling rolls is preferably 0.1 to 30 kg / mm ​​in terms of linear pressure. More preferably 0.1 to 20 kg / mm, even more preferably 0.5 to 10 kg / mm, and particularly preferably 1.0 to 5.0 kg / mm.

[0060] The rolling of thermoplastic liquid crystal polymer resin may be done by simply applying pressure to the resin using a metal elastic roll paired with a metal roll, without calculating the gap. Alternatively, the thickness of the melt-extruded thermoplastic liquid crystal polymer film may be adjusted by adjusting the gap between the pair of rolling rolls.

[0061] In molten resin extrusion molding, stretching may be performed to control orientation. For example, in T-die extrusion molding, after molding the thermoplastic liquid crystal polymer resin extruded from the T-die into a film, stretching in the MD direction of the thermoplastic liquid crystal polymer film can be applied by winding it up faster than the molten extrusion speed. Furthermore, stretching in the TD direction is possible during rolling, and the stretching ratio can be adjusted by the winding speed of the thermoplastic liquid crystal polymer film and the pressure applied by the rolling roll. Film formation may also be performed while simultaneously stretching in the MD and TD directions.

[0062] (Release sheet) In the present invention, the steps of supplying the thermoplastic liquid crystal polymer resin and rolling the resin may be performed with a release sheet supplied to the first roll and / or the second roll. The release sheet is not particularly limited as long as it can be easily peeled off after the thermoplastic liquid crystal polymer film is formed, and examples include heat-resistant resin sheets such as polyimide film, aramid film, and Teflon® film; heat-resistant composite sheets (for example, composite sheets made up of multiple heat-resistant resin sheets); and heat-resistant nonwoven fabrics made of heat-resistant fibers (for example, heat-resistant resin fibers), metal sheets (gold, silver, copper, iron, tin, nickel, aluminum, chromium, or alloys thereof). When multiple release sheets are used, the same release sheet may be used, or two or more types may be used in combination.

[0063] The thickness of the release sheet can be set as appropriate as needed, for example, it may be around 10 to 300 μm, preferably in the range of 20 to 150 μm, and more preferably in the range of 25 to 100 μm.

[0064] Furthermore, to improve the peelability from the thermoplastic liquid crystal polymer film after the rolling process, one or both sides of the release sheet may be treated with a release agent. Examples of release agent methods include applying a heat-resistant release resin coating, such as a silicone resin or fluororesin, to at least one side of the release sheet.

[0065] (Shaping sheet) In the present invention, the steps of supplying the thermoplastic liquid crystal polymer resin and rolling the resin may be performed with the shaped sheet supplied to the first roll and / or the second roll. The shaped sheet is preferably a metal sheet on which at least one surface has a shaped surface. There are no particular restrictions on the metal used to form the shaped sheet; for example, it may be gold, silver, copper, iron, tin, nickel, aluminum, chromium, or alloys thereof. For example, it may be a metal foil formed from the aforementioned metals, and copper foil or stainless steel foil is preferred from the viewpoint of ease of handling and cost. These metal foils can be manufactured by rolling or electrolytic methods, and surface treatments such as roughening may be performed to obtain the desired shaped surface.

[0066] The shaping surface of the shaping sheet may, for example, have a ten-point average roughness (Rzjis) of 1.0 to 7.0 μm. In the manufacturing method of the present invention, it is possible to transfer the ten-point average roughness (Rzjis) of the shaping surface of the shaping sheet to form irregularities on the surface of the thermoplastic liquid crystal polymer film with the same ten-point average roughness (Rzjis) as the shaping sheet. Furthermore, the ten-point average roughness (Rzjis) of the shaping surface of the shaping sheet may preferably be 1.5 to 5.5 μm, more preferably 2.0 to 4.5 μm. Here, the ten-point average roughness (Rzjis) refers to the ten-point average roughness measured using a contact-type surface roughness meter with reference to JIS B 0601:2001, and represents the sum of the average of the five highest peak heights from the highest peak on the roughness curve of a reference length and the average of the five deepest valley depths from the deepest valley bottom.

[0067] From the viewpoint of facilitating separation from the thermoplastic liquid crystal polymer film after the rolling process, the shaping surface of the shaping sheet may be treated with a release agent. A method of release treatment may be, for example, applying a release agent to the shaping surface of the shaping sheet to create a release layer. Examples of release agents include silicone resins and fluororesins.

[0068] The thickness of the shaping sheet can be set as appropriate as needed, for example, it may be around 5 to 50 μm, and more preferably in the range of 9 to 35 μm.

[0069] Hereinafter, exemplary embodiments of the present invention will be described with reference to the drawings. For example, Figure 1 is a schematic diagram showing a rolling apparatus 1 used in a method for manufacturing a thermoplastic liquid crystal polymer film according to the first embodiment of the present invention. The rolling apparatus 1 includes a pair of rolling rolls 10A, an extruder 30 for extruding molten thermoplastic liquid crystal polymer resin 20 toward the rolling rolls 10A, a cooling roll 40, and a winding roll 50. The rolling rolls 10A consist of a first roll 11 and a second roll 12. In this example, the first roll 11 is a metal roll (metal heating roll) equipped with a heating mechanism (not shown), and the second roll 12 is a metal elastic roll consisting of an elastic roll 12a and a metal layer 12b. In the example shown, the extruder 30 includes a hopper 30a into which the resin raw material is fed, a kneading device (extruder) 30b for heating, kneading, and extruding the raw resin, a gear pump 30c, and an extrusion die 30d for extruding the molten resin supplied from the kneading device 30b via the gear pump 30c. The molten thermoplastic liquid crystal polymer resin 20 extruded from the extrusion die 30d is supplied between the first roll 11 and the second roll 12 of the rolling roll 10A, rolled through the first roll 11 and the second roll 12 to form a film, cooled by the cooling roll 40, and wound up as a thermoplastic liquid crystal polymer film 21 by the winding roll 50.

[0070] Figure 2 is a schematic diagram showing a rolling mill 2 used in a method according to a second embodiment of the present invention. In the following figures, components identical to those in the apparatus 1 of Figure 1 are denoted by the same reference numerals and their descriptions are omitted. The rolling mill 2 is equipped with an unwinding roll 70 for unwinding the release sheet 60 on the upstream side of the rolling roll 10A, and two winding rolls 51 and 52 on the downstream side. The release sheet 60 is supplied toward the first roll 11, which is made of metal, before the start of the process of supplying the thermoplastic liquid crystal polymer resin 20, and after being conveyed in contact with the outer circumferential surface 11a of the first roll 11, it is pressed against the molten thermoplastic liquid crystal polymer resin 20 extruded from the extruder 30 in the gap between the first roll 11 and the second roll 12. The thermoplastic liquid crystal polymer resin 20 passes through the gap in the form of a laminate with the release sheet 60, is cooled by the cooling roll 40, is peeled off from the release sheet 60 and wound up in the form of a thermoplastic liquid crystal polymer film 21 by the first winding roll 51, and the release sheet 60 is wound up by the second winding roll 52.

[0071] Figure 3 is a schematic diagram showing a rolling apparatus 3 used in a method for manufacturing a thermoplastic liquid crystal polymer film according to a third embodiment of the present invention. This rolling apparatus 3 has the same configuration as the apparatus shown in Figure 2, except that the first roll 13 constituting the rolling roll 10B is a metal elastic roll consisting of an elastic roll 13a and a metal layer 13b, and the second roll 14 is a metal heating roll. The release sheet 60 is supplied toward the first roll 13 before the start of the process of supplying the thermoplastic liquid crystal polymer resin 20, and after being conveyed in contact with the outer peripheral surface 13c of the first roll 13, it is pressed against the molten thermoplastic liquid crystal polymer resin 20 extruded from the extruder 30 in the gap between the first roll 13 and the second roll 14. The thermoplastic liquid crystal polymer resin 20 passes through the gap in the form of a laminate with the release sheet 60, is cooled by the cooling roll 40, peels off from the release sheet 60 and is wound up in the form of a thermoplastic liquid crystal polymer film 21 by the first winding roll 51, and the release sheet 60 is wound up by the second winding roll 52.

[0072] Figure 4 is a schematic diagram showing a rolling apparatus 4 used in a method for manufacturing a thermoplastic liquid crystal polymer film according to a fourth embodiment of the present invention. In this apparatus, two unwinding rolls 71 and 72 are arranged upstream of the rolling roll 10A, and three winding rolls 51, 52, and 53 and a pair of auxiliary rolls R that assist in peeling off the release sheet 60 are arranged downstream. The release sheet 60 is unwound from the unwinding rolls 71 and 72, respectively, and the supply of the release sheet 60 to the first roll 11 and the second roll 12 and winding by the second and third winding rolls 52 and 53 begin even before the start of the process of supplying the thermoplastic liquid crystal polymer resin 20. The thermoplastic liquid crystal polymer resin 20 extruded in a molten state from the extrusion die 30d of the extruder 30 is formed into a film as it passes between the pair of rolling rolls 10A, cooled by the cooling roll 40, peeled off from the release sheet 60, and wound onto the first winding roll 51 in the form of a thermoplastic liquid crystal polymer film 21.

[0073] Figure 5 is a schematic diagram showing a rolling mill 5 used in a method for manufacturing a thermoplastic liquid crystal polymer film according to a fifth embodiment of the present invention. The configuration of the rolling mill 5 is basically the same as that of the rolling mill 2 used in the second embodiment, but in this embodiment, the shaping sheet 80 is unwound from the unwinding roll 70, and before the start of the process of supplying the thermoplastic liquid crystal polymer resin, the supply of the shaping sheet 80 toward the first roll 11 and winding by the second winding roll 52 are started. The thermoplastic liquid crystal polymer resin 20 extruded in a molten state from the extrusion die 30d of the extruder 30 is pressed onto the shaping sheet 80 as it passes between the rolling rolls 10A and formed into a film, and after being cooled by the cooling roll 40, it is wound up as a thermoplastic liquid crystal polymer film 21A with one side surface shaped by the first winding roll 51.

[0074] Figure 6 is a schematic diagram showing a rolling mill 6 used in a method for manufacturing a thermoplastic liquid crystal polymer film according to the sixth embodiment of the present invention. The configuration of the rolling mill 6 is basically the same as that of the rolling mill 3 used in the third embodiment described above, but in this embodiment, a shaping sheet 80 is unwound from the unwinding roll 70 instead of a release film 60, and before the start of the process of supplying the thermoplastic liquid crystal polymer resin, the supply of the shaping sheet 80 toward the first roll 13 and winding by the second winding roll 52 are started. The thermoplastic liquid crystal polymer resin 20 extruded in a molten state from the extrusion die 30d of the extruder 30 is pressed onto the shaping sheet 80 as it passes between the rolling rolls 10B and formed into a film, and after being cooled by the cooling roll 40, it is wound up as a thermoplastic liquid crystal polymer film 21A with one side surface shaped by the first winding roll 51.

[0075] Figure 7 is a schematic diagram showing a rolling mill 7 used in a method for manufacturing a thermoplastic liquid crystal polymer film according to the seventh embodiment of the present invention. The configuration of the rolling mill 7 is basically the same as that of the rolling mill 4 used in the fourth embodiment described above, but in this embodiment, the supply of the shaped sheet 80 to the first roll 11 and the second roll 12 and winding by the second and third winding rolls 52 and 53 begin before the start of the process in which the shaped sheet 80 is unwound from the first unwinding roll 71 and the second unwinding roll 72 and the molten thermoplastic liquid crystal polymer resin 20 is supplied. The thermoplastic liquid crystal polymer resin 20 extruded in a molten state from the extrusion die 30d of the extruder 30 is formed into a film as it passes between a pair of rolling rolls 10A, cooled by the cooling roll 40, separated from the shaped sheet 80, and wound onto the first winding roll 51 in the form of a thermoplastic liquid crystal polymer film 21B with both sides shaped.

[0076] It should be noted that the embodiments of the present invention are not limited to embodiments 1 to 7 described above, and various modifications are possible. For example, Figure 8 is a schematic diagram showing a modified example of the rolling mill 1 used in the first embodiment shown in Figure 1. In this modified example, the rolling mill 1 is equipped with a cooling mechanism 90 near the second roll 12 of the rolling roll 10, and is configured to prevent overheating of the second roll 12 by blowing cold air onto the metal layer 12b of the second roll 12 during the process of molding the thermoplastic liquid crystal polymer resin 20. Although not shown, the second roll 12 (metal elastic roll) may also be equipped with an internal cooling mechanism. In the second to seventh embodiments shown in Figures 2 to 7, the rolling mills 2 to 7 may also be equipped with a cooling mechanism for cooling the metal elastic rolls (12, 13).

[0077] (Thermoplastic liquid crystal polymer film) The melting point (Tm) of the thermoplastic liquid crystal polymer film is preferably in the range of 200 to 380°C, more preferably in the range of 260 to 370°C, even more preferably in the range of 300 to 360°C, even more preferably in the range of 305 to 355°C, and particularly preferably in the range of 310 to 350°C. It may also be 260°C or higher, preferably in the range of 260 to 380°C, more preferably in the range of 280 to 370°C, and even more preferably in the range of 300 to 360°C. The melting point (Tm) of the thermoplastic liquid crystal polymer film can be obtained by observing the thermal behavior of a thermoplastic liquid crystal polymer film sample using a differential scanning calorimeter. In other words, the melting point (Tm) of the thermoplastic liquid crystal polymer film can be determined by heating a thermoplastic liquid crystal polymer film sample from room temperature (e.g., 25°C) at a rate of 10°C / min until it is completely melted at 400°C, then cooling the molten material to 50°C at a rate of 10°C / min, and finally heating it again at a rate of 10°C / min, and observing the position of the endothermic peak that appears at that point.

[0078] The thickness of the thermoplastic liquid crystal polymer film can be set appropriately depending on the application. For example, when considering its use as a material for the insulating layer of a circuit board, it may be 5 to 500 μm, preferably 10 to 300 μm, more preferably 15 to 250 μm, even more preferably 20 to 200 μm, and particularly preferably 25 to 150 μm.

[0079] <Metal-clad laminate> The thermoplastic liquid crystal polymer film produced in this case may use metal foil and form a laminate as a metal-clad laminate by a known method.

[0080] The thickness of the metal foil may be, for example, 1 to 100 μm, and a surface roughening treatment may be used. The thermoplastic liquid crystal polymer film and the metal foil can be heat-pressed together using a pair of metal rolls, or a metal roll and a rubber roll, by applying a pressure of about 0.1 to 30 kg / mm ​​using a roll-to-roll method while heating at a heating temperature in the range of (Tm-80)°C to (Tm)°C relative to the melting point (Tm) of the thermoplastic liquid crystal polymer film.

[0081] During heat bonding, the overlapping thermoplastic liquid crystal polymer film and metal foil may be bonded together by overlapping them so that a protective material such as a polyimide film is in contact with the outside of the overlapping film, then introducing them into a pair of pressure rolls and heat bonding them to form a metal-clad laminate.

[0082] The metal-clad laminate may be heat-treated. The heat treatment process may be performed downstream of the metal-clad laminate after molding, without winding, or it may be performed after the heat-compression bonding process has been performed and the laminate has been wound.

[0083] From the viewpoint of mitigating the distortion of the thermoplastic liquid crystal polymer film, heat treatment is preferably carried out by a non-contact heating method. Examples of known heating methods include ambient heating and radiant heating using electromagnetic waves such as infrared rays and microwaves, and examples of heat sources include hot air ovens, steam ovens, electric heaters, infrared heaters, ceramic heaters, and microwave irradiators.

[0084] The heat treatment temperature is preferably above the melting point (Tm) of the thermoplastic liquid crystal polymer film. For example, the temperature may be between Tm and Tm+50°C, or in the range of Tm+5°C to Tm+30°C. The heat treatment time may be in the range of 10 to 180 seconds, preferably 15 to 120 seconds, and more preferably 20 to 90 seconds. [Examples]

[0085] The present invention will be described in more detail below with reference to examples, but the present invention is not limited in any way by these examples. In the following examples and comparative examples, various physical properties were measured by the methods described below. In these examples, metal elastic rolls may be abbreviated as MER, metal heating rolls as MR, release sheets as RS, shaping sheets as MS, and thermoplastic liquid crystal polymer resin as LCP.

[0086] [Method for measuring film thickness] For film thickness measurement, three MD30mm x TD500mm sections of thermoplastic liquid crystal polymer film (600mm wide) prepared in the examples and comparative examples were cut from adjacent sections. Five measurements (L, LC, C, RC, R) were taken at 10cm intervals in the width direction, with the center (C) as the reference point. Film thickness was measured using a calibrated and inspected Mitutoyo Corporation micrometer MDC-25MX, and the average of three measurements was taken as the film thickness at each measurement point. The mean and standard deviation were calculated from the obtained film thickness values.

[0087] [Example 1] (Configuration: MR / LCP / MER) As shown in Figure 1, a thermoplastic liquid crystal polymer film was manufactured using an MR / LCP / MER configuration. Specifically, a thermoplastic liquid crystal polymer resin (a copolymer with a monomer composition of 77 mol% p-hydroxybenzoic acid and 23 mol% 6-hydroxy-2-naphthoic acid, with a melting point of 310°C) was extruded at 340°C using the T-die casting method from an extruder equipped with a T-die with a die width of 600 mm and a lip opening of 1.0 mm. The thermoplastic liquid crystal polymer resin extruded from the T-die was rolled between a 400 mm diameter metal heating roll heated to 230°C and a 400 mm diameter metal elastic roll until the film thickness was approximately 25 μm. After that, it was cooled to obtain a thermoplastic liquid crystal polymer film. The metal elastic roll used was a heat-resistant rubber roll with a hardness of 90 degrees, with a metal band with a thickness of 380 μm attached to its outer circumference. The metal surface of the metal elastic roll had a ten-point average roughness Rzjis of 0.2 μm or less. The pressure between the metal heating roll and the metal elastic roll was set to 1.9 kg / mm.

[0088] [Example 2] (Configuration: MR / RS / LCP / MER) As shown in Figure 2, a thermoplastic liquid crystal polymer film was obtained in the same manner as in Example 1, except that a polyimide (Kaneka Corporation's "Apical" registered trademark, 50 μm) was placed as a release sheet between the metal heating roll and the melt-extruded thermoplastic liquid crystal polymer resin.

[0089] [Example 3] (Configuration: MER / RS / LCP / MR) As shown in Figure 3, a thermoplastic liquid crystal polymer film was obtained in the same manner as in Example 1, except that a polyimide (Kaneka Corporation's "Apical" registered trademark, 50 μm) was inserted as a release sheet between the metal elastic roll and the melt-extruded thermoplastic liquid crystal polymer resin. The film thickness was adjusted to approximately 50 μm.

[0090] [Example 4] (Configuration: MR / RS / LCP / RS / MER) As shown in Figure 4, a thermoplastic liquid crystal polymer film was obtained in the same manner as in Example 1, except that polyimide (Kaneka Corporation's "Apical" registered trademark, 50 μm) was placed on both sides of the melt-extruded thermoplastic liquid crystal polymer resin as a release sheet. The film thickness was adjusted to approximately 75 μm.

[0091] [Comparative Example 1] (Configuration: MR / LCP / MR) Using a thermoplastic liquid crystal polymer resin (a copolymer with a monomer composition of 77 mol% p-hydroxybenzoic acid and 23 mol% 6-hydroxy-2-naphthoic acid, with a melting point of 310°C), the resin was extruded at 320°C using the T-die casting method from an extruder equipped with a T-die with a die width of 600 mm and a lip opening of 1.0 mm. The extruded film was then taken up between a pair of 400 mm diameter metal heating rolls heated to 230°C, with a pressure set to 1.9 kg / mm, until the film thickness reached approximately 50 μm, and then cooled to obtain a thermoplastic liquid crystal polymer film.

[0092] [Comparative Example 2] (Configuration: MR / LCP / MR) Using a thermoplastic liquid crystal polymer resin (a copolymer with a monomer composition of 77 mol% p-hydroxybenzoic acid and 23 mol% 6-hydroxy-2-naphthoic acid, with a melting point of 310°C), the resin was extruded at 320°C using the T-die casting method from an extruder equipped with a T-die with a die width of 600 mm and a lip opening of 1.0 mm. The film was then taken up between a pair of metal heating rolls with a diameter of 400 mm heated to 230°C, with a pressure set to 1.9 kg / mm, until the film thickness reached approximately 75 μm, and then cooled to obtain a thermoplastic liquid crystal polymer film.

[0093] [Comparative Example 3] (Configuration: RR / LCP / MR) Using a thermoplastic liquid crystal polymer (a copolymer with a monomer composition of 77 mol% p-hydroxybenzoic acid and 23 mol% 6-hydroxy-2-naphthoic acid, melting point 310°C), the resin was extruded at 320°C using the T-die casting method from an extruder equipped with a T-die with a die width of 600 mm and a lip opening of 1.0 mm. The film was then taken up between a heated roll with a diameter of 400 mm heated to 230°C and a pair of heat-resistant rubber rolls (RR) with a diameter of 400 mm and a hardness of 85 degrees, with a pressure set to 1.9 kg / mm, and the film was taken up to a thickness of approximately 50 μm. However, the thermoplastic liquid crystal polymer film stuck to the surface of the rubber rolls and tore, making it impossible to obtain.

[0094] The standard deviation of the film thickness was evaluated for the thermoplastic liquid crystal polymer films of Examples 1-4 and Comparative Examples 1-3 using the method described above. The results are shown in Table 7.

[0095] [Table 7]

[0096] As shown in Table 7, the use of metallic elastic rolls reduces film thickness variation and improves the standard deviation. [Industrial applicability]

[0097] The method for producing a thermoplastic liquid crystal polymer film of the present invention is suitable for melt film molding applications at high temperatures, and since it yields a thermoplastic liquid crystal polymer film with small film thickness tolerances and excellent smoothness, it can be effectively used as a component in the electrical and electronic fields, office equipment and precision equipment fields, power semiconductor fields, etc., for example, as a circuit board material. According to the present invention, variations in the film thickness of the thermoplastic liquid crystal polymer film can be reduced, and the resulting thermoplastic liquid crystal polymer film can be effectively used as a circuit board material with excellent high-frequency characteristics in circuit applications.

[0098] As described above, preferred embodiments of the present invention have been explained, but those skilled in the art will readily anticipate various changes and modifications within the obvious scope by reviewing this specification. Therefore, such changes and modifications shall be construed as falling within the scope of the invention as defined by the claims. [Explanation of Symbols]

[0099] 1, 2, 3, 4, 5, 6, 7, 8 Rolling mill 10A, 10B Rolling Rolls 11, 13 First Roll 12, 14 Second role 20 Thermoplastic liquid crystal polymer resin 21, 21A, 21B Thermoplastic liquid crystal polymer film 30 Extruder 40 Cooling Rolls 50, 51, 52, 53 Rewinding Rolls 60 release sheets 70, 71, 72 unwinding rolls 80 Forming Sheets 90 Cooling device

Claims

1. A method for producing a polymer film capable of forming an optically anisotropic molten phase (hereinafter referred to as a thermoplastic liquid crystal polymer film) using a pair of rolling rolls, The pair of rolling rolls consist of a first roll and a second roll, both of which have metal surfaces. The process involves supplying a melt-extruded thermoplastic liquid crystal polymer resin between the first roll and the second roll, The system includes at least a rolling step of passing the supplied thermoplastic liquid crystal polymer resin between the pair of rolling rolls to form a thermoplastic liquid crystal polymer film, The first roll and / or the second roll are metal elastic rolls. A method for manufacturing a thermoplastic liquid crystal polymer film.

2. A method for manufacturing a thermoplastic liquid crystal polymer film according to claim 1, wherein one of the pair of rolling rolls is a metal heating roll and the other roll is a metal elastic roll.

3. A method for manufacturing a thermoplastic liquid crystal polymer film according to claim 1 or 2, wherein the pressure between the pair of rolling rolls is 0.1 to 30 kg / mm ​​in terms of linear pressure.

4. A method for producing a thermoplastic liquid crystal polymer film according to claim 1 or 2, comprising the step of cooling the surface of the metal elastic roll.

5. A method for producing a thermoplastic liquid crystal polymer film according to claim 1 or 2, wherein the thickness of the thermoplastic liquid crystal polymer film is 5 μm or more and 500 μm or less.

6. A method for manufacturing a thermoplastic liquid crystal polymer film according to claim 1 or 2, wherein the step of supplying the thermoplastic liquid crystal polymer resin is performed while a release sheet is supplied to the first roll and / or the second roll.

7. A method for manufacturing a thermoplastic liquid crystal polymer film according to claim 1 or 2, wherein the step of supplying the thermoplastic liquid crystal polymer resin is performed while a shaping sheet is being supplied to a first roll and / or a second roll.

8. The manufacturing method according to claim 2, wherein the first roll is a metal heating roll, the second roll is a metal elastic roll, the metal heating roll is MR, the metal elastic roll is MER, the release sheet is RS, the shaping sheet is MS, and the thermoplastic liquid crystal polymer resin is LCP, and the arrangement of MR, MER, RS, MS, and LCP is as follows: MR / LCP / MER MR / RS / LCP / MER MR / LCP / RS / MER MR / RS / LCP / RS / MER MR / MS / LCP / MER MR / LCP / MS / MER, or MR / MS / LCP / MS / MER A method for manufacturing a thermoplastic liquid crystal polymer film, comprising the step of supplying a thermoplastic liquid crystal polymer resin in such a manner.

9. The manufacturing method according to claim 2, wherein the first roll is a metal elastic roll, the second roll is a metal heating roll, the metal elastic roll is MER, the metal heating roll is MR, the release sheet is RS, the shaping sheet is MS, and the thermoplastic liquid crystal polymer resin is LCP, and the arrangement of MER, MR, RS, MS, and LCP is as follows: MER / LCP / MR MER / RS / LCP / MR MER / LCP / RS / MR MER / RS / LCP / RS / MR MER / MS / LCP / MR MER / LCP / MS / MR, or MER / MS / LCP / MS / MR A method for manufacturing a thermoplastic liquid crystal polymer film, comprising the step of supplying a thermoplastic liquid crystal polymer resin in such a manner.

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