WO2024162372A1 - 液晶ポリマーフィルム延伸用３層フィルム、延伸３層フィルム、および延伸液晶ポリマーフィルム、ならびにこれらの製造方法 - Google Patents

液晶ポリマーフィルム延伸用３層フィルム、延伸３層フィルム、および延伸液晶ポリマーフィルム、ならびにこれらの製造方法 Download PDF

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WO2024162372A1
WO2024162372A1 PCT/JP2024/002990 JP2024002990W WO2024162372A1 WO 2024162372 A1 WO2024162372 A1 WO 2024162372A1 JP 2024002990 W JP2024002990 W JP 2024002990W WO 2024162372 A1 WO2024162372 A1 WO 2024162372A1
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liquid crystal
crystal polymer
film
stretching
polymer film
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English (en)
French (fr)
Japanese (ja)
Inventor
悟史 河村
由実 伊藤
優斗 佐藤
イバート
保之 池田
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Toyo Kohan Co Ltd
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Toyo Kohan Co Ltd
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Priority to KR1020257022696A priority patent/KR20250148562A/ko
Publication of WO2024162372A1 publication Critical patent/WO2024162372A1/ja
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—Films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/288—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyketones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0008—Electrical discharge treatment, e.g. corona, plasma treatment; wave energy or particle radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2007/00—Flat articles, e.g. films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/26—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer which influences the bonding during the lamination process, e.g. release layers or pressure equalising layers
    • B32B2037/268—Release layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514—Oriented
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/737—Dimensions, e.g. volume or area
    • B32B2307/7375—Linear, e.g. length, distance or width
    • B32B2307/7376—Thickness

Definitions

  • the present invention relates to a three-layer film for stretching liquid crystal polymer films, a stretched three-layer film, and a stretched liquid crystal polymer film, as well as methods for producing these.
  • Liquid crystal polymer films are known as polymer films used in electronic materials, because they have excellent heat resistance, low water absorption, and small dimensional change rates. Liquid crystal polymer films are also excellent in high frequency characteristics and low dielectric properties, and are expected to be used in flexible printed wiring boards for the fifth generation mobile communication system. However, liquid crystal polymers have a tendency to be molecularly oriented in the flow direction. In the melt extrusion method, a common method for manufacturing films, the polymer is melted and extruded from a T-die or the like to form a film.
  • the liquid crystal polymer in the film manufactured by this method has molecular orientation in the longitudinal direction of the film, and physical properties such as the dielectric constant and linear expansion coefficient have anisotropy depending on the direction of the film, so it cannot be used for flexible printed wiring boards.
  • the anisotropy of the polymer film is eliminated by stretching it in a direction perpendicular to the molecular orientation at a temperature below the melting point of the film.
  • liquid crystal polymer films extruded from a T-die have extremely low tensile strength, especially in the direction perpendicular to the molecular orientation, so they easily break when pulled in a direction perpendicular to the molecular orientation at a temperature below the melting point of the liquid crystal polymer.
  • a method for reducing the anisotropy of such liquid crystal polymer films, a method is known in which a laminate formed by laminating a thermoplastic resin film on a liquid crystal polymer film is stretched at a temperature equal to or higher than the melting point of the liquid crystal polymer, the laminate is cooled, and the thermoplastic resin film is peeled off to produce a liquid crystal polymer film (for example, Patent Document 1).
  • Another method is known in which a three-layer co-extruded film with a liquid crystal polymer layer as the intermediate layer is formed, and both outer layers are peeled off from the intermediate layer and then stretched to produce a liquid crystal polymer film (for example, Patent Document 2).
  • Patent Document 1 Japanese Patent No. 3659721
  • Patent Document 2 International Publication No. 2022/124308
  • the object of the present invention is to provide a three-layer film for stretching liquid crystal polymer film, which can produce a liquid crystal polymer film with reduced anisotropy by stretching at a temperature below the melting point, and a method for producing the three-layer film for stretching liquid crystal polymer film.
  • the present inventors have found that the above-mentioned object can be achieved by a three-layer film for stretching liquid crystal polymer films laminated with a support film having a yield load within a predetermined range in a temperature range of not less than temperature T1 (the glass transition temperature of the liquid crystal polymer) and not more than temperature T2 (the lower of the melting point of the liquid crystal polymer and the melting point of the polymer constituting the support film - 20°C), and have thus completed the present invention.
  • T1 the glass transition temperature of the liquid crystal polymer
  • T2 the lower of the melting point of the liquid crystal polymer and the melting point of the polymer constituting the support film - 20°C
  • a three-layer film for stretching a liquid crystal polymer film comprising a liquid crystal polymer film and a pair of support films laminated on both sides of the liquid crystal polymer film, wherein at any temperature within a range of temperature T1 or more and temperature T2 or less, the sum of the yield loads of the pair of support films is greater than the yield load of the liquid crystal polymer film, the temperature T1 is the glass transition temperature of the liquid crystal polymer constituting the liquid crystal polymer film, and the temperature T2 is the lower of the melting point of the liquid crystal polymer and a temperature of the melting point of the polymer constituting the support film minus 20°C.
  • a three-layer film for stretching a liquid crystal polymer film as described in aspect 1 in which the total value of the maximum point load of a pair of the support films is greater than the maximum point load of the liquid crystal polymer film at any temperature within the range of temperature T1 or more and temperature T2 or less.
  • a three-layer film for stretching a liquid crystal polymer film according to aspect 1 or 2 in which at least one of the pair of support films has a breaking elongation of 200% or more at any temperature within the range of temperature T1 or more and temperature T2 or less.
  • a three-layer film for stretching liquid crystal polymer film according to any one of aspects 1 to 3, in which when the three-layer film for stretching liquid crystal polymer film is wrapped around a cylinder having an outer diameter of 84.2 mm so that one surface of the support film is in contact with the cylinder, the three-layer film for stretching liquid crystal polymer film is deformed at a winding angle of 90° or more, and the three-layer film for stretching liquid crystal polymer film is further wrapped around the cylinder so that the other surface of the support film is in contact with the cylinder, the three-layer film for stretching liquid crystal polymer film is deformed at a winding angle of 90° or more.
  • a three-layer film for stretching a liquid crystal polymer film according to any one of aspects 1 to 5, in which the support film is composed of an aromatic polyether ketone or polyester.
  • a three-layer film for stretching a liquid crystal polymer film according to any one of aspects 1 to 6, in which the thickness of the support film is 5 to 300 ⁇ m.
  • a method for producing a three-layer film for stretching a liquid crystal polymer film comprising the steps of: There is also provided a method for producing a three-layer film for stretching a liquid crystal polymer film, comprising a step of laminating a pair of the support films on both sides of the liquid crystal polymer film by pressure lamination or heat lamination.
  • aspect 10 of the present invention there is provided a method for producing a three-layer film for stretching a liquid crystal polymer film as described in aspect 9, in which the surface treatment is any one of a plasma treatment, a corona treatment, and a chemical conversion treatment.
  • aspect 11 of the present invention there is provided a method for producing a three-layer film for stretching a liquid crystal polymer film according to any one of aspects 1 to 7, in which the three-layer film for stretching a liquid crystal polymer film is produced by a melt extrusion method.
  • a method for producing a stretched three-layer film comprising the step of stretching a three-layer film for stretching a liquid crystal polymer film according to any one of aspects 1 to 7 at least 2.0 to 5.0 times in the TD direction in a temperature range of not less than the glass transition temperature of the liquid crystal polymer and not more than the melting point of the liquid crystal polymer.
  • a method for producing a stretched liquid crystal polymer film comprising a step of peeling off the support film from a stretched three-layer film produced by the method for producing a stretched three-layer film according to aspect 12 or 13.
  • a method for producing a stretched liquid crystal polymer film comprising the steps of peeling the support film from a stretched three-layer liquid crystal polymer film produced by the method for producing a stretched three-layer film described in aspect 12, and heat treating the film at a temperature range equal to or higher than the glass transition temperature of the liquid crystal polymer and equal to or lower than the melting point of the liquid crystal polymer.
  • a stretched liquid crystal polymer film produced by the method for producing a stretched liquid crystal polymer film according to aspect 14 or 15,
  • the stretched liquid crystal polymer film has a ratio of the greater breaking load to the lesser breaking load, measured in two directions, of 6 or less.
  • a stretched liquid crystal polymer film according to aspect 17 in which the melting point of the stretched liquid crystal polymer film is equal to or higher than the melting point of the liquid crystal polymer film before stretching.
  • the three-layer film for stretching liquid crystal polymer films of the present invention makes it possible to produce stretched liquid crystal polymer films with reduced anisotropy.
  • FIG. 1 is a schematic diagram showing a method for evaluating the adhesion between a liquid crystal polymer film and a support film of a three-layer film for stretching a liquid crystal polymer film in an embodiment, and is a cross-sectional view of a three-layer film for stretching a liquid crystal polymer film and a 3-inch core.
  • FIG. 2 is a graph showing the results of the viscoelasticity measurement test of the liquid crystal polymer film used in Example 1.
  • FIG. 3 is a graph showing SS curves obtained by a tensile test of the liquid crystal polymer film and the support film used in Example 4.
  • FIG. 4 is a graph showing SS curves obtained by a tensile test of the liquid crystal polymer film and the support film used in Comparative Example 4.
  • the three-layer film for stretching a liquid crystal polymer film of the present invention is composed of a liquid crystal polymer film and a pair of support films laminated on both sides of the liquid crystal polymer film.
  • the three-layer film for stretching a liquid crystal polymer film of the present invention is used to produce a stretched liquid crystal polymer film by stretching the liquid crystal polymer film and then peeling the support films from the liquid crystal polymer film.
  • the liquid crystal polymer film used in this embodiment is a film made of a liquid crystal polymer.
  • the liquid crystal polymer is not particularly limited, but a liquid crystal polyester exhibiting thermotropic liquid crystal properties is preferable.
  • liquid crystal polyesters include aromatic polyesters that are synthesized from monomers such as aromatic diols, aromatic carboxylic acids, and hydroxycarboxylic acids and exhibit liquid crystal properties when melted. Specific examples include polycondensates of ethylene terephthalate and parahydroxybenzoic acid, polycondensates of phenol, phthalic acid, and parahydroxybenzoic acid, and polycondensates of hydroxynaphthoic acid and parahydroxybenzoic acid.
  • an aromatic polyester-based liquid crystal polymer having 6-hydroxy-2-naphthoic acid and its derivatives as a basic structure and at least one selected from the group consisting of parahydroxybenzoic acid, terephthalic acid, isophthalic acid, 6-naphthalenedicarboxylic acid, 4,4'-biphenol, bisphenol A, hydroquinone, 4,4-dihydroxybiphenol, ethylene terephthalate, and derivatives thereof as a monomer component is preferable.
  • the liquid crystal polyesters may be used alone or in any combination and ratio of two or more kinds.
  • the liquid crystal polyester can be synthesized by any known method, and is not particularly limited. For example, melt polymerization, melt acidolysis, slurry polymerization, etc. can be used. When applying these polymerization methods, acylation or acetylation may be performed according to the usual method.
  • the liquid crystal polymer may contain additives such as polymers such as fluororesins, polyolefins, polycycloolefins, polyetherimides, and silicone-modified polyetherimides, release improvers such as higher fatty acids having 10 to 25 carbon atoms, higher fatty acid esters, higher fatty acid amides, and higher fatty acid metal salts, chain extenders such as aliphatic carbodiimides, alicyclic carbodiimides, and aromatic carbodiimides, colorants such as dyes, pigments, and carbon black, organic fillers, inorganic fillers, hollow particles, antioxidants, heat stabilizers, light stabilizers, ultraviolet absorbers, flame retardants, lubricants, antistatic agents, surfactants, rust inhibitors, foaming agents, defoamers, and fluorescent agents, within the scope of the invention that does not excessively impair the effects of the present invention.
  • additives such as polymers such as fluororesins, polyolefins, polycyclo
  • polymers and additives can be added to the molten resin composition during the formation of the liquid crystal polymer film.
  • each of these polymers and additives can be used alone or in combination of two or more.
  • the content of the polymer and additives is not particularly limited, but from the viewpoint of moldability and thermal stability, it is preferably 0.01 to 50% by mass, more preferably 0.1 to 40% by mass, and even more preferably 0.5 to 30% by mass, based on the total amount of the liquid crystal polymer film.
  • These polymers, additives, etc. may be added to the liquid crystal polymer in advance, or may be added to the liquid crystal polymer when forming the stretched liquid crystal polymer film described below.
  • the liquid crystal polymer film can be manufactured by a known method.
  • a liquid crystal polymer can be formed into a film by melt extrusion film-forming method using a T-die (T-die melt extrusion).
  • a liquid crystal polymer film can be obtained by melt-kneading the liquid crystal polymer in an extruder, extruding the molten resin through a T-die, and solidifying it on a metal roll.
  • touch molding with a rubber roll or a metal roll can also be used.
  • the temperature of the cylinder of the extruder is preferably 230 to 360°C, more preferably 280 to 350°C.
  • the slit interval of the T-die can be appropriately set depending on the type and composition of the liquid crystal polymer used, the performance of the desired film, etc.
  • the slit interval of the T-die is not particularly limited, but is preferably 0.1 to 1.5 mm, more preferably 0.3 to 1.0 mm.
  • the thickness of the liquid crystal polymer film obtained by the above method is not particularly limited, but from the viewpoint of ease of handling during T-die melt extrusion molding and productivity, it is preferably 10 to 500 ⁇ m, more preferably 20 to 300 ⁇ m, and even more preferably 30 to 250 ⁇ m.
  • the melting point of the liquid crystal polymer constituting the liquid crystal polymer film is preferably 250 to 380°C, more preferably 280 to 350°C.
  • the glass transition temperature of the liquid crystal polymer constituting the liquid crystal polymer film is preferably 90 to 150°C, more preferably 100 to 120°C.
  • the support film is a polymer film laminated on the liquid crystal polymer film to prevent the film from breaking when the liquid crystal polymer film is stretched.
  • a crystalline resin for example, aromatic polyetherketone or polyester is preferably used.
  • aromatic polyetherketone include polyetherketone (PEK), polyetheretherketone (PEEK), polyetherketoneketone (PEKK), polyetheretherketoneketone (PEEKK), etc.
  • polyester include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), etc. These polymers can be used alone or in combination of two or more.
  • these films are crystallized or stretched films in terms of high heat resistance and can be stretched at high temperatures.
  • the polymer used as the support film it is preferable to select a polymer that satisfies the requirements of yield load and maximum point load in comparison with the liquid crystal polymer, as will be described later, and that satisfies the predetermined requirements for breaking elongation.
  • the thickness of the support film is preferably 5 to 300 ⁇ m, and more preferably 15 to 100 ⁇ m.
  • the support film used in the present invention has the following characteristics. That is, at any temperature in the range of temperature T1 or more and temperature T2 or less, the total value of the yield load of the pair of support films is greater than the yield load of the liquid crystal polymer film.
  • temperature T1 is the glass transition temperature of the liquid crystal polymer
  • temperature T2 is the lower of the melting point of the liquid crystal polymer and a temperature that is 20°C lower than the melting point of the polymer constituting the support film (a temperature that is 20°C lower than the melting point of the polymer constituting the support film).
  • the three-layer film for stretching liquid crystal polymer film of the present invention can be stretched at a temperature equal to or lower than the melting point of the liquid crystal polymer film and at a stretch ratio of 2 or more, and thus a stretched liquid crystal polymer film with small anisotropy can be produced.
  • the three-layer film for stretching liquid crystal polymer film of the present invention can be stretched at a temperature below the melting point of the liquid crystal polymer and at a stretching ratio of 2 or more because the relationship between the yield load of the support film and the yield load of the liquid crystal polymer satisfies the above conditions.
  • the reason why the liquid crystal polymer film can be stretched at a temperature below the melting point by the yield load of the liquid crystal polymer film and the support film satisfying the above relationship is not clear, but the following is considered.
  • the case where the temperature T2 is the melting point of the liquid crystal polymer that is, the melting point of the liquid crystal polymer is lower than the melting point of the polymer constituting the support film - 20 ° C. is considered.
  • the elastic modulus of the liquid crystal polymer falls below 1000 MPa, and soft parts are generated in the liquid crystal polymer film.
  • a support film is disposed on both sides of the liquid crystal polymer film, and in a temperature range of not less than the glass transition temperature of the liquid crystal polymer and not more than the melting point of the liquid crystal polymer, the total value of the yield load of the pair of support films exceeds the yield load of the liquid crystal polymer film.
  • the stretching load applied when the three-layer film for stretching liquid crystal polymer film is stretched is supported by the support film. Therefore, even if the liquid crystal polymer film becomes thinner by stretching and a portion where the load is reduced occurs, it is possible to suppress the concentration of tensile stress at the portion where the load is reduced. Furthermore, since the support film and the liquid crystal polymer film are in close contact with each other, the stretching force is applied evenly to the liquid crystal polymer film through the interface with the liquid crystal polymer film as the support film is stretched. From the above, it is considered that the liquid crystal film can be stretched without breaking.
  • the liquid crystal film can be stretched without breaking for the same reason.
  • the SS curve obtained by performing a tensile test on the support film used in the present invention has an upward sloping shape in which the stress increases as the elongation increases (see FIG. 3), and the load tends to increase as the film is stretched. Therefore, when the three-layer film for stretching liquid crystal polymer film is stretched, the load increases in the thinner parts of the support film, and the tensile stress applied to the support film acts preferentially on the thicker parts (unstretched parts) of the support film, resulting in the entire support film being stretched uniformly.
  • the support film is in close contact with both sides of the liquid crystal polymer film, so that when the three-layer film for stretching liquid crystal polymer film is stretched, the liquid crystal polymer film is also stretched uniformly as the support film is stretched uniformly, and the thickness of the resulting stretched liquid crystal polymer film can be made uniform.
  • the total value of the yield load of the pair of support films is larger than the yield load of the liquid crystal polymer film over the entire temperature range of temperature T1 or more and temperature T2 or less.
  • temperature T2 is the melting point of the liquid crystal polymer, that is, when the melting point of the liquid crystal polymer is lower than the melting point of the polymer constituting the support film -20 ° C.
  • the total value of the yield load of the pair of support films is larger than the yield load of the liquid crystal polymer film over the entire temperature range of 150 to 280 ° C.
  • temperature T2 is the melting point of the polymer constituting the support film -20 ° C.
  • the total value of the yield load of the pair of support films is larger than the yield load of the liquid crystal polymer film over the entire temperature range of 150 to 260 ° C.
  • the support film used in the present invention preferably has the following characteristics: That is, the total value of the maximum point load of the pair of support films is preferably greater than the maximum point load of the liquid crystal polymer film at any temperature in the range of temperature T1 or more and temperature T2 or less. This allows the three-layer film for stretching liquid crystal polymer film of the present invention to be stretched at a temperature equal to or lower than the melting point of the liquid crystal polymer film, as described below, and thus allows the production of a stretched liquid crystal polymer film with small anisotropy.
  • the support film used in the present invention preferably has a breaking elongation of 200% or more in a temperature range of not less than temperature T1 and not more than temperature T2 . It is sufficient that at least one of the two support films laminated on the liquid crystal polymer film has a breaking elongation of 200% or more.
  • the three-layer film for stretching liquid crystal polymer film of the present invention can be stretched at a temperature not higher than the melting point of the liquid crystal polymer film, and a stretched liquid crystal polymer film with small anisotropy can be produced.
  • the yield load, maximum load, and breaking elongation of the support film can be determined by conducting a tensile test on the support film, obtaining an SS curve with the vertical axis representing stress and the horizontal axis representing elongation, and then determining the yield load, maximum load, and breaking elongation of the support film from the obtained SS curve.
  • the three-layer film for stretching a liquid crystal polymer film of the present invention can be produced by laminating the above-mentioned liquid crystal polymer film, a first support film and a second support film by pressure lamination or heat lamination.
  • the liquid crystal polymer film and the support film are laminated together while being heated by a pair of heated rolls.
  • the conditions for the thermal lamination method can be appropriately selected according to the physical properties of the liquid crystal polymer and the support polymer. Although not particularly limited, it is preferable to perform the heating and compression at a temperature near the melting point of the liquid crystal polymer and at a temperature near the melting point of the support polymer.
  • the bonding surfaces of the liquid crystal polymer and the supporting polymer are subjected to a film surface treatment such as plasma treatment to improve adhesion, and then immediately afterwards the liquid crystal polymer film and the supporting film are pressed down with a roll.
  • a film surface treatment such as plasma treatment to improve adhesion
  • the conditions for the pressure lamination method can be appropriately selected according to the physical properties of the liquid crystal polymer and the supporting polymer.
  • the manufacturing method of a three-layer film for stretching a liquid crystal polymer film it is preferable to carry out a process of performing a surface treatment on the surface of the liquid crystal polymer film that comes into contact with the support film (the bonding surface) and the surface of the support film that comes into contact with the liquid crystal polymer film (the bonding surface) before the process of laminating the liquid crystal polymer film and the first and second support films.
  • Examples of surface treatment methods include plasma treatment in which a gas in a plasma state is irradiated onto the surface by applying electrical energy, corona treatment in which the surface is activated by discharge, activation methods in which the surface is irradiated with ultraviolet rays or electron beams, activation methods in which a flame is applied to the surface, chemical treatments (chemical conversion treatments) in which the surface is oxidized with potassium dichromate or the like, and primer treatments in which a primer is applied.
  • the surface treatment method can be appropriately selected depending on the physical properties of the liquid crystal polymer and the supporting polymer, but from the viewpoint of increasing the adhesion between the liquid crystal polymer film and the supporting film and reducing damage to the stretched liquid crystal polymer film obtained from the three-layer film for stretching liquid crystal polymer film, plasma treatment, corona treatment, and chemical treatment (chemical conversion treatment) are preferred, with plasma treatment being particularly preferred.
  • a three-layer film for stretching liquid crystal polymer film is obtained by laminating a film made of a liquid crystal polymer and a film made of a support polymer, but the method for obtaining a three-layer film for stretching liquid crystal polymer film is not particularly limited to this.
  • a three-layer film for stretching liquid crystal polymer film may be formed by melting the liquid crystal polymer in a first extruder and melting the support polymer in a second extruder, and extruding each polymer into a film so that a layer made of the support polymer is laminated on one or both sides of the layer made of liquid crystal polymer by a melt extrusion method.
  • the support polymer may be the same as the polymer that constitutes the support film.
  • a method for laminating a layer of supporting polymer on one or both sides of a layer of liquid crystal polymer a method for forming a multilayer extrusion film from a T-die can be used.
  • Specific examples include the feedblock method, in which molten liquid crystal polymer and supporting polymer supplied from two extruders are fed to a feedblock, merged, and then extruded from a T-die in the form of a film, and the multi-manifold method, in which molten liquid crystal polymer and supporting polymer are separately fed to a T-die, overlaid, and extruded in the form of a film. From the viewpoint of improving the smoothness of the resulting stretched liquid crystal polymer film, it is preferable to apply the multi-manifold method, taking into consideration cases in which the liquid crystal polymer and supporting polymer have different viscosities and flow characteristics when melted.
  • the stretched three-layer film and the stretched liquid crystal polymer film of the present invention can be produced by the following method.
  • the three-layer film for stretching liquid crystal polymer film obtained by the above method is stretched in the width direction (TD direction) to obtain a stretched three-layer film.
  • the method for stretching the laminated film is not particularly limited, but a tenter transverse stretching method in which both ends of the laminated film are clamped with clips and heated and stretched is preferred.
  • the stretching ratio and stretching speed are appropriately selected so that the support film can be stretched and the shape and physical properties of the film made of liquid crystal polymer after stretching are within the desired range.
  • the stretching ratio is preferably 2 to 5 times.
  • the stretching speed is preferably 1 to 5000%/min, more preferably 50 to 2500%/min.
  • stretching in the longitudinal direction (MD direction) may be added as necessary.
  • the temperature when stretching the three-layer film for stretching liquid crystal polymer film is preferably a temperature of T1 or more and T2 or less.
  • T2 is the melting point of the liquid crystal polymer, that is, when the melting point of the liquid crystal polymer is lower than the melting point of the polymer constituting the support film -20 ° C.
  • the temperature during stretching is preferably a temperature of the glass transition temperature of the liquid crystal polymer film or more and the melting point of the liquid crystal polymer film or less, specifically, it is preferably in the range of 150 to 280 ° C., and more preferably in the range of 170 to 250 ° C.
  • the smoothness of the obtained stretched liquid crystal polymer film can be improved, and the film can be made excellent in film formability without unevenness or streaks in thickness. Furthermore, it is more preferable to set the temperature when stretching the laminated film to a temperature above the glass transition temperature of the liquid crystal polymer, since the liquid crystal polymer film is easily stretched.
  • the sum of the yield loads of the pair of support films is greater than the yield load of the liquid crystal polymer film, so that the three-layer film for stretching liquid crystal polymer film can be stretched at a temperature below the melting point of the liquid crystal polymer.
  • the temperature T2 is a temperature of the melting point of the polymer constituting the support film - 20°C, that is, when the temperature of the melting point of the polymer constituting the support film - 20°C is lower than the melting point of the liquid crystal polymer
  • the temperature during stretching is preferably a temperature that is equal to or higher than the glass transition temperature of the liquid crystal polymer film and equal to or lower than the melting point of the polymer constituting the support film - 20°C, specifically, it is preferably in the range of 150 to 260°C, and more preferably in the range of 150 to 230°C.
  • the stretched three-layer film it is preferable to heat treat the stretched three-layer film at a temperature in the range of not less than the glass transition temperature and not more than the melting point of the liquid crystal polymer film.
  • the time for which the heat treatment is carried out is preferably 1 to 100 hours, and more preferably 3 to 48 hours. By carrying out the heat treatment, it is possible to improve the heat resistance of the stretched liquid crystal polymer film and reduce the linear expansion coefficient.
  • the melting point of the liquid crystal polymer constituting the liquid crystal polymer film in the three-layer film for liquid crystal polymer film orientation after stretching and heat treatment is equal to or higher than the melting point of the liquid crystal polymer constituting the liquid crystal polymer film before stretching.
  • the stretched liquid crystal polymer film produced in this manner has effectively reduced anisotropy.
  • anisotropy of the molecular orientation and the anisotropy of the mechanical properties are effectively reduced.
  • the support film is peeled off after the heat treatment, but the order of the heat treatment and the peeling of the support film is not particularly limited, and the heat treatment may be performed after the peeling of the support film.
  • the support film of the stretched three-layer film may be peeled off immediately before the stretched liquid crystal polymer film is used.
  • the support film can act as a protective film, for example, to prevent scratches during transportation.
  • the planar orientation degree of the molecular orientation of the stretched liquid crystal polymer film is expressed by the following formula (1).
  • the diffraction intensity of the 110 plane is the diffraction intensity of the crystal plane (110 plane) of the liquid crystal polymer.
  • the integrated intensity is calculated by the area when ⁇ is plotted on the horizontal axis and the diffraction intensity on the vertical axis. If the value expressed by the above formula (2) is a positive value, it indicates that the molecular chains are oriented in the longitudinal direction, and if it is a negative value, it indicates that they are oriented in the width direction.
  • the anisotropy of the mechanical properties of the stretched liquid crystal polymer film is determined as follows. First, a tensile test is performed along the TD direction of the stretched liquid crystal polymer film using a tensile tester. The breaking load in the TD direction is determined based on the SS curve obtained from the results of the tensile test. Next, a tensile test is also performed in the MD direction of the stretched liquid crystal polymer film, and the breaking load in the MD direction is determined based on the SS curve.
  • the anisotropy of the mechanical properties of the stretched liquid crystal polymer film is expressed as the ratio of the breaking load in the MD direction to the breaking load in the TD direction.
  • the breaking load ratio is preferably 6 or less, more preferably 3 or less.
  • the lower limit of the breaking load ratio is not particularly limited, but is usually 1 or more. According to the three-layer film for stretching liquid crystal polymer film of the present invention, a stretched liquid crystal polymer film in which the breaking load ratio is controlled within the above range can be
  • the direction of measurement of the breaking load in the anisotropy evaluation of the stretched liquid crystal polymer film is not particularly limited to the TD direction and the MD direction.
  • a tensile test is performed on the stretched liquid crystal polymer film in two different directions to determine the breaking load, and it is sufficient that the ratio of the larger breaking load to the smaller breaking load is within the above range.
  • the ratio of the breaking loads measured along two directions that intersect at right angles on the surface of the stretched liquid crystal polymer film is within the above range.
  • the yield load (upper yield point) of the liquid crystal polymer film was obtained.
  • a tensile test was also performed in the same manner for the support film, and the yield load was obtained.
  • the measured values of the yield load of each film are shown in Table 1. Then, the total value of the yield loads of the two support films (the yield load of one support film may be calculated and doubled) was compared with the yield load of the liquid crystal polymer film, and evaluation was performed.
  • the obtained three-layer film for stretching liquid crystal polymer film was wound around a three-inch core (plastic cylinder) with an outer diameter of 84.2 mm to deform it, and the presence or absence of peeling between the liquid crystal polymer film and the support film was visually confirmed to evaluate the adhesion between the liquid crystal polymer film and the support film.
  • the three-layer film for stretching liquid crystal polymer film 10 was wound around a three-inch core 50 so that the surface of one of the support films 21 was in contact with the three-inch core 50.
  • the angle ⁇ (hereinafter referred to as the winding angle) between both ends 11, 12 of the three-layer film for stretching liquid crystal polymer film 10 and the central axis 51 of the three-inch core 50 was 90° or more.
  • the winding angle ⁇ may be 90° or more, but is usually 160° or less.
  • the three-layer film 10 for stretching liquid crystal polymer film was turned over so that the other support film 22 was in contact with the 3-inch core 50, and was again wound around the 3-inch core 50. Again, the winding angle ⁇ was set to 90° or more. After maintaining this state for 5 seconds, the three-layer film 10 for stretching liquid crystal polymer film was peeled off from the 3-inch core 50. Thereafter, the presence or absence of peeling between the liquid crystal polymer film 30 and the support films 21, 22 of the three-layer film 10 for stretching liquid crystal polymer film was confirmed.
  • FIG. 1 is a schematic diagram showing a method for evaluating the adhesion between the liquid crystal polymer film and the support film of the three-layer film for stretching liquid crystal polymer film in the examples, and is a cross-sectional view of the three-layer film for stretching liquid crystal polymer film and the 3-inch core.
  • ⁇ No peeling occurred between the liquid crystal polymer film and the support film, and the adhesion was excellent.
  • ⁇ Peeling occurred between the liquid crystal polymer film and the support film, and the adhesion was insufficient.
  • FIG. 2 is a graph showing the results of the viscoelasticity measurement test of the liquid crystal polymer film used in Example 1.
  • Example 1 A liquid crystal polymer (LAPEROS A950RX, manufactured by Polyplastics Co., Ltd.) was fed into a twin-screw extruder (screw diameter 32 mm), extruded into a film form from a T-die (lip length 350 mm, lip clearance approximately 1 mm, die temperature 300° C.) at the tip of the extruder, and cooled to obtain a liquid crystal polymer (LCP) film with a thickness of 75 ⁇ m.
  • LCP liquid crystal polymer
  • PEEK polyether ether ketone
  • a PEEK film was thermocompressed onto both sides of the liquid crystal polymer film using a first roll heated to 305°C and a second roll heated to 120°C under conditions of a nip pressure of 0.2 MPa and a conveying speed of 0.5 m/min. After thermocompression, the liquid crystal polymer film and the PEEK film were in close contact. In this way, a three-layer film for stretching liquid crystal polymer film was obtained.
  • the three-layer film for stretching liquid crystal polymer film thus produced was stretched three times in the transverse direction (TD) at a conveying speed of 15 m/min (stretching speed 2500%/min, ultimate stretching temperature 250°C) in a tenter-type transverse stretching machine (furnace temperature 320°C) to obtain a stretched three-layer film.
  • the ultimate stretching temperature means the temperature of the laminated film at the end of stretching.
  • the stretched three-layer film was then heat-treated at 260°C in an oven for three hours, and the PEEK film was peeled off to obtain a stretched liquid crystal polymer film with a thickness of 25 ⁇ m.
  • the peelability of the support film and the stretchability of the three-layer film for stretching liquid crystal polymer film were evaluated. Furthermore, the planar orientation degree, tensile breaking load ratio, and melting point of this stretched liquid crystal polymer film were evaluated. The results are shown in Table 2.
  • Examples 2, 4, 6 to 8> A three-layer film for stretching a liquid crystal polymer film was obtained in the same manner as in Example 1. Then, a stretched liquid crystal polymer film was obtained in the same manner as in Example 1, except that the oven temperature during stretching, the stretching speed, the stretching ratio, and the temperature for heat treatment were changed to the values shown in Table 1, and evaluation was performed in the same manner as in Example 1. The results are shown in Table 2.
  • Example 3 A stretched liquid crystal polymer film was obtained and evaluated in the same manner as in Example 2, except that no heat treatment was performed. The results are shown in Table 2.
  • Example 5 A liquid crystal polymer (Polyplastics Co., Ltd., LAPEROS A950RX) was fed to a twin-screw extruder and melt-kneaded at 300 ° C.
  • a polyether ether ketone (PEEK) polymer (Polypla Evonik, 3300G, melting point 342 ° C.) was fed to a single-screw extruder as a support polymer and melt-kneaded at 380 ° C.
  • Example 9 Except for changing the thickness of the liquid crystal polymer film to 200 ⁇ m and the thickness of the polyether ether ketone film as the support film to 50 ⁇ m, a three-layer film for stretching liquid crystal polymer film and a stretched liquid crystal polymer film were obtained in the same manner as in Example 1 and evaluated in the same manner.
  • Example 10 A three-layer film for stretching a liquid crystal polymer film was produced in the same manner as in Example 5, except that unstretched polybutylene terephthalate (M-PBT) (manufactured by Mitsubishi Engineering Plastics Corporation, Novaduran 5026, melting point 220°C) was used as the support polymer, with a liquid crystal polymer layer of 75 ⁇ m and support polymer layers on both sides of 25 ⁇ m each, for a total of 125 ⁇ m.
  • M-PBT unstretched polybutylene terephthalate
  • the obtained three-layer film for stretching a liquid crystal polymer film was stretched and heat-treated under the conditions shown in Table 2, and the support film was peeled off, and then evaluated in the same manner as in Example 1. The results are shown in Table 2.
  • Example 11 Except for changing the thickness of the liquid crystal polymer film to that shown in Table 2 and using a biaxially stretched PBT film (BO-PBT) (manufactured by Kohjin Film & Chemicals, Boblet, thickness 25 ⁇ m, melting point 220° C.) as the support film, a three-layer film for stretching a liquid crystal polymer film was obtained in the same manner as in Example 1. Using the obtained three-layer film for stretching a liquid crystal polymer film, stretching and heat treatment were performed under the conditions shown in Table 2, and the support film was peeled off, and then evaluation was performed in the same manner as in Example 1.
  • BO-PBT biaxially stretched PBT film
  • Example 2 A three-layer film was obtained in the same manner as in Example 1, except that a liquid crystal polymer film with a thickness of 75 ⁇ m was used as the liquid crystal polymer film and a porous PTFE film (thickness of 50 ⁇ m) was used as the support film.
  • the total value of the yield load of the two support films at 150° C., 200° C., and 250° C. was lower than the yield load of the liquid crystal polymer film at the same temperature.
  • Example 3 As in Example 1, the liquid crystal polymer was extruded into a film shape using a twin-screw extruder to obtain a liquid crystal polymer film having a thickness of 200 ⁇ m. Thereafter, a three-layer film consisting of a liquid crystal polymer film and a pair of support films was obtained in the same manner as in Example 1, except that unstretched polybutylene terephthalate (manufactured by Toyo Kohan Co., Ltd., E-sheet, thickness 50 ⁇ m) was used as the support film. When the yield load and maximum point load of the liquid crystal polymer film and the support film were compared, the total value of the yield load of the two support films at 150° C. and 200° C.
  • unstretched polybutylene terephthalate manufactured by Toyo Kohan Co., Ltd., E-sheet, thickness 50 ⁇ m
  • Example 4 A three-layer film consisting of a liquid crystal polymer film and a pair of support films was obtained in the same manner as in Example 1, except that unstretched polybutylene terephthalate (manufactured by Toyo Kohan Co., Ltd., E-sheet, thickness 35 ⁇ m) was used as the support film.
  • unstretched polybutylene terephthalate manufactured by Toyo Kohan Co., Ltd., E-sheet, thickness 35 ⁇ m
  • the total value of the yield load of the two support films at 150°C and 200°C was lower than the yield load of the liquid crystal polymer film at the same temperature.
  • this three-layer film was stretched under the conditions of a stretching temperature of 200°C, a stretching speed of 2500%/min, and a stretching ratio of 3 times, cracks occurred in the liquid crystal polymer film, and the three-layer film could not be stretched.
  • Example 5 A three-layer film consisting of a liquid crystal polymer film and a pair of support films was obtained in the same manner as in Example 1, except that polymethylpentene (PMP) (thickness 50 ⁇ m) was used as the support film.
  • PMP polymethylpentene
  • the total value of the yield load of the two support films at 150 ° C. and 200 ° C. was lower than the yield load of the liquid crystal polymer film at the same temperature.
  • the total value of the maximum point load of the two support films at 150 ° C. and 200 ° C. was lower than the maximum point load of the liquid crystal polymer film at the same temperature.
  • Example 1 A three-layer film for stretching a liquid crystal polymer film was obtained in the same manner as in Example 1, and a stretched liquid crystal polymer film was obtained in the same manner as in Example 1, except that the stretching ratio was changed to 1.5 times and the heat treatment temperature was changed to 250° C. The results are shown in Table 2.
  • Example 2 A three-layer film for stretching a liquid crystal polymer film was obtained in the same manner as in Example 1, except that the liquid crystal polymer film and the support film were not surface-treated. When the obtained three-layer film for stretching a liquid crystal polymer film was stretched under the conditions shown in Table 2, cracks occurred in the liquid crystal polymer film, and the three-layer film could not be stretched. The results are shown in Table 2.
  • Figure 3 is a graph showing the SS curves obtained by the tensile test of the liquid crystal polymer film and the support film used in Example 4.
  • the horizontal axis shows the elongation (mm) in the tensile test
  • the vertical axis shows the load (N) applied to the film in the tensile test.
  • the tensile test was performed by setting the liquid crystal polymer film (LCP) and the support film (PEEK) samples (25 mm long in the TD direction and 25 mm long in the MD direction) in a tensile tester so that the stretching direction was TD (20 mm between chucks), preheating them in a thermostatic chamber at 150°C for 5 minutes, and then stretching them three times at a stretching speed of 2500%/min (60 mm between chucks).
  • the SS curve of the support film is composed of twice the load measured in the tensile test of the support film (the load of two sheets of support film). As shown in FIG.
  • Examples 1 to 11 by using a three-layer film for stretching liquid crystal polymer film in which the total value of the yield load of the support films exceeds the yield load of the liquid crystal polymer film in a specified temperature range, it was possible to stretch the liquid crystal polymer film at a temperature below the melting point of the liquid crystal polymer and at a stretching ratio of 2 or more, and to obtain a stretched liquid crystal polymer film with a small degree of planar orientation and breaking load ratio, and effectively reduced anisotropy.
  • Figure 4 is a graph showing the SS curves obtained by the tensile test of the liquid crystal polymer film and the support film used in Comparative Example 4.
  • the horizontal axis represents the elongation (mm) in the tensile test
  • the vertical axis represents the load (N) applied to the film in the tensile test.
  • the tensile test was performed by setting the liquid crystal polymer film (LCP) and the support film (PBT) samples (25 mm long in the TD direction and 25 mm long in the MD direction) in a tensile tester so that the stretching direction was TD (20 mm between chucks), preheating them in a thermostatic chamber at 150°C for 5 minutes, and then stretching them three times (60 mm between chucks) at a stretching speed of 2500%/min.
  • the SS curve of the support film is composed of twice the load measured in the tensile test of the support film (the load of two sheets of support film).
  • Comparative Example 4 As shown in Figure 4, in Comparative Example 4, the total value of the yield load of the support film at 150°C was lower than the yield load of the liquid crystal polymer film. As a result, in Comparative Example 4, cracks occurred in the liquid crystal polymer film when the three-layer film was stretched.
  • Reference Signs List 10 Three-layer film for stretching liquid crystal polymer film 11, 12: Ends 21, 22: Support film 30: Liquid crystal polymer film 50: 3-inch core 51: Central axis

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JPH09174786A (ja) * 1995-12-22 1997-07-08 Japan Gore Tex Inc 接着性表面又は金属表面を有する液晶ポリマーフィルム延伸物
JPH1160756A (ja) * 1997-08-12 1999-03-05 Toray Ind Inc 液晶性ポリエステルフィルムおよびその製造方法
JP2000273225A (ja) * 1999-03-25 2000-10-03 Kuraray Co Ltd 熱可塑性液晶ポリマーフィルムとその改質方法
JP2002029002A (ja) * 1999-10-07 2002-01-29 Toray Ind Inc 液晶性樹脂積層フィルム、その製造方法および液晶性樹脂積層フィルムを用いた回路基板
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KR20240001269A (ko) 2020-12-09 2024-01-03 덴카 주식회사 Lcp 압출 필름 및 그의 제조 방법, 연신 처리용 lcp 압출 필름, lcp 연신 필름, 열수축성 lcp 연신 필름, 회로 기판용 절연 재료, 그리고 금속박을 붙인 적층판

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JPH07323506A (ja) * 1993-02-25 1995-12-12 Japan Gore Tex Inc 液晶ポリマーフィルム及びその製造方法
JPH09174786A (ja) * 1995-12-22 1997-07-08 Japan Gore Tex Inc 接着性表面又は金属表面を有する液晶ポリマーフィルム延伸物
JPH1160756A (ja) * 1997-08-12 1999-03-05 Toray Ind Inc 液晶性ポリエステルフィルムおよびその製造方法
JP2000273225A (ja) * 1999-03-25 2000-10-03 Kuraray Co Ltd 熱可塑性液晶ポリマーフィルムとその改質方法
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JPWO2025127113A1 (https=) * 2023-12-12 2025-06-19

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