WO2024075636A1 - 熱可塑性液晶ポリマーフィルムの製造方法 - Google Patents

熱可塑性液晶ポリマーフィルムの製造方法 Download PDF

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WO2024075636A1
WO2024075636A1 PCT/JP2023/035441 JP2023035441W WO2024075636A1 WO 2024075636 A1 WO2024075636 A1 WO 2024075636A1 JP 2023035441 W JP2023035441 W JP 2023035441W WO 2024075636 A1 WO2024075636 A1 WO 2024075636A1
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Prior art keywords
liquid crystal
crystal polymer
bubble
thermoplastic liquid
polymer film
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English (en)
French (fr)
Japanese (ja)
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紀久雄 有本
真一 ▲高▼▲崎▼
渓都 東郷
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Kuraray Co Ltd
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Kuraray Co Ltd
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Priority to CN202380071055.9A priority Critical patent/CN119947882A/zh
Priority to KR1020257011851A priority patent/KR20250083489A/ko
Priority to JP2024555768A priority patent/JPWO2024075636A1/ja
Publication of WO2024075636A1 publication Critical patent/WO2024075636A1/ja
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
    • B29C48/10—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels flexible, e.g. blown foils
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0017—Combinations of extrusion moulding with other shaping operations combined with blow-moulding or thermoforming
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/30—Extrusion nozzles or dies
    • B29C48/32—Extrusion nozzles or dies with annular openings, e.g. for forming tubular articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/885—External treatment, e.g. by using air rings for cooling tubular films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/89—Internal treatment, e.g. by applying an internal cooling fluid stream
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/91—Heating, e.g. for cross linking
    • B29C48/9105—Heating, e.g. for cross linking of hollow articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/911—Cooling
    • B29C48/9115—Cooling of hollow articles
    • B29C48/912—Cooling of hollow articles of tubular films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • 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
    • B29L2023/00—Tubular articles
    • B29L2023/001—Tubular films, sleeves

Definitions

  • the present invention relates to a method for producing a film made of a thermoplastic polymer capable of forming an optically anisotropic molten phase (hereinafter, abbreviated as a thermoplastic liquid crystal polymer) or a polymer composition containing the thermoplastic liquid crystal polymer.
  • a thermoplastic polymer capable of forming an optically anisotropic molten phase
  • a polymer composition containing the thermoplastic liquid crystal polymer hereinafter, abbreviated as a thermoplastic liquid crystal polymer
  • thermoplastic liquid crystal polymers are useful in the electronics and electrical fields because they exhibit excellent electrical properties, low dimensional change rates, high heat resistance, and chemical stability.
  • a method using inflation molding has been proposed as a simple method for producing films made of this thermoplastic liquid crystal polymer.
  • inflation molding air is blown into thermoplastic resin extruded from a ring-shaped die to form bubbles, which are then pulled up to form a film. During this process, the film is stretched in the pulling direction and stretched in the circumferential direction due to the radial expansion of the bubbles, resulting in biaxial stretching of the film.
  • Patent Document 1 Patent No. 46325578 describes an inflation film-forming apparatus that is equipped with a bubble diameter measuring device that measures the amount of change in the bubble's transverse stretch ratio, a molecular orientation measuring device that measures the molecular orientation of the film, and a regulator that controls the bubble diameter by adjusting the supply of air into the bubble based on the measured bubble transverse stretch ratio and molecular orientation.
  • Patent Document 2 JP Patent Publication 5-286032 describes an inflation film molding device in which thermoplastic resin is extruded from a die with an annular slit, expanded by internal pressure, and continuously wound up after cooling and solidifying, and is characterized by the provision of a means for heating the surface of the molten resin bubble extruded from the die from around the bubble between the die and the position where the bubble expands rapidly.
  • Patent No. 4632558 Japanese Patent Application Laid-Open No. 5-286032
  • thermoplastic liquid crystal polymer films In recent years, the demand for thermoplastic liquid crystal polymer films has been increasing, and there is a demand for improved productivity. In order to improve the productivity of films produced by inflation molding, it has been considered to increase the diameter of the die and produce large-diameter films, but when only the die diameter is increased using conventional methods, the cylindrical bubble formed by the solidification of the molten film hangs down, making it difficult to control the molecular orientation. This problem was difficult to solve by simply controlling the supply of air into the bubble, as described in Patent Document 1.
  • Patent Document 2 describes how a heating means installed between the die and the position (neck) where the bubble expands rapidly heats the bubble surface, mitigating melt fracture, making it possible to extrude at low temperatures and take up at high speeds.
  • the purpose of this technology is to improve the transparency of films made of polyethylene and other materials that melt at relatively low temperatures.
  • Thermoplastic liquid crystal polymers have a lower melt viscosity at extremely low shear rates when melted, so the behavior of the melt that forms bubbles is significantly different from that of polyethylene.
  • the present invention aims to provide a method for producing a thermoplastic liquid crystal polymer film by the inflation film forming method, which can achieve the desired degree of molecular orientation by biaxial stretching, even when the resin is extruded through a die with a large aperture to increase bubble productivity.
  • the present invention may include the following aspects.
  • the first aspect is a method for producing a thermoplastic liquid crystal polymer film by an inflation film production method, in which a liquid crystal polymer that exhibits optical anisotropy when molten (hereinafter referred to as a thermoplastic liquid crystal polymer) is melt-extruded into a tubular shape from an annular die, the tubular melt is cooled while gas is supplied into the inner space thereof to expand the tubular melt, forming bubbles, and the bubbles are folded into a sheet shape while being taken up,
  • the bubble is heated by a (for example, planar) heating means provided on the outer periphery of a bubble-forming region, and the bubble is removed while being heated in a state in which the ratio hf/ht of the height hf from the outlet of the die to the frost line of the bubble and the height ht from the outlet of the die to the upper end of the heating means is 50% or more and 100% or less;
  • the present invention relates to a method for
  • the second aspect may be a method for producing a thermoplastic liquid crystal polymer film according to the first aspect, in which the heating means is divided into at least two sections in the height direction, and the temperature is controlled individually in each section.
  • a third aspect may be a method for producing a thermoplastic liquid crystal polymer film according to the first or second aspect, in which the time from when the thermoplastic liquid crystal polymer is extruded from the die until when it solidifies at the frost line is 3 seconds or more.
  • a fourth aspect may be a method for producing a thermoplastic liquid crystal polymer film according to any one of the first to third aspects, in which the height of the frost line of the bubble is set to 0.4 m or more and 3.0 m or less.
  • the fifth aspect may be a method for producing a thermoplastic liquid crystal polymer film according to any one of the first to fourth aspects, in which the bubble diameter of the frost line of the bubble is 300 mm or more.
  • a sixth aspect may be a method for producing a thermoplastic liquid crystal polymer film according to any one of the first to fifth aspects, in which a laminate of a plurality of thermoplastic resin layers including a layer made of the thermoplastic liquid crystal polymer is co-extruded from the die to form a bubble made of the laminate, and the liquid crystal polymer film is peeled off from the laminate film produced by removing the bubble.
  • thermoplastic liquid crystal polymer film with the desired degree of molecular orientation with high productivity.
  • FIG. 1 is a schematic side view showing an example of an inflation film production apparatus used in the method of the present invention.
  • FIG. 2 is a schematic cross-sectional view showing a configuration in the vicinity of a heating means of the inflation film production apparatus shown in FIG. 1.
  • thermoplastic liquid crystal polymer film is a method for producing a liquid crystal polymer film by an inflation film production method in which a liquid crystal polymer that exhibits optical anisotropy when molten (hereinafter referred to as thermoplastic liquid crystal polymer) is melt-extruded into a tube shape from a ring-shaped die, and the tubular melt is cooled while gas is supplied into the inner space to expand it, forming bubbles, and the bubbles are folded into a sheet shape and taken up.
  • thermoplastic liquid crystal polymer a liquid crystal polymer that exhibits optical anisotropy when molten
  • the method is characterized in that the bubbles are heated by a heating means provided on the outer periphery of the bubble-forming region, and the bubbles are taken up while being heated in a state in which the ratio hf/ht of the height from the die exit to the frost line (frost line height) hf and the height from the die exit to the upper end of the heating means is 50% or more and 100% or less, producing a liquid crystal polymer film with a molecular orientation degree SOR of 0.8 to 1.5.
  • FIG. 1 is a schematic side view showing the configuration of an inflation film manufacturing apparatus 10 that can be used in the method of the present invention.
  • the inflation film manufacturing apparatus 10 is equipped with an extrusion means (extruder) 1 that melt-extrudes a thermoplastic resin, and an annular die 2 is installed at the extrusion opening of the extrusion means. Air is blown into the molten resin extruded from the die 2 to form bubbles 3, and the solidified bubbles 3 are crushed by a guide plate 4 that is installed as necessary, passed through pinch rolls 5, transported by one or more rolls R, and taken up by a take-up means 6.
  • the inflation film manufacturing apparatus 10 of the present invention is equipped with an air ring 7 that blows air from the outer periphery of the bubbles 3 above the die 2, and a heating means 8 that heats the bubbles 3.
  • FIG. 2 is a schematic cross-sectional view for explaining the configuration near the die 2 of the inflation film manufacturing apparatus 10.
  • the molten thermoplastic liquid crystal polymer is extruded from the annular die lip (gap) 2a of the annular die 2, while air is blown in from the air inlet 2b (ventilation means) to form a cylindrical bubble 3.
  • the molten resin film forms a cylindrical portion 3a from the die lip 2a (diameter D) to a certain height hc, after which it expands due to the blown in air, and is cooled while expanding its radius in the expanded diameter portion 3b, solidifying at the height hf of the frost line F, and forming a cylindrical solid-phase film in the straight body portion 3c above that.
  • an air ring 7 is installed at a height near the exit from the die 2, and air is blown onto the base of the cylinder portion 3a for cooling, and the heating means 8 is installed above the air ring 7.
  • the heating means 8 may be a single stage, but in this embodiment, it is divided into a first heating section I in the lower stage and a second heating section II in the upper stage, and the bubble 3 is heated at different temperatures.
  • the first heating section I which heats the cylinder portion 3a and the lower portion of the enlarged diameter section 3b, preferably heats the bubble 3 at a temperature 20 to 60°C lower than the melting point Tm of the thermoplastic liquid crystal polymer, for example, a temperature 20 to 40°C lower than Tm
  • the second heating section II which heats from the upper portion of the enlarged diameter section 3b to above the frost line F, preferably heats the bubble 3 at a temperature 40 to 100°C lower than the melting point Tm of the thermoplastic liquid crystal polymer, for example, a temperature about 60 to 100°C lower than Tm.
  • the heating means 8 may be divided into three or more sections, and the bubble 3 may be heated while lowering the heating temperature from the lower section to the upper section.
  • the heating means 8 forms a bubble so that the cylindrical portion 3a, the expanded diameter portion 3b, and a part of the straight body portion 3c are contained within the area surrounded by the heating means 8, and it is preferable to control the frost line height hf to a height of 50 to 100%, preferably 60 to 95%, of the height ht from the outlet of the die 2 to the upper end of the heating means 8.
  • the frost line height hf is the bubble length to the frost line F, measured as the height from the outlet of the die 2 to the frost line F.
  • the ratio of the length hm of the heated portion of the molten bubble 3 in the height direction to the frost line height hm/hf be the above ratio.
  • the heating means (heating device) 8 is not particularly limited as long as it can heat the bubble from the outer periphery in each section almost evenly.
  • it may be a planar heating element such as a cast heater or a highly heat-resistant rubber heater arranged on the back of a heat sink (e.g., a metal plate such as an iron plate) arranged in an axisymmetric cross-sectional shape such as a circle or a polygon with respect to the axis of the bubble 3, or a planar heating element arranged on the inner side of a heat insulating member arranged in an axisymmetric cross-sectional shape, or a heat reflecting plate arranged on the back of a columnar heating element arranged in an axisymmetric shape.
  • the inner dimensions of the heating means 8 may be changed around the upper part 3a of the cylinder and around the enlarged diameter part 3b.
  • the present invention controls the shape of the bubble 3 by heating the periphery of the molten bubble while pulling the film, thereby lengthening the time it takes for the molten resin to solidify at the frost line F compared to when no heating is used.
  • the time it takes for the molten resin extruded from the die 2 to solidify at the frost line F can be set to 3 seconds or more, and in some cases 10 seconds or more. The upper limit of this time may be around 15 seconds.
  • the method of the present invention makes it possible to control the degree of molecular orientation of the film to a desired level, even when large-diameter bubbles are formed.
  • the height hf of the frost line F of the bubble 3 can be set to 0.4 m or more, or 1.0 m or more.
  • the frost line height hf is made too large, the equipment will become larger, so it is appropriate to set the frost line height hf to approximately 3.0 m or less.
  • the bubble diameter in the frost line F can be made 300 mm or more, for example 1000 mm or more, and in some cases 3000 mm. From a practical perspective in equipment design, it is reasonable to make the bubble diameter 3000 mm or less.
  • thermoplastic liquid crystal polymer film may be produced, but a molten laminate made of thermoplastic liquid crystal polymer and other resins or thermoplastic liquid crystal polymers with different melting points may be co-extruded from die 2, and after forming a laminate film according to the above-mentioned method for producing a thermoplastic liquid crystal polymer film, the thermoplastic liquid crystal polymer film may be peeled off.
  • both sides of a three-layer laminate film may be made of thermoplastic liquid crystal polymer film, and after film formation, the film may be peeled off from the core film. This can further improve the productivity of the thermoplastic liquid crystal polymer film.
  • thermoplastic liquid crystal polymer used in the manufacturing method of the present invention is formed from a liquid crystal polymer that can be melt molded.
  • This thermoplastic liquid crystal polymer is a polymer that can form an optically anisotropic melt phase, and as long as it is a liquid crystal polymer that can be melt molded, its chemical structure is not particularly limited, but for example, it can be a thermoplastic liquid crystal polyester, or a thermoplastic liquid crystal polyester amide in which an amide bond is introduced therein.
  • thermoplastic liquid crystal polymer may also be a polymer in which an imide bond, a carbonate bond, a carbodiimide bond, an isocyanate-derived bond such as an isocyanurate bond, or the like is further introduced into an aromatic polyester or an aromatic polyester amide.
  • thermoplastic liquid crystal polymers used in the present invention include the known thermoplastic liquid crystal polyesters and thermoplastic liquid crystal polyester amides derived from the compounds classified into (1) to (4) below and their derivatives.
  • thermoplastic liquid crystal polyesters and thermoplastic liquid crystal polyester amides derived from the compounds classified into (1) to (4) below and their derivatives.
  • thermoplastic liquid crystal polyester amides derived from the compounds classified into (1) to (4) below and their derivatives.
  • Aromatic or aliphatic diol represented are shown in Table 1.
  • Aromatic hydroxycarboxylic acids (representative examples are shown in Table 3)
  • Aromatic diamines, aromatic hydroxyamines, or aromatic aminocarboxylic acids see Table 4 for representative examples.
  • thermoplastic liquid crystal polymers obtained from these raw material compounds include copolymers having the structural units shown in Tables 5 and 6.
  • polymers containing at least p-hydroxybenzoic acid and/or 6-hydroxy-2-naphthoic acid as repeating units 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 at least one aromatic dicarboxylic acid are preferred.
  • 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
  • the molar ratio of repeating units derived from 6-hydroxy-2-naphthoic acid in the aromatic hydroxycarboxylic acid (C) may be, for example, 85 mol% or more, preferably 90 mol% or more, and more preferably 95 mol% or more.
  • the molar ratio of repeating units derived from 2,6-naphthalenedicarboxylic acid in the aromatic dicarboxylic acid (E) may be, for example, 85 mol% or more, preferably 90 mol% or more, and more preferably 95 mol% or more.
  • the ability to form an optically anisotropic molten phase as referred to in the present invention can be confirmed, for example, by placing a sample on a hot stage, heating it in a nitrogen atmosphere, and observing the light transmitted through the sample.
  • the preferred thermoplastic liquid crystal polymer has a melting point (hereinafter referred to as Tm 0 ) in the range of, for example, 200 to 360 ° C., preferably in the range of 240 to 350 ° C., and more preferably in the range of 260 to 330 ° C.
  • Tm 0 melting point
  • the melting point can be obtained by observing the thermal behavior of a thermoplastic liquid crystal polymer sample using a differential scanning calorimeter. That is, the thermoplastic liquid crystal polymer sample is heated at a rate of 10 ° C./min to completely melt, and then the melt is cooled to 50 ° C. at a rate of 10 ° C./min, and the position of the endothermic peak that appears after heating again at a rate of 10 ° C./min is determined as the melting point of the thermoplastic liquid crystal polymer sample.
  • thermoplastic polymers such as polyethylene terephthalate, modified polyethylene terephthalate, polyolefin, polycarbonate, polyarylate, polyamide, polyphenylene sulfide, polyether ether ketone, and fluororesin, various additives, fillers, etc. may be added to the thermoplastic liquid crystal polymer within the range that does not impair the effects of the present invention.
  • a cylindrical sheet melt-extruded from a circular die may be stretched at a predetermined draw ratio (corresponding to the stretch ratio in the MD direction) and blow ratio (corresponding to the stretch ratio in the TD direction) to form a film.
  • the stretch ratio in such extrusion molding may be, for example, about 1.0 to 10 as the stretch ratio (or draw ratio) in the MD direction, preferably about 1.2 to 7, and more preferably about 1.3 to 7.
  • the stretch ratio (or blow ratio) in the TD direction may be, for example, about 1.5 to 20, preferably about 2 to 15, and more preferably about 2.5 to 14.
  • the molecular orientation ratio SOR of the liquid crystal polymer film can be controlled in the range of 0.8 to 1.5.
  • the molecular orientation ratio SOR is preferably 0.9 to 1.3, more preferably 1.0 to 1.2, and particularly preferably 1.0 to 1.1.
  • the molecular orientation ratio SOR (Segment Orientation Ratio) is an index that gives the degree of molecular orientation for the segments that make up the molecule, and is a value that takes into account the thickness of the object.
  • the liquid crystal polymer film is inserted into a microwave resonant waveguide in a microwave molecular orientation measuring device so that the film surface is perpendicular to the direction of microwave propagation, and the electric field intensity (microwave transmission intensity) of the microwave transmitted through the film is measured. Based on this measured value, the m value (referred to as the refractive index) is calculated by the following formula.
  • Z o is an apparatus constant
  • ⁇ z is the average thickness of the object
  • ⁇ max is the frequency that gives the maximum microwave transmission intensity when the microwave frequency is changed
  • ⁇ o is the frequency that gives the maximum microwave transmission intensity when the average thickness is zero (i.e., when there is no object).
  • the m value when the rotation angle of the object with respect to the microwave vibration direction is 0° that is, when the microwave vibration direction coincides with the direction in which the object's molecules are most oriented and which gives the minimum microwave transmission intensity
  • m0 the m value when the rotation angle is 90°
  • m90 the molecular orientation ratio SOR is calculated as m0 / m90 .
  • thermoplastic liquid crystal polymer film may be increased by heating for several hours at (Tm 0 -10)°C or higher (for example, about (Tm 0 -10) to (Tm 0 +30)°C, preferably about (Tm 0 ) to (Tm 0 +20)°C) relative to the melting point (Tm 0) of the thermoplastic liquid crystal polymer.
  • the melting point (Tm) of the thermoplastic liquid crystal polymer film may be, for example, 270 to 380° C., and preferably 280 to 370° C.
  • the melting point (Tm) of the thermoplastic liquid crystal polymer film can be determined using a differential scanning calorimeter, similar to the melting point Tm 0 of the thermoplastic liquid crystal polymer.
  • the thickness of the thermoplastic liquid crystal polymer film can be set appropriately depending on the application. For example, when considering use as a material for the insulating layer of a multilayer circuit board, it may be 10 to 500 ⁇ m, preferably 15 to 250 ⁇ m, and more preferably 25 to 180 ⁇ m.
  • blown films were produced for thermoplastic liquid crystal polymers with different melting points, with one stage or with only heat retention and no heating in the comparative examples, and with two or three stages of temperature control in the examples.
  • a die with a die lip diameter of 200 mm was used.
  • the conditions for each example and comparative example are shown below.
  • hf/ht is the ratio of the frost line height hf to the height ht to the top end of the heating means 8
  • hf/hm is the ratio of the frost line height hf to the length (height direction) hm of the heated area of the molten bubble.
  • thermoplastic liquid crystal polymer films when thermoplastic liquid crystal polymer films are inflation molded, it is possible to produce films with no wrinkles even with large bubbles and with a controlled degree of molecular orientation, thereby improving the productivity of thermoplastic liquid crystal polymer films used in applications such as insulating substrates for electronic devices.
  • Extrusion means (extruder) 2 Annular die 2a Die lip 2b Blowing port 3 Bubble 4 Guide plate 5 Pinch roll 6 Winding means 7 Air ring 8 Heating means

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  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
PCT/JP2023/035441 2022-10-06 2023-09-28 熱可塑性液晶ポリマーフィルムの製造方法 Ceased WO2024075636A1 (ja)

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Publication number Priority date Publication date Assignee Title
WO2025220715A1 (ja) * 2024-04-19 2025-10-23 ポリプラスチックス株式会社 三次元造形物及びその製造方法

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JPH05338010A (ja) * 1992-06-10 1993-12-21 Maruyasu:Kk 押出成形機用熱回収システム及びこれを用いたインフ レーション成形システム
JP2003291210A (ja) * 2002-03-29 2003-10-14 Kuraray Co Ltd 液晶ポリマーフィルムの製造方法および製造装置
JP2004106533A (ja) * 2002-08-30 2004-04-08 Kuraray Co Ltd インフレーションフィルムの製造装置および方法
JP2005001376A (ja) * 2003-05-21 2005-01-06 Kuraray Co Ltd フィルムの製造方法

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JP4632558B2 (ja) 2001-02-19 2011-02-16 株式会社クラレ インフレーション製膜装置
JP2005286032A (ja) 2004-03-29 2005-10-13 Sumitomo Electric Ind Ltd 光半導体デバイス、および光半導体デバイスを製造する方法

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Publication number Priority date Publication date Assignee Title
JPH05338010A (ja) * 1992-06-10 1993-12-21 Maruyasu:Kk 押出成形機用熱回収システム及びこれを用いたインフ レーション成形システム
JP2003291210A (ja) * 2002-03-29 2003-10-14 Kuraray Co Ltd 液晶ポリマーフィルムの製造方法および製造装置
JP2004106533A (ja) * 2002-08-30 2004-04-08 Kuraray Co Ltd インフレーションフィルムの製造装置および方法
JP2005001376A (ja) * 2003-05-21 2005-01-06 Kuraray Co Ltd フィルムの製造方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025220715A1 (ja) * 2024-04-19 2025-10-23 ポリプラスチックス株式会社 三次元造形物及びその製造方法

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