WO2022220204A1 - Composition de résine à base de polyester cristallin liquide, film à base de polyester cristallin liquide utilisant ladite composition, film stratifié métallique utilisant ledit film, et carte de circuit imprimé - Google Patents

Composition de résine à base de polyester cristallin liquide, film à base de polyester cristallin liquide utilisant ladite composition, film stratifié métallique utilisant ledit film, et carte de circuit imprimé Download PDF

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Publication number
WO2022220204A1
WO2022220204A1 PCT/JP2022/017447 JP2022017447W WO2022220204A1 WO 2022220204 A1 WO2022220204 A1 WO 2022220204A1 JP 2022017447 W JP2022017447 W JP 2022017447W WO 2022220204 A1 WO2022220204 A1 WO 2022220204A1
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Prior art keywords
crystalline polyester
liquid crystalline
thermoplastic liquid
film
melting point
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PCT/JP2022/017447
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English (en)
Japanese (ja)
Inventor
多田修悟
甲斐工也
安部隆志
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大倉工業株式会社
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Application filed by 大倉工業株式会社 filed Critical 大倉工業株式会社
Priority to JP2023514635A priority Critical patent/JPWO2022220204A1/ja
Priority to KR1020237030668A priority patent/KR20230142598A/ko
Priority to CN202280017819.1A priority patent/CN116897190A/zh
Publication of WO2022220204A1 publication Critical patent/WO2022220204A1/fr

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Classifications

    • 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
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • 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
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/09—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings

Definitions

  • the present invention relates to a liquid crystalline polyester resin composition containing, as a main component, a thermoplastic liquid crystalline polyester capable of forming an optically anisotropic melt phase.
  • the present invention also relates to a liquid crystal polyester film using the resin composition, and a metal laminate film and a circuit board using the film.
  • thermoplastic liquid crystalline polyesters exhibit excellent mechanical and electrical properties, low dimensional change rate, high heat resistance and chemical stability, and are therefore useful in the electronic and electrical fields.
  • a thermoplastic liquid crystalline polyester having a melting point of 300° C. or more is useful for printed circuit board applications because it can be reflowed with lead-free solder.
  • thermoplastic liquid crystalline polyesters have the property that rigid molecular chains are arranged in an orderly manner even in a molten state, and the molecular chains do not get entangled and flow in a slippery manner. alone does not reach a level that can be used.
  • thermoplastic liquid crystalline polyesters are highly dependent on the shear stress, and a slight increase in the shear stress significantly reduces the melt viscosity. For this reason, when the thermoplastic liquid crystalline polyester is melt extruded by the inflation extrusion molding method, the shear stress generated at the die part causes the melt viscosity to drop rapidly, making it difficult to maintain the shape of the bubble. There is a problem that it is difficult to stably form a film.
  • thermoplastic liquid crystalline polyester has a characteristic that the melt viscosity greatly depends on the temperature, and the melt viscosity is remarkably lowered by a slight temperature rise in the vicinity of the melting point. The higher the melting point of the thermoplastic liquid crystalline polyester, the more pronounced this tendency is.
  • thermoplastic liquid crystalline polyester with a melting point of 300° C. or higher has a low melt viscosity near the melting point. The extruded bubbles are likely to be perforated, making it difficult to stably form a film.
  • Patent Document 2 discloses that the polyester is composed of a polyester that forms an optically anisotropic molten phase at a temperature of 250° C. or higher and a polyester that forms an optically anisotropic molten phase at a temperature of 200° C. or lower. It is an invention relating to a liquid crystalline polyester composition characterized in that by blending a liquid crystalline polyester that forms an optically anisotropic melt phase at a temperature of 200° C. or less, the melt viscosity is reduced and the low temperature moldability is improved. is stated.
  • Patent Document 3 discloses that the liquid crystal polymer (A) has a tensile modulus of elasticity of 20 to 32 GPa and a melting point of 250° C. or more and 330° C. or less, and a liquid crystal polymer (B) whose melting point is 190° C. or more and less than 250° C. It is an invention relating to a liquid crystal polymer blend characterized in that the fluidity during molding and low-temperature workability are improved by blending a liquid crystal polymer exhibiting a low melting point.
  • Patent Documents 2 and 3 only disclose that the composition is formed into a test piece by injection molding, and there is nothing about continuously forming a film by inflation extrusion molding. Not disclosed.
  • JP 2005-1376 Japanese Patent Laid-Open No. 5-186671 JP 2007-119639
  • the present invention has been made in view of such problems, and provides a liquid crystal polyester resin composition that is excellent in mechanical properties, electrical properties, and heat resistance that can stably form a film in inflation extrusion molding. for the purpose.
  • thermoplastic liquid crystal polyester with a high melting point for example, a melting point of 300 ° C. or higher
  • a thermoplastic liquid crystal polyester with a high melting point for example, a melting point of 300 ° C. or higher
  • the degree of reduction is reduced, and that it is possible to stably form a film in inflation extrusion molding, which led to the completion of the present invention.
  • thermoplastic liquid crystalline polyester resin composition containing a thermoplastic liquid crystalline polyester (A) and a thermoplastic liquid crystalline polyester (B), wherein the thermoplastic liquid crystalline polyester (A) and the thermoplastic liquid crystalline polyester (B)
  • the thermoplastic liquid crystal polyester (A) has a melting point difference of 5° C. or more and 95° C. or less, and contains a structural unit derived from p-hydroxybenzoic acid and a structural unit derived from 6-hydroxy-2-naphthoic acid.
  • R 122 ( ⁇ Tm / ⁇ Tm+10 ) is less than 3.4. is provided and (3) The melt viscosity ( ⁇ Tm ) at the melting point of the thermoplastic liquid crystalline polyester (A) measured under the conditions of a shear rate of 1216 sec ⁇ 1 and the thermoplastic liquid crystalline polyester (A) measured under the conditions of a shear rate of 1216 sec ⁇ 1 ) to the melt viscosity ( ⁇ Tm+10 ) at the melting point + 10 ° C.
  • R 1216 ( ⁇ Tm / ⁇ Tm+10 ) at the melting point of the thermoplastic liquid crystalline polyester (A) measured under the condition of a shear rate of 122 sec -1 Melt viscosity ratio R 122 ( ⁇ Tm / ⁇ Tm +10) of the melt viscosity ( ⁇ Tm ) and the melt viscosity ( ⁇ Tm+10 ) at the melting point + 10 ° C. of the thermoplastic liquid crystalline polyester (A) measured under the condition of a shear rate of 122 sec -1 ) having a ratio (R 122 /R 1216 ) of 1.5 or less.
  • thermoplastic liquid crystalline polyester (A) has a melting point of 300° C. or more and the thermoplastic liquid crystalline polyester (B) has a melting point of less than 300° C.
  • a polyester resin composition is provided, (7)
  • the liquid crystal polyester resin composition according to (1) is provided, (8) A liquid crystal polyester film characterized by comprising the resin composition according to any one of (1) to (7) is provided, (9) 0.75 ⁇ F (TD) / F (MD) ⁇ 1.25, where F (MD) is the tensile strength in the machine direction of the film and F (TD) is the tensile strength in the width direction of the film.
  • the liquid crystalline polyester film according to (8) is provided, (10) A method for producing a liquid crystal polyester film according to (9) is provided, wherein the film is formed by an inflation extrusion method, (11) A metal laminate film is provided, wherein a metal layer is laminated on one side or both sides of the liquid crystal polyester film according to (9), (12) Provided is a circuit board comprising at least one conductor layer and the thermoplastic liquid crystal polyester film described in (9).
  • the liquid crystalline polyester resin composition of the present invention is obtained by blending a thermoplastic liquid crystalline polyester having a relatively low melting point with a thermoplastic liquid crystalline polyester having a high melting point and excellent heat resistance. , It is possible to suppress the occurrence of holes in the bubbles extruded from the die, and it is possible to stably form a film, and the excellent mechanical properties of thermoplastic liquid crystalline polyester with a high melting point. , electrical properties, and heat resistance can be maintained. Therefore, the liquid crystal polyester film made of the liquid crystal polyester resin composition of the present invention and the metal laminate film obtained by bonding the liquid crystal polyester film and the metal layer have excellent mechanical properties, electrical properties, and solder reflow properties. and can be suitably used for applications such as laminates for circuit boards suitable for high-speed communication applications.
  • the liquid crystalline polyester resin composition of the present invention is a resin composition containing a thermoplastic liquid crystalline polyester (A) having a high melting point and excellent heat resistance and a thermoplastic liquid crystalline polyester (B) having a lower melting point than the thermoplastic liquid crystalline polyester (A).
  • the difference in melting point between the thermoplastic liquid crystal polyester (A) and the thermoplastic liquid crystal polyester (B) is 5°C or more and 95°C or less.
  • the difference in melting point between the thermoplastic liquid crystal polyester (A) and the thermoplastic liquid crystal polyester (B) is preferably 10°C or higher and 80°C or lower, more preferably 20°C or higher and 60°C or lower, and particularly preferably 25°C or higher and 55°C or lower. .
  • thermoplastic liquid crystalline polyester (A) and the thermoplastic liquid crystalline polyester (B) are liquid crystalline polyesters exhibiting melt anisotropy (polyester capable of forming an optically anisotropic melt phase).
  • melt anisotropy polyethylene glycol
  • the properties of melt anisotropy can be confirmed by a conventional polarization inspection method using crossed polarizers. Specifically, the melting anisotropy was measured by using a polarizing microscope (manufactured by Olympus Co., etc.), melting a sample placed on a hot stage (manufactured by Linkham Co., etc.), and exposing it to a 150-fold magnification in a nitrogen atmosphere. It can be confirmed by observation.
  • a liquid crystalline resin exhibiting optical anisotropy when melted is optically anisotropic and transmits light when inserted between crossed polarizers. If the sample is optically anisotropic, polarized light will be transmitted, for example, even in the still molten liquid state.
  • thermoplastic liquid crystal polyester (A) used in the resin composition of the present invention is derived from structural units derived from p-hydroxybenzoic acid (sometimes referred to as monomer component A) and 6-hydroxy-2-naphthoic acid. (sometimes referred to as monomer component B) is included as an essential unit.
  • the thermoplastic liquid crystalline polyester (A) may contain a monomer component C other than the monomer component A and the monomer component B, and the monomer component C includes an aromatic or aliphatic dicarboxylic acid; an aromatic or aliphatic dihydroxy compounds; aromatic hydroxycarboxylic acids; aromatic diamines, aromatic hydroxyamines or aromatic aminocarboxylic acids;
  • the thermoplastic liquid crystal polyester (A) used in the resin composition of the present invention is preferably a resin having a melting point of 300°C or higher. If the melting point is lower than 300° C., the reflowability of the solder is poor, so if it is used for printed circuit boards and the like, the processing method will be restricted.
  • the melting point of the thermoplastic liquid crystal polyester (A) is not particularly limited, but from the viewpoint of heat resistance and moldability, for example, it is preferably 300° C. or higher and 400° C. or lower, and 305° C. or higher and 370° C. or lower. is more preferably 310° C. or higher and 360° C. or lower, and particularly preferably 315° C. or higher and 345° C. or lower.
  • thermoplastic liquid crystal polyester (A) The melting point of the thermoplastic liquid crystal polyester (A) was obtained by heating the sample at a rate of 10 ° C./min using a differential scanning calorimeter (DSC) to completely melt it, and then heating the melt at 10 ° C./min.
  • the melting point is the position of the endothermic peak that appears when the temperature is increased again at a rate of 10°C/min.
  • thermoplastic liquid crystal polyester (A) having a melting point of 300° C. or higher include, for example, the binary of p-hydroxybenzoic acid (monomer component A) and 6-hydroxy-2-naphthoic acid (monomer component B).
  • System polycondensate Ternary polycondensate of p-hydroxybenzoic acid (monomer component A), 6-hydroxy-2-naphthoic acid (monomer component B), and terephthalic acid (monomer component C); p- hydroxybenzoic acid (monomer component A), 6-hydroxy-2-naphthoic acid (monomer component B), terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-dihydroxybiphenyl, bisphenol A, a ternary or higher polycondensate comprising one or more selected from the group consisting of hydroquinone and ethylene terephthalate (monomer component C); and the like.
  • thermoplastic liquid crystal polyester (B) used in the resin composition of the present invention includes structural units derived from p-hydroxybenzoic acid (sometimes referred to as monomer component A') and 6-hydroxy-2-naphthoic acid.
  • a structural unit derived from (sometimes referred to as monomer component B') as an essential unit, or a structural unit derived from p-hydroxybenzoic acid (sometimes referred to as monomer component A'), and 4,4' -Constituent units derived from dihydroxybiphenyl (sometimes referred to as monomer component B') are included as essential units.
  • the thermoplastic polyester (B) may contain a monomer component C' other than the monomer component A' and the monomer component B', and the monomer component C' includes an aromatic or aliphatic dicarboxylic acid; aliphatic dihydroxy compounds; aromatic hydroxycarboxylic acids; aromatic diamines, aromatic hydroxyamines or aromatic aminocarboxylic acids;
  • the thermoplastic liquid crystal polyester (B) used in the resin composition of the present invention preferably has a melting point of less than 300°C.
  • the melting point of the thermoplastic liquid crystal polyester (B) is not particularly limited, but the heat resistance of the thermoplastic liquid crystal polyester (A), which has excellent heat resistance, is maintained, From the viewpoint of reducing the dependence of melt viscosity on temperature and shear stress, for example, it is preferably 230 ° C. or higher and lower than 300 ° C., more preferably 250 ° C. or higher and 295 ° C. or lower, and 260 ° C. or higher and 290 ° C. or lower. 265° C. or more and 285° C. or less is particularly preferable.
  • the melting point of the thermoplastic liquid crystal polyester (B) may be measured by the same method as the melting point of the thermoplastic liquid crystal polyester (A) described above.
  • thermoplastic liquid crystal polyester (B) having a melting point of less than 300° C. examples include p-hydroxybenzoic acid (monomer component A′) and 6-hydroxy-2-naphthoic acid (monomer component B′).
  • the blending ratio of the thermoplastic liquid crystalline polyester (B) is less than the above range, the film forming processability of the film by inflation extrusion molding of the liquid crystalline polyester resin composition cannot be improved, and stable film formation cannot be performed. becomes difficult. Further, if the blending ratio of the thermoplastic liquid crystal polyester (B) is more than the above range, the film forming processability of the film by inflation extrusion molding of the liquid crystal polyester resin composition cannot be improved, and stable film forming cannot be performed. becomes difficult, and the heat resistance and mechanical properties of the liquid crystal polyester film made of the liquid crystal polyester resin composition are lowered.
  • the liquid crystalline polyester resin composition of the present invention was measured under the conditions of a shear rate of 122 sec -1 and the melt viscosity ( ⁇ Tm ) at the melting point of the thermoplastic liquid crystalline polyester (A) measured under the conditions of a shear rate of 122 sec -1 .
  • the melt viscosity ratio R 122 ( ⁇ Tm / ⁇ Tm+10 ) to the melt viscosity ( ⁇ Tm+10 ) at the melting point +10° C. of the thermoplastic liquid crystalline polyester (A) is preferably less than 3.4.
  • the melt viscosity ratio R 122 ( ⁇ Tm / ⁇ Tm+10 ) is more preferably less than 3.3, still more preferably less than 3.0, and particularly preferably less than 2.5.
  • the lower limit of the melt viscosity ratio ( ⁇ Tm / ⁇ Tm+10 ) is not particularly limited, it is usually 1.0 or more.
  • the liquid crystalline polyester resin composition of the present invention was measured under the conditions of a shear rate of 1216 sec -1 and the melt viscosity ( ⁇ Tm ) at the melting point of the thermoplastic liquid crystalline polyester (A) measured under the conditions of a shear rate of 1216 sec -1 .
  • thermoplastic liquid crystalline polyester (A) measured under the conditions of a shear rate of 122 sec -1 Melt viscosity ratio R 122 ( ⁇ Tm / ⁇ Tm+10 ) ratio ( R122 ( ⁇ Tm / ⁇ Tm+10 )/ R1216 ( ⁇ Tm / ⁇ Tm+10 )) (hereinafter sometimes referred to as R122 / R1216 ) is 1.50 or less Preferably.
  • the value of the ratio (R 122 /R 1216 ) is more preferably 1.45 or less, even more preferably 1.40 or less, and particularly preferably 1.35 or less.
  • the lower limit is not particularly limited, it is, for example, 0.5 or more, preferably 0.7 or more, and more preferably 0.85 or more.
  • the liquid crystalline polyester resin composition of the present invention has a melt viscosity ( ⁇ Tm ) at the melting point of the thermoplastic liquid crystalline polyester (A) measured under the conditions of each shear rate within the range of 122 to 2430 sec ⁇ 1 and The difference (variation) between the maximum value and the minimum value of the melt viscosity ratio R ( ⁇ Tm / ⁇ Tm+10 ) to the melt viscosity ( ⁇ Tm+10 ) at the melting point + 10 ° C.
  • thermoplastic liquid crystalline polyester (A) is less than 1.1 If it is within the above range, the dependence of the melt viscosity on temperature and shear stress is small, so the change in melt viscosity near the extrusion temperature in inflation extrusion molding is small, and the film forming processability of the film by inflation extrusion molding is improved. be improved.
  • the variation within the shear rate range of 122 to 2430 sec ⁇ 1 is more preferably less than 1.1, even more preferably less than 1.0, and particularly preferably less than 0.8. Although the lower limit is not particularly limited, it is, for example, 0.1 or more.
  • the liquid crystalline polyester resin composition of the present invention has a melt viscosity ( ⁇ Tm ) at the melting point of the thermoplastic liquid crystalline polyester (A) measured under the conditions of each shear rate within the range of 6 to 2430 sec ⁇ 1 and The difference (variation) between the maximum value and the minimum value of the melt viscosity ratio R ( ⁇ Tm / ⁇ Tm+10 ) to the melt viscosity ( ⁇ Tm+10 ) at the melting point +10 ° C.
  • thermoplastic liquid crystalline polyester (A) is less than 3.4 If it is within the above range, the dependence of the melt viscosity on temperature and shear stress is small, so the change in melt viscosity near the extrusion temperature in inflation extrusion molding is small, and the film forming processability of the film by inflation extrusion molding is improved. be improved.
  • the variation in the shear rate range of 6 to 2430 sec ⁇ 1 is more preferably less than 3.2, more preferably less than 3.0, particularly preferably less than 2.5, less than 2.0, and less than 1.5. Although the lower limit is not particularly limited, it is, for example, 0.1 or more.
  • the liquid crystalline polyester-based resin composition of the present invention may contain resin components other than the thermoplastic liquid crystalline polyester (A) and the thermoplastic liquid crystalline polyester (B) as long as the effects of the present invention are not impaired.
  • Other resin components include polyarylates, polyphenylene sulfides, polyphenylene ethers, polyetheretherketones, polyetherimides, cycloolefin polymers, polyamides, polyamideimides, polyimides, epoxy group-containing olefin copolymers, styrene resins, and the like.
  • a thermoplastic resin is mentioned.
  • the liquid crystal polyester resin composition of the present invention may also contain additives such as lubricants, antioxidants and fillers.
  • the liquid crystalline polyester-based resin composition of the present invention contains other components, it preferably contains the total amount of the thermoplastic liquid crystalline polyester (A) and the thermoplastic liquid crystalline polyester (B) as the main component.
  • the main component means that the composition ratio of the components constituting the resin composition is 50% by weight or more, preferably 60% by weight or more, and more preferably 80% by weight. or more, more preferably 90% by weight or more, and particularly preferably 95% by weight or more.
  • the present invention also proposes a film made of the resin composition described above and a method for producing the film.
  • the liquid crystalline polyester film of the present invention is obtained by blending the thermoplastic liquid crystalline polyester (A) and the thermoplastic liquid crystalline polyester (B) by a known method to form a film.
  • the resin composition of the present invention is melt-kneaded and granulated prior to film formation in order to provide a stable kneading state. is preferred.
  • Equipment for melt-kneading is not particularly limited, but various known extruders such as batch kneaders, kneaders, co-kneaders, Banbury mixers, roll mills, single-screw or twin-screw extruders, etc. is mentioned. Among these, single-screw extruders and twin-screw extruders are preferably used because of their excellent kneading ability and productivity.
  • thermoplastic liquid crystal polyester (B) By blending the thermoplastic liquid crystal polyester (B) in the resin composition of the present invention, it is possible to suppress a rapid decrease or change in the melt viscosity of the resin composition due to temperature, shear stress, etc. It becomes possible to improve the film forming processability of the film.
  • the resin composition described above is supplied to a melt extruder equipped with an annular slit die, and the molten resin composition is extruded upward or downward in a bubble shape from the annular slit of the extruder, A method of obtaining a film by blowing air or an inert gas into bubbles made of a resin composition in a molten state to expand and stretch the bubbles in a direction (TD direction) perpendicular to the flow direction (MD direction).
  • the cylinder temperature of the melt extruder is usually 280-400°C, preferably 320-380°C.
  • the interval between the annular slits is usually 0.1-5 mm, preferably 0.2-2 mm.
  • the diameter of the annular slit is usually 20-1000 mm, preferably 25-600 mm.
  • the blow ratio is preferably 1.5 or more, more preferably 2.0 or more, still more preferably 4.0 or more, and particularly preferably 4.5 or more. preferable.
  • the upper limit of the blow ratio is not particularly limited, the blow ratio is, for example, 10 or less.
  • the draft ratio is preferably 1.5 or more and 20 or less, more preferably 1.5 or more and 10 or less.
  • the blow ratio is the draw ratio in the TD direction
  • the draft ratio is the draw ratio in the MD direction.
  • the blow ratio in order to improve the anisotropy of the film works in the direction of destabilizing the shape retention of the bubbles made of the resin composition in a molten state. It becomes easy to generate holes.
  • a liquid crystalline polyester having a melting point exceeding 300° C. is expanded and stretched by inflation extrusion molding so that the blow ratio is 4.0 or more, the bubbles frequently perforate, making it difficult to form a film.
  • the resin composition of the present invention can suppress a rapid decrease or change in the melt viscosity of the resin composition due to temperature, shear stress, etc. by blending the thermoplastic liquid crystal polyester (B). Therefore, even if the blow ratio is 4.0 or more, it is possible to stably form a film while suppressing the occurrence of holes in the bubbles and improving the anisotropy of the film.
  • the thickness of the liquid crystal polyester-based film of the present invention is not particularly limited, but is, for example, 0.5 ⁇ m or more and 1000 ⁇ m or less, and considering the handleability and productivity during melt extrusion, it is 5 ⁇ m or more and 500 ⁇ m or less. more preferably 10 ⁇ m or more and 300 ⁇ m or less, and even more preferably 20 ⁇ m or more and 200 ⁇ m or less.
  • the liquid crystal polyester film of the present invention preferably has a tensile strength of 200 MPa or more in the machine direction (MD direction) and the width direction (TD direction). More preferably, the tensile strength is 220 MPa or more, and even more preferably 240 MPa or more. Although the upper limit of the tensile strength is not particularly limited, for example, it is preferably 500 MPa or less, more preferably 400 MPa or less, and even more preferably 350 MPa or less. When the tensile strength is within the above range, the film is excellent in handleability when processed into a circuit board laminate suitable for high-speed communication applications, and can be prevented from being damaged or cracked at the ends of the film.
  • the liquid crystalline polyester film of the present invention preferably has low anisotropy in the machine direction (MD direction) and width direction (TD direction).
  • the tensile strength F(TD) in the film width direction relative to the tensile strength F(MD) in the film machine direction is preferably 0.5 or more and 1.5 or less. , more preferably 0.75 or more and 1.25 or less, still more preferably 0.85 or more and 1.15 or less, and particularly preferably 0.90 or more and 1.10 or less.
  • the anisotropy of the mechanical properties and electrical properties of the film is small, and it is suitable for high-speed communication applications. It can be suitably used for applications such as laminates for circuit boards.
  • the liquid crystalline polyester film of the present invention can be further heat-treated to relax the orientation of the molecular chains and improve the film dimensional stability.
  • a conventionally known method can be used for heat treatment, and examples thereof include contact heat treatment, non-contact heat treatment, and the like, and the type thereof is not particularly limited.
  • the liquid crystalline polyester film of the present invention may be used as a metal laminate film by laminating a metal layer thereon.
  • the surface of the liquid crystalline polyester film on which the metal layer is to be laminated may be subjected to corona discharge treatment, ultraviolet irradiation treatment or plasma treatment in order to increase adhesive strength.
  • Methods for laminating a metal layer on the liquid crystal polyester film of the present invention include, for example, (1) a method of attaching the liquid crystal polyester film to a metal foil by thermocompression bonding, and (2) bonding the liquid crystal polyester film and the metal foil. (3) a method of forming a metal layer on a liquid crystal polyester film by vapor deposition; Among them, the lamination method (1) is a method of press-bonding the liquid crystal polyester film to the metal foil near the flow initiation temperature using a press machine or a heating roll, and is recommended because it can be easily carried out. Examples of adhesives used in the lamination method (2) include hot-melt adhesives and polyurethane adhesives. Among them, an epoxy group-containing ethylene copolymer is preferably used as an adhesive.
  • Examples of the lamination method (3) include an ion beam sputtering method, a high frequency sputtering method, a DC magnetron sputtering method, and a glow discharge method. Among them, the high frequency sputtering method is preferably used.
  • the structure of the metal laminate film thus obtained includes, for example, a two-layer structure of a liquid crystal polyester film and a metal layer, a three-layer structure in which metal layers are laminated on both sides of the liquid crystal polyester film, and a liquid crystal polyester film and a metal layer. A five-layer structure in which metal layers are alternately laminated can be mentioned. For the purpose of developing high strength, the laminate may be subjected to heat treatment, if necessary.
  • the thickness of the metal layer is not particularly limited, it is preferably 1.5 to 1000 ⁇ m, more preferably 2 to 500 ⁇ m, even more preferably 5 to 150 ⁇ m, particularly preferably 7 to 100 ⁇ m. If the thickness is less than the above range, the mechanical strength is inferior, and if the thickness is greater than the above range, the handleability and workability are inferior.
  • the circuit board of the present invention includes at least one conductor layer and at least one insulator (or dielectric) layer. Its form is not particularly limited, and it can be used as various high-frequency circuit boards by known or common means. Also, the circuit board may be a circuit board (or a semiconductor element mounting board) on which a semiconductor element (for example, an IC chip) is mounted.
  • the conductor layer used in the circuit board of the present invention is formed of, for example, at least a metal having conductivity, and a circuit pattern is formed on this conductor layer using a known circuit processing method.
  • a circuit pattern is formed on the metal layer portion of the metal laminate film described above.
  • LCP (1) Thermoplastic liquid crystal polyester (polyplastic LAPEROS (registered trademark) C950RX manufactured by Su Co., Ltd., melting point: 320 ° C.)
  • LCP (2) Thermoplastic liquid crystal polyester (LAPEROS (registered trademark) manufactured by Polyplastics Co., Ltd.) consisting of structural units derived from p-hydroxybenzoic acid and structural units derived from 6-hydroxy-2-naphthoic acid A950RX, melting point: 280°C)
  • LCP (3) Thermoplastic liquid crystal polyester (ENEOS liquid crystal stock Zydar (registered trademark) CX-2199 manufactured by the company, melting point: 280°C)
  • melt viscosity ratio melt viscosity at the melting point of the thermoplastic liquid crystalline polyester (A) ( ⁇ Tm )/melt viscosity at the melting point of the thermoplastic liquid crystalline polyester (A) + 10°C ( ⁇ Tm + 10 )
  • the melt viscosity ratio of the thermoplastic liquid crystal polyester resin alone (reference example) used in Examples and Comparative Examples was measured based on the melting point of LCP (1). .
  • thermoplastic liquid crystal polyester (A) comprising structural units derived from p-hydroxybenzoic acid having a melting point of 320° C., structural units derived from 6-hydroxy-2-naphthoic acid, and structural units derived from terephthalic acid. 3, 5, 10, 20 thermoplastic liquid crystalline polyester (B) consisting of a structural unit derived from p-hydroxybenzoic acid having a melting point of 280 ° C. and a structural unit derived from 6-hydroxy-2-naphthoic acid.
  • the film-forming processability of the film by inflation extrusion molding was improved even at a draw ratio exceeding 0.0.
  • the liquid crystal polyester films composed of the liquid crystal polyester resin compositions of Examples 2 to 5 stable film formation was possible without perforation in bubbles of the molten resin extruded from the die.
  • the liquid crystal polyester films of Examples 1 to 6 maintained the excellent mechanical properties, electrical properties, and heat resistance of thermoplastic liquid crystal polyesters having a melting point of 300 ° C. or higher, and had anisotropic tensile strength. showed small results.
  • thermoplastic liquid crystal polyester (A) comprising structural units derived from p-hydroxybenzoic acid having a melting point of 320° C., structural units derived from 6-hydroxy-2-naphthoic acid, and structural units derived from terephthalic acid.
  • thermoplastic liquid crystal polyester (B) comprising structural units derived from p-hydroxybenzoic acid having a melting point of 280°C, structural units derived from 4,4'-dihydroxybiphenyl, and structural units derived from terephthalic acid.
  • the liquid crystal polyester film of Example 7 maintains the excellent mechanical properties, electrical properties, and heat resistance of the thermoplastic liquid crystal polyester having a melting point of 300 ° C. or higher, and the anisotropy of tensile strength is small. showed that.
  • the liquid crystalline polyester film of Comparative Example 1 made of a resin composition in which 5% by weight of a thermoplastic liquid crystalline polyester (B) having a melting point of 220° C. is blended with a thermoplastic liquid crystalline polyester (A) having a melting point of 320° C. shows a high dependence of melt viscosity on temperature and shear rate, and at a draw ratio of more than 4.0 blow ratio, holes are generated in the bubbles of molten resin extruded from the die, resulting in stable film formation. showed results that could not be done.
  • the liquid crystal polyester film of Comparative Example 1 exhibited a large anisotropy of tensile strength even though the blow ratio was more than 4.0.
  • the liquid crystalline polyester film of Reference Example 1 which consists of only a thermoplastic liquid crystalline polyester with a melting point of 320° C., shows a high degree of dependence of the melt viscosity on temperature and shear rate, and the blow ratio exceeds 4.0 at a draw ratio of more than 4.0.
  • the melted resin extruded from the mold was perforated, and the shape of the bubble became unstable.
  • the liquid crystalline polyester film of Reference Example 2 which consists of only a thermoplastic liquid crystalline polyester having a melting point of 280° C., has a blow ratio of more than 4.0. However, the melting point was low and the solder reflow property was poor.
  • the liquid crystalline polyester film obtained by the present invention can be used for electrical insulation of motors and transformers, flexible solar cell element forming films, etc. by taking advantage of its excellent electrical properties, dimensional stability and heat resistance. It's being used. It can also be used in acoustic fields such as surface protective films and diaphragms.
  • the metal laminate film of the present invention can also be used for circuit boards, capacitors, electromagnetic shielding materials, and the like.
  • the circuit board of the present invention may be used for various transmission lines and antennas (for example, microwave or millimeter wave antennas), and may be used for antenna devices in which an antenna and a transmission line are integrated.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention vise à fournir une composition de résine à base de polyester cristallin liquide qui présente d'excellentes propriétés mécaniques, d'excellentes propriétés électriques et une excellente résistance à la chaleur, et à partir de laquelle un film peut être formé de manière stable par moulage par extrusion-soufflage. L'invention concerne par conséquent une composition de résine à base de polyester cristallin liquide qui contient un polyester cristallin liquide thermoplastique (A) et un polyester cristallin liquide thermoplastique (B), et est caractérisé en ce que la différence de point de fusion entre le polyester cristallin liquide thermoplastique (A) et le polyester cristallin liquide thermoplastique (B) est de 5 à 95 °C, le polyester cristallin liquide thermoplastique (A) comprend une unité structurale dérivée d'acide p-hydroxybenzoïque et d'une unité structurale dérivée de l'acide 6-hydroxy-2-naphtoïque, le polyester cristallin liquide thermoplastique (B) soit comprend une unité structurale dérivée d'acide p-hydroxybenzoïque et une unité structurale dérivée d'acide 6-hydroxy-2-naphtoïque soit comprend une unité structurale dérivée d'acide p-hydroxybenzoïque et une unité structurale dérivée de 4,4'-dihydroxybiphényle, le rapport de mélange du polyester cristallin liquide thermoplastique (A) sur le polyester cristallin liquide thermoplastique (B) est (A)/(B) = 40 à 98 % en poids : 2 à 60 % en poids, et la composition de résine à base de polyester cristallin liquide est destinée à être utilisée pour le moulage par extrusion-soufflage.
PCT/JP2022/017447 2021-04-14 2022-04-09 Composition de résine à base de polyester cristallin liquide, film à base de polyester cristallin liquide utilisant ladite composition, film stratifié métallique utilisant ledit film, et carte de circuit imprimé WO2022220204A1 (fr)

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JP2023514635A JPWO2022220204A1 (fr) 2021-04-14 2022-04-09
KR1020237030668A KR20230142598A (ko) 2021-04-14 2022-04-09 액정 폴리에스터계 수지 조성물, 해당 조성물을 이용한 액정 폴리에스터계 필름, 해당 필름을 이용한 금속 라미네이트 필름, 회로 기판
CN202280017819.1A CN116897190A (zh) 2021-04-14 2022-04-09 液晶聚酯系树脂组合物、使用该组合物的液晶聚酯系薄膜、使用该薄膜的金属层合薄膜、电路基板

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WO2023145489A1 (fr) * 2022-01-28 2023-08-03 住友化学株式会社 Composition de polyester à cristaux liquides, procédé de production de composition de polyester à cristaux liquides, film, et procédé de production de film

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JP2001342243A (ja) * 1999-11-02 2001-12-11 Sumitomo Chem Co Ltd 芳香族液晶性ポリエステルフィルムおよびその製造方法
JP2002060498A (ja) * 2000-08-11 2002-02-26 Sumitomo Chem Co Ltd 熱可塑性樹脂の製造方法
JP2009227807A (ja) * 2008-03-21 2009-10-08 Fujifilm Corp 液晶ポリマーおよびフィルム
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JP5041652B2 (ja) 2003-05-21 2012-10-03 株式会社クラレ フィルムの製造方法
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JP2001342243A (ja) * 1999-11-02 2001-12-11 Sumitomo Chem Co Ltd 芳香族液晶性ポリエステルフィルムおよびその製造方法
JP2002060498A (ja) * 2000-08-11 2002-02-26 Sumitomo Chem Co Ltd 熱可塑性樹脂の製造方法
JP2009227807A (ja) * 2008-03-21 2009-10-08 Fujifilm Corp 液晶ポリマーおよびフィルム
JP2018196953A (ja) * 2017-05-24 2018-12-13 株式会社リコー 立体造形用サポート材、立体造形用モデル材及び立体造形用サポート材のセット、立体造形物の製造方法、並びに立体造形装置
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WO2023145489A1 (fr) * 2022-01-28 2023-08-03 住友化学株式会社 Composition de polyester à cristaux liquides, procédé de production de composition de polyester à cristaux liquides, film, et procédé de production de film

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