WO2021235427A1 - Composition liquide de polyester cristallin liquide, film de polyester cristallin liquide, stratifié et procédé de fabrication de film de polyester cristallin liquide - Google Patents

Composition liquide de polyester cristallin liquide, film de polyester cristallin liquide, stratifié et procédé de fabrication de film de polyester cristallin liquide Download PDF

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WO2021235427A1
WO2021235427A1 PCT/JP2021/018762 JP2021018762W WO2021235427A1 WO 2021235427 A1 WO2021235427 A1 WO 2021235427A1 JP 2021018762 W JP2021018762 W JP 2021018762W WO 2021235427 A1 WO2021235427 A1 WO 2021235427A1
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liquid crystal
crystal polyester
mass
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liquid composition
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PCT/JP2021/018762
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English (en)
Japanese (ja)
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昌平 莇
豊誠 伊藤
理彦 西田
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住友化学株式会社
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Priority to KR1020227043827A priority Critical patent/KR20230014717A/ko
Priority to JP2022524486A priority patent/JPWO2021235427A1/ja
Priority to CN202180036498.5A priority patent/CN115667398B/zh
Publication of WO2021235427A1 publication Critical patent/WO2021235427A1/fr

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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
    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • 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

Definitions

  • the present invention relates to a liquid crystal polyester liquid composition, a liquid crystal polyester film, a laminate, and a method for producing a liquid crystal polyester film.
  • Insulation materials are used for printed circuit boards on which electronic components are mounted.
  • a fluororesin having a good dielectric property is used as a method for improving the dielectric property of the insulating material.
  • a sheet formed after melt-kneading a resin composition containing a fluorine-containing polymer having a carbonyl group-containing group and a liquid crystal polymer or the like has electrical properties, impact resistance, and mechanical strength. It is said to be excellent.
  • the insulating material containing fluororesin has a problem that the adhesion strength with the copper foil is lowered.
  • the present invention has been made to solve the above-mentioned problems, and to provide a liquid crystal polyester liquid composition capable of producing a film having excellent adhesion strength to a copper foil and dielectric properties.
  • Another object of the present invention is to provide a liquid crystal polyester film, a laminate, and a method for manufacturing a liquid crystal polyester film, which are excellent in adhesion strength to a copper foil and dielectric properties.
  • the present inventors can apply a film-forming method capable of producing a film having excellent isotropic properties by using a liquid crystal polyester soluble in an aprotic solvent. Furthermore, they have found that the dielectric properties can be improved while maintaining the adhesion strength with the copper foil by using a fluororesin having a melting point of 305 ° C or less in combination with the liquid crystal polyester, and have completed the present invention.
  • rice field. That is, the present invention has the following aspects.
  • a liquid crystal polyester liquid composition containing a liquid crystal polyester (A) soluble in an aprotic solvent, an aprotic solvent (S), and a fluororesin (B) having a melting point of 305 ° C. or lower.
  • a liquid crystal polyester liquid composition containing a liquid crystal polyester (A) soluble in an aprotic solvent, an aprotic solvent (S), and a fluororesin (B) having a melting point of 305 ° C. or lower.
  • the liquid crystal polyester liquid composition according to the above [1] wherein the liquid crystal polyester (A) contains an amide bond.
  • the liquid crystal polyester (A) contains a structural unit represented by the following formula (A1), a structural unit represented by the following formula (A2), and a structural unit represented by the following formula (A3).
  • A1 liquid crystal polyester liquid composition according to the above [1] or [2].
  • Ar1 represents a 1,4-phenylene group, a 2,6-naphthalenedyl group, or a 4,4'-biphenylene group
  • Ar2 is a 1,4-phenylene group, a 1,3-phenylene group, Or, it represents a 2,6-naphthalenediyl group
  • Ar3 represents a 1,4-phenylene group or a 1,3-phenylene group
  • X represents -NH-
  • Y represents -O- or -NH-.
  • the Ar1 is a 2,6-naphthalenedyl group
  • the Ar2 is a 1,3-phenylene group
  • the Ar3 is a 1,4-phenylene group
  • the Y is —O—.
  • the content ratio of the liquid crystal polyester (A) is 10% by mass or more and 90% by mass or less
  • the content ratio of the fluororesin (B) is 10 with respect to the total content of the solid content of the liquid crystal polyester liquid composition.
  • the liquid crystal polyester liquid composition according to any one of the above [1] to [4], which is by mass% or more and 90% by mass or less.
  • the content ratio of the liquid crystal polyester (A) is 25% by mass or more and 40% by mass or less, and the content ratio of the fluororesin (B) is 25 with respect to the total content of the solid content of the liquid crystal polyester liquid composition.
  • the liquid crystal polyester liquid composition according to any one of the above [1] to [8], wherein the fluororesin (B) has a crystallite size of 2.9 ⁇ 10-8 m or less.
  • the fluororesin (B) is a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (perfluoroalkoxyalkane, PFA), polytetrafluoroethylene (PTFE), or tetrafluoroethylene-hexafluoropropylene copolymer ().
  • the liquid crystal polyester liquid composition according to any one of the above [1] to [9]. [11] The above [1] to [10], wherein the content of the liquid crystal polyester (A) is 0.01 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the aprotic solvent (S). The liquid crystal polyester liquid composition according to any one of the above.
  • the liquid crystal polyester liquid composition according to any one of the above [1] to [11], wherein the aprotic solvent (S) is N-methylpyrrolidone.
  • a liquid crystal polyester (A) and a fluororesin (B) having a melting point of 305 ° C. or lower are contained.
  • the liquid crystal polyester (A) contains a structural unit represented by the following formula (A1), a structural unit represented by the following formula (A2), and a structural unit represented by the following formula (A3).
  • Ar1 represents a 1,4-phenylene group, a 2,6-naphthalenedyl group, or a 4,4'-biphenylene group
  • Ar2 is a 1,4-phenylene group, a 1,3-phenylene group, Or, it represents a 2,6-naphthalenediyl group
  • Ar3 represents a 1,4-phenylene group or a 1,3-phenylene group
  • X represents -NH-
  • Y represents -O- or -NH-.
  • a laminate comprising a metal layer and the liquid crystal polyester film according to the above [13] or [14] laminated on the metal layer.
  • a laminate comprising a metal layer and a liquid crystal polyester film formed by applying the liquid crystal polyester liquid composition according to any one of [1] to [12] on the metal layer.
  • the liquid crystal polyester liquid composition according to any one of the above [1] to [12] is applied onto the support, and the aprotonic solvent (S) is removed from the liquid crystal polyester liquid composition.
  • a method for producing a liquid crystal polyester film which comprises obtaining a liquid crystal polyester film by heat treatment.
  • liquid crystal polyester liquid composition capable of producing a film having excellent adhesion strength to a copper foil and dielectric properties. Further, according to the present invention, it is possible to provide a liquid crystal polyester film, a laminate and a method for manufacturing a liquid crystal polyester film having excellent adhesion strength to a copper foil and dielectric properties.
  • liquid crystal polyester liquid composition the liquid crystal polyester film, the laminate, and the method for producing the liquid crystal polyester film of the present invention will be described.
  • the liquid crystal polyester liquid composition of the embodiment contains a liquid crystal polyester (A) soluble in an aprotic solvent, an aprotic solvent (S), and a fluororesin (B) having a melting point of 305 ° C. or lower. It is a thing.
  • the term "liquid composition” means a solution or dispersion that is liquid at normal temperature and pressure (25 ° C., 1 atm). In the case of a dispersion liquid, it means a dispersion liquid in which the dispersion medium is a liquid at normal temperature and pressure (25 ° C., 1 atm). The dispersion means a dispersion of undissolved solids in the solution.
  • solid content refers to components other than the solvent contained in the liquid composition.
  • the solid content to be dispersed include the above-mentioned fluororesin (B) and the later-described inorganic filler (C).
  • the solvent for example, the aprotic solvent (S) described later corresponds.
  • the ratio of the solid content to the total mass of the liquid composition is not particularly limited, and may be 0.5% by mass or more, and may be 0.5% by mass or more. It may be 80% by mass or less, 1% by mass or more and 70% by mass or less, or 5% by mass or more and 50% by mass or less.
  • liquid crystal polyester liquid composition according to the embodiment of the present invention is also simply referred to as the "liquid composition" of the embodiment.
  • the component (A) is a liquid crystal polyester soluble in the aprotic solvent (S).
  • the component (A) also contributes to increasing the adhesion strength with the metal foil and increasing the mechanical strength when the liquid composition of the embodiment is made into a film on the metal foil.
  • the liquid crystal polyester is a liquid crystal polyester that exhibits liquid crystal properties in a molten state, and is preferably melted at a temperature of 450 ° C. or lower.
  • the liquid crystal polyester may be a liquid crystal polyester amide, a liquid crystal polyester ether, a liquid crystal polyester carbonate, or a liquid crystal polyester imide.
  • the liquid crystal polyester is preferably a total aromatic liquid crystal polyester having only a structural unit derived from an aromatic compound as a raw material monomer.
  • "origin” means that the chemical structure of the functional group that contributes to the polymerization changes due to the polymerization of the raw material monomer, and no other structural change occurs.
  • the liquid crystal polyester (A) preferably contains an amide bond.
  • the liquid crystal polyester (A) contains an amide bond, it is possible to improve the adhesion strength with the copper foil when laminated with the copper foil as a film.
  • liquid crystal polyester (A) containing an amide bond and soluble in an aprotic solvent the structural unit represented by the following formula (A1), the structural unit represented by the following formula (A2), and the following formula (A3). Examples thereof include those including the structural units indicated by.
  • Ar1 represents a 1,4-phenylene group, a 2,6-naphthalenedyl group, or a 4,4'-biphenylene group
  • Ar2 is a 1,4-phenylene group, a 1,3-phenylene group, Or, it represents a 2,6-naphthalenediyl group
  • Ar3 represents a 1,4-phenylene group or a 1,3-phenylene group
  • X represents -NH-
  • Y represents -O- or -NH-. .
  • Ar2 is a 1,3-phenylene group. Since Ar2 is a 1,3-phenylene group, its dissolution in an aprotic solvent becomes even better. It is considered that this is because Ar2 is a 1,3-phenylene group and a bent structure is introduced into the polymer.
  • Ar1 is 2 from the viewpoint that it is well dissolved in an aprotic solvent and the adhesion strength and dielectric properties of the copper foil when laminated as a film are easily exhibited.
  • 6-Naphthalenediyl group Ar2 is preferably a 1,3-phenylene group, Ar3 is a 1,4-phenylene group, and Y is preferably —O—.
  • the ratio of the preferable content of each structural unit in the liquid crystal polyester can be exemplified as follows.
  • the content of the structural unit represented by the above formula (A1) is the total content of all the structural units constituting the liquid crystal polyester (A) (the mass of each structural unit constituting the liquid crystal polyester is the formula amount of each structural unit).
  • the amount of substance equivalent (mol) of each structural unit is obtained, and the total value thereof is preferably 30 mol% or more and 80 mol% or less, and 40 mol% or more and 70 mol% or more. It is more preferably 45 mol% or more and 65 mol% or less.
  • the content of the structural unit represented by the above formula (A2) is preferably 10 mol% or more and 35 mol% or less with respect to the total content of all the structural units constituting the liquid crystal polyester (A). It is more preferably mol% or more and 30 mol% or less, and even more preferably 17.5 mol% or more and 27.5 mol% or less.
  • the content of the structural unit (A2) is not more than the above upper limit value, the liquid crystal property tends to be good, and when it is more than the above lower limit value, the solubility in a solvent tends to be good.
  • the content of the structural unit represented by the above formula (A3) is preferably 10 mol% or more and 35 mol% or less with respect to the total content of all the structural units constituting the liquid crystal polyester (A). It is more preferably mol% or more and 30 mol% or less, and even more preferably 17.5 mol% or more and 27.5 mol% or less.
  • the content of the structural unit (A3) is not more than the above upper limit value, the liquid crystal property tends to be good, and when it is more than the above lower limit value, the solubility in a solvent tends to be good.
  • the content of the structural unit (A2) and the content of the structural unit (A3) in the liquid crystal polyester (A) are equal to each other, but when the contents are different, the structural unit (A2) and the structural unit (A2) and the structural unit (A2) are different.
  • the difference in the content of (A3) is preferably 10 mol% or less. With this difference, the degree of polymerization of the liquid crystal polyester can also be controlled.
  • the ratio of the preferable content of each structural unit in the liquid crystal polyester (A) is the content of the structural unit represented by the above formula (A1) with respect to the total content of all the structural units constituting the liquid crystal polyester (A).
  • the content is 30 mol% or more and 80 mol% or less
  • the content of the structural unit represented by the above formula (A2) is preferably 10 mol% or more and 35 mol% or less
  • the above formula (A3) The content of the structural unit indicated by is preferably 10 mol% or more and 35 mol% or less.
  • the ratio of the preferable content of each structural unit in the liquid crystal polyester (A) is the content of the structural unit represented by the above formula (A1) with respect to the total content of all the structural units constituting the liquid crystal polyester (A).
  • the content is 40 mol% or more and 70 mol% or less
  • the content of the structural unit represented by the above formula (A2) is more preferably 15 mol% or more and 30 mol% or less.
  • the content of the structural unit shown in A3) is 15 mol% or more and 30 mol% or less.
  • the ratio of the preferable content of each structural unit in the liquid crystal polyester (A) is the content of the structural unit represented by the above formula (A1) with respect to the total content of all the structural units constituting the liquid crystal polyester (A). However, it is more preferably 45 mol% or more and 65 mol% or less, and further preferably the content of the structural unit represented by the above formula (A2) is 17.5 mol% or more and 27.5 mol% or less. It is more preferable that the content of the structural unit represented by the above formula (A3) is 17.5 mol% or more and 27.5 mol% or less.
  • the structural unit (A1) may be, for example, a structural unit derived from an aromatic hydroxycarboxylic acid.
  • the structural unit (A2) may be, for example, a structural unit derived from an aromatic dicarboxylic acid.
  • the structural unit (A3) may be, for example, an aromatic diamine or a structural unit derived from an aromatic amine having a phenolic hydroxyl group.
  • an ester or an amide-forming derivative of the above-mentioned structural unit may be used instead of the above-mentioned structural unit.
  • ester-forming derivative of the carboxylic acid examples include a carboxy group in which the carboxy group is a derivative having high reaction activity such as a acid compound and an acid anhydride that promotes a reaction for producing a polyester, and a carboxy group. , Alcohols that form a polyester by transesterification reaction, ethylene glycol, and the like that form an ester.
  • ester-forming derivative of the phenolic hydroxyl group examples include those in which the phenolic hydroxyl group forms an ester with a carboxylic acid.
  • amide-forming derivative of the amino group examples include those in which the amino group forms an amide with a carboxylic acid.
  • Examples of the structural unit of the component (A) used in the present embodiment include, but are not limited to, the following.
  • Examples of the structural unit represented by the formula (A1) include structural units derived from p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4-hydroxy-4'-biphenylcarboxylic acid and the like.
  • the structural unit of species or more may be included in all structural units.
  • a structural unit derived from 6-hydroxy-2-naphthoic acid is preferable.
  • Examples of the structural unit represented by the formula (A2) include structural units derived from terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid and the like, and two or more of the structural units are included in the total structural unit. May be included in. Among these structural units, isophthalic acid-derived structural units are preferable from the viewpoint of solubility in a solvent.
  • Examples of the structural unit represented by the formula (A3) include 3-aminophenol, 4-aminophenol, 1,4-phenylenediamine, 1,3-phenylenediamine, 4-aminobenzoic acid, 4'-hydroxyacetanilide and the like.
  • the structural unit of origin and the like may be mentioned, and two or more kinds of the structural unit may be included in the total structural unit.
  • structural units derived from 4-aminophenol or 4'-hydroxyacetanilide are preferable from the viewpoint of reactivity.
  • the liquid crystal polyester soluble in an aprotic solvent may be a liquid crystal polyester containing a structural unit derived from 4'-hydroxyacetanilide.
  • the liquid crystal polyester soluble in an aprotic solvent is a liquid crystal polyester composed of a structural unit derived from 6-hydroxy-2-naphthoic acid, a structural unit derived from 4'-hydroxyacetanilide, and a structural unit derived from isophthalic acid. May be.
  • the method for producing the component (A) used in the present embodiment is not particularly limited, but for example, an aromatic hydroxy acid corresponding to the structural unit (A1) and an aromatic having a phenolic hydroxyl group corresponding to the structural unit (A3).
  • the phenolic hydroxyl groups and amino groups of group amines and aromatic diamines are acylated with an excess amount of fatty acid anhydride to obtain an acylated product, and the obtained acylated product and the aromatic dicarboxylic acid corresponding to the structural unit (A2) are obtained.
  • Examples thereof include a method of performing melt polymerization by ester-amide exchange (polycondensation) (see JP-A-2002-220444 and JP-A-2002-146003).
  • the amount of the fatty acid anhydride added is preferably 1.0 to 1.2 times the total equivalent of the phenolic hydroxyl group and the amino group, and more preferably 1.05 to 1. It is 1 times equivalent. If the amount of fatty acid anhydride added is too small, acylated substances and raw material monomers tend to sublimate during transesterification / amide exchange (polycondensation), and the reaction system tends to be clogged. The coloring of polyester tends to be remarkable.
  • the acylation reaction is preferably carried out at 130 to 180 ° C. for 5 minutes to 10 hours, and more preferably at 140 to 160 ° C. for 10 minutes to 3 hours.
  • the fatty acid anhydride used in the acylation reaction is not particularly limited, and is, for example, acetic acid anhydride, propionic acid anhydride, butyric acid anhydride, isobutyric acid anhydride, valeric acid anhydride, pivalic acid anhydride, diethylhexanoic acid anhydride, monochloroacetic acid anhydride.
  • acetic anhydride, propionic anhydride, butyric anhydride, or isobutyric anhydride is preferable, and acetic anhydride is more preferable.
  • the acyl group of the acylated product has an equivalent amount of 0.8 to 1.2 times that of the carboxyl group.
  • Transesterification / amide exchange is preferably carried out while raising the temperature up to 400 ° C. at a rate of 0.1 to 50 ° C./min, and up to 350 ° C. at a rate of 0.3 to 5 ° C./min. It is more preferable to do it while doing it.
  • the acylated product and the carboxylic acid are transesterified or amide exchanged (polycondensed)
  • it is preferable that the fatty acid produced as a by-product and the unreacted fatty acid anhydride are distilled off from the system by evaporation or the like.
  • the acylation reaction and transesterification / amide exchange (polycondensation) may be carried out in the presence of a catalyst.
  • a catalyst those conventionally known as catalysts for polymerizing polyester can be used, for example, magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, antimony trioxide and the like.
  • Metal salt catalysts, organic compound catalysts such as N, N-dimethylaminopyridine, N-methylimidazole and the like can be mentioned.
  • heterocyclic compounds containing two or more nitrogen atoms such as N, N-dimethylaminopyridine and N-methylimidazole are preferably used (see JP-A-2002-146003).
  • the catalyst is usually charged at the time of charging the monomers, and it is not always necessary to remove the catalyst even after acylation. If the catalyst is not removed, transesterification can be performed as it is.
  • melt polymerization and solid phase polymerization may be used in combination.
  • the solid phase polymerization is preferably carried out by a known solid phase polymerization method after extracting the polymer from the melt polymerization step and then pulverizing the polymer into powder or flakes. Specifically, for example, a method of heat-treating in a solid phase state at 20 to 350 ° C. for 1 to 30 hours in an inert atmosphere such as nitrogen can be mentioned.
  • Solid-phase polymerization may be carried out with stirring or in a stationary state without stirring.
  • the melt polymerization tank and the solid phase polymerization tank can be made into the same reaction tank by providing an appropriate stirring mechanism.
  • the obtained liquid crystal polyester may be pelletized and molded by a known method.
  • the liquid crystal polyester can be produced, for example, by using a batch device, a continuous device, or the like.
  • the content of the component (A) may be 10% by mass or more and 90% by mass or less, and 15% by mass or more and 50% by mass or less with respect to the total content of the solid content of the liquid composition of the embodiment. It may be 25% by mass or more and 40% by mass or less.
  • the component (S) is an aprotic solvent.
  • Protic and aprotic solvents have the advantages of low corrosiveness and ease of handling.
  • the aprotic solvent is a solvent containing an aprotic compound.
  • the aprotonic solvent includes, for example, halogen-based solvents such as 1-chlorobutane, chlorobenzene, 1,1-dichloroethane, 1,2-dichloroethane, chloroform, 1,1,2,2-tetrachloroethane.
  • Examples thereof include amide-based solvents, nitro-based solvents such as nitromethane and nitrobenzene, sulfide-based solvents such as dimethylsulfoxide and sulfolane, phosphoric acid-based solvents such as hexamethylphosphate amide and tri-n-butylphosphate, and two or more of them. You may use the mixture of.
  • an aprotic compound having no halogen atom is preferably used from the viewpoint of environmental influence, and a solvent having a dipole moment of 3 or more and 5 or less is preferably used from the viewpoint of solubility.
  • an amide-based solvent such as N, N'-dimethylformamide, N, N'-dimethylacetamide, tetramethylurea, N-methylpyrrolidone, or a lactone-based solvent such as ⁇ -butyrolactone is more preferably used.
  • N, N'-dimethylformamide, N, N'-dimethylacetamide, or N-methylpyrrolidone are more preferably used.
  • the ratio of the content of the component (S) to the total mass of the liquid composition is 20 mass from the viewpoint of lowering the viscosity of the liquid composition and facilitating coating on the support. % Or more, 20% by mass or more and 99% by mass or less, and 50% by mass or more and 95% by mass or less.
  • the content of the liquid crystal polyester (A) is preferably 0.01 part by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the aprotic solvent (S), and 1 part by mass. More than 70 parts by mass is more preferable, and 5 parts by mass or more and 40 parts by mass or less is further preferable.
  • the content of the liquid crystal polyester (A) when the content of the liquid crystal polyester (A) is in the above range, it is easy to apply the coating to a support such as a metal foil. Depending on the desired film thickness, the content of the liquid crystal polyester (A) can be appropriately adjusted within the above range.
  • the component (B) is a fluororesin having a melting point of 305 ° C. or lower.
  • the "fluororesin” means a resin containing a fluorine atom in a molecule, and examples thereof include a polymer having a structural unit containing a fluorine atom.
  • Examples of the fluororesin (B) include polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), polychlorotrifluoroethylene (PCTFE), and ethylene-tetrafluoroethylene copolymer.
  • Examples thereof include ethylene-chlorotrifluoroethylene copolymer, polyvinylidene fluoride (PVDF), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (perfluoroalkoxyalkane, PFA) and the like.
  • the fluororesin (B) is a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (perfluoroalkoxyalkane, PFA), polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), poly.
  • the fluororesin (B) is preferably perfluoroalkoxyalkane (PFA) having a melting point of 305 ° C. or lower.
  • the liquid composition of the embodiment may contain two or more kinds of fluororesins.
  • Fluororesin contains a fluorine atom in the molecule, so that the dielectric property of the film containing the fluororesin can be improved.
  • the melting point of the fluororesin (B) according to the embodiment is 305 ° C. or lower, preferably 303 ° C. or lower, and more preferably 301 ° C. or lower.
  • the melting point of the fluororesin (B) is not more than the above upper limit value, the characteristics of the adhesion strength of the film containing the fluororesin (B) to the copper foil can be excellent.
  • the mechanism is not clear, it is considered that the low melting point of the fluororesin reflects the low molecular weight of the fluororesin, which enhances the adhesion to the copper foil. Conceivable.
  • the lower limit of the melting point of the fluororesin (B) according to the embodiment may be 280 ° C. or higher, 290 ° C. or higher, or 295 ° C. or higher in consideration of practicality in applications requiring heat resistance. It may be there.
  • the upper limit value and the lower limit value of the melting point of the fluororesin (B) according to the embodiment can be freely combined.
  • the numerical range of the melting point of the fluororesin (B) it may be 280 ° C. or higher and 305 ° C. or lower, 290 ° C. or higher and 303 ° C. or lower, or 295 ° C. or higher and 301 ° C. or lower.
  • the melting point of the fluororesin (B) shall be measured as the endothermic peak value of differential scanning calorimetry (DSC) in accordance with JISK6935.
  • the melting point of the fluororesin (B) can be adjusted not only by selecting the raw material of the fluororesin but also by controlling the molecular weight of the fluororesin.
  • the molecular weight of the fluororesin can be appropriately adjusted to a desired value by appropriately adjusting the polymerization rate, polymerization time, etc. at the time of production.
  • the fluororesin (B) preferably has a crystallite size of 2.9 ⁇ 10-8 m or less, more preferably 2.7 ⁇ 10-8 m or less, and 2.5. It is more preferably x10-8 m or less.
  • the crystallite size of the fluororesin (B) is not more than the above upper limit value, the characteristics of the adhesion strength of the film containing the fluororesin (B) to the copper foil can be excellent.
  • the small crystallite size of the fluororesin is considered to reflect the low molecular weight of the fluororesin, which enhances the adhesion to the copper foil. It is considered to be.
  • the lower limit of the crystallite size of the fluororesin (B) according to the embodiment may be, for example, 2.0 ⁇ 10-8 m or more, 2.1 ⁇ 10-8 m or more, and 2.2. It may be ⁇ 10-8 m or more.
  • the upper limit value and the lower limit value of the crystallite size of the fluororesin (B) according to the embodiment can be freely combined.
  • the numerical range of the crystallite size of the fluororesin (B) it may be 2.0 ⁇ 10-8 m or more and 2.9 ⁇ 10-8 m or less, and 2.1 ⁇ 10-8 m or more 2 it may be a .7 ⁇ 10 -8 m or less, may be less 2.2 ⁇ 10 -8 m or 2.5 ⁇ 10 -8 m.
  • the crystallite size of the fluororesin (B) can be carried out by the following method using a wide-angle X-ray scattering (WAXS) measuring device.
  • WAXS wide-angle X-ray scattering
  • the fluororesin powder sample is sandwiched between bag-shaped Kapton films, and the X-ray beam size is adjusted to be smaller than the sample size.
  • To fluororesin powder sample, and the incident X-rays in the thickness direction of the Kapton film, subjected to transmitted X-ray intensity measurement and WAXS measurement is performed to obtain the transmitted X-ray intensity A S and WAXS scattering intensity I S.
  • the method for measuring the crystallite size by X-ray diffraction can be carried out as follows.
  • D K ⁇ ⁇ / ⁇ cos ⁇ ⁇ ⁇ ⁇ (2)
  • D is the crystallite size
  • ⁇ is the measured X-ray wavelength
  • ⁇ is the full width at half maximum (radian)
  • ⁇ is the diffraction angle
  • K is the Scherrer constant (0.94).
  • fluororesin satisfying the above-mentioned melting point, crystallite size and half width
  • a commercially available fluororesin may be used, and for example, AGC EA2000 or the like can be used.
  • the liquid composition of the embodiment contains the fluororesin (B), the water absorption rate when made into a film can be made preferable.
  • the fluororesin contained in the liquid composition of the embodiment may be a powder.
  • the volume average particle size of the fluororesin may be 0.1 ⁇ m or more and 30 ⁇ m or less, 0.5 ⁇ m or more and 10 ⁇ m or less, or 1 ⁇ m or more and 5 ⁇ m or less. It is preferable that the volume average particle size of the fluororesin is within the above range because the surface smoothness of the film is excellent.
  • the volume average particle size of the fluororesin can be measured by a laser diffraction / scattering type particle size distribution measuring device in a wet manner using water as a dispersion medium.
  • the shape of the fluororesin contained in the liquid composition of the embodiment is not particularly limited, but for example, spherical, lumpy, fibrous, or scaly ones can be used. In particular, spherical or lumpy ones are preferable from the viewpoint of excellent dispersibility in the liquid crystal polyester liquid composition.
  • the mass ratio (solid content) of the component (A) to the component (B) [(A) component: (B) component] contained in the liquid composition of the embodiment is, for example, 9: 1 to 1: 9. It may be 5: 1 to 1: 5, and may be 3: 2 to 2: 3.
  • the liquid composition containing the component (A) and the component (B) in the above ratio the adhesion strength, the dielectric property and the water resistance of the produced liquid crystal polyester film with the copper foil can be easily improved. Can be done.
  • the content of the component (B) may be 10% by mass or more and 90% by mass or less, 15% by mass or more and 50% by mass or less, 25 by mass, based on the total solid content of the liquid composition. It may be mass% or more and 40 mass% or less.
  • the liquid composition of the embodiment can contain the component (A), the component (B), and the component (S).
  • the content ratio of the component (A) is 10% by mass or more and 90% by mass or less with respect to the total solid content of the liquid composition (B).
  • the content ratio of the component is 10% by mass or more and 90% by mass or less can be exemplified.
  • the combination of these numerical values is an example, and for example, the numerical values exemplified above as an example of the content ratio of each component can be freely combined.
  • the liquid composition of the embodiment contains other components as required, such as a filler, an antioxidant, a heat stabilizer, and an ultraviolet absorber. , Antistatic agents, surfactants, flame retardants, colorants and other additives, and resins that do not fall under the components (A) and (B) may be contained.
  • the filler examples include inorganic fillers (C) such as silica, alumina, titanium oxide, barium titanate, strontium titanate, aluminum hydroxide and calcium carbonate; and cured epoxy resin, crosslinked benzoguanamine resin, crosslinked acrylic resin and the like.
  • examples include organic fillers.
  • a silica filler is preferable from the viewpoint of improving the dielectric loss tangent of the liquid crystal polyester film.
  • the liquid composition containing the fluororesin (B) having a melting point of 305 ° C. or lower is a component of the fluororesin (B) having a melting point of 305 ° C. or lower and an inorganic filler (C) such as a silica filler (hereinafter, (C) component.
  • the above filler is preferably granular.
  • the volume average particle size of the filler may be 0.1 ⁇ m or more and 10 ⁇ m or less, 0.2 ⁇ m or more and 5 ⁇ m or less, or 0.3 ⁇ m or more and 1 ⁇ m or less.
  • the volume average particle size of the filler can be measured by a laser diffraction / scattering type particle size distribution measuring device.
  • the content thereof may be 5% by mass or more and 70% by mass or less, and 20% by mass, based on the total solid content of the liquid composition. It may be% or more and 50% by mass or less, and may be 30% by mass or more and 45% by mass or less.
  • the inorganic filler (C) within the above numerical range, the characteristics of the inorganic filler are satisfactorily exhibited.
  • the dielectric properties of the produced liquid crystal polyester film can be improved.
  • the adhesion strength of the produced liquid crystal polyester film with the copper foil can be improved.
  • the liquid composition of the embodiment can contain a component (A), a component (B), a component (S), and a component (C).
  • the content ratio of the component (A) is 25% by mass or more and 40% by mass or less with respect to the total solid content of the liquid composition (B).
  • the content ratio of the component (C) is 25% by mass or more and 40% by mass or less, and the content ratio of the component (C) is 20% by mass or more and 50% by mass or less.
  • the content ratio of the component (A) is 25% by mass or more and 35% by mass or less with respect to the total solid content of the liquid composition.
  • Examples thereof include those in which the content ratio of the component B) is 25% by mass or more and 35% by mass or less, and the content ratio of the component (C) is 30% by mass or more and 45% by mass or less.
  • the combination of these numerical values is an example, and for example, the numerical values exemplified above as an example of the content ratio of each component can be freely combined.
  • Examples of the component (A) and the resin not corresponding to the component (B) include polypropylene, polyamide, polyester other than liquid crystal polyester, polyphenylene sulfide, polyether ketone, polycarbonate, polyether sulfone, polyphenylene ether and its modified product, and polyether.
  • Thermoplastic resins other than liquid crystal polyesters such as imide; elastomers such as copolymers of glycidyl methacrylate and polyethylene; and thermosetting resins such as phenol resins, epoxy resins, polyimide resins and cyanate resins are mentioned, and their contents are It may be 0 with respect to 100 parts by mass of the liquid crystal polyester, and is preferably 20 parts by mass or less.
  • liquid crystal polyester liquid composition of the embodiment it is possible to produce a film having excellent adhesion strength and dielectric properties with a copper foil.
  • the liquid crystal polyester film is generally manufactured by a melt molding method or a solution casting method in which the liquid crystal polyester is melted.
  • the melt molding method is a method of forming a film by extruding a kneaded product from an extruder.
  • the liquid crystal polyester molecules are oriented in the film forming direction rather than in the lateral direction with respect to the extrusion direction, and it is difficult to obtain a liquid crystal polyester having excellent isotropic properties.
  • the solution casting method since the film is formed without applying a force such as extrusion, the orientation of the liquid crystal polyester is isotropic as compared with the liquid crystal polyester film formed by the melt molding method.
  • liquid crystal polyester (A) is soluble in the aprotic solvent (S)
  • a solution casting method can be applied to obtain a liquid crystal polyester film having excellent isotropic properties. It can be manufactured.
  • the liquid composition of the embodiment further contains the component (C)
  • a film having further excellent dielectric properties and water resistance can be produced. Further, since the liquid composition contains the component (C), it is possible to produce an excellent film having an extremely good balance between the adhesion strength with the copper foil, the dielectric property and the water resistance.
  • the liquid crystal polyester film of the embodiment contains a liquid crystal polyester (A) and a fluororesin (B) having a melting point of 305 ° C. or lower, and the liquid crystal polyester (A) contains an amide bond.
  • the liquid crystal polyester film according to the embodiment of the present invention is also simply referred to as the "film" of the embodiment.
  • FIG. 1 is a schematic diagram showing the configuration of the liquid crystal polyester film 10 of the embodiment.
  • liquid crystal polyester (A) examples include those described as the component (A) above, and detailed description thereof will be omitted here.
  • the liquid crystal polyester (A) in the state of being molded into a film does not have to be soluble in an aprotic solvent due to changes in physical properties through the process of film formation.
  • the above-mentioned change in physical properties is, for example, an increase in the degree of polymerization.
  • the liquid crystal polyester (A) preferably contains a structural unit represented by the following formula (A1), a structural unit represented by the following formula (A2), and a structural unit represented by the following formula (A3).
  • Ar1 represents a 1,4-phenylene group, a 2,6-naphthalenedyl group, or a 4,4'-biphenylene group
  • Ar2 is a 1,4-phenylene group, a 1,3-phenylene group, Or, it represents a 2,6-naphthalenediyl group
  • Ar3 represents a 1,4-phenylene group or a 1,3-phenylene group
  • X represents -NH-
  • Y represents -O- or -NH-. .
  • fluororesin (B) having a melting point of 305 ° C. or lower examples include those described as the component (B) above, and detailed description thereof will be omitted here.
  • the film of the embodiment is the same as the liquid composition of the above-described embodiment, in addition to the component (A) and the component (B), if necessary, other components such as a filler, an antioxidant, and heat stability.
  • Additives such as agents, ultraviolet absorbers, antistatic agents, surfactants, flame retardants, and colorants, and resins that do not correspond to the components (A) and (B) may be included, and a detailed description thereof will be given here. Is omitted.
  • the film of the embodiment preferably contains the above-mentioned component (A), component (B), and inorganic filler (C).
  • the liquid crystal polyester film containing the component (A), the component (B), and the component (C) is unlikely to cause a decrease in the adhesion strength with the copper foil, and has a good balance between the adhesion strength with the copper foil and the dielectric property. It is also excellent in water resistance and has particularly excellent properties.
  • Examples of the inorganic filler (C) include those described as the component (C) described above, and detailed description thereof will be omitted here.
  • the inorganic filler (C) is preferably a silica filler.
  • the content of various components in the film of the embodiment can be the same as the content of various components as the solid content of the liquid composition of the embodiment exemplified above.
  • the film of the embodiment exhibits excellent dielectric properties.
  • the film of the embodiment preferably has a relative permittivity of 3.1 or less, more preferably 3.0 or less, further preferably 2.9 or less, and 2.8 or less at a frequency of 1 GHz. It is particularly preferable to have.
  • the relative permittivity of the film may be 2.3 or more, 2.4 or more, or 2.5 or more.
  • the numerical range of the value of the relative permittivity of the film it may be 2.3 or more and 3.1 or less, 2.4 or more and 3.0 or less, and 2.5 or more. It may be 2.9 or less, and may be 2.5 or more and 2.8 or less.
  • the film of the embodiment has a dielectric loss tangent of 0.005 or less, preferably 0.004 or less, more preferably 0.003 or less, and even more preferably 0.002 or less at a frequency of 1 GHz. , 0.0015 or less is particularly preferable.
  • the dielectric loss tangent of the liquid crystal polyester film may be 0.0003 or more, 0.0005 or more, or 0.0007 or more.
  • the value may be 0.0003 or more and 0.005 or less, 0.0005 or more and 0.004 or less, and 0.0007 or more and 0.
  • the relative permittivity and the dielectric loss tangent of the film at a frequency of 1 GHz can be measured by a capacitive method using an impedance analyzer under the conditions described in Examples.
  • the film of the embodiment can be excellent in isotropic properties.
  • the value of the degree of molecular orientation (MOR) measured by the microwave orientation meter is preferably in the range of 1 to 1.1, more preferably in the range of 1 to 1.08, and 1 It is more preferably in the range of ⁇ 1.06, and particularly preferably in the range of 1 to 1.04.
  • the degree of molecular orientation is measured by a microwave molecular orientation meter (for example, MOA-5012A manufactured by Oji Measuring Instruments Co., Ltd.).
  • the microwave molecular orientation meter is a device that utilizes the fact that the transmission intensity of microwaves differs between the orientation direction and the direction perpendicular to the orientation of the molecule. Specifically, while rotating the sample, the sample is irradiated with a microwave having a constant frequency (12 GHz is used), the intensity of the transmitted microwave that changes depending on the orientation of the molecule is measured, and the maximum / minimum value thereof is measured. Let the ratio be MOR.
  • the interaction between a microwave electric field with a constant frequency and the dipoles that make up the molecule is related to the inner product of the vectors of both. Due to the anisotropy of the dielectric constant of the sample, the intensity of the microwave changes depending on the angle at which the sample is placed, so it is possible to know the degree of orientation.
  • the film of the embodiment preferably has a linear expansion coefficient of 85 ppm / ° C. or less, and more preferably 57 ppm / ° C. or less, which is obtained in a temperature range of 50 to 100 ° C. under the condition of a temperature rise rate of 5 ° C./min. It is more preferably 45 ppm / ° C. or lower, and particularly preferably 40 ppm / ° C. or lower.
  • the lower limit of the coefficient of linear expansion is not particularly limited, but is, for example, 0 ppm / ° C. or higher.
  • the linear expansion coefficient of the copper foil is 18 ppm / ° C.
  • the linear expansion coefficient of the film of the embodiment is preferably a value close to that. That is, the coefficient of linear expansion of the film of the embodiment is preferably 0 ppm / ° C. or higher and 57 ppm / ° C. or lower, more preferably 10 ppm / ° C. or higher and 45 ppm / ° C. or lower, and 20 ppm / ° C. or higher and 40 ppm / ° C. or lower. It is more preferable to have. If the coefficient of linear expansion differs depending on the direction or portion of the film, the higher value shall be adopted as the coefficient of linear expansion of the film.
  • the film of the embodiment satisfying the above numerical range has a low coefficient of linear expansion and high dimensional stability.
  • the film of the embodiment exhibits excellent water resistance.
  • the film of the embodiment preferably has a water absorption rate of 0.8% by mass or less, more preferably 0.5% by mass or less, as measured in accordance with JIS K 7209. , 0.4% by mass or less, more preferably 0.3% by mass or less.
  • the water absorption rate of the film may be 0.05% by mass or more, 0.1% by mass or more, or 0.15% by mass or more.
  • the numerical range of the value of the water absorption rate of the above film it may be 0.05% by mass or more and 0.8% by mass or less, or 0.1% by mass or more and 0.5% by mass or less. It may be 0.15% by mass or more and 0.4% by mass or less, and may be 0.15% by mass or more and 0.3% by mass or less.
  • the thickness of the film of the embodiment is not particularly limited, but the thickness suitable for the film for electronic components is preferably 5 to 50 ⁇ m, more preferably 7 to 40 ⁇ m, and 10 It is more preferably to 33 ⁇ m, and particularly preferably 15 to 30 ⁇ m.
  • the method for producing the film of the embodiment is not particularly limited, and for example, the liquid composition of the embodiment can be obtained by molding into a film. From the viewpoint that a film having excellent isotropic properties can be produced, it is preferable that the film of the embodiment is produced by ⁇ a method for producing a liquid crystal polyester film >> described later.
  • the method for producing a liquid crystal polyester film of the embodiment is to apply the liquid composition of the embodiment on a support and remove the aprotic solvent (S) from the liquid composition to obtain a liquid crystal polyester film. It includes.
  • the production method may correspond to the solution casting method.
  • liquid composition of the embodiment examples include those exemplified in the above ⁇ liquid crystal polyester liquid composition >>.
  • the method for producing a liquid crystal polyester film may include the following steps.
  • the method for producing a liquid crystal polyester film of the embodiment is a step of heat-treating the liquid crystal polyester liquid composition or the precursor of the liquid crystal polyester film from which the aprotic solvent (S) has been removed after the coating step (heat treatment step). ) May be included.
  • the liquid crystal polyester liquid composition of the embodiment is applied onto a support, the aprotonic solvent (S) is removed from the liquid crystal polyester liquid composition, and heat treatment is performed. It may include obtaining a liquid crystal polyester film.
  • the heat treatment the polymerization reaction of the polymer in the liquid crystal polyester liquid composition can be promoted, and further, the volatilization of the aprotic solvent (S) can be promoted.
  • the method for producing the liquid crystal polyester film of the embodiment may include applying the liquid crystal polyester liquid composition of the embodiment on the support and heat-treating the liquid crystal polyester film to obtain the liquid crystal polyester film.
  • the method for producing the liquid crystal polyester film may further include a step (separation step) of separating the support from the laminated body. Since the liquid crystal polyester film can be suitably used as a film for electronic components even when it is formed on the support as a laminated body, the separation step is not an essential step in the manufacturing step of the liquid crystal polyester film.
  • FIG. 3 is a schematic diagram showing an example of a manufacturing process of the liquid crystal polyester film and the laminate of the embodiment.
  • the liquid crystal polyester liquid composition 30 is applied onto the support 12 (FIG. 3A coating step).
  • the liquid composition can be applied onto the support by a roller coating method, a dip coating method, a spray coating method, a spinner coating method, a curtain coating method, a slot coating method, a screen printing method, or the like.
  • a method that can be applied smoothly and evenly on the body can be appropriately selected.
  • an operation of stirring the liquid composition may be performed before coating.
  • the viscosity of the liquid crystal polyester liquid composition 30 is not particularly limited, but the viscosity measured by a B-type viscometer at 23 ° C. is 200 mPa ⁇ s or more and 2000 mPa ⁇ s or less from the viewpoint of simplifying the coating work and shortening the drying time. It is preferably 250 mPa ⁇ s or more and 1500 mPa ⁇ s or less, and more preferably 300 mPa ⁇ s or more and 1000 mPa ⁇ s or less.
  • Examples of the support 12 include a glass plate, a resin film, and a metal foil.
  • a resin film or a metal foil is preferable, and a copper foil is particularly preferable because it has excellent heat resistance, is easy to apply a liquid composition, and is easy to remove from a liquid crystal polyester film.
  • Examples of commercially available polyimide (PI) films include "U-Pylex S” and “U-Pylex R” from Ube Industries, Ltd., “Kapton” from Toray DuPont Co., Ltd., and “SKC Koron PI". "IF30", “IF70” and “LV300” are mentioned.
  • the thickness of the resin film is usually 25 ⁇ m or more and 75 ⁇ m or less, preferably 50 ⁇ m or more and 75 ⁇ m or less.
  • the thickness of the metal foil is usually 3 ⁇ m or more and 75 ⁇ m or less, preferably 5 ⁇ m or more and 30 ⁇ m or less, and more preferably 10 ⁇ m or more and 25 ⁇ m or less.
  • the aprotic solvent is removed from the liquid crystal polyester liquid composition 30 applied on the support 12 (FIG. 3B drying step).
  • the liquid composition from which the aprotic solvent has been removed becomes the liquid crystal polyester film precursor 40 to be heat-treated.
  • the aprotic solvent does not need to be completely removed from the liquid composition, and a part of the aprotic solvent contained in the liquid composition may be removed, and the entire aprotic solvent is removed. May be good.
  • the ratio of the aprotic solvent contained in the liquid crystal polyester film precursor 40 is preferably 50% by mass or less, and preferably 3% by mass or more and 12% by mass or less, based on the total mass of the liquid crystal polyester film precursor. It is more preferably 5% by mass or more and 10% by mass or less.
  • the content of the aprotic solvent in the liquid crystal polyester film precursor is at least the above lower limit value, the possibility that the thermal conductivity of the liquid crystal polyester film is lowered is reduced. Further, when the content of the aprotic solvent in the liquid crystal polyester film precursor is not more than the above upper limit value, the possibility that the appearance of the liquid crystal polyester film is deteriorated due to foaming or the like during heat treatment is reduced.
  • the removal of the aprotic solvent is preferably performed by evaporating the aprotic solvent, and examples thereof include heating, depressurization and ventilation, and these may be combined. Further, the removal of the aprotic solvent may be carried out by a continuous method or a single-wafer method. From the viewpoint of productivity and operability, the removal of the aprotic solvent is preferably performed by heating in a continuous manner, and more preferably by heating while ventilating in a continuous manner.
  • the removal temperature of the aprotic solvent is preferably a temperature lower than the melting point of the liquid crystal polyester (A) and the fluororesin (B), for example, 40 ° C. or higher and 200 ° C. or lower.
  • the time for removing the aprotic solvent is appropriately adjusted so that the aprotic solvent content in the liquid crystal polyester film precursor is, for example, 3 to 12% by mass.
  • the time for removing the aprotic solvent is, for example, 0.2 hours or more and 12 hours or less, preferably 0.5 hours or more and 8 hours or less.
  • the laminate precursor 22 having the support 12 and the liquid crystal polyester film precursor 40 thus obtained is heat-treated to obtain the support 12 and the liquid crystal polyester film 10 (a film obtained by heat-treating the liquid crystal polyester film precursor 40). (FIG. 3C heat treatment step). At this time, the liquid crystal polyester film 10 formed on the support is obtained.
  • the heat treatment conditions include raising the temperature from ⁇ 50 ° C., which is the boiling point of the medium, until the heat treatment temperature is reached, and then heat-treating at a temperature equal to or higher than the melting points of the liquid crystal polyester (A) and the fluororesin (B).
  • the heat treatment may be carried out continuously or in a single-wafered manner, but from the viewpoint of productivity and operability, the heat treatment is preferably carried out in a continuous manner and is aprotic. It is more preferable to carry out the removal of the solvent in a continuous manner.
  • the liquid crystal polyester film 10 can be obtained as a single-layer film by separating the liquid crystal polyester film 10 from the laminate 20 having the support 12 and the liquid crystal polyester film 10 (FIG. 3D separation step).
  • the liquid crystal polyester film 10 may be separated from the laminate 20 by peeling the liquid crystal polyester film 10 from the laminate 20.
  • a resin film is used as the support 12, it is preferable to peel off the resin film or the liquid crystal polyester film 10 from the laminate 20.
  • a metal foil is used as the support 12, it is preferable to separate the metal foil from the laminate 20 by etching and removing the metal foil.
  • the laminate 20 may be used as a metal-clad laminate for a printed wiring board without separating the liquid crystal polyester film from the laminate 20.
  • the laminate of the embodiment includes a metal layer and a liquid crystal polyester film of the embodiment laminated on the metal layer.
  • FIG. 2 is a schematic view showing the configuration of the laminated body 21 according to the embodiment of the present invention.
  • the laminate 21 includes a metal layer 13 and a liquid crystal polyester film 10 laminated on the metal layer 13.
  • Examples of the liquid crystal polyester film 10 included in the laminate include those exemplified above, and the description thereof will be omitted.
  • Examples of the metal layer included in the laminate include those exemplified as a support in ⁇ Method for manufacturing a liquid crystal polyester film >> described later and ⁇ Method for manufacturing a laminate >> described later, and a metal foil is preferable. Copper is preferable as the metal constituting the metal layer from the viewpoint of conductivity and cost, and copper foil is preferable as the metal foil.
  • the thickness of the laminate of the embodiment is not particularly limited, but is preferably 5 to 130 ⁇ m, more preferably 10 to 70 ⁇ m, and even more preferably 15 to 60 ⁇ m.
  • the method for manufacturing the laminated body of the embodiment is not particularly limited, but the laminated body of the embodiment can be manufactured by the ⁇ manufacturing method of the laminated body >> described later.
  • a laminate comprising a metal layer and a liquid crystal polyester film formed by applying the liquid composition of the embodiment on the metal layer.
  • the laminate of the embodiment can be suitably used for a film application for electronic parts such as a printed wiring board.
  • the liquid crystal polyester liquid composition of the embodiment is applied onto the support, the aprotonic solvent (S) is removed from the liquid crystal polyester liquid composition, and the liquid crystal is formed on the support.
  • the present invention includes obtaining a laminate including the support and the film.
  • the method for producing the laminated body of the embodiment may include the following steps.
  • the method for producing a laminate of the embodiment is a liquid crystal polyester film precursor from which the liquid crystal polyester liquid composition or the aprotonic solvent (S) has been removed after the coating step.
  • a step of heat-treating the body (heat treatment step) may be included.
  • the method for producing the laminate of the embodiment is to apply the liquid crystal polyester liquid composition of the embodiment on the support, remove the aprotonic solvent (S) from the liquid crystal polyester liquid composition, heat-treat it, and support it.
  • a liquid crystal polyester film on the body it may include obtaining a laminated body including the support and the film.
  • the heat treatment the polymerization reaction of the polymer in the liquid composition can be promoted, and further, the volatilization of the aprotic solvent (S) can be promoted.
  • the heat treatment can also serve as the above-mentioned drying step. Therefore, in the method for producing a laminated body of the embodiment, the liquid crystal polyester liquid composition of the embodiment is applied onto the support and heat-treated to form a liquid crystal polyester film on the support, thereby forming the liquid crystal polyester film on the support. It may include obtaining a laminate including the film.
  • FIG. 3 is a schematic diagram showing an example of the manufacturing process of the liquid crystal polyester film and the laminate of the embodiment.
  • the method for producing the laminated body exemplified in FIG. 3 is the same as that described in the above-mentioned method for producing a liquid crystal polyester film except that the above-mentioned separation step (FIG. 3D) is not performed, and thus the description thereof will be omitted.
  • the method for manufacturing a laminate of the embodiment it is possible to manufacture the laminate having the liquid crystal polyester film of the embodiment.
  • the liquid crystal polyester (A) contains a structural unit represented by the following formula (A1), a structural unit represented by the following formula (A2), and a structural unit represented by the following formula (A3), and is a liquid crystal polyester liquid composition.
  • Ar1 represents a 1,4-phenylene group, a 2,6-naphthalenedyl group, or a 4,4'-biphenylene group
  • Ar2 is a 1,4-phenylene group, a 1,3-phenylene group, Or, it represents a 2,6-naphthalenediyl group
  • Ar3 represents a 1,4-phenylene group or a 1,3-phenylene group
  • X represents -NH-
  • Y represents -O- or -NH-.
  • the Ar1 is a 2,6-naphthalenedyl group
  • the Ar2 is a 1,3-phenylene group
  • the Ar3 is a 1,4-phenylene group
  • the Y is —O—.
  • the liquid crystal polyester liquid composition contains the liquid crystal polyester (A) and the fluororesin (B) as solids.
  • the content ratio of the liquid crystal polyester (A) is 10% by mass or more and 90% by mass or less, and the content ratio of the fluororesin (B) is 10 with respect to the total content of the solid content of the liquid crystal polyester liquid composition.
  • liquid crystal polyester according to ⁇ 5> wherein the volume average particle size of the silica filler is any one of 0.1 ⁇ m or more and 10 ⁇ m or less, 0.2 ⁇ m or more and 5 ⁇ m or less, and 0.3 ⁇ m or more and 1 ⁇ m or less.
  • Liquid composition. ⁇ 7> The content ratio of the liquid crystal polyester (A) is 25% by mass or more and 40% by mass or less, and the content ratio of the fluororesin (B) is 25 with respect to the total content of the solid content of the liquid crystal polyester liquid composition.
  • the fluorine crystallite size of the resin (B) is, 2.0 ⁇ 10 at -8 m or 2.9 ⁇ 10 -8 m or less, 2.1 ⁇ 10 -8 m or 2.7 ⁇ 10 - 8 m or less, and is either 2.2 ⁇ 10 -8 m or 2.5 ⁇ 10 -8 m or less, the ⁇ 1> to the liquid crystal polyester liquid composition according to any one of ⁇ 7> ..
  • the fluororesin (B) is a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (perfluoroalkoxyalkane, PFA), polytetrafluoroethylene (PTFE), or tetrafluoroethylene-hexafluoropropylene copolymer (. FEP), polychlorotrifluoroethylene (PCTFE), ethylene-tetrafluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer, and at least one fluororesin selected from the group consisting of polyvinylidene fluoride (PVDF).
  • PVDF polyvinylidene fluoride
  • the volume average particle size of the fluororesin (B) is any one of 0.1 ⁇ m or more and 30 ⁇ m or less, 0.5 ⁇ m or more and 10 ⁇ m or less, and 1 ⁇ m or more and 5 ⁇ m or less.
  • the liquid crystal polyester liquid composition according to any one. ⁇ 11> The liquid crystal polyester liquid composition according to any one of ⁇ 1> to ⁇ 10>, wherein the aprotic solvent (S) is N-methylpyrrolidone.
  • a liquid crystal polyester (A) and a fluororesin (B) having a melting point of 305 ° C. or lower are contained.
  • the liquid crystal polyester (A) contains a structural unit represented by the following formula (A1), a structural unit represented by the following formula (A2), and a structural unit represented by the following formula (A3).
  • Ar1 represents a 1,4-phenylene group, a 2,6-naphthalenedyl group, or a 4,4'-biphenylene group
  • Ar2 is a 1,4-phenylene group, a 1,3-phenylene group, Or, it represents a 2,6-naphthalenediyl group
  • Ar3 represents a 1,4-phenylene group or a 1,3-phenylene group
  • X represents -NH-
  • Y represents -O- or -NH-.
  • the Ar1 is a 2,6-naphthalenedyl group
  • the Ar2 is a 1,3-phenylene group
  • the Ar3 is a 1,4-phenylene group
  • the Y is —O—.
  • the content ratio of the liquid crystal polyester (A) is 10% by mass or more and 90% by mass or less
  • the content ratio of the fluororesin (B) is 10% by mass or more and 90% with respect to the total content of the liquid crystal polyester film.
  • the content ratio of the liquid crystal polyester (A) is 25% by mass or more and 40% by mass or less, and the content ratio of the fluororesin (B) is 25% by mass or more and 40% with respect to the total content of the liquid crystal polyester film.
  • the inorganic filler (C) is a silica filler.
  • the liquid crystal polyester film according to any one of ⁇ 12> to ⁇ 18>, wherein the fluororesin (B) has a crystallite size of 2.9 ⁇ 10-8 m or less.
  • the fluororesin (B) is a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (perfluoroalkoxyalkane, PFA), polytetrafluoroethylene (PTFE), or tetrafluoroethylene-hexafluoropropylene copolymer (.
  • the liquid crystal polyester film according to any one of ⁇ 12> to ⁇ 19>. ⁇ 21> Any of the above ⁇ 12> to ⁇ 20> having a thickness of 5 to 50 ⁇ m, preferably 7 to 40 ⁇ m, more preferably 10 to 33 ⁇ m, still more preferably 15 to 30 ⁇ m.
  • the liquid crystal polyester film described in one.
  • the relative permittivity at a frequency of 1 GHz is 2.3 or more and 3.1 or less, preferably 2.4 or more and 3.0 or less, more preferably 2.5 or more and 2.9 or less, and further.
  • the dielectric positive contact at a frequency of 1 GHz is 0.0003 or more and 0.005 or less, preferably 0.0005 or more and 0.004 or less, more preferably 0.0007 or more and 0.003 or less, still more preferable.
  • the value of the degree of molecular orientation (MOR) measured by the microwave orientation meter is 1 to 1.1, preferably in the range of 1 to 1.08, and more preferably 1 to 1.06.
  • ⁇ 25> The linear expansion coefficient obtained in the temperature range of 50 to 100 ° C. under the condition of a temperature rising rate of 5 ° C./min is 0 ppm / ° C.
  • the liquid crystal polyester film according to any one of ⁇ 12> to ⁇ 24>, which is more preferably 20 ppm / ° C. or higher and 40 ppm / ° C. or lower.
  • the water absorption rate measured in accordance with JIS K 7209 is 0.05% by mass or more and 0.8% by mass or less, preferably 0.1% by mass or more and 0.5% by mass or less, and more.
  • ⁇ 27> A laminate comprising a metal layer and the liquid crystal polyester film according to any one of ⁇ 12> to ⁇ 26> laminated on the metal layer.
  • ⁇ 28> A laminate comprising a metal layer and a liquid crystal polyester film formed by applying the liquid crystal polyester liquid composition according to any one of ⁇ 1> to ⁇ 11> on the metal layer.
  • the thickness of the liquid crystal polyester film is 5 to 50 ⁇ m, preferably 7 to 40 ⁇ m, more preferably 10 to 33 ⁇ m, still more preferably 15 to 30 ⁇ m, according to ⁇ 28>.
  • Laminated body. ⁇ 30> A single-sided copper-clad plate of a liquid crystal polyester film measured by peeling the copper foil in a direction of 90 ° with respect to the liquid crystal polyester film at a peeling speed of 50 mm / min.
  • the peel strength (90 ° peel strength) is 6.5 N / cm or more and 10.0 N / cm or less, preferably 7.5 N / cm or more and 9.8 N / cm or less, and more preferably 7.9 N / cm or more and 9.0 N.
  • the relative permittivity of the liquid crystal polyester film at a frequency of 1 GHz is 2.3 or more and 3.1 or less, preferably 2.4 or more and 3.0 or less, and more preferably 2.5 or more and 2.9.
  • the dielectric adjacency of the liquid crystal polyester film at a frequency of 1 GHz is 0.0003 or more and 0.005 or less, preferably 0.0005 or more and 0.004 or less, and more preferably 0.0007 or more and 0.003 or less.
  • the value of the degree of molecular orientation (MOR) measured by the microwave orientation meter of the liquid crystal polyester film is 1 to 1.1, preferably 1 to 1.08, and more preferably 1 to 1.
  • the laminate according to any one of ⁇ 28> to ⁇ 32> which is 0.6, more preferably 1 to 1.04.
  • ⁇ 34> The linear expansion coefficient obtained in the temperature range of 50 to 100 ° C. under the condition of a temperature rise rate of 5 ° C./min of the liquid crystal polyester film is 0 ppm / ° C. or higher and 57 ppm / ° C. or lower, preferably 10 ppm / ° C. or higher.
  • the laminate according to any one of ⁇ 28> to ⁇ 33> which is 45 ppm / ° C. or lower, more preferably 20 ppm / ° C. or higher and 40 ppm / ° C. or lower.
  • the water absorption of the liquid crystal polyester film measured in accordance with JIS K 7209 is 0.05% by mass or more and 0.8% by mass or less, preferably 0.1% by mass or more and 0.5% by mass. % Or less, more preferably 0.15% by mass or more and 0.4% by mass or less, still more preferably 0.15% by mass or more and 0.3% by mass or less.
  • liquid crystal polyester liquid composition according to any one of ⁇ 1> to ⁇ 11> is applied onto the support, and the aprotonic solvent (S) is removed from the liquid crystal polyester liquid composition.
  • a method for producing a liquid crystal polyester film which comprises obtaining a liquid crystal polyester film by heat treatment.
  • the crystallite size was measured by X-ray diffraction as follows.
  • D K ⁇ ⁇ / ⁇ cos ⁇ ⁇ ⁇ ⁇ (2)
  • D is the crystallite size
  • ⁇ is the measured X-ray wavelength
  • ⁇ is the full width at half maximum (radian)
  • ⁇ is the diffraction angle
  • K is the Scherrer constant (0.94).
  • Capacitance method (Device: Impedance analyzer (Agilent model: E4991A)) -Electrode model: 16453A ⁇ Measurement environment: 23 ° C, 50% RH ⁇ Applied voltage: 1V
  • the liquid crystal polyester (A1) is heated from room temperature to 160 ° C. over 2 hours and 20 minutes under a nitrogen atmosphere, then heated from 160 ° C. to 180 ° C. over 3 hours and 20 minutes, and held at 180 ° C. for 5 hours. Thereby, after solid-phase polymerization, the mixture was cooled, and then pulverized with a pulverizer to obtain a powdery liquid crystal polyester (A2).
  • the flow start temperature of this liquid crystal polyester (A2) was 220 ° C.
  • the temperature of the liquid crystal polyester (A2) is raised from room temperature to 180 ° C. for 1 hour and 25 minutes under a nitrogen atmosphere, then the temperature is raised from 180 ° C. to 255 ° C. for 6 hours and 40 minutes, and the temperature is maintained at 255 ° C. for 5 hours. After solid-phase polymerization, the mixture was cooled to obtain a powdery liquid crystal polyester (A).
  • the flow start temperature of the liquid crystal polyester (A) was 302 ° C.
  • liquid crystal polyester solution 8 parts by mass of the liquid crystal polyester (A) is added to 92 parts by mass of N-methylpyrrolidone (boiling point (1 atm) 204 ° C.), and the mixture is stirred at 140 ° C. for 4 hours under a nitrogen atmosphere to prepare a liquid crystal polyester solution (A). bottom.
  • the viscosity of this liquid crystal polyester solution was 955 mPa ⁇ s.
  • Comparative Examples 2 to 4 Silica (SO-C2 manufactured by Admatex, average particle size described in the catalog: 0.5 ⁇ m) was added to the liquid crystal polyester solution obtained above so as to have the blending amount (solid content) shown in Table 2, and a stirring defoaming device (stirring defoaming device) ( The liquid compositions of Comparative Examples 2 to 4 were prepared using AR-500) of Shinky Co., Ltd.
  • Example 6 In the liquid crystal polyester solution obtained above, the fluororesin PFA (EA2000 manufactured by AGC, melting point: 300.82 ° C., crystallite size: 2.28 ⁇ 10-8 m) so as to have the blending amount (solid content) shown in Table 3. , Volume average particle size: 2 ⁇ m), and silica (SO-C2 manufactured by Admatex, average particle size described in the catalog: 0.5 ⁇ m) are added, and a stirring defoaming device (AR-500 of Shinky Co., Ltd.) is used.
  • the liquid compositions of Examples 6 to 10 were prepared.
  • Liquid crystal polyester solutions (A) (Comparative Example 1) to which the liquid compositions of Examples 1 to 10, the liquid compositions of Comparative Examples 2 to 10 and fine particles were not added, were mixed with a copper foil (JX Nippon Mining & Metals JXEFL-V2 thickness).
  • a film applicator with a micrometer manufactured by Tester Sangyo
  • an automatic coating device Teester Sangyo Co., Ltd.
  • the solvent was partially removed from the casting film by drying at 40 ° C.
  • Examples 1 to 10 and Comparative Example 1 A film with a copper foil (liquid crystal polyester film single-sided copper-clad plate) provided with a film of each Example or Comparative Example formed from each of the solutions or liquid compositions of 9 to 9 was obtained.
  • the liquid crystal polyester films of Examples 1 to 10 had higher peel strength values and excellent adhesion strength to the copper foil than the liquid crystal polyester films of Comparative Examples 5 to 10. This is because the liquid crystal polyester films of Examples 1 to 10 were formed from a liquid crystal polyester liquid composition containing a fluororesin PFA (EA2000) having a melting point of 305 ° C. or lower, whereas the liquid crystal polyester films of Comparative Examples 5 to 10 were formed. It is considered that the liquid crystal polyester film of No. 1 is formed from a liquid crystal polyester liquid composition containing a fluororesin PFA (9738-JN) having a higher melting point.
  • EA2000 fluororesin PFA
  • the liquid crystal polyester films of Examples 1 to 5 had the same peel strength as the liquid crystal polyester films of Comparative Example 1, but had improved water absorption, relative permittivity, and dielectric properties of dielectric loss tangent. From this, the liquid crystal polyester film formed from the liquid crystal polyester liquid composition containing both the liquid crystal polyester (A) and the fluororesin (B) having a melting point of 305 ° C. or lower has peel strength, water resistance and dielectric properties. It was shown to be well-balanced and have excellent properties.
  • liquid crystal polyester films of Comparative Examples 2 to 4 in which silica was added to the liquid crystal polyester (A) tended to have a good CTE value, but the degree of improvement in the dielectric property value was poor.
  • the liquid crystal polyester films of Examples 6 to 10 tended to suppress the increase in CTE value as compared with the liquid crystal polyester films of Examples 1 to 5. Further, the liquid crystal polyester films of Examples 6 to 10 have a relative permittivity and a dielectric constant while having the same peel strength as those of Examples 1 and 2 and Comparative Examples 2 and 4 in which the CTE value is not so high. The value of the dielectric property of the positive tangent was improved. In addition, the value of water absorption rate was also good. From this, the liquid crystal polyester film formed from the liquid crystal polyester liquid composition containing the liquid crystal polyester (A), the fluororesin (B) having a melting point of 305 ° C. or lower, and further silica has CTE, water resistance, and peel. It was shown that the balance between strength and dielectric properties was good, and that the properties were particularly excellent.

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

Abstract

La présente invention concerne une composition liquide de polyester cristallin liquide qui comprend : un polyester cristallin liquide (A) qui est soluble dans des solvants aprotiques ; un solvant aprotique (S) ; et une résine fluorée (B) qui a un point de fusion de 305 °C ou moins.
PCT/JP2021/018762 2020-05-21 2021-05-18 Composition liquide de polyester cristallin liquide, film de polyester cristallin liquide, stratifié et procédé de fabrication de film de polyester cristallin liquide WO2021235427A1 (fr)

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JP2022524486A JPWO2021235427A1 (fr) 2020-05-21 2021-05-18
CN202180036498.5A CN115667398B (zh) 2020-05-21 2021-05-18 液晶聚酯液态组合物、液晶聚酯膜、层叠体以及液晶聚酯膜的制造方法

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WO2023210471A1 (fr) * 2022-04-28 2023-11-02 富士フイルム株式会社 Film et stratifié

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JPH09278966A (ja) * 1996-04-10 1997-10-28 Du Pont Mitsui Fluorochem Co Ltd 金属基材被覆用組成物
JP2012149127A (ja) * 2011-01-17 2012-08-09 Sumitomo Chemical Co Ltd 液晶ポリエステル含有液状組成物
JP6844755B1 (ja) * 2019-08-27 2021-03-17 東レ株式会社 液晶ポリエステル樹脂組成物、積層体、液晶ポリエステル樹脂フィルムおよびその製造方法

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KR102557635B1 (ko) * 2015-04-01 2023-07-20 미쓰비시 엔피쯔 가부시키가이샤 불소계 수지 함유 비수계 분산체, 불소계 수지 함유 폴리이미드 전구체 용액 조성물, 이를 이용한 폴리이미드, 폴리이미드 필름, 회로기판용 접착제 조성물 및 그 제조 방법
JP7003434B2 (ja) * 2017-04-11 2022-01-20 Ａｇｃ株式会社 樹脂組成物および成形品

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Publication number Priority date Publication date Assignee Title
JPH09278966A (ja) * 1996-04-10 1997-10-28 Du Pont Mitsui Fluorochem Co Ltd 金属基材被覆用組成物
JP2012149127A (ja) * 2011-01-17 2012-08-09 Sumitomo Chemical Co Ltd 液晶ポリエステル含有液状組成物
JP6844755B1 (ja) * 2019-08-27 2021-03-17 東レ株式会社 液晶ポリエステル樹脂組成物、積層体、液晶ポリエステル樹脂フィルムおよびその製造方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023210471A1 (fr) * 2022-04-28 2023-11-02 富士フイルム株式会社 Film et stratifié

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