WO2022138516A1 - Corps formé d'un film polymère thermoplastique à cristaux liquides ayant une couche colorée et son procédé de production - Google Patents

Corps formé d'un film polymère thermoplastique à cristaux liquides ayant une couche colorée et son procédé de production Download PDF

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WO2022138516A1
WO2022138516A1 PCT/JP2021/046888 JP2021046888W WO2022138516A1 WO 2022138516 A1 WO2022138516 A1 WO 2022138516A1 JP 2021046888 W JP2021046888 W JP 2021046888W WO 2022138516 A1 WO2022138516 A1 WO 2022138516A1
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liquid crystal
crystal polymer
thermoplastic liquid
polymer film
colored layer
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PCT/JP2021/046888
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English (en)
Japanese (ja)
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先文 張
辰也 砂本
啓輔 池田
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株式会社クラレ
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Priority to JP2022571419A priority Critical patent/JPWO2022138516A1/ja
Priority to CN202180086649.8A priority patent/CN116635235A/zh
Priority to KR1020237020855A priority patent/KR20230125199A/ko
Publication of WO2022138516A1 publication Critical patent/WO2022138516A1/fr

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    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/022—Mechanical properties
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
    • H04R7/00—Diaphragms for electromechanical transducers; Cones
    • H04R7/02—Diaphragms for electromechanical transducers; Cones characterised by the construction

Definitions

  • thermoplastic polymer hereinafter referred to as thermoplastic liquid crystal polymer
  • film molded product having a colored layer and capable of forming an optically anisotropic molten phase, and a method for producing the same.
  • thermoplastic liquid crystal polymer film has a milky white color derived from the thermoplastic liquid crystal polymer.
  • a milky white color forms a metal circuit pattern
  • the boundary with the metal circuit pattern tends to be unclear, so that there is a demand for coloring the thermoplastic liquid crystal polymer film.
  • Patent Document 1 International Publication No. 2018/105624
  • a black pigment such as carbon black and a thermoplastic liquid crystal polymer are melt-kneaded and the melt-kneaded product is passed through a filter having a pore size of 40 ⁇ m or less.
  • a black thermoplastic liquid crystal polymer film in which agglomerates of black pigment and generation of high-concentration spots of black pigment are suppressed by molding into a film by a T-die method or an inflation method is disclosed.
  • thermoplastic liquid crystal polymer film can be obtained by adding a black pigment to the thermoplastic liquid crystal polymer film
  • the thermoplastic liquid crystal polymer is derived from a rigid mesogen structure.
  • the pigment is mixed to the extent that the milky white color derived from the thermoplastic liquid crystal polymer is sufficiently colored, it is difficult to effectively utilize the inherent characteristics of the thermoplastic liquid crystal polymer film. ..
  • thermoplastic liquid crystal polymer film to which the black pigment is added for example, the elasticity of the film may change due to the addition of the pigment, and the measured value may deviate from the design value of the thermoplastic liquid crystal polymer film. be.
  • a molded product formed by shaping a thermoplastic liquid crystal polymer film to which a black pigment is added is used for an acoustic diaphragm, the sound quality may be affected due to deterioration of elasticity and vibration damping property.
  • an object of the present invention is to provide a thermoplastic liquid crystal polymer film molded product that is colored while maintaining the original properties of the thermoplastic liquid crystal polymer film.
  • the inventors of the present invention have added a colored layer to the thermoplastic liquid crystal polymer film in order to perform coloring while maintaining the original properties of the thermoplastic liquid crystal polymer film.
  • the thermoplastic liquid crystal polymer film due to the rigid mesogen structure, even if the colored layer is provided on the surface of the molded body, the adhesion to the colored layer is poor, and further. Improves the followability of the colored layer to deformation of the film when the thermoplastic liquid crystal polymer film on which the colored layer is formed is molded into a desired shape or used as an acoustic vibration plate or the like that receives an external force such as vibration.
  • We found the need as a new issue. Therefore, as a result of further research, it was found that problems such as peeling and swelling of the colored layer can be suppressed by performing a specific treatment on the thermoplastic liquid crystal polymer film, and the present invention has been completed.
  • thermoplastic liquid crystal polymer film molded article having a thermoplastic liquid crystal polymer film layer and a colored layer formed on one surface or at least a part of both surfaces of the thermoplastic liquid crystal polymer film layer, wherein JIS P 8115 ( In the folding resistance test according to 2001), the number of reciprocating bendings before cracking exceeds 100 times (preferably more than 200 times, more preferably more than 500 times, still more preferably more than 1000 times), heat.
  • JIS P 8115 In the folding resistance test according to 2001
  • the number of reciprocating bendings before cracking exceeds 100 times (preferably more than 200 times, more preferably more than 500 times, still more preferably more than 1000 times), heat.
  • the adhesiveness evaluation of the colored layer in the cross-cut test by JIS K 5600-5-6 is 3 or less (preferably 2 or less, more preferably 0).
  • Polymer film molded article is 3 or less (preferably 2 or less, more preferably 0).
  • the ratio of the thickness of the colored layer to the thickness of the thermoplastic liquid crystal polymer film layer is 0.001 to 0.9 (preferably 0.005 to 0.5, more preferably 0.005 to 0.5). Is 0.01 to 0.5), a thermoplastic liquid crystal polymer film molded body.
  • thermoplastic liquid crystal polymer film molded body In the thermoplastic liquid crystal polymer film molded body according to any one of aspects 1 to 3, in the X-ray photoelectron spectroscopic analysis result of the surface portion depth of 10 to 100 nm in the adhered region of the thermoplastic liquid crystal polymer film layer, the adhered region was found.
  • the ratio ⁇ CO> of the peak area of [CO bond] to the total peak area of each peak of C (1s) on the surface exceeds 12% (preferably 13.0 to 30.0%, More preferably 16.0 to 28.0%, even more preferably 18.0 to 26.0%, even more preferably 19.0 to 25.0%), a thermoplastic liquid crystal polymer molded body.
  • thermoplastic liquid crystal polymer film molded body In the thermoplastic liquid crystal polymer film molded body according to any one of aspects 1 to 4, the ten-point average roughness (Rz jis ) of the surface of the thermoplastic liquid crystal polymer film layer on the colored layer side is 0.1 to 3.0 ⁇ m (Rz jis).
  • a thermoplastic liquid crystal polymer film molded product preferably 0.30 to 1.90 ⁇ m, more preferably 0.40 to 1.80 ⁇ m, still more preferably 0.50 to 1.70 ⁇ m).
  • thermoplastic liquid crystal polymer film molded body of any one of aspects 1 to 5 the thermoplastic liquid crystal polymer film molding having a storage elastic modulus of 1 GPa or more and 20 GPa or less (preferably 2 to 18 GPa, more preferably 5 to 15 GPa). body.
  • the internal loss is 0.02 or more and 0.1 or less (preferably 0.03 to 0.08, more preferably 0.05 to 0. 08), a thermoplastic liquid crystal polymer film molded body.
  • thermoplastic liquid crystal polymer film molded product made of any one of aspects 1 to 8.
  • the adhered region on at least one surface of the thermoplastic liquid crystal polymer film is subjected to at least one surface treatment selected from the group consisting of plasma treatment, ultraviolet treatment, corrosion treatment, and copper foil replica treatment, and the surface portion is subjected to surface treatment.
  • thermoplastic liquid crystal polymer film molded product comprising a coloring treatment step of forming a colored layer by coating, dry plating, or wet plating on the film to be treated.
  • thermoplastic liquid crystal polymer film molded body means a molded body derived from a laminate in which a colored layer is formed on the thermoplastic liquid crystal polymer film, and for example, a thermoplastic liquid crystal polymer film molded body. Includes both a sheet-like laminate of a thermoplastic liquid crystal polymer film and a colored layer, and a shaped body in which the laminate is shaped into a predetermined shape.
  • the ratio of the peak area of [CO bond] to the total peak area of each peak of C (1s) is defined as ⁇ CO> and the peak area of each peak of C (1s).
  • thermoplastic liquid crystal polymer film molded product of the present invention the followability of the colored layer is good even when the film is shaped together with the colored layer.
  • the present invention is a thermoplastic liquid crystal polymer film molded body having a thermoplastic liquid crystal polymer film layer and a colored layer formed on one surface or at least a part of both surfaces of the thermoplastic liquid crystal polymer film layer.
  • thermoplastic liquid crystal polymer The thermoplastic liquid crystal polymer film is composed of the thermoplastic liquid crystal polymer.
  • the thermoplastic liquid crystal polymer is composed of a liquid crystal polymer that can be melt-molded (or a polymer that can form an optically anisotropic molten phase), and if it is a liquid crystal polymer that can be melt-molded, its chemical composition is particularly high. Examples thereof include, but are not limited to, a thermoplastic liquid crystal polyester, or a thermoplastic liquid crystal polyester amide having an amide bond introduced therein.
  • thermoplastic liquid crystal polymer may be a polymer in which an imide bond, a carbonate bond, an isocyanate-derived bond such as a carbodiimide bond or an isocyanurate bond is further introduced into an aromatic polyester or an aromatic polyester amide.
  • thermoplastic liquid crystal polymer used in the present invention include known thermoplastic liquid crystal polyesters and thermoplastic liquid crystal polyesteramides derived from the compounds classified into the compounds (1) to (4) and their derivatives exemplified below. Can be mentioned. However, it goes without saying that there is an appropriate range in the combination of various raw material compounds in order to form a polymer capable of forming an optically anisotropic molten phase.
  • Aromatic or aliphatic diols (see Table 1 for typical examples)
  • Aromatic diamine, aromatic hydroxyamine or aromatic aminocarboxylic acid (see Table 4 for typical examples).
  • thermoplastic liquid crystal polymers obtained from these raw material compounds include copolymers having repeating units shown in Tables 5 and 6.
  • a polymer containing p-hydroxybenzoic acid and / or 6-hydroxy-2-naphthoic acid as at least a repeating unit is preferable, and (i) p-hydroxybenzoic acid and 6-hydroxy- A copolymer containing a repeating unit with 2-naphthoic acid, or at least one aromatic hydroxycarboxylic acid selected from the group consisting of (ii) p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, and at least one.
  • a copolymer containing a repeating unit of an aromatic diol and / or an aromatic hydroxyamine of at least one aromatic dicarboxylic acid is preferred.
  • the p-hydroxybenzoic acid of the repeating unit (A) if the thermoplastic liquid crystal polymer contains at least a repeating unit of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, the p-hydroxybenzoic acid of the repeating unit (A).
  • At least one aromatic hydroxycarboxylic acid (C) selected from the group consisting of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid and 4,4'-.
  • aromatic diol (D) selected from the group consisting of dihydroxybiphenyl, hydroquinone, phenylhydroquinone, and 4,4'-dihydroxydiphenyl ether, and the group consisting of terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid.
  • the molar ratio of each repeating unit of at least one selected aromatic dicarboxylic acid (E) in the thermoplastic liquid crystal polymer is the aromatic hydroxycarboxylic acid (C): the aromatic diol (D): the aromatic dicarboxylic acid.
  • the molar ratio of the repeating unit derived from 6-hydroxy-2-naphthoic acid in the aromatic hydroxycarboxylic acid (C) may be, for example, 85 mol% or more, preferably 90 mol% or more. It may be preferably 95 mol% or more.
  • the molar ratio of the repeating unit derived from 2,6-naphthalenedicarboxylic acid in the aromatic dicarboxylic acid (E) may be, for example, 85 mol% or more, preferably 90 mol% or more, and more preferably 95 mol%. It may be% or more.
  • optically anisotropic molten phase referred to in the present invention can be formed can be determined, for example, by placing the sample on a hot stage, heating the sample in a nitrogen atmosphere, and observing the transmitted light of the sample.
  • the thermoplastic liquid crystal polymer preferably has a melting point (hereinafter referred to as Tm 0 ) having a melting point in the range of, for example, 200 to 360 ° C., preferably in the range of 240 to 350 ° C., and more preferably Tm 0 .
  • the temperature is 260 to 330 ° C.
  • the melting point of the thermoplastic liquid crystal polymer can be obtained by observing the thermal behavior of the thermoplastic liquid crystal polymer sample using a differential scanning calorimeter. That is, the thermoplastic liquid crystal polymer sample was heated from room temperature (for example, 25 ° C.) at a rate of 10 ° C./min to completely melt it, and then the melt was rapidly cooled to 50 ° C. at a rate of 10 ° C./min. The position of the heat absorption peak that appears after the temperature is raised again at a rate of 10 ° C./min may be recorded as the melting point of the thermoplastic liquid crystal polymer sample.
  • the thermoplastic liquid crystal polymer may have a melt viscosity of 30 to 120 Pa ⁇ s at a shear rate of 1000 / s at (Tm 0 + 20) ° C., preferably a melt viscosity. It may have 50 to 100 Pa ⁇ s.
  • thermoplastic liquid crystal polymer includes thermoplastic polymers such as polyethylene terephthalate, modified polyethylene terephthalate, polyolefin, polycarbonate, polyarylate, polyamide, polyphenylene sulfide, polyether ether ketone, and fluororesin, as long as the effects of the present invention are not impaired. , Various additives may be added. Further, a filler may be added as needed.
  • thermoplastic liquid crystal polymer film may be a cast film of the above-mentioned thermoplastic liquid crystal polymer, or may be an extrusion-molded film obtained by extrusion-molding the thermoplastic liquid crystal polymer.
  • any extrusion molding method can be used, but the well-known T-die film forming stretching method, laminated body stretching method, inflation method and the like are industrially advantageous.
  • thermoplastic liquid crystal polymer film in the inflation method, stress is applied not only in the mechanical axis direction (hereinafter, abbreviated as MD direction) of the thermoplastic liquid crystal polymer film but also in the direction orthogonal to this (hereinafter, abbreviated as TD direction), and the MD direction, Since it can be uniformly stretched in the TD direction, a thermoplastic liquid crystal polymer film having controlled molecular orientation in the MD direction and the TD direction can be obtained. Therefore, as the thermoplastic liquid crystal polymer film, the one obtained by the inflation method is preferable from the viewpoint of the uniformity of physical properties.
  • the thickness of the thermoplastic liquid crystal polymer film may be 10 to 500 ⁇ m, preferably 20 to 200 ⁇ m, more preferably 20 to 150 ⁇ m, and even more preferably 25 to 125 ⁇ m.
  • it may be in the range of 10 to 50 ⁇ m in particular.
  • the thermoplastic liquid crystal polymer film may be molecularly oriented isotropically in the plane direction from the viewpoint of making the vibration characteristics uniform.
  • the molecular orientation degree SOR of the thermoplastic liquid crystal polymer film is 0.80. It may be about 1.40, preferably about 0.85 to 1.25, and more preferably about 0.90 to 1.20.
  • the degree of molecular orientation SOR (Segment Orientation Ratio) is an index that gives the degree of molecular orientation of the segments constituting the molecule, and is a value in consideration of the thickness of the object.
  • the degree of molecular orientation SOR is a value measured by the method described in Examples described later.
  • thermoplastic liquid crystal polymer film A surface treatment step is subsequently performed on the thermoplastic liquid crystal polymer film.
  • the adhered region existing on the surface of the thermoplastic liquid crystal polymer film may be treated, and the adhered region may be a part or the whole of the surface of the thermoplastic liquid crystal polymer film. It may be one side or both sides of the thermoplastic liquid crystal polymer film.
  • Surface treatment includes corrosion treatment with corrosive solution, copper foil replica treatment, ultraviolet treatment, plasma treatment, etc.
  • Treatment with a corrosive solution is a method of roughening the surface of a thermoplastic liquid crystal polymer film by contacting the corrosive solution with the film.
  • a solution showing basicity is preferably used as the corrosive solution.
  • the solution showing basicity include a solution of an inorganic metal hydroxide, a solution of a basic substance such as ammonia and ethylamine, and an inorganic solution such as an alkali metal hydroxide or an alkaline earth metal hydroxide.
  • a solution of metal hydroxide is preferred.
  • alkali metal hydroxide such as potassium hydroxide and sodium hydroxide
  • alkaline earth metal hydroxide such as magnesium hydroxide
  • examples thereof include those dissolved in a solvent such as methanol, ethanol, isopropyl alcohol, etc.).
  • the concentration of the alkali metal hydroxide or alkaline earth metal hydroxide in the solution may be usually 8.5 or more, preferably 8.5 to 16 or more preferably 10 to 15. There may be.
  • the thermoplastic liquid crystal polymer film may be treated by immersing the thermoplastic liquid crystal polymer film in a corrosive solution at a temperature of room temperature or higher for 30 seconds to 120 minutes.
  • the thermoplastic liquid crystal polymer film may be treated at 50 ° C. or higher, preferably 60 to 60 to.
  • the solution may be contacted at a temperature of 90 ° C., more preferably 65-85 ° C.
  • the method of contact is not limited, but it is desirable to immerse the thermoplastic liquid crystal polymer film in the solution for 40 seconds to 120 minutes, preferably 50 seconds to 90 minutes, more preferably 1 to 60 minutes, and then thoroughly wash. ..
  • the surface of the thermoplastic liquid crystal polymer film is chemically treated by laminating the thermoplastic liquid crystal polymer film and the copper foil and then etching to remove the copper foil, and the surface of the copper foil is treated.
  • This is a method of transferring unevenness.
  • a copper foil having a ten-point average roughness (Rz jis ) of 0.10 to 3.0 ⁇ m on the uneven surface to be transferred may be used.
  • the ten-point average roughness (Rz jis ) of the uneven surface of the copper foil is preferably 0.30 to 1.90 ⁇ m, more preferably 0.40 to 1.80 ⁇ m, and further preferably 0.50 to 1.70 ⁇ m. You may.
  • the unevenness of the copper foil can be transferred to the thermoplastic liquid crystal polymer film by superimposing such an uneven surface on the thermoplastic liquid crystal polymer film and laminating by heating and pressurizing.
  • Lamination can be performed by thermocompression bonding or the like, and the conditions may be, for example, a temperature condition of 180 to 350 ° C., preferably 200 to 330 ° C., and a pressure condition of 1 to 10 MPa. It may be, preferably 2 to 8 MPa.
  • the etching solution used for etching is not particularly limited as long as the copper foil can be removed, and examples thereof include ferric chloride solution and cupric chloride solution.
  • the ultraviolet treatment is, for example, ultraviolet rays having a wavelength of 180 to 195 nm (preferably a wavelength of 181 to 190 nm, more preferably a wavelength of 183 to 187 nm) and 240 to 270 nm (preferably a wavelength of 245 to 265 nm, more preferably a wavelength of 250 to 260 nm). , Or a combination of these ultraviolet rays. In particular, it is preferable to simultaneously irradiate ultraviolet rays having wavelengths of 185 ⁇ 1 nm and 254 ⁇ 1 nm.
  • the light source examples include a low-pressure mercury lamp and a high-pressure mercury lamp.
  • the illuminance may be, for example, 1.0 mW / cm 2 or more, preferably 1.0 to 5.0 mW / cm 2 , and more preferably 1.0 to 2.0 mW / cm 2 .
  • the distance between the irradiation surface and the light source may be about 0.3 cm to 5 cm, preferably about 0.4 to 3 cm.
  • the processing time can be appropriately set according to the distance between the irradiation surface and the light source, but may be, for example, about 20 seconds to 5 minutes, preferably about 30 seconds to 3 minutes.
  • Plasma treatment consists of a direct method in which the substrate to be treated is placed in the discharge space and the plasma treatment is performed directly, and a substrate to be treated is placed outside the discharge space and the active species generated in the discharge space is used as the substrate to be treated. It may be any of remote processing in which processing is performed by spraying, but preferably, the processing method may be a direct method from the viewpoint of enabling high output.
  • plasma treatment generates plasma discharge by supplying power between a pair of electrodes of a discharge parallel plate in an atmosphere in which a gas species is introduced in a vacuum or atmospheric pressure, and this is a thermoplastic liquid crystal polymer. This is carried out by irradiating at least a part of the surface of the film with plasma.
  • the output may be 2.5 W / cm 2 or more, preferably 2.8 W / cm 2 or more, and more preferably 3.0 W / cm 2 . Above, more preferably 3.2 W / cm 2 or more may be used.
  • the upper limit of the output in the plasma treatment is not particularly limited, but may be 8.0 W / cm 2 or less, preferably 7.5 W / cm, for example, from the viewpoint of suppressing excessive damage to the surface of the thermoplastic liquid crystal polymer film. It may be cm 2 or less, more preferably 7.0 W / cm 2 or less.
  • the plasma treatment time may be, for example, less than 5 seconds, preferably 4 seconds or less, and more preferably 3 seconds or less.
  • the lower limit of the plasma treatment time is not particularly limited, but may be 0.1 seconds or longer, preferably 0.3 seconds or longer, for example, from the viewpoint of sufficiently modifying the surface of the thermoplastic liquid crystal polymer film. More preferably, it may be 0.5 seconds or longer.
  • the plasma treatment time refers to the time for irradiating the same portion of the thermoplastic liquid crystal polymer film with plasma.
  • the cumulative processing power (value obtained by multiplying the output per unit area by the processing time) obtained by multiplying the output of the plasma processing by the processing time may be 1.2 W ⁇ s / cm 2 or more. It may be preferably 2.0 W ⁇ s / cm 2 or more, and more preferably 2.5 W ⁇ s / cm 2 or more.
  • the upper limit of the output in the plasma treatment is not particularly limited, but may be, for example, 30 W ⁇ s / cm 2 or less, preferably 25 W ⁇ s /, from the viewpoint of suppressing excessive damage to the surface of the thermoplastic liquid crystal polymer film. It may be cm 2 or less, more preferably 20 W ⁇ s / cm 2 or less.
  • the frequency of discharging between the discharge electrodes is not particularly limited, but may be, for example, in the range of 1 kHz to 2.45 GHz, preferably 10 kHz to 100 MHz, and more preferably 30 kHz to 13. It may be 56 MHz.
  • the processing mode in the plasma processing may be the direct plasma mode (DP) or the reactive ion etching (RIE).
  • DP the substrate to be treated is installed on the ground side between the pair of electrodes, and there is an advantage that radicals can act evenly on the entire substrate to be treated.
  • RIE reactive ion etching
  • the substrate to be processed is installed on the RF power source side between the pair of electrodes, and the ions collide with the substrate to be processed while being accelerated.
  • DP direct plasma mode
  • RIE reactive ion etching
  • the plasma processing may be a discharge method in which a voltage having a continuous waveform (AC waveform) is applied, or a discharge method in which a voltage having a pulsed waveform is applied. From the viewpoint of stabilizing the discharge, a discharge method in which a voltage having a pulsed waveform is applied is preferable. In this case, it is possible to uniformly obtain the surface modification effect even with the treatment in a short time as described above.
  • AC waveform a discharge method in which a voltage having a continuous waveform
  • a discharge method in which a voltage having a pulsed waveform is applied is preferable. In this case, it is possible to uniformly obtain the surface modification effect even with the treatment in a short time as described above.
  • the plasma treatment may be a vacuum plasma treatment or an atmospheric pressure plasma treatment.
  • vacuum plasma treatment even if the pressure in the device to be treated is 0.1 to 20 Pa, from the viewpoint that the density of generated electrons and ions is within a sufficient range for surface modification of the thermoplastic liquid crystal polymer film. It may be preferably 0.3 to 15 Pa, more preferably 0.5 to 13 Pa.
  • the gas type used in the plasma treatment of the present invention is not particularly limited as long as the adhered region of the thermoplastic liquid crystal polymer film has high adhesiveness, and examples of the gas type include nitrogen-containing gas, oxygen-containing gas, and Ar. Rare gas, H2 , CF4 and the like. These gas species may be used alone or in combination of two or more.
  • gas types for example, a plurality of nitrogen-containing gases may be combined; a plurality of oxygen-containing gases may be combined; a single or a plurality of nitrogen-containing gases and a single or a plurality of oxygen-containing gases may be combined. May be combined; oxygen-containing gas (eg O 2 ) and CF 4 may be combined.
  • the gas species may contain at least a nitrogen-containing gas and / or an oxygen-containing gas species, and in particular, the gas species may contain at least a nitrogen-containing gas.
  • the nitrogen-containing gas include N 2 , NH 3, NO 2 , and the like. Of these, N 2 is preferably used. These may be used alone or in combination of two or more.
  • the gas type preferably contains N 2 as a nitrogen-containing gas and optionally contains oxygen-containing gas as another gas type. preferable.
  • oxygen-containing gas examples include O 2 , CO, CO 2 , H 2 O and the like. These may be used alone or in combination of two or more. Of these, O 2 and / or H 2 O are preferably used, and both O 2 and H 2 O are particularly preferred.
  • the gas is a nitrogen-containing gas as long as the nitrogen atom is contained.
  • the volume ratio of the nitrogen-containing gas to the oxygen-containing gas may be 30/70 to 100/0, preferably 40/60 to 95/5, and more preferably 40/60 to 95/5. May be 50/50 to 90/10.
  • the distance between the irradiation head of the plasma processing device and the surface of the thermoplastic liquid crystal polymer film may be 3 to 50 mm (for example, 3 to 10 mm). It may be preferably 4 to 30 mm (for example, 4 to 9 mm), more preferably 5 to 25 mm (for example, 5 to 8 mm).
  • the surface treatment step may be performed continuously or in a batch manner.
  • Peak area ratio ⁇ CO> can exceed 12%.
  • ⁇ CO> may be 13.0 to 30.0%, more preferably 16.0 to 28.0%, still more preferably 18.0 to 26.0%, and even more. It may be preferably 19.0 to 25.0%.
  • X-ray photoelectron spectroscopy exists on the surface of a sample by irradiating the surface of the sample with X-rays from the target metal to excite the inner-shell electrons of the atom and detect the kinetic energy of the emitted photoelectrons. This is a method for identifying elements and analyzing chemical bond states.
  • C (1s) in this X-ray photoelectron spectroscopy analysis is a peak obtained by photoelectrons derived from carbon atoms present on the sample surface. This peak further contains various peaks depending on the bonding state of the carbon atom, and the position of each peak on the spectrum is determined by the bonding state.
  • the distribution function that determines the peak shape is a mixture of the Gaussian function and the Lorentz function, and the half width of each peak is as constant as possible.
  • the surface roughness can be adjusted by these surface treatments.
  • the ten-point average roughness (Rz jis ) of the surface of the thermoplastic liquid crystal polymer film may be 0.1 ⁇ m or more, preferably 0.1 ⁇ m or more. It may be 0.3 ⁇ m or more, more preferably 0.4 ⁇ m or more, still more preferably 0.5 or more. Further, it may be 3.0 ⁇ m or less, preferably 1.90 ⁇ m or less, more preferably 1.80 ⁇ m or less, and further preferably 1.70 ⁇ m or less.
  • a colored layer forming step is performed on the thermoplastic liquid crystal polymer film on which the surface treatment step has been performed.
  • the colored layer is preferably formed in the adhered region of the thermoplastic liquid crystal polymer film by coating, dry plating, wet plating, or the like.
  • the coating film layer is composed of a coating film solid content and a pigment, and the coating film solid content is composed of a resin component and an additive.
  • the solvent used when forming the coating film can be appropriately selected according to the affinity with the resin component.
  • a primer layer may be provided as a base for the coating layer.
  • the resin component examples include synthetic resins, rubber derivatives (for example, rubber chloride, cyclized rubber, etc.), cellulose derivatives (acetyl cellulose, nitrocellulose, etc.), and the like.
  • synthetic resins include acrylic resins, polyurethane resins, vinyl chloride resins, polyvinyl acetal resins, acrylic / silicone resins, silicone resins, polyester resins, epoxy resins, fluorine-containing resins, amide resins, and urea resins.
  • Melamine-based resin, alkyd-based resin, phenol-based resin and the like are contained as resin components. These resins are used alone or in combination. Further, a curing agent is appropriately used in combination with these resins as needed.
  • acrylic resins, urethane resins, epoxy resins, polyester resins and the like are preferable.
  • the additive examples include a plasticizer (DBP, DOP, chlorinated paraffin, etc.), a desiccant (lead naphthenate, cobalt naphthenate, etc.), a precipitation inhibitor, and the like.
  • a plasticizer DBP, DOP, chlorinated paraffin, etc.
  • a desiccant lead naphthenate, cobalt naphthenate, etc.
  • a precipitation inhibitor and the like.
  • these resin components are used as solvent-based paints (for example, organic solvent-based paints), solvent-free paints, water-soluble paints, dispersion-type paints (emulsion paints, NAD paints), and powder paints by known or conventional methods.
  • solvent-based paints for example, organic solvent-based paints
  • solvent-free paints for example, water-soluble paints, dispersion-type paints (emulsion paints, NAD paints), and powder paints by known or conventional methods.
  • an organic solvent paint can be obtained by dissolving a resin component and a curing agent in an organic solvent and dispersing and mixing a pigment and the like.
  • the solvent-free paint can be obtained by mixing an oligomer or a prepolymer with a reactive monomer and dispersing and mixing a pigment or the like.
  • the water-soluble paint can be obtained by using an anionic or cationic resin as a resin component, using water instead of an organic solvent, and adding a curing agent and a pigment.
  • the dispersion-type paint is an oil-in-water (W / O-type) emulsion in which resin particles, pigments, and the like are dispersed in an aqueous solvent.
  • W / O-type oil-in-water
  • resin particles, pigments and the like are dispersed in an aliphatic hydrocarbon solvent, and the surface of the resin particles is dissolved in the aliphatic hydrocarbon to ensure the dispersibility of the particles.
  • Pigments include inorganic pigments, organic pigments, metal pigments (aluminum powder, bronze, zinc powder, mica pieces, etc.), extender pigments, functional pigments, etc., which may be used alone or in combination of two or more. May be good.
  • Inorganic pigments include white pigments (titanium white, etc.), red pigments (molybdate orange, chrome vermillion, etc.), brown pigments (bengala, amber, etc.), and yellow pigments (yellow lead, yellow iron oxide, titanium yellow, etc.). , Cadmium yellow, etc.), Green pigments (chrome oxide green, chrome green, emerald green, etc.), blue pigments (cobalt blue, ultramarine, dark blue, etc.), purple pigments (mineral violet, etc.), black pigments (graphite, carbon) Black, iron oxide, etc.).
  • Organic pigments include red pigments (thioindigo maroon, bonmaroon light, permanent red, quinacridon red, etc.), orange pigments (Induslen Brilliant Orange GR, etc.), yellow pigments (first yellow, benzine yellow, etc.), and green. Examples include system pigments (green gold, phthalocyanine green, etc.), blue pigments (phthalocyanine blue, induthron blue, etc.), black pigments (aniline black, etc.) and the like.
  • black pigments are preferable from the viewpoint of being able to color the thermoplastic liquid crystal polymer film black.
  • the coating film can be appropriately formed by air spray, electrostatic spray, curtain coater, roll coater, airless spray, immersion treatment, electrostatic spray treatment, fluid immersion treatment, etc., depending on the type of paint.
  • a curtain coater or a roll coater is preferable from the viewpoint of unwinding the roll-shaped film to continuously form a colored layer.
  • the roll coater examples include a pre-weighing system such as a direct gravure, an offset gravure, a micro gravure coater, and a reverse roll coater, and a post-weighing system such as a Meyer bar, an air knife coater, a knife coater, and a comma direct.
  • a microgravure coater is preferable.
  • the viscosity of the coating liquid is preferably low, and the viscosity of the coating liquid at the time of coating may be, for example, 100 mPa ⁇ s or less, preferably 80 mPa ⁇ s. It may be as follows.
  • the content of the pigment in the coating liquid is not particularly limited as long as it can be adjusted to the above viscosity, but may be, for example, 2 to 17% by weight.
  • the coating amount of the coating liquid may be 0.1 g / m 2 or more and 40 g / m 2 or less, and particularly in the case of an acoustic diaphragm application, from the viewpoint of forming a thin coating film, 0.1 g / m 2 or more and 10 g / m / It is preferably m 2 or less.
  • the coating film can be appropriately cured by post-treatment such as leaving at room temperature, heat treatment, irradiation treatment (UV treatment, etc.) to form a colored layer.
  • post-treatment such as leaving at room temperature, heat treatment, irradiation treatment (UV treatment, etc.) to form a colored layer.
  • a plurality of layers of coating film may be formed, and when a plurality of layers are formed, each coating film may be post-treated, or a plurality of layers of coating film may be post-treated. good.
  • sputtering Ar ions in plasma can be made to collide with a target portion of a thermoplastic liquid crystal polymer film at high speed by utilizing a sputtering phenomenon, and material atoms can be knocked out to form a colored layer.
  • a colored layer may be formed by utilizing light interference, but it is convenient and preferable in design to form a colored layer by utilizing light absorption by a sputtering material. It is carried out by a method known or commonly used by those skilled in the art using a sputtering material.
  • Examples of the metal for sputtering include copper, aluminum, gold, tin, chromium, and alloys of these metals.
  • examples of the metal for sputtering include red (Be 2C , etc.), yellow (YC 2 , LaC 2 , ZrN, etc.), red-yellow (CeC 2 , etc.), and brown (CeC 2, etc.).
  • NbC, TaC, WN, etc. yellowish brown (HfN, etc.), gray (UC, TiC, ZrC, TaN, Cr 2N, Cr 23C 6 , WC, Be 3N 2, etc.), yellowish green (Mg 3 N 2 etc. ) Etc.), yellow bronze color (TiN, etc.), black color (LaN, MnN, etc.) and the like.
  • plating examples include electroplating, electroless plating, and hot dip plating.
  • electroplating a colored layer can be formed by electrolyzing an aqueous solution or a non-aqueous solution containing metal ions and precipitating a metal on a target portion of a thermoplastic liquid crystal polymer film.
  • the metal used in electroplating include magnesium, aluminum, copper, zinc, nickel, gold, silver, tin, chromium, rhodium, and alloys of these metals.
  • a colored layer can be formed by applying a reducing agent to metal ions in an aqueous solution containing metal ions and reducing and precipitating the metal on the target site of the thermoplastic liquid crystal polymer film.
  • a reducing agent to metal ions in an aqueous solution containing metal ions and reducing and precipitating the metal on the target site of the thermoplastic liquid crystal polymer film.
  • the metal used in electroless plating include magnesium, aluminum, copper, zinc, nickel, cobalt, gold, silver, tin, chromium, rhodium, and alloys of these metals.
  • black plating in particular is referred to as black nickel, black chromium, black rhodium, etc., and the alloy composition thereof is known to those skilled in the art. Further, if necessary, the plating layer may be subjected to an oxidation treatment or a chemical conversion treatment to perform a discoloration treatment (for example, blackening).
  • thermoplastic liquid crystal polymer film molded product Since the thermoplastic liquid crystal polymer film molded body on which the colored layer is formed has excellent bending resistance, the number of reciprocating bendings until cracks occur is 100 times in the folding resistance test by JIS P 8115 (2001). Exceeds.
  • the thermoplastic liquid crystal polymer film molded product of the present invention has a colored layer, but has good adhesiveness and followability, is excellent in shaping workability to a desired shape, and has an external force such as vibration. It is useful for applications such as acoustic diaphragms that receive.
  • the number of reciprocating bends until cracks occur is preferably more than 200 times, more preferably more than 500 times, and even more preferably more than 1000 times.
  • the number of reciprocating bends until cracks occur in the bending strength test is a value measured by the method described in Examples described later.
  • thermoplastic liquid crystal polymer film molded product of the present invention has excellent adhesion of the colored layer, and the evaluation of the colored layer in JIS K 5600-5-6 adhesion (cross-cut test) may be 3 or less. , It may be preferably 2 or less, and particularly preferably 0.
  • the evaluation of the colored layer is a value measured by the method described in Examples described later.
  • the thickness of the colored layer is preferably thin from the viewpoint of the followability of the film when the film is molded, and for example, even if it is about 0.001 to 0.9 times the thickness of the film layer. It may be preferably about 0.005 to 0.5 times, more preferably about 0.01 to 0.5 times.
  • the thickness of the colored layer may be 0.01 to 10 ⁇ m, preferably 0.05 to 8 ⁇ m, and more preferably 0.1 to 7 ⁇ m. Even when the colored layers are arranged on both surfaces of the film, the thickness of the colored layer with respect to the thickness of the film is calculated as the thickness of each colored layer with respect to the film. In that case, it is sufficient that at least one colored layer satisfies the above range, and it is preferable that both colored layers satisfy the above range.
  • the hardness of the colored layer is preferably soft from the viewpoint of the followability of the film when the film is molded, and for example, the hardness measured by the nanoindentation method may be 0.01 to 10 GPa. It may be preferably 0.01 to 5 GPa, more preferably 0.01 to 1 GPa, and even more preferably 0.01 to 0.5 GPa.
  • the colored layer may be a coating layer, a dry plating layer, or a wet plating layer. From the viewpoint of the followability of the film when molding the film, it is preferable to contain a component other than the coloring component.
  • the coloring component include a pigment in the coating layer, a metal for sputtering in the case of the sputtering layer in the dry plating layer, and a metal used for electroplating, electroless plating, and hot-dip plating in the wet plating layer.
  • the colored layer may be a coating layer composed of a coating film solid content and a pigment.
  • the colored layer may have a desired color depending on the above pigment or metal, but from the viewpoint of designability, it may be a dark color, preferably black.
  • a black colored layer may be formed by using a black pigment, using a black metal for sputtering, black plating, blackening the plating, or the like.
  • thermoplastic liquid crystal polymer film molded body on which the colored layer is formed may be used as a circuit board, may be used as various sensor circuits (for example, temperature, humidity, strain gauge), or may be used as an acoustic diaphragm (acoustic diaphragm). For example, it may be used as an acoustic diaphragm of a speaker for an electric-acoustic converter).
  • thermoplastic liquid crystal polymer film molded body (or thermoplastic liquid crystal polymer film laminate) on which the colored layer is formed is further formed and formed, if necessary, and has a desired shape. It can be a body (or a thermoplastic liquid crystal polymer film shaped part).
  • the shape of the thermoplastic liquid crystal polymer film shaped body may be a shape that can be formed by shaping the film.
  • it may have various shapes that can be formed on the film by compressed air forming, vacuum forming, press forming or the like.
  • the compressed air forming method may be a method in which the film is softened and then pressed against a mold by applying pressure to the film using air pressure or the like.
  • the vacuum forming method may be a method in which the film is drawn into the mold and shaped by creating a vacuum in the gap between the mold and the film after the film is softened.
  • the press molding method may be a method in which the film is sandwiched between a pair of dies on the upper and lower sides, and the film is softened by heating between the dies to form a shape.
  • the shape of the thermoplastic liquid crystal polymer film shaped body can be appropriately set, for example, depending on the application, and may be various shapes including a dome shape, a cone shape, a cube shape, an indefinite shape, and a combination thereof. good.
  • the thermoplastic liquid crystal polymer film shaped body when used for the acoustic diaphragm, the thermoplastic liquid crystal polymer film shaped body may have a dome shape as shown in FIG. 1, and the arc length (X) at the cut surface at the apex of the dome. / String length (Y)> 0.001 may be used.
  • the arrow height (Z) may be, for example, 0.1 to 10 mm, preferably 0.3 to 8 mm.
  • the thickness of the thermoplastic liquid crystal polymer film molded product can be appropriately selected depending on the thickness of the film layer, but may be, for example, 10 to 500 ⁇ m, preferably 20 to 200 ⁇ m, and more preferably 20 to 20. It may be 150 ⁇ m, more preferably 25 to 125 ⁇ m. Alternatively, in thin material applications, it may be in the range of 10 to 50 ⁇ m in particular.
  • the elongation of the thermoplastic liquid crystal polymer film molded product may be, for example, 2 to 60%.
  • the thermoplastic liquid crystal polymer film molded body may have extensibility in order to improve moldability and prevent peeling of the colored layer, and its elongation. May be preferably 3 to 60%, and more preferably 5 to 50%, particularly when deeper drawing is required.
  • the storage elastic modulus of the molded product may be, for example, 1 GPa or more and 20 GPa or less, preferably 2 to 18 GPa, and more preferably 5 to 15 GPa.
  • the internal loss of the molded product may be, for example, 0.02 or more and 0.1 or less, preferably in the range of 0.03 to 0.08, and more preferably in the range of 0.05 to 0.08. You may.
  • the storage elastic modulus and the internal loss can be measured by dynamic viscoelasticity measurement (DMA), and are values calculated by the method described in Examples described later.
  • DMA dynamic viscoelasticity measurement
  • thermoplastic liquid crystal polymer film molded body is molded by using the thermoplastic liquid crystal polymer film on which the colored layer is formed, it is possible to maintain good elasticity and vibration damping property of the molded body, for example, electricity.
  • good sound quality derived from a thermoplastic liquid crystal polymer film can be achieved.
  • ⁇ Thickness of colored layer and thermoplastic liquid crystal polymer film> The thickness of the colored layer and the thermoplastic liquid crystal polymer film was measured using a Digimatic Indicator manufactured by Mitutoyo Co., Ltd. In the measurement, 100 points were randomly measured from the sample fragment (length 10 cm, width 10 cm), and the average value was taken as the thickness. The thickness of the colored layer was calculated from the difference between the thickness of the entire thermoplastic liquid crystal polymer film having the colored layer and the thickness of the thermoplastic liquid crystal polymer film alone.
  • thermoplastic liquid crystal polymer film sample is inserted into a microwave resonance waveguide so that the sample surface is perpendicular to the traveling direction of the microwave, and the microwave is transmitted through the sample.
  • the electric field strength microwave transmission strength
  • the m value was calculated by the following equation.
  • m (Zo / ⁇ z) X [1- ⁇ max / ⁇ o]
  • Zo is the device constant
  • ⁇ z is the average thickness of the object
  • ⁇ max is the frequency that gives the maximum microwave transmission intensity when the frequency of the microwave is changed
  • ⁇ o is the average thickness of zero (that is, the object is). (When not) is the frequency that gives the maximum microwave transmission intensity.
  • the minimum microwave transmission intensity is given.
  • the molecular orientation SOR was calculated by m 0 / m 90 , where m 0 was the m value when the direction was matched and m 90 was the m value when the rotation angle was 90 °.
  • thermoplastic liquid crystal polymer film produced in Examples and Comparative Examples The surface of the adhered area of the thermoplastic liquid crystal polymer film produced in Examples and Comparative Examples was measured under the following measurement conditions using a scanning X-ray photoelectron spectroscopy analyzer (“PHI Quantera SXM” manufactured by ULVAC-PHI, Inc.). The ratio of the peak area of each of the following coupled states to the whole was calculated.
  • ⁇ Rz jis ( ⁇ m)> Using a stylus type surface roughness meter (Mitutoyo Co., Ltd., Surftest SJ-201P), refer to JIS B 0601-2001 to check the unevenness of the surface of the thermoplastic liquid crystal polymer film on the side that comes into contact with the colored layer. It was measured and Rz jis (10-point average roughness) was calculated. For the measurement, a needle having a cone taper angle of 60 degrees and a tip radius of curvature of 2 ⁇ m was used. These were measured three times at different locations with a reference length of 0.8 mm, and calculated as an average value of the three times.
  • the colored layer is partially or wholly peeled off along the edges of the cut, and / or various parts of the eye are partially or wholly peeled off.
  • the cross-cut area is clearly affected by more than 15% but not more than 35%.
  • 4 The colored layer is partially or wholly peeled off along the edges of the cut, and / or several eyes are partially or wholly peeled off.
  • the cross-cut area is clearly not affected by more than 35%. 5: Any degree of peeling that cannot be classified even in classification 4.
  • thermoplastic liquid crystal polymer film laminate was cut into strips having a width of 1 cm and used as test pieces.
  • this test piece can withstand a load of 1 kgf, a bending angle of 90 °, a radius of curvature of the bent surface of 0.38 mm, and a bending speed of 90 times / minute using a MIT tester.
  • a folding strength test was performed. For each test piece, the presence or absence of cracks was visually confirmed every 100 reciprocating bends, and the number of reciprocating bends at the time of cracking was measured.
  • the crack means a crack (a crack having a length of 0.1 mm or more) that occurs at a bent portion of at least one layer of the thermoplastic liquid crystal polymer film laminate and can be confirmed with an optical microscope (140 times). If a crack occurred when the number of reciprocating bends was 100, it was determined that the number of reciprocating bends until the crack occurred was 100 or less. If no cracks have occurred when the number of reciprocating bends is 100, then check for cracks after every 100 reciprocating bends, and if no cracks have occurred when the number of reciprocating bends is 1000. It was determined that the number of reciprocating bends until cracks occurred exceeded 1000 times. In the test, the test results (number of reciprocating bends) of three times were averaged.
  • Example 1 Thermoplastic liquid crystal polymer film (manufactured by Kuraray Co., Ltd., product name "Vexter FA", thickness 50 ⁇ m, SOR1.1) is used with a plasma continuous processing device in which the film unwinding and winding are installed inside the vacuum chamber. Then, it was set so as to pass between the parallel plate electrodes (distance between the head and the film 20 mm) (direct method). After exhausting the inside of the vacuum chamber with a vacuum pump, N2 was introduced as a gas type, and the pressure inside the vacuum chamber was adjusted to 3 Pa.
  • the processing mode is set to the direct plasma mode (DP), the discharge frequency is 150 kHz, plasma is generated between the electrodes at an output of 5.6 W / cm 2 by a discharge method in which a continuous waveform voltage is applied, and winding is performed at a speed of 3 m / min.
  • DP direct plasma mode
  • plasma treatment on the surface of the thermoplastic liquid crystal polymer film was continuously performed.
  • the ⁇ CO> calculated from the results obtained by X-ray photoelectron spectroscopy on the surface of the thermoplastic liquid crystal polymer film subjected to plasma treatment was 20%.
  • thermoplastic liquid crystal polymer film laminate having a colored layer formed on the thermoplastic liquid crystal polymer film.
  • the thickness of the colored layer was 6.0 ⁇ m, and as a result of the above-mentioned cross-cut test for evaluating the adhesiveness of the colored layer, there was no peeling and the evaluation was “0”. Further, as a result of performing the above-mentioned folding resistance test, no crack was generated even after bending 1000 times.
  • thermoplastic liquid crystal polymer film laminate was shaped at 200 ° C. using a mold having a diameter of ⁇ 20 mm, an arrow height of 2 mm, and an arc length / chord length of 0.03, and the appearance after shaping was performed. It was confirmed.
  • the obtained thermoplastic liquid crystal polymer film shaped body was good in appearance without swelling.
  • Example 2 Same as Example 1 except that the surface of the thermoplastic liquid crystal polymer film is treated with ultraviolet rays using a thermoplastic liquid crystal polymer film (manufactured by Kuraray Co., Ltd., product name "Vexter CTF", thickness 50 ⁇ m, SOR1.1). A thermoplastic liquid crystal polymer film laminate was obtained. Using an ultraviolet irradiation device (manufactured by Sen Engineering Co., Ltd.) equipped with four low-pressure mercury lamps (EUV200US) on the surface of the thermoplastic liquid crystal polymer film (effective irradiation distance: about 200 mm), 184.9 nm and 253.7 nm.
  • EUV200US low-pressure mercury lamps
  • the ultraviolet rays having a wavelength were continuously treated with ultraviolet rays at a speed of 0.5 m / min, with an illuminance of 1.2 mW / cm 2 and a distance of 2 cm between the light source and the irradiation surface.
  • the ⁇ CO> calculated from the results obtained by X-ray photoelectron spectroscopy on the surface of the thermoplastic liquid crystal polymer film treated with ultraviolet rays was 14%.
  • thermoplastic liquid crystal polymer film laminate on which a colored layer was formed.
  • the thickness of the colored layer was 6.0 ⁇ m, and as a result of the above-mentioned cross-cut test for evaluating the adhesiveness of the colored layer, there was no peeling and the evaluation was “0”. Further, as a result of performing the above-mentioned folding resistance test, no crack was generated even after bending 1000 times.
  • thermoplastic liquid crystal polymer film laminate was subjected to a shaping treatment in the same manner as in Example 1, and the appearance after shaping was confirmed.
  • the obtained thermoplastic liquid crystal polymer film shaped body was good in appearance without swelling.
  • Example 3 Thermoplastic in the same manner as in Example 1 except that a colored layer is formed by sputtering using a thermoplastic liquid crystal polymer film (manufactured by Kuraray Co., Ltd., product name “Vexter CTF”, thickness 50 ⁇ m, SOR1.1).
  • a liquid crystal polymer film laminate was obtained.
  • a DC magnetron device was used, aluminum was used as the metal for sputtering, the ultimate vacuum degree was 1 ⁇ 10 -1 Pa or less, and the sputter gas pressure was 0.1 to 5.0 Pa.
  • the treatment was performed with a film power (input power) of 4 kW to obtain a thermoplastic liquid crystal polymer film laminate having a colored layer formed.
  • the thickness of the colored layer was 0.5 ⁇ m, and as a result of the above-mentioned cross-cut test for evaluating the adhesiveness of the colored layer, there was no peeling and the evaluation was “0”. Further, as a result of performing the above-mentioned folding resistance test, no crack was generated even after bending 1000 times.
  • thermoplastic liquid crystal polymer film laminate was subjected to a shaping treatment in the same manner as in Example 1, and the appearance after shaping was confirmed.
  • the obtained thermoplastic liquid crystal polymer film shaped body was good in appearance without swelling.
  • Example 4 Thermoplastic liquid crystal polymer film (manufactured by Kuraray Co., Ltd., product name "Vexter CTF", thickness 50 ⁇ m, SOR1.1) is used, and the colored layer is formed by wet plating, but the heat is the same as in Example 1.
  • a thermoplastic liquid crystal polymer film laminate was obtained. After providing a Zn-plated layer containing molten Mg in advance on the plasma-treated thermoplastic liquid crystal polymer film, the surface layer is plated by contacting with steam in a closed container having an oxygen concentration of 13% or less. The layer was blackened to obtain a thermoplastic liquid crystal polymer film laminate on which a colored layer was formed.
  • the thickness of the colored layer was 2.0 ⁇ m, and the above-mentioned cross-cut test was performed to evaluate the adhesiveness of the colored layer. There was no peeling and the evaluation was "0". Further, as a result of performing the above-mentioned folding resistance test, no crack was generated even after bending 1000 times.
  • thermoplastic liquid crystal polymer film laminate was subjected to a shaping treatment in the same manner as in Example 1, and the appearance after shaping was confirmed.
  • the obtained thermoplastic liquid crystal polymer film shaped body was good in appearance without swelling.
  • Example 5 Same as Example 1 except that the surface of the thermoplastic liquid crystal polymer film is corroded using a thermoplastic liquid crystal polymer film (manufactured by Kuraray Co., Ltd., product name "Vexter CTF", thickness 50 ⁇ m, SOR1.1). A thermoplastic liquid crystal polymer film laminate was obtained. The thermoplastic liquid crystal polymer film was immersed in an alkaline solution (manufactured by Raytec Co., Ltd., "TPE3000”) at 80 ° C. for 1 minute, then taken out, washed thoroughly with water, and dried at room temperature. The ⁇ CO> calculated from the results obtained by X-ray photoelectron spectroscopy on the surface of the thermoplastic liquid crystal polymer film subjected to the corrosion treatment was 23%.
  • a thermoplastic liquid crystal polymer film manufactured by Kuraray Co., Ltd., product name "Vexter CTF", thickness 50 ⁇ m, SOR1.1.
  • a thermoplastic liquid crystal polymer film laminate was obtained.
  • thermoplastic liquid crystal polymer film laminate on which a colored layer was formed.
  • the thickness of the colored layer was 6.0 ⁇ m, and as a result of the above-mentioned cross-cut test for evaluating the adhesiveness of the colored layer, there was no peeling and the evaluation was “0”. Further, as a result of performing the above-mentioned folding resistance test, no crack was generated even after bending 1000 times.
  • thermoplastic liquid crystal polymer film laminate was subjected to a shaping treatment in the same manner as in Example 1, and the appearance after shaping was confirmed.
  • the obtained thermoplastic liquid crystal polymer film shaped body was good in appearance without swelling.
  • Example 6 Example 1 except that the surface treatment of the thermoplastic liquid crystal polymer film is performed by copper foil replica treatment using a thermoplastic liquid crystal polymer film (manufactured by Kuraray Co., Ltd., product name "Vexter CTF", thickness 50 ⁇ m, SOR1.1). In the same manner as above, a thermoplastic liquid crystal polymer film laminate was obtained. Electrolyzed copper foil (manufactured by Fukuda Metal Foil Powder Industry Co., Ltd., CF-H9A-HD2, Rz jis 1.5 ⁇ m) is superposed on the thermoplastic liquid crystal polymer film, and the heating plate is 300 using a vacuum heat press device.
  • a thermoplastic liquid crystal polymer film manufactured by Kuraray Co., Ltd., product name "Vexter CTF", thickness 50 ⁇ m, SOR1.1.
  • Electrolyzed copper foil manufactured by Fukuda Metal Foil Powder Industry Co., Ltd., CF-H9A-HD2, Rz jis 1.5 ⁇ m
  • the heating plate is
  • the temperature was set to 4 MPa and pressure was applied for 10 minutes under a pressure of 4 MPa to prepare a laminate having an electrolytic copper foil / thermoplastic liquid crystal polymer film.
  • the electrolytic copper foil of the obtained laminate was removed with a ferric chloride etching solution.
  • the ⁇ CO> calculated from the results obtained by X-ray photoelectron spectroscopy on the surface of the thermoplastic liquid crystal polymer film subjected to the copper foil replica treatment was 17%.
  • thermoplastic liquid crystal polymer film laminate on which a colored layer was formed.
  • the thickness of the colored layer was 6.0 ⁇ m, and as a result of the above-mentioned cross-cut test for evaluating the adhesiveness of the colored layer, there was no peeling and the evaluation was “0”. Further, as a result of performing the above-mentioned folding resistance test, no crack was generated even after bending 1000 times.
  • thermoplastic liquid crystal polymer film laminate was subjected to a shaping treatment in the same manner as in Example 1, and the appearance after shaping was confirmed.
  • the obtained thermoplastic liquid crystal polymer film shaped body was good in appearance without swelling.
  • thermoplastic liquid crystal polymer film laminate and a thermoplastic liquid crystal polymer film shaped body were obtained in the same manner as in Example 1 except that an untreated film not subjected to plasma treatment was used.
  • the ⁇ CO> calculated from the results obtained by X-ray photoelectron spectroscopy on the surface of the thermoplastic liquid crystal polymer film of the untreated film was 12%.
  • thermoplastic liquid crystal polymer film laminate on which a colored layer was formed.
  • the thickness of the colored layer was 6.0 ⁇ m, and the above-mentioned cross-cut test was performed to evaluate the adhesiveness of the colored layer, but the adhesion was insufficient and the evaluation was “4”. Further, as a result of conducting the above-mentioned folding resistance test, it was confirmed that cracks were generated by observing the bent portion when bent 100 times.
  • thermoplastic liquid crystal polymer film laminate was subjected to a shaping treatment in the same manner as in Example 1, and the appearance after shaping was confirmed.
  • the obtained thermoplastic liquid crystal polymer film shaped body had tears and swelling in appearance.
  • thermoplastic liquid crystal polymer film laminate and a thermoplastic liquid crystal polymer film shaped body were obtained in the same manner as in Example 3 except that an untreated film not subjected to plasma treatment was used.
  • the ⁇ CO> calculated from the results obtained by X-ray photoelectron spectroscopy on the surface of the thermoplastic liquid crystal polymer film of the untreated film was 12%.
  • thermoplastic liquid crystal polymer film laminate on which a colored layer was formed.
  • the thickness of the colored layer was 0.5 ⁇ m, and the above-mentioned cross-cut test was performed to evaluate the adhesiveness of the colored layer, but the peeling was conspicuous and the evaluation was “5”. Further, as a result of conducting the above-mentioned folding resistance test, it was confirmed that cracks were generated by observing the bent portion when bent 100 times.
  • thermoplastic liquid crystal polymer film laminate was subjected to a shaping treatment in the same manner as in Example 1, and the appearance after shaping was confirmed.
  • the obtained thermoplastic liquid crystal polymer film shaped body had tears and swelling in appearance.
  • thermoplastic liquid crystal polymer film laminate and a thermoplastic liquid crystal polymer film shaped body were obtained in the same manner as in Example 4 except that an untreated film not subjected to plasma treatment was used.
  • the ⁇ CO> calculated from the results obtained by X-ray photoelectron spectroscopy on the surface of the thermoplastic liquid crystal polymer film of the untreated film was 12%.
  • thermoplastic liquid crystal polymer film was subjected to a wet plating treatment to obtain a thermoplastic liquid crystal polymer film laminate on which a colored layer was formed.
  • the thickness of the colored layer was 2.0 ⁇ m, and the above-mentioned cross-cut test was performed to evaluate the adhesiveness of the colored layer, but the peeling was conspicuous and the evaluation was “5”. Further, as a result of conducting the above-mentioned folding resistance test, it was confirmed that cracks were generated by observing the bent portion when bent 100 times.
  • thermoplastic liquid crystal polymer film laminate was subjected to a shaping treatment in the same manner as in Example 1, and the appearance after shaping was confirmed.
  • the obtained thermoplastic liquid crystal polymer film shaped body had tears and swelling in appearance.
  • thermoplastic liquid crystal polymer film molded product of the present invention since the thermoplastic liquid crystal polymer film and the colored layer are well adhered to each other, a desired color can be imparted to the milky white thermoplastic liquid crystal polymer. Therefore, it is particularly useful for various applications used as thermoplastic liquid crystal polymer films, circuit boards, acoustic diaphragms, reinforcing plates for flexible circuit boards, circuit surface cover films, various sensor circuits (temperature, humidity, strain gauges), etc. be.

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Abstract

La présente invention concerne un corps formé d'un film polymère thermoplastique à cristaux liquides qui présente une couche colorée. Ce corps formé d'un film polymère thermoplastique à cristaux liquides comprend : une couche de film polymère thermoplastique à cristaux liquides ; et une couche colorée qui est formée sur au moins une partie d'un côté, ou des deux côtés, de la couche de film polymère thermoplastique à cristaux liquides. Dans un essai de résistance à la flexion selon la norme JIS P 8115 (2001), le corps formé d'un film polymère thermoplastique à cristaux liquides a été soumis à une flexion réciproque supérieure à 100 fois avant qu'une craquelure ne commence à se former.
PCT/JP2021/046888 2020-12-25 2021-12-17 Corps formé d'un film polymère thermoplastique à cristaux liquides ayant une couche colorée et son procédé de production WO2022138516A1 (fr)

Priority Applications (3)

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JPH02274098A (ja) * 1989-04-14 1990-11-08 Mitsubishi Electric Corp スピーカー用の振動板とボイスコイルボビンの製造方法
JPH11302402A (ja) * 1998-04-27 1999-11-02 Sumitomo Chem Co Ltd 遮光性フィルム
JP2001506767A (ja) * 1996-12-05 2001-05-22 ヘキスト・セラニーズ・コーポレーション 剥離性の熱可塑性スキン層
JP2007187892A (ja) * 2006-01-13 2007-07-26 Canon Electronics Inc 遮光羽根および光路開閉装置
WO2021095758A1 (fr) * 2019-11-15 2021-05-20 株式会社クラレ Diaphragme acoustique, son procédé de fabrication, et dispositif acoustique

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JP6729718B2 (ja) 2016-12-05 2020-07-22 株式会社村田製作所 黒色液晶ポリマーフィルムおよび多層基板

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Publication number Priority date Publication date Assignee Title
JPH02274098A (ja) * 1989-04-14 1990-11-08 Mitsubishi Electric Corp スピーカー用の振動板とボイスコイルボビンの製造方法
JP2001506767A (ja) * 1996-12-05 2001-05-22 ヘキスト・セラニーズ・コーポレーション 剥離性の熱可塑性スキン層
JPH11302402A (ja) * 1998-04-27 1999-11-02 Sumitomo Chem Co Ltd 遮光性フィルム
JP2007187892A (ja) * 2006-01-13 2007-07-26 Canon Electronics Inc 遮光羽根および光路開閉装置
WO2021095758A1 (fr) * 2019-11-15 2021-05-20 株式会社クラレ Diaphragme acoustique, son procédé de fabrication, et dispositif acoustique

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