WO2022138516A1

WO2022138516A1 - Thermoplastic liquid crystal polymer film-formed body having colored layer, and method for producing same

Info

Publication number: WO2022138516A1
Application number: PCT/JP2021/046888
Authority: WO
Inventors: 先文張; 辰也砂本; 啓輔池田
Original assignee: 株式会社クラレ
Priority date: 2020-12-25
Filing date: 2021-12-17
Publication date: 2022-06-30
Also published as: KR20230125199A; CN116635235A; JPWO2022138516A1; TW202239834A

Abstract

Provided is a thermoplastic liquid crystal polymer film-formed body that has a colored layer. This thermoplastic liquid crystal polymer film-formed body includes: a thermoplastic liquid crystal polymer film layer; and a colored layer which is formed on at least part of one side or both sides of the thermoplastic liquid crystal polymer film layer. In a bending resistance test in accordance with JIS P 8115 (2001), the thermoplastic liquid crystal polymer film-formed body was subjected to reciprocal bending more than 100 times before cracking began to occur.

Description

Thermoplastic liquid crystal polymer film molded body having a colored layer and its manufacturing method

Related application

This application claims the priority of Japanese Patent Application No. 2020-216795 filed on December 25, 2020, and the entire application is cited as a part of this application by reference.

The present invention relates to a 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.

The thermoplastic liquid crystal polymer film has a milky white color derived from the thermoplastic liquid crystal polymer. For example, when such 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.

For example, in 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 μm or less. Then, 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.

International Publication No. 2018/105624

However, in Patent Document 1, although a black 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. As a result, when 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. ..

Further, in the 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.
Further, when 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.

Therefore, 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.

As a result of diligent studies to achieve the above object, 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. On the other hand, in 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.

That is, the present invention can be configured in the following aspects.
[Aspect 1]
A 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. Thermoplastic polymer film molded article.
[Aspect 2]
In the thermoplastic liquid crystal polymer film molded product of the first aspect, 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.
[Aspect 3]
In the thermoplastic liquid crystal polymer film molded body of the first or second aspect, 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.
[Aspect 4]
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.
[Aspect 5]
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 μm (Rz jis). A thermoplastic liquid crystal polymer film molded product preferably 0.30 to 1.90 μm, more preferably 0.40 to 1.80 μm, still more preferably 0.50 to 1.70 μm).
[Aspect 6]
In the 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.
[Aspect 7]
In the thermoplastic liquid crystal polymer film molded product according to any one of aspects 1 to 6, 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.
[Aspect 8]
A thermoplastic liquid crystal polymer film molded product having a dome-like shape in the thermoplastic liquid crystal polymer film molded product according to any one of aspects 1 to 7.
[Aspect 9]
An acoustic diaphragm made of a thermoplastic liquid crystal polymer film molded product according to any one of aspects 1 to 8.
[Aspect 10]
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. In the result of X-ray photoelectron spectroscopy at a depth of 10 to 100 nm, the ratio of the peak area of [CO bond] to the total peak area of each peak of C (1s) on the surface of the adhered region <CO>. In the surface treatment process to obtain a film to be treated with a value of more than 12%,
A method for producing a 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.
[Aspect 11]
A method for producing a thermoplastic liquid crystal polymer film molded product, wherein the colored film to be treated is shaped in the production method according to the tenth aspect.

In the present specification, the 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 is the ratio of the peak area of [CO bond] and [C = O bond] to the total peak area of each peak of C (1s) observed according to each bond state. It is calculated. In the present specification, in the following, 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). The ratio of the peak area of [C = O bond] to the total is expressed as <C = O>.

It should be noted that any combination of at least two components disclosed in the claims and / or the specification and / or the drawings is included in the present invention. In particular, any combination of two or more of the claims described in the claims is included in the invention.

According to the 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.

It is a schematic sectional drawing for demonstrating the dimension of a dome shape.

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.

Further, the 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.

Specific examples of the 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.

(1) Aromatic or aliphatic diols (see Table 1 for typical examples)

(2) Aromatic or aliphatic dicarboxylic acids (see Table 2 for typical examples)

(3) Aromatic hydroxycarboxylic acid (see Table 3 for typical examples)

(4) Aromatic diamine, aromatic hydroxyamine or aromatic aminocarboxylic acid (see Table 4 for typical examples).

Typical examples of thermoplastic liquid crystal polymers obtained from these raw material compounds include copolymers having repeating units shown in Tables 5 and 6.

Among these copolymers, 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.

For example, in the copolymer of (i), 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). The molar ratio (A) / (B) of the acid to the 6-hydroxy-2-naphthoic acid of the repeating unit (B) is (A) / (B) = 10/90 to 90 / in the thermoplastic liquid crystal polymer. It is preferably about 10, more preferably (A) / (B) = about 15/85 to 85/15, and even more preferably (A) / (B) = 20/80 to. It may be about 80/20.

Further, in the case of the copolymer of (ii), 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'-. From the group consisting of at least one 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. (E) = (30 to 80): (35 to 10): may be about (35 to 10), and more preferably (C) :( D) :( E) = (35 to 75) :. (32.5 to 12.5): It may be about (32.5 to 12.5), and more preferably (C) :( D) :( E) = (40 to 70) :( 30). ~ 15): It may be about (30 ~ 15).

Further, 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.

The aromatic diol (D) is a repeating unit derived from two different aromatic diols selected from the group consisting of hydroquinone, 4,4'-dihydroxybiphenyl, phenylhydroquinone, and 4,4'-dihydroxydiphenyl ether. It may be (D1) and (D2), and in that case, the molar ratio of the two aromatic diols may be (D1) / (D2) = 23/77 to 77/23, which is more preferable. May be 25/75 to 75/25, more preferably 30/70 to 70/30.

The molar ratio of the repeating unit derived from the aromatic diol (D) to the repeating unit derived from the aromatic dicarboxylic acid (E) is (D) / (E) = 95/100 to 100/95. Is preferable. If it deviates from this range, the degree of polymerization does not increase and the mechanical strength tends to decrease.

The fact that the 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.

Further, from the viewpoint of melt moldability, 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.

The 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.

The 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. At this time, 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. In particular, 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.

For example, the thickness of the thermoplastic liquid crystal polymer film may be 10 to 500 μm, preferably 20 to 200 μm, more preferably 20 to 150 μm, and even more preferably 25 to 125 μm. Alternatively, in thin material applications, it may be in the range of 10 to 50 μm 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. Specifically, 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. Here, 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.

(Surface treatment process)
A surface treatment step is subsequently performed on the thermoplastic liquid crystal polymer film. In the surface treatment step, 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.

(Corrosion treatment)
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. In the treatment with a corrosive solution, a solution showing basicity is preferably used as the corrosive solution. Examples of 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. As a solution of alkali metal hydroxide or alkaline earth metal hydroxide, alkali metal hydroxide such as potassium hydroxide and sodium hydroxide; alkaline earth metal hydroxide such as magnesium hydroxide is used as water and alcohol ( 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.

In the corrosion treatment, 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. For example, 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. ..

(Copper foil replica processing)
In the copper foil replica treatment, 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. In the copper foil replica treatment, a copper foil having a ten-point average roughness (Rz _jis ) of 0.10 to 3.0 μm 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 μm, more preferably 0.40 to 1.80 μm, and further preferably 0.50 to 1.70 μm. 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. Further, by removing the copper foil by etching, the transferred unevenness is not deformed, so that the unevenness of the copper foil can be reproduced. 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.

(Ultraviolet treatment)
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.

Examples of the light source 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 processing)
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.

In the direct method, 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.

It is preferable to perform plasma treatment at a high output in a short time. For example, 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.

Further, 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.

In the present invention, 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.

In the present invention, in the plasma treatment, 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). In 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. On the other hand, in RIE, 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. In the present invention, it is preferable to use DP as the treatment mode from the viewpoint of causing radicals to act evenly on the entire substrate to be treated and uniformly surface-modifying the surface.

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.

The plasma treatment may be a vacuum plasma treatment or an atmospheric pressure plasma treatment. In the case of 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.
When combining 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.

Preferably, in the plasma treatment in the present invention, 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. Examples of 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.

In plasma treatment containing nitrogen-containing gas or oxygen-containing gas as a gas type, functional groups that contribute to adhesion at the outermost surface portion (range of 5 to 10 nm in the depth direction from the outermost surface) are contained in the plasma treatment with the passage of time after the treatment. It is possible to improve long-term adhesiveness, probably because it is hard to turn over and is not easily affected by the desorption of carbon dioxide. The mechanism is not clear, but when considered at the atomic level, it is deeper than the outermost surface (5 to 10 nm) due to plasma treatment that shortens the treatment time while increasing the output as in the present invention. Perhaps because the effect can be exhibited near the outermost surface (10 to 100 nm), while avoiding fluctuations in the functional groups at the outermost surface, there are functional groups that contribute to adhesiveness near the outermost surface. Therefore, it is considered that the influence of the decrease in adhesiveness can be reduced.

Further, from the viewpoint of sufficiently modifying the surface of the thermoplastic liquid crystal polymer film, the gas type preferably contains N ₂ as a nitrogen-containing gas and optionally contains oxygen-containing gas as another gas type. preferable.

Examples of the oxygen-containing gas 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. When both a nitrogen atom and an oxygen atom are contained as in NO ₂ , the gas is a nitrogen-containing gas as long as the nitrogen atom is contained.

For example, the volume ratio of the nitrogen-containing gas to the oxygen-containing gas (nitrogen-containing gas / 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.

Other conditions in plasma processing may be adjusted as appropriate. For example, the distance between the irradiation head of the plasma processing device and the surface of the thermoplastic liquid crystal polymer film (for example, the distance between the head and the 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).

In the present invention, the surface treatment step may be performed continuously or in a batch manner.

By these surface treatments, in the X-ray photoelectron spectroscopic analysis result of the surface portion depth of 10 to 100 nm in the adhered region, [CO bond] with respect to the total peak area of each peak of C (1s) on the surface of the adhered region. ] Peak area ratio <CO> can exceed 12%. Preferably, <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.

For example, as the peak position of each bond state, [CH bond]: 285 eV, [CN bond]: 285.7 eV, [CO bond]: 286.6 eV, [C = O bond]: 287. It becomes .7 eV, [COO bond]: 289.4 eV, [OCOO bond]: 290 eV, [π-π ^* satellite peak]: 291.9 eV, and is separated into each peak by the waveform separation mechanism attached to the device. be able to. The peak of [CO bond] includes both peaks of ether bond and hydroxy group, and the peak of [COO bond] includes peaks of both ester bond and carboxy group. There is.

Regarding the peak separation method, it is preferable that 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.

Further, after the surface treatment step, the ratio <C = O> of the peak area of the [C = O bond] derived from the carbonyl group to the total peak area of each peak of C (1s) on the surface of the adhered region is high. Is preferable. For example, <C = O> may be 1.0 to 10.0%, preferably 1.5 to 9.0%, more preferably 3.0 to 8.0%, and even more preferably. It may be 3.5 to 6.5%.

Further, the surface roughness can be adjusted by these surface treatments. For example, the ten-point average roughness (Rz _jis ) of the surface of the thermoplastic liquid crystal polymer film may be 0.1 μm or more, preferably 0.1 μm or more. It may be 0.3 μm or more, more preferably 0.4 μm or more, still more preferably 0.5 or more. Further, it may be 3.0 μm or less, preferably 1.90 μm or less, more preferably 1.80 μm or less, and further preferably 1.70 μm or less.

(Colored layer forming process)
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.

(Colored layer by coating)
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. Further, if necessary, a primer layer may be provided as a base for the coating layer.

Examples of the resin component include synthetic resins, rubber derivatives (for example, rubber chloride, cyclized rubber, etc.), cellulose derivatives (acetyl cellulose, nitrocellulose, etc.), and the like. Examples of 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. Among these resins, acrylic resins, urethane resins, epoxy resins, polyester resins and the like are preferable.

Examples of the additive include a plasticizer (DBP, DOP, chlorinated paraffin, etc.), a desiccant (lead naphthenate, cobalt naphthenate, etc.), a precipitation inhibitor, and the like.

For example, 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. Can be used.
For example, 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.
In the NAD paint, 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.

Of these, 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. When the thermoplastic liquid crystal polymer film is in the form of a roll, a curtain coater or a roll coater is preferable from the viewpoint of unwinding the roll-shaped film to continuously form a colored layer.

Examples of the roll coater 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. In particular, a microgravure coater is preferable.

From the viewpoint of forming a thin coating film, 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. In addition, 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.

(Colored layer by dry plating)
Examples of the dry plating include vacuum deposition, ion plating, sputtering, and the like, but sputtering is preferable from the viewpoint of mass productivity.
In 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. In sputtering, 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. When light absorption by a sputtering material is used, 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.

(Colored layer by wet plating)
Examples of plating include electroplating, electroless plating, and hot dip plating. In 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. Examples of the metal used in electroplating include magnesium, aluminum, copper, zinc, nickel, gold, silver, tin, chromium, rhodium, and alloys of these metals.

Further, in electroless plating, 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. Examples of the metal used in electroless plating include magnesium, aluminum, copper, zinc, nickel, cobalt, gold, silver, tin, chromium, rhodium, and alloys of these metals.

Among these, 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. Further, 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.

The 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 μm, preferably 0.05 to 8 μm, and more preferably 0.1 to 7 μm. 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. Examples of 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. Preferably, 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. For example, 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.

The 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).

The sheet-shaped 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. For example, in the case of being formed, 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. Further, 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.
For example, when the thermoplastic liquid crystal polymer film shaped body is 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.
Further, 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 μm, preferably 20 to 200 μm, and more preferably 20 to 20. It may be 150 μm, more preferably 25 to 125 μm. Alternatively, in thin material applications, it may be in the range of 10 to 50 μm in particular.

From the viewpoint of followability between the colored layer and the film layer, the elongation of the thermoplastic liquid crystal polymer film molded product may be, for example, 2 to 60%. In an application for performing shaping processing such as an acoustic diaphragm, 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.
Further, 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.

Since the 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. -When used for the acoustic vibration plate of a speaker for an acoustic converter, good sound quality derived from a thermoplastic liquid crystal polymer film can be achieved.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the present Examples. In the following Examples and Comparative Examples, various physical properties were measured by the following methods.

<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.

<Molecular orientation (SOR)>
In the microwave molecular orientation measuring machine, a 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) was measured. Then, based on this measured value, the m value (referred to as the refractive index) was calculated by the following equation.
m = (Zo / Δz) X [1-νmax / νo]
Here, Zo is the device constant, Δz is the average thickness of the object, νmax is the frequency that gives the maximum microwave transmission intensity when the frequency of the microwave is changed, and νo is the average thickness of zero (that is, the object is). (When not) is the frequency that gives the maximum microwave transmission intensity.

Next, when the rotation angle of the object with respect to the vibration direction of the microwave is 0 °, that is, the vibration direction of the microwave and the direction in which the molecules of the object are most oriented, 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 °.

<XPS analysis>
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. The peak positions of each bond state are [CH bond]: 285 eV, [CO bond]: 286.6 eV, [CN bond]: 285.7 eV, and [C = O bond]: 287.7 eV. , [COO bond]: 289.4 eV, [OCOO bond]: 290 eV, [π-π ^* satellite peak]: 291.9 eV, and each peak is separated by the waveform separation mechanism attached to the apparatus.
X-ray source: monochromatic AlKα (1486.6 eV)
X-ray beam diameter: 100 μmφ (25W, 15kV)
Measurement range: 1000 μm (horizontal) x 300 μm (vertical)
Signal capture angle: 45 °
Charge neutralization condition: Neutralization electron gun, Ar ⁺ ion gun Vacuum degree: 1 × 10 ^-6 Pa or less

<Rz _jis (μm)>
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 μm 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.

<Adhesion state of colored layer (adhesion evaluation)>
With reference to JIS K 5600-5-6 adhesion (cross-cut method), the adhesion state between the colored layer and the thermoplastic liquid crystal polymer film was evaluated on a scale of 0 to 5.
0: The edges of the cut are perfectly smooth and there is no peeling in the eyes of any grid.
1: There is a small peeling of the colored layer at the intersection of the cuts, but the effect at the crosscuts is clearly no more than 5%.
2: The colored layer is peeled off along the edge of the cut and / or at the intersection. The cross-cut area is clearly affected by more than 5% but not more than 15%.
3: 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.

<Bending resistance>
The thermoplastic liquid crystal polymer film laminate was cut into strips having a width of 1 cm and used as test pieces. With reference to JIS P 8115 (2001), 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. Here, 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.

<Storage modulus / internal loss>
Using a dynamic elastic modulus measuring device (FT Leospectra DVE-V4 manufactured by Rheology Co., Ltd.), a rectangular thermoplastic liquid crystal polymer film laminate sample (4 mm × 10 mm) for measurement was used at a frequency of 10 Hz and a heating rate of 3. Measurement was performed at ° C./min (-100 ° C. to + 300 ° C.) and a strain of 0.025%, and at 20 ° C., the real part (E': stored elastic modulus) and the imaginary part (E ": of the obtained complex elastic modulus The loss elastic modulus) was obtained, and the internal loss (tan δ) was further obtained from the ratio (E "/ E').

(Example 1)
Thermoplastic liquid crystal polymer film (manufactured by Kuraray Co., Ltd., product name "Vexter FA", thickness 50 μm, 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. By taking (treatment time 1 second), 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%.

After that, using a gravure device, a coating liquid containing carbon black as a pigment (Lion Specialty Chemicals Co., Ltd., "Lion Paste W-370C", carbon black content 15.5%, viscosity 100 mPa · s or less ) Was applied to the surface-treated surface of the thermoplastic liquid crystal polymer film and dried for 10 minutes after the coating to obtain a 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 μm, 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.

Next, the thermoplastic liquid crystal polymer film laminate was shaped at 200 ° C. using a mold having a diameter of φ20 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 μm, 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. 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%.

Then, in the same manner as in Example 1, a coating liquid was applied to the thermoplastic liquid crystal polymer film to obtain a thermoplastic liquid crystal polymer film laminate on which a colored layer was formed. The thickness of the colored layer was 6.0 μm, 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.

Next, the 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 μm, SOR1.1). A liquid crystal polymer film laminate was obtained.
For the thermoplastic liquid crystal polymer film treated with plasma, 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 μm, 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.

(Example 4)
Thermoplastic liquid crystal polymer film (manufactured by Kuraray Co., Ltd., product name "Vexter CTF", thickness 50 μm, 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 μm, 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.

(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 μm, 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%.

(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 μm, 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 μm) is superposed on the thermoplastic liquid crystal polymer film, and the heating plate is 300 using a vacuum heat press device. 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%.

(Comparative Example 1)
A 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%.

Then, in the same manner as in Example 1, a coating liquid was applied to the thermoplastic liquid crystal polymer film to obtain a thermoplastic liquid crystal polymer film laminate on which a colored layer was formed. The thickness of the colored layer was 6.0 μm, 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.

Next, the 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.

(Comparative Example 2)
A 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%.

Then, in the same manner as in Example 3, sputtering was performed on the thermoplastic liquid crystal polymer film to obtain a thermoplastic liquid crystal polymer film laminate on which a colored layer was formed. The thickness of the colored layer was 0.5 μm, 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.

(Comparative Example 3)
A 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%.

Then, in the same manner as in Example 4, the 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 μm, 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.

In the 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.

As described above, a preferred embodiment of the present invention has been described, but those skilled in the art will easily assume various changes and modifications within a trivial range by looking at the present specification.
Therefore, such changes and amendments are construed as being within the scope of the invention as defined by the claims.

X ... Arc length Y ... String length Z ... Yataka

Claims

A thermoplastic liquid crystal polymer film molded product 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 ( A thermoplastic liquid crystal polymer film molded product in which the number of reciprocating bends until cracks occur exceeds 100 times in the folding resistance test according to 2001).
The thermoplastic liquid crystal polymer film molded product according to claim 1, wherein the adhesiveness evaluation of the colored layer in the cross-cut test according to JIS K 5600-5-6 is 3 or less.
The thermoplastic liquid crystal polymer film molded product according to claim 1 or 2, wherein 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.
In the thermoplastic liquid crystal polymer film molded body according to any one of claims 1 to 3, in the X-ray photoelectron spectroscopic analysis result of the surface portion depth 10 to 100 nm in the adhered region of the thermoplastic liquid crystal polymer film layer, the adhered region A thermoplastic liquid crystal polymer molded product in which the ratio <CO> of the peak area of [CO bond] to the total peak area of each peak of C (1s) on the surface of the surface exceeds 12%.
In the thermoplastic liquid crystal polymer film molded product according to any one of claims 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 μm. A thermoplastic liquid crystal polymer film molded article.
A thermoplastic liquid crystal polymer film molded body having a storage elastic modulus of 1 GPa or more and 20 GPa or less in the thermoplastic liquid crystal polymer film molded body according to any one of claims 1 to 5.
A thermoplastic liquid crystal polymer film molded product having an internal loss of 0.02 or more and 0.1 or less in the thermoplastic liquid crystal polymer film molded product according to any one of claims 1 to 6.
The thermoplastic liquid crystal polymer film molded body according to any one of claims 1 to 7, which has a dome-shaped shape.
An acoustic diaphragm composed of the thermoplastic liquid crystal polymer film molded product according to any one of claims 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. In the result of X-ray photoelectron spectroscopy at a depth of 10 to 100 nm, the ratio of the peak area of [CO bond] to the total peak area of each peak of C (1s) on the surface of the adhered region <CO>. In the surface treatment process to obtain a film to be treated with a value of more than 12%,
A method for producing a 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.
The method for producing a thermoplastic liquid crystal polymer film molded product, wherein the colored film to be treated is shaped in the production method according to claim 10.