Polyarylene sulfide film

Abstract

This invention provides a polyarylene sulfide film with excellent transparency and color tone. The polyarylene sulfide film of this invention is mainly composed of polyarylene sulfide (PAS) resin, and has a transmittance Ta of more than 75% and a b value of less than 5.0 at a wavelength of 550 nm.

Description

Technical Field

[0001] This invention relates to polyarylene sulfide films. Background Technology

[0002] In recent years, glass has been researched for circuit board materials that require transparency. However, glass substrates have disadvantages such as being easily broken, heavy, and difficult to make thin. In addition, there are no sufficiently flexible materials for parts that come into contact with automotive windshields and curved surfaces inside and outside the building.

[0003] Polyaryl sulfide resins possess excellent heat resistance, flame retardancy, rigidity, chemical resistance, electrical insulation, and low hygroscopicity, making them particularly suitable for use in electrical / electronic equipment, mechanical components, and automotive parts. In the electrical and electronic component field, due to the trend towards high speed and large capacity, materials with low transmission loss are needed. Polyaryl sulfide films, represented by polyphenylene sulfide (PPS) films, are being used in circuit materials due to their excellent transmission loss and low hygroscopicity. However, PPS films have low transparency and poor color tone. Therefore, for example, when used as transparent circuit substrates, the visual recognition is easily deteriorated due to the transparency and color tone of the PPS film. Improvements in transparency and color tone are desired.

[0004] To date, techniques for improving the color tone of PPS films have not been sufficiently researched. For example, as a material for improving transparency and slipperiness, a technique for subjecting PPS films to friction treatment has been disclosed (Patent Document 1). In addition, techniques for reducing the content of impurities byproducts of the polymerization reaction and improving volatile components and color tone have been disclosed (Patent Document 2).

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 2013-67748

[0008] Patent Document 2: Japanese Patent Application Publication No. 2009-138206 Summary of the Invention

[0009] The problem that the invention aims to solve

[0010] However, the technology described in Patent Document 1 is insufficient to improve the hue of PPS resin. Furthermore, the technology described in Patent Document 2 suffers from insufficient transparency when applied to membrane applications.

[0011] The objective of this invention is to solve the aforementioned problems, namely, to provide a polyarylether sulfide film with excellent transparency and color tone.

[0012] Problem-solving methods

[0013] To solve the above problems, the polyarylene sulfide membrane of the present invention has the following structure. That is, it is a polyarylene sulfide membrane with polyarylene sulfide (PAS) resin as the main component, and the transmittance Ta of the spectral light at a wavelength of 550 nm is 75% or more, and the b value is 5.0 or less.

[0014] Invention Effects

[0015] The polyarylene sulfide film of the present invention exhibits excellent transparency and color tone. Therefore, utilizing this property, it can be suitable for use as various components in automotive, battery, display, industrial packaging, design, and electrical / electronic materials where transparency is particularly required, such as transparent circuit boards, transparent antenna boards, high-frequency transparent circuit boards, and high-frequency transparent antenna boards. Detailed Implementation

[0016] The polyarylene sulfide film in this invention refers to a sheet-like film made by melting and molding a resin composition with polyarylene sulfide (hereinafter referred to as PAS) resin as the main component, preferably capable of biaxial stretching and heat treatment.

[0017] In this invention, using PAS-type resin as a main component means containing 50% or more, preferably 60% or more, and more preferably 70% or more of PAS-type resin. When the content of PAS-type resin is less than 50% by mass, it may sometimes impair the heat resistance, dimensional stability, and mechanical properties that are characteristics of PAS films.

[0018] The PAS-type resin used in this invention refers to a copolymer having -(Ar-S)- repeating units.

[0019] As Ar, units represented by the following formulas (A) to (K) can be listed.

[0020]

[0021] R1 and R2 are substituents selected from hydrogen, alkyl, alkoxy, and halogen groups. R1 and R2 can be the same or different.

[0022] As a repeating unit, a p-arylene sulfide unit is preferred in the above formula. Examples of such units include polyphenylene sulfide, polysulfone, polyethersulfone, polyphenylene sulfide sulfone, and polyphenylene sulfide ketone. A particularly preferred p-arylene sulfide unit is the p-phenylene sulfide unit, which can be exemplified from the perspectives of membrane properties and economy.

[0023] For the polyarylene sulfide resin used in this invention, it is preferable that its structure is represented by p-phenylene sulfide units, which account for 80 mol% or more and 99.9 mol% of all repeating units, as the main structural units. By setting the PAS resin used in this invention with the above composition, excellent heat resistance and chemical resistance can be exhibited.

[0024]

[0025] In addition, the PAS resin used in this invention can also be copolymerized with copolymer units ranging from 0.01 mol% to 20 mol% of the repeating units.

[0026] Preferred copolymer units can be listed below, with m-phenylene sulfide units being particularly preferred.

[0027]

[0028] Where X represents alkylene, CO, or SO2 units.

[0029]

[0030] Where R represents alkyl, nitro, phenyl, or alkoxy.

[0031] In the main structural unit of the PAS resin used in this invention, there are no particular restrictions on the copolymerization method with the copolymer unit, but random copolymers are preferred.

[0032] In the PAS resin composition constituting the PAS film of the present invention, various additives such as antioxidants, heat stabilizers, antistatic agents, and anti-blocking agents may be contained within a range that does not impair the effects of the present invention.

[0033] The PAS film of the present invention requires a light transmittance (Ta) of 75% or more at a wavelength of 550 nm. By setting Ta to 75% or more, a film with excellent transparency can be obtained. When Ta is below 75%, the film becomes more turbid, and when used as a protective substrate for transparent circuit boards or optical components, transparency may decrease. A light transmittance of 78% or more at a wavelength of 550 nm is more preferably preferred, and even more preferably 80% or more. To achieve a light transmittance of 550 nm within the above-mentioned range, methods for controlling the particles and other resins contained in the film for mobility (described later) and methods for removing impurities by cleaning the polymerized polymer or the obtained film with a solvent (described later) can be used.

[0034] The PAS film of the present invention preferably has a light transmittance (Tb) at a wavelength of 400 nm and a light transmittance (Tc) at a wavelength of 600 nm that satisfies the following formula (i).

[0035] Tc-Tb≤8.2% (i)

[0036] The aforementioned characteristics indicate that there are few impurities absorbing light in the wavelength range of 400 nm to 600 nm, resulting in a film with minimal coloration. Furthermore, when Tc-Tb exceeds 8.2%, coloration and hue reduction may sometimes occur during substrate material fabrication. More preferably, Tc-Tb ≤ 8.0%. To ensure that Tc-Tb falls within the aforementioned range, it can be controlled by reducing residual impurities in the PAS film using the cleaning process described later. In this invention, impurities refer to substances that absorb light in the 400-600 nm range, such as N-methyl-2-pyrrolidone (NMP) as a polymerization solvent, sodium hydrosulfide (NaSH) as a byproduct of polymerization, and 4-chlorobenzenethiolate. The light transmittance at wavelengths of 550 nm, 400 nm, and 600 nm can be evaluated using the method described later.

[0037] The PAS film of the present invention requires a b-value of 5.0 or less, which serves as a yellowness index. By setting the b-value to 5.0 or less, a film with excellent color tone can be obtained. When the b-value exceeds 5.0, visual recognition may sometimes deteriorate due to the color tone when manufacturing transparent circuit boards or protective substrates for optical components, thus causing defects to be missed. More preferably, it is 3.0 or less; even more preferably, it is 2.5 or less; and most preferably, it is 2.0 or less. There is no particular limitation on the lower limit, but from a productivity perspective, it is preferable to have a value of 0.0 or more. To obtain a polyarylene sulfide film with a b-value within the above range, for example, a method can be described later of cleaning the polymerized material or the resulting film with a solvent to remove impurities.

[0038] The PAS film of the present invention preferably has an L value of 85 or higher, which is a brightness indicator. By setting the L value to the above range, a film with excellent color tone can be obtained. If the L value is less than 85, when used as a protective substrate for transparent circuit boards or optical components, the brightness is sometimes low and the visual recognition is poor. More preferably, it is 90 or higher. In order to obtain a PAS film with an L value in the above range, it can be controlled by the particles and other resins contained in the film, as described later, and by the lamination structure of the film, as described later. The L value can be evaluated by the method described later.

[0039] The cleaning process in this invention refers to a step of immersing polymer powder, or a film obtained by melting and molding a polymer, followed by sheet forming and biaxial stretching heat treatment, in a solvent while heating for a predetermined period of time. In this invention, for polymer powder, a method of reacting an alkali metal sulfide such as sodium sulfide with a polyhalogenated aromatic compound such as p-dichlorobenzene in an organic amide solvent such as NMP can be cited as an example (Japanese Patent Publication No. 45-3368), but there are no particular limitations. Especially from the perspective of productivity and efficiency, a method of cleaning the polymer powder obtained by polymerization with a solvent is preferred.

[0040] For cleaning solvents used in the cleaning process, examples include acetone, toluene, and NMP. In particular, considering its use as a polymerization solvent to remove residual impurities, NMP is preferred.

[0041] Next, the present invention will be described using a cleaning method using NMP as an example, but the present invention should not be construed as being limited thereto.

[0042] In this invention, the temperature of the solvent used for cleaning is preferably 100°C or higher and 200°C or lower. By setting the cleaning temperature within this range, the temperature is above the glass transition temperature of the resin, allowing the molecular chains to begin moving. This effectively removes residual impurities, resulting in a film with excellent transparency and color tone. If the temperature is below 100°C, the molecular chains are restricted, sometimes leaving residual impurities, causing discoloration and a deteriorated color tone. Furthermore, above 200°C, the resin's mobility is too high, sometimes allowing extracted impurities to re-enter the resin, causing discoloration and a deteriorated color tone. More preferably, the solvent temperature used for cleaning in this invention is 125°C or higher and 175°C or lower.

[0043] In this invention, the solvent cleaning treatment time is preferably 5 hours or more. By setting the treatment time during cleaning within the above range, solvent degradation can be suppressed, and impurities can be effectively removed. When the time is less than 5 hours, impurities cannot be completely extracted, and sometimes discoloration and a deterioration in color tone may occur. There is no particular upper limit to the treatment time, but from a productivity perspective, it is generally below 30 hours. More preferably, the cleaning treatment time of this invention is 10 hours or more, and even more preferably 20 hours or more.

[0044] Furthermore, in this invention, it is preferable that the cleaning solvent contains microbubbles. Microbubbles in this invention refer to bubbles with a diameter of 100 μm or less. There are no particular limitations on the method for containing microbubbles in the cleaning solvent; for example, a known apparatus illustrated in Japanese Patent Application Publication No. 2007-21343 can be used. By containing microbubbles in the solvent, the wettability of the cleaning solvent to the polymer powder or film is improved, making it easier to penetrate, thus effectively achieving a cleaning effect. Examples of gases contained in the microbubbles include nitrogen (N2), oxygen (O2), and carbon dioxide (CO2), but any type can be used. Oxygen is particularly preferred because it can promote adsorption through interaction with the functional groups of the resin.

[0045] The PAS film of the present invention preferably has a surface roughness (Ra) of at least one surface with a surface roughness of 10 nm or more and 200 nm or less. SRa is a three-dimensional surface roughness parameter, referring to the average roughness of the center surface when the surface roughness curve is approximated by a sine curve, and is defined as the center surface average roughness. The center surface average roughness is a value obtained by extending the centerline average roughness (Ra) of the two-dimensional roughness parameter described in JIS-B0601-1994 to three dimensions, and is obtained by dividing the volume of the portion enclosed by the surface shape surface and the center surface by the measured area. When the center surface is designated as the XY plane, the longitudinal direction is designated as the Z-axis, and the measured surface shape curve is designated as f(x, y), it is defined by the following formula (ii). Here, Lx is the measurement length in the X direction, and Ly is the measurement length in the Y direction.

[0046]

[0047] By setting SRa within the above-described range, a membrane with excellent mobility can be obtained. If the surface roughness (Ra) of the membrane surface is less than 10 nm, the surface is smooth, thus increasing friction during transport and sometimes reducing mobility. If the surface roughness (SRa) of the membrane surface exceeds 200 nm, light reflection occurs due to the surface unevenness, sometimes reducing transparency. A surface roughness (SRa) of 10 nm or more and 100 nm or less is more preferred, and 20 nm or more and 50 nm or less is even more preferred. To achieve the surface roughness (SRa) of the membrane surface within the above-described range, it can be controlled by the particles or other resins contained in the membrane (described later), and also by the lamination structure of the membrane (described later). The surface roughness (SRa) of the membrane surface can be evaluated by the methods described later.

[0048] The PAS membrane of the present invention preferably has at least one surface depth volume (Vv) of 50 μm from a reference plane. 3 Above and 800μm 3 In this invention, depth volume (Vv) refers to the total volume of each depression from a reference plane in one field of view, measured using the VertScan system from Ryukyu Corporation, based on the measurement method described later. In this invention, the reference plane is the plane where the depth volume equals the protrusion volume, and is automatically set using VertScan analysis software. A smaller depth volume (Vv) indicates fewer depressions on the membrane surface.

[0049] By setting the depth volume (Vv) to below the aforementioned upper limit, a membrane with fewer surface depressions and excellent surface quality can be produced. By setting the depth volume (Vv) to above the aforementioned lower limit, excessive friction during transport can be suppressed, resulting in good mobility during processing. A depth volume (Vv) of 100 μm is more preferable. 3 Above and 600μm3 Hereinafter, 150 μm is further preferred. 3 Above and 400μm 3 The following describes how, to achieve the depth volume (Vv) of the membrane surface within the aforementioned range, it can be obtained using methods for controlling the particles and other resins contained in the membrane (described later) or methods for controlling the membrane's lamination structure (described later). The depth volume (Vv) of the membrane surface can be evaluated using methods described later.

[0050] The PAS membrane of the present invention preferably has at least one depth volume (Vv) of its surface from a reference plane (unit: μm). 3 The number of protrusions (n) (unit: number) and the number of protrusions satisfy the following equation (iii). In this invention, the number of protrusions refers to the number of protrusions in each field of view obtained by measuring with VertScan and using a threshold as the reference plane.

[0051] 0.01≤Vv / n≤3.0 Equation (iii).

[0052] Vv / n represents the depth volume relative to one protrusion. For example, when there are scratches on the membrane surface, Vv / n tends to increase in the case of large scratches and tends to decrease in the case of small scratches. By setting Vv / n above the aforementioned lower limit, excessive friction during transport can be suppressed, and good mobility during processing can be achieved. Furthermore, by setting Vv / n below the aforementioned upper limit, good surface quality can be achieved. Vv / n is more preferably 0.1 μm. 3 / or more and 1.5μm 3 / or less, further preferably 0.1μm 3 / or more and 0.5μm 3 / or less. To achieve Vv / n within the above range, it can be controlled by the particles contained in the film, other resins, or the lamination structure of the film described later. Vv / n can be evaluated by the methods described later.

[0053] The PAS film of the present invention preferably has a gloss level of at least one film surface of 140% or higher and less than 200%. By setting the gloss level within this range, surface irregularities that cause optical diffuse reflection of light are reduced, resulting in high surface smoothness. When a metal layer is formed using methods such as evaporation, sputtering, or plating for use in circuits, a circuit with excellent transmission characteristics and minimal surface irregularities can be obtained. Furthermore, when a metal layer is formed by evaporation or sputtering for use as a reflective film, surface irregularities in the metal layer are less likely to occur. By setting the gloss level to the upper limit or below, excessive surface irregularities and the resulting reduction in transmission characteristics and reflection efficiency due to surface irregularities in the metal layer transfer film can be suppressed. Conversely, by setting the gloss level to the lower limit or above, excessive surface smoothness, increased friction during transport, and reduced mobility during processing can be suppressed.

[0054] The PAS membrane of the present invention contains particles and / or dispersions, preferably with a void formation ratio of 10% or less. In the present invention, the void formation ratio refers to the ratio of particles and dispersions with voids forming around them in an FE-SEM image of the membrane cross-section, wherein the voids have a size of 10% or more of the cross-sectional area of ​​the particles and dispersions, and is a value measured using the method described later. By maintaining the void formation ratio within the above range, light diffusion and light reflection within the membrane can be suppressed, and the deterioration of membrane transparency can be prevented, resulting in good color tone. A void formation ratio is more preferably 5.0% or less, and even more preferably 3.0% or less. As a method for maintaining the void formation ratio within the above range, it can be controlled by the particles and other resins contained in the membrane (described later), or by the lamination structure of the membrane (described later).

[0055] To control the surface properties of the aforementioned film, there are methods for containing inert particles in the PAS film, or methods for surface control by containing other thermoplastic resins (X) different from PAS-type resins. Examples of inert particles include inorganic particles such as silica, alumina, calcium carbonate, barium carbonate, barium titanate, barium sulfate, calcium silicate, magnesium oxide, titanium oxide, and zinc oxide. When other thermoplastic resins are included, polyarylates, polyphenylene ether, polyetherimide, polysulfone, polyphenylene sulfone, and polyethersulfone can be used. Considering affinity with PAS-type resins, polysulfone, polyphenylene sulfone, and polyethersulfone are preferred. In this invention, considering transparency, color tone, and mobility, methods containing other thermoplastic resins are preferred.

[0056] The PAS film of the present invention preferably exhibits an infrared absorption spectrum at 1145 cm⁻¹ in an infrared spectrum obtained by Fourier transform infrared spectroscopy (FT-IR). -1 ~1160cm -1There is at least one absorption peak between them. The absorption peaks in the above range refer to the peaks originating from the stretching vibrations of the S=O bond. The affinity between PAS resin and thermoplastic resin (X) is improved, so it is finely and uniformly dispersed in PAS resin, thus achieving transparency. Furthermore, the surface roughness can be imparted by thermoplastic resin (X), enabling the production of films that also possess mobility. To achieve the absorption peaks in the above range, it can be achieved by containing a specified concentration of a resin with sulfonic acid groups, such as polysulfone, polyphenylsulfone, or polyethersulfone, in the thermoplastic resin (X).

[0057] The PAS film of the present invention specifies the content of PAS resin as W. I and the content W of thermoplastic resin (X) that is different from PAS type resins II When the total is specified as 100 parts by weight, the content W of thermoplastic resin (X) II Preferably, the content of thermoplastic resin (X) is 0.01 parts by weight or more and 5.0 parts by weight or less. To balance mobility and transparency, a more preferred content of thermoplastic resin (X) is W. II The content of thermoplastic resin (X) is 0.2 parts by weight or more and 1.0 parts by mass or less. By setting the content of thermoplastic resin (X) to the above upper limit, the deterioration of transparency due to the difference in refractive index of the resin can be suppressed. Furthermore, by setting the content of thermoplastic resin (X) W... II Setting the value above the aforementioned lower limit can suppress the deterioration of membrane mobility and quality.

[0058] The PAS film of the present invention preferably has two or more layers with PAS-type resin as the main component, and at least one outermost layer (layer A) is a layer with PAS-type resin as the main component and contains at least one other thermoplastic resin (X) different from PAS-type resin. By forming two or more layers, multiple properties such as transparency, color tone, runnability, and surface quality can be combined. As a laminated structure, when the layer with PAS-type resin as the main component is designated as layer B, multilayer structures such as A / B, A / B / A, A / B / A / B, and A / B / A / B / A can be listed.

[0059] The PAS film of the present invention has three or more layers with PAS-type resin as the main component. When the two outermost layers are layers (layer A) with PAS-type resin as the main component and containing at least one other thermoplastic resin (X) different from PAS-type resin, it is preferred because it possesses multiple controllable properties. Examples of laminated structures include multilayer structures such as A / B / A and A / B / A / B / A. In the present invention, considering transparency, color tone, surface quality, and mobility, a three-layer configuration of A / B / A is more preferred.

[0060] The PAS film of the present invention preferably has layer A exhibiting an infrared absorption spectrum at 1145 cm⁻¹ obtained by Fourier transform infrared spectroscopy (FT-IR). -1 ~1160cm -1 There is at least one absorption peak between them.

[0061] The PAS film of the present invention preferably contains, in the A layer, a thermoplastic resin (X) different from the PAS-type resin that is incompatible with the PAS-type resin, and the other thermoplastic resin (X) different from the PAS-type resin is included in the PAS-type resin in the form of a dispersion. In the present invention, the other thermoplastic resin (X) different from the PAS-type resin being incompatible with the PAS-type resin and being included in the PAS-type resin in the form of a dispersion means forming an island structure composed of the PAS-type resin and the other thermoplastic resin (X) different from the PAS-type resin, where the PAS-type resin constitutes the sea component and the other thermoplastic resin (X) different from the PAS-type resin constitutes the island component. By having a dispersion incompatible with the PAS-type resin in the A layer, where the PAS-type resin is the main component, the surface unevenness can be formed and controlled, resulting in a film with excellent transparency, mobility, and quality. Furthermore, the shape of the dispersion is not particularly limited. The morphology of the membrane can be confirmed by observing its cross-section using transmission electron microscopy (TEM) or scanning electron microscopy (SEM), and can include circular, elliptical, spindle-shaped, and irregular shapes.

[0062] The PAS film of the present invention preferably has an aspect ratio of 5.0 or more and 15.0 or less, as determined by the measurement method described later. In the present invention, aspect ratio refers to the value calculated from the ratio of the major axis to the minor axis in the dispersion diameter of the thermoplastic resin (X) present as the dispersed phase in the PAS-type resin. An aspect ratio within the above range indicates a stronger interaction between the PAS-type resin and the thermoplastic resin (X). Therefore, voids that would degrade transparency during the stretching process are not formed, thus improving transparency, which is preferred. By setting the aspect ratio of the dispersion to the lower limit or above, the formation of voids during the stretching process, which would degrade transparency, can be suppressed. On the other hand, by setting the aspect ratio of the dispersion to the upper limit or below, it is not necessary to set conditions with extremely high stretching ratios, thus suppressing productivity degradation due to breakage during the film-forming process. The lower limit of the aspect ratio is more preferably 7.0 or more. The upper limit of the aspect ratio is more preferably 12.0 or less, and even more preferably 10.0 or less. The aspect ratio can be controlled by the stretching ratio in the film-forming conditions described later.

[0063] In the PAS film of the present invention, the major diameter of the dispersion is preferably 200 to 2000 nm. Setting the major diameter of the dispersion within this range allows for surface unevenness, improving mobility and surface quality, and is therefore preferred. Setting the major diameter of the dispersion to the lower limit or above results in less surface unevenness and a smoother surface, thereby suppressing increased friction, reduced mobility, and decreased surface quality during transport. Conversely, setting the major diameter of the dispersion to the upper limit or below suppresses the decrease in transparency caused by light diffusion due to the dispersion. The major diameter of the dispersion is more preferably 400 to 1000 nm. The major diameter of the dispersion can be controlled by the stretching ratio in the film-forming conditions described later. In the present invention, the major diameter of the dispersion can be calculated using the method described later.

[0064] In the PAS film of the present invention, the thickness ratio of the A layer is preferably 0.1% or more and 10% or less relative to the overall film thickness. By setting the thickness ratio of the A layer within this range, a dense surface irregularity can be easily formed, and the amount of dispersion in the overall film can be reduced, thus improving transparency and surface quality. Therefore, this is preferred. By setting the thickness ratio of the A layer to the lower limit or above, the formed surface irregularity is reduced, the surface becomes smoother, and as a result, friction during handling increases, which can suppress mobility and reduce surface quality. Furthermore, by setting the thickness ratio of the A layer to the upper limit or below, a dense surface irregularity can be formed, thus resulting in excellent transparency. The thickness ratio of the A layer is more preferably 0.5% or more and 5.0% or less, and even more preferably 1.0% or more and 3.0% or less. The thickness ratio of the A layer can be controlled by the extrusion conditions during film formation. In the present invention, the thickness ratio of the A layer can be calculated by the method described later.

[0065] The thickness of the polyarylene sulfide film of the present invention is not particularly limited, but from the perspective of film-forming properties, it is preferably 10-150 μm, more preferably 20-125 μm, and even more preferably 25-100 μm.

[0066] The method for manufacturing the polyarylene sulfide membrane of the present invention will be described using a method for manufacturing a membrane when polyphenylene sulfide resin (hereinafter sometimes simply referred to as PPS resin) is used as the polyarylene sulfide resin, but the present invention is not limited to this example.

[0067] Sodium sulfide and p-dichlorobenzene are mixed and reacted under high temperature and pressure in an amide-based polar solvent such as N-methyl-2-pyrrolidone (NMP). Copolymer components such as m-dichlorobenzene and trihalomethanes may also be included if necessary. Caustic soda and alkali metal salts of carboxylic acids are added as polymerization degree regulators, and polymerization is carried out at 230–290°C. After polymerization, the polymer is cooled and made into an aqueous slurry. After filtration, wet granular polymer is obtained. An amide-based polar solvent is added to this granular polymer, and the mixture is stirred at 30–100°C for cleaning. It is then washed several times with deionized water at 30–80°C, and several times with aqueous solutions of metal salts such as calcium acetate, and finally dried to obtain polyphenylene sulfide polymer powder.

[0068] In this invention, when cleaning the polymer powder, the obtained polymer powder is subjected to a cleaning treatment in NMP solvent at a temperature of 100-200°C for 6-24 hours, and then washed several times with pure water at 30-80°C to obtain polymer powder (cleaned). The polymer powder is fed into an extruder with a vent, melt-extruded into a filament, cooled with water at 25°C, and then cut to make slices, forming PPS slices.

[0069] The polymer powder and / or cleaned polymer powder obtained above, which is a polyarylene sulfide resin, are mixed with inorganic particles and / or other thermoplastic resins (X) in any proportion to prepare a masterbatch. In this invention, the method for preparing the masterbatch is preferably a method of masterbatch preparation using a device that applies shear stress, such as a twin-screw extruder. In this case, it is preferable to mix the resin in the mixing section such that the resin temperature is within the range of the melting point of the PAS resin (I) +5°C to 80°C, more preferably within the range of the melting point of the PAS resin (I) +10°C to ~80°C, and even more preferably within the range of the melting point of the PAS resin (I) +15°C to 70°C. Furthermore, it is preferable to set the screw speed to a range of 100 rpm to 1500 rpm. By setting the resin temperature and screw speed to the preferred range, the dispersion diameter of the dispersed phase can be controlled.

[0070] In this invention, PPS chips that have been dried under reduced pressure at 180°C for 3 hours are first mixed with masterbatch in a specified ratio and fed to a single-screw extruder with a fully threaded section set at 300-350°C. After passing through a filter, the mixture is discharged from a T-die and rapidly cooled and solidified while being electrostatically charged on a cooling drum with a surface temperature of 20-70°C, resulting in an unstretched film that is essentially in an unoriented state. In the case of forming two or more laminated films, the two types of chips are fed to their respective melt extrusion units and heated to above the melting point of each resin. The raw materials, molten by heating, are laminated in a merging device located between the melt extrusion device and the die outlet in a molten state at any lamination ratio (e.g., 0.3:24.4:0.3, 0.3:24.7) to form two layers: a layer with PPS as the main component and a layer with PPS as the main component and containing at least one other thermoplastic resin different from PPS; or three layers: a layer with PPS as the main component and containing at least one other thermoplastic resin different from PPS, a layer with PPS as the main component, and a layer with PPS as the main component and containing at least one other thermoplastic resin different from PPS. The laminate is then extruded from the die outlet in a slit. The sheet is then pressed together and cooled and solidified on a cooling drum with a surface temperature of 20–70°C, with the PPS layer on one side of the cooling drum, to obtain a two-layer or three-layer laminate that is essentially in an unoriented state. By having the laminated structure described above,

[0071] Next, during biaxial stretching, the unstretched film obtained above is biaxially stretched using a successive biaxial stretching machine or a simultaneous biaxial stretching machine within a range above the glass transition temperature (Tg) and below the cold crystallization temperature (Tcc) of the polyarylether sulfide resin. Then, it undergoes one-stage or multi-stage heat treatment at a temperature ranging from 150 to 280°C to obtain a biaxially oriented film. As stretching methods, successive biaxial stretching (a stretching method that combines stretching in each direction, such as stretching along the length direction followed by stretching in the width direction), simultaneous biaxial stretching (a method that stretches in both the length and width directions simultaneously), or a combination of these methods can be used. Here, a successive biaxial stretching method in which stretching is performed first in the length direction, followed by stretching in the width direction, is illustrated.

[0072] The unstretched film is heated using a set of heated rollers and stretched along its length (MD direction) in one or more stages to a length of 2.0 to 4.5 times, more preferably 2.8 to 4.2 times (MD stretching). The stretching temperature is Tg to Tcc, preferably in the range of (Tg+5) to (Tcc-10)℃. Then, it is cooled using a set of cooling rollers at 20 to 50℃.

[0073] As a method for stretching the film in the width direction (TD direction) after MD stretching, a common method is to use a tenter frame. The two ends of the film are held by clamps and fed into the tenter frame for width stretching (TD stretching). The stretching temperature is preferably Tg to Tcc, more preferably in the range of (Tg+5) to (Tcc-10) °C. Considering the planarity of the film, the stretching ratio is 3.0 to 5.0 times, preferably 3.0 to 4.5 times.

[0074] Next, the stretched film is heat-fixed under tension (heat-fixing treatment). The heat-fixing treatment is carried out in one or more stages at a temperature in the range of 150 to 280°C, and the film is cooled to room temperature. If necessary, the film is cooled and wound up while being relaxed in the length and width directions to obtain a biaxially oriented polyarylether sulfide film.

[0075] In this invention, when cleaning the film, the obtained polyarylene sulfide film is cleaned in NMP solvent at a temperature of 100-200°C for 5-30 hours, and then cleaned with pure water at 30-80°C 3-5 times to obtain the polyarylene sulfide film of this invention.

[0076] The polyarylene sulfide film of the present invention has excellent transparency and color tone, and also has excellent surface mobility and quality. Therefore, it is suitable for use as automotive components, battery components, electrical / electronic materials, especially as various components requiring transparency and industrial packaging materials, such as underplate protection materials for flexible printed circuit boards, and capacitor materials requiring surface quality.

[0077] In addition, the polyarylene sulfide film of the present invention can be coated with various coating agents online or offline on both sides or one side for purposes such as improving weather resistance, adhesion and surface protection.

[0078] A conductive film is formed on the polyaryl sulfide film thus obtained to fabricate a circuit board. When used as a transparent circuit, the conductive film is preferably a transparent or semi-transparent conductor; for example, a conductor formed by laminating one or more layers of a metal film such as Ag film, a metal oxide film such as ITO (indium tin oxide) film, or a resin film containing conductive particles can be cited. For the method of forming the conductor, known methods such as sputtering and paste printing can be cited, but there are no particular limitations. The patterning of the circuit board can be carried out using known methods such as photolithography-based etching and screen printing. Furthermore, the circuit board is obtained by forming through-holes using methods such as drilling, laser, or fused penetration techniques, as needed.

[0079] Circuit boards using the polyarylene sulfide film of the present invention are useful as transparent antenna substrates due to their excellent transparency and color tone.

[0080] [Methods for determining characteristics]

[0081] (1) Light transmittance at wavelengths of 550nm, 400nm, and 600nm

[0082] The following apparatus is used to measure the light transmittance at each wavelength, and the following formula is used to calculate the light transmittance.

[0083] Apparatus: UV meter U-3410 (manufactured by Hitachi Measurement & Control Co., Ltd.)

[0084] Wavelength range: 300nm~800nm

[0085] Measurement speed: 120 nm / min

[0086] Measurement mode: via

[0087] Light transmittance (%) = (Tr1 / Tr0) × 100

[0088] Where Tr1 is the light intensity after passing through the sample, and Tr0 is the light intensity after passing through the same distance in air except through the sample.

[0089] (2) Yellowness (b value)

[0090] The tristimulus values ​​X, Y, and Z were measured using a spectrophotometer CM-3600d (KONICA-MINOLTA) via transmission method according to JIS-Z-8722 (2000). The luminance (L value) was then calculated, and the yellowness (b value) of the Hunter Lab color system was calculated using the following formula.

[0091] b value = 7.0 × (Y - 0.847 × Z) / Y1 / 2.

[0092] (3) Surface roughness (SRa)

[0093] The average centerline roughness (SRa) was determined using a Surfcorder ET30HK manufactured by Kosaka Research Institute under the following conditions.

[0094] Stimulus radius of curvature: 2μm

[0095] Cutoff value: 0.25mm

[0096] Measurement length: 0.5mm

[0097] Measurement interval: 5μm

[0098] Number of measurements: 40.

[0099] (4) Depth volume (Vv), number of protrusions (n)

[0100] Measurements were performed using a Ryukyu Corporation System VertScan 2.0R 5300GL-Lite-AC. The included analysis software was used to perform surface correction on the captured images using a fourth-order polynomial approximation. The threshold was set to 0 nm, and the depth volume (Vv) and the number of protrusions (n) were calculated. The measurement conditions are as follows. For both sides of the film, measurements were performed with n=100, and the average values ​​were used as the depth volume (Vv) and the number of protrusions (n) for each surface. For Examples 26 and 52, measurements were performed on the surface of layer A with n=100, and the average values ​​were used as the depth volume (Vv) and the number of protrusions (n) for each surface.

[0101] Manufacturer: Ryoka Sussex Co., Ltd.

[0102] Device Name: VertScan2.0R 5300GL-Lite-AC

[0103] Measurement conditions: SONY HR-57 1 / 2 inch CCD camera

[0104] Objective lens: 5x

[0105] Intermediate lens: 0.5x

[0106] Wavelength filter: 530nm white

[0107] Measurement mode: Wave

[0108] Measurement software: VS-Measure Version 5.5.1

[0109] Analysis software: VS-Viewer Version 5.5.1

[0110] Measurement area: 0.561mm × 0.561mm.

[0111] (5) Gloss

[0112] According to JIS K-7105 (1981), using a digital variable angle gloss meter UGV-5D manufactured by Suga Testing Machine Co., Ltd., five measurements were taken on the film surface under the conditions of an incident angle of 60° and a light reception angle of 60°. The average value of the measured data was taken as the gloss (%). Measurements were taken on two surfaces of the film, and the values ​​of the surfaces with high gloss were recorded in the table.

[0113] (6) Fourier transform infrared spectroscopy (FT-IR)

[0114] Using a Frontier FT-IR spectrometer manufactured by PerkinElmer Co., Ltd., employing a UATR IR unit, and with the dielectric crystal set to diamond / ZnSe, spectral intensity was measured via attenuated total internal reflection (ATR) method. The spectrometer resolution was set to 1 cm⁻¹. -1 The cumulative number of spectral measurements was set to 16. Spectral intensity was calculated as absorbance (arb.unit) at each wavelength. When measuring the spectrum of the film surface, the film surface was brought into close contact with the dielectric crystal for measurement. This contact was achieved by applying pressure using a clamp provided with the apparatus. The pressure was increased while observing the sample spectrum, and the measurement was performed when the spectral shape did not change due to pressure. Spectral intensity was calculated as absorbance (arb.unit) at each wavelength.

[0115] In this invention, in the case of a single-layer film, measurements are taken from any surface using the method described above, and the 1145 cm⁻¹ is determined from the obtained infrared absorption spectrum. -1 ~1160cm -1 Whether there are absorption peaks. In the case of laminated films, the above method is used to measure from the surface of the outermost layer formed by layer A to determine whether there are absorption peaks. When the laminated structure is unknown, the above method is used to measure from both surfaces to determine whether there are absorption peaks.

[0116] (7) Scanning electron microscopy (SEM) observation of the cut surface

[0117] After embedding the membrane in epoxy resin, the membrane cross-section was cut without flattening in the thickness direction using a slicing machine in a direction parallel to the membrane length and perpendicular to the membrane surface. Next, the cut membrane cross-section was fixed on the sample stage of a scanning electron microscope under conditions that prevented heat-induced material degradation, and subjected to cross-sectional ion polishing using an IM4000PLUS ion polishing apparatus manufactured by Hitachi High Tech Noroges Co., Ltd., followed by Pt evaporation. Then, the obtained membrane cross-section was observed using an electrolytic emission scanning electron microscope JSM-6700F manufactured by NEC Corporation under conditions of accelerating voltage 3.0 kV and working distance 8.0 mm to obtain images.

[0118] (7-1) Pore formation ratio of particles and dispersions

[0119] In calculating the void formation ratio of particles and dispersions, observations were conducted at a magnification of 30,000x, and the resulting images were analyzed. It should be noted that the observation positions were randomly determined based on the observed positions of particles and dispersions within the membrane cross-section; the vertical direction of the image was parallel to the membrane thickness direction, and the horizontal direction was parallel to the membrane surface direction.

[0120] For the obtained observation images, image analysis software (MacViewver 4.0, manufactured by MacViewer Inc.) was used to calculate the area (D1) of each particle, the area (D1') of the dispersion, and the areas (D2) and (D2') of the voids surrounding the particles and dispersions. If the area of ​​D2 is 10% or more of the area of ​​D1, it is determined that a particle has formed a void; if the area of ​​D2' is 10% or more of the area of ​​D1', it is determined that a dispersion has formed a void. During evaluation, measurements were taken at 100 points each for particles and dispersions, and the void formation ratio was calculated from the number of particles and dispersions that formed voids.

[0121] Void formation ratio = (number of void-forming particles + number of void-forming dispersions) / number of measurement points (200 points) × 100.

[0122] (7-2) The major axis and aspect ratio of the dispersion

[0123] The major and minor axes of the dispersions were observed at a magnification of 30,000, and the resulting images were analyzed. The observed images were imported into an image analyzer (Leica Application Suite LAS ver4.6, manufactured by Leica MICROSYSTEMS). Twenty dispersions were selected, and the average diameter of the circumcircle of each dispersed phase was taken as the size of the dispersion. Additionally, the major and minor axes of the dispersed phases were read, and the aspect ratios were calculated.

[0124] (7-3) Lamination thickness and lamination ratio of layer A

[0125] For the lamination thickness and lamination ratio of layer A, observation was conducted at a magnification of 5000x. Based on the analysis of the obtained images, the thickness of layer A at any 5 points was measured, and the average value was taken as the layer thickness of layer A.

[0126] In addition, the overall thickness of the membrane was observed at a magnification of 3000x, and images showing the entire thickness direction of the membrane were acquired. The overall thickness of the membrane was measured from the obtained images. If the overall thickness direction of the membrane could not be confirmed at the above magnification, images of several points along the thickness direction were taken, and the overall image was confirmed by image stitching. Five arbitrary locations were selected for the thickness measurement of the sample, and the average of the measurements of the five samples was taken as the membrane thickness of that sample.

[0127] (8) Transparency

[0128] On black drawing paper, white dots with diameters decreasing in 10μm increments from 200μm are printed. Various films are stacked on this black drawing paper, and the diameter of the white dot that can be visually identified from the top of the film is determined according to the following criteria. C is judged as poor transparency.

[0129] AA: Visually recognizable down to 10μm (excellent transparency)

[0130] A: Visually recognizable down to 50μm (good transparency)

[0131] B: Visually recognizable up to 100μm (normal transparency)

[0132] C: Even at 100μm, it cannot be visually distinguished (poor transparency).

[0133] (9) Hue

[0134] On white drawing paper, create color samples with varying RGB values ​​using dots of 0.5mm diameter. Print dots ranging from R (Red) 255, G (Green) 255, B (Blue) 0 to R 255, G 255, B 250, with B increasing in 10 increments to form color samples. Stack the films on this white drawing paper and determine whether the dots of a particular hue can be visually identified at a distance of 100cm from the top of the film, according to the following criteria. A hue of D is considered poor.

[0135] AA: Able to visually identify R255, G255, B240 and above (superior color tone).

[0136] A: Visually recognizable up to R255, G255, and B230 (good color tone).

[0137] B: Able to visually distinguish between R255, G255, and B200 (tone differences).

[0138] C: Able to visually distinguish up to R255, G255, and B180 (difficult to distinguish colors).

[0139] D: Visually recognizable up to R255, G255, B170 (hue is very difficult).

[0140] (10) Mobility

[0141] Using a Toyo Tester Industrial friction tester, according to ASTM-D1894 (1999), the initial upward resistance value was measured when the film was stacked with one surface in contact with its back surface and rubbed against each other along the MD direction. The maximum value was taken as the static friction coefficient μs. However, when the initial upward resistance was large and exceeded the upper limit of the measurement value (5.0), it was considered unmeasurable. The sample was set as a rectangle with a width of 80 mm and a length of 200 mm, and cut into 5 groups (10 sheets). Five measurements were performed, and the average value was calculated. Based on the calculated static friction coefficient, mobility was judged according to the following criteria. D was judged as poor mobility.

[0142] A: μs = below 0.50 (good mobility)

[0143] B: μs = greater than 0.50 and less than 0.60 (normal mobility)

[0144] C: μs = greater than 0.60 and less than 0.70 (slightly poor mobility)

[0145] D: μs = greater than 0.70 (poor mobility).

[0146] (11) Surface quality

[0147] For 1m 2 The film is illuminated by an LED light source, and scratches on the surface that can be identified by transmitted light are counted, based on each 1m... 2 The number of scratches is used to judge the surface quality according to the following criteria.

[0148] AA: Less than 50 pieces / m 2

[0149] A: 50 pieces / m 2 More than or less than 100 per m 2

[0150] B: 100 pieces / m 2 More than or less than 150 per m 2

[0151] C: 150 pieces / m 2 More than or less than 200 per m 2

[0152] D: 200 pieces / m 2 above.

[0153] Example

[0154] (Refer to Example 1) Method for manufacturing PPS resin (granules)

[0155] In a 1-liter high-pressure vessel equipped with an engineering stirrer, 1.00 mol of 47% sodium hydrosulfide, 1.03 mol of 96% sodium hydroxide, 1.65 mol of N-methyl-2-pyrrolidone (NMP), 0.45 mol of sodium acetate, and 150 g of deionized water were added. While stirring at 240 rpm, nitrogen gas was introduced under normal pressure, and the mixture was slowly heated to 225°C over approximately 3 hours. After distilling off 211 g of water and 4 g of NMP, the reaction vessel was cooled to 160°C.

[0156] Next, 1.00 mol of p-dichlorobenzene (p-DCB) and 1.31 mol of NMP were added. The reaction vessel was then sealed under nitrogen. While stirring at 240 rpm, the temperature was increased from 200°C to 235°C at a rate of 0.6°C / min, and the reaction was continued at 235°C for 95 minutes. Then, the temperature was increased to 270°C at a rate of 0.8°C / min and held for 100 minutes. After reaching 270°C, 1 mol of water was injected into the system over 15 minutes. After 100 minutes at 270°C, the temperature was cooled to 200°C at a rate of 1.0°C / min, and then rapidly cooled to near room temperature. The contents were removed, diluted with 0.4 L of NMP, stirred at 85°C for 30 minutes, and then the solvent and solids were separated by filtration through an 80-mesh sieve. In the post-treatment step, 0.5 L of NMP was added to the obtained solids, and the mixture was stirred at 85°C for 30 minutes and then filtered. The obtained solid was washed three times with 0.9 liters of warm water and then filtered. Next, 1 liter of warm water was added to the obtained particles, and the particles were washed twice and then filtered to obtain polymer particles. These particles were then dried with hot air at 80°C and then dried under reduced pressure at 120°C to obtain polyphenylene sulfide (PPS) resin particles (PPS particles) with a melting point of 280°C and a mass-average molecular weight of 70,000.

[0157] (Refer to Example 2) Method for manufacturing PPS granules

[0158] The PPS resin (granules) prepared in Reference Example 1 was fed into a co-rotating twin-shaft compounding extruder with a vent that was heated to 320°C. The resin was melt-extruded and discharged in the form of a filament. After being cooled with water at 25°C, the granules were immediately cut to produce PPS granules 1.

[0159] (Refer to Example 3) Preparation of PPS granules and thermoplastic resin masterbatch (MB1)

[0160] A co-rotating, vented twin-screw compounding extruder equipped with a kneading paddle mixing section was heated to 320°C. PPS granules obtained in Reference Example 1 were fed into the feed inlet to reach 90 parts by weight, followed by polyethersulfone (PESU: Solbayidan Polimars Co., Ltd., Velade 3600) to reach 10 parts by weight. After melting and mixing at a screw speed of 200 rpm, the mixture was discharged in a filament form, cooled with water at 25°C, and immediately cut to produce a masterbatch (MB1) containing 10 parts by weight of PESU.

[0161] (Refer to Example 4) Production of PPS granules and granule masterbatch (MB2)

[0162] A mixture of 90% by mass of PPS resin (granules) and 10% by mass of calcium carbonate (average particle size 1.0 μm) as inactive particles prepared in Reference Example 1 was melt-blended. Otherwise, the same operation as in Reference Example 3 was performed to prepare a granular masterbatch (MB2) with a particle content of 10% by mass.

[0163] (Refer to Example 5) Preparation of PPS granules and thermoplastic resin masterbatch (MB3)

[0164] A co-rotating, exhaust-type twin-shaft compounding extruder equipped with a kneading paddle mixing section was heated to 320°C. PPS granules obtained in Reference Example 1 were fed into the feed inlet to reach 90 parts by mass, and polyphenylene sulfone (PPSU: Solbayidan Polimars Co., Ltd., Laser R5600-NT) was fed into the extruder to reach 10 parts by mass. After melting and mixing at a screw speed of 200 rpm, the mixture was discharged in a filament form, cooled with water at 25°C, and immediately cut to produce a masterbatch (MB3) containing 10 parts by mass of PPSU.

[0165] Examples 1-12

[0166] The PPS resin (granules) prepared in Reference Example 1 were cleaned using NMP as a solvent under the conditions shown in Table 1-1. The granules were washed three times with pure water at 40°C to obtain cleaned PPS granules. These cleaned PPS granules were then fed into a co-rotating twin-screw extruder with a vent, heated to 320°C, and melt-extruded into a filament. After cooling with water at 25°C, the filaments were immediately cut to produce cleaned PPS granules.

[0167] PPS granules (washed) and PPS masterbatch are uniformly mixed at the ratios in Table 1, dried under reduced pressure at 180°C for 3 hours, and then fed to a single-screw extruder in the melt section which is heated to 315°C.

[0168] Next, the molten polymer was passed through a fiber-sintered stainless steel metal filter (20 μm opening) and extruded from a T-die set at 310°C. While applying electrostatic charge to a casting drum with a surface temperature of 25°C, it was subjected to sealed cooling and solidification to obtain an unstretched film with a thickness of 350 μm. Then, using a longitudinal stretching machine consisting of multiple heated rollers, the unstretched film was stretched at a stretching temperature of 105°C at a ratio of 3.5 times along its length, utilizing the difference in circumferential speed of the rollers. The film was then supported at both ends with clamps and fed into a tenter frame, where it was stretched at a stretching temperature of 100°C at a ratio of 3.5 times along its width. Following heat treatment at 280°C, a 2% relaxation treatment was performed. After cooling to room temperature, the film edges were removed to obtain a polyarylethermon sulfide film with a thickness of 25 μm. The physical properties and characteristics of the obtained film are shown in Table 1-1.

[0169] Example 13

[0170] No cleaning treatment was performed on the PPS resin (particles). Otherwise, the same operation as in Example 1 was performed to obtain a polyarylether sulfide film.

[0171] Example 14

[0172] The PPS resin (granules) was not cleaned; only PPS granules 1 were supplied. Otherwise, the same operation as in Example 1 was performed to obtain a polyarylether sulfide film.

[0173] Comparative Example 1

[0174] PPS granules 1 were mixed with the masterbatch according to the composition and ratio in Table 1-1, and the washing process was carried out under the conditions shown in Table 1-1. Otherwise, the same operation as in Example 1 was performed to obtain a polyarylether sulfide film.

[0175] Comparative Example 2

[0176] Without cleaning the PPS resin (granules), only PPS granules 1 were used. The masterbatch and PPS granules 1 were mixed according to the composition and ratio in Table 1-1. Otherwise, the same operation as in Example 1 was performed to obtain a polyarylether sulfide film.

[0177] Examples 15-25

[0178] The PPS resin (granules) prepared in Reference Example 1 were cleaned using NMP as a solvent under the conditions shown in Table 1-2. The granules were washed three times with pure water at 40°C to obtain cleaned PPS granules. These cleaned PPS granules were then fed into a co-rotating twin-screw extruder with a vent, heated to 320°C, and melt-extruded into filaments. After cooling with water at 25°C, the filaments were immediately cut to produce cleaned PPS granules.

[0179] The raw materials for layers A and B were prepared by preparing PPS granules (washed) and PPS masterbatch with the compositions and ratios shown in Table 1-2. Each raw material was vacuum dried at 180°C for 3 hours and then fed to two single-screw extruders heated to 315°C. While molten, the extruder used a laminating device located above the die to introduce the material in three layers (laminated structure A / B / A) according to the lamination ratios shown in Table 1-2. The material was then discharged from a T-die and rapidly cooled and solidified while applying electrostatic charge to a casting drum with a surface temperature of 25°C, resulting in an unstretched film with a thickness of 350 μm. Next, using a longitudinal stretching machine consisting of multiple heated rollers, the unstretched film was stretched at a stretching temperature of 105°C along its length at a ratio of 3.5 times, utilizing the difference in circumferential speed of the rollers. Then, the film was supported at both ends by clamps and fed into a tenter frame, where it was stretched at a stretching temperature of 100°C along its width at a ratio of 3.5 times. Next, after heat treatment at 280°C, a 2% relaxation treatment was performed. After cooling to room temperature, the membrane edges were removed to obtain a polyarylether sulfide membrane with a thickness of 25 μm. The physical properties and characteristics of the obtained membrane are shown in Table 1-1.

[0180] Example 26

[0181] The lamination structure of the lamination device was set to A / B2 layers, and the lamination ratio was set as shown in Table 1-2. Otherwise, the polyarylether sulfide film was obtained in the same manner as in Example 16.

[0182] Example 27

[0183] The PPS resin (granules) was used as PPS granules 1 without cleaning, and the same operation as in Example 16 was performed to obtain a polyarylether sulfide film.

[0184] Comparative Example 3

[0185] The raw materials were supplied according to the composition and ratio shown in Table 1-2, and the same operation as in Example 15 was performed to obtain a polyarylether sulfide film.

[0186] Examples 28-39

[0187] PPS granules 1 and PPS masterbatch were uniformly mixed according to the ratio in Table 2-1. After drying under reduced pressure at 180°C for 3 hours, the mixture was fed to a single-screw extruder heated to 315°C in the melt section. The molten polymer was then passed through a fiber-bonded stainless steel metal filter (20μm opening) and melt-extruded from a T-die set to 310°C. Simultaneously, electrostatic charge was applied to a casting drum with a surface temperature of 25°C, and the mixture was subjected to tight cooling and solidification to obtain an unstretched film with a thickness of 350μm. Next, using a longitudinal stretching machine consisting of multiple heated rollers, the unstretched film was stretched at a stretching temperature of 105°C along its length at a ratio of 3.5 times, utilizing the difference in circumferential speed of the rollers. Then, the film was supported at both ends with clamps and fed into a tenter frame, where it was stretched at a stretching temperature of 100°C along its width at a ratio of 3.5 times. Next, after heat treatment at 280°C, a 2% relaxation treatment was performed. After cooling to room temperature, the membrane edge was removed to obtain a polyarylether sulfide membrane with a thickness of 25 μm.

[0188] The obtained membrane was cleaned using NMP as the cleaning solvent under the conditions shown in Table 2-1, and washed five times with pure water at 40°C to obtain the cleaned polyarylether sulfide membrane. The physical properties and characteristics of the obtained membrane are shown in Table 2-1.

[0189] [Comparative Example 4]

[0190] PPS granules 1 were mixed with the masterbatch according to the composition and ratio in Table 2-1, and the washing process was carried out under the conditions shown in Table 2-1. Otherwise, the same operation as in Example 28 was performed to obtain a polyarylether sulfide film.

[0191] (Examples 40-50)

[0192] The raw materials for layers A and B were prepared by making PPS granules 1 and PPS masterbatch with the compositions and ratios shown in Table 2-2. Each raw material was vacuum dried at 180°C for 3 hours and then fed to two single-screw extruders heated to 315°C. While molten, the materials were introduced in three layers (laminated structure A / B / A) according to the lamination ratios shown in Table 2-2 using a lamination device located above the die. The extruded material was then discharged from a T-die. While applying electrostatic charge to a casting drum with a surface temperature of 25°C, the film was rapidly cooled and solidified to obtain an unstretched film with a thickness of 350 μm. Next, using a longitudinal stretching machine consisting of multiple heated rollers, the unstretched film was stretched at a stretching temperature of 105°C along its length at a ratio of 3.5 times, utilizing the difference in circumferential speed of the rollers. Then, the film was supported at both ends by clamps and fed into a tenter frame, where it was stretched at a stretching temperature of 100°C along its width at a ratio of 3.5 times. Next, after heat treatment at 280°C, a 2% relaxation treatment was performed. After cooling to room temperature, the membrane edge was removed to obtain a polyarylether sulfide membrane with a thickness of 25 μm.

[0193] The obtained membrane was cleaned using NMP as the cleaning solvent under the conditions shown in Table 2-2, and washed five times with pure water at 40°C to obtain the cleaned polyarylether sulfide membrane. The physical properties and characteristics of the obtained membrane are shown in Table 2-2.

[0194] (Example 51)

[0195] The lamination structure of the lamination device is set to A / B2 layers, and the lamination ratio is set as shown in Table 2-2. Otherwise, the same operation as in Example 41 is performed to obtain a polyarylether sulfide film.

[0196] (Comparative Example 5)

[0197] The raw materials were supplied according to the composition and ratio shown in Table 2-2, and the same operation as in Example 41 was performed to obtain a polyarylether sulfide film.

[0198]

[0199]

[0200]

[0201]

[0202] Industrial availability

[0203] Because of the excellent transparency and color of the polyarylene sulfide film of the present invention, it is suitable for use as a transparent circuit substrate and a transparent antenna substrate.

Claims

1. A polyarylene sulfide (PAS) membrane, comprising a polyarylene sulfide (PAS) resin as the main component, having a transmittance (Ta) of 75% or higher at a wavelength of 550 nm and a b-value of 3.0 or lower. At least one membrane surface has a surface roughness (Ra) of 10 nm or more and 200 nm or less. The transmittance Tb of the polyarylene sulfide film at a wavelength of 400 nm and the transmittance Tc of the polyarylene sulfide film at a wavelength of 600 nm satisfy the following equation (i): Tc-Tb≤8.2% Equation (i), The depth volume (Vv) and the number of protrusions (n) of at least one membrane surface from the reference plane satisfy the following equation (iii): 0.01≤Vv / n≤3.0 Equation (iii).

2. The polyarylene sulfide membrane according to claim 1, wherein the surface roughness (Ra) of at least one membrane surface is 17 nm or more and 115 nm or less.

3. The polyarylene sulfide membrane according to claim 1 or 2, wherein the depth volume (Vv) of at least one membrane surface from the reference plane is 50 μm. 3 Above and 800μm 3 the following.

4. The polyarylene sulfide membrane according to claim 3, wherein at least one membrane surface has a depth volume (Vv) of 330 μm from a reference plane. 3 Above and 750μm 3 the following.

5. The polyarylene sulfide membrane according to claim 1, wherein the depth volume (Vv) and the number of protrusions (n) of at least one membrane surface from the reference plane satisfy the following formula (iv): 0.10≤Vv / n≤2.8 Equation (iv).

6. The polyarylene sulfide film according to claim 1 or 2, wherein the gloss of at least one film surface is greater than 140% and less than 200%.

7. The polyarylene sulfide membrane according to claim 1 or 2, comprising particles and / or dispersions, wherein the void formation ratio of the particles and dispersions is less than 10%.

8. The polyarylene sulfide membrane according to claim 7, comprising particles and / or dispersions, wherein the void formation ratio of the particles and dispersions is less than 1%.

9. The polyarylene sulfide membrane according to claim 1 or 2, in the infrared absorption spectrum obtained by Fourier transform infrared spectroscopy (FT-IR), at 1145 cm⁻¹ -1 ~1160cm -1 There is at least one absorption peak between them.

10. The polyarylene sulfide film according to claim 1 or 2, having two or more layers with polyarylene sulfide resin as the main component, and at least one outermost layer being a layer A, which is a layer with polyarylene sulfide resin as the main component and containing at least one other thermoplastic resin (X) different from polyarylene sulfide resin.

11. The polyarylene sulfide film according to claim 1 or 2, having three or more layers with polyarylene sulfide resin as the main component, and the two outermost layers being layers with polyarylene sulfide resin as the main component and containing one or more other thermoplastic resins (X) different from polyarylene sulfide resin, i.e., layer A.

12. The polyarylene sulfide film according to claim 10, wherein layer A shows an infrared absorption spectrum at 1145 cm⁻¹ obtained using Fourier transform infrared spectroscopy (FT-IR). -1 ~1160cm -1 There is at least one absorption peak between them.

13. The polyarylene sulfide film according to claim 10, wherein other thermoplastic resins (X) different from the polyarylene sulfide resin are incompatible with the polyarylene sulfide resin, and other thermoplastic resins (X) different from the polyarylene sulfide resin are contained in the polyarylene sulfide resin in the form of a dispersion.

14. The polyarylene sulfide membrane according to claim 13, wherein the aspect ratio of the dispersion is 5.0 or more and 15.0 or less, and the major axis of the dispersion is 200 to 2000 nm.

15. The polyarylene sulfide membrane according to claim 10, wherein the thickness ratio of layer A to the overall membrane thickness is 0.1% or more and 10% or less.

16. The polyarylene sulfide film according to claim 1 or 2, used as a transparent circuit substrate.

17. The polyarylene sulfide film according to claim 1 or 2, used in a transparent antenna substrate.

Images