Polyphenylene sulfide resin composition for waveguide antenna, molded article for waveguide antenna, and waveguide antenna

Abstract

The present application provides a molded product for a waveguide antenna, which is excellent in dimensional stability and low warping, and has excellent coating processability and adhesion to a metal thin film, and a waveguide antenna including the molded product, as a subject, and in order to solve the subject, a polyphenylene sulfide resin composition for a waveguide antenna is produced, which contains, relative to 100 parts by weight of a polyphenylene sulfide resin, 60 to 200 parts by weight of a fibrous filler and 0.1 to 120 parts by weight of a non-fibrous filler, characterized in that a molded product obtained by molding under certain test conditions has a linear expansion coefficient in the MD direction (LEC(MD)) and a linear expansion coefficient in the TD direction (LEC(TD)) of 25 ppm / K or less, respectively, and a ratio of LEC(MD) to LEC(TD) (LEC(MD) / LEC(TD)) of 0.8 to 1.1.

Description

Technical Field

[0001] This invention relates to waveguide antennas for communication used in radar systems for base stations and automobiles. Background Technology

[0002] In recent years, there has been a growing expectation for improved radar capabilities to meet the demands of higher speeds and larger capacities in wireless communication, particularly for applications like Beyond 5G (6G), ADAS (Advanced Driver Assistance Systems), and AD (Autonomous Driving). Microstrip antennas have been used in radar antennas to date. However, to meet these increased radar capabilities, antennas require more complex shapes, leading to the development of waveguide antennas capable of three-dimensional wiring designs. A microstrip antenna is a planar antenna consisting of a dielectric substrate, radiating elements printed on its surface, and a grounding conductor printed on its back. The radiating elements are wired two-dimensionally on the substrate, allowing for the formation of various waveguides. A waveguide antenna, on the other hand, is an antenna comprising a waveguide extending along its axis and multiple radiating slots spaced at predetermined intervals along the waveguide's axis. The waveguide is formed by combining first and second waveguide forming members with end-shaped cross-sections in each section extending along the waveguide's direction. By stacking the waveguide forming members, three-dimensional wiring is possible, enabling high performance. This waveguide antenna allows for complex designs. However, to transmit radio waves stably, the waveguide width must be dimensionally stable and conductive under thermal variations, making metal the mainstream material. However, metal waveguide antennas suffer from issues such as heavy weight and poor mass production capabilities, thus necessitating the use of a material with a thin metal film coated on the surface of resin-molded waveguide antennas as an alternative.

[0003] Patent Document 1 describes a waveguide antenna with excellent radio wave radiation efficiency. It is a molded product obtained by coating an injection-molded product with a metal thin film of copper, silver, gold or the like, which has excellent conductivity, onto a resin composition based on thermoplastic resins such as liquid crystal polymer (LCP), polyphenylene sulfide (PPS) and polyacetal (POM) and filled with fillers such as glass fiber (GF) and carbon fiber (CF).

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 2017-85311 Summary of the Invention

[0007] The problem that the invention aims to solve

[0008] In waveguide antennas made of resin molded articles, since radio waves pass through while interfering with the waveguide, dimensional stability of the waveguide width to temperature changes and low warpage (small warpage of the molded article) are required. Furthermore, conductivity is needed for transmitting radio waves, and the resin, as an insulator, requires processability when a metal film is applied and good adhesion to the metal film. Resin compositions with improved properties are required for waveguide antenna applications. However, while Patent Document 1 describes that injection-molded articles of resin compositions based on thermoplastic resins such as liquid crystal polymers (LCP), polyphenylene sulfide (PPS), and polyacetal (POM) with added fillers such as glass fiber (GF) and carbon fiber (CF) are preferred as waveguide antennas, it does not describe means to improve the dimensional stability to temperature changes, low warpage, processability when applying the metal film, and good adhesion to the metal film required for waveguide antennas formed from resin molded articles.

[0009] Therefore, the present invention aims to provide a waveguide antenna molded article with excellent dimensional stability and low warpage to temperature changes, excellent processability when applied to a metal thin film, and excellent adhesion to the metal thin film, as well as a waveguide antenna comprising the molded article.

[0010] Methods for solving problems

[0011] To solve the aforementioned problems, the inventors conducted repeated and in-depth research, and as a result, discovered that a PPS resin composition containing PPS resin, fibrous filler material, and non-fibrous filler material meets the specified characteristics, thereby exhibiting good processability and adhesion to metal films when applied, as well as excellent dimensional stability and low warpage to temperature changes. It was found that molded articles formed from such resin compositions are suitable for waveguide antenna components for communication applications. In other words, the present invention has the following structure.

[0012] [1] A polyphenylene sulfide resin composition for waveguide antennas is a polyphenylene sulfide resin composition for waveguide antennas containing polyphenylene sulfide (component A), fibrous filler material (component B), and non-fibrous filler material (component C), characterized in that, relative to 100 parts by weight of component A, the content of component B is 60 to 200 parts by weight, the content of component C is 0.1 to 120 parts by weight, and in the molded article obtained by molding under the following conditions, the coefficient of linear expansion in the MD direction (LEC(MD)) and the coefficient of linear expansion in the TD direction (LEC(TD)) are both 25 ppm / K or less, and the ratio of LEC(MD) to LEC(TD) (LEC(MD) / LEC(TD)) is 0.8 to 1.1.

[0013] Molding conditions for molded parts

[0014] Prepare a mold having a rectangular space of 80mm × 80mm × 3mm, and having a slit-shaped discharge hole (slit width 1.5mm, slit length 78mm) corresponding to one side of an 80mm square of the rectangular space, and an injection hole on the perpendicular line of the side passing through the midpoint of that side (see reference). Figure 1 The resin composition was discharged and injection molded using an NEX-1000-9E injection molding machine manufactured by Nissei Resin Kogyo Co., Ltd., under the conditions of barrel temperature: 320°C, injection pressure: molding lower limit pressure + 12.8MPa, injection time: 15 seconds, and cooling time: 15 seconds.

[0015] Let MD be the direction from the side with the slit to its opposite side, and TD be the direction orthogonal to MD. Cut a strip of test piece with a length of 10 mm, a width of 5 mm, and a thickness of 3 mm, with the centroid of the test piece coinciding with the centroid of the aforementioned square (see reference). Figure 2 At this point, a test piece with its long side aligned with MD is used as a test piece for LEC(MD) measurement, and a test piece with its long side aligned with TD is used as a test piece for LEC(TD) measurement.

[0016] [2] The polyphenylene sulfide resin composition for waveguide antennas according to [1] above is characterized in that all or part of component (B) is a fibrous filler with an irregular cross section.

[0017] [3] The polyphenylene sulfide resin composition for waveguide antennas according to [1] or [2] above is characterized in that, relative to 100 parts by weight of component (A), it further contains 0.1 to 12 parts by weight of elastomer.

[0018] [4] A molded article for a waveguide antenna, which is formed by molding the waveguide antenna of any one of [1] to [3] above with a polyphenylene sulfide resin composition.

[0019] [5] According to the waveguide antenna molded article described in [4] above, the coefficient of thermal expansion (coefficient of thermal expansion A) in the direction parallel to the surface of the molded article and oriented to component (B), and the coefficient of thermal expansion (coefficient of thermal expansion B) in the direction parallel to the surface of the molded article and perpendicular to the direction oriented to component (B) are both 25 ppm / K or less, and the value obtained by dividing the coefficient of thermal expansion A by the coefficient of thermal expansion B is 0.8 to 1.1.

[0020] [6] A molded article for a waveguide antenna, wherein at least a portion of the surface of the molded article for a waveguide antenna described in [4] or [5] above is formed with a metal thin film, and the arithmetic mean roughness of the portion of the surface of the molded article in which the metal thin film is formed is 10 μm or less.

[0021] [7] According to the waveguide antenna molded article described in [6] above, the metal thin film is formed from at least one selected from silver, copper and aluminum.

[0022] [8] A waveguide antenna comprising a molded article for a waveguide antenna as described in any one of [4] to [7] above.

[0023] The effects of the invention

[0024] According to the present invention, as an alternative to conventional metal waveguide antennas, molded waveguide antenna articles with excellent dimensional stability and low warpage under thermal changes can be provided. Furthermore, resin compositions for waveguide antennas with excellent coating processability and adhesion to metal thin films can be provided. Attached Figure Description

[0025] Figure 1 The shape of the injection-molded article used for measuring the coefficient of linear expansion is shown in (a) as a plan view and (b) as a side view.

[0026] Figure 2 The diagrams showing the cutting positions of the test pieces used for measuring the coefficient of linear expansion are as follows: (a) shows the cutting position of the test piece used for measuring LEC (MD), and (b) shows the cutting position of the test piece used for measuring LEC (TD).

[0027] Figure 3 This is a diagram illustrating the sampling location of the test piece used in the peel strength test. Detailed Implementation

[0028] This invention relates to a polyphenylene sulfide resin composition containing polyphenylene sulfide resin (hereinafter, sometimes referred to as "component (A)"), a fibrous filler material (hereinafter, sometimes referred to as "component (B)"), and a non-fibrous filler material (hereinafter, sometimes referred to as "component (C)"). Under the conditions described later, the polyphenylene sulfide resin composition exhibits a coefficient of linear expansion in the MD direction (LEC(MD)) and a coefficient of linear expansion in the TD direction (LEC(TD)) of 25 ppm / K or less, and a LEC(MD) to LEC(TD) ratio (LEC(MD) / LEC(TD)) of 0.8 to 1.1. Molded articles formed from such a polyphenylene sulfide resin composition exhibit high processability when applied to metal films and excellent adhesion to metal films, as well as excellent dimensional stability and low warpage to temperature changes, making them suitable for waveguide antenna components.

[0029] The embodiments of the present invention will be described below.

[0030] Polyphenylene sulfide resin ((A) component)

[0031] The component (A) used in this invention is a polymer having repeating units as shown in the following structural formula.

[0032]

[0033] From the viewpoint of heat resistance, component (A) preferably contains 70 mol% or more of the repeating unit shown in the above structural formula, and more preferably 90 mol% or more. Component (A) may contain less than 30 mol% of repeating units having the following structure.

[0034]

[0035] Next, the method for obtaining component (A) will be described. The PPS resin can be manufactured using known methods involving pre-processing, polymerization reaction, recycling, and post-processing. Regarding the raw materials and pre-processing steps used in the manufacture of PPS resin, the method described in Japanese Patent Application Publication No. 2017-155221 is preferred. The polymerization reaction, recycling, and post-processing steps will be described below.

[0036] [Polymerization process]

[0037] PPS resin powder can be manufactured by reacting a vulcanizing agent with a polyhalogenated aromatic compound in an organic polar solvent at a temperature range of 200°C to 290°C.

[0038] At the start of the polymerization reaction, it is desirable to add a vulcanizing agent and a polyhalogenated aromatic compound in an organic polar solvent under an inert gas atmosphere and at a temperature range of room temperature to 215°C, preferably 100 to 215°C. Polymerization aids may be added during this stage. The order in which these raw materials are added can be different or simultaneous.

[0039] Such mixtures are typically heated to a temperature range of 200°C to 290°C. There are no particular restrictions on the heating rate, but a rate of 0.01 to 5°C / min is usually chosen, and more preferably, a rate of 0.1 to 3°C / min.

[0040] Generally, the temperature is eventually raised to 250–290°C, at which the reaction typically takes 0.25–50 hours, preferably 0.5–20 hours.

[0041] In the stage before reaching the final temperature, for example, reacting at 200°C to 245°C for a certain time and then raising the temperature to 270°C to 290°C is effective in obtaining a higher degree of polymerization. At this time, the reaction time at 200°C to 245°C is usually selected in the range of 0.25 hours to 20 hours, preferably in the range of 0.25 hours to 10 hours.

[0042] Furthermore, to obtain polymers with higher degrees of polymerization, it is effective to perform polymerization in multiple stages. When performing polymerization in multiple stages, it is effective to raise the temperature to the next stage when the conversion rate of the polyhalogenated aromatic compounds in the system at 245°C reaches 40 mol% or more, preferably 60 mol%.

[0043] [Recycling Process]

[0044] After polymerization is complete, solid substances are recovered from the polymerization reaction products, which contain polymers, solvents, etc.

[0045] The preferred method for recycling PPS resin is under quenching conditions, and flash evaporation is a preferred method for this recycling. Flash evaporation involves subjecting the polymer reactants to high temperature and pressure (typically above 250°C and 8 kg / cm³). 2 The above-mentioned state is flashed into an atmosphere of normal or reduced pressure, and the polymer is recovered in the form of powder granules at the same time as solvent recovery. Here, flash evaporation refers to spraying the polymer reactants from a nozzle. Specifically, the atmosphere for flash evaporation can be, for example, nitrogen or water vapor at normal pressure, and the temperature is usually selected in the range of 150°C to 250°C.

[0046] Flash evaporation can recover solids simultaneously with solvent recovery, and it is also an economically efficient method due to its short recovery time. However, this method tends to introduce ionic compounds, such as sodium, and low-polymerization organic polymers (oligomers) into the polymer during the curing process.

[0047] However, the method for recovering the PPS resin used in the manufacturing method of the present invention is not limited to flash evaporation. Any method that meets the requirements of the present invention can be used to recover the particulate polymer by slowly cooling the polymerization reactants containing polymer, solvent, etc. (quenching method). However, in view of economic considerations, it is more preferable to use PPS resin that has been recovered by flash evaporation.

[0048] [Post-processing steps]

[0049] In the manufacturing process of PPS resin, thermal oxidation treatment can be performed after the aforementioned polymerization and recycling processes. Alternatively, a hot water treatment and acid treatment process can be performed before the thermal oxidation treatment. Furthermore, a washing process using an organic solvent can be included before the acid treatment and hot water treatment processes. The acid treatment, hot water treatment, and washing with organic solvents can also be appropriately combined.

[0050] [Post-processing steps (thermal oxidation treatment)]

[0051] The PPS resin used in this invention is preferably subjected to thermal oxidation treatment after acid treatment, hot water treatment, or washing with an organic solvent. Thermal oxidation treatment involves heating the PPS resin in an oxygen atmosphere or heating it with the addition of peroxides such as hydrogen peroxide or sulfurizing agents such as sulfur. However, for the sake of simplicity, heating in an oxygen atmosphere is particularly preferred.

[0052] The lower limit of the melt flow rate (measured according to ASTM D-1238-70, at a temperature of 315.5°C and a load of 5000g) of the PPS resin preferably used in this invention is preferably 100g / 10min or more, more preferably 300g / 10min or more. The upper limit is preferably 5000g / 10min or less, more preferably 3000g / 10min or less. A melt flow rate of 100g / 10min or more results in a PPS resin with excellent moldability, while a melt flow rate of 5000g / 10min or less results in a PPS resin with excellent mechanical strength, and is therefore preferred.

[0053] Fiber-like filler material ((B) component)

[0054] The polyphenylene sulfide resin composition of the present invention contains component (B). Examples of component (B) include glass fiber, ground glass fiber, carbon fiber, shaped cross-section glass fiber, cut glass fiber, stainless steel fiber, aluminum fiber, brass fiber, and other metal fibers, aromatic polyamide fibers, etc. (Registered Trademark) Organic fibers such as fibrils, gypsum fibers, ceramic fibers, asbestos fibers, zirconium oxide fibers, alumina fibers, silicon dioxide fibers, titanium oxide fibers, silicon carbide fibers, carbon nanotubes, carbon nanotubes, cellulose nanofibers, etc.

[0055] Furthermore, the determination of whether the filler material is fibrous or non-fibrous is as follows: By firing the resin composition in an electric furnace and evaporating component (A), the filler residue is observed using a scanning electron microscope to determine whether it is fibrous or non-fibrous. Here, a fibrous filler is defined as a filler with a fixed cross-sectional diameter and a length (L / D) of 3 or more relative to the diameter of the filler's cross-section (the cross-sectional area being the smallest). Regarding the cross-section, both circular and non-circular cases (including irregular cross-sections) are considered; in the case of irregular cross-sections, the diameter is set to the equivalent circle diameter. Furthermore, since the cross-sectional diameter is fixed, a needle-like shape does not correspond to component (B).

[0056] In component (B), from the viewpoint of mechanical properties and dimensional properties (dimensional stability relative to temperature changes, low warpage of the molded article), it is preferable to use at least one selected from glass fiber, glass abrasive fiber, glass flat fiber, and shaped cross-section glass fiber. The polyphenylene sulfide resin composition of the present invention is suitable for use in melt molding methods such as injection molding, but component (B) is often oriented during molding. Component (B) sometimes greatly contributes to the reinforcing effect of the molded article, but on the other hand, it produces anisotropy in the physical properties of the molded article. From the viewpoint of minimizing the coefficient of linear expansion in the MD direction and the coefficient of linear expansion in the TD direction during molding under the molding conditions described later, and minimizing the ratio of the coefficient of linear expansion in the MD direction to the coefficient of linear expansion in the TD direction, the polyphenylene sulfide resin composition of the present invention preferably uses a fibrous filler material with a shaped cross-section, and particularly preferably uses glass fiber with a shaped cross-section. Glass fibers with irregular cross-sections include, for example, glass fibers with a flat cross-section or plate-like glass fibers. The term "flat cross-section" refers to the ratio (major diameter / minor diameter, hereinafter sometimes referred to as "flatness ratio") of the major diameter (the distance between two points forming the longest distance on the outer perimeter of the cross-section) to the minor diameter (the distance between two points forming the longest line segment orthogonal to the line segment connecting the two points on the outer perimeter of the cross-section that will form the major diameter) in a cross-section perpendicular to the length direction of the glass fiber (major diameter / minor diameter, hereinafter sometimes referred to as "flatness ratio") preferably being 1.3 or more and 10 or less. The flatness ratio is preferably 1.5 or more and 7 or less, more preferably 1.5 or more and 6 or less. If the flatness ratio is 1.3 or more, when the resin composition is molded, a molded article with good low anisotropy can be obtained, and the dimensional stability relative to temperature changes is further excellent. If the flatness ratio is 10 or less, when the resin composition is molded, a molded article with good mechanical strength can be obtained. In addition, the flatness ratio is obtained by observing with a scanning electron microscope, measuring the major and minor axes of the cross-sections of 50 randomly selected glass fibers, calculating their ratio, and then calculating their numerical average.

[0057] Furthermore, the average fiber length of the glass fibers is preferably 50 μm or more, and ideally less than 500 μm. If the average fiber length is less than 50 μm, the flexural strength is significantly reduced; if the length exceeds 500 μm, the weld tensile strength is significantly reduced, and dimensional stability and warping resistance are also reduced. The average fiber length is determined by heating the polyphenylene sulfide resin composition in air to remove the resin. The remaining glass fibers are observed using an optical microscope at 120x magnification, and the fiber lengths of at least 1000 randomly selected glass fibers are measured and calculated as the arithmetic mean.

[0058] (B) Component, especially when (B) is an inorganic fiber, is preferably treated with a binding agent or a surface treatment agent. Examples of binding agents or surface treatment agents include functional compounds such as epoxy compounds, isocyanate compounds, silane compounds, and titanate compounds. Epoxy compounds with a high epoxy content are particularly preferred from the viewpoint of improving the reactivity of the reinforcing fiber.

[0059] Regarding the content of component (B) in the polyphenylene sulfide resin composition of the present invention, as a lower limit, considering mechanical and dimensional properties, it is 60 parts by weight or more, preferably 80 parts by weight or more, and more preferably 100 parts by weight or more, relative to 100 parts by weight of component (A). If it is less than 60 parts by weight relative to 100 parts by weight of component (A), mechanical properties are lost, and the coefficient of linear expansion increases. On the other hand, as an upper limit, considering flowability, rigidity, and dielectric properties during molding, it is 200 parts by weight or less, preferably 150 parts by weight or less, and more preferably 130 parts by weight or less, relative to 100 parts by weight of component (A). If it exceeds 200 parts by weight relative to 100 parts by weight of component (A), excessive surface roughening occurs, and adhesion to the metal film easily deteriorates.

[0060] Non-fibrous filler material ((C) component)

[0061] The polyphenylene sulfide resin composition of the present invention contains component (C). As component (C), for example, fullerenes, talc, wollastonite, zeolite, sericite, mica, kaolin, clay, pyrophyllite, bentonite, asbestos, silicates such as aluminum silicate, silicon dioxide, magnesium oxide, aluminum oxide, zirconium oxide, titanium dioxide, iron oxide, carbonates such as calcium carbonate, magnesium carbonate, and dolomite, sulfates such as calcium sulfate and barium sulfate, glass beads, glass sheets, glass powder, ceramic beads, boron nitride, silicon carbide, carbon black, silicon dioxide, and graphite are used. These components can be hollow, and more than two can be used in combination. Furthermore, they can be pretreated with coupling agents such as isocyanate compounds, organosilane compounds, organotitanate compounds, organoborane compounds, and epoxy compounds before use.

[0062] From the viewpoint of mechanical and dimensional properties, it is preferred to use one or more of calcium carbonate, glass beads and glass sheets.

[0063] Regarding the content of component (C) in the polyphenylene sulfide resin composition of the present invention, as a lower limit, considering dimensional stability relative to temperature changes, it is 0.1 parts by weight or more, preferably 35 parts by weight or more, and more preferably 45 parts by weight or more, relative to 100 parts by weight of component (A). If it is less than 0.1 parts by weight, suitable dimensional characteristics cannot be obtained when the molded article is formed. On the other hand, as an upper limit, considering mechanical and dimensional characteristics, it is preferably 120 parts by weight or less, and more preferably 115 parts by weight or less, relative to 100 parts by weight of component (A). If it exceeds 120 parts by weight, the flowability during molding is impaired, affecting moldability.

[0064] Furthermore, to further improve dimensional properties, the weight ratio of component (C) to component (B) (hereinafter referred to as "(C) / (B)") is preferably 0.6 or more and 1.2 or less. By making (C) / (B) 0.6 or more, the (LEC(MD) / LEC(TD)) described later can be made close to 1.0. In addition, by making (C) / (B) 1.2 or less, the reduction in strength can be suppressed.

[0065] Elastomer ((D) component)

[0066] The polyphenylene sulfide resin composition of the present invention preferably contains an elastomer (hereinafter, sometimes referred to as "(D) component"). The (D) component is dispersed within the (A) component. Regarding the content of the (D) component in the polyphenylene sulfide resin composition of the present invention, as a lower limit, considering the coating processability and adhesion to metal films, it is preferably 0.1 parts by weight or more, more preferably 5 parts by weight or more, and most preferably 8 parts by weight or more, relative to 100 parts by weight of the (A) component. On the other hand, as an upper limit, considering the increase in the coefficient of linear expansion, the decrease in fluidity during molding, and the coating processability and adhesion to metal films, it is preferably 12 parts by weight or less, more preferably 11 parts by weight or less, and most preferably 10 parts by weight or less, relative to 100 parts by weight of the (A) component.

[0067] Examples of (D) components that can be used in this invention include, for example, (co)polymers obtained by polymerizing α-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-octene, 4-methyl-1-pentene, and isobutene alone or in two or more forms; copolymers of α-olefins with α,β-unsaturated acids and their alkyl esters such as acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, and butyl methacrylate, such as ethylene / propylene copolymers (“ / ” indicates copolymerization, the same applies below), ethylene / 1-butene copolymers, ethylene / 1-hexene, ethylene / 1-octene, ethylene / methyl acrylate copolymers, ethylene / ethyl acrylate copolymers, ethylene / butyl acrylate copolymers, ethylene / methyl methacrylate copolymers, ethylene / ethyl methacrylate copolymers, and ethylene / butyl methacrylate copolymers. Furthermore, they may have functional groups such as epoxy groups, isocyanate groups, carbodiimide groups, and amino groups in their molecular structure. From the viewpoint of improving dispersibility relative to component (A), it is preferable to use substances having such functional groups.

[0068] As component (D), it is preferably an α-olefin copolymer having an epoxy group.

[0069] Epoxy-containing α-olefin copolymers are obtained by introducing epoxy-containing components such as glycidyl esters of α,β-unsaturated acids into olefin elastomers. Examples of glycidyl esters of α,β-unsaturated acids include epoxy-containing monomers such as glycidyl acrylate, glycidyl methacrylate, glycidyl ethyl acrylate, glycidyl itaconic acid, and glycidyl citraconic acid. There are no particular limitations on the method of introducing these epoxy-containing components; methods such as copolymerization during the copolymerization of olefin (co)polymers or graft polymerization of olefin (co)polymers using free radical initiators can be used.

[0070] The amount of the epoxy group-containing component introduced is appropriate in the range of 0.001 to 40 mol%, preferably 0.01 to 35 mol%, when the total amount of repeating units derived from olefins is set to 100 mol%.

[0071] As a particularly useful example of α-olefin copolymers with epoxy groups, it is also suitable to use ethylene / propylene-glycidyl methacrylate copolymers (“g” indicates grafting, the same applies below), ethylene / 1-butene-glycidyl methacrylate copolymers, ethylene / glycidyl acrylate copolymers, ethylene / glycidyl methacrylate copolymers, ethylene / methyl acrylate / glycidyl methacrylate copolymers, ethylene / methyl methacrylate / glycidyl methacrylate copolymers, or epoxy-containing olefin copolymers obtained by copolymerizing α-olefins such as ethylene and propylene with glycidyl esters of α,β-unsaturated acids and monomers with aliphatic carbon-carbon unsaturated bonds other than the monomers mentioned above.

[0072] Furthermore, regarding component (D), it is preferable to use an α-olefin copolymer having epoxy groups in combination with an olefin polymer that does not have polar functional groups to obtain excellent formability, coating processability and adhesion to metal films.

[0073] Examples of olefin-based polymers that do not have polar functional groups include polymers or copolymers obtained by polymerizing α-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-octene, 4-methyl-1-pentene, and isobutene alone or using two or more of them. Examples include ethylene / propylene copolymers, ethylene / 1-butene copolymers, ethylene / 1-hexene copolymers, and ethylene / 1-octene copolymers.

[0074] As component (D), when using an α-olefin copolymer with epoxy groups and an olefin polymer without polar functional groups in combination, there is no particular limitation on their ratio. However, considering the moldability and adhesion to the metal film, the preferred weight ratio is (α-olefin copolymer with epoxy groups) / (olefin (co)polymer without polar functional groups) = 5 / 95 to 95 / 5, more preferably in the range of 10 / 90 to 90 / 10.

[0075] Without impairing the effects of the present invention, the polyphenylene sulfide resin composition of the present invention may contain silane compounds for the purpose of improving mechanical strength, toughness, etc. Examples of silane compounds include, for instance, alkoxysilane compounds containing isocyanate groups such as γ-isocyanate-propyltriethoxysilane, γ-isocyanate-propyltrimethoxysilane, γ-isocyanate-propylmethyldimethoxysilane, γ-isocyanate-propylmethyldiethoxysilane, γ-isocyanate-propylethyldimethoxysilane, γ-isocyanate-propylethyldiethoxysilane, and γ-isocyanate-propyltrichlorosilane, as well as γ-epoxypropoxypropyl... Silane compounds containing epoxy groups, such as trimethoxysilane, γ-epoxypropoxypropyltriethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; silane compounds containing amino groups, such as γ-(2-aminoethyl)aminopropylmethyldimethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane, and γ-aminopropyltrimethoxysilane; and modified silicone oils containing epoxy, amino, isocyanate, or hydroxyl groups, are also included. Among these, alkoxysilanes containing epoxy, amino, isocyanate, or hydroxyl groups are particularly suitable for achieving excellent mechanical strength and resistance to thermal shock. The suitable content of such silane compounds in the polyphenylene sulfide resin composition is preferably in the range of 0.05 to 3 parts by weight relative to 100 parts by weight of component (A). The content of such silane compounds in the polyphenylene sulfide resin composition can be determined by fluorescence X-ray analysis of the polyphenylene sulfide resin composition particles.

[0076] Furthermore, without impairing the effects of the present invention, the polyphenylene sulfide resin composition of the present invention can be further blended with other resins for use. There are no particular limitations on such blendable resins; specific examples include polyamides, polyethylene terephthalate, polyetheretherketone resins, and vinyl aromatic compound block copolymers.

[0077] Further concerning the polyphenylene sulfide resin composition of the present invention, to maintain heat resistance and thermal stability without impairing the effects of the invention, it may contain one or more antioxidants selected from phenolic compounds and phosphorus compounds. The content of such antioxidants in the polyphenylene sulfide resin composition is, from the viewpoint of improving heat resistance, 0.01 parts by weight or more, particularly preferably 0.02 parts by weight or more, relative to 100 parts by weight of component (A) resin; and from the viewpoint of reducing gas components generated during molding, preferably 5 parts by weight or less, particularly preferably 1 part by weight or less. Furthermore, the combined use of phenolic antioxidants and phosphorus antioxidants is particularly preferred due to their significant effect on maintaining heat resistance and thermal stability.

[0078] There are no particular limitations on the preparation method of the polyphenylene sulfide resin composition of the present invention. Representative examples include feeding the raw materials into conventionally known melt mixers such as single-screw or twin-screw extruders, Banbury mixers, kneaders, and mixing rollers, and mixing them at a temperature of 280–380°C. There are also no particular limitations on the mixing order of the raw materials. Methods such as mixing all the raw materials and then melt-mixing them using the above method, mixing a portion of the raw materials, then melt-mixing them using the above method and further mixing the remaining raw materials and then melt-mixing them, or mixing a portion of the raw materials and then using a side feeder to mix the remaining raw materials during melt-mixing in a single-screw or twin-screw extruder, etc., are all acceptable. Furthermore, regarding small amounts of additive components, other components can be granulated after being mixed using the above methods and then added before molding.

[0079] The polyphenylene sulfide resin composition of the present invention obtained by this operation can be used for various molding processes such as injection molding, extrusion molding, blow molding, and transfer molding, but is particularly suitable for injection molding.

[0080] The polyphenylene sulfide resin composition of the present invention requires that the linear expansion coefficients (LEC(MD)) in both the MD direction and the TD direction (LEC(TD)) of the molded article obtained by molding under the following molding conditions be 25 ppm / K or less, and their ratio (LEC(MD) / LEC(TD)) is 0.8 to 1.1. This results in excellent dimensional stability and low warpage under thermal changes, making it suitable for applications such as waveguide antenna components with complex shapes and requiring dimensional stability under thermal changes. Furthermore, the molding conditions for measuring the linear expansion coefficient are as described below. The linear expansion coefficient is measured according to ISO 11359-2 (2021) in the range of -40 to 150°C, and the specific measurement method is as described in the examples. In addition, if melt molding is performed, generally, the MD direction is aligned with the resin flow direction, and also with the orientation direction of component (B).

[0081] Molding conditions for molded parts

[0082] Prepare a mold having a rectangular space of 80mm × 80mm × 3mm, and having a slit-shaped discharge hole (slit width 1.5mm, slit length 78mm) corresponding to one side of an 80mm square of the rectangular space, and an injection hole on the perpendicular line of the side passing through the midpoint of that side (see reference). Figure 1The resin composition was discharged and injection molded using an NEX-1000-9E injection molding machine manufactured by Nissei Resin Kogyo Co., Ltd., under the conditions of barrel temperature: 320°C, injection pressure: molding lower limit pressure + 12.8MPa, injection time: 15 seconds, and cooling time: 15 seconds.

[0083] The direction perpendicular to one side with the slit and parallel to the face of the square is designated as MD, and the direction orthogonal to MD is designated as TD. A strip-shaped test piece with a length of 10 mm, a width of 5 mm, and a thickness of 3 mm was cut with the centroid of the test piece coinciding with the centroid of the square. (Refer to...) Figure 2 At this point, a test piece is obtained with its long side aligned with MD (and...). Figure 2 The symbol 5 corresponds to the test piece used for LEC (MD) measurement and the test piece whose long side is in the same direction as TD (and). Figure 2 The symbol 6 corresponds to the test piece used for LEC(TD) determination. These test pieces are provided for determination.

[0084] in addition, Figure 1 The shape of the resin composition that has been injection molded is shown, but can be considered to be equal to the internal dimensions of the space within the mold.

[0085] As the lower limit for LEC(MD) and LEC(TD), considering the conformity of the coating to the metal film during expansion and contraction caused by changes in ambient temperature, it is preferably 10 ppm / K or higher, and more preferably 15 ppm / K or higher. On the other hand, as the upper limit, considering the conformity of the coating to the metal film and dimensional stability, it is preferably 23 ppm / K or lower.

[0086] In order to make the coefficient of linear expansion of the molded article obtained under the above molding conditions less than 25 ppm / K, it is convenient to make component (B) a glass fiber with a flat cross-section, a plate-shaped glass fiber, or to make (C) / (B) 0.6 or more and 1.2 or less in the polyphenylene sulfide resin composition of the present invention.

[0087] Furthermore, regarding LEC(MD) / LEC(TD), considering the conformity with the coating of the metal thin film, the lower limit is preferably 0.9 or more, the upper limit is preferably 1.05 or less, and the most preferred value is 1.0, that is, the values ​​of LEC(MD) and LEC(TD) are equal.

[0088] To achieve an LEC(MD) / LEC(TD) ratio of 0.8 to 1.1, as described above, it is convenient to include any of the following in the PPS resin composition: glass fibers that are effective in improving low anisotropy, shaped cross-section glass fibers, and glass sheets.

[0089] When assumed to be used in waveguide antennas, from the viewpoint of reducing radio wave loss, a smooth surface after the metal thin film is formed is required. However, the smoothness of the surface after the metal thin film is formed is significantly affected by the smoothness of the surface of the molded article before the metal thin film is formed. Therefore, it is required that the surface roughness (Ra) of the molded article formed from the polyphenylene sulfide resin composition of the present invention is small, and the surface of the molded article is smooth. As a lower limit, considering the surface roughness limit of the mold, it is preferably 0.1 μm or more. As an upper limit, it is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 1.0 μm or less.

[0090] To achieve an arithmetic mean roughness (Ra) of the surface of the molded article formed from the PPS resin composition of the present invention of less than 10 μm, this is achieved by mixing component (D) into the PPS resin composition.

[0091] There are no particular limitations on the processing method for forming a metal thin film on the surface of a molded article formed from the polyphenylene sulfide resin composition of the present invention. However, considering the surface smoothness of the portion where the metal thin film is formed, a processing method that does not roughen the surface of the metal thin film is preferred. Specifically, as a processing method that does not roughen the surface, methods such as sputtering, vapor deposition, or plating can be cited, after performing activation treatments on the surface of the molded article such as UV treatment or plasma treatment. If these treatments are performed, the surface roughness of the portion where the metal thin film is formed can be reduced to 10 μm or less. Furthermore, as a processing method that improves the adhesion between the molded article and the metal thin film, a processing method that roughens the surface of at least a portion of the molded article by etching, sandblasting, or the like before forming the metal thin film can be cited. However, since the surface smoothness after forming the metal thin film is significantly affected by the surface roughness of the molded article, methods that only partially process the surface of the molded article are not preferred.

[0092] From the viewpoint of reducing radio wave loss, the metal thin film formed on the molded article made from the polyphenylene sulfide resin composition of the present invention is preferably made of a metal with high conductivity, particularly one or more selected from silver, copper, and aluminum. Furthermore, from the viewpoint of reducing radio wave loss, the thickness of the metal thin film is preferably 1 μm or more, more preferably 5 μm or more, and even more preferably 10 μm or more. As an upper limit for the thickness of the metal thin film, a certain thickness is sufficient for waveguide performance when manufacturing a waveguide; therefore, although there is no particular limitation, it is around 50 μm.

[0093] Molded articles formed from the polyphenylene sulfide resin composition of the present invention are suitable for waveguide antenna components for communication applications such as base stations and automotive radars due to improved coating processability and adhesion between the resin and the metal film, as well as excellent dimensional stability and low warpage relative to temperature changes. Furthermore, without sacrificing the various inherent properties of PPS resin, the coating processability and adhesion between the molded article and the metal film are improved. In addition, molded articles formed from the polyphenylene sulfide resin composition of the present invention are suitable for electrical / electronic components due to the excellent electromagnetic wave shielding and surface thermal conductivity provided by the metal film. In particular, they can prevent mutual interference caused by electromagnetic waves. Considering the above characteristics, the molded articles of the present invention are excellent for use in sensor component housings and ECU component housings.

[0094] Furthermore, the polyphenylene sulfide resin composition of the present invention can also be applied to, for example, sensors, capacitors, variable capacitor housings, oscillators, various terminal blocks, transformers, plugs, printed circuit boards, small electric motors, semiconductors, liquid crystals, and parabolic antennas. Additionally, examples include mechanical components such as office computer components, telephone components, and fax machine components; optical equipment and precision mechanical components such as microscopes, binoculars, cameras, and watches; valve alternator terminals, alternator connectors, IC regulators, dimmer potentiometer bases, exhaust valves, and various other valves; fuel-related / exhaust / intake system pipes; intake manifolds; fuel pumps; engine coolant connectors; carburetor bodies; carburetor spacers; water pump housings; engine cooling modules; turbine blades; wiper motor components; distributors; starter switches; starter relays; air conditioning panel switch boards; and electrical component insulation boards, among other automotive / vehicle-related components.

[0095] Example

[0096] The following examples further illustrate the present invention, but the present invention is not limited to the description of these examples.

[0097] [Evaluation methods for PPS resins manufactured in each manufacturing example]

[0098] (1) Melt Flow Rate (MFR)

[0099] The melt flow rate of polyphenylene sulfide resin was determined according to ASTM-D1238-70 under the conditions of 315.5°C and 5000g load.

[0100] However, for low-viscosity polyphenylene sulfide resins, the MFR was calculated using the following method. The flow rate (ER, in g / 10 min) of the polyphenylene sulfide resin was determined according to ASTM-D1238-70 at a test temperature of 315.5°C and a load of 345 g. The MFR (in g / 10 min) was then calculated using the following formula (1).

[0101] MFR=15.8×4.4×ER formula (1).

[0102] [Manufacturing Example 1] Polymerization of PPS (PPS-1)

[0103] Add 8.27 kg (70.00 mol) of 47.5% sodium hydrosulfide, 2.91 kg (69.80 mol) of 96% sodium hydroxide, 11.45 kg (115.50 mol) of N-methyl-2-pyrrolidone (NMP), and 10.5 kg of ion-exchanged water to a 70-liter high-pressure vessel equipped with a stirrer and a bottom stop valve. While purging nitrogen gas at atmospheric pressure, slowly heat the mixture to 245°C for about 3 hours. After distilling off 14.78 kg of water and 0.28 kg of NMP, cool the reaction vessel to 200°C.

[0104] The residual water content in the system relative to 1 mole of added alkali metal sulfide, including the water consumed by the hydrolysis of NMP, is 1.06 moles. Furthermore, the amount of hydrogen sulfide escaping is 0.02 moles relative to 1 mole of added alkali metal sulfide. The mixture was then cooled to 200°C, and 10.48 kg (71.27 moles) of p-dichlorobenzene and 9.37 kg (94.50 moles) of NMP were added. The reaction vessel was sealed under nitrogen, and the temperature was increased from 200°C to 270°C at a rate of 0.6°C / min while stirring at 240 rpm. After reacting at 270°C for 100 minutes, the bottom valve of the autoclave was opened, and the contents were flash-evaporated into a vessel equipped with a stirrer for 15 minutes under nitrogen pressure. The mixture was then stirred briefly at 250°C to remove most of the NMP.

[0105] The obtained solid material and 76 liters of ion-exchanged water were added to an autoclave equipped with a stirrer. After washing at 70°C for 30 minutes, the mixture was filtered through a glass filter. Then, 76 liters of ion-exchanged water heated to 70°C were injected into the glass filter, and the mixture was filtered again to obtain a filter cake.

[0106] The resulting filter cake and 90 liters of deionized water were added to an autoclave equipped with a stirrer, and acetic acid was added to achieve a pH of 7. After purging the autoclave with nitrogen, the temperature was raised to 192°C and maintained for 30 minutes. The autoclave was then cooled, and the contents were removed.

[0107] After filtering the contents through a glass filter, 76 liters of deionized water at 70°C were injected and filtered again to obtain a filter cake. The resulting filter cake was dried at 120°C under a nitrogen stream to obtain dried PPS. This dried PPS was then heat-treated at 200°C under an oxygen stream until the MFR (Mean Factor Flow Rate) became 150 g / 10 min, yielding cross-linked PPS-1. The resulting polymer had an MFR of 130 g / 10 min.

[0108] [Manufacturing Example 2] Polymerization of PPS (PPS-2)

[0109] In a high-pressure reactor equipped with a stirrer and a bottom stopper valve, 8267.4 g (70.0 mol) of 47.5% sodium hydrosulfide, 2925.0 g (70.2 mol) of 96% sodium hydroxide, 13860.0 g (140.0 mol) of N-methyl-2-pyrrolidone (NMP), 1894.2 g (23.1 mol) of sodium acetate, and 10500.0 g of deionized water were added. The mixture was slowly heated to 240°C for approximately 3 hours while nitrogen was introduced at atmospheric pressure. After distilling off 14772.1 g of water and 280.0 g of NMP, the reaction vessel was cooled to 160°C. The residual water content in the system relative to each mole of added alkali metal sulfide, including water consumed by the hydrolysis of NMP, was 1.08 mol. Furthermore, the amount of hydrogen sulfide escaping relative to each mole of added alkali metal sulfide was 0.023 mol.

[0110] Next, 10646.7 g (72.4 mol) of p-dichlorobenzene (p-DCB) and 6444.9 g (65.1 mol) of NMP were added. The reaction vessel was sealed under nitrogen atmosphere, and the temperature was increased from 200 °C to 270 °C at a rate of 0.6 °C / min while stirring at 240 rpm. The temperature was maintained at 270 °C for 70 minutes. The outlet valve at the bottom of the autoclave was opened, and the contents were flash-evaporated into a vessel equipped with a stirrer for 15 minutes while pressurizing with nitrogen atmosphere. The mixture was stirred briefly at 250 °C to remove most of the NMP.

[0111] The obtained solid material and 53 liters of ion-exchanged water were added to an autoclave equipped with a stirrer. After washing at 70°C for 30 minutes, the mixture was filtered through a glass filter with a pore size of 10–16 μm. Then, 60 liters of ion-exchanged water heated to 70°C were injected into the glass filter with a pore size of 10–16 μm and filtered to obtain 18,000 g of PPS resin filter cake (containing 7,550 g of PPS resin).

[0112] 18,000 g of the PPS resin filter cake, 40 liters of deionized water, and 43 g of acetic acid were added to an autoclave equipped with a stirrer. The autoclave was purged with nitrogen, and the temperature was raised to 192°C and maintained for 30 minutes for acid treatment. The pH during acid treatment was 7. After cooling, the contents were filtered through a glass filter with a pore size of 10–16 μm. Next, 60 liters of deionized water heated to 70°C were injected into the glass filter, and the mixture was filtered through suction to obtain a filter cake. The resulting filter cake was dried at 120°C for 4 hours under a nitrogen atmosphere to obtain acid-treated linear PPS-2. The MFR of the obtained polymer was 6300 g / 10 min.

[0113] [Manufacturing Example 3] Polymerization of PPS (PPS-3)

[0114] In a high-pressure reactor equipped with a stirrer and a bottom stopper valve, 8,267.4 g (70.0 mol) of 47.5% sodium hydrosulfide, 2,925.0 g (70.2 mol) of 96% sodium hydroxide, 13,860.0 g (140.0 mol) of N-methyl-2-pyrrolidone (NMP), 1,894.2 g (23.1 mol) of sodium acetate, and 10,500.0 g of deionized water were added. The mixture was slowly heated to 240°C for approximately 3 hours while nitrogen was introduced at atmospheric pressure. After distilling off 14,772.1 g of water and 280.0 g of NMP, the reaction vessel was cooled to 160°C. The residual water content in the system relative to each mole of added alkali metal sulfide, including water consumed by the hydrolysis of NMP, was 1.08 mol. Furthermore, the amount of hydrogen sulfide escaping relative to each mole of added alkali metal sulfide was 0.023 mol.

[0115] Next, 10,646.7 g (72.4 mol) of p-dichlorobenzene (p-DCB) and 6,444.9 g (65.1 mol) of NMP were added. The reaction vessel was sealed under nitrogen atmosphere, and the temperature was increased from 200 °C to 270 °C at a rate of 0.6 °C / min while stirring at 240 rpm. The temperature was maintained at 270 °C for 70 minutes. The outlet valve at the bottom of the autoclave was opened, and the contents were flash-evaporated into a vessel equipped with a stirrer for 15 minutes under nitrogen pressure. The mixture was stirred briefly at 250 °C to remove most of the NMP.

[0116] The obtained solid material and 53 L of ion-exchanged water were added to an autoclave equipped with a stirrer. After washing at 70 °C for 30 minutes, the mixture was filtered through a glass filter with a pore size of 10–16 μm. Then, 60 L of ion-exchanged water heated to 70 °C was injected into the glass filter with a pore size of 10–16 μm and filtered again to obtain 18,000 g of PPS resin filter cake (containing 7,550 g of PPS resin).

[0117] 18,000 g of the PPS resin filter cake, 40 L of deionized water, and 43 g of acetic acid were added to an autoclave equipped with a stirrer. The autoclave was purged with nitrogen, and the temperature was raised to 192°C and maintained for 30 minutes for acid treatment. The pH during acid treatment was 7. After cooling, the contents were filtered through a glass filter with a pore size of 10–16 μm. Then, 60 L of deionized water heated to 70°C was injected into the glass filter, and the mixture was filtered through suction to obtain a filter cake. The obtained filter cake was dried at 120°C for 4 hours under a nitrogen atmosphere to obtain acid-treated PPS resin powder. Next, the PPS resin powder was added to a 100 L heating device equipped with a stirrer and subjected to thermal oxidation treatment at 220°C and 2% oxygen concentration for 2 hours to obtain cross-linked PPS-3. The resulting polymer had an MFR of 420 g / 10 min.

[0118] [Manufacturing Example 4] Polymerization of PPS (PPS-4)

[0119] In a high-pressure reactor equipped with a stirrer and a bottom stopper valve, 8267.4 g (70.0 mol) of 47.5% sodium hydrosulfide, 2925.0 g (70.2 mol) of 96% sodium hydroxide, 13860.0 g (140.0 mol) of N-methyl-2-pyrrolidone (NMP), 1894.2 g (23.1 mol) of sodium acetate, and 10500.0 g of deionized water were added. The mixture was slowly heated to 240°C for approximately 3 hours while nitrogen was introduced at atmospheric pressure. After distilling off 14772.1 g of water and 280.0 g of NMP, the reaction vessel was cooled to 160°C. The residual water content in the system relative to each mole of added alkali metal sulfide, including water consumed by the hydrolysis of NMP, was 1.08 mol. Furthermore, the amount of hydrogen sulfide escaping relative to each mole of added alkali metal sulfide was 0.023 mol.

[0120] Next, 10646.7 g (72.4 mol) of p-dichlorobenzene (p-DCB) and 6444.9 g (65.1 mol) of NMP were added. The reaction vessel was sealed under nitrogen atmosphere, and the temperature was increased from 200 °C to 270 °C at a rate of 0.6 °C / min while stirring at 240 rpm. The temperature was maintained at 270 °C for 70 minutes. The outlet valve at the bottom of the autoclave was opened, and the contents were flash-evaporated into a vessel equipped with a stirrer for 15 minutes while pressurizing with nitrogen atmosphere. The mixture was stirred briefly at 250 °C to remove most of the NMP.

[0121] The obtained solid material and 53 liters of ion-exchanged water were added to an autoclave equipped with a stirrer. After washing at 70°C for 30 minutes, the mixture was filtered through a glass filter with a pore size of 10–16 μm. Then, 60 liters of ion-exchanged water heated to 70°C were injected into the glass filter with a pore size of 10–16 μm and filtered again to obtain 18,000 g of PPS resin filter cake (containing 7,550 g of PPS resin).

[0122] 18,000 g of the PPS resin filter cake, 40 liters of deionized water, and 43 g of acetic acid were added to an autoclave equipped with a stirrer. The autoclave was purged with nitrogen, and the temperature was raised to 192°C and maintained for 30 minutes for acid treatment. The pH during acid treatment was 7. After cooling, the contents were filtered through a glass filter with a pore size of 10–16 μm. Next, 60 liters of deionized water heated to 70°C was injected into the glass filter, and suction filtration was performed to obtain a filter cake. The resulting filter cake was dried at 120°C for 4 hours under a nitrogen atmosphere to obtain acid-treated linear PPS.

[0123] Linear PPS was added to a 100-liter heating device equipped with a stirrer and subjected to thermal oxidation treatment at 220°C and 2% oxygen concentration for 2 hours to obtain cross-linked PPS-4. The resulting polymer had an MFR of 5000 g / 10 min.

[0124] [Manufacturing Example 5] Polymerization of PPS (PPS-5)

[0125] In a 70°C high-pressure reactor equipped with a stirrer and a bottom stopper valve, 8.27 kg (70.00 mol) of 47.5% sodium hydrosulfide, 2.91 kg (69.80 mol) of 96% sodium hydroxide, 11.45 kg (115.50 mol) of N-methyl-2-pyrrolidone (NMP), and 10.5 kg of deionized water were added. The mixture was slowly heated to 245°C over approximately 3 hours while nitrogen was introduced at atmospheric pressure. After distilling off 14.78 kg of water and 0.28 kg of NMP, the reaction vessel was cooled to 200°C. The residual water content in the system relative to each mole of added alkali metal sulfide, including water consumed by the hydrolysis of NMP, was 1.06 mol. Furthermore, the amount of hydrogen sulfide escaping was 0.02 mol relative to each mole of added alkali metal sulfide.

[0126] The mixture was then cooled to 200°C, and 10.48 kg (71.27 mol) of p-dichlorobenzene and 9.37 kg (94.50 mol) of NMP were added. The reaction vessel was sealed under nitrogen atmosphere, and the temperature was increased from 200°C to 270°C at a rate of 0.6°C / min while stirring at 240 rpm. After reacting at 270°C for 100 minutes, the bottom stop valve of the autoclave was opened, and the contents were flash-evaporated into a vessel equipped with a stirrer over 15 minutes while pressurizing with nitrogen. The mixture was then stirred briefly at 250°C to remove most of the NMP.

[0127] The obtained solid material and 76 liters of ion-exchanged water were added to an autoclave equipped with a stirrer. After washing at 70°C for 30 minutes, the mixture was filtered through a glass filter. Then, 76 liters of ion-exchanged water heated to 70°C were injected into the glass filter, and the mixture was filtered again to obtain a filter cake.

[0128] The resulting filter cake and 90 liters of deionized water were added to an autoclave equipped with a stirrer, and acetic acid was added to achieve a pH of 7. The autoclave was then purged with nitrogen, heated to 192°C, and maintained at that temperature for 30 minutes. The autoclave was then cooled, and the contents were removed.

[0129] The contents were filtered through a glass filter, and then 76 liters of ion-exchanged water at 70°C were added for further filtration to obtain a filter cake. The resulting filter cake was dried at 120°C under a nitrogen stream to obtain dried PPS-5. The ER of the obtained PPS-5 was 90 g / 10 min, which translates to an MFR of 6257 g / 10 min.

[0130] [Manufacturing Example 6] Polymerization of PPS (PPS-6)

[0131] In a high-pressure reactor equipped with a stirrer and a bottom stopper valve, 8267.4 g (70.0 mol) of 47.5% sodium hydrosulfide, 2925.0 g (70.2 mol) of 96% sodium hydroxide, 13860.0 g (140.0 mol) of N-methyl-2-pyrrolidone (NMP), 1894.2 g (23.1 mol) of sodium acetate, and 10500.0 g of deionized water were added. The mixture was slowly heated to 240°C for approximately 3 hours while nitrogen was introduced at atmospheric pressure. After distilling off 14772.1 g of water and 280.0 g of NMP, the reaction vessel was cooled to 160°C. The residual water content in the system relative to each mole of added alkali metal sulfide, including water consumed by the hydrolysis of NMP, was 1.08 mol. Furthermore, the amount of hydrogen sulfide escaping relative to each mole of added alkali metal sulfide was 0.023 mol.

[0132] Next, 10646.7 g (72.4 mol) of p-dichlorobenzene (p-DCB) and 6444.9 g (65.1 mol) of NMP were added. The reaction vessel was sealed under nitrogen atmosphere, and the temperature was increased from 200 °C to 270 °C at a rate of 0.6 °C / min while stirring at 240 rpm. The temperature was maintained at 270 °C for 70 minutes. The outlet valve at the bottom of the autoclave was opened, and the contents were flash-evaporated into a vessel equipped with a stirrer for 15 minutes while pressurizing with nitrogen atmosphere. The mixture was stirred briefly at 250 °C to remove most of the NMP.

[0133] The obtained solid material and 53 liters of ion-exchanged water were added to an autoclave equipped with a stirrer. After washing at 70°C for 30 minutes, the mixture was filtered through a glass filter with a pore size of 10–16 μm. Then, 60 liters of ion-exchanged water heated to 70°C were injected into the glass filter with a pore size of 10–16 μm and filtered again to obtain 18,000 g of PPS resin filter cake (containing 7,550 g of PPS resin).

[0134] 18,000 g of the PPS resin filter cake, 40 liters of deionized water, and 43 g of acetic acid were added to an autoclave equipped with a stirrer. The autoclave was purged with nitrogen, and the temperature was raised to 192°C and maintained for 30 minutes for acid treatment. The pH during acid treatment was 7. After cooling, the contents were filtered through a glass filter with a pore size of 10–16 μm. Next, 60 liters of deionized water heated to 70°C was injected into the glass filter, and the mixture was filtered through suction to obtain a filter cake. The obtained filter cake was dried at 120°C for 4 hours under a nitrogen atmosphere to obtain acid-treated PPS resin powder. This PPS resin powder was then added to a 100-liter heating device equipped with a stirrer and subjected to thermal oxidation treatment at 200°C and an oxygen concentration of 21% for 2 hours. The thermal oxidation treatment was carried out in an air atmosphere of 1.96 liters / minute to obtain cross-linked PPS-6. The resulting polymer had an MFR of 554 g / 10 min.

[0135] [Manufacturing Example 7] Polymerization of PPS (PPS-7)

[0136] In a 70°C high-pressure reactor equipped with a stirrer and a bottom stopper valve, 8.27 kg (70.00 mol) of 47.5% sodium hydrosulfide, 2.94 kg (70.63 mol) of 96% sodium hydroxide, 11.45 kg (115.50 mol) of N-methyl-2-pyrrolidone (NMP), 1.89 kg (23.1 mol) of sodium acetate, and 5.50 kg of deionized water were added. The mixture was slowly heated to 245°C for 3 hours while nitrogen was introduced at atmospheric pressure. After distilling off 9.77 kg of water and 0.28 kg of NMP, the reaction vessel was cooled to 200°C. The residual water content in the system relative to each mole of added alkali metal sulfide, including water consumed by the hydrolysis of NMP, was 1.06 mol. Furthermore, the amount of hydrogen sulfide escaping was 0.02 mol relative to each mole of added alkali metal sulfide.

[0137] The mixture was then cooled to 200°C, and 10.42 kg (70.86 mol) of p-dichlorobenzene and 9.37 kg (94.50 mol) of NMP were added. The reaction vessel was sealed under nitrogen atmosphere, and the temperature was increased from 200°C to 270°C at a rate of 0.6°C / min while stirring at 240 rpm. The reaction was carried out at 270°C for 140 minutes. Then, while cooling from 270°C to 250°C over 15 minutes, 2.40 kg (133 mol) of water was added by pressure. The mixture was then slowly cooled from 250°C to 220°C over 75 minutes, and then quenched to near room temperature before the contents were removed. The contents were diluted with 35 liters of NMP to form a slurry, stirred at 85°C for 30 minutes, and then filtered through an 80-mesh metal screen (0.175 mm aperture) to obtain a solid substance.

[0138] The obtained solid matter was similarly washed and filtered using 35 liters of NMP. The obtained solid matter was diluted with 70 liters of deionized water, stirred at 70°C for 30 minutes, and then filtered through an 80-mesh metal screen to recover the solid matter. This operation was repeated a total of 3 times. The obtained solid matter and 32 g of calcium acetate were diluted with 70 liters of deionized water, stirred at 70°C for 30 minutes, and then filtered through an 80-mesh metal screen. The resulting solid matter was further diluted with 70 liters of deionized water, stirred at 70°C for 30 minutes, and then filtered through an 80-mesh metal screen to recover the solid matter.

[0139] The solid obtained by this operation was dried at 120°C under a nitrogen gas flow to obtain dried PPS-7. The MFR of the obtained PPS-7 was 600 g / 10 min.

[0140] [Examples 1-5, Comparative Examples 1-4]

[0141] Using a twin-screw extruder (Toshiba Machine Co., Ltd. TEM-26SS) with a 26mm diameter intermediate feed port, the barrel temperature was set to 320°C and the screw speed to 400 rpm. Components (A), (C), and (D) obtained in Manufacturing Examples 1-7 were added from the feed port to the extrusion port to form a molten state, and component (B) was supplied from the intermediate feed port. Particles were obtained by melt mixing at a discharge rate of 30 kg / hour. The properties of these particles were evaluated. The results are shown in Tables 1 and 2.

[0142] The following shows the raw materials used in this invention.

[0143] PPS resin (component A)

[0144] PPS-1: PPS resin polymerized by the method described in Example 1

[0145] PPS-2: PPS resin polymerized by the method described in Manufacturing Example 2

[0146] PPS-3: PPS resin polymerized by the method described in Example 3.

[0147] PPS-4: PPS resin polymerized by the method described in Example 4.

[0148] PPS-5: PPS resin polymerized by the method described in Example 5.

[0149] PPS-6: PPS resin polymerized by the method described in Example 6

[0150] PPS-7: PPS resin polymerized by the method described in Example 7.

[0151] Fiber-like filler material ((B) component)

[0152] B-1: Circular cross-section glass fiber (T-760H manufactured by Nippon Electric Glass Co., Ltd., 3mm length, average fiber diameter 10.5μm, flatness ratio 1)

[0153] B-2: Irregular cross-section glass fiber (T-760FGF manufactured by Nippon Electric Glass Co., Ltd., 3mm length, 7μm short diameter, 28μm long diameter, flatness ratio 4)

[0154] B-3: Short-cut raw yarn (T-747GH manufactured by Nippon Electric Glass Co., Ltd., 3mm length, average fiber diameter 10μm)

[0155] B-4: Short-cut raw yarn (T-702 manufactured by Nippon Electric Glass Co., Ltd., 3mm length, average fiber diameter 13μm).

[0156] Non-fibrous filler material ((C) component)

[0157] C-1: Heavy calcium carbonate (Co., Ltd.) Company structure KSS1000)

[0158] C-2: Heavy calcium carbonate (manufactured by Sankyo Flour Milling Co., Ltd.) )

[0159] C-3: Glass sheet: Alkali-free glass (REFG-112 manufactured by Japan Sheet Glass Co., Ltd.).

[0160] Elastomer ((D) component)

[0161] D-1: Ethylene / glycidyl methacrylate / methyl acrylate copolymer (manufactured by Sumitomo Chemical Co., Ltd.) E)

[0162] D-2: Ethylene / glycidyl methacrylate / methyl acrylate copolymer (manufactured by Sumitomo Chemical Co., Ltd.) 7M, ethylene 67% by mass, glycidyl methacrylate 6% by mass, methyl acrylate 27% by mass)

[0163] D-3: Ethylene / n-butyl acrylate copolymer ( (Company) 35BA40)

[0164] D-4: Ethylene / α-olefin copolymer (manufactured by Mitsui Chemicals Co., Ltd.) TX650

[0165] D-5: Olefin copolymer (Engage 8842 manufactured by The Dow Chemical Company).

[0166] [Methods for determining and evaluating molded articles formed from resin compositions]

[0167] The methods for determining and evaluating molded articles formed from resin compositions are as follows.

[0168] (1) Tensile strength

[0169] The tensile strength of the molded article was determined according to ISO 527-1, 2 (2012). Specifically, the determination was performed as follows: Resin composition particles used as samples were dried in a hot air dryer at 130°C for 3 hours, then fed into an injection molding machine (SE-50D) manufactured by Sumitomo Heavy Industries, Ltd., with the barrel temperature set at 310°C and the mold temperature at 145°C. Using a mold of type A1 test piece shape (4mm thickness) as specified in ISO 20753 (2008), injection molding was performed under conditions where the average velocity of the molten resin passing through the cross-sectional area of ​​the central parallel section was 400±50mm / s, resulting in a test piece. After conditioning the test piece at 23°C and 50% relative humidity for 16 hours, the tensile strength was determined according to ISO 527-1, 2 (2012) under an atmosphere of 23°C and 50% relative humidity, with a fixture distance of 115mm and a test speed of 5mm / min. If the strength is above 120MPa, it can be said to be a product level that is practically sound. However, the higher the value, the better the mechanical strength, making it the preferred choice.

[0170] (2) Bending strength

[0171] The determination was performed according to ISO 178 (2001). Specifically, the determination was performed as follows: Resin composition particles, which served as the test sample, were fed into an injection molding machine (SE50DUZ-C160) manufactured by Sumitomo Heavy Industries, Ltd., with the barrel temperature set at 310°C and the mold temperature at 145°C. The sample was filled with a filling time of 0.8 s and injection molded at 75% of the filling pressure to obtain a type B2 test piece shape as specified in ISO 20753 (2008). After conditioning the test piece for 16 hours at 23°C and 50% relative humidity, the determination was performed at 23°C and 50% relative humidity, with a spacing of 64 mm and a strain rate of 2 mm / min.

[0172] (3) Coefficient of linear expansion

[0173] Prepare a mold with a rectangular space of 80mm × 80mm × 3mm, and a slit-shaped vent hole (corresponding to the gate; slit width 1.5mm, slit length 78mm) corresponding to one side of the 80mm square of the rectangular space, and an injection hole (main runner) on the perpendicular line of the side passing through the midpoint of that side (see reference). Figure 1 Injection molding was performed using a NEX-1000-9E injection molding machine manufactured by Nissei Resin Industries, Ltd., with the resin composition discharged under the following conditions: barrel temperature: 320°C, injection pressure: lower molding limit pressure + 12.8 MPa, injection time: 15 seconds, and cooling time: 15 seconds. Additionally, in... Figure 2In the design, the part corresponding to the main runner is represented by symbol 1, the part corresponding to the runner is represented by symbol 2, the part corresponding to the gate is represented by symbol 3, and the sampling plate part is represented by symbol 4. In addition, the corners of the runner part of the mold are machined into rounded corners with a radius of 2mmφ.

[0174] The direction from the side with the slit to its opposite side is designated MD, and the direction orthogonal to MD is designated TD. A strip-shaped test piece with a length of 10 mm, a width of 5 mm, and a thickness of 3 mm is cut out, with the centroid of the test piece coinciding with the centroid of the aforementioned square (see reference). Figure 2 At this point, test pieces with the long side aligned with MD are used as test pieces for LEC(MD) measurement, and test pieces with the long side aligned with TD are used as test pieces for LEC(TD) measurement.

[0175] The coefficient of linear expansion was determined for the obtained strip-shaped test pieces. The coefficient of linear expansion was determined according to ISO 11359-2 (2021), using... (Co., Ltd.) manufactures TMA-100, which heats a temperature range of -50℃ to 200℃ with a load of 2g at a rate of 5℃ / minute, and the values ​​are expressed in the temperature range of -40℃ to 150℃.

[0176] (4) Surface roughness of the molded part before the metal film is formed (arithmetic mean roughness Ra)

[0177] The surface roughness of the molded article before the metal film formation was measured using the following steps. First, a cuboid of 80 mm × 80 mm × 3 mm was formed using the method described in item "(3) Coefficient of Linear Expansion" above. Next, as follows... Figure 3 As shown, a strip test piece 7 with a width of 15 mm (denoted as L2 in the figure), a length of 80 mm, and a thickness of 3 mm was cut out. Furthermore, the initial strip test piece 7 was cut 10 mm from the side of the square, with each test piece spaced 7.5 mm apart. The cut strip test pieces 7 were then measured using a Mitumoto surface roughness measuring machine (SV-2100) according to JIS-B-0601 to determine the arithmetic mean roughness Ra.

[0178] (5) Adhesion between resin molded articles and metal films (peel strength)

[0179] First, a molded article with a metal thin film layer was produced by the following method. The strip test piece obtained by the same method as "(4) Surface roughness (arithmetic mean roughness Ra) of the molded article before metal film formation" was irradiated with ultraviolet light from a height of 30 mm above the test piece surface for 60 minutes using a small ultraviolet irradiation device (manufactured by Koto Electric, KOL1-300S) equipped with a high-output low-pressure mercury lamp (300W) with main wavelengths of 184.9 nm and 253.7 nm. Then, it was immersed in a 20% by weight potassium hydroxide aqueous solution for 12 minutes to perform a surface treatment process.

[0180] Next, the surface of the surface-treated molded product will be treated with 0.3 g / dm³ 3 A palladium dichloride aqueous solution was used as the catalyst solution, and this catalyst solution was coated onto the surface of the molded article using 20 g / dm³. 3 A sodium phosphonate aqueous solution was used to reduce the Pd catalyst on the PPS resin surface to metal, thereby forming a metal core that facilitates the electroless NiP plating process (catalyst application and activation processes). Next, an electroless copper plating process was performed on the molded article with palladium deposited on its surface obtained through the above process. Then, further electroplating with copper sulfate and nickel plating was performed to achieve a plating thickness of 3 μm or more, resulting in a molded article with a metal thin film layer.

[0181] The adhesion strength of the metal film layer in the molded article with the metal film layer was determined according to the adhesion strength test method specified in Appendix 1 of JIS H8630:2006. The case of no metal film formation was marked as *, the case of peel strength less than 0.5 N / cm was marked as D, the case of peel strength greater than or equal to 0.5 N / cm but less than 1 N / cm was marked as C, the case of peel strength greater than or equal to 1 N / cm but less than 10 N / cm was marked as B, and the case of peel strength greater than or equal to 10 N / cm was marked as A. A or C was evaluated as acceptable. Furthermore, A was the best.

[0182] In Examples 1-5, by using glass fibers with a flat cross-section or plate-shaped glass fibers as component (B), or by making (C) / (B) 0.6 or more and 1.2 or less, excellent results are achieved in maintaining high mechanical properties while exhibiting low linear expansion and low anisotropy. Based on the above, Examples 1-5 are suitable for waveguide antenna components requiring dimensional stability under thermal changes.

[0183] It can be seen that because of the use of irregularly shaped cross-section glass fiber in Examples 2 to 4, the results are further superior in terms of low linear expansion and low anisotropy, making them more suitable for waveguide antenna components.

[0184] It can be seen that Comparative Examples 1 to 4 do not use irregularly shaped glass fibers, and (C) / (B) is less than 0.6, therefore the coefficient of linear expansion is large and the anisotropy is poor.

[0185] Furthermore, the results from Examples 1 to 5 show that the content of component (D) is particularly effective in improving the adhesion of the metal film when it is 0.1 to 12 parts by weight relative to 100 parts by weight of component (A).

[0186] Based on the above, it can be seen that Examples 1 to 3 are particularly suitable for waveguide antenna components that require tight adhesion to metal thin films and dimensional stability under thermal changes.

[0187] [Table 1]

[0188]

[0189] [Table 2]

[0190]

[0191] Industry availability

[0192] According to the present invention, as an alternative to conventional metal waveguide antennas, a resin waveguide antenna can be provided that exhibits excellent dimensional stability under thermal changes, low warpage of the molded product, and excellent coating processability and adhesion to metal thin films.

[0193] Explanation of symbols

[0194] 1. Mainstream Road Corresponding Section

[0195] 2. Corresponding part of the flow channel

[0196] 3. Corresponding part of the gate

[0197] 4. Sampling plate section

[0198] 5, 6, 7. The cutout position of the long strip test piece or the long strip test piece.

Claims

1. A polyphenylene sulfide resin composition for waveguide antennas, comprising component (A), component (B), and component (C), wherein component (A) is polyphenylene sulfide resin, component (B) is a fibrous filler material, and component (C) is a non-fibrous filler material, characterized in that, Relative to 100 parts by weight of component (A), the content of component (B) is 60 to 200 parts by weight, and the content of component (C) is 0.1 to 120 parts by weight. Under the following molding conditions, the resulting molded article exhibits a coefficient of linear expansion (LEC(MD)) in the MD direction and a coefficient of linear expansion (LEC(TD)) in the TD direction of less than 25 ppm / K, and a ratio of LEC(MD) to LEC(TD) of 0.8 to 1.

1. Molding conditions for molded parts Referring to Figure 1, a mold is prepared having a rectangular space of 80mm × 80mm × 3mm, and having a slit-shaped discharge hole corresponding to one side of an 80mm square of the rectangular space, and an injection hole on the perpendicular line of the side passing through the midpoint of that side. The slit-shaped discharge hole has a slit width of 1.5mm and a slit length of 78mm. An injection molding machine NEX-1000-9E manufactured by Nissei Resin Kogyo Co., Ltd. is used to discharge the resin composition and perform injection molding under the following conditions: barrel temperature: 320°C, injection pressure: molding lower limit pressure + 12.8MPa, injection time: 15 seconds, cooling time: 15 seconds. Referring to Figure 2, the direction from the side with the slit to its opposite side is designated as MD, and the direction orthogonal to MD is designated as TD. A strip-shaped test piece with a length of 10 mm, a width of 5 mm, and a thickness of 3 mm is cut out so that the centroid of the test piece is consistent with the centroid of the square. At this time, the test piece with the long side in the same direction as MD is used as the test piece for LEC(MD) measurement, and the test piece with the long side in the same direction as TD is used as the test piece for LEC(TD) measurement.

2. The polyphenylene sulfide resin composition for waveguide antennas according to claim 1, characterized in that, (B) All or part of the components are fibrous fillers with irregular cross sections.

3. The polyphenylene sulfide resin composition for waveguide antennas according to claim 1 or 2, characterized in that, Relative to 100 parts by weight of component (A), it also contains 0.1 to 12 parts by weight of elastomer.

4. A molded article for a waveguide antenna, which is formed by molding the waveguide antenna of claim 1 or 2 using a polyphenylene sulfide resin composition.

5. The waveguide antenna molded article according to claim 4, wherein the coefficient of thermal expansion, i.e., the coefficient of thermal expansion A, in the direction parallel to the surface of the molded article and oriented to component (B), and the coefficient of thermal expansion, i.e., the coefficient of thermal expansion B, in the direction parallel to the surface of the molded article and perpendicular to the direction oriented to component (B), are both 25 ppm / K or less, and the value obtained by dividing the coefficient of thermal expansion A by the coefficient of thermal expansion B is 0.8 to 1.

1.

6. A molded article for a waveguide antenna, wherein at least a portion of the surface of the molded article for a waveguide antenna according to claim 4 is formed with a metal thin film, and the arithmetic mean roughness of the portion of the surface of the molded article in which the metal thin film is formed is 10 μm or less.

7. The molded article for waveguide antenna according to claim 6, wherein the metal thin film is formed from at least one selected from silver, copper and aluminum.

8. A waveguide antenna comprising a molded article for a waveguide antenna as described in claim 4.

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