WO2022138118A1 - ポリアリーレンサルファイド樹脂組成物、成形品、及び光フェルール - Google Patents
ポリアリーレンサルファイド樹脂組成物、成形品、及び光フェルール Download PDFInfo
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- WO2022138118A1 WO2022138118A1 PCT/JP2021/044776 JP2021044776W WO2022138118A1 WO 2022138118 A1 WO2022138118 A1 WO 2022138118A1 JP 2021044776 W JP2021044776 W JP 2021044776W WO 2022138118 A1 WO2022138118 A1 WO 2022138118A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/0204—Polyarylenethioethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/0204—Polyarylenethioethers
- C08G75/0209—Polyarylenethioethers derived from monomers containing one aromatic ring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/02—Polythioethers; Polythioether-ethers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D181/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur, with or without nitrogen, oxygen, or carbon only; Coating compositions based on polysulfones; Coating compositions based on derivatives of such polymers
- C09D181/02—Polythioethers; Polythioether-ethers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J181/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur, with or without nitrogen, oxygen, or carbon only; Adhesives based on polysulfones; Adhesives based on derivatives of such polymers
- C09J181/02—Polythioethers; Polythioether-ethers
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
- G02B6/24—Coupling light guides
- G02B6/36—Mechanical coupling means
- G02B6/38—Mechanical coupling means having fibre to fibre mating means
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
- G02B6/24—Coupling light guides
- G02B6/36—Mechanical coupling means
- G02B6/38—Mechanical coupling means having fibre to fibre mating means
- G02B6/3807—Dismountable connectors, i.e. comprising plugs
- G02B6/381—Dismountable connectors, i.e. comprising plugs of the ferrule type, e.g. fibre ends embedded in ferrules, connecting a pair of fibres
Definitions
- the present invention relates to a polyarylene sulfide resin composition, a molded product, and an optical ferrule.
- Polyphenylene sulfide resin represented by polyphenylene sulfide resin has high heat resistance, mechanical properties, chemical resistance, dimensional stability, and flame retardancy. For this reason, polyarylene sulfide resins are widely used in electrical / electronic equipment component materials, automobile equipment component materials, chemical equipment component materials, and the like, and are particularly used in applications where the operating environment temperature is high.
- the use of such polyarylene sulfide resin for example, the use of forming an optical ferrule constituting a connector for an optical fiber is known.
- the molding material for optical ferrules is required to have excellent dimensional stability, mechanical properties, flame retardancy and the like.
- a polyarylene sulfide resin composition containing (B) silica is known (see Patent Document 1).
- the amount of information communicated is increasing day by day in information communication terminals used by connecting to an optical communication network. Therefore, in the optical ferrule, the number of cores, which is the number of optical fibers, is increasing in order to cope with the increase in the amount of information communication.
- the increase in the number of cores of the optical ferrule leads to insufficient strength of the optical ferrule when processing the optical ferrule or when assembling it to the adapter. Under these circumstances, the polyarylene sulfide resin composition is required to have further improvement in mechanical strength such as toughness.
- the present invention has been made in view of the above problems, and includes a polyarylene sulfide resin composition that provides a molded product having excellent toughness, and a molded product and an optical ferrule manufactured by using the polyarylene sulfide resin composition.
- the purpose is to provide.
- the present inventors have added (A) polyarylene sulfide resin having a melt viscosity of 35 to 80 Pa ⁇ s in a polyarylene sulfide resin composition containing (A) polyarylene sulfide resin and (B) silica particles. It has been found that the above-mentioned problems can be solved by using (B) silica particles having a particle diameter of 45 ⁇ m or more and a small content of coarse powder in a predetermined amount, respectively, and the present invention has been completed. More specifically, the present invention provides the following.
- a polyarylene sulfide resin composition containing (A) a polyarylene sulfide resin and (B) silica particles.
- the melt viscosity of (A) polyarylene sulfide resin measured at a temperature of 310 ° C. and a shear rate of 1200 sec -1 is 35 to 80 Pa ⁇ s
- the content of (A) polyarylene sulfide resin is the polyarylene sulfide resin composition.
- 25-40% by mass with respect to the mass of (B) silica particles include (B1) small particle size silica particles and (B2) large particle size silica particles.
- the content of (B1) small particle size silica particles is 35 to 120 parts by mass with respect to 100 parts by mass of (A) polyarylene sulfide resin.
- the content of (B2) large particle size silica particles is 100 to 240 parts by mass with respect to 100 parts by mass of (A) polyarylene sulfide resin.
- (B1) Small particle size The average particle size of the silica particles is 1 ⁇ m or less.
- B2) Large particle size The average particle size of silica particles is 2 ⁇ m or more and 10 ⁇ m or less.
- the ratio of the mass of (B) silica particles on the sieve to the total mass of (B) the sample of silica particles is 10.
- a polyarylene sulfide resin composition having a mass of ppm or less.
- the ratio of the mass of the (B1) small particle size silica particles to the total of the mass of the (B1) small particle size silica particles and the mass of the (B2) large particle size silica particles is 14 to 43% by mass.
- the polyarylene sulfide resin composition according to any one of (1) to (3).
- a molded product comprising the polyarylene sulfide resin composition according to any one of (1) to (4).
- a resin portion containing one or more optical fibers and one or more optical fibers is provided.
- An optical ferrule in which the resin portion comprises the polyarylene sulfide resin composition according to any one of (1) to (4).
- the present invention it is possible to provide a polyarylene sulfide resin composition that gives a molded product having excellent toughness, and a molded product and an optical ferrule manufactured by using the polyarylene sulfide resin composition.
- the polyarylene sulfide resin composition contains (A) a polyarylene sulfide resin and (B) silica particles.
- the melt viscosity of the polyarylene sulfide resin is 35 to 80 Pa ⁇ s. The melt viscosity is measured at a temperature of 310 ° C. and a shear rate of 1200 sec -1 .
- the content of the polyarylene sulfide resin is 25 to 40% by mass with respect to the mass of the polyarylene sulfide resin composition.
- the (B) silica particles include (B1) small particle size silica particles and (B2) large particle size silica particles.
- the content of the (B1) small particle size silica particles is 35 to 120 parts by mass with respect to 100 parts by mass of the (A) polyarylene sulfide resin.
- the content of the (B2) large particle size silica particles is 100 to 240 parts by mass with respect to 100 parts by mass of the (A) polyarylene sulfide resin.
- (B1) Small particle size The average particle size of silica particles is 1 ⁇ m or less.
- (B2) Large particle size The average particle size of silica particles is 2 ⁇ m or more and 10 ⁇ m or less.
- the ratio of the mass of (B) silica particles on the sieve to the total mass of (B) the sample of silica particles is 10.
- the mass is ppm or less.
- a polyarylene sulfide resin composition that meets the above requirements gives a molded product with excellent toughness. Therefore, it is suitably used as a material for producing an optical ferrule containing the above-mentioned polyarylene sulfide resin composition optical fiber.
- the polyarylene sulfide resin (hereinafter, also referred to as “PAS resin”) is a polymer compound mainly composed of ⁇ (Ar—S) ⁇ (where “Ar” indicates an arylene group) as a repeating unit. Is. In this embodiment, a PAS resin having a generally known molecular structure can be used.
- the arylene group is not particularly limited, and is, for example, a p-phenylene group, an m-phenylene group, an o-phenylene group, a substituted phenylene group, a p, p'-diphenylene sulphon group, a p, p'-biphenylene group, p. , P'-diphenylene ether group, p, p'-diphenylene carbonyl group, naphthalene group and the like.
- allylene sulfide groups composed of such arylene groups in addition to homopolymers using the same repeating unit, polymers containing repeating different kinds of allylene sulfide groups are preferable depending on the application.
- homopolymer a homopolymer having a p-phenylene sulfide group as a repeating unit as an arylene group is preferable.
- Homopolymers having a p-phenylene sulfide group as a repeating unit have extremely high heat resistance, and exhibit high strength, high rigidity, and high dimensional stability in a wide temperature range. By using such a homopolymer, a molded product having very excellent physical characteristics can be obtained.
- a combination of two or more allylen sulfide groups different from each other among the allylene sulfide groups including the above-mentioned allylene groups can be used.
- a combination containing a p-phenylene sulfide group and an m-phenylene sulfide group is preferable from the viewpoint that a molded product having high physical properties such as heat resistance, moldability and mechanical properties can be obtained.
- a polymer containing a p-phenylene sulfide group in a proportion of 70 mol% or more is more preferable, and a polymer containing a p-phenylene sulfide group in a proportion of 80 mol% or more is further preferable.
- the PAS resin having a phenylene sulfide group is a polyphenylene sulfide resin (hereinafter, also referred to as “PPS resin”).
- PPS resin polyphenylene sulfide resin
- a high molecular weight polymer having a substantially linear structure obtained by polycondensation from a monomer mainly composed of a bifunctional halogen aromatic compound can be particularly preferably used.
- the PAS resin used in this embodiment may be a mixture of two or more different molecular weight PAS resins.
- a small amount of a monomer such as a polyhalo aromatic compound having three or more halogen substituents was used at the time of depolymerization to partially form a branched structure or a crosslinked structure.
- the PAS resin can be produced by a conventionally known polymerization method.
- the PAS resin produced by a general polymerization method is usually washed several times with water or acetone in order to remove by-product impurities and the like. After that, it may be further washed with acetic acid, ammonium chloride or the like.
- the PAS resin has a melt viscosity of 35 to 80 Pa ⁇ s, including the case of the above-mentioned mixed system, as a melt viscosity (hereinafter, simply referred to as “melt viscosity”) measured at a temperature of 310 ° C. and a shear rate of 1200 sec -1 . show.
- melt viscosity measured at a temperature of 310 ° C. and a shear rate of 1200 sec -1 . show.
- the melt viscosity of the PAS resin after mixing may be within the above range.
- the melt viscosity of the PAS resin is preferably 40 to 75 Pa ⁇ s, preferably 45 to 70 Pa. -S is more preferable.
- the melt viscosity of the PAS resin can be adjusted by a method of adjusting the molecular weight by adjusting the polymerization conditions, a method of introducing cross-linking into the molecular chain by the use of a polyfunctional monomer, a method of thermal oxidation cross-linking, or the like. ..
- PAS resin contains two or more kinds of PAS resins
- two or more kinds of PAS resins may be mixed in advance by a method such as melt kneading before preparing the resin composition.
- two or more kinds of PAS resins may be separately mixed and homogenized together with the silica particles (B).
- the content of the PAS resin (A) is 25 to 40% by mass, preferably 26 to 38% by mass, and more preferably 27 to 35% by mass with respect to the mass of the PAS resin composition.
- the PAS resin composition contains the amount of (A) PAS resin within such a range, it is easy to obtain a PAS resin composition having desired mechanical properties and good moldability.
- the (B) silica particles include (B1) small particle size silica particles and (B2) large particle size silica particles.
- the content of the (B1) small particle size silica particles is 35 to 120 parts by mass with respect to 100 parts by mass of the (A) PAS resin.
- the content of the (B2) large particle size silica particles is 100 to 240 parts by mass with respect to 100 parts by mass of the (A) PAS resin.
- (B1) Small particle size The average particle size of silica particles is 1 ⁇ m or less.
- (B2) Large particle size The average particle size of silica particles is 2 ⁇ m or more and 10 ⁇ m or less.
- the ratio of the mass of (B) silica particles on the sieve to the total mass of (B) the sample of silica particles is 10.
- the mass is ppm or less.
- the silica particles various conventionally known silica particles can be used as long as the above requirements are satisfied.
- the silica particles are (B) on the sieve with respect to the total mass of the sample of the (B) silica particles when the sample of the (B) silica particles is sieved by a wet method with a sieve having an opening diameter of 45 ⁇ m.
- the mass ratio of the silica particles is 10 mass ppm or less, preferably 7 mass ppm or less, more preferably 5 mass ppm or less, still more preferably 3 mass ppm or less.
- silica particles include silica powder produced by a method of producing spherical silica powder by the combustion heat of the burner in a reaction vessel having a built-in burner.
- a method for producing such silica powder for example, a method for exploding metallic silicon powder, a flame hydrolysis method, a flame melting method, and the like are known.
- So-called colloidal silica produced by a wet method can also be used as (B) silica particles.
- the (B) silica particles produced by such a method inevitably contain coarse particles.
- the present inventors have examined that in the PAS resin composition containing silica particles, the coarse particles contained in the silica particles adversely affect the mechanical properties of the molded product of the PAS resin composition. The present inventors have found.
- the method for reducing the content of coarse powder having a particle size of more than 45 ⁇ m in the silica particles is not particularly limited.
- a typical method is sieving. The sieving may be performed dry or wet. Classification by air flow is also applicable as (B) a method of removing coarse powder from silica particles.
- the (B) silica particles include (B1) small particle size silica particles and (B2) large particle size silica particles.
- (B1) Small particle size The average particle size of silica particles is 1 ⁇ m or less.
- (B2) Large particle size The average particle size of silica particles is 2 ⁇ m or more and 10 ⁇ m or less.
- the (B) silica particles include (B3) other silica particles that do not fall under any of (B1) small particle size silica particles and (B2) large particle size silica particles as long as the desired effect is not impaired. You may go out.
- the total ratio of (B1) the mass of the small particle size silica particles to the mass of the (B2) large particle size silica particles is preferably 80% by mass or more, more preferably 90% by mass or more. It is preferable, 95% by mass or more is more preferable, and 100% by mass is particularly preferable. That is, it is preferable that the (B) silica particles are composed of only (B1) small particle size silica particles and (B2) large particle size silica particles.
- the average particle size of the small particle size silica particles and (B2) the average particle size of the large particle size silica particles mean a median size of 50% of the integrated value in the particle size distribution measured by the laser diffraction / scattering method.
- (B) When the sample of (B) silica particles is sieved by a wet method with a sieve having an opening diameter of 45 ⁇ m as the whole silica particles, (B) (B) on the sieve with respect to the total mass of the sample of silica particles.
- the ratio of the mass of the silica particles may be 10 mass ppm or less.
- the ratio of the mass of the coarse particles having a particle diameter of more than 45 ⁇ m was measured for the (B1) small particle size silica particles according to the above method, the (B1) small particle size silica particles on the sieve (B1) with respect to the total mass of the sample.
- the mass ratio of the small particle size silica particles may be more than 10 mass ppm, but is preferably 10 mass ppm or less, more preferably 7 mass ppm or less, still more preferably 5 mass ppm or less, and 3 mass ppm. The following are particularly preferred.
- the mass ratio of the small particle size silica particles is preferably 10 mass ppm or less, more preferably 7 mass ppm or less, further preferably 5 mass ppm or less, and particularly preferably 3 mass ppm or less.
- (B) As a method for measuring the ratio of coarse particles having a particle diameter of more than 45 ⁇ m to the mass of silica particles, more specifically, a method including the following steps 1) to 6) is preferable.
- the dispersion medium for example, an ethylene glycol aqueous solution having a concentration of 5% by mass can be used.
- the amount of the dispersion medium used is not particularly limited as long as the sample of (B) silica particles can be well dispersed in the dispersion medium.
- the container containing the (B) silica particles and the dispersion medium may be shaken or ultrasonic waves may be applied to the container.
- the ratio of the mass of the (B1) small particle size silica particles to the total of the mass of the (B1) small particle size silica particles and the mass of the (B2) large particle size silica particles is preferably 14 to 43% by mass, 16 It is more preferably from 40% by mass, still more preferably 20 to 35% by mass.
- the content of (B) silica particles in the PAS resin composition is not particularly limited as long as the content of (B1) small particle size silica particles and the content of (B2) large particle size silica particles satisfy the above conditions. ..
- the content of (B) silica particles is preferably 150 to 300 parts by mass with respect to 100 parts by mass of (A) PAS resin, and 170 to 290. Parts by mass are more preferable, and parts by mass of 200 to 270 are even more preferable.
- the PAS resin composition contains (B) an inorganic filler other than silica particles, an organic filler, a flame retardant, and promotion of crystallization in order to impart desired physical properties to the extent that the desired effect is not impaired. Toughness of agents, crystal nucleating agents, various antioxidants, ultraviolet absorbers, heat stabilizers, light stabilizers, weathering stabilizers, corrosion inhibitors, colorants such as dyes and pigments, carbon black, silane coupling agents, etc. It may contain additives such as improvers, mold release agents, lubricants and plasticizers.
- the PAS resin composition is (B) an inorganic filler other than silica particles and an organic filler. It is preferable that it does not contain an agent.
- the method for producing the PAS resin composition is not particularly limited as long as the components in the resin composition can be uniformly mixed, and can be appropriately selected from the conventionally known methods for producing the resin composition.
- a method in which each component is melt-kneaded and extruded using a melt-kneading device such as a single-screw or twin-screw extruder, and then the obtained resin composition is processed into a desired form such as powder, flakes, and pellets. can be mentioned.
- the molded product is made of the above-mentioned PAS resin composition.
- the molded product is produced by using a known molding method such as injection molding or extrusion molding for the above PAS resin composition.
- the optical ferrule includes one or more optical fibers and a resin portion containing the above-mentioned one or more optical fibers, and the resin portion is made of the above-mentioned PAS resin composition.
- the resin portion in such an optical ferrule there may be a thin portion having a thickness of about several hundred ⁇ m at a position such as between optical fibers.
- the PAS resin composition described above provides a molded product having excellent mechanical properties such as tensile fracture strain.
- the PAS resin composition also has excellent fluidity. Therefore, by molding the above-mentioned resin portion using the above-mentioned PAS resin composition, it is possible to manufacture an optical ferrule having excellent dimensional accuracy and strength.
- the shape and size of the optical ferrule are not particularly limited.
- the size of a general optical ferrule is 3 mm ⁇ 7 mm ⁇ 8 mm.
- the optical ferrule is typically produced by using an optical fiber as an insert material and insert molding using the PAS resin composition described above. Normally, when forming an optical ferrule in this way, after polishing the end face where the optical fiber is exposed, the two optical ferrules are pressed and assembled so that the fibers come into contact with each other.
- 4 to 12 cores have been conventionally stored on a 3 mm ⁇ 7 mm surface, but the number of optical ferrules has increased, and recently, the number of cores has increased to 24 cores or more.
- the strength of the optical ferrule becomes weaker. Therefore, particularly for an optical ferrule having a large number of cores, a resin material having higher toughness is required in order to avoid damage during assembly. Since the above-mentioned PAS resin composition has excellent toughness, even a multi-core optical ferrule can be satisfactorily processed and assembled to an adapter.
- PAS resin> PPS resin, Fortron KPS (manufactured by Kureha Corporation, melt viscosity 20 Pa ⁇ s (shear rate 1200 sec -1 , 310 ° C))
- A2 PPS resin, Fortron KPS (manufactured by Kureha Corporation, melt viscosity 30 Pa ⁇ s (shear rate 1200 sec -1 , 310 ° C))
- A3 PPS resin, Fortron KPS (manufactured by Kureha Corporation, melt viscosity 130 Pa ⁇ s (shear rate 1200 sec -1 , 310 ° C)) (Measurement of melt viscosity of PPS resin) Using a capillograph manufactured by Toyo Seiki Seisakusho, the melt viscosity was measured at a barrel temperature of 310 ° C. and a shear rate of 1200 sec -1 . A flat die of 1 mm ⁇ ⁇ 20 mmL was
- Silane coupling agent alkoxysilane compound: manufactured by Shin-Etsu Chemical Co., Ltd., KBE-903P
- the tensile fracture strain was measured and the melt viscosity was measured according to the following method. The results of these measurements are shown in Table 1. Regarding the melt viscosity, 600 Pa ⁇ s or less was judged to be ⁇ , and more than 600 Pa ⁇ s was judged to be ⁇ .
- ⁇ Measurement of tensile fracture strain > Using the above pellets, a test piece (width 10 mm, thickness 4 mmt) conforming to ISO3167 was produced by injection molding at a cylinder temperature of 320 ° C. and a mold temperature of 150 ° C. Using this test piece, the tensile fracture strain (%) was measured according to ISO527-1 and ISO. When the value of the tensile fracture strain was 0.8% or more, it was judged as ⁇ , and when it was less than 0.8%, it was judged as ⁇ .
- ⁇ Fluidity Melt viscosity (Pa ⁇ s)> Using a capillograph manufactured by Toyo Seiki Seisakusho, the melt viscosity was measured at a barrel temperature of 310 ° C. and a shear rate of 1000 sec -1 . A flat die of 1 mm ⁇ ⁇ 20 mmL was used as a capillary.
- PAS resin having a melt viscosity of 35 to 80 Pa ⁇ s, (B1) small particle size silica particles having an average particle size of 1 ⁇ m or less, and an average particle size of 2 ⁇ m.
- the resin has both excellent tensile fracture strain and excellent fluidity. Therefore, it can be seen that the PAS resin composition of the present embodiment is suitable for the PAS resin composition used for molding the optical ferrule.
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Abstract
Description
光フェルールの多芯化は、光フェルールを加工する際やアダプタに組み付ける際の、光フェルールの強度不足を招く。このような事情から、ポリアリーレンサルファイド樹脂組成物について、靭性のような機械的強度のさらなる向上が求められている。
(A)ポリアリーレンサルファイド樹脂の、温度310℃及びせん断速度1200sec-1で測定した溶融粘度が35~80Pa・sであり、(A)ポリアリーレンサルファイド樹脂の含有量が、ポリアリーレンサルファイド樹脂組成物の質量に対して25~40質量%であり、
(B)シリカ粒子が、(B1)小粒子径シリカ粒子と、(B2)大粒子径シリカ粒子とを含み、
(B1)小粒子径シリカ粒子の含有量が、(A)ポリアリーレンサルファイド樹脂100質量部に対して、35~120質量部であり、
(B2)大粒子径シリカ粒子の含有量が、(A)ポリアリーレンサルファイド樹脂100質量部に対して、100~240質量部であり、
(B1)小粒子径シリカ粒子の平均粒子径が、1μm以下であり、
(B2)大粒子径シリカ粒子の平均粒子径が、2μm以上10μm以下であり、
開口径45μmの篩で、湿式法で(B)シリカ粒子の試料を篩分した場合に、(B)シリカ粒子の試料の全質量に対する、篩上の(B)シリカ粒子の質量の比率が10質量ppm以下である、ポリアリーレンサルファイド樹脂組成物。
樹脂部が、(1)~(4)のいずれか1つに記載のポリアリーレンサルファイド樹脂組成物からなる光フェルール。
ポリアリーレンサルファイド樹脂組成物は、(A)ポリアリーレンサルファイド樹脂と、(B)シリカ粒子とを含む。
(A)ポリアリーレンサルファイド樹脂の溶融粘度は、35~80Pa・sである。溶融粘度は、温度310℃及びせん断速度1200sec-1で測定される。
(A)ポリアリーレンサルファイド樹脂の含有量は、ポリアリーレンサルファイド樹脂組成物の質量に対して25~40質量%である。
(B)シリカ粒子は、(B1)小粒子径シリカ粒子と、(B2)大粒子径シリカ粒子とを含む。
(B1)小粒子径シリカ粒子の含有量は、(A)ポリアリーレンサルファイド樹脂100質量部に対して、35~120質量部である。
(B2)大粒子径シリカ粒子の含有量は、(A)ポリアリーレンサルファイド樹脂100質量部に対して、100~240質量部である。
(B1)小粒子径シリカ粒子の平均粒子径は、1μm以下である。
(B2)大粒子径シリカ粒子の平均粒子径は、2μm以上10μm以下である。
開口径45μmの篩で、湿式法で(B)シリカ粒子の試料を篩分した場合に、(B)シリカ粒子の試料の全質量に対する、篩上の(B)シリカ粒子の質量の比率が10質量ppm以下である。
(A)ポリアリーレンサルファイド樹脂(以下、「PAS樹脂」とも記す)は、繰り返し単位として、-(Ar-S)-(なお、「Ar」はアリーレン基を示す)を主として構成された高分子化合物である。本実施形態では一般的に知られている分子構造のPAS樹脂を使用することができる。
これらのPAS樹脂の中では、2官能性ハロゲン芳香族化合物を主体とするモノマーから縮重合によって得られる実質的に直鎖状構造の高分子量ポリマーが、特に好ましく使用できる。本実施形態に用いるPAS樹脂は、異なる2種類以上の分子量のPAS樹脂を混合して用いてもよい。
直鎖状構造のPAS樹脂以外にも、縮重合させるときに、3個以上のハロゲン置換基を有するポリハロ芳香族化合物等のモノマーを少量用いて、部分的に分岐構造又は架橋構造を形成させたポリマーや、低分子量の直鎖状構造ポリマーを酸素等の存在下、高温で加熱して酸化架橋又は熱架橋により溶融粘度を上昇させ、成形加工性を改良したポリマーも挙げられる。
(A)PAS樹脂の引張破壊ひずみの高さと、PAS樹脂組成物の優れた流動性との両立の点から、(A)PAS樹脂の溶融粘度は、40~75Pa・sが好ましく、45~70Pa・sがより好ましい。
(A)PAS樹脂の溶融粘度は、重合条件を調整することによって分子量を調整する方法や、多官能モノマーの使用や熱酸化架橋等の方法によって分子鎖に架橋を導入する方法等により調整しうる。
PAS樹脂組成物が、かかる範囲内の量の(A)PAS樹脂を含むことにより、所望する機械的特性と良好な成形性とを兼ね備える、PAS樹脂組成物を得やすい。
(B)シリカ粒子は、(B1)小粒子径シリカ粒子と、(B2)大粒子径シリカ粒子とを含む。
(B1)小粒子径シリカ粒子の含有量は、(A)PAS樹脂100質量部に対して、35~120質量部である。
(B2)大粒子径シリカ粒子の含有量は、(A)PAS樹脂100質量部に対して、100~240質量部である。
(B1)小粒子径シリカ粒子の平均粒子径は、1μm以下である。
(B2)大粒子径シリカ粒子の平均粒子径は、2μm以上10μm以下である。
開口径45μmの篩で、湿式法で(B)シリカ粒子の試料を篩分した場合に、(B)シリカ粒子の試料の全質量に対する、篩上の(B)シリカ粒子の質量の比率が10質量ppm以下である。
湿式法で製造された所謂コロイダルシリカを(B)シリカ粒子として用いることもできる。
(B)シリカ粒子の質量に対する、(B1)小粒子径シリカ粒子の質量と、(B2)大粒子径シリカ粒子の質量との合計の比率は、80質量以上が好ましく、90質量%以上がより好ましく、95質量%以上がさらに好ましく、100質量%が特に好ましい。
つまり、(B)シリカ粒子は、(B1)小粒子径シリカ粒子、及び(B2)大粒子径シリカ粒子のみからなるのが好ましい。
(B1)小粒子径シリカ粒子について、上記の方法に従って、粒子径45μm超の粗大粒子の質量の比率を測定した場合、(B1)小粒子径シリカ粒子の試料の全質量に対する、篩上の(B1)小粒子径シリカ粒子の質量の比率は、10質量ppm超であってもよいが、10質量ppm以下が好ましく、7質量ppm以下がより好ましく、5質量ppm以下がさらに好ましく、3質量ppm以下が特に好ましい。
(B2)大粒子径シリカ粒子について、上記の方法に従って、粒子径45μm超の粗大粒子の質量の比率を測定した場合、(B2)大粒子径シリカ粒子の試料の全質量に対する、篩上の(B2)小粒子径シリカ粒子の質量の比率は、10質量ppm以下が好ましく、7質量ppm以下がより好ましく、5質量ppm以下がさらに好ましく、3質量ppm以下が特に好ましい。
分散媒としては、例えば、濃度5質量%のエチレングリコール水溶液を用いることができる。
分散媒の使用量は、(B)シリカ粒子の試料を分散媒中に良好に分散させることができる限り特に限定されない。分散媒中に(B)シリカ粒子を分散させる際には、(B)シリカ粒子と分散媒とが入った容器を振盪したり、容器に超音波を印加したりすればよい。
1)(B)シリカ粒子の試料100gを秤量する。
2)容器中で、(B)シリカ粒子の試料100gを分散媒中に分散させる。
3)分散媒中に分散された(B)シリカ粒子の試料100gを、開口径45μmの篩上に注ぐ。
4)篩に対して超音波を印加し、シリカ粒子の凝集体をほぐしつつ、粒子径45μm以下のシリカ粒子を、篩を通過させる。
5)粒子径45μm超の粗大なシリカ粒子が付着した状態の篩を乾燥器内で乾燥させる。
6)乾燥された篩に付着する、粗大なシリカ粒子の質量W(g)を測定する。
上記の方法で測定されたWの値を用いて、(B)シリカ粒子の質量に対する、粒子径45μm超の粗大粒子の比率である粗大粒子比率(質量ppm)が下記式により算出される。
粗大粒子比率(質量ppm)=W/100×1000000
PAS樹脂組成物は、上記成分の他に、所望する効果を阻害しない範囲で、所望の物性付与のために、(B)シリカ粒子以外の無機充填剤、有機充填剤、難燃剤、結晶化促進剤、結晶核剤、各種酸化防止剤、紫外線吸収剤、熱安定剤、光安定剤、耐候性安定剤、腐食防止剤、染料や顔料等の着色剤、カーボンブラック、シランカップリング剤等の靭性改良剤、離型剤、潤滑剤、可塑剤等の添加剤を含んでいてもよい。
PAS樹脂組成物の精密成形性や、PAS樹脂組成物からなる成形品の機械的特性や異方性の点で、PAS樹脂組成物は、(B)シリカ粒子以外の無機充填剤、及び有機充填剤を含まないのが好ましい。
PAS樹脂組成物の製造方法は、この樹脂組成物中の成分を均一に混合できる方法であれば特に限定されず、従来知られる樹脂組成物の製造方法から適宜選択することができる。例えば、1軸又は2軸押出機等の溶融混練装置を用いて、各成分を溶融混練して押出した後、得られた樹脂組成物を粉末、フレーク、ペレット等の所望の形態に加工する方法が挙げられる。
成形品は、上記のPAS樹脂組成物からなる。成形品は、上記のPAS樹脂組成物を、射出成形、押出成形等の公知の成形方法により製造される。
光フェルールは、1以上の光ファイバーと、前述の1以上の光ファイバーを内包する樹脂部とを備え、樹脂部が前述のPAS樹脂組成物からなる。
このような光フェルールにおける樹脂部では、光ファイバー間等の位置に厚さ数百μm程度の薄肉部がある場合がある。しかし、前述のPAS樹脂組成物は、引張破壊ひずみのような機械的特性に優れる成形品を与える。また、PAS樹脂組成物は、優れた流動性も兼ね備えている。このため、前述のPAS樹脂組成物を用いて上記の樹脂部を成形することにより、寸法精度、及び強度に優れる光フェルールを製造できる。
光フェルールの形状やサイズは特に限定されない。一般的な光フェルールのサイズは、3mm×7mm×8mmである。
光フェルールは、典型的には、光ファイバーをインサート材とし、前述のPAS樹脂組成物を用いてインサート成形することにより製造される。通常、このようにして光フェルールを形成する際には、光ファイバーが露出する端面を研磨したうえで、ファイバー同士が接触するように2つの光フェルールが、押し付けられて組み付けられる。
従来、光フェルールでは、3mm×7mmの面に従来4~12芯が収められていたところ、光フェルールの多芯化が進み、最近では、24芯やそれ以上に芯数が増加している。一般的に光ファイバーの芯数が増加すると光フェルールの強度は弱くなるため、特に芯数の多い光フェルールでは組付け時の破損を避けるため、より高靭性の樹脂材料が求められる。前述のPAS樹脂組成物は靭性に優れるため、多芯化された光フェルールであっても、良好に加工やアダプタへの組み付けができる。
実施例及び比較例ではPAS樹脂組成物の材料として、以下の材料を用いた。
A1:PPS樹脂、フォートロンKPS((株)クレハ製、溶融粘度20Pa・s(せん断速度1200sec-1、310℃))
A2:PPS樹脂、フォートロンKPS((株)クレハ製、溶融粘度30Pa・s(せん断速度1200sec-1、310℃))
A3:PPS樹脂、フォートロンKPS((株)クレハ製、溶融粘度130Pa・s(せん断速度1200sec-1、310℃))
(PPS樹脂の溶融粘度の測定)
東洋精機製作所製キャピログラフを用い、バレル温度310℃、せん断速度1200sec-1での溶融粘度を測定した。キャピラリーとして1mmφ×20mmLのフラットダイを使用した。結果を表1に示す。
小粒子径シリカB1(平均粒子径0.5μm、45μ超の粗粉含有率0質量ppm、(株)アドマテックス製、アドマファインSC2500-SQ)
小粒子径シリカB1’(平均粒子径0.5μm、45μ超の粗粉含有率100質量ppm、(株)アドマテックス製、アドマファインSO-C2)
大粒子径シリカB2(平均粒子径4.2μm、45μ超の粗粉含有率0質量ppm、デンカ(株)製、FB-5SDC)
シランカップリング剤(アルコキシシラン化合物:信越化学工業(株)製、KBE-903P)
上記ペレットを用いて、射出成形により、シリンダー温度320℃、金型温度150℃で、ISO3167に準じた試験片(幅10mm、厚み4mmt)を作製した。この試験片を用い、ISO527-1,2に準じて引張破壊ひずみ(%)を測定した。
引張破壊ひずみの値が0.8%以上である場合を○と判定し、0.8%未満である場合を×と判定した。
<流動性:溶融粘度(Pa・s)>
東洋精機製作所製キャピログラフを用い、バレル温度310℃、せん断速度1000sec-1での溶融粘度を測定した。キャピラリーとして1mmφ×20mmLのフラットダイを使用した。
Claims (6)
- (A)ポリアリーレンサルファイド樹脂と、(B)シリカ粒子とを含むポリアリーレンサルファイド樹脂組成物であって、
前記(A)ポリアリーレンサルファイド樹脂の、温度310℃及びせん断速度1200sec-1で測定した溶融粘度が35~80Pa・sであり、
前記(A)ポリアリーレンサルファイド樹脂の含有量が、前記ポリアリーレンサルファイド樹脂組成物の質量に対して25~40質量%であり、
前記(B)シリカ粒子が、(B1)小粒子径シリカ粒子と、(B2)大粒子径シリカ粒子とを含み、
前記(B1)小粒子径シリカ粒子の含有量が、前記(A)ポリアリーレンサルファイド樹脂100質量部に対して、35~120質量部であり、
前記(B2)大粒子径シリカ粒子の含有量が、前記(A)ポリアリーレンサルファイド樹脂100質量部に対して、100~240質量部であり、
前記(B1)小粒子径シリカ粒子の平均粒子径が、1μm以下であり、
前記(B2)大粒子径シリカ粒子の平均粒子径が、2μm以上10μm以下であり、
開口径45μmの篩で、湿式法で前記(B)シリカ粒子の試料を篩分した場合に、前記(B)シリカ粒子の試料の全質量に対する、篩上の前記(B)シリカ粒子の質量の比率が10質量ppm以下である、ポリアリーレンサルファイド樹脂組成物。 - 前記(B)シリカ粒子が、前記(B1)小粒子径シリカ粒子、及び前記(B2)大粒子径シリカ粒子のみからなる、請求項1に記載のポリアリーレンサルファイド樹脂組成物。
- 前記(B)シリカ粒子の含有量が、前記(A)ポリアリーレンサルファイド樹脂100質量部に対して150~300質量部である、請求項1又は2に記載のポリアリーレンサルファイド樹脂組成物。
- 前記(B1)小粒子径シリカ粒子の質量と、前記(B2)大粒子径シリカ粒子の質量との合計に対する、前記(B1)小粒子径シリカ粒子の質量の比率が、14~43質量%である、請求項1~3のいずれか1項に記載のポリアリーレンサルファイド樹脂組成物。
- 請求項1~4のいずれか1項に記載の前記ポリアリーレンサルファイド樹脂組成物からなる成形品。
- 1以上の光ファイバーと、1以上の前記光ファイバーを内包する樹脂部とを備え、
前記樹脂部が、請求項1~4のいずれか1項に記載のポリアリーレンサルファイド樹脂組成物からなる光フェルール。
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| JP2000204252A (ja) * | 1999-01-14 | 2000-07-25 | Idemitsu Petrochem Co Ltd | ポリアリ―レンスルフィド樹脂組成物 |
| JP2000273304A (ja) * | 1999-03-23 | 2000-10-03 | Idemitsu Petrochem Co Ltd | 光通信部品用ポリアリーレンスルフィド樹脂組成物 |
| JP2017500404A (ja) * | 2013-08-27 | 2017-01-05 | ティコナ・エルエルシー | 射出成形用の耐熱性強化熱可塑性組成物 |
| JP2019183156A (ja) * | 2018-04-12 | 2019-10-24 | ポリプラスチックス株式会社 | ポリアリーレンサルファイド樹脂組成物及びインサート成形品 |
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| Publication number | Publication date |
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| US11932730B2 (en) | 2024-03-19 |
| US20240043620A1 (en) | 2024-02-08 |
| CN116601222A (zh) | 2023-08-15 |
| CN116601222B (zh) | 2023-12-01 |
| JP7096454B1 (ja) | 2022-07-05 |
| JPWO2022138118A1 (ja) | 2022-06-30 |
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