WO2005037924A1 - 樹脂成形金属腐食防止剤、金属腐食防止性樹脂組成物及び樹脂成形金型腐食防止方法 - Google Patents
樹脂成形金属腐食防止剤、金属腐食防止性樹脂組成物及び樹脂成形金型腐食防止方法 Download PDFInfo
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- WO2005037924A1 WO2005037924A1 PCT/JP2004/015957 JP2004015957W WO2005037924A1 WO 2005037924 A1 WO2005037924 A1 WO 2005037924A1 JP 2004015957 W JP2004015957 W JP 2004015957W WO 2005037924 A1 WO2005037924 A1 WO 2005037924A1
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- Prior art keywords
- resin
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- corrosion
- weight
- molding
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/70—Maintenance
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
Definitions
- the present invention relates to a resin-molded metal corrosion inhibitor comprising an aminoalkoxysilane compound, particularly an aminoalkoxysilane compound and a zinc compound such as zinc oxide, a metal-corrosion-inhibiting resin composition containing the same, and a resin-molding mold corrosion inhibitor.
- a resin-molded metal corrosion inhibitor comprising an aminoalkoxysilane compound, particularly an aminoalkoxysilane compound and a zinc compound such as zinc oxide, a metal-corrosion-inhibiting resin composition containing the same, and a resin-molding mold corrosion inhibitor.
- Japanese Patent Application Laid-Open No. H11-105505 (Claims 1 to 5, see paragraph [0000]) states that PPS generates a metal corrosive gas depending on the resin structure and manufacturing raw materials. Therefore, a technique is disclosed in which zinc oxide wiping power or phosphoric acid, or hypophosphorous acid, or a salt thereof is blended to trap metal corrosive gas.
- Japanese Patent Application Laid-Open No. H11-158820 (Claim 5, Paragraph Nos. 0 13] is selected from vinylalkoxysilane, epoxyalkoxysilane, aminoalkoxysilane and mercaptoalkoxysilane
- a method for producing a polyphenylene sulfide resin by melt-kneading a polyphenylene sulfide resin having a branched structure and a linear polyphenylene sulfide resin together with at least one silane compound.
- the above technology aims to increase the melt viscosity so as not to generate burrs, and does not teach anything about metal corrosion prevention.
- An object of the present invention is to provide a corrosion inhibitor for resin-molded metal, a metal corrosion-inhibiting resin composition containing the same, and a method for preventing corrosion of a resin molding die using the same. Disclosure of the invention
- the present inventors have found that by adding an aminoalkoxysilane compound, particularly an aminoalkoxysilane compound and a zinc compound such as zinc oxide, to a resin, it is possible to prevent corrosion of a formed metal and the like, thereby completing the present invention. Reached.
- the first aspect of the present invention provides a resin molded metal corrosion inhibitor comprising an aminoalkoxysilane compound.
- a second aspect of the present invention is the second aspect of the present invention, which further comprises 400 parts by weight or less of a zinc compound selected from the group consisting of zinc oxide, zinc carbonate, and a mixture thereof based on 100 parts by weight of the aminoalkoxysilane compound.
- a third aspect of the present invention is that the aminoalkoxysilane compound is selected from the group consisting of aminopropyltrimethoxysilane, aminopropyltriethoxysilane, ⁇ - (2-aminoethyl) aminopropyltriethoxysilane, and a mixture thereof. 3.
- the resin molded metal corrosion inhibitor according to the first or second aspect of the present invention is selected from the group consisting of aminopropyltrimethoxysilane, aminopropyltriethoxysilane, ⁇ - (2-aminoethyl) aminopropyltriethoxysilane, and a mixture thereof.
- a fourth aspect of the present invention is that the resin molding metal comprises a resin molding die, a resin injection molding machine, a resin extrusion molding machine, an insert molding metal, an outsert molding metal, a hoop molding metal, a resin plating metal, and a resin vapor deposition metal.
- the present invention provides a resin-molded metal corrosion inhibitor according to any one of the first to third aspects of the present invention, which is at least one member selected from the group.
- a fifth aspect of the present invention is that a metal corrosive resin (100 parts by weight) and an aminoalkoxysilane compound
- the present invention provides a metal corrosion-inhibiting resin composition comprising 0.2 to 2.0 parts by weight.
- a sixth aspect of the present invention is directed to the sixth aspect of the present invention, which further comprises 400 parts by weight or less of a zinc compound selected from the group consisting of zinc oxide, zinc carbonate and a mixture thereof with respect to 100 parts by weight of the aminoalkoxysilane compound. 5.
- a seventh aspect of the present invention is the metal corrosion inhibitor according to the fifth or sixth aspect of the present invention, wherein the metal corrosive resin is a polyphenylene sulfide, a polysulfone, a mixture thereof, or an alloy thereof with another resin.
- a resin composition is provided.
- An eighth aspect of the present invention provides the metal corrosion inhibiting resin composition according to the fifth or sixth aspect of the present invention, wherein the metal corrosive resin contains a metal corrosive resin additive.
- a ninth aspect of the present invention is that when molding using a mold, zinc oxide and zinc carbonate are used with respect to 100 parts by weight of the aminoalkoxysilane compound and, if necessary, 100 parts by weight of the aminoalkoxysilane compound. And a method for preventing corrosion of resin molding dies by adding not more than 400 parts by weight of a zinc compound selected from the group consisting of these mixtures. According to the present invention, when molding a metal-corrosive resin such as a PPS resin, corrosion of a metal such as a molding die can be suppressed.
- aminoalkoxysilane compound according to the present invention examples include, for example, aminopropyltrimethoxysilane, aminopropyltriethoxysilane, aminopropylpyrmethyldimethoxysilane, aminopropylmethylethoxysilane, N- ( ] 3-Aminoethyl) 1-aminopropyltrimethoxysilane, N- (3-aminoethyl) 1-aminopropylmethyldimethoxysilane, N-phenyl Monoaminopropyltrimethoxysilane and the like.
- aminoalkoxysilane compounds can be used alone or in combination of two or more.
- alkoxysilane compounds may be used alone, but a polymer corresponding to a structure obtained by polymerizing the above simple substances, a copolymer corresponding to a structure obtained by copolymerizing two or more kinds, or an oligomer thereof is also used in advance. can do.
- the compounding ratio of the aminoalkoxysilane compound is 0.2 to 2.0 parts by weight, preferably 0.3 to 1.5 parts by weight, more preferably 0 to 100 parts by weight of the resin. It is 5 to 1.2 parts by weight.
- the aminoalkoxysilane compound may contain, as necessary, 400 parts by weight or less of a zinc compound, preferably 20 to 200 parts by weight, more preferably 3 to 100 parts by weight of the aminoalkoxysilane compound. 0 to 150 parts by weight can be blended.
- Examples of the zinc compound according to the present invention include zinc oxide, zinc oxynitride Zn 2 ⁇ which is a solid solution of Zn and Z ⁇ , zinc carbonate, zinc hydroxycarbonate (including sian ore), and zinc hydroxide. Double salts and the like, and mixtures thereof. Preferably, it is zinc oxide, zinc carbonate or a mixture thereof.
- the form of the zinc compound is not particularly limited, and powdery, acicular, whisker, and the like can be used, and acicular or whisker force can be preferably used.
- Zinc oxide whiskers have an average fiber diameter (short The diameter is preferably from 0.1 to 5 m, the average fiber length (major diameter) is from 2 to 100 / im, and the average aspect ratio is preferably 5 or more.
- zinc oxide having a three-dimensional tetrapot shape is one of the compounds suitable as whiskers having the above-mentioned shape, but is not limited thereto.
- any silane compound having at least one epoxy group in one molecule and having two or three alkoxy groups is effective. Examples include silane and benzylicidoxypropyltriethoxysilane.
- the resin-molded metal corrosion inhibitor according to the present invention is effective for a resin or a resin composition that generates a metal corrosive substance.
- a halogen compound such as halogen, a halogen atom, a halogen ion, a halide ion or hydrogen halide (where octogen is fluorine, chlorine or bromine ), Sulfur, hydrogen sulfide, sulfur oxides, sulfur oxide ions, and mixtures thereof.
- the resin that generates such a corrosion-causing substance include a polymer that is polymerized by dechlorinated sodium or a hapten-containing polymer.
- Polymers that are polymerized by sodium chloride removal include polyphenylene sulfide (PAS) such as polyphenylene sulfide (PPS), and polysulfone.
- PAS polyphenylene sulfide
- PPS polyphenylene sulfide
- PES polyphenylene sulfone
- polyester resin such as polyethersulfone (PTES); interfacial polymerization polycarbonate; interfacial polymerization polyarylate.
- PAS may be any type such as a cross-linked type, a linear type, and a high toughness cross-linked type, and there is no particular limitation on the molecular weight, melting point, and the like.
- PAS is a repeating unit — (Ar—S) — (where Ar is an arylene group)
- Ar is an arylene group
- the arylene group include p-phenylene group, m-phenylene group, o-phenylene group, substituted phenylene group, ⁇ , ⁇ ′-diphenylene sulfone group, p. ⁇ ′— Biphenylene group, ⁇ ' ⁇ '-diphenyleneether group, ⁇ , -diphenylenecarbonyl group, naphthalene group and the like can be used.
- a heterogeneous repeating unit in view of processability of the composition.
- a homopolymer those having a ⁇ -phenylene sulfide group as a repeating unit using a ⁇ -phenylene group as an arylene group are particularly preferably used.
- the copolymer two or more different combinations of arylene sulfide groups comprising the above-mentioned arylene group can be used.
- ⁇ -phenylene sulfide group and m A combination containing a phenylene sulfide group is particularly preferably used.
- those containing a p-phenylene sulfide group in an amount of 70 mol% or more, preferably 80 mol% or more are suitable in terms of physical properties such as heat resistance, moldability, and mechanical properties.
- PASs a high molecular weight polymer having a substantially linear structure obtained by condensation polymerization from a monomer mainly composed of a bifunctional halogen aromatic compound can be particularly preferably used.
- PAS having a structure
- a polymer in which a partially branched or cross-linked structure is formed by using a small amount of a monomer such as a polyhalo aromatic compound having three or more halogen substituents during condensation polymerization A polymer in which a low molecular weight linear polymer is heated at a high temperature in the presence of oxygen or an oxidizing agent to increase the melt viscosity by oxidative crosslinking or thermal crosslinking to improve moldability can also be used. .
- the PAS is mainly composed of a linear PAS (viscosity at 310 ° C., shear rate 1200 / sec of 10 to 300 Pa ⁇ s), and a part thereof (1 to 30% by weight, preferably 2 to 25% by weight).
- a linear PAS viscosity at 310 ° C., shear rate 1200 / sec of 10 to 300 Pa ⁇ s
- mixed systems with branched or crosslinked PAS having a relatively high viscosity 300 to 3000 Pa ⁇ s, preferably 500 to 2000 Pa's
- the PAS used in the present invention is subjected to deionization treatment such as acid washing, hot water washing, and organic solvent washing (or a combination thereof) after polymerization to remove and purify by-product impurities and the like, thereby obtaining an alkali metal.
- deionization treatment such as acid washing, hot water washing, and organic solvent washing (or a combination thereof) after polymerization to remove and purify by-product impurities and the like,
- the resin may be a mixture alloy or the like.
- examples of the PAS alloy include other resins such as polyolefin, fluororesin, nylon-based, polyetherimide, cyclic olefin-based resin, and polyphenylene ether.
- the mold corrosion-causing substances include halogen-based resin additives such as flame retardants (where halogen is fluorine, chlorine or bromine), cationic antistatic agents, fillers, and other additives. , And a mixture thereof.
- halogen-based resin additives such as flame retardants (where halogen is fluorine, chlorine or bromine), cationic antistatic agents, fillers, and other additives. , And a mixture thereof.
- the resin molding die corrosion inhibitor according to the present invention also has an effect on such a resin composition containing a die corrosion-causing substance.
- the metal corrosion inhibiting resin composition according to the present invention is obtained by mixing an aminoalkoxysilane compound or an aminoalkoxysilane compound and a zinc compound with the above metal corrosive substance generating resin or resin composition.
- the metal corrosion inhibiting resin composition is, for example, premixed with a resin, an aminoalkoxysilane compound, and a zinc compound added as required, melt-kneaded, extruded into a strand, and pelletized. Melt kneading conditions are selected according to the type of resin and the like.
- the melt-kneading temperature is 290 to 350 ° (: preferably 310 to 330 ° C
- the melt-kneading time is the kneading temperature, the molten resin. It takes 0.5 to 3.0 minutes, depending on the shearing force experienced.
- melt kneader a single-screw or multi-screw extruder, kneader, mixer or the like is used.
- the resin composition for preventing corrosion of a mold according to the present invention may contain a resin additive or the like.
- the resin additives used in the present invention include a plasticizer, a heat stabilizer, a lubricant, an antiblocking agent, a crystallization nucleating agent, a photodegradation accelerator, a biodegradation accelerator, an autoxidizer, an antioxidant, and an ultraviolet light stabilizer.
- fillers glass fiber, carbon fiber, boron fiber, silicon carbide fiber, alumina fiber, amorphous fiber, silicon 'titanium' carbon fiber; polyethylene fiber, polypropylene fiber, polyester fiber, polyamide fiber, fluorine fiber; Titanate power, silicon carbide whisker, graphite whisker, silicon nitride whisker, alumina boron monoxide power; light carbon dioxide, heavy or finely divided calcium carbonate, special carbon filler, etc.
- Calcium powder nepheline syenite fine powder; clay such as montmorillonite and bentonite; calcined clay and silane-modified clay (aluminum silicate powder); talc; fused silica and silica such as crystalline silica (silicon dioxide) ) Powder; Natural minerals such as pumice powder, slate powder, mai power, mica powder, and asbestos, and pulverized products; alumina-containing compounds such as alumina, alumina colloid (alumina sol), alumina white, and aluminum sulfate; Minerals such as barium sulfate, lithobon, calcium sulfate, molybdenum disulfide, and graphite (graphite); glass-based fillers such as glass beads, glass flakes and foamed glass beads; fly ash spheres, volcanic glass hollow bodies, pumice balms 1, synthetic hollow inorganic bodies, hollow carbon spheres; anthracite powder, artificial cryolite (cryolite
- the blending amount of the filler with respect to 100 parts by weight of the resin is 400 parts by weight or less, preferably 0 to 250 parts by weight.
- the pellets thus obtained can be molded by a generally known thermoplastic resin molding method such as injection molding, extrusion molding, vacuum molding, compression molding, etc., but injection molding is most preferred.
- fuzzy steel SC system, SCM system
- pre-hardened steel SC system, SCM system, SUS system, SKD system
- Quenched and tempered steel SUS, SKD
- aging steel maraging steel, non-magnetic steel, SKD
- non-ferrous metals such as aluminum and ZAS.
- the metal surface may be subjected to a surface treatment such as Cr plating or Ni plating to have an effect of preventing burning, corrosion, and peeling.
- SCM440 is used as a material for an extruder
- SKD-11 or SKD-11 is used as a mold material. If the generation of corrosive gas is a problem, SUS prehardened steel aging steel is preferably used.
- metal used in the insert or artsert molding or the hoop molding examples include iron, copper, aluminum, gold, silver, tin, chromium, nickel, titanium, and various alloys.
- nuts, knurls, splines, chassis, steel strips, foils, etc. may be mentioned.
- Metals used for plating, vapor deposition, film formation, etc. include aluminum, copper, zinc, tin, silver, chromium, lead, gold, platinum, titanium, etc .; alloys or metals such as nickel-chromium, cobalt-nickel, IT0 Examples include oxide conductive materials and M0 semiconductors.
- Resin 1-1 Polyphenylene sulfide resin (Nippon Kagaku Kogyo Co., Ltd., Phototron KPS, linear type, melt viscosity 30 Pa's (310 ° C, shear rate 1200 / se C))
- Resin 1-2 Polysulfone (Solvay Advanced Polymers Co., Ltd., Udel P-1700, MFR: 7 gZl 0 min (ASTM D-1238)) • Aminoalkoxysilane compound
- Aminoalkoxysilane compound 2_1 araminopropyltriethoxysilane (Shin-Etsu Chemical Co., Ltd.)
- Aminoalkoxysilane compound 2-2 r- (2-aminoethyl) aminopropyltriethoxysilane (Shin-Etsu Chemical Co., Ltd.)
- test piece 15 ⁇ 160 ⁇ 2 mm was suspended in the middle of the test tube.
- the test tube was capped at the top, heated at 350 ° C for 3 hours, air-cooled, and the test piece was taken out. Thereafter, the specimen was left for 24 hours in an environment at 23 ° C and a relative humidity of 95% or more, and the weight of the test piece was measured. The amount of weight increase of the test piece was defined as the amount of corrosion. Measurement of corrosive gas generation
- a high-sensitivity toxic gas monitor (FP300, detection tape FC-005) manufactured by Riken Keiki Co., Ltd., precisely weigh 2 to 2.0 g of pellets in the ceramic port, and set in a heating furnace set at 350T. And the amount of gaseous hydrogen chloride generated was measured. The amount of hydrogen chloride was expressed as a concentration (unit: ppm) obtained by dividing the amount of generated hydrogen chloride ( ⁇ g) generated at 350 ° C for 40 minutes by the weight of the charged sample (g).
- ppm concentration obtained by dividing the amount of generated hydrogen chloride ( ⁇ g) generated at 350 ° C for 40 minutes by the weight of the charged sample (g).
- the aminoalkoxysilane compounds 2-1 to 2-2 and, if necessary, the zinc compound 3-:! At a weight ratio shown in Table 1 with respect to 100 parts by weight of the resin 111 or the resin 112. Add ⁇ 3-4 and premix for 2-5 minutes with a Henschel mixer. If necessary, the above glass fibers are added at the weight ratio shown in Table 1 and mixed for 2 minutes.Then, the mixture is fed to a twin-screw extruder having a cylinder temperature of 320 ° C, extruded into strands, cut and cut. Pellets were used. Using the obtained pellets, the above-mentioned metal corrosion amount and corrosive gas generation amount were measured.
- the mold when the raw material pellet is injection-molded, the mold is significantly less corroded, so that the mold needs to be cleaned less frequently and the life is extended.
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Priority Applications (1)
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JP2005514894A JPWO2005037924A1 (ja) | 2003-10-22 | 2004-10-21 | 樹脂成形金属腐食防止剤、金属腐食防止性樹脂組成物及び樹脂成形金型腐食防止方法 |
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JP2003362539 | 2003-10-22 | ||
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WO2005037924A1 true WO2005037924A1 (ja) | 2005-04-28 |
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Cited By (2)
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CN110914362A (zh) * | 2017-07-14 | 2020-03-24 | 乐天尖端材料株式会社 | 热塑性树脂组合物和由其制造的模制品 |
CN111574834A (zh) * | 2020-07-08 | 2020-08-25 | 四川明道和化学新材料有限公司 | 聚苯硫醚树脂复合材料及其制备方法 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0812886A (ja) * | 1994-07-04 | 1996-01-16 | Polyplastics Co | ポリアリーレンサルファイド樹脂組成物 |
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2004
- 2004-10-21 JP JP2005514894A patent/JPWO2005037924A1/ja active Pending
- 2004-10-21 WO PCT/JP2004/015957 patent/WO2005037924A1/ja active Application Filing
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
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JPH0812886A (ja) * | 1994-07-04 | 1996-01-16 | Polyplastics Co | ポリアリーレンサルファイド樹脂組成物 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN110914362A (zh) * | 2017-07-14 | 2020-03-24 | 乐天尖端材料株式会社 | 热塑性树脂组合物和由其制造的模制品 |
US11518874B2 (en) | 2017-07-14 | 2022-12-06 | Lotte Advanced Materials Co., Ltd. | Thermoplastic resin composition and molded product manufactured therefrom |
CN111574834A (zh) * | 2020-07-08 | 2020-08-25 | 四川明道和化学新材料有限公司 | 聚苯硫醚树脂复合材料及其制备方法 |
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