WO2011058992A1 - ポリブチレンテレフタレート樹脂組成物 - Google Patents
ポリブチレンテレフタレート樹脂組成物 Download PDFInfo
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- WO2011058992A1 WO2011058992A1 PCT/JP2010/069998 JP2010069998W WO2011058992A1 WO 2011058992 A1 WO2011058992 A1 WO 2011058992A1 JP 2010069998 W JP2010069998 W JP 2010069998W WO 2011058992 A1 WO2011058992 A1 WO 2011058992A1
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- polybutylene terephthalate
- terephthalate resin
- resin composition
- compound
- mass
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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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K3/2279—Oxides; Hydroxides of metals of antimony
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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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
-
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
Definitions
- the present invention relates to a polybutylene terephthalate resin composition excellent in heat shock resistance, flame retardancy, and hydrolysis resistance, and further, heat shock resistance formed by insert molding the resin composition and a metal or an inorganic solid.
- the present invention relates to an insert molded product having excellent properties.
- Polybutylene terephthalate resin has various excellent properties such as mechanical properties, electrical properties, physical properties, and chemical properties, and has good workability, so it can be used for automobile parts, electrical / electronic components, etc. It is used for various purposes.
- Polybutylene terephthalate resin can be used as a polybutylene terephthalate resin composition reinforced with fibrous filler because it can improve heat resistance and strength by blending fibrous filler such as glass fiber. There are many.
- the polybutylene terephthalate resin has excellent properties, since it is a polyester resin, it also has a drawback of easily causing deterioration in physical properties due to hydrolysis. For this reason, it is widely known to improve hydrolysis resistance by blending a carbodiimide compound with polybutylene terephthalate resin.
- the polybutylene terephthalate resin composition improved in physical properties by blending a fibrous filler and a carbodiimide compound is used as a housing material for sensors and engine control units used for electric control, particularly in the automotive field.
- the product used for such an application is an insert molded product, it is used in an environment where the temperature rises and falls sharply, such as in an automobile engine room. Cracks are likely to occur. For this reason, products used for such applications are required to have heat shock resistance, which is unlikely to cause cracks due to severe temperature differences. Moreover, high flame retardancy may be requested
- Patent Document 1 A polybutylene terephthalate resin composition (Patent Document 1) has been proposed.
- the present invention has been made to solve the above-mentioned problems, and its object is to provide a polybutylene terephthalate resin composition having excellent heat shock resistance, flame retardancy, and hydrolysis resistance. To do.
- the inventors of the present invention have made extensive studies to solve the above problems. As a result, the inventors found that the above-mentioned problems can be solved by preparing a polybutylene terephthalate resin composition by blending a polybutylene terephthalate resin with a halogenated benzyl acrylate compound, an antimony oxide compound, and a carbodiimide compound. It came to be completed. More specifically, the present invention provides the following.
- a polybutylene terephthalate resin composition comprising (A) a polybutylene terephthalate resin, (B) a halogenated benzyl acrylate compound, (C) an antimony oxide compound, and (D) a carbodiimide compound.
- a polybutylene terephthalate resin composition by containing a polybutylene terephthalate resin composition, a polybutylene terephthalate resin, a halogenated benzyl acrylate compound, an antimony oxide compound, and a carbodiimide compound, heat shock resistance, flame retardancy, and A polybutylene terephthalate resin composition having excellent hydrolysis resistance is obtained.
- A polybutylene terephthalate resin
- B halogenated benzyl acrylate compound
- C antimony oxide compound
- D carbodiimide compound
- E filler
- F elastomer, other components
- polybutylene The manufacturing method of a terephthalate resin composition is demonstrated in order.
- the polybutylene terephthalate resin (A) used in the polybutylene terephthalate resin composition of the present invention contains at least a dicarboxylic acid component containing terephthalic acid or an ester-forming derivative thereof (C1-C6 alkyl ester, acid halide, etc.), and at least A polybutylene terephthalate resin obtained by polycondensation with a glycol component containing a C4 alkylene glycol (1,4-butanediol) or an ester-forming derivative thereof.
- the polybutylene terephthalate resin is not limited to a homopolybutylene terephthalate resin, and may be a copolymer containing 60 mol% or more (particularly 75 mol% or more and 95 mol% or less) of a butylene terephthalate unit.
- the amount of terminal carboxyl groups of the (A) polybutylene terephthalate resin used in the present invention is not particularly limited as long as the object of the present invention is not impaired.
- the terminal carboxyl group amount of the polybutylene terephthalate resin used in the present invention is preferably 30 meq / kg or less, and more preferably 25 meq or less.
- the resulting polybutylene terephthalate resin composition is particularly excellent in heat shock resistance, and the strength is reduced by hydrolysis in a humid heat environment. More difficult to receive.
- the lower limit value of the terminal carboxyl group amount of the polybutylene terephthalate resin is not particularly limited, but is preferably 5 meq / kg or more. In general, it is difficult to produce a polybutylene terephthalate resin having a terminal carboxyl group of less than 5 meq / kg. Moreover, when using the polybutylene terephthalate resin of this amount of terminal carboxyl groups, it is easy to prepare a polybutylene terephthalate resin composition having excellent heat shock resistance.
- the intrinsic viscosity of the (A) polybutylene terephthalate resin used in the present invention is not particularly limited as long as the object of the present invention is not impaired.
- the intrinsic viscosity (IV) of the polybutylene terephthalate resin is preferably 0.60 dL / g or more and 1.2 dL / g or less. More preferably, it is 0.65 dL / g or more and 0.9 dL / g or less.
- the resulting polybutylene terephthalate resin composition has particularly excellent moldability.
- the intrinsic viscosity can be adjusted by blending polybutylene terephthalate resins having different intrinsic viscosities.
- a polybutylene terephthalate resin having an intrinsic viscosity of 0.9 dL / G is prepared by blending a polybutylene terephthalate resin having an intrinsic viscosity of 1.0 dL / g and a polybutylene terephthalate resin having an intrinsic viscosity of 0.7 dL / g. Can do.
- the intrinsic viscosity (IV) of the polybutylene terephthalate resin can be measured, for example, in o-chlorophenol at a temperature of 35 ° C.
- examples of dicarboxylic acid components (comonomer components) other than terephthalic acid and its ester-forming derivatives include, for example, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 4 C8-C14 aromatic dicarboxylic acids such as 4,4'-dicarboxydiphenyl ether; C4-C16 alkyl dicarboxylic acids such as succinic acid, adipic acid, azelaic acid and sebacic acid; C5-C10 cycloalkyl such as cyclohexanedicarboxylic acid Dicarboxylic acids; ester-forming derivatives of these dicarboxylic acid components (C1-C6 alkyl ester derivatives, acid halides, etc.). These dicarboxylic acid components can be used alone or in combination of two or more.
- C8 to C12 aromatic dicarboxylic acids such as isophthalic acid
- C6 to C12 alkyl dicarboxylic acids such as adipic acid, azelaic acid, and sebacic acid are more preferable.
- glycol components (comonomer components) other than 1,4-butanediol for example, ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butylene glycol, hexamethylene glycol, C2-C10 alkylene glycol such as neopentyl glycol and 1,3-octanediol; polyoxyalkylene glycol such as diethylene glycol, triethylene glycol and dipropylene glycol; alicyclic diol such as cyclohexanedimethanol and hydrogenated bisphenol A; Aromatic diols such as bisphenol A and 4,4′-dihydroxybiphenyl; ethylene oxide 2-mole adduct of bisphenol A, propylene of bisphenol A Such emission oxide 3 moles adduct, alkylene oxide adducts of C2 ⁇ C4 of bisphenol A; or ester-forming derivatives of these glycols
- C2-C6 alkylene glycols such as ethylene glycol and trimethylene glycol
- polyoxyalkylene glycols such as diethylene glycol
- alicyclic diols such as cyclohexanedimethanol
- any of the polybutylene terephthalate copolymers obtained by copolymerizing the comonomer components described above can be suitably used as the (A) polybutylene terephthalate resin. Moreover, you may use combining a homopolybutylene terephthalate polymer and a polybutylene terephthalate copolymer as (A) polybutylene terephthalate resin.
- the polybutylene terephthalate resin composition of the present invention contains (B) a halogenated benzyl acrylate compound as a flame retardant.
- the polybutylene terephthalate resin composition of the present invention is a combination of (B) a halogenated benzyl acrylate compound and a (D) carbodiimide compound described later, thereby imparting high flame retardancy to the polybutylene terephthalate resin composition, It shows a significant improvement in heat shock resistance.
- (D) a carbodiimide compound and (B) another flame retardant of a halogenated benzyl acrylate compound are combined and blended in a polybutylene terephthalate resin, the effect of improving heat shock resistance is small.
- the (B) halogenated benzyl acrylate compound used in the present invention is a polymer containing units derived from pentabromobenzyl acrylate and / or pentabromobenzyl methacrylate.
- the molecular weight of the halogenated benzyl acrylate compound is not limited as long as the object of the present invention is not impaired, and is preferably 10,000 or more and 100,000 or less.
- Specific examples of the halogenated benzyl acrylate compound that can be suitably used in the present invention include a pentabromobenzyl acrylate polymer that is a homopolymer of pentabromobenzyl acrylate.
- the amount of (B) halogenated benzyl acrylate compound used in the present invention is not particularly limited as long as the object of the present invention is not impaired.
- the amount of the (B) halogenated benzyl acrylate compound used is preferably 10 parts by mass or more and 35 parts by mass or less, and more preferably 15 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the (A) polybutylene terephthalate resin.
- the polybutylene terephthalate resin composition of the present invention contains (C) an antimony oxide compound as a flame retardant aid.
- examples of the (C) antimony oxide compound used in the present invention include antimony trioxide, antimony pentoxide, and sodium antimonate.
- the amount of the antimony oxide compound used is not particularly limited as long as the object of the present invention is not impaired.
- the amount of the antimony oxide compound used is preferably 1 part by mass or more and 20 parts by mass or less, and more preferably 2 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the (A) polybutylene terephthalate resin.
- the (D) carbodiimide compound used in the present invention is not particularly limited as long as it is a compound having a carbodiimide group (—N ⁇ C ⁇ N—) in the molecule.
- the group bonded to the carbodiimide group is not particularly limited, and an aliphatic group, an alicyclic group, an aromatic group, or a group to which these organic groups are bonded (for example, a benzyl group). Phenethyl group, 1,4-xylylene group, etc.).
- Examples of the carbodiimide compound preferably used in the present invention include an aliphatic carbodiimide compound in which an aliphatic group is linked to a carbodiimide group, an alicyclic carbodiimide compound in which an alicyclic group is linked to a carbodiimide group, and a carbodiimide group.
- Examples thereof include aromatic carbodiimide compounds in which an aromatic group or a group containing an aromatic group is linked.
- a carbodiimide compound may be used individually by 1 type, and may be used in combination of 2 or more type.
- aliphatic carbodiimide compound examples include diisopropyl carbodiimide, dioctyl decyl carbodiimide and the like, and specific examples of the alicyclic carbodiimide compound include dicyclohexyl carbodiimide and the like.
- aromatic carbodiimide compounds include diphenylcarbodiimide, di-2,6-dimethylphenylcarbodiimide, N-tolyl-N′-phenylcarbodiimide, di-p-nitrophenylcarbodiimide, di-p-aminophenylcarbodiimide, di- -P-hydroxyphenylcarbodiimide, di-p-chlorophenylcarbodiimide, di-p-methoxyphenylcarbodiimide, di-3,4-dichlorophenylcarbodiimide, di-2,5-chlorophenylcarbodiimide, di-o-chlorophenylcarbodiimide, p-phenylene- Bis-di-o-tolylcarbodiimide, p-phenylene-bis-dicyclohexylcarbodiimide, p-phenylene-bis-dichlorochlorocarbodiimide, ethylene-bis
- the molecular weight is preferably 2000 or more.
- di-2,6-dimethylphenylcarbodiimide di-2,6-dimethylphenylcarbodiimide, poly (4,4′-diphenylmethanecarbodiimide), poly (phenylenecarbodiimide), poly (triisopropylphenylenecarbodiimide), etc. are used. Is more preferable.
- the amount of the (D) carbodiimide compound used is not particularly limited as long as the object of the present invention is not impaired.
- the amount of the carbodiimide compound used is preferably such that when the terminal carboxyl group amount of the (A) polybutylene terephthalate resin is 1, the amount of the carbodiimide functional group is from 0.3 equivalents to 5.0 equivalents, An amount that is 0.5 equivalent or more and 3.0 equivalent or less is more preferable.
- the polybutylene terephthalate resin composition of the present invention is further filled with (E) An agent may be included.
- E) As the filler various fillers such as fibrous and non-fibrous (powder and plate) are used depending on the purpose. These fillers may be used in combination of two or more.
- fillers as fibrous fillers, glass fibers, carbon fibers, potassium titanate fibers, silica / alumina fibers, zirconia fibers, silica fibers, boron nitride fibers, silicon nitride fibers, boron fibers, aluminum borate fibers, Examples include, but are not limited to, metal fibers and organic fibers.
- the granular fillers include silica, quartz powder, glass beads, glass powder, calcium silicate, kaolin, diatomaceous earth, silicates such as wollastonite, metal oxides such as iron oxide, titanium oxide, zinc oxide and alumina.
- silicates such as wollastonite
- metal oxides such as iron oxide, titanium oxide, zinc oxide and alumina.
- examples include, but are not limited to, metal carbonates such as calcium carbonate and magnesium carbonate, metal sulfates such as calcium sulfate and barium sulfate, silicon carbide, silicon nitride, boron nitride and various metal powders.
- the plate-like filler include mica and glass flakes, but are not limited thereto.
- the resulting polybutylene terephthalate resin composition has excellent mechanical properties.
- the fibrous fillers it is preferable to use glass fibers from the viewpoint of the balance between the effect of improving the mechanical properties and the cost.
- the glass fiber used in the present invention is not limited by the fiber diameter, cross-sectional shape (for example, circular shape, bowl shape, oval shape, etc.), and any known glass fiber can be preferably used. Moreover, the thing of various forms, such as a chopped strand, a milled fiber, and a roving, can be used for glass fiber.
- the type of glass constituting the glass fiber is not particularly limited, but E glass or corrosion resistant glass containing zirconium element is preferably used in terms of quality.
- the filler (E) when used, it is preferable to use a filler surface-treated with an organic treatment agent such as an aminosilane compound or an epoxy compound for the purpose of improving the interface characteristics between the filler and the resin matrix.
- an organic treatment agent such as an aminosilane compound or an epoxy compound
- the amount of the organic treatment agent used is preferably 0.03% by mass or more and 5% by mass or less with respect to the mass of the surface-treated filler, 0.3 mass. % To 2% by mass is more preferable.
- the amount of the organic treatment agent used can be known by measuring the heat loss value of the surface-treated filler.
- the organic treatment agent used for the surface treatment of the filler is not particularly limited, and various surface treatment agents conventionally used as the surface treatment of the filler can be used.
- the amount of the (E) filler used in the polybutylene terephthalate resin composition of the present invention is not particularly limited as long as the object of the present invention is not impaired.
- the amount of the filler used is preferably 20 parts by mass or more and 100 parts by mass or less, more preferably 20 parts by mass or more and 80 parts by mass or less, with respect to 100 parts by mass of the (A) polybutylene terephthalate resin, and 30 parts by mass.
- the amount is particularly preferably 60 parts by mass or less.
- the polybutylene terephthalate resin composition of the present invention comprises (F) a polybutylene terephthalate resin, (B) a halogenated benzyl acrylate compound, (C) an antimony oxide compound, and (D) a carbodiimide compound. Those containing an elastomer are more preferred.
- By blending the (F) elastomer in the polybutylene terephthalate resin composition a higher effect of improving heat shock resistance can be obtained.
- (F) elastomer is mix
- thermoplastic elastomers that can be used in the present invention include thermoplastic elastomers and core-shell elastomers.
- thermoplastic elastomer include grafted olefin elastomers, styrene elastomers, polyester elastomers, and the like.
- the amount of the (F) elastomer used in the polybutylene terephthalate resin composition of the present invention is not particularly limited as long as the object of the present invention is not impaired.
- the amount of the elastomer used is preferably 5 parts by mass or more and 30 parts by mass or less, and more preferably 10 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the (A) polybutylene terephthalate resin.
- heat shock resistance can be made especially excellent.
- grafted olefin-based elastomer used as the elastomer (D) in the present invention, a copolymer having ethylene and / or propylene as a main component, and (a-1) an ethylene-unsaturated carboxylic acid, is used.
- Examples thereof include a graft copolymer in which one or two or more kinds of polymers or copolymers composed of repeating units are chemically bonded in a branched or crosslinked structure.
- R represents a hydrogen atom or a C1-C6 alkyl group
- X represents —COOCH 3 , —COOC 2 H 5 , —COOC 4 H 9 , —COOCH 2 CH (C 2 H 5 ) C. It represents one or more groups selected from the group consisting of 4 H 9 , phenyl group, and cyano group.
- (A-1) Specific examples of the ethylene-unsaturated carboxylic acid alkyl ester copolymer include ethylene-methyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene -Random copolymers such as vinyl acetate-ethyl acrylate copolymer. Further, (a-1) the ethylenically unsaturated carboxylic acid alkyl ester copolymer may be a copolymer of unsaturated carboxylic acid such as acrylic acid and methacrylic acid as long as the object of the present invention is not impaired. . These copolymers can be used by mixing two or more kinds.
- examples of the ⁇ -olefin which is one monomer constituting the olefin copolymer of (a-2) include ethylene, propylene, butene-1, etc. Among these, ethylene is more preferably used.
- the glycidyl ester of ⁇ , ⁇ -unsaturated acid which is another monomer constituting the component (a-2) is a compound represented by the following general formula (2), such as glycidyl acrylate, glycidyl methacrylate, Examples include ethacrylic acid glycidyl ester. Among these glycidyl esters of ⁇ , ⁇ -unsaturated acids, glycidyl methacrylate is particularly preferably used.
- R 1 represents a hydrogen atom or a C1-C6 alkyl group.
- An olefin copolymer comprising an ⁇ -olefin such as ethylene and a glycidyl ester of an ⁇ , ⁇ -unsaturated acid is obtained by subjecting an ⁇ -olefin and a glycidyl ester of an ⁇ , ⁇ -unsaturated acid to a radical polymerization reaction according to a conventional method. It can be obtained by copolymerization.
- the preferred ratio of ⁇ -olefin to ⁇ , ⁇ -unsaturated glycidyl ester in the production of the copolymer is 70% by mass to 99% by mass of ⁇ -olefin, and glycidyl of ⁇ , ⁇ -unsaturated fatty acid. It is 1 mass% or more and 30 mass% or less of ester.
- the polymer or copolymer (b) to be graft-polymerized with the olefin copolymer (a-1) or (a-2) is a homopolymer comprising only one type of repeating unit represented by the general formula (1). Or a copolymer composed of two or more.
- Specific examples of the polymer or copolymer (b) include polymethyl methacrylate, polyethyl acrylate, polybutyl acrylate, polyacrylic acid (2-ethylhexyl), polystyrene, polyacrylonitrile, acrylonitrile-styrene copolymer.
- butyl acrylate-methyl methacrylate copolymer butyl acrylate-styrene copolymer and the like.
- these polymers or copolymers (b) it is particularly preferable to use a butyl acrylate-methyl methacrylate copolymer.
- These polymers or copolymers (b) can be prepared by radical polymerization of the corresponding vinyl monomers according to a conventional method.
- the graft copolymer preferably used in the present invention is a branched or olefinic copolymer (a-1) or (a-2) and a polymer or copolymer (b) chemically bonded at least at one point. It is a graft copolymer having a crosslinked structure. Since the graft copolymer has such a branched or crosslinked structure, the olefin copolymer (a-1), (a-2), or the polymer or copolymer (b) alone is a polybutylene terephthalate resin composition. The effect of improving the heat shock resistance superior to the case of blending into a product can be obtained.
- the ratio of (a-1) or (a-2) to (b) constituting the graft copolymer is preferably 95: 5 to 5:95, and 80:20 to 20 in mass ratio. : 80 is more preferable.
- styrene elastomer As the styrenic elastomer used as the elastomer (F) in the present invention, a block copolymer composed of a polystyrene block and an elastomer block having a polyolefin structure is preferably used.
- styrene-based elastomers include styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene / propylene-styrene block copolymer (SEPS), and styrene-ethylene / butylene-styrene block copolymer (SEBS). And styrene-ethylene / ethylene / propylene-styrene block copolymer (SEEPS).
- SIS styrene-isoprene-styrene block copolymer
- SEPS styrene-ethylene / prop
- the core-shell type elastomer used as the elastomer (F) in the present invention has a multilayer structure composed of a core layer (core portion) and a shell layer covering at least a part of the surface of the core layer.
- the core layer of the core-shell elastomer is preferably composed of a rubber component (soft component), and acrylic rubber is suitably used as the rubber component.
- the rubber component used for the core layer preferably has a glass transition temperature (Tg) of less than 0 ° C. (eg ⁇ 10 ° C. or less), and ⁇ 20 ° C. or less (eg ⁇ 180 ° C. or more and ⁇ 25 ° C. or less). More preferably, it is ⁇ 30 ° C. or lower (for example, ⁇ 150 ° C. or higher and ⁇ 40 ° C. or lower).
- the acrylic rubber used as the rubber component is preferably a polymer obtained by polymerizing an acrylic monomer such as alkyl acrylate as a main component.
- the alkyl acrylate used as the monomer for the acrylic rubber is preferably a C1-C12 alkyl ester of acrylic acid such as butyl acrylate, and more preferably a C2-C6 alkyl ester of acrylic acid.
- the acrylic rubber may be a homopolymer of an acrylic monomer or a copolymer.
- the acrylic rubber may be a copolymer of acrylic monomers or a copolymer of an acrylic monomer and another unsaturated bond-containing monomer.
- the acrylic rubber may be a copolymer of a crosslinkable monomer.
- the polyester elastomer used as the elastomer (F) is not particularly limited as long as the flexural modulus is 1000 MPa or less, preferably 700 MPa or less, and various types can be used. Either can be used.
- the polyether-type polyester elastomer is a polyester elastomer having an aromatic polyester unit as a hard segment and a polyester composed of a polymer of oxyalkylene glycol and a dicarboxylic acid as a soft segment.
- the aromatic polyester unit in the hard segment is a polycondensate of a dicarboxylic acid compound and a dihydroxy compound, a polycondensate of an oxycarboxylic acid compound, or a polycondensate of a dicarboxylic acid compound, a dihydroxy compound, and an oxycarboxylic acid compound. It is a derived unit.
- Specific examples of the hard segment include units derived from polybutylene terephthalate.
- the soft segment is introduced into the polyester elastomer by a compound formed by polycondensation of a polyalkylene ether and a dicarboxylic acid compound.
- Specific examples of the soft segment include a unit derived from an ester compound of polyoxytetramethylene glycol derived from tetrahydrofuran.
- polyether type elastomer a synthesized one or a commercially available one may be used.
- examples of commercially available polyether type elastomers include Perprene P-30B, P-70B, p-90B, P-208B manufactured by Toyobo Co., Ltd .; Hytrel 4057, 4767 manufactured by Toray DuPont Co., Ltd. 6347, 7247; Light Flex 655 manufactured by Chicona Corporation.
- the polyester type elastomer is a polyester elastomer having an aromatic polyester unit as a hard segment and an amorphous polyester unit as a soft segment.
- the aromatic polyester unit in the hard segment is the same as that of the polyether type elastomer.
- Examples of the amorphous polyester unit in the soft segment include a unit derived from a ring-opening polymer of lactone or a polycondensate of an aliphatic dicarboxylic acid and an aliphatic diol.
- the polyester type elastomer may be a synthesized one or a commercially available one.
- Examples of commercially available polyester elastomers include Perprene S-1002 and S-2002 manufactured by Toyobo Co., Ltd.
- fluorine-based resin suitable as an anti-drip agent examples include homo- or copolymers of fluorine-containing monomers such as tetrafluoroethylene, chlorotrifluoroethylene, vinylidene fluoride, hexafluoropropylene, perfluoroalkyl vinyl ether, and the fluorine-containing monomers. And a copolymer of a copolymerizable monomer such as ethylene, propylene, and (meth) acrylate. These fluororesins can be used alone or in combination of two or more.
- fluororesins examples include homopolymers such as polytetrafluoroethylene, polychlorotrifluoroethylene, and polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymers, and tetrafluoroethylene-perfluoro.
- copolymers such as alkyl vinyl ether copolymers, ethylene-tetrafluoroethylene copolymers, and ethylene-chlorotrifluoroethylene copolymers.
- the addition amount of the fluororesin is preferably 10 parts by mass or less, more preferably 0.1 part by mass or more and 5 parts by mass or less, and more preferably 0.2 part by mass or more and 1. part by mass with respect to 100 parts by mass of the (A) polybutylene terephthalate resin. 5 parts by mass or more is more preferable.
- the polybutylene terephthalate resin composition of the present invention further comprises an antioxidant, a heat stabilizer, an ultraviolet absorber, an antistatic agent, a dye, a pigment, a lubricant, a plasticizer, a release agent, and crystallization promotion depending on the purpose.
- an antioxidant e.g., a heat stabilizer, an ultraviolet absorber, an antistatic agent, a dye, a pigment, a lubricant, a plasticizer, a release agent, and crystallization promotion depending on the purpose.
- Various additives such as an agent, a crystal nucleating agent, and an epoxy compound may be included.
- the polybutylene terephthalate resin composition of the present invention can be produced by various methods conventionally known as a method for producing a thermoplastic resin composition.
- a suitable method for producing the polybutylene terephthalate resin composition of the present invention is, for example, a method in which each component is melt-kneaded into an extruded pellet using a melt-kneader such as a single-screw or twin-screw extruder. Can be mentioned.
- the carbodiimide compound can also be blended as a masterbatch using a thermoplastic resin as a matrix.
- the master batch of the (D) carbodiimide compound is preferably one using a polybutylene terephthalate resin as a matrix, but one using another thermoplastic resin such as a polyethylene terephthalate resin as a matrix can also be used.
- the polybutylene terephthalate resin composition of the present invention can have a melt viscosity of 300 Pa ⁇ s or less, more preferably 250 Pa ⁇ s or less, measured at a temperature of 260 ° C. and a shear rate of 1000 sec ⁇ 1 , measured according to ISO11443. Since the polybutylene terephthalate resin composition of the present invention exhibits such melt viscosity, it exhibits excellent fluidity during molding, and the occurrence of molding defects such as short shots is small.
- the polybutylene terephthalate resin composition of the present invention obtained as described above is excellent in heat shock resistance, flame retardancy, and hydrolysis resistance, and is therefore suitably used for various applications such as insert parts. In particular, even when subjected to intense temperature rise and fall, cracks due to heat shock are unlikely to occur, and therefore it is suitably used as a material for insert moldings for automobile applications.
- the insert molded product referred to in the present invention is a compound molded product in which a metal or the like is mounted in advance on a molding die and the resin composition is filled on the outside thereof.
- a molding method for filling the resin with the mold there are an injection molding method, an extrusion molding method, a compression molding method and the like, and the injection molding method is general.
- the material to be inserted into the resin is used for the purpose of taking advantage of its characteristics and compensating for the defects of the resin, a material that does not change its shape or melt when it comes into contact with the resin during molding is used.
- metals such as aluminum, magnesium, copper, iron, brass and their alloys, and inorganic solids such as glass and ceramics, which are previously formed into rods, pins, screws and the like.
- the member inserted into the molded product is preferably a thin plate, and the size and thickness of these members can be determined by the size and structure of the molded product into which these members are inserted.
- the member to be inserted of the molded product does not have to be the entire molded product, and may be a part of the molded product.
- the shape, size, thickness, etc. of the molded product are not particularly limited as long as they are equipped (assembled integrally) with high-voltage-resistant components, and are plate-shaped (discs, polygons, etc.). Any of a columnar shape, a box shape, a bowl shape, a tray shape and the like may be used. In the case of a large molded product or a complex molded product, the thickness of all parts of the molded product does not need to be uniform, and the molded product may be provided with reinforcing ribs.
- the insert-molded product of the present invention exhibits excellent flame retardancy and heat shock resistance, it is suitable for electric appliances, mechanical mechanism parts, and automobile parts incorporated in OA equipment, including general home appliances.
- the parts for electric vehicles are not particularly limited, but include power modules, step-up DC / DC converters, step-down DC / DC converters, capacitors, insulators, motor terminal blocks, batteries, electric compressors, battery current sensors, and junction blocks. It is preferable as a material for a case for storing the like.
- Examples 1 to 3 and Comparative Examples 1 to 8 > In Examples 1 to 3 and Comparative Examples 1 to 8, the following materials were used as components of the polybutylene terephthalate resin composition.
- A-1 manufactured by Wintech Polymer Co., Ltd. (intrinsic viscosity 0.69, terminal carboxyl group amount 24 meq / kg) ⁇ Flame retardants ⁇
- B-1 Brominated benzyl acrylate (Bromochem Far East, FR1025, bromine content 72 mass%)
- B-2 Brominated polycarbonate (manufactured by Teijin Chemicals Ltd., Fireguard 7500, bromine content 56 mass%)
- B-3 Brominated phthalimide (manufactured by Albemarle Japan, SAYTEX BT93W, bromine content 67% by mass)
- B-4 Brominated epoxy compound (Sakamoto Yakuhin Kogyo Co., Ltd., SRT5000S, bromine content 53%)
- C-1 Antimony trioxide (Nippon Seiko Co., Ltd., PATOX-M)
- C-2 Antimony pentoxide (manufactured by Nissan Chemical
- the components shown in Table 1 were dry blended in the proportions (parts by mass) shown in Table 1, and using a twin screw extruder (TEX-30 manufactured by Nippon Steel), the cylinder temperature was 260 ° C. and the discharge amount Pellets of polybutylene terephthalate resin composition were prepared by melt-kneading under conditions of 15 kg / hr and screw rotation speed 150 rpm. A test piece was prepared using the obtained pellet, and heat shock resistance, tensile strength, tensile elongation, bending strength, bending elastic modulus, Charpy impact strength, flame retardancy, and polybutylene terephthalate resin composition, and Hydrolysis resistance (pressure cooker test) was measured.
- Table 1 shows the measurement results of heat shock resistance, tensile strength, tensile elongation, bending strength, bending elastic modulus, Charpy impact strength, and flame retardancy of the polybutylene terephthalate resin compositions of Examples 1 to 5.
- the measurement results of hydrolysis resistance are shown in Table 3.
- Table 2 shows the measurement results of heat shock resistance, tensile strength, tensile elongation, bending strength, bending elastic modulus, Charpy impact strength, and flame retardancy of the polybutylene terephthalate resin compositions of Comparative Examples 1 to 8.
- Table 4 shows the hydrolysis resistance measurement results.
- each physical property of the polybutylene terephthalate resin composition was measured according to the following method.
- ⁇ Heat shock resistance> Insert molding so that the minimum thickness of some resin parts is 1 mm in a mold that inserts an iron core 18 mm long, 18 mm wide, 30 mm high inside a prism with a length of 22 mm, a width of 22 mm, and a height of 51 mm.
- the product was injection molded to produce a test piece.
- Charpy impact strength was measured according to ISO179 / 1eA.
- test piece (0.75 mm thickness) was subjected to UL-94 standard vertical combustion test by Underwriters Laboratories.
- the polybutylene terephthalate resin compositions of Examples 1 to 5 in which a brominated benzyl acrylate compound (flame retardant B-1), an antimony oxide compound, and a carbodiimide compound were blended with the polybutylene terephthalate resin. Is excellent in heat shock resistance, flame retardancy, and hydrolysis resistance, and the mechanical properties are not impaired.
- Example 1 From a comparison between Example 1 and Comparative Examples 4, 6, and 8, a polybutylene terephthalate resin composition using a carbodiimide compound and a brominated polycarbonate, brominated phthalimide, or brominated epoxy compound as a flame retardant. Then, even if a carbodiimide compound is used, it turns out that heat shock resistance is only slightly improved.
- Example 1 By comparing Example 1 with Example 2 and Example 3, in addition to the brominated benzyl acrylate compound (flame retardant B-1), antimony oxide compound, and carbodiimide compound, the elastomer was added to the polybutylene terephthalate resin composition. It can be seen that a particularly excellent heat shock resistance improving effect can be obtained by blending.
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Abstract
Description
本発明のポリブチレンテレフタレート樹脂組成物において用いる(A)ポリブチレンテレフタレート樹脂は、少なくともテレフタル酸又はそのエステル形成性誘導体(C1~C6のアルキルエステルや酸ハロゲン化物等)を含むジカルボン酸成分と、少なくとも炭素原子数4のアルキレングリコール(1,4-ブタンジオール)又はそのエステル形成性誘導体を含むグリコール成分とを重縮合して得られるポリブチレンテレフタレート系樹脂である。ポリブチレンテレフタレート樹脂はホモポリブチレンテレフタレート樹脂に限らず、ブチレンテレフタレート単位を60モル%以上(特に75モル%以上95モル%以下)含有する共重合体であってもよい。
本発明のポリブチレンテレフタレート樹脂組成物は難燃剤として(B)ハロゲン化ベンジルアクリレート化合物を含有する。本発明のポリブチレンテレフタレート樹脂組成物は(B)ハロゲン化ベンジルアクリレート化合物と、後述する(D)カルボジイミド化合物を組みあわて用いることにより、ポリブチレンテレフタレート樹脂組成物に高い難燃性を付与しつつ、顕著な耐ヒートショック性の改善効果を示す。(D)カルボジイミド化合物と、(B)ハロゲン化ベンジルアクリレート化合物の他の難燃剤とを組みあわてポリブチレンテレフタレート樹脂に配合した場合は、耐ヒートショック性の改善効果は小さい。
本発明のポリブチレンテレフタレート樹脂組成物は難燃助剤として(C)酸化アンチモン化合物を含有する。本発明において用いる(C)酸化アンチモン化合物としては、三酸化アンチモン、五酸化アンチモン、又はアンチモン酸ナトリウム等が挙げられる。
本発明において用いる(D)カルボジイミド化合物は、分子中にカルボジイミド基(-N=C=N-)を有する化合物で有れば特に制限されない。本発明で用いる(D)カルボジイミド化合物において、カルボジイミド基に結合する基は特に制限されず、脂肪族基、脂環族基、芳香族基、又はこれらの有機基が結合した基(例えば、ベンジル基、フェネチル基、1,4-キシリレン基等)等が挙げられる。本発明において好適に使用されるカルボジイミド化合物の例としては、カルボジイミド基に脂肪族基が連結した脂肪族カルボジイミド化合物、カルボジイミド基に脂環族基が連結した脂環族カルボジイミド化合物、及び、カルボジイミド基に芳香族基又は芳香族基を含む基が連結した芳香族カルボジイミド化合物等が挙げられる。(D)カルボジイミド化合物は、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。
本発明のポリブチレンテレフタレート樹脂組成物は、(A)ポリブチレンテレフタレート樹脂、(B)ハロゲン化ベンジルアクリレート化合物、(C)酸化アンチモン化合物、及び、(D)カルボジイミド化合物に加え、さらに(E)充填剤を含むものであってもよい。(E)充填剤は、目的に応じて繊維状、非繊維状(粉粒状、板状)等の各種充填剤が用いられる。これらの充填剤は2種以上のものを組み合わせて用いてもよい。
本発明のポリブチレンテレフタレート樹脂組成物は、上記の(A)ポリブチレンテレフタレート樹脂、(B)ハロゲン化ベンジルアクリレート化合物、(C)酸化アンチモン化合物、及び、(D)カルボジイミド化合物に加え、(F)エラストマーを含むものがより好ましい。ポリブチレンテレフタレート樹脂組成物に(F)エラストマーを配合することにより、より高い耐ヒートショック性の改善効果が得られる。本発明のポリブチレンテレフタレート樹脂組成物に(F)エラストマーを配合する場合、前述の(E)充填剤を(F)エラストマーと共に配合してもよい。
本発明において(D)エラストマーとして用いるグラフト化されたオレフィン系エラストマーとして好適なものとしては、エチレン及び/又はプロピレンを主成分とする共重合体であって、(a-1)エチレン-不飽和カルボン酸アルキルエステル共重合体、又は、(a-2)α-オレフィンとα,β-不飽和酸のグリシジルエステルとからなるオレフィン系共重合体と、(b)主として下記一般式(1)で示される繰り返し単位からなる重合体又は共重合体の1種又は2種以上が分岐又は架橋構造的に化学結合したグラフト共重合体が挙げられる。
本発明において(F)エラストマーとして用いるスチレン系エラストマーとしては、ポリスチレンブロックとポリオレフィン構造のエラストマーブロックとで構成されたブロック共重合体が好適に用いられる。スチレン系エラストマーの具体例としては、スチレン-イソプレン-スチレンブロック共重合体(SIS)、スチレン-エチレン・プロピレン-スチレンブロック共重合体(SEPS)スチレン-エチレン・ブチレン-スチレンブロック共重合体(SEBS)、スチレン-エチレン・エチレン/プロピレン-スチレンブロック共重合体(SEEPS)等が挙げられる。
本発明において(F)エラストマーとして用いるコアシェル系エラストマーは、コア層(コア部)と、このコア層の表面の少なくとも一部を被覆するシェル層とで構成される多層構造を有する。コアシェル系エラストマーのコア層は、ゴム成分(軟質成分)で構成されるのが好ましく、ゴム成分としてはアクリル系ゴムが好適に用いられる。コア層に用いるゴム成分は、ガラス転移温度(Tg)が0℃未満(例えば-10℃以下)であるのが好ましく、-20℃以下(例えば-180℃以上-25℃以下)であるのがより好ましく、-30℃以下(例えば-150℃以上-40℃以下)であるのが特に好ましい。
本発明において(F)エラストマーとして用いるポリエステル系エラストマーは、曲げ弾性率が1000MPa以下、好ましくは700MPa以下のものであれば特に制限されず、種々のものを使用でき、ポリエーテル型、又はポリエステル型の何れも使用できる。
成形品の用途によっては、UL規格94の難燃区分「V-0」であることを要求される場合がある。その場合には、本発明のポリブチレンテレフタレート樹脂組成物にフッ素系樹脂等の滴下防止剤を難燃剤と共に用いることが好ましい。
本発明のポリブチレンテレフタレート樹脂組成物は、従来、熱可塑性樹脂組成物の製造方法として知られる種々の方法によって製造することができる。本発明のポリブチレンテレフタレート樹脂組成物の製造方法として好適な方法としては、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ペレットとする方法が挙げられる。
本発明で言うインサート成形品とは、成形用金型に金属等をあらかじめ装着し、その外側に上記樹脂組成物を充填して複合成形品としたものである。樹脂を金型に充填するための成形法としては射出成形法、押出成形法、圧縮成形法などがあるが、射出成形法が一般的である。また、樹脂にインサートする素材は、その特性を生かし且つ樹脂の欠点を補う目的で使用されるため、成形時に樹脂と接触したとき、形が変化したり溶融しないものが使用される。このため、主としてアルミニウム、マグネシウム、銅、鉄、真鍮及びそれらの合金などの金属類やガラス、セラミックスのような無機固体類であらかじめ棒、ピン、ネジ等に成形されているものが使用される。
実施例1~3、及び比較例1~8において、ポリブチレンテレフタレート樹脂組成物の成分として、以下の材料を用いた。
A-1:ウィンテックポリマー株式会社製(固有粘度0.69、末端カルボキシル基量24meq/kg)
〔難燃剤〕
B-1:ブロモ化ベンジルアクリレート(ブロモケム・ファーイースト(株)製、FR1025、臭素含有量72質量%)
B-2:ブロモ化ポリカーボネート(帝人化成(株)製、ファイヤーガード7500、臭素含有量56質量%)
B-3:ブロモ化フタルイミド(アルベマール日本(株)製、SAYTEX BT93W、臭素含有量67質量%)
B-4:ブロモ化エポキシ化合物(阪本薬品工業(株)製、SRT5000S、臭素含有量53%)
〔アンチモン化合物〕
C-1:三酸化アンチモン(日本精鉱(株)製、PATOX-M)
C-2:五酸化アンチモン(日産化学工業(株)製、サンエポックNA1030)
〔カルボジイミド化合物〕
D-1芳香族カルボジイミド(ラインケミージャパン(株)製、STABAXOL P)
〔ガラス繊維〕
E-1:ガラスファイバー(日東紡績製、CS3J948S)
〔エラストマー〕
F-1:コアシェル系エラストマー(ローム・アンド・ハース・ジャパン(株)製、パラロイド EXL2314)
F-2:オレフィン系エラストマー(日油(株)製、モディパーA5300)
F-3:スチレン系エラストマー((株)クラレ製、セプトン4055)
〔PTFE〕
ポリテトラフルオロエチレン樹脂(旭硝子(株)製、フルオンCD-076)
〔可塑剤〕
ピロメリット酸混合アルコールエステル((株)ADEKA製、アデカサイザー UL-100)
縦22mm、横22mm、高さ51mmの角柱内部に縦18mm、横18mm、高さ30mmの鉄芯をインサートする金型にて、一部の樹脂部の最小肉厚が1mmとなるようにインサート成形品を射出成形して試験片を製造した。得られたインサート成形品について、冷熱衝撃試験機を用いて140℃にて1時間30分加熱後、-40℃に降温して1時間30分冷却後、さらに140℃に昇温する過程を1サイクルとする耐ヒートショック試験を行い、成形品にクラックが入るまでのサイクル数を測定し、耐ヒートショック性を評価した。400サイクルまで試験を行った。
ISO1143に準拠しシリンダー温度260℃、剪断速度1000sec-1で測定した。
ISO527-1,2に準拠し、引張り強さ、及び引張り伸びの測定を行った。
ISO178に準拠し、曲げ強さ、及び曲げ弾性率の測定を行った。
ISO179/1eAに準拠し、シャルピー衝撃強さの測定を行った。
試験片(0.75mm厚み)について、アンダーライターズ・ラボラトリーズのUL-94規格垂直燃焼試験により実施した。
樹脂温度260℃、金型温度80℃、射出時間15秒、冷却時間15秒の条件で射出成形し、ISO3167の引張り試験片を作成し、ISO527-1,2に従い得られた試験片の引張り強さと引張り伸びとを測定した。次いで、引張り試験片をプレッシャークッカー試験機で121℃、100%RHの条件でそれぞれ25hr、50hr、75hr暴露し、暴露後の試験片の引張り強さと引張り弾性率とを測定して暴露前の試験片に対する暴露後の試験片の引張り強さ保持率、引張り伸び保持率を測定した。
Claims (8)
- (A)ポリブチレンテレフタレート樹脂、(B)ハロゲン化ベンジルアクリレート化合物、(C)酸化アンチモン化合物、及び、(D)カルボジイミド化合物を含む、ポリブチレンテレフタレート樹脂組成物。
- 前記(D)カルボジイミド化合物の含有量が、前記(A)ポリブチレンテレフタレート樹脂の末端カルボキシル当量を1とした場合、カルボジイミド官能基量が0.3当量以上5.0当量以下となる量である、請求項1に記載のポリブチレンテレフタレート樹脂組成物。
- 前記(A)ポリブチレンテレフタレート樹脂の末端カルボキシル量が30meq/kg以下である、請求項1又は2に記載のポリブチレンテレフタレート樹脂組成物。
- さらに、(E)充填剤を含む、請求項1~3何れか記載のポリブチレンテレフタレート樹脂組成物。
- 前記(E)充填剤がガラス繊維である、請求項4に記載のポリブチレンテレフタレート樹脂組成物。
- さらに、(F)エラストマーを含む、請求項1~5何れか記載のポリブチレンテレフタレート樹脂組成物。
- さらに(A)ポリブチレンテレフタレート樹脂100質量部に対し、(B)ハロゲン化ベンジルアクリレート化合物が10質量部以上35質量部以下、(C)酸化アンチモン化合物が1質量部以上20質量部以下である、請求項1~6までのいずれか記載のポリブチレンテレフタレート樹脂組成物。
- 請求項1~7のいずれか記載の樹脂組成物と金属または無機固体とをインサート成形してなるインサート成形品。
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| CN201080050564.6A CN102612540B (zh) | 2009-11-10 | 2010-11-10 | 聚对苯二甲酸丁二醇酯树脂组合物 |
| JP2011540517A JP5758809B2 (ja) | 2009-11-10 | 2010-11-10 | ポリブチレンテレフタレート樹脂組成物 |
| US13/508,653 US8530555B2 (en) | 2009-11-10 | 2010-11-10 | Polybutylene terephthalate resin composition |
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| JP2009256749 | 2009-11-10 | ||
| JP2009-256749 | 2009-11-10 |
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| WO2011058992A1 true WO2011058992A1 (ja) | 2011-05-19 |
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| US (1) | US8530555B2 (ja) |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013002267A1 (ja) * | 2011-06-28 | 2013-01-03 | ウィンテックポリマー株式会社 | 樹脂成形体 |
| CN103562310A (zh) * | 2011-05-30 | 2014-02-05 | 胜技高分子株式会社 | 嵌入成型体 |
| US20140058015A1 (en) * | 2011-04-26 | 2014-02-27 | Win Tech Polymer Ltd. | Insert molded article |
| WO2016076136A1 (ja) * | 2014-11-14 | 2016-05-19 | 東洋紡株式会社 | 柔軟で高流動性のポリエステル樹脂組成物 |
| WO2016076135A1 (ja) * | 2014-11-14 | 2016-05-19 | 東洋紡株式会社 | 柔軟で接着力に優れたポリエステル樹脂組成物 |
| JP2018058231A (ja) * | 2016-10-03 | 2018-04-12 | 三菱エンジニアリングプラスチックス株式会社 | 金属樹脂複合体及びその製造方法 |
| WO2020100727A1 (ja) * | 2018-11-13 | 2020-05-22 | ポリプラスチックス株式会社 | 難燃性ポリブチレンテレフタレート樹脂組成物 |
| JP2020084002A (ja) * | 2018-11-22 | 2020-06-04 | 三菱エンジニアリングプラスチックス株式会社 | ポリエステル樹脂組成物 |
| WO2021095681A1 (ja) * | 2019-11-12 | 2021-05-20 | ポリプラスチックス株式会社 | 難燃性ポリブチレンテレフタレート樹脂組成物の耐トラッキング性向上方法 |
| WO2021140565A1 (ja) * | 2020-01-07 | 2021-07-15 | ポリプラスチックス株式会社 | 難燃性ポリブチレンテレフタレート樹脂組成物 |
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| WO2013002267A1 (ja) * | 2011-06-28 | 2013-01-03 | ウィンテックポリマー株式会社 | 樹脂成形体 |
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| WO2016076135A1 (ja) * | 2014-11-14 | 2016-05-19 | 東洋紡株式会社 | 柔軟で接着力に優れたポリエステル樹脂組成物 |
| JPWO2016076135A1 (ja) * | 2014-11-14 | 2017-08-17 | 東洋紡株式会社 | 柔軟で接着力に優れたポリエステル樹脂組成物 |
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| JP2018058231A (ja) * | 2016-10-03 | 2018-04-12 | 三菱エンジニアリングプラスチックス株式会社 | 金属樹脂複合体及びその製造方法 |
| WO2020100727A1 (ja) * | 2018-11-13 | 2020-05-22 | ポリプラスチックス株式会社 | 難燃性ポリブチレンテレフタレート樹脂組成物 |
| JPWO2020100727A1 (ja) * | 2018-11-13 | 2021-09-30 | ポリプラスチックス株式会社 | 難燃性ポリブチレンテレフタレート樹脂組成物 |
| JP7256822B2 (ja) | 2018-11-13 | 2023-04-12 | ポリプラスチックス株式会社 | 難燃性ポリブチレンテレフタレート樹脂組成物 |
| JP2020084002A (ja) * | 2018-11-22 | 2020-06-04 | 三菱エンジニアリングプラスチックス株式会社 | ポリエステル樹脂組成物 |
| JP7174602B2 (ja) | 2018-11-22 | 2022-11-17 | 三菱エンジニアリングプラスチックス株式会社 | ポリエステル樹脂組成物 |
| WO2021095681A1 (ja) * | 2019-11-12 | 2021-05-20 | ポリプラスチックス株式会社 | 難燃性ポリブチレンテレフタレート樹脂組成物の耐トラッキング性向上方法 |
| WO2021140565A1 (ja) * | 2020-01-07 | 2021-07-15 | ポリプラスチックス株式会社 | 難燃性ポリブチレンテレフタレート樹脂組成物 |
| JP2022057305A (ja) * | 2020-09-30 | 2022-04-11 | ポリプラスチックス株式会社 | ポリブチレンテレフタレート樹脂の耐アルカリ溶液性向上方法 |
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Also Published As
| Publication number | Publication date |
|---|---|
| US20120232200A1 (en) | 2012-09-13 |
| CN102612540B (zh) | 2014-05-28 |
| JP5758809B2 (ja) | 2015-08-05 |
| TW201124443A (en) | 2011-07-16 |
| CN102612540A (zh) | 2012-07-25 |
| JPWO2011058992A1 (ja) | 2013-04-04 |
| US8530555B2 (en) | 2013-09-10 |
| TWI549985B (zh) | 2016-09-21 |
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