WO2012070592A1 - 自動車ランプエクステンション成形体 - Google Patents
自動車ランプエクステンション成形体 Download PDFInfo
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- WO2012070592A1 WO2012070592A1 PCT/JP2011/076960 JP2011076960W WO2012070592A1 WO 2012070592 A1 WO2012070592 A1 WO 2012070592A1 JP 2011076960 W JP2011076960 W JP 2011076960W WO 2012070592 A1 WO2012070592 A1 WO 2012070592A1
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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
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
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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
- C08K5/13—Phenols; Phenolates
-
- 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
- C08K5/49—Phosphorus-containing compounds
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21S—NON-PORTABLE LIGHTING DEVICES; SYSTEMS THEREOF; VEHICLE LIGHTING DEVICES SPECIALLY ADAPTED FOR VEHICLE EXTERIORS
- F21S41/00—Illuminating devices specially adapted for vehicle exteriors, e.g. headlamps
- F21S41/50—Illuminating devices specially adapted for vehicle exteriors, e.g. headlamps characterised by aesthetic components not otherwise provided for, e.g. decorative trim, partition walls or covers
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21S—NON-PORTABLE LIGHTING DEVICES; SYSTEMS THEREOF; VEHICLE LIGHTING DEVICES SPECIALLY ADAPTED FOR VEHICLE EXTERIORS
- F21S43/00—Signalling devices specially adapted for vehicle exteriors, e.g. brake lamps, direction indicator lights or reversing lights
- F21S43/50—Signalling devices specially adapted for vehicle exteriors, e.g. brake lamps, direction indicator lights or reversing lights characterised by aesthetic components not otherwise provided for, e.g. decorative trim, partition walls or covers
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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
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
Definitions
- the present invention relates to an automobile lamp extension molded body.
- thermosetting resins such as unsaturated polyester resins, bulk molding compounds (BMC), or aluminum materials have been widely used.
- Thermosetting resins are superior in that they are lighter than aluminum materials, but still require further weight reduction because their specific gravity exceeds 2.0.
- there are also problems such as the complexity of post-processing work of the molded product and contamination of the working environment due to dust and the like peculiar to thermosetting resins. Therefore, as materials used for parts around automobile lamps, the conversion of materials from thermosetting resins and aluminum materials to thermoplastic resins such as polyetherimide and high heat-resistant polycarbonate that can be directly deposited on aluminum is possible. Progressing. However, even these thermoplastic resins are insufficient in terms of light weight, and materials with a lower specific gravity are desired in consideration of environmental and energy saving aspects.
- Polyphenylene ether resin has excellent properties such as mechanical properties, electrical properties, acid resistance, alkali resistance, heat resistance, low specific gravity, low water absorption, and good dimensional stability. ing. Therefore, it is widely used as a material for home appliances, OA equipment, office machines, information equipment, automobiles, etc., especially in applications that require high heat resistance and rigidity such as parts around automobile lamps. Demand for resin compositions designed with a high ratio of ether resin content is expected.
- thermoplastic resin containing a polyphenylene ether resin As a method for improving the heat resistance and mechanical properties of a thermoplastic resin containing a polyphenylene ether resin, a method of adding an inorganic filler such as glass fiber, carbon fiber, mica or talc is generally used.
- an inorganic filler such as glass fiber, carbon fiber, mica or talc
- the resin composition obtained by the above method has many applications that cannot be used. In particular, it is extremely difficult to apply in automotive extension member applications.
- HIPS rubber-reinforced polystyrene
- inorganic filler a small amount of rubber-reinforced polystyrene is blended.
- the brightness of the resulting molded product tends to be impaired.
- Patent Document 1 The resin composition described in Patent Document 1 is certainly excellent in heat resistance and molding fluidity due to the addition of liquid crystal polyester, but on the other hand, the addition of a crystalline polymer impairs the brightness of the molded product. As a material applied to the automotive lamp extension molded body, it is not always sufficient and there is room for improvement.
- the conventionally proposed polyphenylene ether resin composition for automobile lamp members can be applied to molded articles for automobile lamp members for various uses, but on the surface of the molded article after aluminum vapor deposition.
- Patent Document 2 certainly improves the heat aging resistance by adding a specific stabilizer.
- Patent Document 2 describes white spots in a molded article after aluminum deposition and its improvement. There is no description about the above, and the claims and examples have not been studied on a technique effective in improving white spots after aluminum deposition in an automotive lamp extension molded body.
- the present invention provides an automotive lamp extension molded article having a low specific gravity, a good balance between heat resistance and molding fluidity, and further comprising a resin composition having excellent molded product gloss and brightness.
- the purpose is to do.
- the present invention is as follows.
- An automotive lamp extension molded article comprising a resin composition containing 50 to 95% by mass of polyphenylene ether (A) and having a specific gravity in the range of 1.00 to 1.12.
- the resin composition comprises at least one resin component (B) 5 to 5 selected from the group consisting of a styrene resin (B1) not reinforced with rubber, a styrene thermoplastic elastomer (B2), and a polycarbonate resin (B3).
- the automotive lamp extension molded article according to any one of [1] to [3], further containing 50% by mass.
- the component (B2) comprises a hydrogenated styrene-conjugated diene compound block copolymer (B2-1) having a bound styrene content of 45 to 80% by mass and a styrene-conjugated compound having a bound styrene content of 20 to 40% by mass.
- the automotive lamp extension molded article according to any one of [6] to [6].
- the resin composition has an MFR (measured at 280 ° C., 10 kg) of 20 g / 10 min or more and a Vicat softening temperature (according to ISO 306, measured at a test load of 50 N and a heating rate of 120 ° C./hr) of 160 ° C. or more.
- MFR measured at 280 ° C., 10 kg
- Vicat softening temperature according to ISO 306, measured at a test load of 50 N and a heating rate of 120 ° C./hr
- a molded article having a low specific gravity, a good balance between heat resistance and fluidity, and further comprising a resin composition excellent in gloss and brightness of the molded article.
- the molded body can be used well as a molded body for an automobile lamp extension.
- the present embodiment a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail.
- this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.
- the automobile lamp extension molded article according to the present embodiment includes a resin composition containing 50 to 95% by mass of polyphenylene ether (A) and having a specific gravity in the range of 1.00 to 1.12.
- the resin composition used in the present embodiment contains 50 to 95% by mass of polyphenylene ether (A) and has a specific gravity in the range of 1.00 to 1.12.
- the present inventors have a low specific gravity, a good balance between heat resistance and fluidity, and also excellent brightness on the glossy surface of the molded product. It has been found that an automotive lamp extension molded body can be obtained.
- each component of the above resin composition will be described in detail.
- the reduced viscosity of the polyphenylene ether (A) used in the present embodiment is preferably in the range of 0.25 to 0.45 dl / g, more preferably 0.25 to 0.40 dl / g, and still more preferably Is 0.25 to 0.38 dl / g, particularly preferably in the range of 0.25 to 0.35 dL / g.
- the reduced viscosity of the polyphenylene ether (A) is preferably 0.25 dl / g or more from the viewpoint of sufficient mechanical properties, and is preferably 0.45 dl / g or less from the viewpoint of molding processability and brightness of the molded body.
- the reduced viscosity is a value obtained by measuring at 30 ° C. using a chloroform solvent.
- the polyphenylene ether (A) is a homopolymer having a repeating unit of [a] or [b] of the following formula (1) and the structural unit consisting of [a] or [b] of the general formula (1). Or a copolymer (copolymer).
- R1, R2, R3, R4, R5 and R6 are each independently an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms. And monovalent residues such as halogen and hydrogen. However, in this case, the case where R5 and R6 are simultaneously hydrogen is excluded. Further, the alkyl group preferably has 1 to 3 carbon atoms, the aryl group preferably has 6 to 8 carbon atoms, and more preferably hydrogen among the monovalent residues.
- the number of repeating units in [a] and [b] in (1) is not particularly limited because it varies depending on the molecular weight distribution of the polyphenylene ether (A).
- the homopolymer of polyphenylene ether is not limited to the following, but examples thereof include poly (2,6-dimethyl-1,4-phenylene) ether and poly (2-methyl-6-ethyl-1,4-phenylene) ether.
- the copolymer of polyphenylene ether is not limited to the following, but examples thereof include a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, and a copolymer of 2,6-dimethylphenol and o-cresol. Examples thereof include those mainly composed of a polyphenylene ether structure, such as a copolymer and a copolymer of 2,3,6-trimethylphenol and o-cresol. Among them, a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol is preferable from the viewpoint of easy availability of raw materials and processability, and 2,6-dimethylphenol from 90 to 70 from the viewpoint of improving physical properties. More preferred is a copolymer of 10% by mass with 2,3,6-trimethylphenol by mass.
- Polyphenylene ether (A) may be used alone or in combination of two or more.
- polyphenylene ether (A) may contain other various phenylene ether units as partial structures as long as they do not deviate from the desired effects of the present embodiment.
- a phenylene ether unit is not limited to the following, but is, for example, 2- (dialkylaminomethyl) -6-methylphenylene ether described in JP-A-01-297428 and JP-A-63-301222. Units and 2- (N-alkyl-N-phenylaminomethyl) -6-methylphenylene ether units.
- a small amount of diphenoquinone or the like may be bonded to the main chain of polyphenylene ether.
- a part or all of the polyphenylene ether is substituted with an acyl functional group and at least one selected from the group consisting of carboxylic acid, acid anhydride, acid amide, imide, amine, orthoester, hydroxy and ammonium carboxylate.
- a functionalized polyphenylene ether may be obtained by reacting (modifying) with a functionalizing agent.
- the ratio of the weight average molecular weight Mw to the number average molecular weight Mn (Mw / Mn value) of the polyphenylene ether (A) is preferably 2.0 to 5.5, more preferably 2.5 to 4.5, More preferably, it is 3.0 to 4.5.
- the Mw / Mn value is preferably 2.0 or more from the viewpoint of molding processability of the resin composition, and preferably 5.5 or less from the viewpoint of mechanical properties of the resin composition.
- the weight average molecular weight Mw and the number average molecular weight Mn can be measured by gel permeation chromatography (GPC), and are obtained from the polystyrene equivalent molecular weight.
- the residual volatile content of the polyphenylene ether (A) is preferably 0.3% by mass (3000 ppm) or less from the viewpoint of improving the surface appearance of the molded article. More preferably, it is 0.1 mass% (1000 ppm) or less.
- the polyphenylene ether having a residual volatile content of 0.3% by mass or less is not limited to the following, but can be suitably manufactured by adjusting the drying temperature and drying time after polymerization of the polyphenylene ether, for example.
- the drying temperature include 40 to 200 ° C., preferably 80 to 180 ° C., and more preferably 120 to 170 ° C. 40 ° C. or higher is desirable from the viewpoint of drying efficiency, and drying at 200 ° C. or lower is desirable from the viewpoint of seizure by melting and prevention of deterioration.
- the drying time is 0.5 to 72 hours, preferably 2 to 48 hours, more preferably 6 to 24 hours.
- the polymerization is not adversely affected, the environment is hardly adversely affected, and It is preferable to polymerize in advance using a polymerization solvent having a relatively low boiling point and being easily volatilized.
- the polymerization solvent include, but are not limited to, toluene. More specifically, after polymerizing a polyphenylene ether having a reduced viscosity within the above range by a known polymerization method, the resulting polymer is sufficiently dried using a vacuum dryer or the like, thereby remaining. A polyphenylene ether having a volatile content within the above range can be produced. In addition, even if it uses things other than the above-mentioned preferable polymerization solvent, the polyphenylene ether whose residual volatile matter is in the said range can be manufactured by fully drying.
- the content of polyphenylene ether (A) used in the present embodiment is in the range of 50 to 95% by mass in 100% by mass of the resin composition. It is preferably in the range of 60 to 90% by mass, more preferably 65 to 85% by mass.
- the content of the polyphenylene ether (A) is 50% by mass or more from the viewpoint of heat resistance required for this application, and is 95% by mass or less from the viewpoint of appearance of the molded body and maintenance of brightness.
- the resin composition used in the present embodiment includes a styrene-based resin (B1), a styrene-based thermoplastic elastomer (B2), and a polycarbonate that are not reinforced with rubber from the viewpoint of improving moldability, appearance of the molded body, and brightness. It is preferable to further contain 5 to 50% by mass of at least one resin component (B) selected from the group consisting of the resin (B3).
- the content of the resin component (B) is more preferably 10 to 40% by mass, still more preferably 15 to 35% by mass in 100% by mass of the resin composition.
- the content of the resin component (B) is preferably 50% by mass or less from the viewpoint of heat resistance required for this application, and 5% by mass from the viewpoint of impact resistance, brightness, and molding fluidity improvement of the molded product. % Or more is preferable.
- the resin component (B) is at least one selected from the group consisting of a styrene resin (B1), a polycarbonate resin (B2), and a styrene thermoplastic elastomer (B3) that are not reinforced with rubber.
- the non-rubber-reinforced styrene resin (B1) used in the present embodiment is a styrene compound or a styrene compound and a compound copolymerizable with the styrene compound. It is a synthetic resin obtained by polymerization in the presence.
- a styrene-type compound means the compound represented by following formula (2).
- R is hydrogen, lower alkyl or halogen
- Z is one or more selected from the group consisting of vinyl group, hydrogen, halogen and lower alkyl group
- p is an integer of 0 to 5 It is.
- styrene examples include, but are not limited to, styrene, ⁇ -methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, p-methylstyrene, p-tert-butylstyrene. And ethyl styrene.
- examples of the compound copolymerizable with the styrene compound include methacrylic acid esters such as methyl methacrylate and ethyl methacrylate; unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile; and acid anhydrides such as maleic anhydride.
- a preferred styrene resin (B1) is a styrene-acrylonitrile (AS) resin having an acrylonitrile (AN) unit content of 5 to 15% by mass.
- the content of the acrylonitrile unit in the AS resin is preferably 5 to 15% by mass from the viewpoint of improving the surface appearance of the obtained molded product and ensuring sufficient miscibility with polyphenylene ether. Preferably it is 5 to 12% by mass, and even more preferably 7 to 10% by mass.
- the styrene resin (B1) that is not reinforced with rubber used in the present embodiment may be used alone or in combination of two or more.
- the content of the styrene resin (B1) not reinforced with rubber used in the present embodiment is preferably in the range of 5 to 40% by mass with respect to 100% by mass of the entire resin composition, The content is preferably 8 to 30% by mass, more preferably 8 to 25% by mass, and particularly preferably 8 to 20% by mass.
- the content of the styrene-based resin (B1) not reinforced with rubber is preferably 5% by mass or more from the viewpoint of improving the appearance of the molded product and improving the molding fluidity, and 40% by mass or less from the viewpoint of sufficient heat resistance. preferable.
- the styrenic thermoplastic elastomer (B2) is a hydrogenated product of a block copolymer having a styrene block and a conjugated diene compound block (hereinafter also referred to as “styrene block-conjugated diene compound block copolymer”). Is preferred.
- the conjugated diene compound block is preferably hydrogenated at a hydrogenation rate of at least 50% from the viewpoint of thermal stability. The hydrogenation rate is more preferably 80% or more, and even more preferably 95% or more.
- Styrenic thermoplastic elastomer (B2) may be used alone or in combination of two or more.
- conjugated diene compound block examples include, but are not limited to, polybutadiene, polyisoprene, poly (ethylene / butylene), poly (ethylene / propylene), and vinyl-polyisoprene.
- the said conjugated diene compound block may be used individually by 1 type, and may be used in combination of 2 or more type.
- the arrangement of the repeating units constituting the styrene block-conjugated diene compound block copolymer may be a linear type or a radial type.
- the block structure constituted by the polystyrene block and the rubber intermediate block may be any of two types, three types, and four types. Among these, from the viewpoint that the desired effect can be sufficiently exerted in the present embodiment, a three-type linear block copolymer composed of a polystyrene-poly (ethylene / butylene) -polystyrene structure is preferable.
- the conjugated diene compound block may contain butadiene units within a range not exceeding 30% by mass.
- a functionalized styrene thermoplastic elastomer obtained by introducing a functional group such as a carbonyl group or an amino group into a styrene thermoplastic elastomer. is there.
- the carbonyl group is introduced by modification with an unsaturated carboxylic acid or a functional derivative thereof.
- unsaturated carboxylic acids or functional derivatives thereof include, but are not limited to, for example, maleic acid, fumaric acid, itaconic acid, halogenated maleic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, and Endo-cis-bicyclo [2,2,1] -5-heptene-2,3-dicarboxylic acid, and anhydrides, ester compounds, amide compounds and imide compounds of these dicarboxylic acids, as well as acrylic acid and methacrylic acid, and These monocarboxylic acid ester compounds and amide compounds may be mentioned.
- maleic anhydride is preferred from the viewpoint of maintaining the surface appearance of the molded body and imparting impact resistance.
- the above amino group is introduced by reacting an imidazolidinone compound or a pyrrolidone compound with a styrene thermoplastic elastomer.
- the amount of bonded styrene is 45 to 80% by mass as the component (B2) from the viewpoint of improving the gloss of the molded product, imparting further impact resistance, and preventing delamination of the molded product. It is preferable to contain a hydrogenated product (B2-1) of a styrene-conjugated diene compound block copolymer.
- (B2-1) / (B2) and a hydrogenated product (B2-2) of a styrene-conjugated diene compound block copolymer having a bound styrene content of 20 to 40% by mass are represented by (B2-1) / (B2 -2) It is more preferable to use in combination at a mass ratio of 4/1 to 1/4.
- the component (B2-2) is more preferably blended so as to achieve such a mass ratio.
- the component (B2-2) is preferably blended so as to achieve such a mass ratio.
- the amount of bound styrene of the component (B2-1) is selected from the range of 45 to 80% by mass, preferably 50 to 75% by mass, more preferably 55 to 70% by mass.
- the amount of bound styrene of the component (B2-1) is preferably 45% by mass or more from the viewpoint of suppressing delamination due to mixing with the component (B2-2), and preferably 80% by mass or less from the viewpoint of maintaining impact resistance.
- the amount of bound styrene of the component (B2-2) is selected from the range of 20 to 40% by mass, preferably 25 to 40% by mass, more preferably 25 to 35% by mass.
- the amount of bound styrene of the component (B2-2) is preferably 20% by mass or more from the viewpoint of miscibility with the component (A), and preferably 40% by mass or less from the viewpoint of imparting sufficient impact resistance.
- the number average molecular weight of the component (B2-1) is preferably 5,000 to 150,000, more preferably 10,000 to 120,000, and still more preferably 30,000 to 100,000.
- the number average molecular weight of the component (B2-1) is preferably in the range of 5,000 to 150,000 from the viewpoint of miscibility with the component (B2-2).
- the number average molecular weight of the component (B2-2) is preferably 50,000 to 500,000, more preferably 100,000 to 400,000, and still more preferably 150,000 to 300,000.
- the number average molecular weight of the component (B2-2) is preferably in the range of 50,000 to 500,000 from the viewpoint of imparting sufficient impact resistance.
- the ratio of the weight average molecular weight Mw to the number average molecular weight Mn (Mw / Mn value) of the component (B2) is preferably 1.0 to 3.0, more preferably 1.0 to 2.0, and even more. Preferably it is in the range of 1.0 to 1.5. From the viewpoint of mechanical properties, a range of 1.0 to 3.0 is preferable.
- the weight average molecular weight Mw and the number average molecular weight Mn can be measured by gel permeation chromatography (GPC), and are obtained from the polystyrene-equivalent molecular weight.
- the content of the styrenic thermoplastic elastomer (B2) used in the present embodiment is preferably in the range of 1 to 15% by weight, more preferably 2 to 2% with respect to 100% by weight of the entire resin composition. It is 12% by mass, more preferably 4 to 10% by mass, and particularly preferably 4 to 8% by mass.
- the content of the styrenic thermoplastic elastomer (B2) is preferably 1% by mass or more from the viewpoint of imparting impact resistance and improving the appearance of the molded article, and preferably 15% by mass or less from the viewpoint of heat resistance and rigidity retention.
- the component (B) preferably contains a polycarbonate resin (B3).
- the component (B) preferably contains a styrene-acrylonitrile (AS) resin and a polycarbonate resin (B3) having an acrylonitrile (AN) unit content of 5 to 15% by mass.
- AS styrene-acrylonitrile
- AN acrylonitrile
- Polycarbonate resin (B3) may be used individually by 1 type, and may be used together 2 or more types.
- Examples of the polycarbonate resin (B3) include aromatic polycarbonates, aliphatic polycarbonates, and aromatic-aliphatic polycarbonates. In the present embodiment, aromatic polycarbonates are preferable.
- An aromatic polycarbonate is obtained by reacting a dihydric phenol and a carbonate precursor.
- reaction method examples include an interfacial polycondensation method, a melt transesterification method, a solid phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound.
- dihydric phenol examples include hydroquinone, resorcinol, 4,4′-biphenol, 1,1-bis (4-hydroxyphenyl) ethane, and 2,2-bis (4-hydroxyphenyl) propane (commonly referred to as bisphenol A).
- a preferable dihydric phenol is bis (4-hydroxyphenyl) alkane, and bisphenol A is more preferable from the viewpoint of impact resistance.
- Examples of the carbonate precursor include carbonyl halide, carbonate ester, haloformate, and the like, and specifically, phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, and the like.
- Antioxidant to prevent oxidation of catalyst, terminal terminator and dihydric phenol as necessary when producing aromatic polycarbonate by interfacial polymerization method using the dihydric phenol and the carbonate precursor An agent or the like may be used.
- the aromatic polycarbonate is a branched aromatic polycarbonate obtained by copolymerization of a trifunctional or higher polyfunctional aromatic compound, or a polyester carbonate obtained by copolymerization of an aromatic or aliphatic (including alicyclic) difunctional carboxylic acid.
- a copolymer polycarbonate obtained by copolymerizing a bifunctional alcohol (including an alicyclic group) and a polyester carbonate obtained by copolymerizing the bifunctional carboxylic acid and the difunctional alcohol together may be included.
- the mixture which mixed 2 or more types of the obtained polycarbonate may be sufficient.
- trifunctional or higher polyfunctional aromatic compound examples include 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl). Ethane etc. can be used.
- the proportion is preferably 0.001 to 1 mol%, more preferably 0.005 to 0, based on the total amount of the aromatic polycarbonate. 0.9 mol%, more preferably 0.01 to 0.8 mol%.
- a branched structure may be generated as a side reaction.
- the amount of the branched structure is also 0.001 to 1 mol% in the total amount of the aromatic polycarbonate. Is more preferably 0.005 to 0.9 mol%, and still more preferably 0.01 to 0.8 mol%.
- the content of the polyfunctional compound and the amount of branched structure can be calculated by 1 H-NMR measurement.
- the aliphatic difunctional carboxylic acid is preferably ⁇ , ⁇ -dicarboxylic acid.
- aliphatic difunctional carboxylic acid examples include, for example, sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, icosanedioic acid and other linear saturated aliphatic dicarboxylic acids, and cyclohexane.
- Aliphatic dicarboxylic acids such as dicarboxylic acids are preferred.
- an alicyclic diol is preferable, and examples thereof include cyclohexanedimethanol, cyclohexanediol, and tricyclodecane dimethanol.
- aromatic polycarbonate a polycarbonate-polyorganosiloxane copolymer obtained by copolymerizing polyorganosiloxane units can be used.
- the aromatic polycarbonate includes two types of aromatic polycarbonates such as the above-described aromatic polycarbonates having different dihydric phenols, aromatic polycarbonates containing a branched component, various polyester carbonates, and polycarbonate-polyorganosiloxane copolymers. A mixture of the above may be used.
- the reaction by the interfacial polycondensation method is usually a reaction of dihydric phenol and phosgene, and it is preferable to carry out the reaction in the presence of an acid binder and an organic solvent.
- an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used.
- organic solvent for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used.
- a catalyst such as a tertiary amine such as triethylamine, tetra-n-butylammonium bromide, tetra-n-butylphosphonium bromide, a quaternary ammonium compound, or a quaternary phosphonium compound may be used. it can.
- the reaction temperature is preferably 0 to 40 ° C.
- the reaction time is preferably about 10 minutes to 5 hours
- the pH during the reaction is 9 or more. Is preferably maintained.
- a terminal terminator in the polymerization reaction by the interfacial polycondensation method.
- monofunctional phenols can be used.
- monofunctional phenols for example, monofunctional phenols such as phenol, p-tert-butylphenol, and p-cumylphenol are preferably used.
- examples of the monofunctional phenols include decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol, docosylphenol, and triacontylphenol.
- end terminator may be used alone or in combination of two or more.
- the reaction by the melt transesterification method in the polymerization reaction of an aromatic polycarbonate is usually a transesterification reaction between a dihydric phenol and a carbonate ester, and the dihydric phenol and the carbonate ester are heated in the presence of an inert gas. It is preferably carried out by a method in which the resulting alcohol or phenol is distilled while mixing.
- the reaction temperature in the melt transesterification method varies depending on the boiling point of the alcohol or phenol produced, but is usually preferably in the range of 120 to 350 ° C. In the latter stage of the reaction, it is preferable to facilitate the distillation of the alcohol or phenol produced by reducing the pressure of the reaction system to about 1.33 ⁇ 10 3 to 13.3 Pa.
- the reaction time is usually preferably about 1 to 4 hours.
- carbonate ester examples include esters such as an aryl group having 6 to 10 carbon atoms, an aralkyl group, or an alkyl group having 1 to 4 carbon atoms which may have a substituent. Among them, diphenyl carbonate is preferable.
- a polymerization catalyst can be used to increase the polymerization rate in the melt transesterification method.
- the polymerization catalyst include alkali metal compounds such as sodium hydroxide, potassium hydroxide, sodium salt and potassium salt of dihydric phenol; alkaline earth metal compounds such as calcium hydroxide, barium hydroxide and magnesium hydroxide; Catalysts such as nitrogen-containing basic compounds such as methylammonium hydroxide, tetraethylammonium hydroxide, trimethylamine, and triethylamine can be used.
- alkali (earth) metal alkoxides alkali (earth) metal organic acid salts, boron compounds, germanium compounds, antimony compounds, titanium compounds, zirconium compounds, etc.
- the catalyst used for the exchange reaction can be used.
- the polymerization catalyst may be used alone or in combination of two or more.
- the amount of these polymerization catalysts used is preferably 1 ⁇ 10 ⁇ 8 to 1 ⁇ 10 ⁇ 3 equivalent, more preferably 1 ⁇ 10 ⁇ 7 to 5 ⁇ 10 ⁇ 4, etc., relative to 1 mol of dihydric phenol as a raw material. Selected in a range of quantities.
- 2-chlorophenylphenyl carbonate 2-methoxycarbonyl is used after the end or after the end of the polycondensation reaction in order to reduce phenolic end groups.
- Compounds such as phenylphenyl carbonate and 2-ethoxycarbonylphenyl phenyl carbonate may be added.
- the stability of the polymer can be improved by reducing the number of phenolic end groups.
- melt transesterification method it is preferable to use a deactivator that neutralizes the activity of the catalyst.
- the amount of the deactivator is preferably 0.5 to 50 mol with respect to 1 mol of the remaining catalyst.
- the amount of the deactivator is preferably 0.01 to 500 ppm, more preferably 0.01 to 300 ppm, still more preferably 0.01 to 100 ppm based on the aromatic polycarbonate after polymerization. Use as a percentage.
- Preferred examples of the deactivator include phosphonium salts such as tetrabutylphosphonium dodecylbenzenesulfonate and ammonium salts such as tetraethylammonium dodecylbenzyl sulfate.
- the aromatic polycarbonate preferably has a viscosity average molecular weight of 10,000 or more, more preferably 15,000 to 50,000.
- the lower limit of the viscosity average molecular weight is more preferably 16000, still more preferably 17000, and still more preferably 18000.
- the upper limit of the viscosity average molecular weight is more preferably 26000, still more preferably 25000, and still more preferably 23000.
- the aromatic polycarbonate may be a mixture of two or more different aromatic polycarbonates as described above. In this case, an aromatic polycarbonate having a viscosity average molecular weight outside the above range is mixed. Of course it is also possible.
- a mixture with an aromatic polycarbonate having a viscosity average molecular weight exceeding 50000 has a high entropy elasticity, and has a characteristic that a molded product is not likely to be defective due to rheological behavior represented by jetting. Therefore, when the appearance defect of a molded object arises, it is a suitable aspect to suppress an appearance defect by using a mixture with the aromatic polycarbonate whose viscosity average molecular weight exceeds 50000.
- gas injection molding and the like are advantageous because the gas injection amount is stable, and foam molding is advantageous because the foam cells are stable and fine and homogeneous cells are easily formed.
- it is a mixture with an aromatic polycarbonate having a viscosity average molecular weight of 80,000 or more, and more preferably a mixture with an aromatic polycarbonate having a viscosity average molecular weight of 100,000 or more. That is, an aromatic polycarbonate capable of observing a molecular weight distribution of two or more peaks in a measuring method such as GPC (gel permeation chromatography) can be preferably used.
- GPC gel permeation chromatography
- the phenolic hydroxyl group content is preferably 30 eq / ton or less, more preferably 25 eq / ton or less, and further preferably 20 eq / ton or less.
- the value of the phenolic hydroxyl group amount can be substantially 0 eq / ton by sufficiently reacting the terminal terminator.
- the amount of the phenolic hydroxyl group is measured by 1 H-NMR, and the molar ratio of a divalent phenol unit having a carbonate bond, a divalent phenol unit having a phenolic hydroxyl group, and a unit of a terminal terminator is calculated. It is calculated
- the viscosity average molecular weight of the aromatic polycarbonate can be determined as follows. First, the specific viscosity is calculated by the following formula (I). In the following formula (I), the drop time (t 0 ) of methylene chloride and the drop time (t) of the sample solution were obtained by using a solution obtained by dissolving 0.7 g of aromatic polycarbonate at 20 ° C. in 100 ml of methylene chloride. It can be determined by an Ostwald viscometer. The specific viscosity can be inserted into the following formula (II) to determine the viscosity average molecular weight M.
- the viscosity average molecular weight M is determined by inserting the determined specific viscosity into the following formula (II).
- aromatic polycarbonates are different in dihydric phenol, those using and not using a terminator, linear ones and branched ones, those having different production methods, and terminal terminations.
- Two or more kinds of aromatic polycarbonates such as those having different agents, aromatic polycarbonates and polyester carbonates, and those having different viscosity average molecular weights can be mixed and used.
- the polycarbonate resin (B3) used in the present embodiment is a polycarbonate resin (particularly aromatic) produced by the melt transesterification method (non-phosgene method) from the viewpoint of moldability of the molded body and appearance (white spots) improvement.
- Polycarbonate resin is preferred.
- a polycarbonate resin produced by the melt transesterification method is used, an automobile lamp extension molded body with less white spots and a better appearance can be obtained as compared with the case where a polycarbonate produced by the phosgene method is used.
- the polycarbonate resin (B3) used in the present embodiment is preferably an aromatic polycarbonate resin containing a dihydric phenol residue in the molecular skeleton.
- the polycarbonate resin (B3) used in the present embodiment contains a bisphenol residue having a cyclohexane ring introduced in the molecular skeleton from the viewpoint of heat resistance, thermal stability and chemical resistance of the molded product.
- a polycarbonate resin is preferred.
- the melt flow rate (MFR) of the polycarbonate resin (B3) used in the present embodiment is preferably selected from the range of 0.1 to 70 g / 10 min, more preferably 0.5 to 35 g / 10 min, still more preferably The range is 0.5 to 25 g / 10 min, particularly preferably 1 to 20 g / 10 min.
- the MFR is preferably 0.1 g / 10 min or more from the viewpoint of imparting sufficient fluidity, and preferably 70 g / 10 min or less from the viewpoint of sufficient miscibility with the polyphenylene ether resin and suppression of hydrolysis during extrusion molding.
- the MFR is a value measured at a measurement temperature of 300 ° C. and a load of 1.2 kg in accordance with the test method ISO1133.
- the water content of the polycarbonate resin (B3) used in the present embodiment is preferably 2500 ppm or less. More preferably, it is 2000 ppm or less, More preferably, it is 1000 ppm or less, Most preferably, it is 500 ppm or less. From the viewpoint of strand take-out stability at the time of extrusion and suppression of generation of silver on the surface of the molded product due to hydrolysis at the time of molding, the moisture content of the polycarbonate resin (B3) is preferably 2500 ppm or less. The water content can be measured with a Karl Fischer moisture meter or the like.
- the polycarbonate resin (B3) used in the present embodiment may contain a polycarbonate oligomer in order to improve the appearance of the molded body and the fluidity.
- the polycarbonate oligomer has a viscosity average molecular weight (Mv) of preferably 1,500 to 9,500, more preferably 2,000 to 9,000.
- the method for measuring the viscosity average molecular weight (Mv) is the same as the method for measuring the viscosity average molecular weight of the aromatic polycarbonate.
- the content of the polycarbonate oligomer is preferably 30% by mass or less in the polycarbonate resin (B3).
- the content of the polycarbonate resin (B3) used in the present embodiment is preferably in the range of 5 to 40% by mass, more preferably 8 to 30% by mass with respect to 100% by mass of the entire resin composition. %, Even more preferably 8 to 25% by weight, and particularly preferably 8 to 20% by weight.
- the polycarbonate resin (B3) is preferably blended in an amount of 5% by mass or more from the viewpoint of improving the appearance (white spots) of the molded product, and 40% by mass or less from the viewpoint of maintaining sufficient heat resistance, appearance of the molded product, and maintaining low specific gravity. Is preferable.
- the polycarbonate resin (B3) is blended as the component (B) used in the present embodiment, it is preferable to use the AS resin together from the viewpoint of improving the miscibility of the component (B3) and the appearance of the molded product (white spots).
- the polycarbonate resin (B3) not only virgin resin but also polycarbonate resin regenerated from used products, so-called material-recycled polycarbonate resin may be used.
- Used products include, for example, optical recording media such as optical disks, light guide plates, vehicle window glass, vehicle headlamp lenses, windshields, and other vehicle transparent members, water bottle containers, glasses lenses, soundproof walls, glass windows, etc. ⁇ Construction materials such as corrugated sheet.
- non-conforming products, pulverized products obtained from sprues, runners, etc., or pellets obtained by melting them can be used.
- the use ratio of the regenerated polycarbonate resin is preferably 80% by mass or less, more preferably 50% by mass or less, based on the virgin resin.
- the resin composition used in the present embodiment further comprises 0.01 to 5% by mass of the thermal stabilizer component (C) from the viewpoint of improving the thermal stability of the resin composition and the surface appearance and brightness of the molded product. It is preferable to contain.
- the content of the heat stabilizer component (C) is more preferably 0.1 to 3% by mass, even more preferably 0.2 to 2% by mass, with respect to 100% by mass of the resin composition. is there.
- Component heat stabilizers include hindered phenol and phosphorus heat stabilizers.
- Specific examples of the hindered phenol heat stabilizer include 3,3 ′, 3 ′′, 5,5 ′, 5 ”-hexa-tert-butyl-a, a ′, a ′′-(mesitylene-2, 4,6-triyl) tri-p-cresol, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 ( 1H, 3H, 5H) -trione, etc.
- phosphorus-based heat stabilizer examples include tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-dicumyl). Phenyl) pentaerythritol diphosphite, 3,9-bis (2,6-di-tert-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphapyro [5,5] An undecane etc. are mentioned.
- the heat stabilizer of component (C) used in the present embodiment is preferably a heat stabilizer having a melting point of 180 ° C. or higher from the viewpoint of improving the appearance (white spots) of the molded product.
- the melting point of the component (C) is more preferably (180 to 300 ° C., more preferably 180 to 280 ° C.
- the melting point of the component (C) is the melting point It can be measured with a measuring instrument model: B-545 (manufactured by Shibata Kagaku).
- the resin composition used in the present embodiment does not contain the polycarbonate resin (B3), it is preferable to use a hindered phenol heat stabilizer from the viewpoint of improving the appearance (white spots).
- the polycarbonate resin (B3) is included in the resin composition used in the present embodiment, it is preferable to use a phosphorus-based heat stabilizer from the viewpoint of improving the appearance (white spots) and suppressing the hydrolysis of the polycarbonate. .
- the resin composition used in the present embodiment preferably does not contain an inorganic filler as a reinforcing agent from the viewpoint of maintaining the brightness of the molded product.
- the inorganic filler as the reinforcing agent is generally used for reinforcing a thermoplastic resin, and examples thereof include glass fiber, carbon fiber, glass flake, talc, mica and the like.
- the resin composition used in the present embodiment preferably does not contain a crystalline polymer from the viewpoint of maintaining the brightness of the molded product.
- crystalline polymer examples include polyamide, polypropylene, polyethylene, polyphenylene sulfide, polyacetal, polyethylene terephthalate, polybutylene terephthalate, and liquid crystal polymer.
- the resin composition used in the present embodiment has an MFR (measured at 280 ° C., 10 kg load) from the viewpoint of balance between thin-wall molding processability for weight reduction, long-term heat resistance and durability retention of the molded body.
- the Vicat softening temperature (based on ISO 306, measured at a test load of 50 N and a heating rate of 120 ° C./hr) is preferably 160 ° C. or higher.
- the MFR is in a range of 20 to 150 g / min and the Vicat softening temperature is in a range of 160 to 210 ° C., and even more preferably, the MFR is in a range of 25 to 90 g / min and the Vicat softening temperature is in a range of 170 to 200 ° C. Within range.
- a polyphenylene ether (A) component having a reduced viscosity within the range of 0.25 to 0.38 dl / g is used.
- Method a method of using general purpose polystyrene (GPPS) and AN 5-15% AS resin together as component (B1), and a combination of AN 5-15% AS resin and (B3) polycarbonate resin as component (B1) And the method used.
- GPPS general purpose polystyrene
- B3 polycarbonate resin
- the resin composition used in the present embodiment has a specific gravity of 1 from the viewpoint of the balance between the advantages of reducing the environmental burden due to weight reduction and the material design that maintains sufficient performance (heat resistance, mechanical strength, appearance of molded product, etc.). It is within the range of 0.001 to 1.12, preferably within the range of 1.04 to 1.10, and more preferably within the range of 1.05 to 1.08.
- the inorganic filler is not blended, or the blending amount of the polycarbonate resin as the component (B3) is set to 40% by mass or less in the entire resin composition. And so on.
- the specific gravity of the resin composition can be measured using an electronic hydrometer SD-200L manufactured by Alpha Mirage.
- the resin composition used for this Embodiment can be manufactured by melt-kneading said each component, for example, said (A) component, said (B) component, and / or said (C) component.
- the conditions for melting and kneading the component (A), the component (B) and / or the component (C) for producing the resin composition are not particularly limited, but are desired in the present embodiment. From the viewpoint of stably obtaining a large amount of a resin composition capable of sufficiently exhibiting the above effect, it is preferable to use a twin screw extruder.
- the resin composition used in the present embodiment is produced using a larger twin screw extruder (screw diameter of 40 to 90 mm), it should be noted that the above-mentioned resin produced during extrusion into extruded resin pellets.
- the component (A) is introduced from the most upstream (top feed) raw material inlet and the oxygen concentration inside the shooter at the uppermost inlet is set to 3% by volume or less. The oxygen concentration is more preferably 1% by volume or less.
- the inside of the raw material storage hopper is sufficiently replaced with nitrogen, and a tape is put in the middle of the feed line from the raw material storage hopper to the raw material inlet of the extruder to prevent air from entering and exiting.
- This can be achieved by adjusting the nitrogen feed amount and adjusting the opening of the vent hole after improving the sealing performance.
- the oxygen concentration inside the shooter is preferably 3% by volume or less.
- the automobile lamp extension molded body of the present embodiment can be obtained by molding the above resin composition.
- the molding method in the case of producing an automotive lamp extension molded body using the resin composition is not limited to the following, but preferable examples include injection molding, extrusion molding, vacuum molding and pressure molding, and particularly molding appearance. In view of brightness and brightness, injection molding is more preferably used.
- the automotive lamp extension molded body is a relatively large light reflecting component that exists between a reflector that is a light reflecting component behind the light source beam of the headlight of the vehicle and the lamp front cover, It plays a role of collecting the reflected light from the light source and the reflector.
- heat resistance as high as that of a reflector is not required, it has a good brightness on the glossy surface of the molded product, a surface appearance after aluminum deposition, a sufficient balance between heat resistance and molding fluidity, and light weight (a low specific gravity material). Is required at a higher level.
- the molding temperature of the automobile lamp extension molded body of the present embodiment is selected from the range of the cylinder set temperature (maximum temperature part) 270 to 340 ° C., for example.
- the molding temperature is preferably 280 to 330 ° C, more preferably 290 to 320 ° C, still more preferably 300 to 320 ° C. 270 ° C. or higher is preferable from the viewpoint of sufficient molding fluidity, and 340 ° C. or lower is preferable from the viewpoint of thermal stability of the resin composition.
- the average thickness of the automobile lamp extension molded body of the present embodiment is preferably selected from the range of 0.8 to 3.2 mm.
- the average thickness is more preferably 1.0 to 3.0 mm, still more preferably 1.2 to 2.5 mm, and particularly preferably 1.2 to 2.0 mm.
- the average thickness is preferably 3.2 mm or less from the viewpoint of lightness, and preferably 0.8 mm or more from the viewpoint of sufficient moldability and strength retention.
- the automotive lamp extension molded body of the present embodiment is molded using a mirror mold that has been polished to a very small level (average surface roughness of 0.2 ⁇ m or less) with diamond paste or the like. It is preferable. # 1000 or more is preferable, # 2000 or more is more preferable, and # 5000 or more is particularly preferable. From the viewpoint of sufficient mirror appearance, the polishing count is preferably # 1000 or more.
- the gloss value of the mirror surface portion of the automotive lamp extension molded body of this embodiment is a material design that retains sufficient reflectivity of light emitted from the light source and sufficient physical properties (heat resistance, mechanical strength, appearance of molded product, etc.) From the viewpoint of balance, it is preferably in the range of 90 to 140% when measured at a measurement angle of 20 °.
- the gloss value is more preferably in the range of 90 to 140%, and even more preferably in the range of 100 to 140%.
- the gloss value of the mirror surface portion of the molded body can be within the above range.
- the gloss value can be measured by the method described in the examples described later.
- the automobile lamp extension molded body of the present embodiment is preferably subjected to aluminum vapor deposition treatment on a part or all of the surface of the molded body after molding.
- the automobile lamp extension molded body of the present embodiment is preferably subjected to plasma treatment in advance because the adhesion of the aluminum film can be improved by activating the surface of the molded body before aluminum deposition.
- the number of white spots (referring to protrusions having a crater-like depression having a diameter of 30 ⁇ m or more) existing within a certain area (52.4 mm 2 ) of the mirror surface portion is further increased. From the viewpoint of maintaining a good appearance of the molded product, the number is preferably 40 or less.
- the number of vitiligo is more preferably 30 or less, still more preferably 20 or less, and particularly preferably 10 or less.
- the number of vitiligo can be measured by the method described in the examples described later.
- the automobile lamp extension molded body of the present embodiment can be molded by partially blending a rework (recycled) material (such as a crushed product of a molded product once molded). is there.
- the blending ratio of the rework material in the automotive lamp extension molded body is preferably in the range of 0 to 40% by mass, more preferably 2 to 25% by mass, and even more preferably 5 to 15% by mass. It is particularly preferably within the range of 5 to 10% by mass. From the viewpoint of sufficient physical properties and appearance maintenance, it is preferable that the content is 40% by mass or less.
- the resin composition pellets obtained in Examples and Comparative Examples were dried in a hot air dryer at 120 ° C. for 3 hours.
- the dried resin composition pellets are molded by an injection molding machine (IS-80EPN, manufactured by Toshiba Machine Co., Ltd.) at a cylinder temperature of 300 ° C., a mold temperature of 120 ° C., and an injection speed (panel set value) of 85%, and a width of 13 mm.
- a dumbbell-shaped molded piece having a thickness of 3.2 mm or a tanzaza-shaped molded piece having a width of 13 mm and a thickness of 6.4 mm was obtained.
- Fluidity The resin composition pellets obtained in Examples and Comparative Examples were dried in a hot air dryer at 120 ° C. for 3 hours. After drying, MFR (melt flow rate) was measured using a melt indexer (P-111, manufactured by Toyo Seiki Co., Ltd.) at a cylinder set temperature of 280 ° C. and a load of 10 kg. As an evaluation standard, it was determined that the higher the MFR, the better the fluidity and the more advantageous the material design for this application.
- IZOD Impact Value In accordance with ASTM D256, a test piece shape of 64 mm ⁇ 13 mm ⁇ thickness of 6.4 mm prepared by cutting the tangerine shaped piece was measured at 23 ° C. with a notch. As an evaluation standard, it was determined that the higher the IZOD impact value, the more advantageous in terms of material design for this application.
- Gloss value (Gloss: Measurement angle 20 °) The gloss value (gross) at a measurement angle of 20 ° was measured for the central portion of the dumbbell specimen having a thickness of 3.2 mm produced by the above molding method using a gloss meter (VG7000, manufactured by Nippon Denshoku Industries Co., Ltd.). As an evaluation standard, the higher the gloss value, the higher the gloss of the molded piece and the better the brightness.
- Luminance after thermal aging (visual) Using a dumbbell test piece having a thickness of 3.2 mm, after performing 250 hr aging in an oven set at 150 ° C., the brightness of the molded piece was visually evaluated. The case where no problem was observed in the brightness feeling was rated as “Good”, and the case where the cast piece surface was fogged and the brightness feeling was clearly lower than before aging was marked as “cloudy”. It was judged that those marked with ⁇ can be suitably used in this application.
- the resin composition pellets obtained in the examples and comparative examples were dried in a hot air dryer at 120 ° C. for 3 hours.
- the resin composition after drying was subjected to cylinder injection by an injection molding machine (IS-80EPN, manufactured by Toshiba Machine Co., Ltd.) equipped with a film gate mirror mold having a size of 100 mm ⁇ 100 mm ⁇ 2 mm with the mold surface polished to # 5000.
- a molded flat plate was obtained by molding at a temperature of 320 ° C., a mold temperature of 120 ° C., an injection pressure (gauge pressure of 70 MPa), and an injection speed (panel set value) of 85%.
- the obtained shaped flat plate is placed in a vacuum deposition apparatus, an inert gas and oxygen are introduced into the device, the inside of the chamber is brought into a plasma state, and plasma treatment is performed to activate the shaped flat plate surface.
- aluminum was deposited on the formed flat plate in a vacuum deposition apparatus.
- plasma polymerization treatment was performed to form a silicon dioxide polymer film.
- the aluminum film thickness was 80 nm and the silicon dioxide film thickness was 50 nm.
- a 40 ⁇ magnified photograph was taken with a digital microscope (model: VHX1000, manufactured by Keyence Corporation) at the center of the aluminum vapor deposition surface of the formed flat plate (hereinafter also referred to as “aluminum vapor deposition flat plate”) on which this aluminum vapor deposition was performed.
- the total of the number of projections having crater-like depressions with a diameter of 30 ⁇ m or more existing in one field of view (area: 52.4 mm 2 ) (the traces of gas escape during molding) for all five mirror-molded flat plates was divided by 5 to calculate the average number per field of view. The average number was defined as the number of vitiligo.
- the ratio (tensile strength retention rate (%)) of the tensile strength of the test piece after immersion with respect to the case where the tensile strength of the normal sample was 100% was determined (number of tests n 3).
- ⁇ (hadan) means that the tensile strength could not be measured because all three test pieces broke during immersion.
- PPE-1 Reduced viscosity (measured at 30 ° C. using chloroform solvent) 0.48 dl / g poly (2,6-dimethyl-1,4-phenylene) ether (hereinafter “PPE-1”) Sometimes it is.)
- PPE-2 Reduced viscosity (measured at 30 ° C. using chloroform solvent) 0.40 dl / g of poly (2,6-dimethyl-1,4-phenylene) ether (hereinafter “PPE-2”) Sometimes it is.)
- PPE-3 Reduced viscosity (measured at 30 ° C. using chloroform solvent) 0.35 dl / g poly (2,6-dimethyl-1,4-phenylene) ether (hereinafter “PPE-3”) Sometimes it is.)
- PPE-4 Reduced viscosity (measured at 30 ° C. using a chloroform solvent) 0.30 dl / g of poly (2,6-dimethyl-1,4-phenylene) ether (hereinafter referred to as “PPE-4”) Sometimes it is.)
- PPE-5 Reduced viscosity (measured at 30 ° C. using chloroform solvent) 0.25 dl / g of poly (2,6-dimethyl-1,4-phenylene) ether (hereinafter “PPE-5”) Sometimes it is.)
- PPE-6 Reduced viscosity (measured at 30 ° C. using chloroform solvent) 0.22 dl / g of poly (2,6-dimethyl-1,4-phenylene) ether (hereinafter referred to as “PPE-6”) Sometimes it is.)
- GPPS General purpose polystyrene (polystyrene 680 [registered trademark], manufactured by PS Japan Ltd.) was used. (Hereafter, it may be referred to as “GPPS”). Note that general-purpose polystyrene is polystyrene that does not contain a rubber component, that is, polystyrene that is not rubber-reinforced.
- (AS) Styrene-acrylonitrile resin A styrene-acrylonitrile resin produced as follows was used. A mixed solution consisting of 4.7 parts by mass of acrylonitrile, 73.3 parts by mass of styrene, 22 parts by mass of ethylbenzene, and 0.02 parts by mass of t-butylperoxy-isopropyl carbonate as a polymerization initiator was added at 2.5 liters / hour. The polymer was continuously fed at a flow rate to a 5 liter fully mixed reactor and polymerized at 142 ° C. to obtain a polymerization solution.
- the resulting polymerization solution is continuously led to an extruder with a vent, and unreacted monomers and solvent are removed under conditions of 260 ° C. and 40 Torr, the polymer is continuously cooled and solidified, and chopped into particulate styrene.
- -Acrylonitrile resin hereinafter sometimes referred to as "AS" was obtained.
- composition analysis of this styrene-acrylonitrile resin by infrared absorption spectroscopy revealed that it was 9% by mass of acrylonitrile units and 91% by mass of styrene units.
- the melt flow rate of this styrene-acrylonitrile resin was 78 g / 10 min (according to ASTM D 1238, measured at 220 ° C., 10 kg load).
- a styrene-based thermoplastic elastomer having a hydrogenation rate of 99.9% in the butadiene block portion was used (hereinafter also referred to as “elastomer 2”).
- PC-1 MFR (Test conditions: ISO 1133, measured at 300 ° C., 1.2 kg load) Aromatic polycarbonate resin (Wonderlite PC-110 [registered trademark], Asahi Kasei Co., Ltd.) produced by the melt transesterification method of 10 g / 10 min (Hereinafter also referred to as “PC-1”).
- PC-2 MFR (Test conditions: ISO 1133, measured at 300 ° C., 1.2 kg load) Aromatic polycarbonate resin (Wonderlite PC-122 [registered trademark], Asahi Kasei Co., Ltd.) produced by a 22 g / 10 min melt transesterification method (Hereinafter also referred to as “PC-2”).
- PC-3 MFR (Test conditions: ISO 1133, measured at 300 ° C. under a load of 1.2 kg) 1.1 g / 10 min polycarbonate resin containing about 41% bisphenol structure having cyclohexane rings introduced into the molecular skeleton (APEC 1800 [ Registered trademark] (manufactured by Bayer)) (hereinafter also referred to as “PC-3”).
- PC-4 MFR (Test conditions: ISO 1133, measured at 300 ° C. under a 1.2 kg load) Aromatic polycarbonate resin produced by the phosgene method of 10 g / 10 min (Panlite L-1225Y [registered trademark], manufactured by Teijin Chemicals Ltd.) (Hereinafter also referred to as “PC-4”).
- C-1 A hindered phenol heat stabilizer having a melting point of 242 ° C. Chemical name: 3,3 ′, 3 ′′, 5,5 ′, 5 ”-hexa-tert-butyl-a, a ′, a ′′-( Mesitylene-2,4,6-triyl) tri-p-cresol (trade name: Irganox 1330 (registered trademark), manufactured by BASF) was used (hereinafter also referred to as “C-1”).
- C-2 A hindered phenol heat stabilizer having a melting point of 221 ° C.
- C-3 Phosphorus heat stabilizer having a melting point of 184 ° C.
- C-4 A hindered phenol heat stabilizer having a melting point of 158 ° C.
- C-5 Hindered amine heat stabilizer with a melting point of 156 ° C. Chemical name: N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) N, N′-diformylhexamethylenediamine ( Trade name: Uvinil 4050FF (registered trademark), manufactured by BASF) was used (hereinafter also referred to as “C-5”).
- C-6 Hindered amine heat stabilizer having a melting point of 133 ° C.
- a polycondensate of 1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine (trade name: Chimassorb 2020 (registered trademark), manufactured by BASF) was used. (Hereafter, sometimes referred to as “C-6”).
- C-7 Hindered amine heat stabilizer having a melting point of 118 ° C. Chemical name: Pentaerythritol tetrekis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: Irganox 1010 [registered trademark] ] (Manufactured by BASF) (hereinafter sometimes referred to as “C-7”).
- C-8 A hindered phenol heat stabilizer having a melting point of 52 ° C. Chemical name: Octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (trade name: Irganox 1076 (registered trademark)) BASF) (hereinafter also referred to as “C-8”).
- C-10 A hindered phenol heat stabilizer having a melting point of 14 ° C. Chemical name: 4,6-bis (octylthiomethyl) -O-cresol (trade name: Irganox 1520 (registered trademark), manufactured by BASF) was used. (Hereafter, it may be referred to as “C-10”).
- C-11 Sulfur heat stabilizer having a melting point of 65 ° C.
- C-12 Phosphorus heat stabilizer having a melting point of 235 ° C.
- C-13 Phosphorus heat stabilizer having a melting point of 225 ° C.
- the melting point of the heat stabilizer was measured with a melting point measuring device model: B-545 (manufactured by Shibata Kagaku Co.).
- the disk is fed from the most upstream part (top feed) of the disk R: 6 and the kneading disk N: 2), the cylinder temperature is 300 ° C., the screw speed is 250 rpm, and the vent vacuum is 7.998 kPa (60 Torr). And kneaded to obtain a resin composition.
- the physical property measurement results of the obtained resin composition are shown in Table 1 below.
- Example 2 80 parts by mass of PPE-2, 10 parts by mass of GPPS, and 10 parts by mass of AS were melt-kneaded in the same manner as in Example 1 to obtain a resin composition.
- the physical property measurement results of the obtained resin composition are shown in Table 1 below.
- Example 3 80 parts by mass of PPE-4 and 20 parts by mass of GPPS were melt-kneaded in the same manner as in Example 1 to obtain a resin composition.
- the physical property measurement results of the obtained resin composition are shown in Table 1 below.
- Example 4 80 parts by mass of PPE-2, 20 parts by mass of GPPS, 5 parts by mass of polyamide 6 (trade name: 1013B [registered trademark], manufactured by Ube Industries, Ltd., hereinafter also referred to as “PA”), and 3 parts by mass of elastomer 1 Were melt-kneaded in the same manner as in Example 1 to obtain a resin composition.
- the physical property measurement results of the obtained resin composition are shown in Table 1 below.
- Example 5 Except for replacing polyamide 6 of Example 4 with 5 parts by mass of polypropylene (trade name: Novatec PP SA08 [registered trademark], manufactured by Nippon Polypropylene Co., Ltd., hereinafter also referred to as “PP”), the same as in Example 4 And kneaded to obtain a resin composition.
- the physical property measurement results of the obtained resin composition are shown in Table 1 below.
- Example 6 80 parts by mass of PPE-2, 20 parts by mass of GPPS, and 5 parts by mass of rubber-reinforced polystyrene (trade name: H9405 [registered trademark], manufactured by Asahi Kasei Chemicals) were melt-kneaded in the same manner as in Example 1. A resin composition was obtained. The physical property measurement results of the obtained resin composition are shown in Table 1 below.
- Example 7 60 parts by mass of PPE-2, 40 parts by mass of GPPS, and 5 parts by mass of elastomer 1 were melt-kneaded in the same manner as in Example 1 to obtain a resin composition.
- the physical property measurement results of the obtained resin composition are shown in Table 1 below.
- Example 8 60 parts by mass of PPE-1, 40 parts by mass of GPPS, 2 parts by mass of elastomer 1, and 3 parts by mass of elastomer 2 were melt-kneaded in the same manner as in Example 1 to obtain a resin composition.
- the physical property measurement results of the obtained resin composition are shown in Table 1 below.
- Example 9 60 parts by mass of PPE-2, 40 parts by mass of GPPS, 2 parts by mass of elastomer 1, and 3 parts by mass of elastomer 2 were melt-kneaded in the same manner as in Example 1 to obtain a resin composition.
- the physical property measurement results of the obtained resin composition are shown in Table 1 below.
- Example 10 60 parts by mass of PPE-2, 40 parts by mass of GPPS, 1 part by mass of elastomer 1, and 4 parts by mass of elastomer 2 were melt-kneaded in the same manner as in Example 1 to obtain a resin composition.
- the physical property measurement results of the obtained resin composition are shown in Table 1 below.
- Example 11 60 parts by mass of PPE-2, 40 parts by mass of GPPS, 4 parts by mass of elastomer 1, and 1 part by mass of elastomer 2 were melt-kneaded in the same manner as in Example 1 to obtain a resin composition.
- the physical property measurement results of the obtained resin composition are shown in Table 1 below.
- Example 12 60 parts by mass of PPE-2, 40 parts by mass of GPPS, and 5 parts by mass of elastomer 2 were melt-kneaded in the same manner as in Example 1 to obtain a resin composition.
- the physical property measurement results of the obtained resin composition are shown in Table 1 below.
- Example 13 90 parts by mass of PPE-2, 5 parts by mass of GPPS, 5 parts by mass of AS, 2 parts by mass of elastomer 1, and 2 parts by mass of elastomer 2 were melt-kneaded in the same manner as in Example 1 to obtain a resin composition. I got a thing. The physical property measurement results of the obtained resin composition are shown in Table 1 below.
- Example 14 90 parts by mass of PPE-4, 5 parts by mass of GPPS, 5 parts by mass of AS, 2 parts by mass of elastomer 1, and 2 parts by mass of elastomer 2 were melt-kneaded in the same manner as in Example 1 to obtain a resin composition. I got a thing. The physical property measurement results of the obtained resin composition are shown in Table 1 below.
- Example 15 60 parts by mass of PPE-4, 32 parts by mass of GPPS, 2 parts by mass of elastomer 1, and 6 parts by mass of elastomer 2 were melt-kneaded in the same manner as in Example 1 to obtain a resin composition.
- the physical property measurement results of the obtained resin composition are shown in Table 2 below.
- Example 16 60 parts by mass of PPE-4, 32 parts by mass of AS, 2 parts by mass of elastomer 1, and 6 parts by mass of elastomer 2 were melt-kneaded in the same manner as in Example 1 to obtain a resin composition.
- the physical property measurement results of the obtained resin composition are shown in Table 2 below.
- Example 17 In the case of Example 1, 60 parts by mass of PPE-4, 31.5 parts by mass of GPPS, 2 parts by mass of elastomer 1, 6 parts by mass of elastomer 2, and 0.5 parts by mass of C-1 Similarly, the resin composition was obtained by melt-kneading. The physical property measurement results of the obtained resin composition are shown in Table 2 below.
- Example 18 60 parts by mass of PPE-4, 31 parts by mass of GPPS, 2 parts by mass of elastomer 1, 6 parts by mass of elastomer 2, and 1 part by mass of C-1 were melt kneaded in the same manner as in Example 1. Thus, a resin composition was obtained. The physical property measurement results of the obtained resin composition are shown in Table 2 below.
- Example 19 In the case of Example 1, 60 parts by mass of PPE-4, 21 parts by mass of GPPS, 10 parts by mass of AS, 2 parts by mass of elastomer 1, 6 parts by mass of elastomer 2, and 1 part by mass of C-1
- the resin composition was obtained by melt-kneading in the same manner as described above.
- the physical property measurement results of the obtained resin composition are shown in Table 2 below.
- Example 20 60 parts by mass of PPE-4, 30 parts by mass of GPPS, 2 parts by mass of elastomer 1, 6 parts by mass of elastomer 2, and 2 parts by mass of C-1 were melt kneaded in the same manner as in Example 1. Thus, a resin composition was obtained. The physical property measurement results of the obtained resin composition are shown in Table 2 below.
- Example 21 95 parts by mass of PPE-5, 3 parts by mass of elastomer 1, and 2 parts by mass of elastomer 2 were melt-kneaded in the same manner as in Example 1 to obtain a resin composition.
- the physical property measurement results of the obtained resin composition are shown in Table 2 below.
- Example 22 94 parts by mass of PPE-5, 3 parts by mass of elastomer 1, 2 parts by mass of elastomer 2, and 1 part by mass of C-1 were melt-kneaded in the same manner as in Example 1 to obtain a resin composition. Got. The physical property measurement results of the obtained resin composition are shown in Table 2 below.
- Example 23 70 parts by mass of PPE-4, 21 parts by mass of GPPS, 2 parts by mass of elastomer 1, 6 parts by mass of elastomer 2, and 1 part by mass of C-2 were melt kneaded in the same manner as in Example 1. Thus, a resin composition was obtained. The physical property measurement results of the obtained resin composition are shown in Table 2 below.
- Example 24 A resin composition was obtained by melt-kneading in the same manner as in Example 23 except that C-2 was changed to C-3.
- the physical property measurement results of the obtained resin composition are shown in Table 2 below.
- Example 25 A resin composition was obtained by melt-kneading in the same manner as in Example 23 except that C-2 was changed to C-4.
- the physical property measurement results of the obtained resin composition are shown in Table 2 below.
- Example 26 A resin composition was obtained by melt-kneading in the same manner as in Example 23 except that C-2 was changed to C-5.
- the physical property measurement results of the obtained resin composition are shown in Table 2 below.
- Example 27 A resin composition was obtained by melt-kneading in the same manner as in Example 23 except that C-2 was changed to C-6.
- the physical property measurement results of the obtained resin composition are shown in Table 2 below.
- Example 28 A resin composition was obtained by melt-kneading in the same manner as in Example 23 except that C-2 was changed to C-7.
- the physical property measurement results of the obtained resin composition are shown in Table 2 below.
- Example 29 A resin composition was obtained by melt-kneading in the same manner as in Example 23 except that C-2 was changed to C-9.
- the physical property measurement results of the obtained resin composition are shown in Table 2 below.
- Example 30 A resin composition was obtained by melt-kneading in the same manner as in Example 23 except that C-2 was changed to C-11.
- the physical property measurement results of the obtained resin composition are shown in Table 2 below.
- Example 31 80 parts by mass of PPE-5, 7 parts by mass of GPPS, 7 parts by mass of AS, 1 part by mass of elastomer 1, 4 parts by mass of elastomer 2, 0.5 part by mass of C-3, and C-7 0.5 parts by mass was melt-kneaded in the same manner as in Example 1 to obtain a resin composition.
- the physical property measurement results of the obtained resin composition are shown in Table 2 below.
- Example 32 80 parts by mass of PPE-5, 6 parts by mass of GPPS, 7 parts by mass of AS, 1 part by mass of elastomer 1, 4 parts by mass of elastomer 2, 1 part by mass of C-5, and 1 part by mass of C-7 Were melt-kneaded in the same manner as in Example 1 to obtain a resin composition.
- the physical property measurement results of the obtained resin composition are shown in Table 2 below.
- Example 33 80 parts by mass of PPE-5, 6 parts by mass of GPPS, 7 parts by mass of AS, 1 part by mass of elastomer 1, 4 parts by mass of elastomer 2, 1 part by mass of C-8, and 1 part by mass of C-10 Were melt-kneaded in the same manner as in Example 1 to obtain a resin composition.
- the physical property measurement results of the obtained resin composition are shown in Table 2 below.
- Example 34 85 parts by mass of PPE-2, 10.5 parts by mass of GPPS, 2 parts by mass of elastomer 1, and 2.5 parts by mass of elastomer 2 were melt-kneaded in the same manner as in Example 1 to obtain a resin composition. Got. The physical property measurement results of the obtained resin composition are shown in Table 3 below.
- Example 35 85 parts by mass of PPE-2, 2 parts by mass of elastomer 1, 2.5 parts by mass of elastomer 2, and 10.5 parts by mass of PC-1 were melt-kneaded in the same manner as in Example 1. Thus, a resin composition was obtained. The physical property measurement results of the obtained resin composition are shown in Table 3 below.
- Example 36 A resin composition was obtained by melt-kneading in the same manner as in Example 35 except that PC-1 was replaced with PC-3.
- the physical property measurement results of the obtained resin composition are shown in Table 3 below.
- Example 37 75 parts by mass of PPE-2, 10.5 parts by mass of GPPS, 10 parts by mass of AS, 2 parts by mass of elastomer 1, and 2.5 parts by mass of elastomer 2 were melt kneaded in the same manner as in Example 1. Thus, a resin composition was obtained. The physical property measurement results of the obtained resin composition are shown in Table 3 below.
- Example 38 In the case of Example 1, 75 parts by weight of PPE-2, 10.5 parts by weight of AS, 2 parts by weight of elastomer 1, 2.5 parts by weight of elastomer 2, and 10 parts by weight of PC-4 Similarly, the resin composition was obtained by melt-kneading. The physical property measurement results of the obtained resin composition are shown in Table 3 below.
- Example 39 A resin composition was obtained by melt-kneading in the same manner as in Example 38 except that PC-4 was replaced with PC-3.
- the physical property measurement results of the obtained resin composition are shown in Table 3 below.
- Example 40 In the case of Example 1, 75 parts by weight of PPE-2, 10.5 parts by weight of GPPS, 2 parts by weight of elastomer 1, 2.5 parts by weight of elastomer 2, and 10 parts by weight of PC-1 Similarly, the resin composition was obtained by melt-kneading. The physical property measurement results of the obtained resin composition are shown in Table 3 below.
- Example 41 A resin composition was obtained by melt-kneading in the same manner as in Example 40 except that GPPS was replaced with AS.
- the physical property measurement results of the obtained resin composition are shown in Table 3 below.
- Example 42 In the case of Example 1, 80 parts by weight of PPE-2, 10.5 parts by weight of AS, 2 parts by weight of elastomer 1, 2.5 parts by weight of elastomer 2, and 5 parts by weight of PC-3 Similarly, the resin composition was obtained by melt-kneading. The physical property measurement results of the obtained resin composition are shown in Table 3 below.
- Example 43 75 parts by mass of PPE-4 and 25 parts by mass of PC-1 were melt-kneaded in the same manner as in Example 1 to obtain a resin composition.
- the physical property measurement results of the obtained resin composition are shown in Table 4 below.
- Example 44 60 parts by mass of PPE-4 and 40 parts by mass of PC-1 were melt-kneaded in the same manner as in Example 1 to obtain a resin composition.
- the physical property measurement results of the obtained resin composition are shown in Table 4 below.
- Example 45 100 parts by mass of PPE-4 and 30 parts by mass of PC-2 were melt-kneaded in the same manner as in Example 1 to obtain a resin composition.
- the physical property measurement results of the obtained resin composition are shown in Table 4 below.
- Example 46 84 parts by mass of PPE-4, 3 parts by mass of elastomer 1, 3 parts by mass of elastomer 2, and 10 parts by mass of PC-1 were melt-kneaded in the same manner as in Example 1 to obtain a resin composition. Got. The physical property measurement results of the obtained resin composition are shown in Table 4 below.
- Example 47 84 parts by mass of PPE-4, 2 parts by mass of AS, 3 parts by mass of elastomer 1, 3 parts by mass of elastomer 2, and 8 parts by mass of PC-1 were melt kneaded in the same manner as in Example 1. Thus, a resin composition was obtained. The physical property measurement results of the obtained resin composition are shown in Table 4 below.
- Example 48 84 parts by mass of PPE-4, 6 parts by mass of AS, 3 parts by mass of elastomer 1, 3 parts by mass of elastomer 2, and 4 parts by mass of PC-1 were melt kneaded in the same manner as in Example 1. Thus, a resin composition was obtained. The physical property measurement results of the obtained resin composition are shown in Table 4 below.
- Example 49 83 parts by weight of PPE-4, 3 parts by weight of elastomer 1, 3 parts by weight of elastomer 2, 1 part by weight of C-1, 10 parts by weight of PC-1, Similarly, the resin composition was obtained by melt-kneading. The physical property measurement results of the obtained resin composition are shown in Table 4 below.
- Example 50 84 parts by mass of PPE-5, 3 parts by mass of elastomer 1, 3 parts by mass of elastomer 2, and 10 parts by mass of PC-2 were melt-kneaded in the same manner as in Example 1 to obtain a resin composition. Got. The physical property measurement results of the obtained resin composition are shown in Table 4 below.
- Example 51 In the case of Example 1, 83 parts by weight of PPE-5, 3 parts by weight of elastomer 1, 3 parts by weight of elastomer 2, 1 part by weight of C-1, and 10 parts by weight of PC-2 Similarly, the resin composition was obtained by melt-kneading. The physical property measurement results of the obtained resin composition are shown in Table 4 below.
- Example 52 70 parts by mass of PPE-4, 9 parts by mass of AS, 3 parts by mass of elastomer 1, 3 parts by mass of elastomer 2, and 15 parts by mass of PC-1 were melt kneaded in the same manner as in Example 1. Thus, a resin composition was obtained. The physical property measurement results of the obtained resin composition are shown in Table 4 below.
- Example 53 100 parts by mass of PPE-4, 3 parts by mass of elastomer 1, 3 parts by mass of elastomer 2, and 30 parts by mass of PC-1 were melt-kneaded in the same manner as in Example 1 to obtain a resin composition. Got. The physical property measurement results of the obtained resin composition are shown in Table 4 below.
- Example 54 Implementation of 70 parts by weight of PPE-4, 8 parts by weight of AS, 3 parts by weight of elastomer 1, 3 parts by weight of elastomer 2, 1 part by weight of C-1, and 15 parts by weight of PC-1
- the resin composition was obtained by melt-kneading in the same manner as in Example 1.
- the physical property measurement results of the obtained resin composition are shown in Table 4 below.
- Example 55 Implementation of 65 parts by weight of PPE-4, 13 parts by weight of AS, 3 parts by weight of elastomer 1, 3 parts by weight of elastomer 2, 1 part by weight of C-1, and 15 parts by weight of PC-1
- the resin composition was obtained by melt-kneading in the same manner as in Example 1.
- the physical property measurement results of the obtained resin composition are shown in Table 4 below.
- Example 56 Implementation of 75 parts by weight of PPE-4, 10 parts by weight of AS, 2 parts by weight of elastomer 1, 2 parts by weight of elastomer 2, 1 part by weight of C-1, and 10 parts by weight of PC-1
- the resin composition was obtained by melt-kneading in the same manner as in Example 1.
- the physical property measurement results of the obtained resin composition are shown in Table 4 below.
- Example 57 75 parts by weight of PPE-4, 10.75 parts by weight of AS, 2 parts by weight of elastomer 1, 2 parts by weight of elastomer 2, 0.25 parts by weight of C-3, and 10 parts by weight of PC-1 Were melt-kneaded in the same manner as in Example 1 to obtain a resin composition.
- the physical property measurement results of the obtained resin composition are shown in Table 4 below.
- Example 58 75 parts by weight of PPE-4, 10.5 parts by weight of AS, 2 parts by weight of elastomer 1, 2 parts by weight of elastomer 2, 0.5 parts by weight of C-3, and 10 parts by weight of PC-1 Were melt-kneaded in the same manner as in Example 1 to obtain a resin composition.
- the physical property measurement results of the obtained resin composition are shown in Table 4 below.
- Example 59 75 parts by weight of PPE-4, 10.5 parts by weight of AS, 2 parts by weight of elastomer 1, 2 parts by weight of elastomer 2, 0.5 parts by weight of C-12, and 10 parts by weight of PC-1 Were melt-kneaded in the same manner as in Example 1 to obtain a resin composition.
- the physical property measurement results of the obtained resin composition are shown in Table 4 below.
- Example 60 75 parts by weight of PPE-4, 10.5 parts by weight of AS, 2 parts by weight of elastomer 1, 2 parts by weight of elastomer 2, 0.5 parts by weight of C-13, and 10 parts by weight of PC-1 Were melt-kneaded in the same manner as in Example 1 to obtain a resin composition.
- the physical property measurement results of the obtained resin composition are shown in Table 4 below.
- both content of polyphenylene ether (A) is outside the range of the resin composition used for this Embodiment. Therefore, the molded body made of the resin composition of Comparative Example 1 is cloudy on the surface of the molded body, and the brightness of the molded body after heat aging is insufficient, and the molded body made of the resin composition of Comparative Example 2 is The Vicat softening temperature, which is an index of heat resistance, was insufficient.
- the molded body made of the resin composition of Examples 4 and 5 is blended with a crystalline polymer in the resin composition, the gloss value of the molded body, the brightness after heat aging, and the peelability of the molded body are not necessarily limited. The result was not enough.
- the molded body made of the resin composition of Example 6 was blended with rubber-reinforced polystyrene in the resin composition, the gloss value of the molded body and the brightness feeling after heat aging were not necessarily satisfactory. .
- the molded body made of the resin composition of Example 7 contains the styrene thermoplastic elastomer (B2-2) having a low amount of bound styrene (33%) alone in the resin composition, SFD high-speed injection molding Since peeling occurred in the piece, the result was not necessarily sufficient in the peelability of the molded body.
- the resin composition of Reference Example 1 could not be molded because the reduced viscosity of the polyphenylene ether (A) used was low ( ⁇ sp / c : 0.22 dl / g). It was.
- the molded bodies made of the resin compositions of Example 15, Example 16, Example 21, and Examples 24 to 33 were not necessarily satisfactory in appearance and appearance of the aluminum vapor-deposited flat plate. 20, a hindered phenol heat stabilizer having a melting point of 180 ° C. or higher in the composition of the resin composition not containing the polycarbonate resin (B3). Therefore, it has been found that the appearance of vitiligo and aluminum vapor-deposited flat plates is good and can be used more favorably with automobile lamp extension molded articles.
- Example 35, Example 36, and Examples 38 to 42 are molded articles made of a resin composition in which a polycarbonate resin (B3) is blended as the component (B), and none of them is blended with a polycarbonate (B3). It was found that the molded products of Examples 34 and 37, which are resin compositions, were excellent in vitiligo, the appearance of the aluminum vapor-deposited flat plate, and the chemical resistance, and could be more suitably used in the automotive lamp extension molded product.
- the molded body made of the resin composition of Comparative Example 4 has a higher specific gravity because 50% by mass of the polycarbonate resin (B3) is blended as the component (B). Since the appearance of the vapor-deposited flat plate was also lowered, it was insufficient.
- the molded bodies made of the resin compositions of Examples 49 to 60 are all molded bodies made of a resin composition in which the polycarbonate resin (B3) is blended as the component (B), and both the white spots and the appearance of the aluminum vapor-deposited flat plate are good. there were.
- the molded products made of the resin compositions of Examples 57 to 60 are blended with the phosphorous heat stabilizer as component (C), so that the number of vitiligo is further increased compared to other molded products.
- the appearance of the aluminum vapor-deposited flat plate is improved, and it has been found that it can be used even more suitably as an automobile lamp extension molded body.
- Japanese Patent Application No. 2010-261661 Japanese patent application filed on September 27, 2011
- Japanese Patent Application No. 2011-212235 Japanese patent application filed on September 27, 2011
- Japanese Patent Application No. 2011-246747 Japanese patent application filed on September 27, 2011
- the molded body made of the resin composition of the present invention is effective as an automotive lamp extension molded body because of its low specific gravity, good balance between heat resistance and fluidity, and excellent gloss and brightness of the molded product. Can be used.
Abstract
Description
ポリフェニレンエーテル(A)50~95質量%を含有し、比重が1.00~1.12の範囲内である樹脂組成物を含む、自動車ランプエクステンション成形体。
前記(A)成分の還元粘度(クロロホルム溶媒を用いて30℃で測定)が0.25~0.45dl/gである、前記[1]に記載の自動車ランプエクステンション成形体。
前記(A)成分の還元粘度(クロロホルム溶媒を用いて30℃で測定)が0.25~0.38dl/gである、前記[1]又は[2]に記載の自動車ランプエクステンション成形体。
前記樹脂組成物が、ゴム強化されていないスチレン系樹脂(B1)、スチレン系熱可塑性エラストマー(B2)及びポリカーボネート樹脂(B3)からなる群より選択される少なくとも1種の樹脂成分(B)5~50質量%をさらに含有する、前記[1]~[3]のいずれかに記載の自動車ランプエクステンション成形体。
前記(B1)成分が、アクリロニトリル(AN)単位含有量5~15質量%のスチレン-アクリロニトリル(AS)樹脂である、前記[4]に記載の自動車ランプエクステンション成形体。
前記(B2)成分が、スチレン-共役ジエン化合物ブロック共重合体の水素添加物である、前記[4]又は[5]に記載の自動車ランプエクステンション成形体。
前記(B2)成分が、結合スチレン量が45~80質量%のスチレン-共役ジエン化合物ブロック共重合体の水素添加物(B2-1)と、結合スチレン量が20~40質量%のスチレン-共役ジエン化合物ブロック共重合体の水素添加物(B2-2)とを、(B2-1)/(B2-2)=4/1~1/4の質量比率で併用したものである、前記[4]~[6]のいずれかに記載の自動車ランプエクステンション成形体。
前記(B3)成分が、分子骨格内に、二価フェノール残基を含有する芳香族ポリカーボネート樹脂である、前記[4]~[7]のいずれかに記載の自動車ランプエクステンション成形体。
前記(B3)成分が、分子骨格中に、シクロヘキサン環を導入したビスフェノール残基を含有するポリカーボネート樹脂である、前記[4]~[8]のいずれかに記載の自動車ランプエクステンション成形体。
前記(B3)成分のMFR(試験方法ISO1133に準拠。測定温度300℃、1.2kg荷重で測定)が、0.5~25g/10minの範囲内である、前記[4]~[9]のいずれかに記載の自動車ランプエクステンション成形体。
前記樹脂組成物が、前記(B3)成分を5~40質量%含有する、前記[4]~[10]のいずれかに記載の自動車ランプエクステンション成形体。
前記(B)成分が、アクリロニトリル(AN)単位含有量5~15質量%のスチレン-アクリロニトリル(AS)樹脂とポリカーボネート樹脂とを含有する、前記[4]~[11]のいずれかに記載の自動車ランプエクステンション成形体。
前記樹脂組成物が、熱安定剤成分(C)0.01~5質量%をさらに含有する、前記[1]~[12]のいずれかに記載の自動車ランプエクステンション成形体。
前記(C)成分が、融点が180℃以上の熱安定剤である、前記[13]に記載の自動車ランプエクステンション成形体。
前記(C)成分が、ヒンダードフェノール系熱安定剤である、前記[13]又は[14]に記載の自動車ランプエクステンション成形体。
前記(C)成分がリン系熱安定剤である、前記[13]又は[14]に記載の自動車ランプエクステンション成形体。
前記樹脂組成物が、MFR(280℃、10kgで測定)が20g/10min以上で、かつ、ビカット軟化温度(ISO306に準拠、試験荷重50N、昇温速度120℃/hrで測定)が160℃以上である、前記[1]~[16]のいずれかに記載の自動車ランプエクステンション成形体。
測定角20°での光沢値が90~140%の範囲内である光沢面を有する、前記[1]~[17]のいずれかに記載の自動車ランプエクステンション成形体。
成形体の鏡面部分の面積52.4mm2内に存在する白斑(直径30μm以上のクレーター状の窪みを有する突起物を指す)が、40個以下である、前記[1]~[18]のいずれかに記載の自動車ランプエクステンション成形体。
本実施の形態に係る自動車ランプエクステンション成形体は、ポリフェニレンエーテル(A)50~95質量%を含有し、比重が1.00~1.12の範囲内である樹脂組成物を含む。
本実施の形態に用いる樹脂組成物は、ポリフェニレンエーテル(A)を50~95質量%含有し、比重が1.00~1.12の範囲内である。
本実施の形態に用いるポリフェニレンエーテル(A)の還元粘度は、0.25~0.45dl/gの範囲であることが好ましく、より好ましくは0.25~0.40dl/gであり、さらに好ましくは0.25~0.38dl/gであり、特に好ましくは0.25~0.35dL/gの範囲である。ポリフェニレンエーテル(A)の還元粘度は、十分な機械物性の観点から0.25dl/g以上が好ましく、成形加工性と成形体の輝度感との観点から0.45dl/g以下が好ましい。なお、本実施の形態において、還元粘度は、クロロホルム溶媒を用いて30℃で測定し、得られた値である。
本実施の形態に用いる樹脂組成物は、成形加工性及び成形体の外観、輝度感を向上させる観点から、ゴム強化されていないスチレン系樹脂(B1)、スチレン系熱可塑性エラストマー(B2)及びポリカーボネート樹脂(B3)からなる群より選択される少なくとも1種の樹脂成分(B)5~50質量%をさらに含有することが好ましい。樹脂成分(B)の含有量は、樹脂組成物100質量%中において、より好ましくは10~40質量%であり、さらにより好ましくは15~35質量%の範囲内である。樹脂成分(B)の含有量は、本用途に要求される耐熱性の観点から、50質量%以下が好ましく、成形品の耐衝撃性、輝度感及び成形流動性改良等の観点から、5質量%以上が好ましい。
本実施の形態に使用する、ゴム強化されていないスチレン系樹脂(B1)とは、スチレン系化合物、又はスチレン系化合物と該スチレン系化合物と共重合可能な化合物とを、ゴム質重合体の非存在下で重合して得られる合成樹脂である。スチレン系化合物とは、下記式(2)で表される化合物を意味する。
スチレン系熱可塑性エラストマー(B2)は、スチレンブロックと共役ジエン化合物ブロックとを有するブロック共重合体(以下、「スチレンブロック-共役ジエン化合物ブロック共重合体」とも記す。)の水素添加物であることが好ましい。前記共役ジエン化合物ブロックは、熱安定性の観点から、少なくとも水素添加率50%以上で水素添加されたものが好ましい。該水素添加率は、より好ましくは80%以上、さらにより好ましくは95%以上である。
前記(B)成分は、ポリカーボネート樹脂(B3)を含むことが好ましい。また、前記(B)成分は、上述のアクリロニトリル(AN)単位含有量5~15質量%のスチレン-アクリロニトリル(AS)樹脂とポリカーボネート樹脂(B3)とを含むことがより好ましい。このような(B)成分を含む樹脂組成物は、耐熱性、流動性のバランスが良好となり、該樹脂組成物から、成形体表面の白斑が極めて少なく、外観が良好な成形体を得ることができる。
ポリカーボネート樹脂(B3)としては、芳香族ポリカーボネート、脂肪族ポリカーボネート、芳香族-脂肪族ポリカーボネートが挙げられるが、本実施の形態においては、芳香族ポリカーボネートが好ましい。
[t0は塩化メチレンの落下秒数、tは試料溶液の落下秒数]
[η]=1.23×10-4M0.83
c=0.7
本実施の形態に用いる樹脂組成物は、樹脂組成物の熱安定性、並びに成形品の表面外観及び輝度感を向上させる観点から、熱安定剤成分(C)0.01~5質量%をさらに含有することが好ましい。熱安定剤成分(C)の含有量は、樹脂組成物100質量%に対して、より好ましくは0.1~3質量%であり、さらにより好ましくは0.2~2質量%の範囲内である。
本実施の形態に用いる樹脂組成物には、成形品の輝度感保持の観点から、強化剤としての無機フィラーは含まないことが好ましい。強化剤としての無機フィラーとしては、一般的に、熱可塑性樹脂の補強に用いられるものであり、例えば、ガラス繊維、炭素繊維、ガラスフレーク、タルク、マイカ等が挙げられる。
本実施の形態に用いる樹脂組成物は、軽量化のための薄肉成形加工性と、成形体の長期耐熱性、耐久性保持との兼ね合いの観点から、MFR(280℃、10kg荷重で測定)が20g/min以上で、かつ、ビカット軟化温度(ISO306に準拠、試験荷重50N、昇温速度120℃/hrで測定)が160℃以上であることが好ましい。より好ましくは、前記MFR20~150g/min、かつ、前記ビカット軟化温度160~210℃の範囲内であり、さらにより好ましくは、前記MFR25~90g/min、かつ、前記ビカット軟化温度170~200℃の範囲内である。
本実施の形態に用いる樹脂組成物は、上記各成分、例えば、前記(A)成分、前記(B)成分及び/又は、前記(C)成分を溶融混錬することにより製造することができる。前記樹脂組成物を製造するための、前記(A)成分、前記(B)成分及び/又は、前記(C)成分の溶融混錬の条件については、特に制限されないが、本実施の形態の所望の効果を十分に発揮し得る樹脂組成物を大量且つ安定的に得るという観点から、二軸押出機を用いることが好適である。一例として、ZSK25二軸押出機(独国Werner&Pfleiderer社製、バレル数10、スクリュー径25mm、L/D=44);ニーディングディスクL:2個、ニーディングディスクR:6個、及びニーディングディスクN:2個を有するスクリューパターン)を用いた場合に、シリンダー温度270~340℃、スクリュー回転数150~450rpm、及びベント真空度11.0~1.0kPaの条件で溶融混練する方法が挙げられる。
本実施の形態の自動車ランプエクステンション成形体は、上述の樹脂組成物を成形することにより得ることができる。
本実施の形態の自動車ランプエクステンション成形体の平均厚みは、0.8~3.2mmの範囲から選ばれることが好ましい。該平均厚みは、1.0~3.0mmがより好ましく、1.2~2.5mmがさらにより好ましく、1.2~2.0mmが特により好ましい。該平均厚みは、軽量性の観点から3.2mm以下が好ましく、十分な成形性と強度保持の観点から0.8mm以上が好ましい。
前提として、物性測定に用いた成形片は、いずれも以下のように作製した成形片とした。
アルファーミラージュ社製の電子比重計SD-200Lを用いて測定した。
上記ダンベル成形片を切削して作製した、試験片形状35mm×13mm×3.2mm厚の試験片を用いて、ISO306に準拠、HDTテスター S-6M型(東洋精機製作所社製)を使用して、試験荷重:50N、圧子先端形状:円柱状 断面積1mm2、昇温速度120℃/hr、測定数n=2の条件で測定した。
評価基準としては、ビカット軟化温度が高い値である程、耐熱性に優れ、本用途の材料設計面において有利であると判定した。
実施例及び比較例で得られた樹脂組成物ペレットを120℃の熱風乾燥機中で3時間乾燥した。乾燥後、メルトインデクサー(P-111、東洋精機社製)を用いて、シリンダー設定温度280℃、10kg荷重にて、MFR(メルトフローレート)を測定した。
評価基準としては、MFRが高い値である程、流動性に優れ、本用途の材料設計面において有利であると判定した。
ASTM D256に従い、上記タンザク成形片を切削して作製した試験片形状64mm×13mm×厚み6.4mmのタンザク試験片を用いて、ノッチ有り、23℃で測定した。
評価基準としては、IZOD衝撃値が高い値である程、本用途の材料設計面において有利であると判定した。
上記の成形方法で作製した厚み3.2mmのダンベル試験片の中央部を、グロスメーター(VG7000、日本電色工業社製)により、測定角20°における光沢値(グロス)を測定した。
評価基準としては、光沢値が高い値である程、見た目にも成形片の艶が高く、輝度感に優れる。
射出成形機(IS-80EPN、東芝機械社製)を用いて、1mm厚みSFD(スパイラルフロー)成形品を以下のとおり作製した。
下記の実施例及び比較例でで得られた樹脂組成物のペレットを、120℃で3時間乾燥させた。乾燥後の樹脂組成物を、上記射出成形機を用い、ゲージ圧120MPa、射出速度95%、成形サイクル:射出時間/冷却時間=10sec/10secの条件で成形し、上記成形品を得た。得られた成形品の剥離の有無を確認した。剥離無しの場合を○、剥離有りの場合を×とし、○の場合を、本用途の材料設計面において有利であると判定した。
厚み3.2mmのダンベル試験片を用いて、150℃に設定したオーブン内に250hrエージングを行なった後、成形片の輝度感を目視で評価した。輝度感に問題が見られないものを○、成形片表面に曇りが生じてエージング前と比較して輝度感低下が明らかなものを“曇り有り”とした。○のものが、本用途において好適に使用可能であると判断した。
実施例及び比較例で得られた樹脂組成物のペレットを、120℃の熱風乾燥機中で3時間乾燥した。乾燥後の樹脂組成物を、金型表面を#5000で磨き上げた寸法100mm×100mm×2mm厚みのフィルムゲート鏡面金型を備え付けた射出成形機(IS-80EPN、東芝機械社製)により、シリンダー温度320℃、金型温度120℃、射出圧力(ゲージ圧70MPa)、射出速度(パネル設定値)85%で成形して成形平板を得た。さらにこの得られた成形平板を真空状態下の蒸着装置内に設置し、該装置内に不活性ガス及び酸素を導入し、チャンバー内をプラズマ状態にして、成形平板表面を活性化させるプラズマ処理を行ない、真空下の蒸着装置内で成形平板のアルミニウム蒸着を行なった。さらに、アルミニウム蒸着面の保護膜として、プラズマ重合処理を行ない、二酸化珪素重合膜を形成させた。アルミニウム膜厚は80nm、二酸化珪素膜厚は50nmであった。このアルミニウム蒸着を行なった成形平板(以下、「アルミ蒸着平板」とも記す。)のアルミニウム蒸着面中央部をデジタルマイクロスコープ(型式:VHX1000、キーエンス社製)により、40倍の拡大写真を撮影した。1撮影視野(面積:52.4mm2)内に存在する直径30μm以上のクレーター状の窪みを有する突起物(成形時にガスが抜けた跡)の個数を鏡面成形平板5枚分すべてにおいてカウントした合計を5で割って、1撮影視野当たりの平均個数を算出した。該平均個数を白斑の個数とした。
上記の方法で作製したアルミ蒸着平板のアルミニウム蒸着面を、目視で観察し、以下のランクに応じて○~×で評価した。目視では白斑が認められず外観が良好なものを○、白斑が認められるものの概ね外観が良好なものを△、白斑が多数認められて外観不良が明らかであるものを×とし、○のものが本用途においてより好適に使用可能であると判定した。
厚み3.2mmのダンベル試験片を、1%歪のベンディングフォームに取り付けて、イソプロピルアルコール(IPA)/シクロヘキサン(CHX)=60/40質量%混合溶液中に浸漬させ23℃で30分放置させた。その後、試験片をベンディングフォームから取り外して、ティシュペーパーで十分に溶剤を拭き取って23℃で2時間以上放置した。その後、浸漬後の試験片について、引張試験(ASTM D638に準拠)を行なって、引張強度(TY)を求めた。通常サンプルの引張強度を100%とした場合に対する浸漬後の試験片の引張強度の割合(引張強度保持率(%))を求めた(試験本数n=3)。なお、表3中、「×(ハダン)」とは、いずれも浸漬中に試験片が3本とも破断したため、引張強度の測定不可であったことを意味する。
厚み3.2mmのダンベル試験片を、1%歪のベンディングフォームに取り付けて、ダンベル中心線上に3mm幅でリノール酸を塗布して、23℃で30分放置させた。その後、ダンベル試験片を、ベンディングフォームから取り外し、リノール酸をティシュペーパーで拭き取り、さらにエタノールで洗浄した後、23℃で2時間以上放置した。その後、放置後の試験片について、引張試験(ASTM D638に準拠)を行なって、引張強度(TY)を求めた。通常サンプルの引張強度を100%とした場合に対する放置後の試験片の引張強度の割合(引張強度保持率(%))とを求めた(試験本数n=3)。
以下のように製造したスチレン-アクリロニトリル樹脂を用いた。
アクリロニトリル4.7質量部、スチレン73.3質量部、エチルベンゼン22質量部、重合開始剤としてのt-ブチルパーオキシ-イソプロピルカーボネート0.02質量部よりなる混合液を、2.5リットル/時間の流速で、容量5リットルの完全混合型反応機に連続的に供給し、142℃で重合を行って重合液を得た。
化学名:3,3‘,3“,5,5’,5”-ヘキサ-tert-ブチル-a,a‘,a“-(メシチレン-2,4,6-トリイル)トリ-p-クレゾール(商品名:Irganox1330〔登録商標〕、BASF社製)を用いた(以下、「C-1」ということもある)。
化学名:1,3,5-トリス(3,5-ジ-tert-ブチル-4-ヒドロキシベンジル)-1,3,5-トリアジン-2,4,6(1H,3H,5H)-トリオン(商品名:Irganox3114〔登録商標〕、BASF社製)を用いた(以下、「C-2」ということもある)。
化学名:トリス(2,4-ジ-tert-ブチルフェニル)フォスファイト(商品名:Irgafos168〔登録商標〕、BASF社製)を用いた(以下、「C-3」ということもある)。
化学名:N,N‘-ヘキサン-1,6-ジイルビス〔3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオンアミド〕(商品名:Irganox1098〔登録商標〕、BASF社製)を用いた(以下、「C-4」ということもある)。
化学名:N,N‘-ビス(2,2,6,6-テトラメチル-4-ピペリジル)N,N’-ジホルミルヘキサメチレンジアミン(商品名:Uvinil4050FF〔登録商標〕、BASF社製)を用いた(以下、「C-5」ということもある)。
化学名:ジブチルアミン・1,3,5-トリアジン・N,N‘-ビス(2,2,6,6-テトラメチル-4-ピペリジル)-1,6-ヘキサメチレンジアミンとN-(2,2,6,6-テトラメチル-4-ピペリジル)ブチルアミンとの重縮合物(商品名:Chimassorb2020〔登録商標〕、BASF社製)を用いた(以下、「C-6」ということもある)。
化学名:ペンタエリスリトールテトレキス〔3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオネート〕(商品名:Irganox1010〔登録商標〕、BASF社製)を用いた(以下、「C-7」ということもある)。
化学名:オクタデシル-3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオネート(商品名:Irganox1076〔登録商標〕、BASF社製)を用いた(以下、「C-8」ということもある)。
化学名:2,6-ジ-tert-ブチル-4-(4,6-ビス(オクチルチオ)-1,3,5-トリアジン-2-イルアミノ)フェノール(商品名:Irganox565〔登録商標〕、BASF社製)を用いた(以下、「C-9」ということもある)。
化学名:4,6-ビス(オクチルチオメチル)-O-クレゾール(商品名:Irganox1520〔登録商標〕、BASF社製)を用いた(以下、「C-10」ということもある)。
化学名:ジオクタデシル3,3‘-チオジプロピオネート(商品名:Irganox PS802〔登録商標〕、BASF社製)を用いた(以下、「C-11」ということもある)。
化学名:3,9-ビス(2,6-ジ-tert-ブチル-4-メチルフェノキシ)-2,4,8,10-テトラオキサ-3,9-ジホスファスピロ[5,5]ウンデカン(商品名:アデカスタブPEP-36〔登録商標〕、アデカ社製)を用いた(以下、「C-12」ということもある)。
化学名:ビス(2,4-ジクミルフェニル)ペンタエリスリトールジホスファイト(商品名:DoverPhos S-9228〔登録商標〕、ドーバーケミカル社製)を用いた(以下、「C-13」ということもある)。
PPE-2を80質量部とGPPS20質量部とを、独国Werner&Pfleiderer社製、バレル数10、スクリュー径25mm、L/D=44のZSK25二軸押出機(ニーディングディスクL:2個、ニーディングディスクR:6個、ニーディングディスクN:2個を有するスクリューパターン)の最上流部(トップフィード)から供給して、シリンダー温度300℃、スクリュー回転数250rpm、ベント真空度7.998kPa(60Torr)で溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表1に示す。
PPE-2を80質量部と、GPPS10質量部と、AS10質量部とを、実施例1の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表1に示す。
PPE-4を100質量部、実施例1の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表1に示す。
PPE-4を80質量部と、GPPS20質量部とを、実施例1の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表1に示す。
PPE-2を80質量部と、GPPS20質量部と、ポリアミド6(商品名:1013B〔登録商標〕、宇部興産社製、以下「PA」とも記す。)を5質量部と、エラストマー1を3質量部とを、実施例1の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表1に示す。
実施例4のポリアミド6を、ポリプロピレン(商品名:ノバテックPP SA08〔登録商標〕、日本ポリプロピレン社製、以下「PP」とも記す。)5質量部に置き換えた以外は、実施例4の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表1に示す。
PPE-2を80質量部と、GPPS20質量部と、ゴム強化ポリスチレン(商品名:H9405〔登録商標〕、旭化成ケミカルズ社製)5質量部とを、実施例1の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表1に示す。
PPE-2を60質量部と、GPPS40質量部と、エラストマー1を5質量部とを、実施例1の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表1に示す。
PPE-1を60質量部と、GPPS40質量部と、エラストマー1を2質量部と、エラストマー2を3質量部とを、実施例1の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表1に示す。
PPE-2を60質量部と、GPPS40質量部と、エラストマー1を2質量部と、エラストマー2を3質量部とを、実施例1の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表1に示す。
PPE-2を60質量部と、GPPS40質量部と、エラストマー1を1質量部と、エラストマー2を4質量部とを、実施例1の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表1に示す。
PPE-2を60質量部と、GPPS40質量部と、エラストマー1を4質量部と、エラストマー2を1質量部とを、実施例1の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表1に示す。
PPE-2を60質量部と、GPPS40質量部と、エラストマー2を5質量部とを、実施例1の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表1に示す。
PPE-2を50質量部と、GPPS25質量部と、AS25質量部と、エラストマー1を2質量部と、エラストマー2を3質量部とを、実施例1の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表1に示す。
PPE-2を90質量部と、GPPS5質量部と、AS5質量部と、エラストマー1を2質量部と、エラストマー2を2質量部とを、実施例1の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表1に示す。
PPE-4を90質量部と、GPPS5質量部と、AS5質量部と、エラストマー1を2質量部と、エラストマー2を2質量部とを、実施例1の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表1に示す。
PPE-4を60質量部と、GPPS32質量部と、エラストマー1を2質量部と、エラストマー2を6質量部とを、実施例1の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表2に示す。
PPE-4を60質量部と、AS32質量部と、エラストマー1を2質量部と、エラストマー2を6質量部とを、実施例1の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表2に示す。
PPE-4を60質量部と、GPPS31.5質量部と、エラストマー1を2質量部と、エラストマー2を6質量部と、C-1を0.5質量部とを、実施例1の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表2に示す。
PPE-4を60質量部と、GPPS31質量部と、エラストマー1を2質量部と、エラストマー2を6質量部と、C-1を1質量部とを、実施例1の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表2に示す。
PPE-4を60質量部と、GPPS21質量部と、AS10質量部と、エラストマー1を2質量部と、エラストマー2を6質量部と、C-1を1質量部とを、実施例1の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表2に示す。
PPE-4を60質量部と、GPPS30質量部と、エラストマー1を2質量部と、エラストマー2を6質量部と、C-1を2質量部とを、実施例1の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表2に示す。
PPE-5を95質量部と、エラストマー1を3質量部と、エラストマー2を2質量部とを、実施例1の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表2に示す。
PPE-5を94質量部と、エラストマー1を3質量部と、エラストマー2を2質量部と、C-1を1質量部とを、実施例1の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表2に示す。
PPE-6を94質量部と、エラストマー1を3質量部と、エラストマー2を2質量部と、C-1を1質量部とを、実施例1の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の成形を試みたが、成形品が脆く、割れやスプルーブッシュ詰まりが発生して、成形ができない状態であった。従って、物性測定結果は出せなかった。
PPE-4を70質量部と、GPPS21質量部と、エラストマー1を2質量部と、エラストマー2を6質量部と、C-2を1質量部とを、実施例1の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表2に示す。
C-2を、C-3に変えた以外は、実施例23の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表2に示す。
C-2を、C-4に変えた以外は、実施例23の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表2に示す。
C-2を、C-5に変えた以外は、実施例23の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表2に示す。
C-2を、C-6に変えた以外は、実施例23の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表2に示す。
C-2を、C-7に変えた以外は、実施例23の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表2に示す。
C-2を、C-9に変えた以外は、実施例23の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表2に示す。
C-2を、C-11に変えた以外は、実施例23の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表2に示す。
PPE-5を80質量部と、GPPS7質量部と、AS7質量部と、エラストマー1を1質量部と、エラストマー2を4質量部と、C-3を0.5質量部と、C-7を0.5質量部とを、実施例1の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表2に示す。
PPE-5を80質量部と、GPPS6質量部と、AS7質量部と、エラストマー1を1質量部と、エラストマー2を4質量部と、C-5を1質量部と、C-7を1質量部とを、実施例1の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表2に示す。
PPE-5を80質量部と、GPPS6質量部と、AS7質量部と、エラストマー1を1質量部と、エラストマー2を4質量部と、C-8を1質量部と、C-10を1質量部とを、実施例1の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表2に示す。
PC-3の物性測定結果を下記表3に示す。
PPE-2を85質量部と、GPPS10.5質量部と、エラストマー1を2質量部と、エラストマー2を2.5質量部とを、実施例1の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表3に示す。
PPE-2を85質量部と、エラストマー1を2質量部と、エラストマー2を2.5質量部と、PC-1を10.5質量部とを、実施例1の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表3に示す。
PC-1を、PC-3に置き換えた以外は、実施例35の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表3に示す。
PPE-2を75質量部と、GPPS10.5質量部と、AS10質量部と、エラストマー1を2質量部と、エラストマー2を2.5質量部とを、実施例1の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表3に示す。
PPE-2を75質量部と、AS10.5質量部と、エラストマー1を2質量部と、エラストマー2を2.5質量部と、PC-4を10質量部とを、実施例1の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表3に示す。
PC-4を、PC-3に置き換えた以外は、実施例38の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表3に示す。
PPE-2を75質量部と、GPPS10.5質量部と、エラストマー1を2質量部と、エラストマー2を2.5質量部と、PC-1を10質量部とを、実施例1の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表3に示す。
GPPSを、ASに置き換えた以外は、実施例40の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表3に示す。
PPE-2を80質量部と、AS10.5質量部と、エラストマー1を2質量部と、エラストマー2を2.5質量部と、PC-3を5質量部とを、実施例1の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表3に示す。
PPE-4を75質量部と、PC-1を25質量部とを、実施例1の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表4に示す。
PPE-4を60質量部と、PC-1を40質量部とを、実施例1の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表4に示す。
PPE-4を100質量部と、PC-2を30質量部とを、実施例1の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表4に示す。
PPE-4を50質量部と、PC-1を50質量部とを、実施例1の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表4に示す。
PPE-4を84質量部と、エラストマー1を3質量部と、エラストマー2を3質量部と、PC-1を10質量部とを、実施例1の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表4に示す。
PPE-4を84質量部と、AS2質量部と、エラストマー1を3質量部と、エラストマー2を3質量部と、PC-1を8質量部とを、実施例1の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表4に示す。
PPE-4を84質量部と、AS6質量部と、エラストマー1を3質量部と、エラストマー2を3質量部と、PC-1を4質量部とを、実施例1の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表4に示す。
PPE-4を83質量部と、エラストマー1を3質量部と、エラストマー2を3質量部と、C-1を1質量部と、PC-1を10質量部とを、実施例1の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表4に示す。
PPE-5を84質量部と、エラストマー1を3質量部と、エラストマー2を3質量部と、PC-2を10質量部とを、実施例1の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表4に示す。
PPE-5を83質量部と、エラストマー1を3質量部と、エラストマー2を3質量部と、C-1を1質量部と、PC-2を10質量部とを、実施例1の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表4に示す。
PPE-4を70質量部と、AS9質量部と、エラストマー1を3質量部と、エラストマー2を3質量部と、PC-1を15質量部とを、実施例1の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表4に示す。
PPE-4を100質量部と、エラストマー1を3質量部と、エラストマー2を3質量部と、PC-1を30質量部とを、実施例1の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表4に示す。
PPE-4を70質量部と、AS8質量部と、エラストマー1を3質量部と、エラストマー2を3質量部と、C-1を1質量部と、PC-1を15質量部とを、実施例1の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表4に示す。
PPE-4を65質量部と、AS13質量部と、エラストマー1を3質量部と、エラストマー2を3質量部と、C-1を1質量部と、PC-1を15質量部とを、実施例1の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表4に示す。
PPE-4を75質量部と、AS10質量部と、エラストマー1を2質量部と、エラストマー2を2質量部と、C-1を1質量部と、PC-1を10質量部とを、実施例1の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表4に示す。
PPE-4を75質量部と、AS10.75質量部と、エラストマー1を2質量部と、エラストマー2を2質量部と、C-3を0.25質量部と、PC-1を10質量部とを、実施例1の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表4に示す。
PPE-4を75質量部と、AS10.5質量部と、エラストマー1を2質量部と、エラストマー2を2質量部と、C-3を0.5質量部と、PC-1を10質量部とを、実施例1の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表4に示す。
PPE-4を75質量部と、AS10.5質量部と、エラストマー1を2質量部と、エラストマー2を2質量部と、C-12を0.5質量部と、PC-1を10質量部とを、実施例1の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表4に示す。
PPE-4を75質量部と、AS10.5質量部と、エラストマー1を2質量部と、エラストマー2を2質量部と、C-13を0.5質量部と、PC-1を10質量部とを、実施例1の場合と同様に溶融混練して樹脂組成物を得た。得られた樹脂組成物の物性測定結果を下記表4に示す。
Claims (19)
- ポリフェニレンエーテル(A)50~95質量%を含有し、比重が1.00~1.12の範囲内である樹脂組成物を含む、自動車ランプエクステンション成形体。
- 前記(A)成分の還元粘度(クロロホルム溶媒を用いて30℃で測定)が0.25~0.45dl/gである、請求項1に記載の自動車ランプエクステンション成形体。
- 前記(A)成分の還元粘度(クロロホルム溶媒を用いて30℃で測定)が0.25~0.38dl/gである、請求項1又は2に記載の自動車ランプエクステンション成形体。
- 前記樹脂組成物が、ゴム強化されていないスチレン系樹脂(B1)、スチレン系熱可塑性エラストマー(B2)及びポリカーボネート樹脂(B3)からなる群より選択される少なくとも1種の樹脂成分(B)5~50質量%をさらに含有する、請求項1~3のいずれか一項に記載の自動車ランプエクステンション成形体。
- 前記(B1)成分が、アクリロニトリル(AN)単位含有量5~15質量%のスチレン-アクリロニトリル(AS)樹脂である、請求項4に記載の自動車ランプエクステンション成形体。
- 前記(B2)成分が、スチレン-共役ジエン化合物ブロック共重合体の水素添加物である、請求項4又は5に記載の自動車ランプエクステンション成形体。
- 前記(B2)成分が、結合スチレン量が45~80質量%のスチレン-共役ジエン化合物ブロック共重合体の水素添加物(B2-1)と、結合スチレン量が20~40質量%のスチレン-共役ジエン化合物ブロック共重合体の水素添加物(B2-2)とを、(B2-1)/(B2-2)=4/1~1/4の質量比率で併用したものである、請求項4~6のいずれか一項に記載の自動車ランプエクステンション成形体。
- 前記(B3)成分が、分子骨格内に、二価フェノール残基を含有する芳香族ポリカーボネート樹脂である、請求項4~7のいずれか一項に記載の自動車ランプエクステンション成形体。
- 前記(B3)成分が、分子骨格中に、シクロヘキサン環を導入したビスフェノール残基を含有するポリカーボネート樹脂である、請求項4~8のいずれか一項に記載の自動車ランプエクステンション成形体。
- 前記(B3)成分のMFR(試験方法ISO1133に準拠。測定温度300℃、1.2kg荷重で測定)が、0.5~25g/10minの範囲内である、請求項4~9のいずれか一項に記載の自動車ランプエクステンション成形体。
- 前記樹脂組成物が、前記(B3)成分を5~40質量%含有する、請求項4~10のいずれか一項に記載の自動車ランプエクステンション成形体。
- 前記(B)成分が、アクリロニトリル(AN)単位含有量5~15質量%のスチレン-アクリロニトリル(AS)樹脂とポリカーボネート樹脂とを含有する、請求項4~11のいずれか一項に記載の自動車ランプエクステンション成形体。
- 前記樹脂組成物が、熱安定剤成分(C)0.01~5質量%をさらに含有する、請求項1~12のいずれか一項に記載の自動車ランプエクステンション成形体。
- 前記(C)成分が、融点が180℃以上の熱安定剤である、請求項13に記載の自動車ランプエクステンション成形体。
- 前記(C)成分が、ヒンダードフェノール系熱安定剤である、請求項13又は14に記載の自動車ランプエクステンション成形体。
- 前記(C)成分がリン系熱安定剤である、請求項13又は14に記載の自動車ランプエクステンション成形体。
- 前記樹脂組成物が、MFR(280℃、10kgで測定)が20g/10min以上で、かつ、ビカット軟化温度(ISO306に準拠、試験荷重50N、昇温速度120℃/hrで測定)が160℃以上である、請求項1~16のいずれか一項に記載の自動車ランプエクステンション成形体。
- 測定角20°での光沢値が90~140%の範囲内である光沢面を有する、請求項1~17のいずれか一項に記載の自動車ランプエクステンション成形体。
- 成形体の鏡面部分の面積52.4mm2内に存在する白斑(直径30μm以上のクレーター状の窪みを有する突起物を指す)が、40個以下である、請求項1~18のいずれか一項に記載の自動車ランプエクステンション成形体。
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US13/884,025 US8895655B2 (en) | 2010-11-24 | 2011-11-22 | Automotive lamp extension molding |
EP11843397.8A EP2644655B1 (en) | 2010-11-24 | 2011-11-22 | Automotive lamp extension molding |
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CN103221484A (zh) | 2013-07-24 |
CN103221484B (zh) | 2016-04-13 |
MY161180A (en) | 2017-04-14 |
US20130267641A1 (en) | 2013-10-10 |
US8895655B2 (en) | 2014-11-25 |
EP2644655A4 (en) | 2017-03-08 |
JPWO2012070592A1 (ja) | 2014-05-19 |
MX355310B (es) | 2018-04-16 |
EP2644655A1 (en) | 2013-10-02 |
JP5868871B2 (ja) | 2016-02-24 |
MX2013005424A (es) | 2013-07-05 |
EP2644655B1 (en) | 2021-06-30 |
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