WO2022091881A1 - Composition de résine thermoplastique et article moulé l'utilisant - Google Patents

Composition de résine thermoplastique et article moulé l'utilisant Download PDF

Info

Publication number
WO2022091881A1
WO2022091881A1 PCT/JP2021/038647 JP2021038647W WO2022091881A1 WO 2022091881 A1 WO2022091881 A1 WO 2022091881A1 JP 2021038647 W JP2021038647 W JP 2021038647W WO 2022091881 A1 WO2022091881 A1 WO 2022091881A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
graft copolymer
vinyl
copolymer
graft
Prior art date
Application number
PCT/JP2021/038647
Other languages
English (en)
Japanese (ja)
Inventor
上田隆志
佐藤大輔
森戸昭等
Original Assignee
東レ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 東レ株式会社 filed Critical 東レ株式会社
Priority to JP2021565893A priority Critical patent/JPWO2022091881A1/ja
Publication of WO2022091881A1 publication Critical patent/WO2022091881A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • 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
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates

Definitions

  • the present invention relates to a thermoplastic resin composition suitable for molding using a mold such as injection molding, and also relates to a molded product using the thermoplastic resin composition.
  • Polycarbonate resin has excellent heat resistance and impact resistance, so it is widely used in a wide range of fields including the fields of automobiles, home appliances, OA equipment, and building materials.
  • rubber-reinforced styrene resin represented by ABS resin has excellent workability and mechanical properties, so that various constituent members can be molded in a wide range of fields such as automobiles, home appliances, and OA equipment. It is used as a material.
  • Polycarbonate resin is inferior to rubber-reinforced styrene resin in molding processability and secondary processability during injection molding. Therefore, in order to compensate for the drawbacks of polycarbonate resin, polycarbonate resin and rubber-reinforced styrene resin are melt-mixed. It is generally alloyed. In particular, in the field of automobiles, in addition to heat resistance, impact resistance, moldability, etc., dimensional stability is also required, and in order to improve this, attempts have been made to add an inorganic filler such as talc.
  • silicate compound-based inorganic fillers such as rubber-reinforced styrene resin and talc produced through emulsion polymerization / acid coagulation / neutralization steps may exhibit alkalinity, and when blended with polycarbonate resin, the resin There was a problem that defects in the appearance of molded products such as silver streaks due to alkaline decomposition of polycarbonate occurred.
  • This Silver Streak has one of the appearance defects that appears as a streak pattern due to a large number of fine bubbles, and it is named after it because it looks silver due to the reflection of light at the interface between the bubbles and the resin composition. There is. It is considered that the generation of bubbles is generated by the decomposition of the resin, and that the streaky pattern is generated along the flow of the resin at the time of molding to appear as streaks. Further, the shear stress at the interface between the mold and the resin composition may cause the bubbles to be stretched, resulting in a more serious appearance defect.
  • Patent Document 1 describes an aromatic polycarbonate resin, a styrene resin, and a crystalline resin. And a resin composition containing an inorganic filler in a specific composition is disclosed.
  • Patent Document 2 discloses a resin composition containing an aromatic polycarbonate resin, a styrene resin, a phosphoric acid ester compound, and talc in a specific composition.
  • a crystalline resin is blended in order to suppress the generation of silver streaks, and the filler is embedded in the crystalline resin due to the affinity between the inorganic filler and the crystalline resin.
  • the aromatic polycarbonate resin may be alkaline-decomposed by the filler that comes into contact with the polycarbonate resin before being embedded in the resin, and the effect of suppressing the generation of silver streaks was not sufficient.
  • Patent Document 2 has a certain effect in suppressing the generation of silver streaks due to the use of the rubber-reinforced styrene resin obtained by emulsion polymerization, but brings about sufficient effectiveness. Has not been reached.
  • thermoplastic resin composition capable of further suppressing the generation of silver streaks when made into a molded product, and to provide a molded product using the thermoplastic resin composition. do.
  • the present invention is composed of the following (1) to (5).
  • Polycarbonate resin (I), graft copolymer (II), and talc (IV) are blended, and when the weight of talc (IV) is 100% by weight, the contents of iron component and calcium component are high. , 0.19% by weight or less as Fe 2 O 3 and 1.9% by weight or less as CaO, respectively.
  • the graft copolymer (II) graft-polymerizes a monomer mixture containing at least an aromatic vinyl-based monomer and a cyanide vinyl-based monomer in the presence of a diene-based rubbery polymer.
  • thermoplastic resin composition according to (1) which is a graft copolymer (II-2) obtained by graft-polymerizing a monomer mixture containing at least a body and a vinyl cyanide-based monomer.
  • thermoplastic resin composition according to (1) or (2) which further contains a vinyl-based copolymer (III).
  • thermoplastic resin composition according to any one of (1) to (3) further comprising one or both of a condensed phosphoric acid ester (V) and a crystalline resin (VI).
  • the generation of silver streak in a molded product can be suppressed.
  • the silver streak tends to worsen when the temperature of the molding machine cylinder or the hot runner of the mold is raised, but the temperature can be raised by using the resin composition capable of suppressing the generation of the silver streak of the present invention. Therefore, a large-sized molded product, a molded product having a complicated shape, and a thin-walled molded product can be obtained by injection molding. Therefore, it is possible not only to adapt to the increase in size and complexity of the product, but also to reduce the cost of the product by reducing the wall thickness.
  • FIG. 1 (a) and 1 (b) are explanatory views schematically showing a rectangular flat plate produced in the section of Examples, FIG. 1 (a) is a plan view, and FIG. 1 (b) is FIG. 1 (a). It is a cross-sectional view of AA'.
  • thermoplastic resin composition of the present invention and its molded product will be specifically described.
  • Polycarbonate resin (I) The polycarbonate resin (I) used in the present invention is generally known as a resin having a repeating structural unit represented by the following general formula (1).
  • Z represents a substituted or unsubstituted alkylidene group, cyclohexylidene group, oxygen atom, sulfur atom or sulfonyl group having 2 to 5 carbon atoms.
  • R 1 , R 2 , R 3 and R 4 are hydrogen. It is an atom or an alkyl group having 1 to 6 carbon atoms, and may be the same or different from each other).
  • Z is an isopropanol group and R 1 to R 4 are hydrogen atoms.
  • the polycarbonate resin (I) is represented by an aromatic dihydroxy compound represented by 2,2-bis (4-hydroxyphenyl) propane and 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane. , Can be obtained by reaction with a carbonate precursor exemplified by phosgene.
  • the content of the polycarbonate resin (I) is the polycarbonate resin (I), the graft copolymer (II), the vinyl-based copolymer (III) used as an optional component, and the talc.
  • the total content of (IV) is 100% by weight, it is preferably in the range of 60 to 90% by weight, more preferably 65 to 85% by weight, and further preferably 70 to 80% by weight.
  • the content of the polycarbonate resin (I) is less than 60% by weight, the fluidity is excellent, but the impact resistance and the heat resistance may be lowered.
  • the content exceeds 90% by weight some products may not be molded due to insufficient fluidity during injection molding, although they are excellent in impact resistance and heat resistance.
  • the viscosity average molecular weight ( MV ) of the polycarbonate resin (I) is not particularly limited, but is preferably 10,000 or more and 21,000 or less, more preferably 12,000 or more and 20,000 or less. Most preferably, it is 15,000 or more and 18,000 or less.
  • the MV is 10,000 or more, mechanical properties such as impact resistance and heat resistance tend to improve, and when it is 21,000 or less, the fluidity tends to improve and the appearance of the molded product tends to improve. Yes, preferred.
  • the viscosity average molecular weight ( MV ) of the polycarbonate resin (I) can be determined by the following method.
  • Specific viscosity ( ⁇ SP ) (tt 0 ) / t 0 [T 0 is the number of seconds for methylene chloride to fall, and t is the number of seconds for the sample solution to fall]
  • the viscosity average molecular weight MV can be calculated from the obtained specific viscosity ( ⁇ SP ) by the following Schnell's formula.
  • the graft copolymer (II) constituting the thermoplastic resin composition of the present invention includes an aromatic vinyl-based monomer (B) and a vinyl cyanide-based monomer (B) in the presence of a diene-based rubbery polymer (A1).
  • acrylic rubber polymer (A2) Acrylic rubber polymer obtained by copolymerizing an acrylic acid ester monomer and a polyfunctional monomer
  • A2 graft copolymer obtained by graft-polymerizing a monomer mixture containing at least an aromatic vinyl-based monomer (B) and a cyanide vinyl-based monomer (C) in the presence. Is preferable.
  • the diene-based rubbery polymer (A1) that can be used for the graft copolymer (II-1) is preferably one having a glass transition temperature of 0 ° C. or lower, and its lower limit is practically about -80 ° C. Is.
  • diene-based rubbery polymers that can be used include polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, styrene-butadiene block copolymer, and butyl acrylate-butadiene copolymer. Of these, polybutadiene is preferably used.
  • the weight average particle size of the diene-based rubbery polymer (A1) is not particularly limited, but is preferably 100 to 1200 nm, and more preferably 200 to 1200 nm. If a diene-based rubber polymer (A1) having a weight average particle size of less than 100 nm is used, the impact resistance may decrease, while when a diene-based rubber polymer (A1) having a weight average particle size of more than 1200 nm is used. May reduce fluidity.
  • particles having a weight average particle diameter of 200 to 400 nm and particles having a weight average particle diameter of 450 to 1200 nm are used from the viewpoint of achieving both impact resistance and fluidity. It is preferable to use them in combination, more preferably particles having a weight average particle diameter of 280 to 400 nm and particles having a weight average particle diameter of 600 to 1200 nm, and more preferably particles having a weight average particle diameter of 320 to 380 nm and particles having a weight average particle diameter of 700 to 1100 nm. be.
  • the weight ratio of the particles having a low particle size to the particles having a high particle size is 90:10 or more from the viewpoint of impact resistance and fluidity. It is preferably in the range of 50:50, more preferably 80:20 to 60:40, and even more preferably 75:25 to 65:35.
  • the weight average particle size of the diene-based rubbery polymer (A1) is the sodium alginate method according to "Rubbaer Age Vol. 88 p.484-490 (1960) by E. Schmidt, PH Bidison".
  • the particle size of the cumulative weight fraction of 50% is obtained from the concentration ratio of sodium alginate and the cumulative weight fraction of the sodium alginate concentration).
  • the weight fraction of the diene-based rubbery polymer (A1) in the graft copolymer (II-1) is preferably 40 to 65% by weight, more preferably 40 to 60% by weight, still more preferably. It is 40 to 50% by weight.
  • the weight fraction is 40% by weight or more, the impact resistance is improved, while when it is 65% by weight or less, the fluidity is improved, which is preferable.
  • aromatic vinyl-based monomer (B) contained in the monomer mixture examples include styrene, ⁇ -methylstyrene, vinyltoluene, o-ethylstyrene, p-methylstyrene, chlorostyrene and bromostyrene.
  • styrene is particularly preferably adopted.
  • Examples of the vinyl cyanide-based monomer (C) contained in the monomer mixture include acrylonitrile, methacrylonitrile, etacrylonitrile, and the like, and acrylonitrile is particularly preferably adopted.
  • vinyl-based monomers copolymerizable with the aromatic vinyl-based monomer (B) and the vinyl cyanide-based monomer (C) to the extent that the effect of the present invention is not lost in the monomer mixture.
  • other vinyl-based monomers include N-phenylmaleimide, N-methylmaleimide, and methyl methacrylate, which can be selected according to the purpose, and these may be used alone or in a plurality of types. However, it can be used. If there is an intention to further improve heat resistance and flame retardancy, it is preferable to use N-phenylmaleimide. Further, if the improvement of hardness is emphasized, methyl methacrylate is preferably used.
  • the weight fraction of the aromatic vinyl-based monomer (B) in the graft copolymer (II-1) is preferably 26 to 43% by weight, more preferably 30 to 41% by weight, and particularly preferably 35 to 41% by weight. %.
  • the weight fraction of the aromatic vinyl-based monomer (B) is 26% by weight or more, it tends to be difficult to color, while when it is 43% by weight or less, graft polymerization is likely to proceed and the graft ratio is high. Is improved, and the impact resistance tends to be improved.
  • the weight fraction of the vinyl cyanide-based monomer (C) in the graft copolymer (II-1) is preferably 9 to 17% by weight, more preferably 10 to 16% by weight, still more preferably 12 to 16% by weight. %.
  • the weight fraction of the vinyl cyanide-based monomer (C) is 9% by weight or more, the graft polymerization tends to proceed, the graft ratio is improved, and the impact resistance tends to be improved, which is 17% by weight. In the following cases, it tends to be difficult to color.
  • the graft ratio of the graft copolymer (II-1) is not particularly limited. From the viewpoint of the balance between impact resistance and fluidity, the graft ratio is preferably 7 to 30%, more preferably 20 to 28%, still more preferably 22 to 26%.
  • any method such as an emulsion polymerization method, a suspension polymerization method, a continuous massive polymerization method, and a solution continuous polymerization method can be used, and two or more of these can be combined. You may combine them.
  • the emulsion polymerization method is most preferable because it is easy to control the temperature during polymerization.
  • graft copolymer (II-1) examples include acrylonitrile / acrylonitrile / styrene graft copolymer (ABS resin), methylmethacrylate / butadiene / styrene graft copolymer (MBS resin), and methylmethacrylate / acrylonitrile / butadiene / styrene graft.
  • ABS resin acrylonitrile / acrylonitrile / styrene graft copolymer
  • MVS resin methylmethacrylate / butadiene / styrene graft copolymer
  • MABS resin acrylonitrile-butadiene-styrene graft copolymer
  • ABS resin acrylonitrile-butadiene-styrene graft copolymer
  • thermoplastic resin composition containing the graft copolymer (II-2) has excellent weather resistance.
  • Acrylic rubber polymer (A2) obtained by copolymerizing an acrylic acid ester-based monomer (a) that can be used for the graft copolymer (II-2) and a polyfunctional monomer (b).
  • acrylic acid ester-based monomer (a) constituting the above those having an alkyl group having 1 to 10 carbon atoms are preferable, and for example, methyl acrylate, ethyl acrylate, n-butyl acrylate, t-acrylic acid. Examples include butyl and octyl acrylate. Two or more of these may be used. Among these, n-butyl acrylate is preferable.
  • the polyfunctional monomer (b) constituting the acrylic rubbery polymer (A2) is not particularly limited as long as it has two or more functional groups, and examples of the functional group include an allyl group and (meth). ) A group having a carbon-carbon double bond such as an acryloyl group can be mentioned.
  • the polyfunctional monomer (b) include allyl compounds such as allyl acrylate, allyl methacrylate, diallyl maleate, triallyl cyanurate, and triallyl isocyanurate, divinylbenzene, ethylene glycol dimethacrylate, and diethylene glycol. Examples thereof include di (meth) acrylic acid ester compounds such as dimethacrylate and propylene glycol dimethacrylate.
  • allyl methacrylate is used because it is easy to adjust the gel swelling degree of the acrylic rubber polymer (A2) described later in toluene and the graft ratio of the graft copolymer (II-2) within a desired range. It is preferable to use it.
  • the acrylic rubbery polymer (A2) in the present invention is an acrylic acid ester-based monomer based on 100% by weight of the total of the acrylic acid ester-based monomer (a) and the polyfunctional monomer (b). It is preferable to obtain (a) 97 to 99.5% by weight and the polyfunctional monomer (b) 3 to 0.5% by weight by copolymerizing.
  • the acrylic acid ester-based monomer (a) is 97% by weight or more and the polyfunctional monomer (b) is 3% by weight or less, the acrylic rubbery polymer (A2) described later in toluene.
  • the degree of gel swelling tends to increase, and the graft ratio of the graft copolymer (II-2) described later tends to decrease.
  • the fluidity of the thermoplastic resin composition is improved, and further, since the graft copolymer (II-2) particles can have an aggregated structure, the impact strength and surface impact resistance of the molded product are improved. ..
  • the acrylic acid ester-based monomer (a) is 98% by weight or more and the polyfunctional monomer (b) is 2% by weight or less. It is more preferable that the acrylic acid ester-based monomer (a) is more than 98.5% by weight and the polyfunctional monomer (b) is less than 1.5% by weight.
  • the acrylic acid ester-based monomer (a) is 99.5% by weight or less and the polyfunctional monomer (b) is 0.5% by weight or more
  • the graft copolymer (II-) described later will be described. It is preferable because the graft ratio of 2) is improved and the impact strength and surface impact property of the molded product are improved.
  • the acrylic acid ester-based monomer (a) is more preferably 99.3% by weight or less, still more preferably 99.0% by weight or less. Further, the polyfunctional monomer (b) is more preferably 0.7% by weight or more, still more preferably 1.0% by weight or more.
  • any method such as an emulsion polymerization method, a suspension polymerization method, a continuous massive polymerization method, and a solution continuous polymerization method can be used, and two or more of these can be combined. You may combine them.
  • the emulsification polymerization method or the massive polymerization method is preferable.
  • the emulsion polymerization method is most preferable because it is easy to adjust the volume average particle size to a desired range by removing heat during polymerization.
  • the emulsifier used in the emulsification polymerization method is not particularly limited, and various surfactants can be used.
  • an anionic surfactant such as a carboxylate type, a sulfate ester salt type, or a sulfonate type is preferably used. Two or more of these may be used.
  • anionic surfactants include caprylate, caprinate, laurylate, mythylate, palmitate, stearate, oleate, linoleate, linolenate, and rosinate.
  • the salt referred to here include alkali metal salts such as ammonium salt, sodium salt, lithium salt and potassium salt.
  • the initiator used for the polymerization is not particularly limited, and coumenhydroperoxide is preferable as the peroxide, azobisisobutyronitrile as the azo compound, potassium persulfate as the persulfate, and the like, and two or more of these initiators are used. You may use it.
  • the graft copolymer (II-2) used in the present invention is an aromatic vinyl-based monomer (B) and a vinyl cyanide-based monomer (B) in the presence of the acrylic rubbery polymer (A2). It is obtained by graft-polymerizing a monomer mixture containing at least C). That is, the graft copolymer (II-2) is obtained by graft-polymerizing an acrylic rubber polymer (A2) with a monomer mixture containing an aromatic vinyl-based monomer and a cyanide vinyl-based monomer. It is a copolymer.
  • the weight fraction of the acrylic rubber polymer (A2) in the graft copolymer (II-2) is preferably 20% by weight or more, and more preferably 30% by weight or more.
  • the weight fraction of the acrylic rubber polymer (A2) is preferably 70% by weight or less, more preferably 60% by weight or less.
  • the weight fraction of the monomer mixture is preferably 30% by weight or more, more preferably 40% by weight or more.
  • the weight fraction of the monomer mixture is preferably 80% by weight or less, more preferably 70% by weight or less.
  • the monomer mixture constituting the graft copolymer (II-2) contains an aromatic vinyl-based monomer (B) and a vinyl cyanide-based monomer (C), and can be copolymerized with these if necessary. It may further contain a monomer.
  • aromatic vinyl-based monomer (B) examples include styrene, ⁇ -methylstyrene, p-methylstyrene, m-methylstyrene, o-methylstyrene, t-butylstyrene and the like. Two or more of these may be used. Among these, styrene is preferable.
  • vinyl cyanide-based monomer (C) examples include acrylonitrile, methacrylonitrile, and etacrylonitrile. Two or more of these may be used. Of these, acrylonitrile is preferred.
  • the other copolymerizable monomer is not particularly limited as long as it does not impair the effect of the present invention.
  • the unsaturated carboxylic acid alkyl ester-based monomer is methyl (meth) acrylate.
  • the saturated fatty acid is preferably methacrylic acid
  • the acrylamide-based monomer is preferably acrylamide or methacrylamide
  • the maleimide-based monomer is preferably N-phenylmaleimide, and two or more of these may be used.
  • the mixing ratio of the monomer mixture was 60 to 80% by weight for the aromatic vinyl-based monomer (B) and 20 to 20 to 80% by weight for the vinyl cyanide-based monomer (C) in 100% by weight of the total amount of the monomer mixture. It is preferably in the range of 40% by weight and 0 to 20% by weight of other copolymerizable monomers.
  • the graft ratio ( ⁇ ) of the graft copolymer (II-2) is preferably 5 to 40%.
  • the graft ratio ( ⁇ ) is an index showing the compatibility of the graft copolymer (II-2), and if the graft ratio is 5% or more, the graft copolymer (II-2) in the thermoplastic resin composition
  • the compatibility of the molded product is improved, and the impact strength and surface impact resistance of the molded product can be further improved. 8% or more is more preferable.
  • the graft ratio is 40% or less, the particles of the graft copolymer (II-2) are likely to aggregate in the thermoplastic resin composition, and the impact strength and surface impact resistance of the molded product are further improved. be able to. 35% or less is more preferable, and 30% or less is further preferable.
  • the graft ratio (%) is calculated by the following equation. The specific measurement method is as described in the section of Examples.
  • Graft rate (%) [amount of vinyl polymer graft-polymerized on acrylic rubber polymer] / [rubber content of graft copolymer] x 100.
  • the graft ratio of the graft copolymer (II-2) is adjusted to a desired range by, for example, using the acrylic rubber polymer (A2) described above and adjusting the amount of the chain transfer agent, emulsifier, initiator and the like used for the polymerization. can do.
  • any method such as an emulsion polymerization method, a suspension polymerization method, a continuous massive polymerization method, and a solution continuous polymerization method can be used, and two or more of these can be combined. You may combine them.
  • the emulsion polymerization method is most preferable because it is easy to control the temperature during polymerization.
  • Examples of the emulsifier used in the emulsification polymerization method of the graft copolymer (II-2) include those exemplified as the emulsifier used in the emulsification polymerization method of the acrylic rubbery polymer (A2).
  • examples of the polymerization initiator used for the polymerization of the graft copolymer (II-2) include those exemplified as the initiator used for the polymerization of the acrylic rubbery polymer (A2).
  • a chain transfer agent can also be used for the purpose of adjusting the degree of polymerization and the graft ratio of the graft copolymer (II-2).
  • Specific examples of the chain transfer agent include n-octyl mercaptan, t-dodecyl mercaptan, n-dodecyl mercaptan, n-tetradecyl mercaptan, mercaptan such as n-octadecyl mercaptan, and terpenes such as terpinolen. Two or more of these may be used. Among these, n-octyl mercaptan and t-dodecyl mercaptan are preferably used.
  • the acrylic rubbery polymer (A2) and the monomer mixture are mixed. It is preferable to use 0.05 to 0.5 parts by weight of the chain transfer agent, 0.5 to 5 parts by weight of the emulsifier, and 0.1 to 0.5 parts by weight of the initiator with respect to 100 parts by weight of the total.
  • graft copolymer (II-2) examples include acrylonitrile / acrylic rubber polymer / styrene graft copolymer (ASA resin), methyl methacrylate / acrylic rubber polymer / styrene graft copolymer (MSA resin). , Methyl methacrylate, acrylonitrile, acrylic rubbery polymer, styrene graft copolymer (MASA resin) and the like. Of these, acrylonitrile, acrylic rubbery polymer, and styrene graft copolymer (ASA resin) are preferable.
  • the graft copolymer (II) used in the present invention may be alkaline depending on the manufacturing method used.
  • the graft copolymer (II) is typically grafted by adding a coagulant to the aqueous dispersion (latex) of the graft copolymer (II) produced by emulsion polymerization.
  • the copolymer (II) can be recovered.
  • the coagulant an acid or a water-soluble salt is used, but in the present invention, coagulation with an acid is preferable from the viewpoint of mold contamination.
  • Specific examples of the coagulant include sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid and the like, and two or more of these can be used.
  • the acid adheres to the graft copolymer (II) and remains, and the remaining acid may cause corrosion of metal equipment during the production process.
  • a method of recovering the graft copolymer (II) after neutralizing the acid remaining in the graft copolymer (II) with an alkaline compound (neutralizing agent) is preferable.
  • the neutralizing agent adheres to the graft copolymer (II)
  • the graft copolymer (II) is often alkaline.
  • sodium hydroxide is preferable as the neutralizing agent.
  • the graft copolymer (II) exhibits alkalinity can be determined by the following method. That is, first, the graft copolymer (II) is mixed with water to obtain a slurry having a solid content concentration of 10% by weight. Then, this is placed in a water bath at 90 ° C. for 3 hours, and then the graft copolymer (II) is removed using a filter paper (Type 5 A: JIS P3801). Then, the temperature of the obtained filtrate is lowered to 20 ° C., and the pH of the filtrate is measured with a pH meter. If the pH is above 7, it is alkaline.
  • the content of the graft copolymer (II) is the polycarbonate resin (I), the graft copolymer (II), the vinyl-based copolymer (III) used as an optional component, and the like.
  • the total content of the talc (IV) is 100% by weight, it is preferably in the range of 3 to 15% by weight, more preferably 4 to 12% by weight, and further preferably 5 to 9% by weight. .. If the content of the graft copolymer (II) is less than 3% by weight, the impact resistance tends to decrease, and if it exceeds 15% by weight, the fluidity tends to decrease, which may not be preferable. ..
  • the thermoplastic resin composition of the present invention may further contain a vinyl-based copolymer (III).
  • the vinyl-based copolymer (III) is a vinyl-based copolymer obtained by copolymerizing at least an aromatic vinyl-based monomer (D) and a vinyl cyanide-based monomer (E).
  • the aromatic vinyl-based monomer (D) is preferably 60 to 85% by weight, and the cyanide vinyl-based monomer (E) is preferably 15 to 40% by weight, more preferably aromatic.
  • the vinyl-based monomer (D) is 65 to 80% by weight, the cyanide vinyl-based monomer (E) is 20 to 35% by weight, and more preferably, the aromatic vinyl-based monomer (D). Is 70 to 80% by weight, and the vinyl cyanide-based monomer (E) is 20 to 30% by weight.
  • the aromatic vinyl-based monomer (D) When the aromatic vinyl-based monomer (D) is 60% by weight or more, the compatibility with the polycarbonate resin (I) is improved, and the mechanical properties such as impact resistance are improved. Further, when the aromatic vinyl-based monomer (D) is 85% by weight or less, the impact resistance tends to be improved by improving the compatibility with the graft copolymer (II), which is preferable.
  • the vinyl-based copolymer (III) does not contain the diene-based rubbery polymer (A1) and the acrylic-based rubbery polymer (A2). That is, it is assumed that the copolymer is different from the graft copolymer (II-1) and the graft copolymer (II-2).
  • Styrene ⁇ -methylstyrene, vinyltoluene, o-ethylstyrene, p-methylstyrene, m-methylstyrene, t-butylstyrene, vinyltoluene, chlorostyrene, bromostyrene and the like.
  • Styrene is preferably used. These do not necessarily have to be used alone, and may be used in combination of a plurality of types. Of these, styrene is particularly preferably adopted.
  • acrylonitrile, methacrylonitrile, etacrylonitrile and the like can be mentioned, and acrylonitrile is particularly preferably adopted. These do not necessarily have to be used alone, and may be used in combination of a plurality of types.
  • the aromatic vinyl-based monomer (D) and the vinyl cyanide-based monomer also in the vinyl-based copolymer (III) similarly to the graft copolymer (II), the aromatic vinyl-based monomer (D) and the vinyl cyanide-based monomer also in the vinyl-based copolymer (III) to the extent that the effect of the present invention is not lost.
  • Other vinyl-based monomers copolymerizable with (E) may be used.
  • Specific examples of other vinyl-based monomers include N-phenylmaleimide, N-methylmaleimide, and methyl methacrylate, which can be selected according to their respective purposes, and these may be used alone or in combination of two or more. It is possible. N-Phenylmaleimide is preferable if there is an intention to further improve heat resistance and flame retardancy. Further, if the improvement of hardness is emphasized, methyl methacrylate is preferably used.
  • the weight average molecular weight of the vinyl-based copolymer (III) is not particularly limited, but is preferably 110,000 or less, more preferably 105,000 or less, and further preferably 100,000 or less.
  • the lower limit of the weight average molecular weight is preferably 90,000 or more from the viewpoint of impact resistance.
  • Examples of the vinyl-based copolymer (III) include an acrylonitrile / styrene copolymer (AS resin), a methyl methacrylate / styrene copolymer (MS resin), and the like. Of these, an acrylonitrile-styrene copolymer (AS resin) is preferable.
  • AS resin acrylonitrile / styrene copolymer
  • MS resin methyl methacrylate / styrene copolymer
  • AS resin acrylonitrile-styrene copolymer
  • the content of the vinyl-based copolymer (III) is the polycarbonate resin (I), the graft copolymer (II), the vinyl-based copolymer (III), and the talc (IV). ) Is 100% by weight, it is preferably in the range of 0 to 12% by weight, more preferably 4 to 10% by weight, and further preferably 4 to 8% by weight. If the content of the vinyl-based copolymer (III) exceeds 12% by weight, the impact resistance may decrease, which may not be preferable.
  • the MFR (g / 10 min) of the vinyl-based copolymer (III) at 240 ° C. and 10 kg and the polycarbonate resin (I) at 240 ° C. and 10 kg are used.
  • the ratio to the MFR (g / 10 minutes) (MFR of (III) / MFR of (I)) is preferably 7 or more and 12 or less. More preferably, it is 7 or more and 11 or less, and further preferably 8 or more and 11 or less. If it is less than 7, the occurrence of silver streak tends to increase, and if it exceeds 12, the liquidity tends to decrease.
  • the graft copolymer (II) may be alkaline, and such a graft copolymer (II) is a polycarbonate resin.
  • a graft copolymer (II) is a polycarbonate resin.
  • the polycarbonate resin comes into contact with the polymer, the polycarbonate resin is decomposed into an alkali, and the decomposition causes bubbles (gas) to be generated, resulting in appearance defects such as silver streaks.
  • Alkali decomposition is known as a phenomenon in which an alkali such as a hydroxide ion acts as a catalyst on a carbonate-bonded portion to promote hydrolysis and generate a gas such as carbon dioxide or a low molecular weight component.
  • a resin composition containing two or more kinds of resins they tend to be compatible when the ratio of the melt viscosities of the respective resins is small. In other words, if the ratio of the melt viscosity of the resin is large, the phase separation tends to be easy.
  • the vinyl-based copolymer (III) is made of polycarbonate by setting the difference in melt viscosity at 240 ° C. within a specific range for the vinyl-based copolymer (III) and the polycarbonate resin (I). It promotes phase separation from the resin (I).
  • the vinyl-based copolymer (III) is phase-separated from the polycarbonate resin (I)
  • the vinyl-based copolymer (III) is considered to be unevenly distributed around the graft copolymer (II) having a more similar chemical structure, and is alkaline. It is presumed that the frequency of contact between the graft copolymer (II) exhibiting the above and the polycarbonate resin (I) becomes smaller, which suppresses the decomposition of the polycarbonate resin and further suppresses the generation of silver streaks. ..
  • the method for producing the vinyl-based copolymer (III) is not particularly limited, and bulk polymerization, suspension polymerization, bulk suspension polymerization, solution polymerization, emulsion polymerization, precipitation polymerization and combinations thereof are used. .. There is no particular limitation on the method of charging the monomer, and the monomer may be added all at once at the initial stage, or the method of addition may be divided into several times in order to give or prevent the composition distribution of the copolymer. ..
  • the initiator used for the polymerization of the vinyl-based copolymer (III) the initiator mentioned in the graft copolymer (II-1) is preferably used.
  • chain transfer agent such as mercaptan or terpene
  • the chain transfer agent include n-octyl mercaptan, t-dodecyl mercaptan, n-dodecyl mercaptan, n-tetradecyl mercaptan, n-octadecyl mercaptan and terpinolene.
  • n-octyl mercaptan, t-dodecyl mercaptan and n-dodecyl mercaptan are preferably used.
  • chain transfer agents they are used alone or in combination of two or more.
  • the talc (IV) constituting the thermoplastic resin composition of the present invention contains a specific amount of an iron component and a calcium component.
  • the amount of iron component and calcium component in talc can be calculated by converting the amount of elements measured and detected by a fluorescent X-ray analyzer into the amount of the corresponding oxide.
  • the iron (Fe) component contained as an impurity is 0.19% by weight or less as Fe 2 O 3 . It is more preferably 0.17% by weight or less, still more preferably 0.15% by weight or less.
  • the calcium (Ca) component is 1.9% by weight or less as CaO. It is more preferably 1.7% by weight or less, still more preferably 1.5% by weight or less.
  • Fe 2 O 3 exceeds 0.19% by weight, or CaO exceeds 1.9% by weight, silver streak is generated more frequently, which is not preferable.
  • the lower limit is not particularly limited, but Fe 2 O 3 and Ca O can each be contained in an amount of 0.001% by weight or more.
  • iron and calcium are ionized, coordinated to the ester bond portion of the polycarbonate resin, and promote alkaline hydrolysis by catalytic action. It is estimated to be.
  • the average particle size of talc used in the present invention is not particularly limited, but is preferably 1.0 to 30.0 ⁇ m because of mechanical properties, dimensional stability and retention stability, and a high balance of the appearance of the molded product. Yes, more preferably 2.0 to 20.0 ⁇ m, still more preferably 3.0 to 16.0 ⁇ m.
  • the average particle size is 1.0 ⁇ m or more, the retention stability and the dimensional stability tend to be improved, and when the average particle size is 7.0 ⁇ m or less, the mechanical properties are improved and the appearance of the molded product is improved. There is a tendency and it is preferable.
  • the content of talc (IV) is the polycarbonate resin (I), the graft copolymer (II), the vinyl-based copolymer (III) used as an optional component, and the talc (
  • the total content of IV) is 100% by weight, it is preferably in the range of 5 to 20% by weight, more preferably 6 to 19% by weight, and further preferably 7 to 18% by weight. If the content of talc (IV) is less than 5% by weight, the mechanical properties and dimensional stability tend to decrease, and if it exceeds 20% by weight, the retention stability decreases, and the silver streak of the molded product It tends to occur more often, which is not preferable.
  • the resin composition of the present invention does not exclude the inclusion of an inorganic filler other than talc (IV).
  • thermoplastic resin composition of the present invention can preferably contain a condensed phosphate ester (V), and as such, for example, a compound represented by the following general formula (2) can be used.
  • R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom or a monovalent organic group, but of R 1 , R 2 , R 3 and R 4 . At least one of them is a monovalent organic group.
  • X is a divalent organic group, k, l, m and n are 0 or 1 independently of each other, and N is an integer of 0 to 10.
  • the monovalent organic group includes an alkyl group, an aryl group and a cycloalkyl group which may be substituted, and examples of the substituent when substituted include an alkyl group and an alkoxy. Examples thereof include a group, an alkylthio group, an aryl group, an aryloxy group and an arylthio group, and a group in which these substituents are combined (arylalkoxyalkyl group, etc.) or these substituents are bonded with an oxygen, sulfur, nitrogen atom or the like.
  • the combined group (arylsulfonylaryl group, etc.) may be a substituent.
  • a 2,6-dimethylphenyl group is preferable.
  • the divalent organic group includes, for example, an alkylene group, a phenylene group which may have a substituent, a polyhydric phenol, and a group derived from a polynuclear phenol (bisphenol, etc.).
  • resorcinol is preferable as the divalent organic group.
  • Suitable specific examples of these phosphate ester compounds (V) include trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, trihexyl phosphate, tricyclohexyl phosphate, trioctyl phosphate, and triphenyl phosphate.
  • the thermoplastic resin composition of the present invention can preferably contain a crystalline resin (VI), and the resin is not particularly limited as long as it has a melting point and can be melt-molded, but it is molded.
  • the resin has a melting point of preferably 150 ° C. or higher, more preferably 180 ° C. or higher, still more preferably 200 ° C. or higher, and particularly preferably 220 ° C. or higher.
  • the upper limit of the melting point is not particularly limited, but is preferably 300 ° C. or lower, more preferably 280 ° C. or lower, and further preferably 250 ° C. or lower.
  • the melting point of the crystalline resin (VI) is 40 ° C. to 300 ° C. in 10 mg of pellets of the crystalline resin (VI) in the differential scanning calorimetry using "DSC-60" manufactured by Shimadzu Corporation.
  • Tm1 heat absorption peak temperature
  • the temperature was maintained at 300 ° C. for 1 minute, and then the temperature was lowered to 20 ° C./min.
  • Tm2 heat absorption peak temperature
  • the crystalline resin (VI) include polyolefin resins such as polyethylene resin and polypropylene resin, polyvinyl alcohol resin, polyvinylidene chloride resin, polyester resin, polyamide resin, polyacetal resin, polyether ether ketone resin, and poly.
  • polyolefin resins such as polyethylene resin and polypropylene resin, polyvinyl alcohol resin, polyvinylidene chloride resin, polyester resin, polyamide resin, polyacetal resin, polyether ether ketone resin, and poly.
  • ether ketone resin, polyketone resin, polyimide resin and copolymers thereof examples of the crystalline resin (VI)
  • polyamide resins and polyester resins are preferable in terms of heat resistance, moldability, fluidity and mechanical properties.
  • the above-mentioned polyamide resin is a polyamide resin having a melting point, and examples thereof include a ring-opening polymer of cyclic lactam, a polycondensate of aminocarboxylic acid, and a polycondensate of dibasic acid and diamine, and specific examples thereof.
  • the polyester resin is a polyester resin having a melting point, and is obtained from a polycondensate of dicarboxylic acid and glycol, a ring-opening polymer of cyclic lactone, a polycondensate of hydroxycarboxylic acid, and a polycondensate of dibasic acid and glycol.
  • Specific examples thereof include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polycyclohexanedimethylene terephthalate and polyethylene-1,2-bis (phenoxy).
  • Semi-aromatic polyesters such as ethane-4,4'-dicarboxylate, polyethylene-1,2-bis (phenoxy) ethane-4,4'-dicarboxylate / isophthalate copolymer, polybutylene terephthalate.
  • Semi-aromatic polyesters having a melting point such as / decandicarboxylate copolymers and polycyclohexanedimethylene terephthalates / isophthalate copolymers, and crystalline polyesters composed of a mixture thereof within the range having a melting point can be mentioned. can.
  • thermotropic liquid crystallinity consisting of a structural unit selected from an aromatic oxycarbonyl unit, an aromatic dioxy unit, an aromatic dicarbonyl unit, an aromatic aminooxy unit, an ethylene oxide unit, etc. is used. You can also do it.
  • aromatic oxycarbonyl unit referred to here a structural unit produced from p-hydroxybenzoic acid 6-hydroxy-2-naphthoic acid and 4'-hydroxydiphenyl-4-carboxylic acid can be exemplified.
  • aromatic dioxy unit examples include structural units produced from 4,4'-dihydroxybiphenyl, hydroquinone, and t-butylhydroquinone.
  • aromatic dicarbonyl unit include structural units produced from terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid.
  • aromatic aminooxy unit for example, a structural unit produced from 4-aminophenol can be exemplified.
  • polyester it is also possible to use polylactic acid obtained by using lactic acid and / or lactide as a main raw material, and an aliphatic polyester such as a copolymer thereof within a range having a melting point.
  • Semi-aromatic polyester is particularly preferable as the crystalline polyester suitable for the present invention, and specifically, polyethylene terephthalate resin, polypropylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, and co-polyesters having a melting point.
  • polyethylene terephthalate resin polypropylene terephthalate resin
  • polybutylene terephthalate resin polyethylene naphthalate resin
  • co-polyesters having a melting point examples thereof include polymers and mixtures, more preferably polyethylene terephthalate resin and polybutylene terephthalate resin, and most preferably polybutylene terephthalate resin.
  • the molecular weight of such a polyester resin is not particularly limited, and an intrinsic viscosity measured at 25 ° C. using a mixed solvent of phenol / tetrachloroethane 1: 1 is usually used. However, those having an intrinsic viscosity of 0.25 to 2.50 dl / g, particularly preferably 0.40 to 2.25 dl / g can be used.
  • a known impact resistance improving material or a known matting improving material can be used as long as the object of the present invention is not impaired.
  • Molding aids such as modified polytetrafluoroethylene, flame retardants / flame retardants, antibacterial agents typified by silver-based antibacterial agents, antifungal agents, carbon black, titanium oxide, mold release agents, lubricants, pigments. And dyes and the like can also be added.
  • the thermoplastic resin composition of the present invention can be obtained by melting and mixing each of the constituent resin components and inorganic components.
  • the melting and mixing method is not particularly limited, but a heating device, a method of melting and mixing using a single-screw or biaxial screw in a cylinder having a vent, and the like can be adopted.
  • the heating temperature at the time of melting and mixing is usually selected from the range of 230 to 320 ° C., but the temperature gradient at the time of melting and mixing can be freely set within a range that does not impair the object of the present invention.
  • biaxial screws When biaxial screws are used, they may rotate in the same direction or in different directions. Further, either a meshing type screw or a non-meshing type screw may be used.
  • the molding method for producing a molded product using the thermoplastic resin composition of the present invention is not particularly limited, but it is suitably molded by injection molding.
  • Injection molding can be carried out, preferably in a temperature range of 240 to 300 ° C., usually in the temperature range for molding the thermoplastic resin assembly.
  • the mold temperature during injection molding is preferably in the temperature range of 30 to 80 ° C. used for normal molding.
  • thermoplastic resin composition of the present invention can suppress the generation of silver streaks in the molded product, and the thermoplastic resin composition containing the graft copolymer (II-2) is further excellent in weather resistance. Therefore, the thermoplastic resin composition of the present invention is suitably provided for a molded product having a large or complicated shape.
  • the resin composition of the present invention can be suitably used not only for power window panels, center consoles, center clusters, console shutters, lever controllers, console boxes, etc. for automobile interiors, but also for automobile exterior materials, that is, rear spoilers. It can also be applied to grills, garnishes, door mirrors, roofs, fenders, bumpers, etc. Further, it can be suitably used for electrical and electronic applications, OA equipment applications, and housing / building material applications.
  • Graft rate of graft copolymer (II-1) Weigh the graft copolymer (II-1) in a predetermined amount (m; about 1 g), add 200 ml of acetone to it, and bathe in a hot water bath at a temperature of 70 ° C. Reflux in the solution for 3 hours and apply this solution to 8800 r. p. m. After centrifuging at (10000 G) for 40 minutes, the insoluble material was filtered. The obtained insoluble acetone was dried under reduced pressure at 60 ° C. for 5 hours, and its mass (n; unit g) was measured. The graft ratio was calculated from the following formula.
  • L is the rubber content of the graft copolymer (a real number exceeding 0 and less than 1).
  • Graft ratio (% by mass) ⁇ [(n)- ⁇ (m) ⁇ L ⁇ ] / [(m) ⁇ L] ⁇ ⁇ 100.
  • L is the rubber content (% by weight) of the graft copolymer (that is, the content (mass%) of the acrylic rubbery polymer (A2) in the graft copolymer (II-2)).
  • Graft ratio (% by mass) ⁇ [(n)-((m) x L / 100)] / [(m) x L / 100] ⁇ x 100.
  • FIGS. 1 (a) and 1 (b) A square flat plate P having a width of 70 mm, a length of 150 mm, and a thickness of 3 mm having an edge of 45 ° was formed (FIG. 1 (a) is a plan view of the square flat plate P, and FIG. 1 (b) is a square flat plate. It is a cross-sectional view taken along the line AA of P. The position of the injection molding gate is indicated by a white arrow). In the obtained molded product, the less the occurrence of silver streak, the better.
  • Heat resistance deflection temperature under load
  • Heat distortion temperature Measured according to ISO75-2 (2013) (measured under 1.8 MPa conditions).
  • the test piece was obtained by molding a multipurpose test piece type A1 specified in JIS K 7139 (2009) using an injection molding machine in which the cylinder temperature was set to 250 ° C. and the mold temperature was set to 60 ° C.
  • graft copolymer (II-1) This was added to an aqueous solution of dilute sulfuric acid to aggregate it, then neutralized with an aqueous solution of sodium hydroxide, and then washed, dehydrated and dried to prepare a graft copolymer (II-1).
  • the graft rate was 25%.
  • the graft copolymer (II-1) exhibited alkaline (pH 8).
  • graft copolymer (II-2) ⁇ Preparation of graft copolymer (II-2)>
  • Step for obtaining acrylic rubber polymer (A2) 130 parts by weight of pure water and 1 part by weight of an aqueous solution of disproportionated potassium rosinate (in terms of solid content) as an emulsifier are charged in a reaction vessel, heated to 75 ° C., and stirred to 19.8 parts by weight of n-butyl acrylate. And 0.2 parts by weight of allyl methacrylate (mixture 1) were continuously added over 1 hour (first addition step).
  • Step for obtaining graft copolymer (II-2) Subsequently, a mixture of 13.2 parts by weight of pure water, 0.48 parts by weight of anhydrous glucose, 0.26 parts by weight of sodium pyrophosphate and 0.01 parts by weight of ferrous sulfate, 0.4 parts by weight of potassium oleate and pure A mixture of 12.5 parts by weight of water, 50 parts by weight of acrylic rubber polymer (A2) latex (in terms of solid content) and 94.3 parts by weight of pure water were charged in a reaction vessel, heated to 58 ° C., and stirred.
  • ⁇ Preparation of vinyl-based copolymer (III)> A slurry obtained by suspend-polymerizing a monomer mixture consisting of 76% by weight of styrene and 24% by weight of acrylonitrile is subjected to washing, dehydration and drying steps, and has a weight average molecular weight of 99,000 and a melt flow rate of 274 g / 10 min. A vinyl-based copolymer (III) was prepared.
  • ⁇ Talc (IV)> The talc used was Fe 2 O 3 , CaO equivalent content, and average particle size shown in the table below. The average particle size was measured by a laser diffraction method.
  • Examples 1 to 8, Comparative Examples 1 to 10 The weight ratios of the polycarbonate resin (I), the graft copolymer (II), the vinyl copolymer (III), the inorganic filler (IV), and the phosphate ester compound (V) are as shown in the table. And kneaded by melting and kneading with a twin-screw extruder (temperature range: 240 to 260 ° C.) rotating in the same direction with a screw diameter of 30 mm to obtain pellets. The obtained pellets were evaluated as described above.
  • test piece was prepared from the obtained pellets using an injection molding machine (molding temperature 250 ° C., mold temperature 60 ° C.), and evaluated by the above-mentioned method.
  • injection molding machine molding temperature 250 ° C., mold temperature 60 ° C.
  • the molded product for silver streak evaluation according to (4) was produced under the conditions described in (4) above. The evaluation results are shown in the table.
  • thermoplastic resin compositions of Examples 1 to 8 can suppress the generation of silver streaks in the molded product.
  • occurrence of silver streak could not be sufficiently suppressed in Comparative Examples 1 to 10 using talc that deviates from this specified value.
  • the present invention is a thermoplastic resin composition capable of suppressing the generation of silver streaks in molded products, and in the automobile field, automobile exterior parts such as rear spoilers, wheel caps, door mirrors, radiator grills, power window panels, center consoles, etc. Automotive interior parts such as center clusters, lever controllers and console boxes, and automotive exterior parts such as rear spoilers, grilles, garnishes, door mirrors, roofs, fenders and bumpers. It can be suitably used in fields other than the automobile field, such as OA equipment, home appliances, housing building materials, suitcases and bags.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Le problème décrit par la présente invention est de fournir une composition de résine thermoplastique qui, lorsqu'un article moulé est obtenu à partir de celle-ci, peut supprimer l'apparition de traînées d'argent. La solution selon l'invention porte sur une composition de résine thermoplastique qui est obtenue par mélange d'une résine de polycarbonate (I), d'un copolymère greffé (II) et d'un talc (IV), et contient, lorsque le poids du talc (IV) est défini comme étant de 100 % en poids, des composants fer et des composants calcium dans des quantités inférieures à 0,19 % en poids et inférieures à 1,9 % en poids, respectivement, lorsqu'ils sont définis en tant que Fe2O3 et CaO.
PCT/JP2021/038647 2020-10-29 2021-10-19 Composition de résine thermoplastique et article moulé l'utilisant WO2022091881A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2021565893A JPWO2022091881A1 (fr) 2020-10-29 2021-10-19

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2020181009 2020-10-29
JP2020-181009 2020-10-29

Publications (1)

Publication Number Publication Date
WO2022091881A1 true WO2022091881A1 (fr) 2022-05-05

Family

ID=81383802

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2021/038647 WO2022091881A1 (fr) 2020-10-29 2021-10-19 Composition de résine thermoplastique et article moulé l'utilisant

Country Status (2)

Country Link
JP (1) JPWO2022091881A1 (fr)
WO (1) WO2022091881A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09137054A (ja) * 1995-11-17 1997-05-27 Sumika A B S Latex Kk ポリカーボネート樹脂組成物
JP2004520469A (ja) * 2001-01-25 2004-07-08 バイエル アクチェンゲゼルシャフト 低い鉄含量のポリカーボネート組成物
JP2006342199A (ja) * 2005-06-07 2006-12-21 Teijin Chem Ltd 外観に優れたハウジング成形品
JP2015096569A (ja) * 2013-11-15 2015-05-21 三菱エンジニアリングプラスチックス株式会社 ポリカーボネート樹脂組成物及びポリカーボネート樹脂成形品
JP2015131876A (ja) * 2014-01-09 2015-07-23 三菱エンジニアリングプラスチックス株式会社 芳香族ポリカーボネート樹脂組成物及びその成形品

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09137054A (ja) * 1995-11-17 1997-05-27 Sumika A B S Latex Kk ポリカーボネート樹脂組成物
JP2004520469A (ja) * 2001-01-25 2004-07-08 バイエル アクチェンゲゼルシャフト 低い鉄含量のポリカーボネート組成物
JP2006342199A (ja) * 2005-06-07 2006-12-21 Teijin Chem Ltd 外観に優れたハウジング成形品
JP2015096569A (ja) * 2013-11-15 2015-05-21 三菱エンジニアリングプラスチックス株式会社 ポリカーボネート樹脂組成物及びポリカーボネート樹脂成形品
JP2015131876A (ja) * 2014-01-09 2015-07-23 三菱エンジニアリングプラスチックス株式会社 芳香族ポリカーボネート樹脂組成物及びその成形品

Also Published As

Publication number Publication date
JPWO2022091881A1 (fr) 2022-05-05

Similar Documents

Publication Publication Date Title
EP0845496B1 (fr) Masses à mouler à brillance élevée du type ABS
JP6610680B2 (ja) 熱可塑性樹脂組成物およびその成形品
WO2009118114A1 (fr) Compositions de polycarbonate à résilience modifiée présentant une bonne combinaison d'argile brute et de stabilité à l'hydrolyse et à la fusion
JP6024757B2 (ja) 天然ゴム含有熱可塑性樹脂組成物およびその成形品
KR20150002604A (ko) 고무 그래프트 공중합체와 고무 그래프트 공중합체를 함유하는 열가소성 수지 조성물
WO2001062812A1 (fr) Compositions polymeres ayant une meilleure constance des proprietes
KR100602045B1 (ko) 고효율 그래프트 고무 성분 기재 열가소성 성형 조성물
EP1141057B1 (fr) Matiere moulable abs aux associations de proprietes ameliorees
WO2022091881A1 (fr) Composition de résine thermoplastique et article moulé l'utilisant
JP6904482B2 (ja) 熱可塑性樹脂組成物およびその成形品
JP3565989B2 (ja) 熱可塑性成形組成物
EP2148902A2 (fr) Compositions de polycarbonate à résilience modifiée
EP2147952B1 (fr) Composition de résine thermoplastique et article moulé en résine
JP4333857B2 (ja) 難燃性熱可塑性樹脂組成物およびその再生成形材料
JP2015168814A (ja) 熱可塑性樹脂組成物およびその成形品
JP2019157016A (ja) ブロー成形用熱可塑性樹脂組成物およびその成形品
JP2006016524A (ja) 熱可塑性樹脂組成物およびその成形品
JP2022129758A (ja) 熱可塑性樹脂組成物、その製造方法および成形品
JP2024012142A (ja) 熱可塑性樹脂組成物
KR101005512B1 (ko) 내충격성이 향상된 열가소성 수지 조성물
CN114174418A (zh) 树脂组合物
JP2013082821A (ja) 熱可塑性樹脂組成物及び成形品

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2021565893

Country of ref document: JP

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21886000

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21886000

Country of ref document: EP

Kind code of ref document: A1