WO2017057092A1 - Composition de résine de polycarbonate et son procédé de production - Google Patents

Composition de résine de polycarbonate et son procédé de production Download PDF

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Publication number
WO2017057092A1
WO2017057092A1 PCT/JP2016/077679 JP2016077679W WO2017057092A1 WO 2017057092 A1 WO2017057092 A1 WO 2017057092A1 JP 2016077679 W JP2016077679 W JP 2016077679W WO 2017057092 A1 WO2017057092 A1 WO 2017057092A1
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Prior art keywords
polycarbonate resin
resin
resin composition
mass
styrene
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PCT/JP2016/077679
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English (en)
Japanese (ja)
Inventor
竜次 内村
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三菱エンジニアリングプラスチックス株式会社
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Priority claimed from JP2016145676A external-priority patent/JP6114447B2/ja
Priority claimed from JP2016145675A external-priority patent/JP2017075297A/ja
Application filed by 三菱エンジニアリングプラスチックス株式会社 filed Critical 三菱エンジニアリングプラスチックス株式会社
Priority to KR1020187003603A priority Critical patent/KR102071812B1/ko
Priority to CN201680049306.3A priority patent/CN107922723B/zh
Priority to US15/580,400 priority patent/US10385207B2/en
Publication of WO2017057092A1 publication Critical patent/WO2017057092A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • 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 polycarbonate resin composition and a method for producing the same, and more particularly, a polycarbonate resin composition having excellent mechanical properties and moisture and heat resistance and no mold contamination due to mold deposits, and a method for producing the polycarbonate resin composition with high production efficiency.
  • a polycarbonate resin composition having excellent mechanical properties and moisture and heat resistance and no mold contamination due to mold deposits, and a method for producing the polycarbonate resin composition with high production efficiency.
  • Polycarbonate resin is a resin excellent in heat resistance, mechanical properties, and electrical characteristics, and is widely used for, for example, automobile materials, electrical and electronic equipment materials, housing materials, and other parts manufacturing materials in industrial fields.
  • many polymer alloys with other thermoplastic resins have been developed.
  • polymer alloys with styrenic resins represented by ABS resins are more cost-effective and have higher moldability and impact resistance than polycarbonate resins. It has been improved and is widely used as a part of various electronic devices such as various computers, personal computers, various portable terminals, printers, copying machines, and OA information devices.
  • ABS resin used for the polycarbonate / styrene resin composition those manufactured by emulsion polymerization are often used from the viewpoints of cost, compatibility with various varieties, and easy quality improvement due to high rubber.
  • a product produced by bulk polymerization is sometimes used because of its excellent heat and humidity resistance (the same document, claim 8 and paragraph [0024]).
  • Styrenic resin by bulk polymerization is expensive, and it is conceivable to use an emulsion polymerization product for cost reduction, but the polycarbonate resin composition containing the emulsion polymerization styrene resin is surely inferior in heat and moisture resistance. Has drawbacks.
  • Emulsion polymerization ABS resin usually uses higher fatty acid soap or rosin acid soap as an emulsifier, and performs emulsion polymerization of butadiene with a water-soluble polymerization initiator to obtain a polymer latex, and then the polymer particles and the emulsifier In the presence of water, styrene and acrylonitrile are polymerized to obtain an ABS polymer latex, to which a coagulant such as an inorganic acid or a divalent metal salt is added to separate the polymer, which is washed and dried. Manufactured. From the viewpoint of economy, the emulsifier that has not been completely removed remains in the product because the emulsifier is not completely removed in the washing step.
  • the present invention has an object (problem) to provide a polycarbonate resin composition containing an emulsion-polymerized styrene resin, in which the problems of heat and moisture resistance and mold deposit are solved, and a method for producing the same with high production efficiency.
  • the inventor is a resin composition containing a specific amount of a polycarbonate resin and a specific emulsion-polymerized styrene resin, and the resin composition is 280 ° C., 10 ° C.
  • Polycarbonate / styrene resin composition whose total gas amount when heated for a minute is 3000 mass ppm or less in terms of decane mass is excellent in mechanical properties and heat and humidity resistance, and there is no problem of mold contamination due to mold deposit I found.
  • an emulsion-polymerized styrene-based resin which is an additive component and a small amount component compared to the polycarbonate resin, is first added to the root of the extruder.
  • the above problem is solved by venting under reduced pressure to devolatilize the gas generating component derived from the emulsifier, and supplying the polycarbonate resin as the main component from the raw material supply port downstream from the vent port and melt-kneading.
  • This invention is the manufacturing method of the following polycarbonate resin compositions, its molded article, and the following polycarbonate resin compositions.
  • a resin composition comprising 60 to 95% by weight of a polycarbonate resin (A) and 40 to 5% by weight of an emulsion-polymerized styrene-based resin (B) based on a total of 100% by weight of (A) and (B).
  • the emulsion polymerization styrene resin (B) is a graft copolymer comprising a styrene monomer-vinyl cyanide monomer and / or an alkyl (meth) acrylate monomer-rubber polymer,
  • a polycarbonate resin composition wherein the total gas amount when the resin composition is heated at 280 ° C.
  • the styrene resin (B) is dispersed in an island shape in the matrix of the polycarbonate resin (A), the volume average dispersion diameter (dv) is 2.5 ⁇ m or less, and the styrene resin (B The ratio of the volume average particle diameter (dv) to the number average particle diameter (dn) (dv / dn) is in the range of 1.0 to 1.5.
  • the polycarbonate resin composition according to the above [1] or [2], wherein the impact strength retention after heat-moisture treatment for 400 hours in an environment of a temperature of 90 ° C and a relative humidity of 95% is 50% or more.
  • the emulsion polymerization styrene resin (B) is a graft copolymer comprising a styrene monomer-vinyl cyanide monomer and / or an alkyl (meth) acrylate monomer-rubber polymer, A polycarbonate resin composition, wherein the total gas amount when the resin composition is heated at 280 ° C.
  • the emulsion-polymerized styrene resin (B) is dispersed in islands in the matrix of the polycarbonate resin (A), the volume average dispersion diameter (dv) is 2.5 ⁇ m or less, and the emulsion-polymerized styrene
  • the ratio of the volume average particle diameter (dv) to the number average particle diameter (dn) (dv / dn) of the resin (B) is in the range of 1.0 to 1.5.
  • the polycarbonate resin composition in any one.
  • the extruder has a first raw material supply port on the upstream side and one or more second raw material supply ports on the downstream side thereof,
  • the supply amount of the emulsion polymerization styrene resin (B) is B (1)
  • the supply amount of the polycarbonate resin (A) from the first raw material supply port is A (1)
  • a (2) When the supply amount from the mouth is A (2), the sum of A (1) and A (2) is the total supply amount of the polycarbonate resin (A), From the first raw material supply port, styrene resin (B) and polycarbonate resin (A), Formula: B (1)> A (1) (However, A (1) includes 0.) Supply to meet and After melt-kneading, after degassing the gas component from the vent port under reduced pressure, A method for producing a polycarbonate resin composition, comprising: supplying a polycarbonate resin (A) in an amount of A (2) from a second raw material supply port downstream of the vent port. [12] The method for producing a polycarbonate resin composition according to [11], wherein the gas component includes a gas component derived from an emulsifier.
  • a method of manufacturing by melt-kneading with an extruder The extruder has a first raw material supply port on the upstream side and a water injection part and a vent port in the kneading part on the downstream side, and further has one or more second raw material supply ports on the downstream side.
  • the supply amount of the emulsion polymerization styrene resin (B) is B (1)
  • the supply amount of the polycarbonate resin (A) from the first raw material supply port is A (1)
  • a (2) When the supply amount from the mouth is A (2), the sum of A (1) and A (2) is the total supply amount of the polycarbonate resin (A), From the first raw material supply port, styrene resin (B) and polycarbonate resin (A), Formula: B (1)> A (1) (However, A (1) includes 0.) Supply to meet and Then, after injecting water from the water injection part provided in the kneading part and melt-kneading, after degassing the gas component from the vent port, A method for producing a polycarbonate resin composition, characterized in that the polycarbonate resin (A) is supplied in an amount of A (2) from a second raw material supply port downstream of the vent port.
  • the polycarbonate resin composition of the present invention is excellent in mechanical properties and moisture and heat resistance, and has no problem of mold contamination due to mold deposit.
  • the method for producing a polycarbonate resin composition of the present invention can produce a polycarbonate resin composition having excellent mechanical properties and heat-and-moisture resistance and no problem of mold contamination due to mold deposits with high productivity.
  • FIG. 2 is a SEM photograph (magnification 1500 times) of a core part of a molded product obtained in Example 1.
  • FIG. 2 is a SEM photograph (magnification 3000 times) of a core part of a molded product obtained in Example 1.
  • FIG. 3 is a SEM photograph (magnification 1500 times) of a core part of a molded product obtained in Comparative Example 1.
  • 2 is a SEM photograph (magnification 3000 times) of a core part of a molded product obtained in Comparative Example 1. It is a top view of the drop mold used for evaluation of mold contamination.
  • the polycarbonate resin composition of the present invention contains 60 to 95% by weight of the polycarbonate resin (A) and 40 to 5% by weight of the emulsion polymerization styrene resin (B) based on a total of 100% by weight of (A) and (B).
  • a resin composition comprising:
  • the emulsion polymerization styrene resin (B) is a graft copolymer comprising a styrene monomer-vinyl cyanide monomer and / or an alkyl (meth) acrylate monomer-rubber polymer,
  • the total gas amount when the resin composition is heated at 280 ° C. for 10 minutes is 3000 mass ppm or less in terms of decane mass.
  • the production method of the polycarbonate resin composition of the present invention is based on a total of 100% by mass of (A) and (B), 60 to 95% by mass of the polycarbonate resin (A), and 40 to 5% by mass of the emulsion-polymerized styrene resin (B).
  • a polycarbonate resin composition containing 2% by melt-kneading with a vented twin screw extruder The extruder has a first raw material supply port on the upstream side and one or more second raw material supply ports on the downstream side thereof,
  • the supply amount of the emulsion polymerization styrene resin (B) is B (1)
  • the supply amount of the polycarbonate resin (A) from the first raw material supply port is A (1)
  • the sum of A (1) and A (2) is the total supply amount of the polycarbonate resin (A), From the first raw material supply port, styrene resin (B) and polycarbonate resin (A), Formula: B (1)> A (1) (However, A (1) includes 0.) Supply to meet and After melt-kneading, after degassing the gas component from the vent port under reduced pressure, The polycarbonate resin (A) is supplied in an amount of A (2) from the second raw material supply port downstream from the vent port. Furthermore, in the production method of the present invention, it is preferable to perform water injection in the above.
  • Polycarbonate resin (A) examples of the polycarbonate resin (A) used in the present invention include aromatic polycarbonate resins, aliphatic polycarbonate resins, and aromatic-aliphatic polycarbonate resins. Preferred are aromatic polycarbonate resins. Specifically, A thermoplastic aromatic polycarbonate polymer or copolymer obtained by reacting an aromatic dihydroxy compound with phosgene or a diester of carbonic acid is used.
  • Aromatic dihydroxy compounds include 2,2-bis (4-hydroxyphenyl) propane (ie, bisphenol A), tetramethylbisphenol A, ⁇ , ⁇ '-bis (4-hydroxyphenyl) -p-diisopropylbenzene, hydroquinone , Resorcinol, 4,4′-dihydroxydiphenyl, and the like. Further, in order to improve flame retardancy, a compound in which one or more tetraalkylphosphonium sulfonates are bonded to the aromatic dihydroxy compound described above, a polymer having both ends phenolic OH groups having a siloxane structure, or an oligomer thereof is used. Also good.
  • the polycarbonate resin (A) include 2,2-bis (4-hydroxyphenyl) propane as a dihydroxy compound, that is, a polycarbonate resin in which bisphenol A or a combination of bisphenol A and another aromatic dihydroxy compound is used. .
  • the polycarbonate resin may be a homopolymer composed of one type of repeating unit or a copolymer having two or more types of repeating units.
  • the copolymer can be selected from various copolymerization forms such as a random copolymer and a block copolymer.
  • the molecular weight of the polycarbonate resin (A) is not limited, but is preferably from 10,000 to 40,000, more preferably from 14,000 to 32,000 in terms of viscosity average molecular weight (Mv). When the viscosity average molecular weight is within this range, the resulting resin composition has good moldability and a molded product having high mechanical strength is easily obtained.
  • the most preferred viscosity average molecular weight range of the polycarbonate resin (A) is 16,000 to 30,000.
  • the method for producing the polycarbonate resin (A) is not particularly limited, and a polycarbonate resin produced by any of the phosgene method (interfacial polymerization method) and the melting method (transesterification method) can also be used. Moreover, the polycarbonate resin which performed the post-process which adjusts the amount of terminal OH groups to the polycarbonate resin manufactured by the melting method is also preferable.
  • the polycarbonate resin (A) may contain a polycarbonate oligomer.
  • the viscosity average molecular weight [Mv] of this polycarbonate oligomer is usually 1,500 or more, preferably 2,000 or more, and usually 9,500 or less, preferably 9,000 or less.
  • the polycarbonate ligomer contained is preferably 30% by mass or less of the polycarbonate resin (including the polycarbonate oligomer).
  • the polycarbonate resin (A) is not limited to virgin raw materials, but it is also possible to use aromatic polycarbonate resin recycled from used products, so-called material recycled aromatic polycarbonate resin.
  • Used products include optical recording media such as optical disks, light guide plates, automotive window glass and automotive headlamp lenses, vehicle transparent members such as windshields, containers such as water bottles, glasses lenses, soundproof walls and glass windows, corrugated plates
  • Preferred examples include building members such as
  • the recycled polycarbonate resin non-conforming product, pulverized product obtained from sprue or runner, or pellets obtained by melting them can be used.
  • Emssion polymerization styrene resin (B) The emulsion polymerization styrene resin (B) used in the present invention uses an emulsion polymer product produced by emulsion polymerization using an emulsifier.
  • the content of the emulsion polymerization styrene resin (B) is 40 to 5% by mass based on the total of 100% by mass of (A) and (B), and the polycarbonate resin (A) is 60 to 95% as the main component. % By mass. If the amount of the styrene-based resin (B) is less than 5% by mass, the fluidity at the time of molding is insufficient, and the moldability is lowered.
  • the amount of the styrenic resin (B) is preferably 35% by mass or less, preferably 10% by mass or more, more preferably 15% by mass or more, and further preferably 20% by mass or more.
  • the emulsion polymerization styrene resin (B) includes an emulsion polymerization graft copolymer comprising a styrene monomer-vinyl cyanide monomer and / or an alkyl (meth) acrylate monomer-rubber polymer. used.
  • Styrene monomers include styrene, ⁇ -methylstyrene, o-methylstyrene, p-methylstyrene, vinylxylene, ethylstyrene, dimethylstyrene, p-tert-butylstyrene, vinylnaphthalene, methoxystyrene, and monobromostyrene.
  • Styrene derivatives such as dibromostyrene, fluorostyrene, tribromostyrene and the like, and styrene is particularly preferable. These may be used alone or in combination of two or more.
  • vinyl monomers copolymerizable with these styrene monomers include vinyl cyanide monomers and / or alkyl (meth) acrylate monomers.
  • (meth) acrylate refers to one or both of “acrylate” and “methacrylate”. The same applies to “(meth) acryl” and “(meth) acrylo”.
  • vinyl cyanide monomer examples include acrylonitrile, methacrylonitrile, ethacrylonitrile and the like, and acrylonitrile is most preferably used. These can be used alone or in combination of two or more.
  • Alkyl (meth) acrylate monomers include alkyl acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, cyclohexyl acrylate, and dodecyl acrylate.
  • Methacrylic acid aryl esters such as phenyl methacrylate and benzyl methacrylate
  • alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, cyclohexyl methacrylate, and dodecyl methacrylate
  • An epoxy group-containing methacrylic acid ester such as glycidyl methacrylate
  • an aryl ester of acrylic acid such as phenyl acrylate and benzyl acrylate.
  • copolymerizable vinyl monomers other than the above include maleimide monomers such as maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide; acrylic acid, methacrylic acid, (meth) acrylic Examples include ⁇ , ⁇ -unsaturated carboxylic acids such as glycidyl acid, glycidyl itaconate, maleic acid, maleic anhydride, phthalic acid and itaconic acid, and anhydrides thereof. These vinyl monomers may be used alone or in a combination of two or more.
  • a rubber having a glass transition temperature of 10 ° C. or lower is suitable.
  • Specific examples of such a rubbery polymer include diene rubber, acrylic rubber, ethylene / propylene rubber, silicon rubber and the like, and preferably, diene rubber and acrylic rubber.
  • diene rubber examples include butadiene such as polybutadiene, styrene-butadiene random copolymer and block copolymer, acrylonitrile-butadiene copolymer, butyl acrylate-butadiene copolymer, and butadiene-methyl methacrylate copolymer.
  • -(Meth) acrylic acid lower alkyl ester copolymer polyisoprene, ethylene-isoprene copolymer, butadiene-isoprene copolymer, ethylene-propylene-butadiene copolymer, ethylene-propylene-hexadiene copolymer, etc.
  • examples thereof include ethylene, propylene, non-conjugated diene terpolymers, and lower alkyl ester copolymers of butadiene-styrene- (meth) acrylic acid.
  • acrylic rubber examples include acrylic acid alkyl ester rubber, and the alkyl group preferably has 1 to 8 carbon atoms.
  • alkyl acrylate examples include ethyl acrylate, butyl acrylate, ethyl hexyl acrylate, and the like.
  • An ethylenically unsaturated monomer may optionally be used in the acrylic acid alkyl ester rubber.
  • such compounds include di (meth) acrylate, divinylbenzene, trivinylbenzene, triallyl cyanurate, allyl (meth) acrylate, butadiene, isoprene and the like.
  • acrylic rubber examples include a core-shell type polymer having a crosslinked diene rubber as a core.
  • emulsion polymerization styrene resin (B) examples include acrylonitrile-butadiene-styrene copolymer (ABS resin), methyl methacrylate-butadiene rubber-styrene copolymer (MBS resin), and methyl methacrylate by emulsion polymerization.
  • MABS resin Acrylonitrile-butadiene-styrene copolymer
  • MB resin methyl methacrylate-butadiene rubber copolymer
  • AS resin acrylonitrile-acrylic rubber-styrene copolymer
  • AS resin acrylonitrile- (ethylene / propylene / diene rubber)- Styrene copolymer
  • AES resin acrylonitrile-butadiene-styrene- ⁇ -methylstyrene copolymer
  • acrylonitrile-butadiene-styrene-N-phenylmaleimide copolymer and the like.
  • ABS resin Acrylonitrile-butadiene-styrene copolymer
  • MBS resin methyl methacrylate-butadiene rubber-styrene copolymer
  • MABS resin methyl methacrylate-acrylonitrile-butadiene-styrene copolymer
  • ABS resin is particularly preferable.
  • a styrenic resin (B) can also be used individually or in mixture of 2 or more types.
  • the styrene resin (B) uses an emulsion polymer product produced by emulsion polymerization, but the method for producing the emulsion polymerized styrene resin (B) is well known. Alternatively, a commercially available emulsion polymerization product may be used.
  • an ABS resin As a method for producing an emulsion-polymerized styrene resin (B) by emulsion polymerization, an ABS resin will be described as an example.
  • a general method thereof is as follows.
  • the emulsifier usually, a rosin acid soap which is a salt of abietic acid or a higher fatty acid soap which is a salt of a saturated or unsaturated fatty acid having 12 to 32 carbon atoms is used, and the diene monomer is potassium peroxodisulfate.
  • Emulsion polymerization is carried out using a water-soluble polymerization initiator such as ⁇ -cumyl hydroperoxide to obtain a polymer latex.
  • a polymer latex is obtained by polymerizing the polymer particles, the aromatic vinyl monomer and the vinyl cyanide monomer in the presence of a further emulsifier, and an inorganic acid, a divalent metal salt, etc.
  • the ABS coagulant is added to separate the ABS resin, washed and dried.
  • the above-described emulsifier or a component derived therefrom remains in the emulsion polymerization ABS resin, and abietic acid and / or Alternatively, higher fatty acids or salts thereof are contained in the emulsion polymerized product, and the component derived from such an emulsifier affects the hydrolysis of the polycarbonate resin and lowers the heat and moisture resistance. Oligomer remains, and it is considered that this oligomer component generates gas during molding and becomes mold deposit and causes mold contamination.
  • the higher fatty acid is preferably a saturated or unsaturated fatty acid having 12 to 32 carbon atoms, and typical examples thereof include oleic acid, stearic acid, palmitic acid, myristic acid and the like.
  • Metal salts particularly sodium salts, potassium salts, ammonium salts and the like are preferred.
  • Abietic acid and / or higher fatty acid or a salt thereof will be present as a gas generating component in the resin composition obtained as it is, and gas will be generated at the time of molding, resulting in mold deposits and mold contamination. It affects the hydrolysis of the polycarbonate resin and lowers the heat and moisture resistance.
  • oligomers remain in the emulsion-polymerized styrene resin, and the oligomer component is considered to cause mold contamination and gas generation.
  • the polycarbonate resin composition of the present invention contains 40 to 5% by mass of the emulsion-polymerized styrene resin (B), and the total gas amount when the resin composition is heated at 280 ° C. for 10 minutes. It is 3000 mass ppm or less in terms of decane mass. When the total gas amount is 3000 mass ppm or less, the polycarbonate resin composition of the present invention is excellent in mechanical properties and wet heat resistance, and can solve the problem of mold contamination due to mold deposits.
  • the total gas amount is preferably 2700 mass ppm or less, more preferably 2500 mass ppm or less, and its preferred lower limit is 500 mass ppm. If it is less than 500 ppm by mass, the releasability at the time of molding is extremely deteriorated, and the appearance of the molded product, particularly the surface glossiness, is liable to be impaired.
  • the amount of gas derived from the emulsifier can be 380 mass ppm or less in terms of decane mass. By setting it to 380 mass ppm or less, the heat-and-moisture resistance can be made extremely good.
  • the gas generating component derived from the emulsifier here refers to an emulsifier component used in the emulsion polymerization of the styrene resin (B). As described above, generally, higher fatty acid soap or rosin acid is used. It is a component derived from soap, and more specifically, is abietic acid and a saturated or unsaturated fatty acid having 12 to 32 carbon atoms or a metal salt thereof.
  • the amount of gas generated from the emulsifier is specifically the total gas amount of abietic acid and saturated or unsaturated fatty acid having 12 to 32 carbon atoms as the generated gas when the resin composition is heated at 280 ° C. for 10 minutes.
  • decane mass it is preferably 380 mass ppm or less, and the heat and humidity resistance is extremely good by making the total gas amount of abietic acid and saturated or unsaturated fatty acids having 12 to 32 carbon atoms be 380 mass ppm or less. can do.
  • it is 300 mass ppm or less, More preferably, it is 200 mass ppm or less, Furthermore, it is preferable that it is 100 mass ppm or less.
  • the preferable lower limit is 50 mass ppm in view of the releasability during molding and the appearance of the molded product.
  • the generated gas also contains those derived from the oligomer component remaining in the styrene resins (B) and (C).
  • this oligomer component is a problem of mold contamination due to mold deposits and the like. Cause. Therefore, it is particularly preferable that the total gas amount when heated at 280 ° C. for 10 minutes is 3000 ppm by mass or less in terms of decane mass from the viewpoint of mold contamination and wet heat resistance.
  • the polycarbonate resin composition of the present invention may further contain a styrene resin (C) other than the emulsion polymerization styrene resin (B).
  • a styrene resin (C) other than the emulsion polymerization styrene resin (B).
  • Other styrenic resin (C) is contained in an amount of 0 to 30% by mass.
  • suspension polymerization AS resin is a copolymer obtained by suspension polymerization of acrylonitrile and styrene, and may contain other components.
  • acrylonitrile preferably occupies 10 to 50 mol%, more preferably 15 to 40 mol%.
  • styrene preferably accounts for 50 to 90 mol%, and more preferably 60 to 85 mol%.
  • the ABS resin is a resin obtained by copolymerizing a rubbery polymer copolymerizable with a styrene monomer and a vinyl cyanide monomer, and preferably 40 to 80% by mass of a styrene monomer component, cyanide. It comprises 10 to 30% by mass of vinyl fluoride monomer component, 10 to 30% by mass of diene rubber polymer component, and 0 to 30% by mass of other copolymerizable vinyl monomer components.
  • these styrene monomers, vinyl cyanide monomers, diene rubber polymers, and other copolymerizable vinyl monomers those described in the emulsion polymerization styrene resin (B) The same can be used in the same way.
  • ABS resin as the styrene-based resin (C)
  • a block polymerization ABS resin produced by block polymerization is used.
  • the bulk polymerization method is well known, and a known method may be applied. Examples thereof include a continuous bulk polymerization method.
  • polymerization may be performed in one stage or in multiple stages.
  • the polycarbonate resin composition of the present invention is preferably produced by the above-described method for producing a polycarbonate resin composition of the present invention.
  • the emulsion polymerization styrene resin (B) which is a small component
  • the polycarbonate resin (B) which is the main component
  • a polycarbonate resin composition having excellent mechanical properties and heat-and-moisture resistance and no problem of mold contamination due to mold deposit can be produced very efficiently with high productivity.
  • a polycarbonate resin composition containing 60 to 95% by weight of a polycarbonate resin (A) and 40 to 5% by weight of an emulsion-polymerized styrene resin (B) based on the total of 100% by weight of (A) and (B) is vented.
  • the extruder has a first raw material supply port on the upstream side and one or more second raw material supply ports on the downstream side thereof,
  • the supply amount of the styrene resin (B) is B (1)
  • the supply amount of the polycarbonate resin (A) from the first raw material supply port is A (1)
  • the second raw material supply port of the polycarbonate resin (A) is B (1)
  • the total amount of A (1) and A (2) is the total amount of polycarbonate resin (A) From the first raw material supply port, styrene resin (B) and polycarbonate resin (A), Supply so as to satisfy the formula: B (1)> A (1) (where A (1) includes 0)
  • the extruder has a first raw material supply port on the upstream side and a water injection part and a vent port in the kneading part on the downstream side, and further has one or more second raw material supply ports on the downstream side.
  • the supply amount of the styrene resin (B) is B (1)
  • the supply amount of the polycarbonate resin (A) from the first raw material supply port is A (1)
  • the second raw material supply port of the polycarbonate resin (A) is the total amount of polycarbonate resin (A) From the first raw material supply port, styrene resin (B) and polycarbonate resin (A), Supply so as to satisfy the formula: B (1)> A (1) (where A (1) includes 0), Then, after injecting water from the water injection part provided in the kneading part and melt-kneading, after degassing the gas component from the vent port, Manufactured by a method in which the polycarbonate resin (A) is supplied in an amount of A (2) from the second raw material supply port downstream of the vent port.
  • a vent type twin screw extruder is used, and both screw rotations can be used in the same direction and in different directions.
  • a co-rotating twin-screw extruder is suitable for efficiently removing the gas generating components in the system resin (B).
  • the extruder has a first raw material supply port at the root of the uppermost stream and a vent port downstream thereof.
  • the emulsion polymerization styrene resin (B) is supplied from the first raw material supply port.
  • the emulsion-polymerized styrene resin (B) is heated and melted in the extruder, and then becomes a decompression expansion region connected to the vent port.
  • the vent port By connecting the vent port to a vacuum pump and venting under reduced pressure, the emulsion-polymerization styrene resin (B) Can be devolatilized under reduced pressure.
  • the position where the vent port is installed may be a melting portion of the emulsion polymerization styrene resin (B).
  • Two or more vent ports may be provided as desired.
  • the supply amount of the polycarbonate resin (A) at that time is as described above. It is preferable that the formula: B (1)> A (1) is satisfied, that is, less than the supply amount of the emulsion polymerization styrene resin (B).
  • B (1)> A (1) is satisfied, that is, less than the supply amount of the emulsion polymerization styrene resin (B).
  • the polycarbonate resin (A) is supplied at a supply amount of (A2) from the second raw material supply port located downstream.
  • (A2) is the remaining amount obtained by subtracting (A1) from the total supply amount of the polycarbonate resin (A).
  • (A1) In the case of 0, (A2) is the total supply amount of the polycarbonate resin (A).
  • the polycarbonate resin (A) supplied from the second raw material supply port merges with the molten resin from the upstream, and is further melt-kneaded.
  • the polycarbonate resin composition of the present invention is produced by side-feeding the polycarbonate resin (A) as the main component in the polycarbonate resin composition of the present invention. It can be manufactured with good efficiency and very efficiently.
  • the polycarbonate resin composition of the present invention preferably contains another styrene resin (C) other than the emulsion polymerization styrene resin.
  • C another styrene resin
  • it can be supplied from either the first supply port or the second supply port.
  • suspension polymerization AS resin or bulk polymerization ABS resin since it does not contain an emulsifier, it may be supplied from the second supply port, but it is preferable to supply from the first supply port in consideration of the residual oligomer.
  • the extruder is provided with a first raw material supply port at the most upstream root, an inlet for injecting water downstream thereof, and a vent port further downstream.
  • the emulsion-polymerized styrene resin (B) is supplied from the first raw material supply port, and after the styrene resin (B) is heated and melted in the extruder, water is pumped from the water injection port provided in the resin-filled area. It is poured and kneaded.
  • the injected water is dispersed in the styrene resin (B).
  • a seal ring downstream to increase the pressure.
  • the seal ring When passing through the seal ring, it becomes a reduced pressure expansion region connected to the vent port, and the water dispersed in the styrene resin (B) is foamed under reduced pressure.
  • the position where the vent port is installed may be a melting part of the styrene resin (B).
  • Two or more vent ports may be provided as desired.
  • the vacuum degree of the decompression vent is preferably 50 mmHg or less, more preferably 20 mmHg or less, and further preferably 10 mmHg or less.
  • the vent type twin screw extruder preferably has a water injection part and a vent port in multiple stages, and it is preferable to perform water injection and vacuum devolatilization in multiple stages.
  • the emulsion polymerization styrene resin (B) and the polycarbonate resin (A) are supplied from the first raw material supply port in the first stage in the same manner as described above in the amount of B (1)> A (1).
  • water injection, kneading, devolatilization by a vacuum vent, water injection, kneading, and vacuum venting are further performed in the second stage on the downstream side. There may be a plurality of steps of water injection and vacuum devolatilization in the second stage.
  • the amount of water to be injected is preferably 0.01 to 5% by mass, more preferably 0 to 100% by mass of the styrene resin (B) and / or the polycarbonate resin (A) that is the target at the time of injection. .1% by mass or more, preferably 0.5% by mass or more, more preferably 3% by mass or less, further 2% by mass or less, and particularly preferably 1% by mass or less.
  • the amount of water injected is 0.01% by mass or less, the removal of gas generating components tends to be insufficient, and when it exceeds 5% by mass, the hydrolysis of the polymer proceeds and the physical properties tend to be lowered.
  • the resin temperature (or set temperature) when the resin supplied from the first raw material supply port is melt-kneaded is preferably 240 to 350 ° C., more preferably 250 to 350 ° C.
  • the resin temperature (or set temperature) downstream from the second raw material supply port is preferably 280 to 360 ° C, more preferably 290 to 350 ° C.
  • the amount of water contained in advance is preferably about 0.01 to 5% by mass, similar to the amount of water described above.
  • the polycarbonate resin composition of the present invention preferably contains a stabilizer, and the stabilizer is preferably a phosphorus stabilizer or a phenol stabilizer.
  • any known one can be used.
  • Specific examples include phosphorus oxo acids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, and polyphosphoric acid; acidic pyrophosphate metal salts such as acidic sodium pyrophosphate, acidic potassium pyrophosphate, and acidic calcium pyrophosphate; phosphoric acid Group 1 or Group 2B metal phosphates such as potassium, sodium phosphate, cesium phosphate and zinc phosphate; organic phosphate compounds, organic phosphite compounds, organic phosphonite compounds, etc. Particularly preferred.
  • Organic phosphite compounds include triphenyl phosphite, tris (monononylphenyl) phosphite, tris (monononyl / dinonyl phenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, monooctyl Diphenyl phosphite, dioctyl monophenyl phosphite, monodecyl diphenyl phosphite, didecyl monophenyl phosphite, tridecyl phosphite, trilauryl phosphite, tristearyl phosphite, 2,2-methylene bis (4,6-di- tert-butylphenyl) octyl phosphite and the like.
  • organic phosphite compounds include, for example, “ADEKA STAB 1178”, “ADEKA STAB 2112”, “ADEKA STAB HP-10” manufactured by ADEKA, “JP-351” manufactured by Johoku Chemical Industry Co., Ltd., “ JP-360 ”,“ JP-3CP ”,“ Irgaphos 168 ”manufactured by BASF, and the like.
  • 1 type may contain phosphorus stabilizer and 2 or more types may contain it by arbitrary combinations and a ratio.
  • the content of the phosphorus stabilizer is usually 0.001 parts by mass or more, preferably 0.01 parts by mass or more, with respect to 100 parts by mass in total of the polycarbonate resin (A) and the styrene resins (B) and (C). More preferably, it is 0.03 parts by mass or more, and is usually 1 part by mass or less, preferably 0.7 parts by mass or less, more preferably 0.5 parts by mass or less. If the content of the phosphorus stabilizer is less than the lower limit of the range, the thermal stability effect may be insufficient, and if the content of the phosphorus stabilizer exceeds the upper limit of the range, the effect May stop and become economical.
  • phenolic stabilizers include hindered phenolic antioxidants. Specific examples thereof include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl).
  • phenolic antioxidants include “Irganox 1010”, “Irganox 1076” manufactured by BASF, “Adekastab AO-50”, “Adekastab AO-60” manufactured by ADEKA, and the like. Is mentioned.
  • 1 type may contain the phenol type stabilizer, and 2 or more types may contain it by arbitrary combinations and a ratio.
  • the content of the phenol-based stabilizer is usually 0.001 part by mass or more, preferably 0.01 part by mass or more with respect to 100 parts by mass in total of the polycarbonate resin (A) and the styrene resin (B) and (C). Moreover, it is 1 mass part or less normally, Preferably it is 0.5 mass part or less.
  • the content of the phenol-based stabilizer is less than the lower limit of the range, the effect as the phenol-based stabilizer may be insufficient, and the content of the phenol-based stabilizer exceeds the upper limit of the range. If this is the case, the effect may reach its peak and not economical.
  • the polycarbonate resin composition of the present invention preferably contains a release agent.
  • the release agent includes at least one compound selected from the group consisting of aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15000, and polysiloxane silicone oils. Preferably mentioned.
  • the aliphatic carboxylic acid examples include saturated or unsaturated aliphatic monovalent, divalent or trivalent carboxylic acid.
  • the aliphatic carboxylic acid includes alicyclic carboxylic acid.
  • preferred aliphatic carboxylic acids are monovalent or divalent carboxylic acids having 6 to 36 carbon atoms, and aliphatic saturated monovalent carboxylic acids having 6 to 36 carbon atoms are more preferred.
  • aliphatic carboxylic acids include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, mellicic acid, tetrariacontanoic acid, montanic acid, adipine Examples include acids and azelaic acid.
  • aliphatic carboxylic acid in the ester of an aliphatic carboxylic acid and an alcohol examples of the alcohol include saturated or unsaturated monovalent or polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, a monovalent or polyvalent saturated alcohol having 30 or less carbon atoms is preferable, and an aliphatic saturated monohydric alcohol or polyhydric alcohol having 30 or less carbon atoms is more preferable.
  • aliphatic includes alicyclic compounds.
  • alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol and the like. Is mentioned.
  • esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture based on myricyl palmitate), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostearate
  • esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture based on myricyl palmitate), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostearate
  • examples thereof include rate, glycerol distearate, glycerol tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastea
  • Examples of the aliphatic hydrocarbon having a number average molecular weight of 200 to 15000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, Fischer-Tropsch wax, and ⁇ -olefin oligomer having 3 to 12 carbon atoms.
  • the aliphatic hydrocarbon alicyclic hydrocarbon is also included.
  • these hydrocarbon compounds may be partially oxidized.
  • paraffin wax, polyethylene wax, or a partial oxide of polyethylene wax is preferable, and paraffin wax and polyethylene wax are more preferable.
  • the number average molecular weight is preferably 200 to 5,000.
  • These aliphatic hydrocarbons may be a single substance, or may be a mixture of various constituent components and molecular weights, as long as the main component is within the above range.
  • polysiloxane silicone oil examples include dimethyl silicone oil, phenylmethyl silicone oil, diphenyl silicone oil, and fluorinated alkyl silicone. Two or more of these may be used in combination.
  • a release agent When a release agent is used, it is usually 0.05 to 2 parts by mass, preferably 0.1 to 1 part by mass with respect to 100 parts by mass in total of the polycarbonate resin (A) and the styrene resin (B) and (C). It is. If the content of the release agent is not less than the above lower limit value, the effect of improving the releasability can be sufficiently obtained, and if it is not more than the above upper limit value, degradation of hydrolysis resistance due to excessive mixing of the release agent, injection Problems such as mold contamination during molding can be prevented.
  • the polycarbonate resin composition of the present invention preferably contains a colorant (dye pigment).
  • the colorant (dye pigment) include inorganic pigments, organic pigments, and organic dyes.
  • examples of inorganic pigments include sulfide pigments such as carbon black, cadmium red, and cadmium yellow; silicate pigments such as ultramarine blue; zinc white, petal, chromium oxide, titanium oxide, iron black, titanium yellow, and zinc- Oxide pigments such as iron-based brown, titanium cobalt-based green, cobalt green, cobalt blue, copper-chromium black, copper-iron-based black; chromic pigments such as yellow lead, molybdate orange; Examples include Russian pigments.
  • Organic pigments and organic dyes include phthalocyanine dyes such as copper phthalocyanine blue and copper phthalocyanine green; azo dyes such as nickel azo yellow; thioindigo, perinone, perylene, quinacridone, dioxazine, and isoindolinone. And condensed polycyclic dyes such as quinophthalone; anthraquinone, heterocyclic, and methyl dyes and the like. Two or more of these may be used in combination. Among these, carbon black, titanium oxide, cyanine-based, quinoline-based, anthraquinone-based, and phthalocyanine-based compounds are preferable from the viewpoint of thermal stability.
  • the content of the colorant (dye pigment) is usually 5 masses with respect to a total of 100 parts by mass of the polycarbonate resin (A), the styrene resin (B), and (C). Part or less, preferably 3 parts by weight or less, more preferably 2 parts by weight or less. When the content of the colorant (dye pigment) exceeds 5 parts by mass, the impact resistance may not be sufficient.
  • the polycarbonate resin composition of the present invention may contain other components in addition to those described above as necessary, as long as the desired physical properties are not significantly impaired.
  • examples of other components include resins other than those described above and various resin additives.
  • 1 type may contain other components and 2 or more types may contain them by arbitrary combinations and ratios.
  • thermoplastic polyester resins such as polyethylene terephthalate resin, polytrimethylene terephthalate, and polybutylene terephthalate resin
  • polyolefin resins such as polyethylene resin and polypropylene resin
  • polyamide resins such as polyimide resins; polyetherimide resins
  • examples include resins; polyphenylene ether resins; polyphenylene sulfide resins; polysulfone resins and various elastomers.
  • 1 type may contain other resin and 2 or more types may contain it by arbitrary combinations and ratios.
  • the resin additive examples include a flame retardant, an ultraviolet absorber, an antistatic agent, an antifogging agent, an antiblocking agent, a fluidity improver, a plasticizer, a dispersant, and an antibacterial agent.
  • 1 type may contain resin additive and 2 or more types may contain it by arbitrary combinations and a ratio.
  • the styrenic resin (B) is island-shaped in the matrix of the polycarbonate resin (A) by side-feeding the polycarbonate resin (A) from the second raw material supply port. It was confirmed to show a morphological structure that was finely dispersed.
  • the volume average dispersion diameter (dv) of the styrene resin (B) is characteristically as small as 2.5 ⁇ m.
  • the resin composition of the present invention has an excellent impact strength retention (wet heat resistance).
  • the Charpy impact strength (according to ISO 179-1 and 179-2, with notch, 23 ° C.) after a wet heat treatment at a temperature of 90 ° C. and a relative humidity of 95% for 400 hours is preferably 50% or more. More preferably 60% or more, still more preferably 70% or more, and particularly preferably 80% or more.
  • the morphology of the polycarbonate resin composition can be observed by observing the cross section of the molded product with an optical microscope, SEM (scanning electron microscope), TEM (transmission electron microscope) or the like. Specifically, using a SEM, STEM, or TEM analyzer, the pellet cross section is observed at a magnification of 400 to 10,000 times under an acceleration voltage of 3 kv.
  • FIG. 1 and 2 show an example of the morphology of the resin composition of the present invention, and are SEM photographs of the pellet cross section obtained in Example 1 of the present invention.
  • 1 is a photograph at a magnification of 1500 times
  • FIG. 2 is a photograph at a magnification of 3000 times.
  • the white sea is the matrix phase of the polycarbonate resin
  • the black islands dispersed in it are the ABS resin phase, which are finely and finely dispersed in the polycarbonate resin phase.
  • FIG. 3 (magnification 1500 times) and FIG. 4 (magnification 3000 times) show the morphology of Comparative Example 1, but it can be seen that fine dispersion as shown in FIGS. 1 and 2 cannot be achieved.
  • the volume average particle diameter (dv) of the styrene resin in which the styrene resin (B) phase is dispersed in the polycarbonate resin phase is 2.5 ⁇ m or less, preferably 2.2 ⁇ m or less, more preferably 2 0.0 ⁇ m or less, more preferably 1.5 ⁇ m or less, and preferably 0.5 ⁇ m or more. If the volume average particle diameter (dv) exceeds 2.5 ⁇ m, the impact strength retention after wet heat of the resin composition tends to be extremely lowered, which is not preferable.
  • the ratio (dv / dn) of the volume average particle diameter (dv) and the number average particle diameter (dn) of the styrene resin (B) dispersed in the polycarbonate resin is in the range of 1.0 to 1.5. Preferably, it is 1.1 or more, more preferably 1.15 or more, more preferably 1.45 or less, and further preferably 1.4 or less.
  • the meaning of the numerical value of dv / dn means a uniform state in which the dispersed particle diameters of the styrenic resin are uniform when dv / dn is 1, and when the particle diameter is larger than 1, the dispersed particle diameters are not uniform and uneven. It is shown that.
  • this dv / dn is closely related to the volume average diameter (dv) of the dispersed styrene resin described above, except that the dispersed particle diameter is simply uniform. That is, even if dv / dn is in the range of 1.0 to 1.5, if the volume average diameter of the dispersed styrene resin is increased, it is difficult to obtain the effect of improving heat and moisture resistance.
  • the average particle diameter (dn) and the volume average particle diameter (dv) of the styrene resin (B) are obtained by observing with a scanning electron microscope (SEM). Details thereof are as described in Examples.
  • the emulsion-polymerized styrene-based resin (B) exhibits such a volume average particle size (dv) and a morphology having a dv / dn ratio, which means that the emulsion-polymerized styrene-based resin (B) is well melt-kneaded, It can be judged that the devolatilization of the emulsifier-derived component is also highly advanced.
  • the polycarbonate resin composition of the present invention is formed by various molding methods, for example, injection molding method, ultra-high speed injection molding method, injection compression molding method, two-color molding method, hollow molding method such as gas assist, molding using a heat insulating mold.
  • Method molding method using rapid heating mold, foam molding (including supercritical fluid), insert molding, IMC (in-mold coating molding) molding method, extrusion molding method, sheet molding method, thermoforming method, rotational molding method It is formed into a molded product by a lamination molding method, a press molding method or the like.
  • Examples of molded products include parts such as electrical and electronic equipment, OA equipment, information terminal equipment, machine parts, home appliances, vehicle parts, building members, various containers, and lighting equipment. Among these, it is particularly suitable for various parts of vehicle parts, electric / electronic devices, and OA devices.
  • parts means “parts by mass” based on mass standards unless otherwise specified.
  • the raw material supply port is provided with a side feeder (“TSF-45E” manufactured by Kubota Corporation) and supplied from there.
  • the screw arrangement includes a full flight screw portion for conveyance, a kneading screw portion for plasticization, and a kneading screw portion for kneading from the supply portion side, and a full flight screw portion for conveyance corresponding to the second raw material supply port.
  • the kneading kneading screw part is provided.
  • the emulsion polymerization ABS resin (B1) described in Table 1 was continuously supplied at a supply rate of 105 kg / hr (corresponding to 30 parts by mass).
  • the screw rotation speed is 800 rpm
  • the cylinder set temperature is 330 ° C.
  • water is supplied from the water inlet provided in the latter half of the kneading screw part at 0.88 kg / hr. (The ratio of 0.25% by mass with respect to the total discharge amount).
  • a seal ring is provided further rearward of the kneading screw part, and the mixture with water is kneaded with an increase in pressure in the kneading screw part for kneading, and then the vent port provided downstream thereof is in a reduced pressure state of 20 mmHg. Then, foaming devolatilization was performed while the mixture of the resin and water was foamed while being dispersed. Next, a pre-blend of the polycarbonate resin (A) described in Table 1 and the release agents (D1, D2), stabilizers (E1, E2) and colorant (F) described in Table 1 was supplied to the second supply port. To 245 kg / hr (corresponding to 70 parts by mass).
  • D1 and D2 components are 0.10% by mass
  • E1 and E2 components are 0.03% by mass and 0.05% by mass, respectively, with respect to 100% by mass of the final resin composition.
  • the polycarbonate resin pre-blended product was kneaded while being combined with the devolatilized ABS resin from the upstream at a cylinder set temperature of 330 ° C., and water was again supplied from the water inlet at 0.88 kg / hr (0. 25 mass%).
  • the vent port is reduced in pressure to 20 mmHg, foamed and devolatilized, extruded and strand cut to obtain pellets of the resin composition It was.
  • the motor current value at the time of extrusion was 236 A
  • the resin temperature at the die outlet was 333 ° C.
  • the resin pressure at the die tip was 1.1 MPa. Considering the long-term operational stability of the extruder, these are important because the load on the motor is preferably smaller, and in general, the resin temperature tends to be lower in order to suppress the decomposition of the resin composition. It becomes a judgment index.
  • Example 2 In Example 1, as described in Table 2, in the same manner as in Example 1 except that the water injection amounts of the first stage and the second stage were both 0.5% by mass, Pellets were obtained.
  • Example 3 In Example 1, as described in Table 2, the resin composition was prepared in the same manner as in Example 1 except that the cylinder set temperature was 300 ° C. and the first and second stages of water injection were not performed. Pellets were obtained.
  • Example 4 In Example 2, as shown in Table 2, pellets of the resin composition were made in the same manner as in Example 2 except that the second stage water injection was not performed and the degree of vacuum at the vent port was 10 mmHg. Got.
  • Example 5 In Example 2, as shown in Table 2, the polycarbonate resin pre-blend was supplied from the first raw material supply port at a feed rate of 87.5 kg / hr (corresponding to 25 parts by mass), and the ABS resin (B1) was 105 kg. / Hr (equivalent to 30 parts by mass), polycarbonate resin is supplied from the second supply port at a rate of 157.5 kg / hr (equivalent to 45 parts by mass), and the degree of vacuum at the vent port is adjusted. Except having set it as 10 mmHg, it carried out similarly to Example 2, and obtained the pellet of the resin composition.
  • Example 6 In Example 1, as shown in Table 3, the styrene resin supplied to the first raw material supply port was 52.5 kg / hr (equivalent to 15 parts by mass) of the emulsion polymerization ABS resin (B2) described in Table 1. And suspension polymerization AS resin (C1) listed in Table 1 at a supply rate of 52.5 kg / hr (corresponding to 15 parts by mass), and the degree of vacuum at the vent port was 10 mmHg. In the same manner as above, pellets of the resin composition were obtained.
  • Example 7 In Example 5, as described in Table 3, the styrene resin supplied to the first raw material supply port was changed to the emulsion polymerization MBS resin (B3) and the suspension polymerization AS resin (C1) described in Table 1. The pellets of the resin composition were obtained in the same manner as in Example 5 except that the amounts of water injected in the first stage and the second stage were both 1.0% by mass. It was.
  • Example 8 In Example 1, as described in Table 3, Example 1 except that the emulsion polymerization ABS resin (B1) and the bulk polymerization ABS resin (C2) were supplied from the first raw material supply port in the amounts shown in Table 3. In the same manner as above, pellets of the resin composition were obtained.
  • Example 9 In Example 1, as described in Table 3, the styrene resin supplied to the first raw material supply port was 140 kg / hr (equivalent to 40 parts by mass) of the emulsion polymerization ABS resin (B1) described in Table 1. A pellet of the resin composition was obtained in the same manner as in Example 1 except that the polycarbonate resin pre-blend was supplied from the second raw material supply port at a supply rate of 210 kg / hr (corresponding to 60 parts by mass).
  • Example 10 In Example 1, as described in Table 3, the styrene resin supplied to the first raw material supply port was 28 kg / hr (equivalent to 8 parts by mass) of the emulsion polymerization ABS resin (B2) described in Table 1. And the polycarbonate resin preliminary blend was supplied from the second raw material supply port at a supply rate of 322 kg / hr (corresponding to 92 parts by mass), and the degree of vacuum at the vent port was 10 mmHg, as in Example 1, A pellet of the resin composition was obtained.
  • the styrene resin supplied to the first raw material supply port was 28 kg / hr (equivalent to 8 parts by mass) of the emulsion polymerization ABS resin (B2) described in Table 1.
  • the polycarbonate resin preliminary blend was supplied from the second raw material supply port at a supply rate of 322 kg / hr (corresponding to 92 parts by mass), and the degree of vacuum at the vent port was 10 mmHg, as in Example 1, A pellet of the resin composition was obtained
  • Example 1 Comparative Example 1
  • the polycarbonate resin pre-blend from the first raw material supply port was supplied at a feed rate of 245 kg / hr (corresponding to 70 parts by mass), and the ABS resin (B1) was 105 kg / hr.
  • the pellets of the resin composition were obtained in the same manner except that the polycarbonate resin was not supplied from the second supply port.
  • Example 2 In Example 2, as shown in Table 4, the polycarbonate resin pre-blend from the first raw material supply port was supplied at a feed rate of 245 kg / hr (corresponding to 70 parts by mass), and the ABS resin (B1) was 105 kg / hr. The pellets of the resin composition were obtained in the same manner except that the polycarbonate resin was not supplied from the second supply port.
  • Example 2 (Comparative Examples 3 to 4)
  • the cylinder set temperature was 300 ° C.
  • the polycarbonate resin pre-blend was fed from the first raw material feed port at a feed rate of 140 kg / hr (corresponding to 40 parts by mass)
  • ABS Resin (B1) is supplied at a supply rate of 105 kg / hr (corresponding to 30 parts by mass)
  • polycarbonate resin is supplied from the second supply port at a supply rate of 105 kg / hr (corresponding to 30 parts by mass).
  • Pellets of the resin composition were obtained in the same manner except that the water injection amount of the stage and the second stage and the degree of vacuum at the vent port were as shown in Table 3.
  • Example 7 In Example 7, as described in Table 4, the polycarbonate resin pre-blend was supplied from the first raw material supply port at a supply rate of 245 kg / hr (corresponding to 70 parts by mass), and from the second supply port. Resin composition pellets were obtained in the same manner as in Example 7 except that the polycarbonate resin was not supplied and the first and second water injection amounts shown in Table 4 were used.
  • Comparative Example 6 Comparative Example 6,
  • the styrene resin supplied to the first raw material supply port was 175 kg / hr (equivalent to 50 parts by mass) of the emulsion polymerization ABS resin (B1) described in Table 4, and the second raw material supply port.
  • Resin composition pellets were obtained in the same manner as in Comparative Example 2 except that the polycarbonate resin pre-blend was supplied at a supply rate of 175 kg / hr (corresponding to 50 parts by mass).
  • Comparative Example 7 In Comparative Example 6, the styrene resin supplied to the first raw material supply port was 10.5 kg / hr (corresponding to 3 parts by mass) of the emulsion polymerization ABS resin (B1) described in Table 4 and the bulk polymerization ABS resin (C2 ) 112 kg / hr (corresponding to 32 parts by mass), and Comparative Example 6 except that the polycarbonate resin pre-blend was supplied from the second raw material supply port at a supply rate of 227.5 kg / hr (corresponding to 65 parts by mass). In the same manner as above, pellets of the resin composition were obtained.
  • Carrier gas Helium 3ml / min
  • the emulsifier origin component the oligomer of the styrene resin, and other components (oligomer of polycarbonate resin, raw material monomer of polycarbonate resin, release agent, etc.) were measured by decane conversion.
  • the emulsifier-derived component was measured for the amounts of abietic acid and saturated or unsaturated fatty acids having 12 to 32 carbon atoms.
  • As the fatty acid, oleic acid, stearic acid, palmitic acid or myristic acid was detected in the amounts (unit: mass ppm) shown in Tables 2 to 4.
  • the drop mold shown in FIG. 5 is a mold designed so that the resin composition is introduced from the gate G so that the generated gas easily accumulates at the tip.
  • the gate G has a width of 1 mm and a thickness of 1 mm.
  • the notched Charpy impact strength (unit: kJ / m 2 ) of the test pieces before and after the wet heat treatment was measured at 23 ° C. according to ISO179.
  • the obtained pellet was made into a cross-section using an ultramicrotome system UC7 (diamond knife) for section preparation manufactured by Leica, and evaporated to a film thickness of 25 nm using a multi-coater VES-10 manufactured by Vacuum Device Co., Ltd.
  • an image obtained by SEM observation (apparatus: SU8020 manufactured by Hitachi High-Tech, measurement condition: 3 kV-400 to 10000 times, direction perpendicular to the flow direction) is used as image analysis software “A Image-kun” manufactured by Asahi Kasei Engineering. Image analysis was performed.
  • the diameter (dnj) when converted into a perfect circle from the area of the dispersed particles of the styrene resin is calculated from the following formula, and the number average particle diameter (dn), volume average particle diameter (dv), and volume The ratio (dv / dn) between the average particle diameter (dv) and the number average particle diameter (dn) was determined.
  • the calculation formula of the diameter (dnj) when converted into a perfect circle from the area of the dispersed particles of the styrene resin is as follows.
  • A is the particle area of the dispersed styrene resin obtained by image analysis of the SEM photograph.
  • the calculation formula of the number average particle diameter (dn) of the dispersed styrene resin is as follows.
  • the formula for calculating the volume average particle diameter (dv) of the dispersed styrene resin is as follows.
  • the polycarbonate resin composition of the present invention is excellent in mechanical properties and heat-and-moisture resistance, and has no problem of mold contamination due to mold deposit. Therefore, electrical and electronic equipment, OA equipment, information terminal equipment, machine parts, home appliances, vehicle parts, It can be widely used for building members, various containers, lighting equipment, and the like, and according to the production method of the present invention, such a polycarbonate resin composition can be produced with high productivity, so that its industrial utility is high. is there.

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Abstract

La présente invention concerne : une composition de résine de polycarbonate qui présente d'excellentes propriétés mécaniques et une excellente résistance à la chaleur humide, tout en étant exempte du problème de contamination du moule en raison d'un dépôt sur le moule ; et un procédé de production permettant de produire ladite composition de résine de polycarbonate avec une productivité élevée. Ladite composition de résine de polycarbonate contient de 60 à 95 % en masse d'une résine de polycarbonate (A) et de 40 à 5 % en masse d'une résine de styrène polymérisée en émulsion (B) par rapport aux 100 % en masse du total des constituants (A) et (B), et est caractérisée en ce que : la résine de styrène polymérisée en émulsion (B) est un copolymère greffé qui est obtenu à partir d'un monomère styrène-monomère cyanure de vinyle et/ou d'un monomère (méth)acrylate d'alkyle-polymère caoutchouteux ; et la quantité totale de gaz dans les cas où la composition de résine est chauffée à 280 °C pendant 10 minutes est inférieure ou égale à 3 000 ppm en termes de masse de décane.
PCT/JP2016/077679 2015-10-02 2016-09-20 Composition de résine de polycarbonate et son procédé de production WO2017057092A1 (fr)

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KR1020187003603A KR102071812B1 (ko) 2015-10-02 2016-09-20 폴리카르보네이트 수지 조성물 및 그 제조 방법
CN201680049306.3A CN107922723B (zh) 2015-10-02 2016-09-20 聚碳酸酯树脂组合物和其制造方法
US15/580,400 US10385207B2 (en) 2015-10-02 2016-09-20 Polycarbonate resin composition and method for producing same

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JP2015-196835 2015-10-02
JP2015196835 2015-10-02
JP2015-204209 2015-10-16
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JP2016145676A JP6114447B2 (ja) 2015-10-02 2016-07-25 ポリカーボネート樹脂組成物の製造方法
JP2016-145675 2016-07-25
JP2016145675A JP2017075297A (ja) 2015-10-16 2016-07-25 ポリカーボネート樹脂組成物
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Citations (5)

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JPH10292053A (ja) * 1997-02-18 1998-11-04 Asahi Chem Ind Co Ltd 樹脂組成物の製造方法
JP2002154114A (ja) * 2000-09-08 2002-05-28 Asahi Kasei Corp 難燃性ポリカーボネート樹脂組成物の製造方法
JP2003511506A (ja) * 1999-10-04 2003-03-25 バイエル アクチェンゲゼルシャフト 熱可塑性ポリマー配合物の連続製造方法および装置ならびにそれらの使用
JP2006182841A (ja) * 2004-12-27 2006-07-13 Sumitomo Dow Ltd 熱可塑性樹脂組成物およびそれを成形してなる成形品
JP2012518063A (ja) * 2009-02-19 2012-08-09 バイエル・マテリアルサイエンス・アクチェンゲゼルシャフト 揮発性有機化合物の含有量を減らしたポリマー組成物を製造する混練方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10292053A (ja) * 1997-02-18 1998-11-04 Asahi Chem Ind Co Ltd 樹脂組成物の製造方法
JP2003511506A (ja) * 1999-10-04 2003-03-25 バイエル アクチェンゲゼルシャフト 熱可塑性ポリマー配合物の連続製造方法および装置ならびにそれらの使用
JP2002154114A (ja) * 2000-09-08 2002-05-28 Asahi Kasei Corp 難燃性ポリカーボネート樹脂組成物の製造方法
JP2006182841A (ja) * 2004-12-27 2006-07-13 Sumitomo Dow Ltd 熱可塑性樹脂組成物およびそれを成形してなる成形品
JP2012518063A (ja) * 2009-02-19 2012-08-09 バイエル・マテリアルサイエンス・アクチェンゲゼルシャフト 揮発性有機化合物の含有量を減らしたポリマー組成物を製造する混練方法

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