WO2023157910A1 - ポリカーボネート系樹脂組成物 - Google Patents

ポリカーボネート系樹脂組成物 Download PDF

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WO2023157910A1
WO2023157910A1 PCT/JP2023/005416 JP2023005416W WO2023157910A1 WO 2023157910 A1 WO2023157910 A1 WO 2023157910A1 JP 2023005416 W JP2023005416 W JP 2023005416W WO 2023157910 A1 WO2023157910 A1 WO 2023157910A1
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polycarbonate
group
carbon atoms
polyorganosiloxane
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English (en)
French (fr)
Japanese (ja)
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優希 小草
康弘 石川
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Idemitsu Kosan Co Ltd
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Idemitsu Kosan Co Ltd
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Priority to US18/837,839 priority Critical patent/US20250145819A1/en
Priority to DE112023001016.1T priority patent/DE112023001016T8/de
Priority to KR1020247027264A priority patent/KR20240144213A/ko
Priority to JP2024501425A priority patent/JPWO2023157910A1/ja
Priority to CN202380021642.7A priority patent/CN118696094A/zh
Publication of WO2023157910A1 publication Critical patent/WO2023157910A1/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/18—Block or graft polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/18—Block or graft polymers
    • C08G64/186—Block or graft polymers containing polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/445—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences
    • C08G77/448—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences containing polycarbonate sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Definitions

  • the present invention relates to a polycarbonate-based resin composition and a molded article thereof.
  • PC-POS copolymers Polycarbonate-polyorganosiloxane copolymers
  • PC-POS copolymers have attracted attention due to their excellent properties such as high impact resistance, chemical resistance, and flame retardancy. ing. Therefore, it is expected to be widely used in various fields such as electric/electronic equipment field and automobile field. In particular, it has been widely used in housings for mobile phones, mobile personal computers, digital cameras, video cameras, power tools, and other daily necessities.
  • a homopolycarbonate using 2,2-bis(4-hydroxyphenyl)propane commonly known as bisphenol A
  • bisphenol A 2,2-bis(4-hydroxyphenyl)propane
  • Patent Document 1 a polycarbonate-polyorganosiloxane copolymer using polyorganosiloxane as a copolymerization monomer is known.
  • Patent Document 2 a method using a polyorganosiloxane having a long chain length is known, as disclosed in Patent Document 2.
  • this method has a problem that the transparency is lowered.
  • Patent Documents 3 and 4 a method using polyorganosiloxane having a relatively short chain length is known (see Patent Documents 3 and 4).
  • Patent Document 5 attempts to improve transparency while maintaining excellent impact resistance by blending two types of polycarbonate-polyorganosiloxane copolymers with different light transmittances. was not sufficient.
  • An object of the present invention is to provide a polycarbonate-based resin composition containing a PC-POS copolymer having a relatively high viscosity-average molecular weight and excellent transparency and impact resistance, and a molded article thereof.
  • the present inventor solved the above problems by using a polycarbonate-based resin composition in which a PC-POS copolymer having a specific viscosity-average molecular weight and an aromatic polycarbonate-based resin other than the PC-POS copolymer having a specific viscosity-average molecular weight are combined. found to be resolved. That is, the present invention relates to the following [1] to [12].
  • Polycarbonate-polyorganosiloxane copolymer (S-1) and a polycarbonate-based resin (S) containing an aromatic polycarbonate-based resin (S-2) other than the polycarbonate-polyorganosiloxane copolymer (S-1) A polycarbonate-based resin composition
  • the polycarbonate resin (S) has a viscosity average molecular weight Mv PC of 20,000 or more and 30,000 or less
  • the content of the polyorganosiloxane block (A-2) in the polycarbonate-polyorganosiloxane copolymer (S-1) is 0.5% by mass or more and 9% by mass or less
  • the average chain length n of the polyorganosiloxane block (A-2) is
  • R 1 and R 2 each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms.
  • X is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a fluorenediyl group, carbon represents an arylalkylene group having 7 to 15 carbon atoms, an arylalkylidene group having 7 to 15 carbon atoms, -S-, -SO-, -SO 2 -, -O- or -CO-.
  • R 3 and R 4 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms.
  • a and b each independently represents an integer of 0 to 4;
  • the difference Mv Si ⁇ Mv PC between the viscosity average molecular weight Mv PC of the polycarbonate resin (S) and the viscosity average molecular weight Mv Si of the polycarbonate-polyorganosiloxane copolymer (S-1) is ⁇ 1,500 or more .
  • the content of the polyorganosiloxane block (A-2) in the polycarbonate-polyorganosiloxane copolymer (S-1) is 0.5% by mass or more and 8% by mass or less, ] to [4], the polycarbonate-based resin composition according to any one of items.
  • the polyorganosiloxane block (A-2) is a block unit represented by any of the following general formulas (II-I), (II-II) and (II-III), ] The polycarbonate resin composition according to any one of [5].
  • R 3 to R 6 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, and a plurality of R 3 to R 6 of may be the same or different.
  • Y is -R 7 O-, -R 7 COO-, -R 7 NH-, -R 7 NR 8 -, -COO-, -S-, -R 7 COO-R 9 -O-, or -R 7 represents OR 10 -O-, and a plurality of Y's may be the same or different.
  • R 7 above represents a single bond, a linear, branched or cyclic alkylene group, an aryl-substituted alkylene group, a substituted or unsubstituted arylene group, or a diarylene group.
  • R8 represents an alkyl group, alkenyl group, aryl group or aralkyl group.
  • R9 represents a diarylene group.
  • R 10 represents a linear, branched or cyclic alkylene group, or a diarylene group.
  • ⁇ represents a divalent group derived from a diisocyanate compound or a divalent group derived from a dicarboxylic acid or a halide of a dicarboxylic acid.
  • n is as described above, and p is an integer of 1 or more and n-2 or less.
  • n is as described above, and p is an integer of 1 or more and n-2 or less.
  • n is as described above, and p is an integer of 1 or more and n-2 or less.
  • n is as described above, and p is an integer of 1 or more and n-2 or less.
  • n is as described above, and p is an integer of 1 or more and n-2 or less.
  • haze value measured in accordance with ISO 14782:1999 is 0.1 or more and 1.0 or less in the molded article having a thickness of 3 mm.
  • the polycarbonate-based resin composition according to any one of the above
  • R 21 to R 24 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms.
  • R 25 is an alkyl group having 1 to 6 carbon atoms, a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 14 carbon atoms.
  • Q 2 is a divalent aliphatic group having 1 to 10 carbon atoms.
  • m represents the average chain length and is an integer of 10 or more.
  • a polycarbonate-based resin composition containing a PC-POS copolymer having a relatively high viscosity-average molecular weight and excellent transparency and impact resistance a polycarbonate-based resin composition containing a PC-POS copolymer having a relatively high viscosity-average molecular weight and excellent transparency and impact resistance, and a molded article thereof.
  • FIG. 1 is a cross-sectional view of a test piece used for evaluating chemical resistance.
  • FIG. 2 is a transverse cross-sectional view of a jig used for chemical resistance evaluation.
  • FIG. 3 is a schematic diagram of a test piece fixed to a jig used for chemical resistance evaluation.
  • the polycarbonate-based resin composition of the present invention comprises a polycarbonate block (A-1) containing a specific repeating unit and a polyorganosiloxane block (A-2) containing a specific repeating unit - a polycarbonate-polyorganosiloxane copolymer ( S-1) and a polycarbonate resin composition containing a polycarbonate resin (S) containing an aromatic polycarbonate resin (S-2) other than the polycarbonate-polyorganosiloxane copolymer (S-1),
  • the polycarbonate-polyorganosiloxane copolymer (S-1) has a viscosity average molecular weight Mv Si of 20,000 or more and 30,000 or less,
  • the content of the polyorganosiloxane block (A-2) in the polycarbonate-polyorganosiloxane copolymer (S-1) is 0.5% by mass or more and 9.0% by mass or less,
  • the polycarbonate-based resin composition of the present invention comprises a polycarbonate-polyorganosiloxane copolymer (S-1) and an aromatic polycarbonate-based resin (S-2) other than the polycarbonate-polyorganosiloxane copolymer (S-1). Contains a polycarbonate resin (S) containing.
  • the polycarbonate-based resin (S) constituting the polycarbonate-based resin composition of the present invention is represented by a polycarbonate block (A-1) containing a repeating unit represented by the following general formula (I) and the following general formula (II).
  • the polycarbonate-polyorganosiloxane copolymer (S-1) has a viscosity average molecular weight Mv Si of 20,000 or more and 30,000 or less
  • the content of the polyorganosiloxane block (A-2) in the polycarbonate-polyorganosiloxane copolymer (S-1) is 0.5% by mass or more and 9.0% by mass or less
  • the average chain length n of the polyorganosiloxane block (A-2) is 20 or more and less than 60
  • R 1 and R 2 each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms.
  • X is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a fluorenediyl group, carbon represents an arylalkylene group having 7 to 15 carbon atoms, an arylalkylidene group having 7 to 15 carbon atoms, -S-, -SO-, -SO 2 -, -O- or -CO-.
  • R 3 and R 4 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms.
  • a and b each independently represents an integer of 0 to 4; ]
  • Polycarbonate-polyorganosiloxane copolymer (S-1) comprises a polycarbonate block (A-1) containing a repeating unit represented by the general formula (I) and a repeating unit represented by the general formula (II). including a polyorganosiloxane block (A-2) containing The content of the polyorganosiloxane block (A-2) in the polycarbonate-polyorganosiloxane copolymer (S-1) is 0.5% by mass or more and 9.0% by mass or less, The average chain length n of the polyorganosiloxane block (A-2) is 20 or more and less than 60.
  • the polycarbonate-polyorganosiloxane copolymer (S-1) may be abbreviated as "PC-POS copolymer (S-1)".
  • halogen atoms independently represented by R 1 and R 2 include fluorine, chlorine, bromine and iodine atoms.
  • the alkyl groups independently represented by R 1 and R 2 include methyl group, ethyl group, n-propyl group, isopropyl group, and various butyl groups ("various" means linear and branched groups). The same applies hereinafter in the specification.), various pentyl groups, and various hexyl groups.
  • alkoxy groups independently represented by R 1 and R 2 include those having the above alkyl group as the alkyl group moiety.
  • Examples of the alkylene group represented by X include methylene group, ethylene group, trimethylene group, tetramethylene group, hexamethylene group and the like, and an alkylene group having 1 to 5 carbon atoms is preferred.
  • Examples of the alkylidene group represented by X include an ethylidene group and an isopropylidene group.
  • the cycloalkylene group represented by X includes a cyclopentanediyl group, a cyclohexanediyl group, a cyclooctanediyl group and the like, and a cycloalkylene group having 5 to 10 carbon atoms is preferable.
  • the cycloalkylidene group represented by X includes, for example, a cyclohexylidene group, a 3,5,5-trimethylcyclohexylidene group, a 2-adamantylidene group and the like, and a cycloalkylidene group having 5 to 10 carbon atoms is preferred. , a cycloalkylidene group having 5 to 8 carbon atoms is more preferable.
  • the aryl moiety of the arylalkylene group represented by X includes aryl groups having 6 to 14 ring-forming carbon atoms such as a phenyl group, naphthyl group, biphenyl group and anthryl group, and the alkylene group includes the above-mentioned alkylene.
  • the aryl moiety of the arylalkylidene group represented by X includes aryl groups having 6 to 14 ring-forming carbon atoms such as a phenyl group, a naphthyl group, a biphenyl group and an anthryl group, and examples of the alkylidene group include the alkylidene groups described above. can be done.
  • a and b each independently represents an integer of 0 to 4, preferably 0 to 2, more preferably 0 or 1; Among them, a and b are 0 and X is a single bond or an alkylene group having 1 to 8 carbon atoms, or a and b are 0 and X is an alkylidene group having 3 carbon atoms, particularly an isopropylidene group. Some are preferred.
  • the polycarbonate block (A-1) preferably consists essentially of repeating units represented by general formula (I) above.
  • the polyorganosiloxane block (A-2) is a structural unit present between the two closest polycarbonate bonds on the main chain of the PC-POS copolymer (S-1), and has the general formula (II ) contains at least one repeating unit.
  • the halogen atom represented by R 3 or R 4 includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the alkyl group represented by R 3 or R 4 includes methyl group, ethyl group, n-propyl group, isopropyl group, various butyl groups, various pentyl groups and various hexyl groups.
  • Examples of the alkoxy group represented by R 3 or R 4 include cases in which the alkyl group portion is the aforementioned alkyl group.
  • Examples of the aryl group represented by R 3 or R 4 include a phenyl group and a naphthyl group. Both R 3 and R 4 are preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, and both are methyl groups. is more preferred.
  • the average chain length n of the polyorganosiloxane block (A-2) contained in the PC-POS copolymer (S-1) is 20 or more and less than 60, preferably 20 or more and 55 or less, more preferably 25 or more and 50. Below, more preferably more than 30 and 43 or less. If the average chain length is within the above range, it is possible to obtain a polycarbonate-based resin composition having more excellent transparency and impact resistance, especially impact resistance at low temperatures.
  • the PC-POS copolymer (S-1) substantially contains block units derived from polyorganosiloxane having an average chain length of 60 or more as the polyorganosiloxane block (A-2).
  • the average chain length of the polyorganosiloxane block (A-2) is the polyorganosiloxane present between the two closest polycarbonate bonds on the main chain of the PC-POS copolymer (S-1). It is the average number of —SiR 3 R 4 — groups contained in the block (A-2). Further, the average repeating number of repeating units represented by the general formula (II) contained in the polyorganosiloxane block (A-2) is n-1.
  • the average chain length n of the polyorganosiloxane block (A-2) contained in the PC-POS copolymer (S-1) is calculated by nuclear magnetic resonance (NMR) measurement.
  • the content of the polyorganosiloxane block (A-2) in the PC-POS copolymer (S-1) (also referred to as polyorganosiloxane content) is 0.5% by mass or more and 9% by mass or less. If the amount of polyorganosiloxane in the PC-POS copolymer (S-1) is within the above range, a polycarbonate resin composition having excellent transparency and impact resistance can be obtained.
  • the content of the polyorganosiloxane block (A-2) in the PC-POS copolymer (S-1) is preferably 0.5% by mass or more and 8% by mass or less, more preferably 0.5% by mass or more and 8 It is less than mass %, more preferably 2 mass % or more and 7.5 mass % or less, still more preferably 4 mass % or more and 7 mass % or less, and particularly preferably 5 mass % or more and 7 mass % or less.
  • the content of the polyorganosiloxane block (A-2) in the PC-POS copolymer (S-1) refers to the polycarbonate block (A-1), the general formula (II) and It is the mass percentage of the general formula (II) with respect to the total mass of the terminal structure derived from the terminal terminator described later, which is optionally included in the PC-POS copolymer (S-1).
  • content of polyorganosiloxane block (A-2) in polycarbonate resin (S) and “content of polyorganosiloxane block (A-2) in polycarbonate resin composition” described later. be.
  • the content of the polyorganosiloxane block (A-2) in the PC-POS copolymer (S-1) is calculated by nuclear magnetic resonance (NMR) measurement. Specifically, 1 H-NMR measurement is performed, and the peak derived from formula (I), the peak derived from formula (II), and the peak derived from the terminal group are calculated from the integrated value.
  • NMR nuclear magnetic resonance
  • a preferred embodiment of the polyorganosiloxane block (A-2) containing a repeating unit represented by the general formula (II) is a block represented by any one of the following general formulas (II-I) to (II-III) Units.
  • R 3 to R 6 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms
  • a plurality of R 3 to R 6 may be the same or different.
  • Y is -R 7 O-, -R 7 COO-, -R 7 NH-, -R 7 NR 8 -, -COO-, -S-, -R 7 COO-R 9 -O-, or -R 7 represents OR 10 -O-, and plural Y's may be the same or different.
  • R7 represents a single bond, a linear, branched or cyclic alkylene group, an aryl-substituted alkylene group, a substituted or unsubstituted arylene group, or a diarylene group.
  • R 8 represents an alkyl group, alkenyl group, aryl group or aralkyl group.
  • R 9 represents a diarylene group.
  • R 10 represents a linear, branched or cyclic alkylene group, or a diarylene group.
  • ⁇ represents a divalent group derived from a diisocyanate compound or a divalent group derived from a dicarboxylic acid or a halide of a dicarboxylic acid.
  • n is as described above.
  • p is an integer of 1 or more and n-2 or less. ]
  • Halogen atoms independently represented by R 3 to R 6 include fluorine, chlorine, bromine and iodine atoms.
  • Examples of the alkyl group independently represented by R 3 to R 6 include methyl group, ethyl group, n-propyl group, isopropyl group, various butyl groups, various pentyl groups and various hexyl groups.
  • Examples of the alkoxy groups independently represented by R 3 to R 6 include cases where the alkyl group portion is the aforementioned alkyl group.
  • Examples of the aryl group independently represented by R 3 to R 6 include a phenyl group and a naphthyl group.
  • Each of R 3 to R 6 is preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms. All of R 3 to R 6 in general formulas (II-I), (II-II) and/or (II-III) are preferably methyl groups.
  • R 7 is bonded to the Si atom.
  • -COO- represented by Y the C atom is bonded to the Si atom.
  • the linear or branched alkylene group represented by R 7 in above includes an alkylene group having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms.
  • Cyclic alkylene groups represented by R 7 include cycloalkylene groups having 5 to 15 carbon atoms, preferably 5 to 10 carbon atoms.
  • the aryl-substituted alkylene group represented by R7 may have a substituent such as an alkoxy group or an alkyl group on the aromatic ring. Specific structures thereof include, for example, the following general formula (i) or ( ii) structure can be shown. Here, when R 7 represents an aryl-substituted alkylene group, the alkylene group is bonded to the Si atom.
  • the arylene group is attached to the oxygen, carbon or nitrogen atom adjacent to R 7 .
  • c represents a positive integer, usually an integer of 1 to 6.
  • the diarylene group represented by R 7 , R 9 and R 10 is a group in which two arylene groups are linked directly or via a divalent organic group, specifically -Ar 1 -W- It is a group having a structure represented by Ar 2 —.
  • Ar 1 and Ar 2 represent arylene groups
  • W represents a single bond or a divalent organic group.
  • the divalent organic group represented by W is, for example, an isopropylidene group, a methylene group, a dimethylene group and a trimethylene group.
  • Arylene groups represented by R 7 , Ar 1 and Ar 2 include arylene groups having 6 to 14 ring carbon atoms such as phenylene group, naphthylene group, biphenylene group and anthrylene group. These arylene groups may have arbitrary substituents such as alkoxy groups and alkyl groups.
  • the alkyl group represented by R 8 has 1 to 8 carbon atoms, preferably 1 to 5, straight or branched chain.
  • Alkenyl groups represented by R 8 include those having 2 to 8 carbon atoms, preferably 2 to 5, straight or branched chains.
  • Examples of the aryl group represented by R 8 include a phenyl group and a naphthyl group.
  • Examples of the aralkyl group represented by R 8 include a phenylmethyl group and a phenylethyl group.
  • the linear, branched or cyclic alkylene group represented by R 10 is the same as R 7 .
  • Y is preferably -R 7 O-, where R 7 is an aryl-substituted alkylene group.
  • R 7 is more preferably a residue of a phenolic compound having an alkyl group, and more preferably an organic residue derived from allylphenol or an organic residue derived from eugenol.
  • ⁇ represents a divalent group derived from a diisocyanate compound or a divalent group derived from a dicarboxylic acid or a halide of a dicarboxylic acid, for example, a divalent group represented by the following general formulas (iii) to (vii) is mentioned.
  • block units represented by the following general formula (II-I) include block units represented by the following general formulas (II-I-1) to (II-I-11).
  • R 3 to R 6 , n-1 and R 8 are the same as above and preferred ones are also the same.
  • c represents a positive integer, usually an integer of 1-6.
  • the block unit represented by the general formula (II-I-1) is preferable from the viewpoint of ease of polymerization of polyorganosiloxane. From the standpoint of easy availability, the block unit represented by the above general formula (II-I-2) and the block unit represented by the above general formula (II-I-3) are preferred.
  • polyorganosiloxane block (A-2) is a block unit represented by the following general formula (II-IV).
  • the PC-POS copolymer (S-1), in one of its preferred embodiments, has the following general formula (IV) as the polyorganosiloxane block (A-2) does not substantially contain the block unit (A-3) represented by
  • R 21 to R 24 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms.
  • R 25 is an alkyl group having 1 to 6 carbon atoms, a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 14 carbon atoms.
  • Q 2 is a divalent aliphatic group having 1 to 10 carbon atoms.
  • m represents the average chain length and is an integer of 10 or more.
  • Halogen atoms independently represented by R 21 to R 24 include fluorine, chlorine, bromine and iodine atoms.
  • alkyl groups independently represented by R 21 to R 24 include methyl group, ethyl group, n-propyl group, isopropyl group, various butyl groups, various pentyl groups and various hexyl groups.
  • alkoxy groups independently represented by R 21 to R 24 include cases where the alkyl group portion is the above alkyl group.
  • Examples of the aryl group independently represented by R 21 to R 24 include a phenyl group and a naphthyl group.
  • Examples of the alkyl group having 1 to 6 carbon atoms represented by R 25 include methyl group, ethyl group, n-propyl group, isopropyl group, various butyl groups, various pentyl groups and various hexyl groups.
  • Halogen atoms represented by R 25 include fluorine, chlorine, bromine and iodine atoms.
  • Examples of the alkoxy group having 1 to 6 carbon atoms represented by R 25 include cases where the alkyl group portion is the aforementioned alkyl group.
  • Examples of the aryl group having 6 to 14 carbon atoms represented by R 25 include a phenyl group, a toluyl group, a dimethylphenyl group and a naphthyl group.
  • the divalent aliphatic group having 1 to 10 carbon atoms represented by Q 2 is preferably a linear or branched divalent saturated aliphatic group having 1 to 10 carbon atoms.
  • the number of carbon atoms in the saturated aliphatic group is preferably 1 or more and 8 or less, more preferably 2 or more and 6 or less, still more preferably 3 or more and 6 or less, and even more preferably 4 or more and 6 or less.
  • m is the average chain length and is an integer of 10 or more.
  • repeating unit (A-3) include structures represented by the following formula (IV-I).
  • the main chain of the PC-POS copolymer (S-1) comprises a polycarbonate block (A-1), a polyorganosiloxane block (A-2) and the necessary It consists only of the terminal structure derived from the terminal terminator described later according to.
  • the viscosity-average molecular weight of the PC-POS copolymer (S-1) is preferably 18,500 or more and 25,000 or less, more preferably 20,000. 25,000 or less, more preferably 20,000 or more and 24,000 or less, particularly preferably 21,000 or more and 23,500 or less. If the viscosity-average molecular weight Mv Si is within the above range, it is possible to obtain a polycarbonate-based resin composition having superior transparency and impact resistance, especially impact resistance at low temperatures.
  • the viscosity-average molecular weight (Mv) of the PC-POS copolymer (S-1) can be appropriately adjusted by using a molecular weight modifier (terminal terminator) or the like so as to achieve the desired molecular weight depending on the application or product used. be able to.
  • the viscosity-average molecular weight (Mv) is a value calculated from the following Schnell formula by measuring the intrinsic viscosity [ ⁇ ] of a methylene chloride solution at 20°C.
  • the PC-POS copolymer (S-1) can be produced by known methods such as an interfacial polymerization method (phosgene method), a pyridine method, and a transesterification method. It can be manufactured by a method.
  • an interfacial polymerization method phosgene method
  • a pyridine method a pyridine method
  • transesterification method a transesterification method. It can be manufactured by a method.
  • the interfacial polymerization method is adopted, the process of separating the organic phase containing the PC-POS copolymer from the aqueous phase containing unreacted substances, catalyst residues, etc. is easy, and alkali washing, acid washing, pure water It is easy to separate the organic phase containing the PC-POS copolymer and the aqueous phase in each washing step such as washing. Therefore, a PC-POS copolymer can be obtained efficiently.
  • a method for producing a PC-POS copolymer for example, the method described in
  • a polycarbonate oligomer is prepared in advance by polymerizing a dihydric phenol compound and a carbonate precursor such as phosgene, and then the polycarbonate oligomer, polyorganosiloxane and, if necessary, a divalent A PC-POS copolymer (S-1) is produced by polymerizing a phenolic compound.
  • a pre-produced polycarbonate oligomer and polyorganosiloxane which will be described later, are dissolved in a water-insoluble organic solvent (methylene chloride, etc.), and an alkaline compound aqueous solution (bisphenol A, etc.) of a dihydric phenol compound (bisphenol A, etc.) sodium hydroxide aqueous solution, etc.), using a tertiary amine (triethylamine, etc.) or a quaternary ammonium salt (trimethylbenzylammonium chloride, etc.) as a polymerization catalyst, and a terminal terminator (monohydric phenol such as p-tert-butylphenol ), it can be produced by an interfacial polycondensation reaction.
  • the PC-POS copolymer (S-1) can also be produced, for example, by copolymerizing polyorganosiloxane, a dihydric phenol-based compound, and phosgene, carbonate
  • raw material polyorganosiloxane those represented by the following general formulas (1), (2) and/or (3) can be used.
  • R 3 to R 6 , Y, ⁇ , n and p are as defined above.
  • Specific examples and preferred ones of R 3 to R 6 , Y, ⁇ , n and p are also as described above.
  • Z represents a hydrogen atom or a halogen atom, and multiple Z's may be the same or different.
  • polyorganosiloxane represented by general formula (1) includes compounds represented by general formulas (1-1) to (1-11) below.
  • R 3 to R 6 , n-1 and R 8 are the same as above, and preferred ones are also the same.
  • c represents a positive integer, usually an integer of 1-6.
  • the phenol-modified polyorganosiloxane represented by the general formula (1-1) is preferable from the viewpoint of ease of polymerization of the polyorganosiloxane.
  • one having the following general formula (4) may be used as the polyorganosiloxane raw material.
  • the method for producing the polyorganosiloxane is not particularly limited.
  • cyclotrisiloxane and disiloxane are reacted in the presence of an acidic catalyst to synthesize ⁇ , ⁇ -dihydrogenorganopentasiloxane, followed by A phenolic compound (eg, 2-allylphenol, 4-allylphenol, eugenol, 2-propenylphenol, etc.) is added to the ⁇ , ⁇ -dihydrogenorganopentasiloxane in the presence of a hydrosilylation reaction catalyst.
  • a crude polyorganosiloxane can be obtained.
  • octamethylcyclotetrasiloxane and tetramethyldisiloxane are reacted in the presence of sulfuric acid (acidic catalyst) to obtain ⁇ , ⁇ -dihydrogenorgano
  • a crude polyorganosiloxane can be obtained by subjecting a polysiloxane to an addition reaction with a phenolic compound or the like in the presence of a hydrosilylation reaction catalyst in the same manner as described above.
  • the ⁇ , ⁇ -dihydrogenorganopolysiloxane may be used by appropriately adjusting its chain length n according to the polymerization conditions, or commercially available ⁇ , ⁇ -dihydrogenorganopolysiloxane may be used. .
  • the one described in JP-A-2016-098292 can be used.
  • a polycarbonate oligomer can be produced by reacting a dihydric phenolic compound with a carbonate precursor such as phosgene or triphosgene in an organic solvent such as methylene chloride, chlorobenzene or chloroform.
  • a polycarbonate oligomer is produced using the transesterification method, it can also be produced by reacting a dihydric phenolic compound with a carbonate precursor such as diphenyl carbonate.
  • a dihydric phenol compound it is preferable to use a dihydric phenol compound represented by the following general formula (viii).
  • R 1 , R 2 , a, b and X are as defined above.
  • Examples of the dihydric phenol compound represented by the general formula (viii) include 2,2-bis(4-hydroxyphenyl)propane [bisphenol A], bis(4-hydroxyphenyl)methane, 1,1- bis(4-hydroxyphenyl)ethane, bis(hydroxyphenyl)alkanes such as 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 4,4′-dihydroxydiphenyl, bis(4-hydroxy phenyl)cycloalkane, bis(4-hydroxyphenyl)oxide, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)ketone, etc.
  • bisphenol A 2,2-bis(4-hydroxyphenyl)propane
  • 1,1- bis(4-hydroxyphenyl)ethane bis(hydroxyphenyl)alkanes such as 2,2-bis(4-hydroxy
  • dihydric phenol compounds may be used singly or in combination of two or more. Among these, bis(hydroxyphenyl)alkane-based dihydric phenols are preferred, and bisphenol A is more preferred.
  • dihydric phenol compounds other than bisphenol A include bis(hydroxyaryl)alkanes, bis(hydroxyaryl)cycloalkanes, dihydroxyaryl ethers, dihydroxydiarylsulfides, dihydroxydiarylsulfoxides, and dihydroxydiarylsulfones. , dihydroxydiphenyls, dihydroxydiarylfluorenes, dihydroxydiaryladamantanes, and the like. These dihydric phenol compounds may be used singly or in combination of two or more.
  • bis(hydroxyaryl)alkanes include bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)butane, 2,2- Bis(4-hydroxyphenyl)octane, bis(4-hydroxyphenyl)phenylmethane, bis(4-hydroxyphenyl)diphenylmethane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, bis(4-hydroxy phenyl)naphthylmethane, 1,1-bis(4-hydroxy-3-tert-butylphenyl)propane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 2,2-bis(4-hydroxy -3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3-chlorophenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane
  • Bis(hydroxyaryl)cycloalkanes include, for example, 1,1-bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl) -3,5,5-trimethylcyclohexane, 2,2-bis(4-hydroxyphenyl)norbornane, 1,1-bis(4-hydroxyphenyl)cyclododecane and the like.
  • dihydroxyaryl ethers include 4,4'-dihydroxydiphenyl ether and 4,4'-dihydroxy-3,3'-dimethylphenyl ether.
  • dihydroxydiarylsulfides include 4,4'-dihydroxydiphenylsulfide and 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfide.
  • dihydroxydiarylsulfoxides include 4,4'-dihydroxydiphenylsulfoxide and 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfoxide.
  • dihydroxydiarylsulfones include 4,4'-dihydroxydiphenylsulfone and 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfone.
  • dihydroxydiphenyls examples include 4,4'-dihydroxydiphenyl.
  • dihydroxydiarylfluorenes include 9,9-bis(4-hydroxyphenyl)fluorene and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene.
  • dihydroxydiaryladamantanes examples include 1,3-bis(4-hydroxyphenyl)adamantane, 2,2-bis(4-hydroxyphenyl)adamantane, 1,3-bis(4-hydroxyphenyl)-5,7- dimethyladamantane and the like.
  • dihydric phenolic compounds other than the above examples include 4,4′-[1,3-phenylenebis(1-methylethylidene)]bisphenol, 10,10-bis(4-hydroxyphenyl)-9-anthrone, 1 ,5-bis(4-hydroxyphenylthio)-2,3-dioxapentane and the like.
  • a terminal terminator (molecular weight modifier) can be used to adjust the molecular weight of the resulting PC-POS copolymer.
  • Examples of terminal terminator include phenol, p-cresol, p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol, p-nonylphenol, m-pentadecylphenol and p-tert-amylphenol. Mention may be made of monohydric phenols. These monohydric phenols may be used singly or in combination of two or more.
  • the aqueous phase and the organic solvent phase are separated by standing appropriately [separation step], and the organic solvent phase is washed (preferably washed with a basic aqueous solution, an acidic aqueous solution, and water in this order) and [washed]. step], concentrating the obtained organic phase [concentrating step], and drying [drying step] to obtain a PC-POS copolymer (S-1).
  • the polycarbonate-based resin (S) further includes an aromatic polycarbonate-based resin (S-2) other than the PC-POS copolymer (S-1).
  • the aromatic polycarbonate resin (S-2) has a repeating unit whose main chain is represented by the following general formula (III).
  • As the polycarbonate-based resin various known polycarbonate-based resins can be used without any particular limitation.
  • the aromatic polycarbonate-based resin may be used alone or in combination of two or more.
  • the aromatic polycarbonate resin (S-2), unlike the PC-POS copolymer (S-1), does not have a polyorganosiloxane block as represented by formula (II).
  • the aromatic polycarbonate-based resin (S-2) is preferably a homopolycarbonate resin, more preferably a homopolycarbonate resin in which the main chain has substantially only repeating units represented by the following general formula (III).
  • R 9 and R 10 each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.
  • X' is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, -S-, -SO -, -SO 2 -, -O- or -CO-.
  • d and e each independently represent an integer of 0 to 4; ]
  • R 9 and R 10 are the same as those of R 1 and R 2 above, and the preferred ones are also the same.
  • R 9 and R 10 are more preferably an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms.
  • Specific examples of X' are the same as those of X above, and the preferred ones are also the same.
  • d and e are each independently preferably 0 to 2, more preferably 0 or 1;
  • the viscosity average molecular weight of the aromatic polycarbonate resin (S-2) is preferably 11,000 or more and 30,000 or less, more preferably 13,500 or more and 26,000. Below, more preferably 16,000 or more and 24,000 or less. If the viscosity-average molecular weight is within the above range, it is possible to obtain a polycarbonate-based resin composition having more excellent transparency and impact resistance, especially impact resistance at low temperatures.
  • the aromatic polycarbonate resin (S-2) is prepared, for example, in the presence of an organic solvent inert to the reaction and an alkaline aqueous solution, with a dihydric phenol compound and phosgene.
  • Interfacial polymerization method in which a polymerization catalyst such as a tertiary amine or a quaternary ammonium salt is added after the reaction; a basic catalyst is added to a dihydric alcohol and a diester carbonate in a molten state without using a solvent.
  • Melt polymerization method in which a dihydric phenolic compound is dissolved in pyridine or a mixed solution of pyridine and an inert solvent, and phosgene is introduced to directly produce a conventional polycarbonate production such as a pyridine method. Obtained by law.
  • a molecular weight modifier terminal terminator
  • branching agent a branching agent and the like are used.
  • the dihydric phenol compound is a compound having two phenolic hydroxyl groups in the molecule, and examples thereof include those represented by the following general formula (III').
  • R 9 , R 10 , X′, d and e are as defined above, and preferred ones are also the same.
  • dihydric phenol compound examples include those mentioned above in the method for producing PC-POS (S-1), and the preferred ones are also the same. Among them, bis(hydroxyphenyl)alkane-based dihydric phenols are preferred, and bisphenol A is more preferred.
  • the viscosity-average molecular weight MvPC of the polycarbonate-based resin (S) is 20,000 or more and 30,000 or less. If the viscosity-average molecular weight Mv PC is within the above range, a polycarbonate-based resin composition having excellent transparency, impact resistance, and chemical resistance can be obtained.
  • the viscosity average molecular weight Mv PC of the polycarbonate resin (S) is preferably 20,000 or more and 27,000 or less, more preferably 20,000 or more and 25,000 or less, still more preferably 20,000 or more and 22,000 or less. It is preferably 21,000 or more and 22,000 or less.
  • the polycarbonate-based resin (S) contains PC-POS (S-1) and an aromatic polycarbonate-based resin (S-2) other than the PC-POS copolymer (S-1), the polycarbonate-based resin (S) and the viscosity-average molecular weight Mv Si of the PC -POS copolymer (S-1) do not necessarily match, and there may be a difference.
  • the difference Mv Si -Mv PC between the viscosity average molecular weight Mv PC of the polycarbonate resin (S) and the viscosity average molecular weight Mv Si of the PC-POS copolymer (S-1) is -3,100 or more and 6,000 or less . be.
  • Mv Si -Mv PC is within the above range, a polycarbonate resin composition having excellent transparency and impact resistance can be obtained.
  • the difference Mv Si -Mv PC between the viscosity average molecular weight Mv PC of the polycarbonate resin (S) and the viscosity average molecular weight Mv Si of the PC -POS copolymer (S-1) is preferably -1,500 or more and 6,000. Below, it is more preferably -500 or more and 6,000 or less, still more preferably -500 or more and 4,000 or less, and particularly preferably -500 or more and 3,000 or less.
  • Mv Si -Mv PC is within the above range, it is possible to obtain a polycarbonate-based resin composition having superior transparency and impact resistance, especially low-temperature impact resistance and chemical resistance.
  • the content of the polyorganosiloxane block (A-2) in the polycarbonate resin (S) is preferably 0.5% by mass or more and less than 8% by mass, more preferably 1% by mass or more and 6% by mass or less, and still more preferably 2.7% by mass or more and 5% by mass or less, particularly preferably 3.1% by mass or more and 5% by mass or less. If the content of the polyorganosiloxane block (A-2) in the polycarbonate-based resin (S) is within the above range, the polycarbonate-based resin having better transparency and impact resistance, especially impact resistance at low temperatures. A composition can be obtained.
  • the content of the polyorganosiloxane block (A-2) in the polycarbonate resin (S) is the same as the content of the polyorganosiloxane block (A-2) in the PC-POS copolymer (S-1). , calculated by nuclear magnetic resonance (NMR) measurements.
  • the content of the polyorganosiloxane block (A-2) in the polycarbonate-based resin (S) and the viscosity-average molecular weight Mv PC of the polycarbonate-based resin (S) are, for example, PC-POS copolymer (S-1) and aromatic It can be prepared according to the content ratio of the group polycarbonate resin (S-2).
  • the content of the PC-POS copolymer (S-1) in the polycarbonate resin (S) is preferably 5% by mass or more and 99% by mass or less, more preferably 15% by mass or more and 90% by mass or less, and still more preferably 30% by mass.
  • the content of the aromatic polycarbonate resin (S-2) in the polycarbonate resin (S) is preferably 1% by mass or more and 95% by mass or less, more preferably 10% by mass or more and 85% by mass or less, still more preferably 20% by mass. % or more and 70 mass % or less, more preferably 30 mass % or more and 60 mass % or less, particularly preferably 30 mass % or more and 50 mass % or less.
  • the polycarbonate-based resin composition of the present invention may further contain other additives as long as the effects of the present invention are not impaired.
  • other components include anti-hydrolysis agents, antioxidants, ultraviolet absorbers, flame retardants, flame retardant aids, reinforcing materials, fillers, elastomers for improving impact resistance, pigments, and dyes.
  • antioxidants include antioxidants.
  • an antioxidant By adding an antioxidant to the polycarbonate-based resin composition, oxidative deterioration of the polycarbonate-based resin composition during melting can be suppressed, and coloration or the like due to oxidative deterioration can be suppressed.
  • the antioxidant a phosphorus-based antioxidant and/or a phenol-based antioxidant or the like is preferably used.
  • Phenolic antioxidants include, for example, n-octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2,6-di-tert-butyl-4-methylphenol, 2 , 2′-methylenebis(4-methyl-6-tert-butylphenol), pentaerythrityl-tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and other hindered phenols mentioned.
  • antioxidants bis(2,6-di-tert-butyl 4-methylphenyl) pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite Those having a pentaerythritol diphosphite structure and triphenylphosphine are preferred.
  • Examples of commercially available phenolic antioxidants include Irganox 1010 (manufactured by BASF Japan Ltd., trade name), Irganox 1076 (manufactured by BASF Japan Ltd., trade name), Irganox 1330 (manufactured by BASF Japan Ltd., trade name), Irganox 3114 (manufactured by BASF Japan Ltd., trade name, BHT (manufactured by Takeda Pharmaceutical Co., Ltd., trade name), CYANOX1790 (manufactured by SOLVAY, trade name) and Sumilizer GA-80 (manufactured by Sumitomo Chemical Co., Ltd., trade name), etc. can be mentioned.
  • Irganox 1010 manufactured by BASF Japan Ltd., trade name
  • Irganox 1076 manufactured by BASF Japan Ltd., trade name
  • Irganox 1330 manufactured by BASF Japan Ltd., trade name
  • Irganox 3114 manufactured by BASF Japan Ltd.,
  • Phosphorus-based antioxidants include, for example, triphenylphosphite, diphenylnonylphosphite, diphenyl(2-ethylhexyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, tris(nonylphenyl) phosphites, diphenylisooctylphosphite, 2,2′-methylenebis(4,6-di-tert-butylphenyl)octylphosphite, diphenylisodecylphosphite, diphenylmono(tridecyl)phosphite, phenyldiisodecylphosphite, Phenyldi(tridecyl)phosphite, Tris(2-ethylhexyl)phosphite, Tris(isodecyl)pho
  • Examples of commercially available phosphorus-based antioxidants include Irgafos 168 (manufactured by BASF Japan Ltd., trade name), Irgafos 12 (manufactured by BASF Japan Ltd., trade name), and Irgafos 38 (manufactured by BASF Japan Ltd., trade name).
  • ADEKA STAB 2112 (manufactured by ADEKA Corporation, trade name), ADEKA STAB C (manufactured by ADEKA Corporation, trade name), ADEKA STAB 329K (manufactured by ADEKA Corporation, trade name), ADEKA STAB PEP36 (manufactured by ADEKA Corporation, trade name), JC -263 (manufactured by Johoku Chemical Co., Ltd., trade name), Sandstab P-EPQ (manufactured by Clariant, trade name), Doverphos S-9228PC (manufactured by Dover Chemical, trade name), and the like.
  • the above antioxidants can be used singly or in combination of two or more.
  • the content of the antioxidant in the polycarbonate-based resin composition of the present invention is preferably 0.001 parts by mass or more and 0.5 parts by mass or less, preferably 0, per 100 parts by mass of the polycarbonate-based resin (S). 0.01 parts by mass or more and 0.3 parts by mass or less, more preferably 0.05 parts by mass or more and 0.3 parts by mass or less. If the content of the antioxidant with respect to 100 parts by mass of the polycarbonate-based resin (S) is within the above range, a sufficient antioxidant action can be obtained and mold contamination during molding can be suppressed.
  • UV absorber Another specific example of other additives is an ultraviolet absorber.
  • Benzotriazole-based compounds, benzoxazine-based compounds, salicylate-based compounds, malonic acid ester-based compounds, oxalylalanide-based compounds, triazine-based compounds, benzophenone-based compounds, cyanoacrylate-based compounds, and the like are suitably used as UV absorbers.
  • benzotriazole compounds include 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-amyl phenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2- [2′-hydroxy-3′,5′-bis( ⁇ , ⁇ -dimethylbenzyl)phenyl]-2H-benzotriazole, 2,2′-methylene-bis[4-methyl-6-(benzotriazole-2- yl)phenol], 2,2′-methylenebis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol) and the like.
  • triazine compounds include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(hexyloxy)phenol, 2-(4,6-bis- 2,4-dimethylphenyl-1,3,5-triazin-2-yl)-5-(hexyloxy)phenol and the like.
  • benzophenone compounds include 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-methoxy-benzophenone, and 2-hydroxy-4-ethoxy-benzophenone.
  • cyanoacrylate compounds include 2-ethyl-2-cyano-3,3-diphenyl acrylate, 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate, 1,3-bis-[2 '-Cyano-3,3'-diphenylacryloyloxy]-2,2-bis-[(2-cyano-3',3'-diphenylacryloyl)oxy]methylpropane and the like.
  • At least one selected from the group consisting of benzotriazole-based compounds, malonic acid ester-based compounds, triazine-based compounds and benzoxazine-based compounds is preferred.
  • examples of commercially available ultraviolet absorbers include SEESORB 709 (manufactured by Shipro Kasei Co., Ltd., trade name), KEMISORB 79 (manufactured by Chemipro Kasei Co., Ltd., trade name), KEMISORB 279 (manufactured by Chemipro Kasei Co., Ltd., trade name), and HOSTAVIN.
  • B-CAP (manufactured by Clariant, trade name), Tinuvin 234 (manufactured by BASF Japan Ltd., trade name), Tinuvin 1577 (manufactured by BASF Japan Ltd., trade name), CYASORB UV-3638 F (manufactured by SOLVAY), etc. be able to.
  • the above ultraviolet absorbers can be used singly or in combination of two or more.
  • the content of the ultraviolet absorber in the polycarbonate-based resin composition of the present invention is preferably 0.01 parts by mass or more and 1 part by mass or less, more preferably 0.01 part by mass or more and 1 part by mass or less, relative to 100 parts by mass of the polycarbonate-based resin (S). 05 mass parts or more and 0.7 mass parts or less. If the content of the ultraviolet absorber is within the above range, sufficient lightfastness can be obtained, and if it is 1 part by mass or less, contamination of molds used during molding can be sufficiently suppressed.
  • the polycarbonate-based resin composition of the present invention can have both excellent transparency and impact resistance.
  • the polycarbonate-based resin composition of the present invention has excellent transparency. Transparency can be evaluated, for example, by haze value.
  • the polycarbonate resin composition of the present invention has a haze value measured in accordance with ISO 14782:1999 (JIS K 7136:2000) in a molded article having a thickness of 3 mm, preferably 0.1 or more and 1.0 or less. It is more preferably 0.2 or more and 0.9 or less, and still more preferably 0.3 or more and 0.6 or less.
  • the polycarbonate-based resin composition of the present invention has excellent impact resistance, especially at low temperatures. Impact resistance can be evaluated, for example, by Charpy impact strength, as shown in Examples described later.
  • the polycarbonate-based resin composition of the present invention has excellent chemical resistance. Chemical resistance can be evaluated, for example, by the method shown in Examples described later.
  • a domain (d) containing the polyorganosiloxane block (A-2) in a matrix mainly composed of the aromatic polycarbonate-based resin (S-2) component exists.
  • the normalized variance of the average domain size of domain (d) is preferably 40% or less, more preferably 20% or less, and even more preferably 18% or less.
  • the average domain size of domain (d) and its normalized dispersion can be evaluated by small angle X-ray scattering (SAXS) according to the description in JP-A-2011-102364.
  • SAXS small angle X-ray scattering
  • a three-stage plate width 50 mm, length 90 mm, thickness from the gate side of 3.0 mm (length 20 mm), 2.0 mm (length 45 mm), 1.0 mm (length 25 mm) and an arithmetic average surface roughness (Ra) of 0.03 ⁇ m
  • Ra arithmetic average surface roughness
  • the content of the polyorganosiloxane block (A-2) in the polycarbonate-based resin composition is preferably 0.5% by mass or more and less than 8% by mass, more preferably 1% by mass or more and 6% by mass or less, and still more preferably 2% by mass. .7% by mass or more and 5% by mass or less, particularly preferably 3.1% by mass or more and 5% by mass or less. If the content of the polyorganosiloxane block (A-2) in the polycarbonate-based resin composition is within the above range, it is possible to obtain a polycarbonate-based resin composition having superior transparency and low-temperature impact resistance. can.
  • the content of the polyorganosiloxane block (A-2) in the polycarbonate resin (S) is the same as the content of the polyorganosiloxane block (A-2) in the PC-POS copolymer (S-1). , calculated by nuclear magnetic resonance (NMR) measurements.
  • melt-kneaded polycarbonate resin composition of the present invention or the obtained pellets as raw materials
  • Various moldings can be produced by a foam molding method or the like.
  • pellets obtained by melt-kneading can be suitably used for production of injection-molded articles by injection molding and injection compression molding.
  • Molded articles made of the polycarbonate resin composition of the present invention can be used, for example, in televisions, radios, cameras, video cameras, audio players, DVD players, air conditioners, mobile phones, smartphones, transceivers, displays, computers, tablet terminals, mobile phones, etc.
  • Game machines stationary game machines, wearable electronic devices, cash registers, calculators, copiers, printers, facsimiles, communication base stations, batteries, exterior and internal parts of parts for electric and electronic equipment such as robots, automobiles, railways, It can be suitably used as exterior and internal parts of ships, aircraft, space industry equipment, medical equipment, and parts of building materials.
  • Probe 50TH5AT/FG2 Measurement nucleus: 1H Observation range: -5 to 15 ppm Observation center: 5 ppm Pulse repetition time: 9 seconds Pulse width: 45° NMR sample tube: 5 ⁇ Sample amount: 30-40mg Solvent: deuterated chloroform Measurement temperature: room temperature Accumulation times: 256 For allylphenol-terminated polydimethylsiloxane A: Integrated value of methyl group in dimethylsiloxane moiety observed around ⁇ -0.02 to 0.5 B: ⁇ 2.
  • Viscosity average molecular weight The viscosity average molecular weight (Mv) is obtained by measuring the viscosity of a methylene chloride solution at 20 ° C. using an Ubbelohde viscometer, and obtaining the intrinsic viscosity [ ⁇ ] from this, using the following formula (Schnell formula) Calculated by
  • Step 1 Production of polycarbonate-polyorganosiloxane copolymer (S-1-1) (PC-PDMS (S-1-1))>
  • Step 1 Production of polycarbonate oligomer
  • Sodium dithionite was added to a 5.6% by weight aqueous sodium hydroxide solution so that the amount of sodium dithionite was 2000 ppm with respect to bisphenol A (BPA) to be dissolved later.
  • BPA bisphenol A
  • BPA bisphenol A
  • the reaction was carried out by adding 0.07 L/hr of a sodium hydroxide aqueous solution of 0.07 L/hr by mass, 17 L/hr of water, and 0.64 L/hr of a 1 mass % triethylamine aqueous solution.
  • the reaction liquid overflowing from the tank-type reactor was continuously withdrawn and allowed to stand to separate and remove the aqueous phase, and the methylene chloride phase was collected.
  • the polycarbonate oligomer thus obtained had a concentration of 341 g/L and a chloroformate group concentration of 0.71 mol/L.
  • Step 2 Production of PC-PDMS
  • PCO polycarbonate oligomer solution
  • MC methylene chloride
  • PDMS o-allylphenol-terminated polydimethylsiloxane having an average polydimethylsiloxane chain length n of 37 (iii) dissolved in 2 L (v) of methylene chloride
  • TAA triethylamine
  • PTBP p-tert-butylphenol
  • bisphenol A sodium hydroxide aqueous solution sodium hydroxide 562 g (xi) and 1.7 g (xii) of sodium dithionite (Na 2 S 2 O 4 ) dissolved in 8.2 L (xiii) of pure water, and 826 g (xiv) of bisphenol A dissolved therein.
  • PC-PDMS polycarbonate-polydimethylsiloxane copolymer
  • aqueous phase containing excess bisphenol A and sodium hydroxide.
  • the organic phase was isolated.
  • the methylene chloride solution of PC-PDMS thus obtained is washed with 15% by volume of 0.03 mol/L sodium hydroxide aqueous solution and 0.2 mol/L hydrochloric acid in sequence, and then the aqueous phase after washing Washing with pure water was repeated until the electric conductivity inside became 5 ⁇ S/cm or less.
  • PC-PDMS PC-PDMS (S-1-1).
  • the content of the polyorganosiloxane block (A-2) obtained by NMR of the obtained PC-PDMS (S-1-1) was 6.0% by mass, and the average chain length of the polyorganosiloxane block (A-2) was 37 and the viscosity average molecular weight Mv was 17,700.
  • PC-PDMS (S-1-2) to (S-1-9) Production of PC-PDMS (S-1-2) to (S-1-9))> PC-PDMS (S-1-2) to (S-1-9) were prepared in the same manner as in Production Example 1 except that the values (i) to (xv) shown in Table 1 were changed as shown in the table. ) was manufactured.
  • Table 1 shows the content of the polyorganosiloxane block (A-2), the average chain length of the polyorganosiloxane block (A-2), and the viscosity-average molecular weight Mv of each PC-PDMS.
  • Antioxidant IRGAFOS 168 (trade name) [tris (2,4-di-tert-butylphenyl) phosphite, manufactured by BASF Japan Ltd.]
  • UV absorber CYASORB UV-3638 F (trade name) [2,2′-(p-phenylene)di-3,1-benzoxazin-4-one, manufactured by SOLVAY]
  • UV absorber KEMISORB 79 (trade name) [2-benzotriazolyl-4-tert-octylphenol, manufactured by Chemipro Kasei Co., Ltd.]
  • FIG. prepared Three cylindrical shafts made of SUS304, each having a diameter of 10 mm and a length of 70 mm, were fixed in parallel with each other so that both ends in the longitudinal direction were aligned and the cross section in the short direction was shown in FIG. prepared. Specifically, one cylindrical shaft is used as the central shaft 22 and the other two shafts are both end shafts 23, and the plane including both the center axes 21 of the two end shafts 23 and the center axis 21 of the center shaft 22 The vertical distance was 11.3 mm, and the distance L between the central axes 21 of the shafts 23 at both ends was 60 mm. Each test piece was fixed to the jig as shown in FIG.
  • each test piece 31 is in contact with the central shaft 32
  • the top surface is in contact with both end shafts 33
  • the longitudinal direction of the test piece 31 is perpendicular to the longitudinal direction of each shaft. fixed to the tool.
  • the vertical distance G between the tangent plane 36 on the central shaft 32 containing the points of contact between the central shaft 32 and the specimen 31 and the tangent plane 35 on the double shaft 33 containing the points of contact between the shaft 33 and the specimen 31 is 1. 3 mm
  • the distance L between the shafts 33 on both ends was 60 mm.
  • a sunscreen agent "NIVEA (trademark) SUN Protect and Moisture Lotion SPF30” (manufactured by Beiersdorf) was applied in a width of 1 cm on each side in the longitudinal direction from the center of the upper surface of the test piece. After 72 hours at 23°C, the presence or absence of cracks was visually confirmed, and the change in appearance was evaluated. The thickness t m of the test piece was obtained. Table 3 shows the results.
  • Examples 13-14 A pellet sample for evaluation was obtained in the same manner as in Example 1, except that each component was mixed in the proportion shown in Table 4. Using this pellet sample for evaluation, in the same manner as in Example 1, the PDMS content and Mv of the polycarbonate-based resin composition were measured, and the transparency, impact resistance and chemical resistance were evaluated. Also in Examples 13 and 14, excellent transparency, impact resistance and chemical resistance were exhibited. In addition, in Examples 13 and 14 containing an ultraviolet absorber, it is expected that light fastness is exhibited.
  • central shaft 21 central axis of shaft 22 central shaft 23 double-ended shaft 31 test piece 32 central shaft 33 double-ended shaft 34 test piece center 35 tangential plane 36 on double-ended shaft containing contact points of both shafts and test piece contact points of central shaft and test piece tangent plane on the central shaft containing

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Silicon Polymers (AREA)
PCT/JP2023/005416 2022-02-17 2023-02-16 ポリカーボネート系樹脂組成物 Ceased WO2023157910A1 (ja)

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KR1020247027264A KR20240144213A (ko) 2022-02-17 2023-02-16 폴리카보네이트계 수지 조성물
JP2024501425A JPWO2023157910A1 (https=) 2022-02-17 2023-02-16
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