JP2019038895A - Resin composition and molded article - Google Patents

Abstract

To provide a resin composition capable of giving a molded article excellent in flame retardancy and excellent in impact resistance.SOLUTION: The resin composition according to the present invention contains a polycarbonate resin having a branched structure, and an inorganic filler. The volume average particle diameter of the inorganic filler is 6 μm or less. The content of the inorganic filler is 10 pts.wt. or more and 45 pts.wt. or less based on 100 pts.wt. of the polycarbonate resin having a branched structure.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a resin composition containing a polycarbonate resin. The present invention also relates to a molded body containing a polycarbonate resin.

  Thermoplastic resins such as polycarbonate resins are excellent in durability, light weight, moldability, and the like. For this reason, the thermoplastic resin is used in various fields such as the construction field, the home appliance field, and the transportation field.

  One of the uses of the thermoplastic resin is an interior material of a transport device such as a railway vehicle, an aircraft, a ship, and an automobile. However, since thermoplastic resins are generally flammable and vulnerable to impact, studies for improving the flame retardancy and impact resistance of thermoplastic resins have been widely conducted.

  For example, Patent Document 1 below discloses a composition containing an aromatic polycarbonate or aromatic polyester carbonate, a silicone / acrylate composite rubber, talc, and a flameproofing agent. In the example of Patent Document 1, an aromatic polycarbonate having no branched structure is used.

WO2010 / 07723A1

  In the molded product obtained from the composition described in Patent Document 1, the impact resistance can be improved to some extent. However, the molded product obtained from the composition described in Patent Document 1 may have insufficient flame retardancy.

  The objective of this invention is providing the resin composition which can obtain the molded object which is excellent in a flame retardance and excellent in impact resistance. Another object of the present invention is to provide a molded body using the above resin composition.

  According to a wide aspect of the present invention, a polycarbonate resin having a branched structure and an inorganic filler, the volume average particle diameter of the inorganic filler being 6 μm or less, and 100 parts by weight of the polycarbonate resin having the branched structure A resin composition in which the content of the inorganic filler is 10 parts by weight or more and 45 parts by weight or less is provided.

  On the specific situation with the resin composition which concerns on this invention, content of the said inorganic filler is 35 weight part or less with respect to 100 weight part of polycarbonate resin which has the said branched structure.

  On the specific situation with the resin composition which concerns on this invention, the said resin composition contains a phosphorus containing compound.

  In a specific aspect of the resin composition according to the present invention, the resin composition includes core-shell particles, and in the core-shell particles, an organic compound constituting the core and an organic compound constituting the shell are chemically bonded. ing.

  In a specific aspect of the resin composition according to the present invention, the resin composition includes core-shell particles, and in the core-shell particles, an organic compound constituting the core and an organic compound constituting the shell are chemically bonded. The weight ratio of the content of the core-shell particles to the content of the phosphorus-containing compound is 0.4 or more and 2.5 or less.

  According to a wide aspect of the present invention, a molded body in which the above-described resin composition is molded is provided.

In a specific aspect of the molded article according to the present invention, the Izod impact value measured in accordance with JIS K7110: 1999 is 200 J / m or more, and from the heat generation rate measured in accordance with ISO5660-1: 2002. The maximum average heat generation rate required in accordance with the European railway standard EN455545-2 is 120 kW / m ² or less.

  The resin composition according to the present invention comprises a polycarbonate resin having a branched structure and an inorganic filler, wherein the inorganic filler has a volume average particle diameter of 6 μm or less, and 100 parts by weight of the polycarbonate resin having the branched structure. The content of the inorganic filler is 10 parts by weight or more and 45 parts by weight or less. Since the resin composition according to the present invention has the above-described configuration, a molded body having excellent flame retardancy and excellent impact resistance can be obtained.

FIG. 1 is a diagram showing the relationship between the volume average particle diameter (D50) of talc (inorganic filler), the Izod impact value of a molded article, and the maximum average heat generation rate. FIG. 2 is a diagram showing the relationship between the content of talc (inorganic filler) having a volume average particle diameter (D50) of 3.9 μm, the Izod impact value of the molded product, and the maximum average heat generation rate. FIG. 3 is a diagram showing the relationship between the content of talc (inorganic filler) having a volume average particle diameter (D50) of 2.5 μm, the Izod impact value of the molded product, and the maximum average heat generation rate.

  Hereinafter, the present invention will be described in detail.

  The resin composition according to the present invention includes a polycarbonate resin having a branched structure and an inorganic filler. In the resin composition according to the present invention, the inorganic filler has a volume average particle diameter (D50) of 6 μm or less. In the resin composition which concerns on this invention, content of the said inorganic filler is 10 to 45 weight part with respect to 100 weight part of polycarbonate resin which has the said branched structure.

  Since the resin composition according to the present invention has the above-described configuration, a molded body having excellent flame retardancy and excellent impact resistance can be obtained.

  In the present invention, since the inorganic filler of a specific size is used, the center-of-gravity distance between adjacent inorganic fillers is smaller than when using an inorganic filler having a large volume average particle diameter (D50), and the inorganic filler particles A molded product having a large number can be obtained. A molded body having a small center-of-gravity distance between adjacent inorganic fillers and a large number of inorganic filler particles is excellent in flame retardancy and gas barrier properties. If the center-of-gravity distance between adjacent inorganic fillers is small and the number of inorganic filler particles is large, the amount of oxygen flowing into the gaps between the inorganic fillers can be suppressed even if the molded product burns, and the combustible that occurs during combustion The release of sex gases can be suppressed.

  In addition, a molded article having a small center-of-gravity distance between adjacent inorganic fillers and a large number of inorganic filler particles tends to have excellent impact resistance.

  Hereinafter, details of components contained in the resin composition according to the present invention will be described.

[Polycarbonate resin having a branched structure]
The polycarbonate resin used in the present invention is a polycarbonate resin having a branched structure from the viewpoint of improving moldability, heat resistance, flame retardancy, impact resistance, and the like.

  As for the polycarbonate resin which has a branched structure contained in the said resin composition, only 1 type may be used and 2 or more types may be used together.

  The polycarbonate resin having the branched structure can be produced by a conventionally known method. Examples of the method for producing the polycarbonate resin having the branched structure include (1) phase interface method and (2) melt polymerization method.

  (1) As a method of producing the polycarbonate resin having the branched structure by the phase interface method, a diphenol compound, a halogenated carbonate compound or an aromatic dicarboxylic acid dihalide, a branching agent, and a chain termination as required The method of making it react with an agent is mentioned. In this method, a carbonic acid halogen compound may be used, an aromatic dicarboxylic acid dihalide may be used, or a carbonic acid halogen compound and an aromatic dicarboxylic acid dihalide may be used.

  (2) As a method of producing the polycarbonate resin having the branched structure by the melt polymerization method, there is a method of reacting a diphenol compound, a diphenyl carbonate compound, a branching agent, and a chain terminator as necessary. It is done.

  The diphenol compound used in the phase interface method or the melt polymerization method is not particularly limited. A conventionally well-known diphenol compound can be used as said diphenol compound. As for the said diphenol compound, only 1 type may be used and 2 or more types may be used together.

From the viewpoint of obtaining good polycarbonate resin having a branched structure, the diphenol compounds, dihydroxy diphenol, bis - (hydroxyphenyl) -C 1 _-C 5 _- alkanes, bis - (hydroxyphenyl) -C ₅ ~ C ₆ -cycloalkane, bis- (hydroxyphenyl) ether, bis- (hydroxyphenyl) sulfoxide, bis- (hydroxyphenyl) ketone, bis- (hydroxyphenyl) -sulfone, and α, α-bis- (hydroxyphenyl) -Diisopropyl-benzene is preferred. In these diphenol compounds, the aromatic ring may be brominated, the aromatic ring may be chlorinated, or the aromatic ring may be brominated and chlorinated.

  From the viewpoint of obtaining a polycarbonate resin having a branched structure even better, the diphenol compound is 4,4′-dihydroxydiphenyl, 2,4-bis- (4-hydroxyphenyl) -2-methylbutane, 1, 1-bis- (4-hydroxyphenyl) -cyclohexane, 1,1-bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxy More preferred is diphenylsulfone. From the viewpoint of obtaining a polycarbonate resin having the above branched structure even better, the diphenol compound is more preferably 2,2-bis- (4-hydroxyphenyl) -propane (bisphenol A). These diphenol compounds may have 2 to 4 bromine atoms or 2 to 4 chlorine atoms.

  Examples of the diphenol compound having 2 to 4 bromine atoms or the diphenol compound having 2 to 4 chlorine atoms include 2,2-bis- (3-chloro-4-hydroxyphenyl) -propane, Examples include 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) -propane and 2,2-bis- (3,5-dibromo-4-hydroxyphenyl) -propane.

  The halogenated carbonate compound is not particularly limited. A conventionally known halogen carbonate compound can be used as the halogen carbonate compound. As for the said halogenated carbonate compound, only 1 type may be used and 2 or more types may be used together.

  The aromatic dicarboxylic acid dihalide is not particularly limited. As the aromatic dicarboxylic acid dihalide, a conventionally known aromatic dicarboxylic acid dihalide can be used. Only 1 type may be used for the said aromatic dicarboxylic acid dihalide, and 2 or more types may be used together.

  From the viewpoint of obtaining a polycarbonate resin having the above branched structure, the aromatic dicarboxylic acid dihalide is preferably benzene dicarboxylic acid dihalide.

  The diphenyl carbonate compound is not particularly limited. A conventionally well-known diphenyl carbonate compound can be used as said diphenyl carbonate compound. As for the said diphenyl carbonate compound, only 1 type may be used and 2 or more types may be used together.

  From the viewpoint of obtaining a polycarbonate resin having a branched structure, the diphenyl carbonate compound is preferably a dialkyl carbonate such as diaryl carbonate, dimethyl carbonate, and dimethyl carbonate.

  The branching agent is preferably an aromatic compound having a branched structure. By using the aromatic compound having the branched structure as the branching agent, it is considered that steric hindrance caused by the skeleton structure of the aromatic compound having the branched structure is generated, and the impact resistance of the molded article is improved.

  The branching agent is not particularly limited. A conventionally known branching agent can be used as the branching agent. As for the said branching agent, only 1 type may be used and 2 or more types may be used together.

  From the viewpoint of favorably obtaining the polycarbonate resin having the branched structure, the branching agent is preferably a trifunctional phenol compound, a tetrafunctional phenol compound, or the like. The trifunctional phenol compound, the tetrafunctional phenol compound, and the like may have an amine group.

  From the viewpoint of obtaining the polycarbonate resin having the branched structure even better, the branching agent is more preferably a triphenol compound, a tetraphenol compound, or the like, and a phenol having at least three functional groups with low reactivity. More preferably, it is a compound. Examples of the phenol compound include 1,1,1-tris- (p-hydroxyphenyl) ethane, α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, and Examples include 1- [α-methyl-α- (4′-hydroxyphenyl) ethyl] -4- [α ′, α′-bis (4 ″ -hydroxylphenyl) ethyl] benzene.

  The chain terminator is a compound that stops the terminal reactivity of the polymer compound, particularly the polycondensation reaction, by reacting with the terminal functional group of the polymer compound.

  The chain terminator is not particularly limited. A conventionally known chain terminator can be used as the chain terminator. As for the said chain terminator, only 1 type may be used and 2 or more types may be used together.

  From the viewpoint of favorably obtaining the polycarbonate resin having the branched structure, the chain terminator is phenol; p-chlorophenol; p-tert-butylphenol; 2,4,6-tribromophenol; 4- (1,3 -Tetramethylbutyl) -phenol; long chain alkylphenols such as monoalkylphenols having 8-20 carbon atoms in the alkyl substituent; and 3,5-di-tert-butylphenol, p-isooctylphenol, p-tert- Dialkylphenols such as octylphenol, p-dodecylphenol and 2- (3,5-dimethylheptyl) -phenol, 4- (3,5-dimethylheptyl) -phenol are preferred.

[Inorganic filler]
The inorganic filler is an inorganic compound contained in the resin composition. The inorganic filler has a specific size. As for the said inorganic filler, only 1 type may be used and 2 or more types may be used together.

  Examples of the inorganic filler include oxide compounds such as silica, alumina and titanium oxide; hydroxide compounds such as calcium hydroxide and magnesium hydroxide; carbonate compounds such as calcium carbonate and magnesium carbonate; calcium silicate, talc, clay and mica. Silicate compounds such as montmorillonite; nitrogen compounds; iron powder; carbon black; graphite; and glass fibers.

  The talc may be compressed talc. When the talc is compressed talc, the resin composition can be easily processed.

  The talc may be talc containing alumina, talc containing magnesium oxide, or talc containing alumina and magnesium oxide.

  From the viewpoint of obtaining a molded article that is more excellent in flame retardancy and more excellent in impact resistance, the inorganic filler is preferably talc containing alumina, talc containing magnesium oxide, or talc containing alumina and magnesium oxide. .

  The inorganic filler may be subjected to a surface treatment such as silanization. When the inorganic filler is a surface-treated inorganic filler such as silanized, the compatibility with the polycarbonate resin having the branched structure is further improved.

  From the viewpoint of obtaining a molded article that is more excellent in flame retardancy and more excellent in impact resistance, the volume average particle diameter (D50) of the inorganic filler is 6 μm or less, preferably 1 μm or more, preferably 4 μm or less. . When the volume average particle diameter (D50) of the inorganic filler is not more than the above upper limit, a molded article having a small center of gravity distance between adjacent inorganic fillers and a large number of inorganic filler particles can be obtained. A molded article having a small center-of-gravity distance between adjacent inorganic fillers and a large number of inorganic filler particles is more excellent in flame retardancy and gas barrier properties. If the center-of-gravity distance between adjacent inorganic fillers is small and the number of inorganic filler particles is large, the amount of oxygen flowing into the gaps between the inorganic fillers can be suppressed even if the molded product burns, and the combustible that occurs during combustion The release of sex gases can be suppressed. In addition, a molded article having a small center-of-gravity distance between adjacent inorganic fillers and a large number of inorganic filler particles tends to have excellent impact resistance.

  The volume average particle diameter of the inorganic filler is an average diameter measured on a volume basis, and is a median diameter (D50) value of 50%. The volume average particle diameter (D50) can be measured by a laser diffraction / scattering method, an image analysis method, a Coulter method, a centrifugal sedimentation method, or the like. The volume average particle diameter (D50) of the inorganic filler is preferably obtained by measurement by a laser diffraction / scattering method.

  From the viewpoint of obtaining a molded article that is more excellent in flame retardancy and more excellent in impact resistance, the content of the inorganic filler is 10 parts by weight or more, preferably 100 parts by weight or more, preferably 100 parts by weight of the polycarbonate resin having the branched structure. 15 parts by weight or more and 45 parts by weight or less, preferably 35 parts by weight or less. When the content of the inorganic filler is not less than the above lower limit, a molded article having excellent gas barrier properties can be obtained favorably. When the content of the inorganic filler is not more than the above upper limit, the inorganic filler is well dispersed, and a molded article excellent in gas barrier properties can be obtained.

[Phosphorus-containing compound]
The resin composition preferably contains a phosphorus-containing compound. The phosphorus-containing compound is used as a flame retardant.

  A flame retardant, when added to the resin composition, can impart flame retardancy to the molded body obtained from the resin composition, and prevents the fire from spreading even if the molded body ignites. It is a substance.

  As for the said phosphorus containing compound, only 1 type may be used and 2 or more types may be used together.

  The phosphorus-containing compound may be a phosphorus-containing compound having no halogen atom or a mixture of a phosphorus-containing compound having no halogen atom and a phosphorus-containing compound having a halogen atom.

  The phosphorus-containing compound may be a compound containing a phosphorus atom, and may be a compound derived from resorcinol, hydroquinone, bisphenol A, diphenylphenol, or the like. The phosphorus-containing compound is preferably a compound derived from bisphenol A.

  The phosphorus-containing compound may contain a phosphate ester. Examples of the phosphate ester include tributyl phosphate, triphenyl phosphate, tricresyl phosphate, diphenyl cresyl phosphate, diphenyl octyl phosphate, diphenyl-2-ethyl cresyl phosphate, tri- (isopropylphenyl) phosphate, resorcinol cross-linked diphosphate, And bisphenol A cross-linked diphosphate. The phosphate ester is preferably an oligomeric phosphate ester derived from bisphenol A.

  The content of the phosphorus-containing compound is preferably 1 part by weight or more, more preferably 2 parts by weight or more, still more preferably 3 parts by weight or more, preferably 50 parts by weight with respect to 100 parts by weight of the polycarbonate resin having the branched structure. Part or less, more preferably 45 parts by weight or less, still more preferably 40 parts by weight or less. When the content of the phosphorus-containing compound is not less than the above lower limit and not more than the above upper limit, good flame retardancy can be imparted to the molded body.

[Core shell particles]
From the viewpoint of obtaining a molded body that is more excellent in flame retardancy, the resin composition preferably includes core-shell particles. The core shell particles are used as an impact resistance agent.

  An impact-resistant agent is a substance that imparts impact properties to a molded body obtained from the resin composition. The impact resistance agent generally has rubber elasticity.

  The core-shell particle is a particle including a core and a shell disposed on the surface of the core. From the viewpoint of obtaining a molded article that is more excellent in flame retardancy, in the core-shell particles, it is preferable that the organic compound constituting the core and the organic compound constituting the shell are chemically bonded. The chemical bond is preferably a graft bond. As for the said core-shell particle, only 1 type may be used and 2 or more types may be used together.

  Examples of the core-shell particles include diene-based core-shell type rubbery polymers such as methyl methacrylate-butadiene-styrene copolymer resin (MBS resin) and acrylonitrile-butadiene-styrene copolymer resin (ABS resin); acrylate-styrene-acrylonitrile. Acrylic core-shell type rubbery polymer such as copolymer resin (ASA resin) and acrylate-methyl methacrylate copolymer resin; silicone-acrylate-methyl methacrylate copolymer resin, silicone-acrylate-acrylonitrile-styrene copolymer resin And silicone-based core-shell type rubbery polymers such as those modified with maleic anhydride and glycidyl methacrylate. As the core-shell particles, a silicone-based core-shell type rubbery polymer is preferable.

  From the viewpoint of improving the appearance of the molded body and obtaining a molded body having excellent impact resistance, the volume average particle diameter (D50) of the core-shell particles is preferably 100 nm or more, more preferably 250 nm or more, preferably 800 nm. It is as follows. Core-shell particles having a volume average particle diameter (D50) that is not less than the above lower limit and not more than the above upper limit can be produced by an emulsion polymerization method.

  The volume average particle diameter of the core-shell particles is an average diameter measured on a volume basis, and is a median diameter (D50) value of 50%. The volume average particle diameter (D50) can be measured by a laser diffraction / scattering method, an image analysis method, a Coulter method, a centrifugal sedimentation method, or the like. The volume average particle diameter (D50) of the core-shell particles is preferably obtained by measurement by a laser diffraction / scattering method.

  A commercial item can also be used for the said core-shell particle. Commercially available products of the core-shell particles include methabrene S-2001, S-2006, S-2501, S-2030, S-2100, S-2200, SRK200A, SX-005, SX-006, W-300A, W- 450A, W-600A, W-337, E-860A, E-870A, E-875A, C-223A, C-215A, C-201A, C-140A, etc. (all are manufactured by Mitsubishi Rayon Co., Ltd.) Can be mentioned.

  In general, natural rubber, fluorine elastomer, ethylene-propylene rubber (EPR), ethylene-butene rubber, ethylene-propylene-diene monomer rubber (EPDM), acrylate as other optional impact agents other than the core-shell particles are used. Graft copolymer modified with elastomer such as rubber, hydrogenated nitrile rubber (HNBR), silicone elastomer, silicone oil, styrene-butadiene-styrene (SBS); styrene-butadiene rubber (SBR); styrene-ethylene-butadiene-styrene ( SEBS); acrylonitrile-butadiene-styrene (ABS); styrene-acrylonitrile (SAN), acrylonitrile-ethylene-propylene-diene-styrene (AES), styrene-isoprene-styrene (S) S), methyl methacrylate - butadiene - styrene (MBS), and high rubber graft (HRG) ABS and the like are known.

  The other optional impact resistance agents may be used in combination with the core-shell particles from the viewpoint of imparting impact resistance, low smoke density, low smoke toxicity, and good mechanical properties to the molded article. it can.

  The content of the core-shell particles is preferably 1 part by weight or more, more preferably 3 parts by weight or more, more preferably 5 parts by weight or more, preferably 50 parts by weight with respect to 100 parts by weight of the polycarbonate resin having the branched structure. Hereinafter, it is more preferably 45 parts by weight or less, and still more preferably 40 parts by weight or less. When the content of the core-shell particles is not less than the above lower limit and not more than the above upper limit, the impact resistance of the molded body is improved, and good mechanical properties can be imparted to the obtained molded body.

  The weight ratio of the core-shell particle content to the phosphorus-containing compound content (core-shell particle content / phosphorus-containing compound content) is preferably 0.4 or more, more preferably 0.6 or more, preferably 2.5 or less, more preferably 1.5 or less. When the weight ratio of the core-shell particle content to the phosphorus-containing compound content (core-shell particle content / phosphorus-containing compound content) is not less than the above lower limit and not more than the above upper limit, the flame retardancy is further improved. In addition, a molded body that is more excellent in impact resistance can be obtained.

[Other ingredients]
The resin composition includes a fluorinated polymer, an antioxidant, a thermal stabilizer, an ultraviolet light (UV) stabilizer, a plasticizer, a lubricant, and a release agent as long as the object of the present invention is not impaired. Etc. may be included.

  Examples of the fluorinated polymer include a homopolymer having a fluorinated alpha-olefin monomer as a structural unit, and a copolymer containing a fluorinated alpha-olefin monomer as a structural unit. As for the said fluorinated polymer, only 1 type may be used and 2 or more types may be used together.

  The fluorinated alpha-olefin monomer is an alpha-olefin monomer containing a substituent having at least one fluorine atom.

Examples of the fluorinated alpha-olefin monomer include tetrafluoroethylene (CF ₂ = CF ₂ ), CHF = CF ₂ , vinylidene fluoride (CH ₂ = CF ₂ ), CH ₂ = CHF, and chlorotrifluoroethylene (CCIF = CF ₂ ), CCl ₂ = CF ₂ , CClF = CClF, CHF = CCl ₂ , CH ₂ = CClF, CCl ₂ = CClF, hexafluoropropylene (CF ₂ = CFCF ₃ ), CF ₃ CF = CHF, CF ₃ CH = CF ₂ , CF ₃ CH═CH ₂ , CF ₃ CF═CHF, CHF ₂ CH═CHF, CF ₃ CH═CH _{2 and the} like.

  Examples of the fluorinated polymer include poly (tetrafluoroethylene) homopolymer (PTFE), poly (hexafluoroethylene), poly (tetrafluoroethylene-hexafluoroethylene), and poly (tetrafluoroethylene-ethylene-propylene). Can be mentioned. The poly (tetrafluoroethylene) homopolymer (PTFE) may be fiber-forming or non-fiber-forming.

  By containing the fluorinated polymer in the resin composition, it is possible to prevent the resin composition or a fragment of the molded body from melting and dropping when the molded body is produced, when the molded body is ignited, and when the molded body is burned. The flame retardancy of the molded body can be improved.

  The above-mentioned antioxidant is a substance that prevents deterioration and deterioration such as a decrease in strength and cracks caused by the molded body being oxidized by heat in the air or during processing. As for the said antioxidant, only 1 type may be used and 2 or more types may be used together.

  Examples of the antioxidant include tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, Organophosphites such as distearyl pentaerythritol diphosphite; alkylated monophenols; alkylated polyphenols; polyphenols and dienes such as tetrakis [methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate)] methane Alkylation reaction product of para-cresol or dicyclopentadiene; alkylation hydroquinone; hydroxylated thiodiphenyl ether; alkylidene-bisphenol; benzyl compound; beta- (3,5-di-tert-butyl- -Hydroxyphenyl) propionic acid and esters of mono- or polyhydric alcohols; beta- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid and esters of mono- or polyhydric alcohols; distearyl thiopro Pionate, dilauryl thiopropionate, ditridecyl thiodipropionate, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythrityl-tetrakis [3- (3 And esters of thioalkyl or thioaryl compounds such as 5-di-tert-butyl-4-hydroxyphenyl) propionate; and amide compounds of beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid. It is done.

  The ultraviolet light (UV) stabilizer is a substance that absorbs ultraviolet energy and part of chemical bonds in the polycarbonate is transferred to suppress deterioration of the molded body. As for the said ultraviolet light (UV) stabilizer, only 1 type may be used and 2 or more types may be used together.

  Examples of the ultraviolet light (UV) stabilizer include 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) -benzotriazole, and 2-hydroxy-4. -Benzotriazoles such as n-octoxybenzophenone and hydroxybenzophenone; hydroxybenzotriazole; hydroxybenzotriazine; cyanoacrylate; oxanilide; benzoxazinone; 2- (2H-benzotriazol-2-yl) -4- (1,1 , 3,3-tetramethylbutyl) -phenol; 2-hydroxy-4-n-octyloxybenzophenone; 2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine-2 -Yl] -5- (octyloxy) -phenol, 2,2 ' (1,4-phenylene) bis (4H-3,1-benzoxazin-4-one); 1,3-bis [(2-cyano-3,3-diphenylacryloyl) oxy] -2,2-bis [ [(2-cyano-3,3-diphenylacryloyl) oxy] methyl] propane; 2,2 ′-(1,4-phenylene) bis (4H-3,1-benzoxazin-4-one); 1,3 -Bis [(2-cyano-3,3-diphenylacryloyl) oxy] -2,2-bis [[(2-cyano-3,3-diphenylacryloyl) oxy] methyl] propane; and titanium oxide, cerium oxide, Examples thereof include inorganic substances such as zinc oxide.

  By containing the ultraviolet light (UV) stabilizer in the resin composition, ultraviolet absorption can be favorably absorbed, and deterioration (coloring) of the molded product can be suppressed.

  As for the said plasticizer, the said lubricant, or the said mold release agent, only 1 type may be used and 2 or more types may be used together. Many compounds used as plasticizers also have lubricant and template properties, and many compounds used as lubricants also have template and plasticizer properties and are used as template agents. Many of the compounds obtained also have properties of plasticizers and lubricants.

  Examples of the plasticizer, the lubricant, or the release agent include phthalic acid esters such as dioctyl-4,5-epoxy-hexahydrophthalate; tris- (octoxycarbonylethyl) isocyanurate, tristearin, poly-α Olefin, epoxidized soybean oil, ester; fatty acid ester such as alkyl stearyl ester; stearate such as methyl stearate, stearyl stearate, pentaerythritol tetrastearate; methyl stearate and glycol polymer and hydrophilic or hydrophobic non-hydrophilic Mixtures with ionic surfactants, mixtures of methyl stearate and polyethylene-polypropylene glycol copolymers; and waxes such as beeswax, wax, montan wax, paraffin wax, and the like.

  Examples of the glycol polymer include a polyethylene glycol polymer, a polypropylene glycol polymer, and a poly (ethylene glycol-co-propylene glycol) copolymer.

  The relative amount of each component such as a fluorinated polymer, an antioxidant, a heat stabilizer, an ultraviolet light (UV) stabilizer, a plasticizer, a lubricant, and a release agent is determined according to the flame retardancy of the obtained molded body, Significantly affects impact resistance, low smoke density, low smoke toxicity, and mechanical properties. In order to improve a certain characteristic of a molded object, even if it mix | blends a certain component many, another characteristic may fall.

(Molded body)
A molded body can be obtained by molding the resin composition according to the present invention. This molded body is excellent in flame retardancy and excellent in impact resistance.

  In the molded product according to the present invention, the Izod impact value measured in accordance with JIS K7110: 1999 is preferably 200 J / m or more, more preferably 250 J / m or more. When the Izod impact value is not less than the above lower limit, the molded article has a considerably excellent impact resistance.

The molded product according to the present invention preferably has a maximum average heat generation rate determined in accordance with European Railway Standard EN455545-2 from a heat generation rate measured in accordance with ISO 5660-1: 2002, preferably 120 kW / m ² or less. More preferably, it is 100 kW / m ² or less. When the maximum average heat generation rate is not more than the above upper limit, the flame retardancy of the molded article is considerably excellent.

  The molded body according to the present invention is suitably used as an interior material for transportation equipment such as railway vehicles, aircraft, ships, and automobiles.

  The molded body according to the present invention can be molded by a known method using the resin composition according to the present invention.

  For example, a molded body can be obtained by heating and molding and curing the resin composition at 230 to 300 ° C.

  Hereinafter, the present invention will be specifically described by giving examples and comparative examples. The present invention is not limited to the following examples.

  The following materials were prepared.

(Polycarbonate resin having a branched structure)
Aromatic polycarbonate resin having a branched structure (1,1,1-tris- (p-hydroxyphenyl) ethane is used as a branching agent)

(Inorganic filler)
Talc (Imeris “Jet Fine 0.7CA”: volume average particle size 2.5 μm)
Talc (“Jet Fine 3CA” manufactured by Imeris Co., Ltd .: volume average particle diameter 3.9 μm)
Talc (“Luzenac HAR W92” manufactured by Imeris Co., Ltd .: volume average particle diameter 10 μm)

  The volume average particle size (D50) of talc was determined by measuring the particle size distribution using a laser diffraction particle size distribution measuring device (“SALD-3100” manufactured by Shimadzu Corporation). Specifically, in the obtained particle size distribution, the particle size at which the cumulative volume calculated from the small diameter side was 50% was defined as the talc volume average particle size (D50).

(Phosphorus-containing compound)
Phosphorus-containing compound ("SOL-DP" manufactured by ICL Industrial Products)

(Core shell particles)
Core shell particles (Metbrene SX-005 manufactured by Mitsubishi Rayon Co., Ltd.)

Example 1
(Preparation of resin composition)
A polycarbonate resin having a branched structure, an inorganic filler, a phosphorus-containing compound, and core-shell particles were mixed to obtain a resin composition. The polycarbonate resin having a branched structure, the inorganic filler, the core-shell particles, and the phosphorus-containing compound were used in the blending amounts (parts by weight) shown in Table 1 below.

(Production of molded body)
The obtained resin composition was melt-extruded in a twin-screw extruder set at a melting temperature of about 270 ° C., a pressure of about 0.7 bar, and a rotational speed of about 150 rpm, and the size was 3 mm thick × 300 mm wide × 400 mm deep. Molded into. Next, the molded body was produced by drying at about 120 ° C. for about 5 hours.

(Example 2-8, Comparative Example 1-5)
The volume average particle diameter (D50) of the used inorganic filler (talc) and the blending amount of each component were the same as in Example 1 except that the blending amount (parts by weight) was set as shown in Table 1 below. A resin composition and a molded body were obtained.

(Evaluation)
(1) Maximum average heat generation rate A test piece having a length of 100 mm, a width of 100 mm, and a depth of 3 mm was cut out from the obtained molded product, and radiant heat of 50 kW / m ² and measurement conditions for 20 minutes were conformed to ISO 5660-1: 2002. The exotherm rate was measured below. From the obtained heat generation rate, the maximum average heat generation rate (MARHE) was calculated in accordance with the European railway standard EN455545-2.

[Criteria for maximum average heat generation rate]
○: maximum average heat generation rate of 120 kW / ^{m 2} or less △: maximum average heat generation rate exceeds the ^{120kW / m 2, 140kW / m} 2 less ×: maximum average heat generation rate of 140kW / ^{m 2} or more

(2) Izod impact value A test piece having a length of 80 mm, a width of 10 mm, and a depth of 3 mm was cut out from the obtained molded product, and the Izod impact value was measured in accordance with JIS K7110: 1999.

[Judgment criteria for Izod impact value]
○: Izod impact value of 200 J / m or more Δ: Izod impact value of 150 J / m or more and less than 200 J / m ×: Izod impact value of less than 150 J / m

(3) Comprehensive judgment The obtained molded object was evaluated according to the following judgment criteria from the maximum average heat generation rate calculated | required by said (1) and (2), and an Izod impact value.

[Comprehensive criteria]
○○: The judgment of the maximum average heat generation rate is ○, and the judgment of the Izod impact value is ○
○: The determination of the maximum average heat generation rate is ○, and the determination of the Izod impact value is Δ, or the determination of the maximum average heat generation rate is Δ, and the determination of the Izod impact value is ○
Δ: The determination of the maximum average heat generation rate is Δ, and the determination of the Izod impact value is Δ
×: Determination of at least one of maximum average heat generation rate and Izod impact value is ×

  The composition and results are shown in Table 1 below.

  FIG. 1 shows the relationship between the volume average particle diameter (D50) of talc (inorganic filler) obtained from Comparative Example 1, Example 2, and Example 6, the Izod impact value, and the maximum average heat generation rate. From FIG. 1, it can confirm that it is excellent in a flame retardance and impact resistance, when the volume average particle diameter (D50) of talc is small. When the volume average particle diameter (D50) of talc is small, a compact having a small center of gravity distance between adjacent talcs and a large number of talc particles is obtained. For this reason, it is presumed that the gas barrier property is improved and the flame retardancy is improved by reducing the amount of combustion gas passing through the gap of talc.

  FIG. 2 shows the content of talc (inorganic filler) having a volume average particle diameter (D50) of 3.9 μm, the Izod impact value, and the maximum average heat generation, obtained from Comparative Example 2, Comparative Example 3, and Example 1-4. Expresses the relationship with speed.

  FIG. 3 shows the content of talc (inorganic filler) having a volume average particle diameter (D50) of 2.5 μm, the Izod impact value, and the maximum average heat generation, obtained from Comparative Example 4, Comparative Example 5, and Example 5-8. Expresses the relationship with speed.

  2 and 3, it can be confirmed that the smaller the talc content, the better the impact resistance. On the other hand, although there exists a tendency for flame retardance to be excellent, so that there is much content of talc, it can confirm that there is a threshold in content of talc which improves flame retardance.

  Therefore, it is understood that both the volume average particle diameter (D50) and the content of talc are important in order to obtain a molded article having excellent flame retardancy and excellent impact resistance.

Claims (7)

Including a polycarbonate resin having a branched structure and an inorganic filler,
The volume average particle diameter of the inorganic filler is 6 μm or less,
The resin composition whose content of the said inorganic filler is 10 to 45 weight part with respect to 100 weight part of polycarbonate resin which has the said branched structure.   The resin composition according to claim 1, wherein the content of the inorganic filler is 35 parts by weight or less with respect to 100 parts by weight of the polycarbonate resin having the branched structure.   The resin composition according to claim 1 or 2, comprising a phosphorus-containing compound. Including core-shell particles,
The resin composition according to any one of claims 1 to 3, wherein in the core-shell particles, the organic compound constituting the core and the organic compound constituting the shell are chemically bonded. Including core-shell particles,
In the core-shell particles, the organic compound constituting the core and the organic compound constituting the shell are chemically bonded,
The resin composition of Claim 3 whose weight ratio of content of the said core-shell particle with respect to content of the said phosphorus containing compound is 0.4 or more and 2.5 or less.   The molded object in which the resin composition of any one of Claims 1-5 was shape | molded. The Izod impact value measured in accordance with JIS K7110: 1999 is 200 J / m or more,
The molded product according to claim 6, wherein a maximum average heat generation rate determined in accordance with European Railway Standard EN455545-2 from a heat generation rate measured in accordance with ISO5660-1: 2002 is 120 kW / m ² or less.