JP2019203091A - Resin composition and molding - Google Patents

Abstract

To provide a resin composition which is excellent in moldability and can enhance flame retardancy of the obtained molding.SOLUTION: A resin composition contains a polycarbonate resin and an inorganic filler, in which a content of the inorganic filler is 10 pts.wt. or more and 40 pts.wt. or less with respect to 100 pts.wt. of the polycarbonate resin, and when a plate-like body having a size of a longitudinal length of 100 mm, a transverse length of 100 mm and a thickness of 1.5 mm is obtained by molding the resin composition and the obtained plate-like boy is left at a temperature of 23°C and a humidity of 50% for 240 hours, a content of water in the plate-like body after leaving is 550 ppm or more and 1,000 ppm or less.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.

  Specific applications of the thermoplastic resin include interior materials for transport equipment such as railway vehicles, aircraft, ships, and automobiles.

  In said use, it is calculated | required that it is excellent in the flame retardance of the molded object using a thermoplastic resin. Since thermoplastic resins are generally flammable, studies have been widely conducted to improve the flame retardancy of molded articles using thermoplastic resins.

  For example, Patent Document 1 below discloses a polycarbonate resin composition containing a polycarbonate resin and a glass filler, and having an average major axis of 1000 μm or less. In this polycarbonate resin composition, the total amount of the organometallic salt of sulfonic acid and the organometallic salt of sulfonamide is 1% by mass or less based on the total amount of the polycarbonate resin and the glass filler.

Patent Document 2 below includes a first glass cloth layer containing a thermosetting resin, a first polycarbonate resin layer, and a second glass cloth layer, and the thermosetting resin is condensation-reactive. A polycarbonate resin laminate is disclosed in which the first glass cloth layer that is a silicone resin and contains the thermosetting resin is the outermost layer. In this polycarbonate resin laminate, when the polycarbonate resin laminate is heated in accordance with the cone calorimeter exothermic test specified in ISO 5560-1, the maximum heat generation rate in the 10 minutes from the start of heating is 300 kW / m ^2. It is as follows.

JP-A-2018-9130 Japanese Patent Laid-Open No. 2006-150562

  In the molded article of the resin composition described in Patent Document 1, flame retardance can be improved to some extent, but further improvement in flame retardancy is desired. For example, in the molded body of the resin composition described in Patent Document 1, the gas barrier performance due to the glass filler is not sufficient, and a combustible gas may be released during combustion of the molded body. Moreover, in the resin composition of patent document 1, since the glass filler is contained, when shape | molding by vacuum forming etc., the tensile elongation property at high temperature is not enough, and a moldability may be inferior. .

  In the resin composition used as the material of the molded article described in Patent Document 2, since a thermosetting resin is included, the tensile elongation at high temperature is not sufficient when molding by vacuum molding or the like, and molding is performed. May be inferior.

  The objective of this invention is providing the resin composition which is excellent in a moldability and can improve the flame retardance of the molded object obtained. 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, the resin composition includes a polycarbonate resin and an inorganic filler, and the content of the inorganic filler is 10 parts by weight or more and 40 parts by weight or less with respect to 100 parts by weight of the polycarbonate resin. To obtain a plate-like body having a size of 100 mm in length, 100 mm in width and 1.5 mm in thickness, and when the obtained plate-like body was allowed to stand at a temperature of 23 ° C. and a humidity of 50% for 240 hours, A resin composition is provided in which the content of water in the plate-like body is 550 ppm or more and 1000 ppm or less.

  In a specific aspect of the resin composition according to the present invention, a compound that includes core-shell rubber particles having a core-shell structure, and which forms a core and a compound that forms a shell are chemically bonded.

  On the specific situation with the resin composition which concerns on this invention, the said core-shell rubber particle contains a silicone compound.

  On the specific situation with the resin composition which concerns on this invention, content of the said core-shell rubber particle is 5 to 30 weight part with respect to 100 weight part of said polycarbonate resins.

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

In a specific aspect of the molded body according to the present invention, when the maximum heat generation rate is calculated using the heat generation rate measured in accordance with ISO 5660-1: 2002, the maximum heat generation rate is 280 kW / m ² or less. The tensile fracture strain at 210 ° C. measured in accordance with JIS K7161 is 160% or more.

  The resin composition according to the present invention includes a polycarbonate resin and an inorganic filler. In the resin composition according to the present invention, the content of the inorganic filler is 10 parts by weight or more and 40 parts by weight or less with respect to 100 parts by weight of the polycarbonate resin. In the resin composition according to the present invention, a resin composition is molded to obtain a plate-like body having a size of 100 mm in length, 100 mm in width, and 1.5 mm in thickness, and the obtained plate-like body has a temperature of 23 ° C. and a humidity of 50. %, The content of water in the plate after standing is 550 ppm to 1000 ppm. In the resin composition which concerns on this invention, since said structure is provided, it is excellent in a moldability and can improve the flame retardance of the molded object obtained.

FIG. 1 is a diagram showing the relationship between the content of an inorganic filler, the maximum heat generation rate of the molded body, and the tensile fracture strain. FIG. 2 is a diagram showing the relationship between the content of core-shell rubber particles, the maximum heat generation rate of the molded body, and the tensile fracture strain.

  Hereinafter, the present invention will be described in detail.

  The resin composition according to the present invention includes a polycarbonate resin and an inorganic filler. In the resin composition according to the present invention, the content of the inorganic filler is 10 parts by weight or more and 40 parts by weight or less with respect to 100 parts by weight of the polycarbonate resin. In the resin composition according to the present invention, a resin composition is molded to obtain a plate-like body having a size of 100 mm in length, 100 mm in width, and 1.5 mm in thickness, and the obtained plate-like body has a temperature of 23 ° C. and a humidity of 50. %, The content of water in the plate after standing is 550 ppm to 1000 ppm.

  In the resin composition which concerns on this invention, since said structure is provided, it is excellent in a moldability and can improve the flame retardance of the molded object obtained.

  Moreover, in the resin composition which concerns on this invention, since said structure is provided, generation | occurrence | production and expansion of craze can be suppressed at the time of shaping | molding, and the molded object which does not produce a crack or a crack easily can be obtained. As a result, in the resin composition according to the present invention, a molded body having a good appearance can be obtained.

  Moreover, in the resin composition which concerns on this invention, since said structure is provided, the molded object which is excellent in impact resistance can be obtained.

  From the viewpoint of enhancing the flame retardancy of the molded body, the resin composition according to the present invention is obtained by molding the resin composition to obtain a plate-like body having a size of 100 mm in length, 100 mm in width, and 1.5 mm in thickness. When the obtained plate-like body is allowed to stand for 240 hours at a temperature of 23 ° C. and a humidity of 50%, the content of water in the plate-like body after being left is 550 ppm to 1000 ppm.

  Specifically, the plate-like body is produced as follows.

  The resin composition is heated at 230 ° C. or more and 300 ° C. or less to soften (or melt) the resin composition, and then solidify to obtain a plate-like body. It is preferable that the resin composition is heated at 270 ° C. to soften (or melt) the resin composition and then solidify to obtain a plate-like body. The resin composition may be molded into a size of 100 mm in length, 100 mm in width, and 1.5 mm in thickness to obtain a plate-like body. After the resin composition is molded to obtain a molded body, the molded body may be cut to obtain a plate-like body having a size of 100 mm in length, 100 mm in width, and 1.5 mm in thickness.

  Specifically, the water content is measured as follows.

  A plate-like body (plate-like body after standing) after leaving for 240 hours at a temperature of 23 ° C. and a humidity of 50% is cut out to obtain a test piece. The size of the test piece is not particularly limited, but is preferably 20 mm × 1 mm × 1.5 mm. About the obtained test piece, a moisture content is measured by a coulometric titration method (heating vaporization method) using a trace moisture measuring device under conditions of a heating vaporization temperature of 130 ° C. and an extraction time of 5 minutes.

  The content of water in the plate after standing is preferably 600 ppm or more, and preferably 800 ppm or less. The flame retardance of a molded object can be improved further as content of the said water is more than the said minimum and below the said upper limit.

  In the molded body according to the present invention, the size of the molded body may not be 100 mm in length, 100 mm in width, and 1.5 mm in thickness. The plate-like body is produced in order to measure the water content.

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

[Polycarbonate resin]
The resin composition according to the present invention includes a polycarbonate resin. A conventionally known polycarbonate resin can be used as the polycarbonate resin. As for the said polycarbonate resin, only 1 type may be used and 2 or more types may be used together.

  The polycarbonate resin may be a polycarbonate resin having no branched structure or a polycarbonate resin having a branched structure.

  The polycarbonate resin is preferably a polycarbonate resin having a branched structure from the viewpoint of further improving moldability, and obtaining a molded body that is more excellent in flame retardancy, heat resistance, and impact resistance.

  From the viewpoint of further improving the moldability and obtaining a molded article that is more excellent in flame retardancy, the polycarbonate resin is preferably an aromatic polycarbonate resin, and may be an aromatic polycarbonate resin having a branched structure. More preferred.

  As for the polycarbonate resin which has the said branched structure, 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 for producing a polycarbonate resin having the above branched structure by a phase interface method, a diphenol compound, a carbonic acid halogen compound or an aromatic dicarboxylic acid dihalide, a branching agent, and a chain terminator as necessary And a method of reacting with. 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) Examples of a method for producing a polycarbonate resin having the above branched structure by a melt polymerization method include a method of reacting a diphenol compound, a diphenyl carbonate compound, a branching agent, and a chain terminator as necessary. .

  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, or 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, or 4,4′- More preferred is dihydroxydiphenyl sulfone. 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 favorably obtaining the polycarbonate resin having the 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 occurs, and the impact resistance of the molded product can be improved. It is done.

  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 satisfactorily obtaining the polycarbonate resin having the branched structure, the branching agent is preferably a trifunctional phenol compound or a tetrafunctional phenol compound. The trifunctional phenol compound and the tetrafunctional phenol compound 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 or a tetraphenol compound, and a phenol compound having at least three functional groups with low reactivity. More preferably. 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; or 3,5-di-tert-butylphenol, p-isooctylphenol, p-tert Preferred are dialkylphenols such as -octylphenol, p-dodecylphenol and 2- (3,5-dimethylheptyl) -phenol, 4- (3,5-dimethylheptyl) -phenol.

[Inorganic filler]
The resin composition according to the present invention includes an inorganic filler. 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. A moldability can be made favorable as the said talc is a compression talc.

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

  From the viewpoint of making the moldability even better, and from the viewpoint of obtaining a molded product that is more excellent in flame retardancy and impact resistance, the inorganic filler contains talc containing alumina, talc containing magnesium oxide, or alumina and magnesium oxide. Talc containing is preferable.

  The inorganic filler may be subjected to a surface treatment such as silanization. When the inorganic filler is an inorganic filler subjected to surface treatment such as silanization, the compatibility with the polycarbonate resin is further improved.

  From the viewpoint of obtaining a molded article that is more excellent in flame retardancy and impact resistance, the volume average particle diameter (D50) of the inorganic filler is preferably 1 μm or more, more preferably 2 μm or more, preferably 6 μm or less, more preferably 4 μm. It is as follows. When the volume average particle diameter (D50) of the inorganic filler is not more than the above upper limit, a molded body 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.

  In the resin composition according to the present invention, the content of the inorganic filler is 10 parts by weight or more and 40 parts by weight or less with respect to 100 parts by weight of the polycarbonate resin. When the content of the inorganic filler is less than 10 parts by weight relative to 100 parts by weight of the polycarbonate resin, flame retardancy may be inferior. When content of the said inorganic filler with respect to 100 weight part of said polycarbonate resins exceeds 40 weight part, a moldability and a flame retardance may be inferior.

  The content of the inorganic filler is preferably 5 parts by weight or more, more preferably 10 parts by weight or more, preferably 30 parts by weight or less, more preferably 20 parts by weight or less with respect to 100 parts by weight of the polycarbonate resin. When the content of the inorganic filler is not less than the above lower limit and not more than the above upper limit, a molded article excellent in flame retardancy and 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 can be well dispersed, the moldability can be improved, and a molded article excellent in flame retardancy and gas barrier properties can be obtained.

[Core shell rubber particles]
From the viewpoint of improving moldability and obtaining a molded body that is more excellent in flame retardancy, the resin composition preferably includes core-shell rubber particles. The core shell rubber particles have a core shell structure. The resin composition according to the present invention preferably includes core-shell rubber particles having a core-shell structure.

  The core shell rubber particles are generally used as an impact resistance agent. The impact resistance agent is a substance that imparts impact resistance to a molded body obtained from the resin composition. The impact resistance agent generally has rubber elasticity. Therefore, the impact resistance of the molded product can be improved by using the core-shell rubber particles.

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

  The compound constituting the core is preferably an organic compound. The compound constituting the shell is preferably an organic compound.

  From the viewpoint of further improving moldability, and from the viewpoint of obtaining a molded body that is more excellent in flame retardancy and impact resistance, the core-shell rubber particles preferably contain a silicone compound. When the core-shell rubber particles contain a silicone compound, the core may contain the silicone compound, the shell may contain a silicone compound, and the core and the shell contain a silicone compound. Also good.

  From the viewpoint of further improving the moldability, and from the viewpoint of obtaining a molded body that is further excellent in flame retardancy and impact resistance, the core preferably contains the silicone compound.

  Examples of the core-shell rubber particles include diene-based core-shell rubbery polymers such as methyl methacrylate-butadiene-styrene copolymer resin (MBS resin) and acrylonitrile-butadiene-styrene copolymer resin (ABS resin); acrylate-styrene- Acrylic core-shell type rubbery polymer such as acrylonitrile copolymer resin (ASA resin) and acrylate-methyl methacrylate copolymer resin; silicone-acrylate-methyl methacrylate copolymer resin, silicone-acrylate-acrylonitrile-styrene copolymer Examples thereof include silicone-based core-shell type rubbery polymers (core-shell rubber particles containing a silicone compound) such as resins; and modified products of these with maleic anhydride, glycidyl methacrylate, and the like.

  From the viewpoint of enhancing the moldability, the viewpoint of improving the appearance of the molded body, and the viewpoint of obtaining a molded body having excellent flame retardancy and impact resistance, the volume average particle diameter (D50) of the core shell rubber particles is preferably 100 nm. Above, more preferably 250 nm or more, preferably 800 nm or less. The core-shell rubber particles having a volume average particle diameter (D50) of not less than the above lower limit and not more than the above upper limit can be prepared by an emulsion polymerization method.

  The volume average particle diameter of the core-shell rubber 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 rubber particles is preferably obtained by measurement by a laser diffraction / scattering method.

  A commercial item can also be used for the said core-shell rubber particle. Commercially available products of the core-shell rubber particles include Methbrene 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.) Is mentioned.

  The content of the core shell rubber particles with respect to 100 parts by weight of the polycarbonate resin is preferably 1 part by weight or more, more preferably 3 parts by weight or more, still more preferably 4 parts by weight or more, and particularly preferably 5 parts by weight or more. is there. The content of the core-shell rubber particles with respect to 100 parts by weight of the polycarbonate resin is preferably 50 parts by weight or less, more preferably 45 parts by weight or less, still more preferably 30 parts by weight or less, and particularly preferably 20 parts by weight or less. is there. If the content of the core-shell particles is not less than the above lower limit and not more than the above upper limit, the moldability can be further improved, and a molded body that is more excellent in flame retardancy and impact resistance can be obtained.

[Other ingredients]
The resin composition includes an impact resistance agent other than the core-shell rubber particles, a fluorinated polymer, an antioxidant, a thermal stabilizer, an ultraviolet light (UV) stabilizer, and a plasticizer, as long as the object of the present invention is not impaired. , A lubricant, a release agent, and the like may be included.

  Examples of impact agents other than the above-mentioned core-shell rubber particles include natural rubber, fluorine elastomer, ethylene-propylene rubber (EPR), ethylene-butene rubber, ethylene-propylene-diene monomer rubber (EPDM), acrylate rubber, hydrogenated nitrile rubber (HNBR). ), Silicone elastomers, silicone oils, graft copolymers modified with elastomers such as 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 (SIS), methyl methacrylate Over DOO - butadiene - styrene (MBS), and high rubber graft (HRG) ABS, and the like. By using these impact resistance agents in combination with the above core-shell rubber particles, impact resistance, low smoke density, low smoke toxicity, and good mechanical properties can be imparted to the molded article. Only one type of impact agent other than the core-shell rubber particles may be used, or two or more types may be used in combination.

  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.

  Specific examples of the fluorinated polymer include poly (tetrafluoroethylene) homopolymer (PTFE), poly (hexafluoroethylene), poly (tetrafluoroethylene-hexafluoroethylene), and poly (tetrafluoroethylene-ethylene). -Propylene) and the like. The poly (tetrafluoroethylene) homopolymer (PTFE) may be fiber-forming or non-fiber-forming.

  By including the fluorinated polymer in the resin composition, the resin composition or a fragment of the molded body melts and drops when the molded body is produced, when the molded body is ignited, and when the molded body is burned. Can be suppressed, and the flame retardancy of the molded product 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. -Benzotriazole 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, it is possible to absorb ultraviolet rays well and to suppress deterioration (coloring) of the molded product.

  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. Moreover, since the resin composition according to the present invention is excellent in moldability and can suppress the generation and expansion of crazing during molding, cracks or cracks are unlikely to occur in the resulting molded product. As a result, the obtained molded body has a good appearance.

  The molded body according to the present invention is a molded body obtained by molding the above-described resin composition.

In the molded product according to the present invention, when the maximum heat generation rate is calculated using the heat generation rate measured according to ISO 5660-1: 2002, the maximum heat generation rate is preferably 280 kW / m ² or less. Preferably it is 250 kW / m ² or less. When the maximum heat generation rate is not more than the above upper limit, the flame retardancy of the molded article is considerably excellent. The lower the maximum heat generation rate, the better.

  The maximum heat generation rate can be calculated by obtaining the maximum value of the heat generation rate measured according to ISO5660-1: 2002.

  In the molded body according to the present invention, the tensile fracture strain at 210 ° C. measured in accordance with JIS K7161 is preferably 160% or more, more preferably 240% or more. When the tensile fracture strain is not less than the above lower limit, the moldability can be made quite good, and the appearance of the molded body can be made quite good.

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

(Inorganic filler)
Talc ("Jet Fine 3CA" manufactured by Imeris Co., Ltd., volume average particle size 3.9 μm)
Glass filler (Nippon Electric Glass “EPH80M-10A”, average length 82 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).

(Core shell rubber particles)
Core-shell rubber particles (core-shell rubber particles containing a silicone compound, “Metablene SX-005” manufactured by Mitsubishi Rayon Co., Ltd., volume average particle diameter 300 nm)

(Other)
Sodium alkylbenzene sulfonate (manufactured by Wako Pure Chemical Industries, Ltd.)

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

(Production of molded body)
The obtained resin composition was melt-kneaded in a lab plast mill set at a melting temperature of about 270 ° C. and a rotation speed of about 120 rpm, and using a hand press at about 270 ° C., the length was 100 mm, the width was 100 mm, and the thickness was 1.5 mm. A molded body was produced by molding into a size of.

(Examples 2-7, Comparative Examples 1-5)
A resin composition and a molded body were obtained in the same manner as in Example 1 except that the blending amount (parts by weight) of each component was changed as shown in Tables 1 and 2 below.

(Evaluation)
(1) Content of water The obtained molded body (plate-shaped body) having a size of 100 mm in length, 100 mm in width and 1.5 mm in thickness was left at a temperature of 23 ° C. and a humidity of 50% for 240 hours. The plate-like body after being left out was cut into a size of 20 mm × 1 mm × 1.5 mm to obtain a test piece. About the obtained test piece, the moisture content under the conditions of a heating vaporization temperature of 130 ° C. and an extraction time of 5 minutes by a coulometric titration method (heating vaporization method) using a trace moisture measuring device (“AQ-2000” manufactured by Hiranuma Sangyo Co., Ltd.) Was measured.

[Criteria for water content]
○: Water content 600 ppm or more and 800 ppm or less △: Water content 550 ppm or more and less than 600 ppm, or more than 800 ppm and 1000 ppm or less ×: Water content less than 550 ppm or more than 1000 ppm

(2) Ignition time About the obtained molded object, based on ISO5660-1: 2002, the radiation heat of 50 kW / m < ² > was given for 10 minutes. At that time, the time from the start of the test until the molded body was ignited was measured and defined as the ignition time.

(3) Maximum exothermic rate About the obtained molded object, according to ISO5660-1: 2002, the exothermic rate was measured on the measurement conditions of 50 kW / m < ² > of radiant heat and 10 minutes. The maximum heat generation rate was calculated from the obtained heat generation rate.

[Criteria for maximum heat generation rate]
○: Maximum heat generation rate is 250 kW / m ² or less Δ: Maximum heat generation rate exceeds 250 kW / m ² and 280 kW / m ² or less ×: Maximum heat generation rate exceeds 280 kW / m ²

(4) Tensile Fracture Strain A dumbbell-shaped test piece having a shape conforming to JIS K7161 was produced from the obtained molded body using an automatic dumbbell production machine (YONEMURA MFG. Co, ADM TYPE). Using an autograph (“AG-10TB” manufactured by Shimadzu Corporation), the tensile fracture strain at 210 ° C. of the obtained dumbbell-shaped test piece was measured according to JIS K7161.

[Criteria for tensile fracture strain]
○: Tensile fracture strain is 240% or more Δ: Tensile fracture strain is 160% or more and less than 240% ×: Tensile fracture strain is less than 160%

(5) General determination (1) From the determination result of water content, (3) maximum heat release rate, and (4) tensile fracture strain, the obtained molded body was evaluated according to the following determination criteria.

[Comprehensive criteria]
○○: The judgment result of water content, maximum heat generation rate and tensile fracture strain is ○
○: Among the determination results of water content, maximum heat generation rate, and tensile fracture strain, the determination result of 2 items is ○, and the determination result of 1 item is Δ
Δ: Among the determination results of water content, maximum heat generation rate, and tensile fracture strain, the determination result of 2 items is Δ, the determination result of 1 item is ○, or the determination result of 3 items is Δ
×: Does not correspond to the above criteria of ○○, ○, and △

  The compositions and results are shown in Tables 1 and 2 below.

  In FIG. 1, the relationship between the content of the inorganic filler with respect to 100 parts by weight of the polycarbonate resin obtained from Examples 2, 5 to 7 and Comparative Examples 3 and 4, and the maximum heat generation rate and tensile fracture strain of the molded body is shown. In addition, although the measurement result of the tensile fracture strain of Comparative Example 3 was larger than 500%, FIG. 1 plots it at the position of 500%.

  From FIG. 1, it can confirm that the molded object which was excellent in a moldability and was excellent in a flame retardance as content of the inorganic filler with respect to 100 weight part of polycarbonate resin is 10 weight part or more and 40 weight part or less can be confirmed. . Moreover, in the molded object obtained from the resin composition whose content of the said inorganic filler is 10 to 40 weight part, it was obtained from the resin composition whose content of the said inorganic filler is less than 10 weight part It can be confirmed that the flame retardancy can be improved as compared with the molded body. This is considered to be because the combustible gas is less likely to be emitted from the molded product obtained from the resin composition according to the present invention than the conventional molded product. Further, in a molded body obtained from a resin composition having a content of the inorganic filler of 10 parts by weight or more and 40 parts by weight or less, a molding obtained from a resin composition in which the content of the inorganic filler exceeds 40 parts by weight. It can be confirmed that the moldability and flame retardancy can be improved compared to the body.

  In FIG. 2, the relationship between content of the core-shell rubber particle with respect to 100 weight part of polycarbonate resin calculated | required from Examples 1-4 and the comparative example 2, the maximum heat release rate of a molded object, and a tensile fracture strain is shown.

FIG. 2 confirms that the molded product obtained from the resin composition containing core-shell rubber particles is more excellent in moldability and flame retardancy than the molded product obtained from the resin composition not containing core-shell rubber particles. it can. Further, when the content of the core-shell rubber particles with respect to 100 parts by weight of the polycarbonate resin is 5 parts by weight or more, the moldability and flame retardancy are further improved, and when the content of the core-shell rubber particles is 30 parts by weight or less It can confirm that it is excellent in property.

Claims (6)

Including polycarbonate resin and inorganic filler,
The content of the inorganic filler is 10 to 40 parts by weight with respect to 100 parts by weight of the polycarbonate resin,
When the resin composition was molded to obtain a plate-like body having a size of 100 mm in length, 100 mm in width and 1.5 mm in thickness, and the obtained plate-like body was left at a temperature of 23 ° C. and a humidity of 50% for 240 hours, The resin composition whose content of the water in the plate-shaped body after leaving is 550 ppm or more and 1000 ppm or less. Including core-shell rubber particles having a core-shell structure;
The resin composition according to claim 1, wherein the compound constituting the core and the compound constituting the shell are chemically bonded.   The resin composition according to claim 2, wherein the core-shell rubber particles contain a silicone compound.   The resin composition according to claim 2 or 3, wherein the content of the core-shell rubber particles is 5 parts by weight or more and 30 parts by weight or less with respect to 100 parts by weight of the polycarbonate resin.   The molded object in which the resin composition of any one of Claims 1-4 was shape | molded. When the maximum heat generation rate is calculated using the heat generation rate measured in accordance with ISO 5660-1: 2002, the maximum heat generation rate is 280 kW / m ² or less,
The molded object of Claim 5 whose tensile fracture strain in 210 degreeC measured based on JISK7161 is 160% or more.

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