WO2023234367A1 - Composition de résine de polycarbonate et article façonné - Google Patents

Composition de résine de polycarbonate et article façonné Download PDF

Info

Publication number
WO2023234367A1
WO2023234367A1 PCT/JP2023/020343 JP2023020343W WO2023234367A1 WO 2023234367 A1 WO2023234367 A1 WO 2023234367A1 JP 2023020343 W JP2023020343 W JP 2023020343W WO 2023234367 A1 WO2023234367 A1 WO 2023234367A1
Authority
WO
WIPO (PCT)
Prior art keywords
parts
core
weight
elastic body
polyester resin
Prior art date
Application number
PCT/JP2023/020343
Other languages
English (en)
Japanese (ja)
Inventor
文祐 稲谷
Original Assignee
株式会社カネカ
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社カネカ filed Critical 株式会社カネカ
Publication of WO2023234367A1 publication Critical patent/WO2023234367A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates

Definitions

  • the present invention relates to a resin composition containing a polycarbonate resin and a molded article thereof.
  • Molded bodies made of polycarbonate resin have excellent transparency, impact resistance, heat resistance, dimensional stability, self-extinguishing properties (flame retardancy), etc., and are used in electrical, electronic, and OA equipment, optical parts, precision machinery, It is used in a wide range of fields including automobiles, security/medical care, building materials, and miscellaneous goods.
  • Patent Document 1 As a method for improving the impact resistance of molded bodies made of polycarbonate resin, it is known to mix crystalline polyester resin or thermoplastic elastomer components with polycarbonate resin (for example, Patent Document 1 (See 3). It is also known to impart flame retardancy by blending a flame retardant into a polycarbonate resin (for example, see Patent Document 3).
  • an object of the present invention is to provide a polycarbonate resin composition having a good balance of impact resistance, flame retardance, and fluidity when melted, and a molded article thereof.
  • the present invention provides polycarbonate resin (A), Amorphous polyester resin (B), core-shell type elastic body (C), and Contains a flame retardant (D),
  • the content of the amorphous polyester resin (B) is 15 to 35% by weight of the total of the polycarbonate resin (A) and the amorphous polyester resin (B),
  • the amorphous polyester resin (B) contains glycol-modified polyethylene terephthalate (b1), Of the amorphous polyester resin (B), the content of the glycol-modified polyethylene terephthalate (b1) is 15 to 100% by weight
  • the content of the core-shell type elastic body (C) is 1 to 30 parts by weight based on a total of 100 parts by weight of the polycarbonate resin (A) and the amorphous polyester resin (B),
  • the core-shell type elastic body (C) has a volume average particle diameter of 100 nm or more
  • the core-shell type elastic body (C) relates to a resin composition containing a phosphoric
  • the present invention it is possible to provide a polycarbonate resin composition having a good balance of impact resistance, flame retardance, and fluidity during melting, and a molded article thereof. Further, according to a preferred embodiment of the present invention, since flame retardancy can be improved, it is possible to obtain the advantage that the amount of flame retardant added to the polycarbonate resin composition can be reduced.
  • the polycarbonate resin composition according to the present disclosure contains at least a polycarbonate resin (A), an amorphous polyester resin (B), a core-shell type elastic body (C), and a flame retardant (D).
  • Polycarbonate resin (A) As the polycarbonate resin (A), commonly used polycarbonate resins can be used. For example, polycarbonate resins produced by interfacial polycondensation of divalent phenol and carbonyl halide, or by melt polymerization of divalent phenol and carbonic acid diester (ester exchange method), etc. can be used.
  • divalent phenol examples include 4,4'-dihydroxybiphenyl, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, and 2,2-bis(4-hydroxyphenyl).
  • propane 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl) Cyclohexane, bis(4-hydroxyphenyl) ether, bis(4-hydroxyphenyl) sulfide, bis(4-hydroxyphenyl) sulfone, bis(4-hydroxyphenyl) sulfoxide, bis(4-hydroxyphenyl) ketone, hydroquinone, resorcinol , catechol, and the like.
  • bis(hydroxyphenyl)alkanes are preferred, and 2,2-bis(4-hydroxyphenyl)propane is particularly preferred.
  • carbonate precursors include carbonyl halides, carbonyl esters, haloformates, and the like. Specifically, phosgene; diaryl carbonates such as dihaloformates of divalent phenols, diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, and m-cresyl carbonate; dimethyl carbonate, diethyl carbonate, diisopropyl carbonate, dibutyl carbonate, and diaryl carbonate; Examples include aliphatic carbonate compounds such as mill carbonate and dioctyl carbonate.
  • the polycarbonate resin may be a resin in which the molecular structure of the polymer chain is a linear structure, or may be a resin in which the molecular structure of the polymer chain is a branched structure.
  • branching agents for introducing such a branched structure include 1,1,1-tris(4-hydroxyphenyl)ethane, ⁇ , ⁇ ', ⁇ ''-tris(4-hydroxyphenyl)-1, Examples include 3,5-triisopropylbenzene, phloroglucin, trimellitic acid, isatin bis(o-cresol), etc.
  • molecular weight regulators phenol, pt-butylphenol, pt-octylphenol, p-cumyl Phenol etc. can be used.
  • the polycarbonate resin may be a polymer having only a polycarbonate structural unit, which is produced using only the divalent phenol and a carbonate precursor, but it may have a polycarbonate structural unit and a polyorganosiloxane structural unit. It may be a copolymer, or it may be a resin composition containing the polymer and the copolymer. It may also be a polyester-polycarbonate resin obtained by carrying out a polymerization reaction of divalent phenol or the like in the presence of a difunctional carboxylic acid such as terephthalic acid or its ester-forming precursor.
  • the polycarbonate resin composition according to the present disclosure contains an amorphous polyester resin (B).
  • amorphous polyester resin (B) By blending the amorphous polyester resin (B), crystallization of the polyester phase in the polycarbonate resin composition is suppressed, distortion caused by the polyester phase is less likely to occur, and the impact of the polycarbonate resin composition is reduced. Strength and flame retardancy can be increased.
  • the polyester resin may be an aromatic polyester having a structure in which an aromatic dicarboxylic acid or an ester derivative component thereof and a diol component such as an aliphatic diol or an alicyclic diol are linked through an ester reaction.
  • the polyester resin for example, one obtained by polycondensing the above-mentioned components by a known method can be used.
  • Aromatic dicarboxylic acids are not particularly limited, but include, for example, terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalene dicarboxylic acid, 2,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,2' -Biphenyldicarboxylic acid, 3,3'-biphenyldicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-diphenyl etherdicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid , 4,4'-diphenylisopropylidenedicarboxylic acid, 1,2-bis(phenoxy)ethane-4,4'-dicarboxylic acid, 2,5-anthracenedicarboxylic acid, 2,6-anthracenedicarboxylic
  • the aliphatic diol is not particularly limited, but includes, for example, ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, 2-methyl-1,3-propanediol, diethylene glycol, triethylene glycol, and the like.
  • Examples of the alicyclic diol include 1,4-cyclohexanedimethanol.
  • the diol component only one type may be used, or two or more types may be used in combination.
  • the polyester resin may have a structural component derived from a trifunctional or higher functional monomer such as glycerin, trimethylolpropane, pentaerythritol, trimellitic acid, and pyromellitic acid.
  • a trifunctional or higher functional monomer such as glycerin, trimethylolpropane, pentaerythritol, trimellitic acid, and pyromellitic acid.
  • the amorphous polyester resin that is component (B) can usually be identified by not having a clear endothermic peak in differential scanning calorimetry (DSC).
  • a clear endothermic peak refers to a peak whose half-width is within 15° when measured at a heating rate of 10°C/min in differential scanning calorimetry (DSC). say.
  • a polyester resin having a clear endothermic peak is called a crystalline polyester resin.
  • the amorphous polyester resin usually has a relatively high glass transition temperature (Tg). Specifically, the amorphous polyester resin preferably has a Tg of 40 to 90°C, more preferably 45 to 85°C. Tg can be measured using a differential scanning calorimeter.
  • the content of the amorphous polyester resin (B) is 15 to 35% by weight of the total of the polycarbonate resin (A) and the amorphous polyester resin (B). It is. If the content of the amorphous polyester resin (B) is less than 15% by weight, good impact resistance may not be achieved or fluidity during melting may become insufficient. Moreover, if it exceeds 35% by weight, good impact resistance and/or flame retardancy may not be achieved.
  • the content of the amorphous polyester resin (B) is preferably 20 to 35% by weight, more preferably 25 to 30% by weight.
  • the amorphous polyester resin (B) contains at least glycol-modified polyethylene terephthalate (b1). Thereby, the impact resistance and/or flame retardance of the polycarbonate resin composition can be improved.
  • Glycol-modified polyethylene terephthalate (b1) refers to a copolymer containing at least terephthalic acid, ethylene glycol, and 1,4-cyclohexanedimethanol (CHDM) as monomer components.
  • Specific examples include PETG resin and PCT resin. Only one type of these may be used, or two or more types may be used in combination. Among these, it is preferable to use PETG resin.
  • PETG resins include, for example, Easter GN-001, Easter GN-071, Easter 6763, etc. manufactured by Eastman Chemical Company, USA.
  • PCT resins include, for example, Eastman Chemical Co., USA, under the trade name Easter DN-001, Kodar THERM X6761, Easter AN-004, and Tritan TX1501HF.
  • the amorphous polyester resin (B) may be composed only of glycol-modified polyethylene terephthalate (b1), but may contain amorphous polyethylene terephthalate (b2) in addition to (b1). Good too.
  • Amorphous polyethylene terephthalate refers to polyethylene terephthalate other than glycol-modified polyethylene terephthalate, and highly transparent polyethylene terephthalate that does not substantially have a crystal structure.
  • the amorphous polyethylene terephthalate can be produced by rapid cooling to facilitate development of a crystalline structure.
  • Amorphous polyethylene terephthalate is commonly known as A-PET.
  • recycled polyethylene terephthalate recovered from PET bottles or the like may be used as (b2)
  • the content of glycol-modified polyethylene terephthalate (b1) is 15 to 100% by weight or more. If the content of glycol-modified polyethylene terephthalate (b1) is less than 15% by weight, good impact resistance and/or flame retardance may not be achieved. From the viewpoint of impact resistance and/or flame retardancy, the content of glycol-modified polyethylene terephthalate (b1) is preferably 30% by weight or more, preferably 40% by weight or more, and more preferably 50% by weight or more. It is even more preferably 70% by weight or more, particularly preferably 80% by weight or more.
  • the resin composition according to the present disclosure contains a core-shell type elastic body (C). Thereby, good impact resistance can be achieved.
  • the core-shell type elastic body (C) may be composed of polymer particles that are a graft copolymer.
  • the core-shell type elastic body (C) preferably consists of a shell layer and one or more core layers.
  • the shell layer refers to a polymer layer located on the surface side of a polymer particle, and is also referred to as a graft layer.
  • the core layer refers to a polymer layer located inside the polymer particle than the shell layer, and is composed of a rubbery polymer.
  • the core layer may be composed of only one layer, or may be composed of two or more layers having mutually different monomer compositions.
  • the shell layer covers the surface of the core layer, but is not limited to covering the entire surface of the core layer, and may just cover at least a portion of the surface of the core layer.
  • the core layer is composed of a rubbery polymer.
  • the rubbery polymer preferably contains one or more selected from the group consisting of natural rubber, diene rubber, acrylate rubber, and polyorganosiloxane rubber, including diene rubber, acrylate rubber, and polyorganosiloxane rubber. It is more preferable to include one or more selected from the group consisting of rubbers.
  • a diene rubber is an elastic body containing a constitutional unit derived from a diene monomer as a constitutional unit.
  • the core layer is made of a diene-based material because the glass transition temperature of the resulting elastic body can be lowered, the resulting polycarbonate-based resin composition has a high impact resistance improvement effect on molded products, and the raw material cost is low. It is more preferable to contain rubber, and diene rubber is particularly preferable.
  • diene monomer examples include 1,3-butadiene, isoprene (2-methyl-1,3-butadiene), and 2-chloro-1,3-butadiene. These diene monomers may be used alone or in combination of two or more.
  • the diene rubber may further contain, as a structural unit, a structural unit derived from a vinyl monomer other than the diene monomer copolymerizable with the diene monomer.
  • vinyl monomers other than diene monomers that can be copolymerized with diene monomers include (a) styrene, ⁇ -methylstyrene; Aromatic vinyl monomers such as , monochlorostyrene, and dichlorostyrene; (b) Vinyl carboxylic acids such as acrylic acid and methacrylic acid; (c) Ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and methyl methacrylate , (meth)alkyl acrylates such as ethyl methacrylate and butyl methacrylate; (d) hydroxyl group-containing vinyl monomers such as 2-hydroxyethyl methacrylate and 4-hydroxybutyl acrylate; (e) glycidyl methacrylate , 4-hydroxybutyl acrylate glycidyl ether, and other glycidyl group-containing vinyl monomers
  • the content of the structural unit derived from the vinyl monomer A in the diene rubber is not particularly limited.
  • the diene rubber contains 50 to 100% by weight of structural units derived from diene monomers and 0 to 50% by weight of structural units derived from vinyl monomer A out of 100% by weight of structural units. is preferred.
  • Diene rubber has polyfunctional monomers such as diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, divinylbenzene, allyl methacrylate, ethylene glycol dimethacrylate, and 1,3-butylene dimethacrylate as structural units. It may further contain a structural unit derived from. That is, these polyfunctional monomers may be used in the polymerization of diene rubber.
  • Suitable diene rubbers include butadiene rubber (polybutadiene rubber), styrene/butadiene copolymer rubber (poly(styrene/butadiene) rubber), poly(acrylonitrile/butadiene) rubber, butadiene/acrylic ester copolymer, etc. Can be mentioned.
  • Butadiene rubber is an elastic body containing 50 to 100% by weight of structural units derived from 1,3-butadiene in 100% by weight of structural units.
  • the diene rubber is preferably a butadiene rubber containing 50 to 100% by weight of structural units derived from 1,3-butadiene and 0 to 50% by weight of structural units derived from vinyl monomer A.
  • a 1,3-butadiene homopolymer containing 100% by weight of structural units derived from 1,3-butadiene is more preferable.
  • the glass transition temperature of the obtained elastic body can be lowered, the obtained polycarbonate resin composition can achieve good flame retardancy, the effect of improving impact resistance is high, and the raw material cost is low.
  • the core layer contains butadiene rubber or styrene/butadiene copolymer rubber.
  • (acrylate rubber) is an elastic body containing, as a structural unit, a structural unit derived from a (meth)acrylate monomer.
  • Examples of (meth)acrylate monomers include (a) methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and (meth)acrylate 2.
  • - Alkyl (meth)acrylates having an alkyl group having 1 to 22 carbon atoms such as ethylhexyl, octyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, behenyl (meth)acrylate, etc.
  • Aromatic ring-containing (meth)acrylic esters such as phenoxyethyl (meth)acrylate and benzyl (meth)acrylate;
  • (e ) (meth)acrylic acid alkoxyalkyl esters and the like are examples of these (meth)acrylate monomers may be used alone or in combination of two or more.
  • the acrylate rubber may further contain, as a structural unit, a structural unit derived from a vinyl monomer other than the (meth)acrylate monomer that is copolymerizable with the (meth)acrylate monomer.
  • Vinyl monomers other than (meth)acrylate monomers that can be copolymerized with (meth)acrylate monomers include (a) the diene monomers mentioned above, and (b) vinyl monomers. Monomers other than (meth)acrylate monomers among body A may be mentioned.
  • the acrylic rubber has a crosslinked structure.
  • a crosslinking agent and/or a grafting agent can be used when polymerizing the monomer components to synthesize the polymer of the core layer.
  • crosslinking agents and grafting agents include (a) allyl (meth)acrylates such as allyl (meth)acrylate and allyl alkyl (meth)acrylate; (b) monoethylene glycol di(meth)acrylate and triethylene glycol di(meth)acrylate; Polyfunctional (meth)acrylates such as (meth)acrylate and tetraethylene glycol di(meth)acrylate; (c) Polyfunctional monomers such as diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, and divinylbenzene Examples include. These crosslinking agents and grafting agents may be used alone or in combination of two or more.
  • Suitable examples of the acrylate rubber include acrylate rubbers such as polybutyl acrylate rubber and butyl acrylate/2-ethylhexyl acrylate copolymer rubber.
  • Polybutyl acrylate rubber is an elastic body containing 50 to 100% by weight of structural units derived from butyl acrylate out of 100% by weight of structural units.
  • Suitable examples of the polyorganosiloxane rubber include silicone rubber and silicone/acrylate rubber.
  • silicone rubber examples include polymethyl silicone rubber and polymethylphenyl silicone rubber.
  • silicone/acrylate rubber examples include polyorganosiloxane/butyl acrylate copolymer.
  • the core layer preferably includes one or more selected from the group consisting of butadiene rubber, styrene/butadiene copolymer rubber, acrylate rubber, and silicone rubber, which improves impact resistance and reduces cost. From this point of view, it is more preferable to include butadiene rubber or styrene/butadiene copolymer rubber.
  • the weight ratio of the core layer to the entire core-shell elastic body (C) is 50 to 99% by weight from the viewpoint of compatibility between the core-shell elastic body (C) and the polycarbonate resin and from the viewpoint of improving impact resistance. is preferable, 60 to 95% by weight is more preferable, and even more preferably 70 to 90% by weight.
  • the shell layer is preferably formed from a polymer containing a structural unit derived from a vinyl monomer.
  • the vinyl monomer include aromatic vinyl compounds, vinyl cyanide compounds, unsaturated carboxylic acid esters, acrylamide monomers, maleimide monomers, and the like.
  • aromatic vinyl compounds examples include styrene, ⁇ -methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, t-butylstyrene, ⁇ -methylvinyltoluene, dimethylstyrene, chlorstyrene, and dichlorostyrene. , bromostyrene, dibromstyrene, etc. are preferably mentioned.
  • Suitable examples of the vinyl cyanide compound include acrylonitrile, methacrylonitrile, ethacrylonitrile, and the like.
  • Examples of the unsaturated carboxylic acid ester include (a) methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, dodecyl acrylate, stearyl acrylate, behenyl acrylate, etc.
  • acrylamide monomer examples include acrylamide, methacrylamide, N-methylacrylamide, and the like.
  • the maleimide monomers include N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-hexylmaleimide, N-octylmaleimide, N-dodecylmaleimide, N-cyclohexylmaleimide, N- -Phenylmaleimide, etc. are preferably mentioned.
  • the polymer constituting the shell layer preferably contains at least one member selected from the group consisting of methyl methacrylate, styrene, and butyl acrylate as a constituent monomer. Note that these may be used alone or in combination of two or more.
  • the polymer constituting the shell layer has at least one constituent monomer selected from the group consisting of a carboxyl group-containing vinyl monomer, a hydroxyl group-containing vinyl monomer, and a glycidyl group-containing vinyl monomer. It may further contain one type of reactive vinyl monomer.
  • the reactive vinyl monomer as a constituent monomer in the shell layer, it is possible to impart reactivity with the polycarbonate resin to the core-shell type elastic body (C), and as a result, in the polycarbonate resin, The dispersibility of the core-shell type elastic body (C) is improved, and the effect of improving impact resistance can be enhanced.
  • the reactive vinyl monomers carboxyl group-containing vinyl monomers are preferred because they have particularly good reactivity with polycarbonate resins.
  • the reactive vinyl monomers may be used alone or in combination of two or more.
  • carboxyl group-containing vinyl monomer examples include acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, fumaric acid, isocrotonic acid, vinyloxyacetic acid, allyloxyacetic acid, 2-(meth)acryloylpropanoic acid, 3-( Preferred examples include meth)acryloylbutanoic acid, 4-vinylbenzoic acid, 2-methacryloyloxyethylsuccinic acid, 2-methacryloyloxyethylmaleic acid, 2-methacryloyloxyethyl phthalic acid, and 2-methacryloyloxyethylhexahydrophthalic acid. It will be done. Among these, acrylic acid and/or methacrylic acid are preferred, and methacrylic acid is more preferred.
  • the hydroxyl group-containing vinyl monomers include hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and (meth)acrylate.
  • Preferred examples include (meth)acrylic acid hydroxyalkyl esters having an alkyl group having 1 to 22 carbon atoms and a hydroxyl group, such as 4-hydroxybutyl acrylate.
  • Suitable examples of the glycidyl group-containing vinyl monomer include glycidyl (meth)acrylate.
  • the amount of the reactive vinyl monomer used can be appropriately set depending on the desired effect, and is not particularly limited, but if the reactive vinyl monomer is a carboxyl group-containing vinyl monomer, the core-shell type
  • the proportion of the carboxyl group-containing vinyl monomer in the entire polymer particles serving as the elastic body (C) may be, for example, 0.01 to 5% by weight.
  • the weight ratio of the shell layer to the entire core-shell type elastic body (C) is 1 to 50% by weight from the viewpoint of compatibility between the core-shell type elastic body (C) and the polycarbonate resin and the effect of improving impact resistance. is preferable, 5 to 40% by weight is more preferable, and even more preferably 10 to 30% by weight.
  • the volume average particle diameter of the core-shell type elastic body (C), which is a polymer particle is 100 nm or more from the viewpoint of improving impact resistance. Since impact resistance tends to improve as the particle size increases, the volume average particle size is preferably 120 nm or more, more preferably 150 nm or more, even more preferably 200 nm or more, and particularly preferably 250 nm or more. On the other hand, when the particle size of the polymer particles becomes large, the polymerization reaction takes time and productivity tends to decrease. Therefore, the volume average particle size is preferably 700 nm or less, more preferably 500 nm or less.
  • volume average particle diameter of the polymer particles is a value measured by using a particle diameter measuring device in the latex state of the polymer particles, as shown in the Examples section. Further, the volume average particle diameter of the polymer particles can also be calculated from a transmission electron microscope (TEM) image of the polycarbonate resin composition.
  • the particle size of the polymer particles can be controlled by the type and amount of the polymerization initiator, chain transfer agent, redox agent, emulsifier, etc., polymerization temperature, polymerization time, etc.
  • the method for producing the core-shell type elastic body (C) may be any conventional method and is not particularly limited.
  • any one of bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization can be employed, but emulsion polymerization, that is, emulsion graft polymerization is preferable.
  • emulsion graft polymerization first, a latex of particles corresponding to the core layer is produced by emulsion polymerization, and monomer components for the shell layer, a polymerization initiator, etc. are added to the latex, and the monomer components are polymerized. do it.
  • a phosphoric acid emulsifier or a sulfonic acid emulsifier is used because it can suppress the decomposition of the polycarbonate resin and improve the impact resistance and/or flame retardance of the resin composition. It is preferable.
  • Specific examples of phosphoric acid emulsifiers or sulfonic acid emulsifiers include alkyl sulfate salts, alkylbenzene sulfonate salts, alkyl phosphoric acid ester salts, and the like. These may be used alone or in combination of two or more.
  • the resulting core-shell type elastomer (C) may contain the phosphoric acid emulsifier or the sulfonic acid emulsifier.
  • Ethylenediaminetetraacetic acid disodium salt, sodium formaldehyde sulfoxylate, ferrous sulfate, etc. may be used as a cocatalyst for polymerization, sodium sulfate, etc. may be used as a latex viscosity modifier, and sodium hydroxide, etc. may be used as a pH adjuster.
  • Radical initiators used in the emulsion polymerization method include organic hydroperoxides such as t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, para-menthane hydroperoxide, and t-butyl peroxylaurate; A redox initiator consisting of a combination of an oxidizing agent consisting of the above organic hydroperoxides and a reducing agent such as sulfite, hydrogen sulfite, thiosulfate, first metal salt, sodium formaldehyde sulfoxylate; potassium persulfate; Persulfates such as ammonium persulfate; azo compounds such as azobisisobutyronitrile, dimethyl-2,2'-azobisisobutyrate, and 2-carbamoylazaisobutyronitrile; benzoyl peroxide, lauroyl peroxide, etc. Organic peroxides and the like can be
  • chain transfer agents used in the emulsion polymerization method include mercaptans such as octylmercaptan, n-dodecylmercaptan, t-dodecylmercaptan, n-hexylmercaptan, n-hexadecylmercaptan, n-tetradecylmercaptan, and t-tetradecylmercaptan.
  • mercaptans such as octylmercaptan, n-dodecylmercaptan, t-dodecylmercaptan, n-hexylmercaptan, n-hexadecylmercaptan, n-tetradecylmercaptan, and t-tetradecylmercaptan.
  • hydrocarbon salts such as tetraethylthiuram sulfide, carbon tetrachloride, ethylene bromide, and pentane phenylethane; terpenes, acrolein, methacrolein, allyl alcohol, 2-ethylhexylthioglycol, ⁇ -methylstyrene dimer, and the like.
  • the chain transfer agent is preferably a mercaptan, more preferably t-dodecylmercaptan. These may be used alone or in combination of two or more.
  • the polymerization time can be changed depending on the monomers, emulsifiers, radical initiators, chain transfer agents used if necessary, and their amounts, but may be, for example, 1 hour to 50 hours, preferably 5 hours. Hours to 24 hours.
  • the polymerization temperature can be adjusted depending on the monomers, emulsifiers, radical initiators, chain transfer agents used if necessary, and their amounts, and may be, for example, 10°C to 90°C, preferably 40°C. °C ⁇ 80°C.
  • the latex containing the obtained core-shell type elastic body (C) may be powdered, for example, by a coagulation method.
  • a method is used in which the latex obtained by the emulsion polymerization method is treated with a coagulation method such as salt coagulation or acid coagulation, a method in which powder is obtained by spray drying the latex, etc. be able to.
  • the latex may be brought into contact with a coagulant such as an inorganic salt (preferably a divalent inorganic salt, more preferably calcium chloride) or an acid.
  • a core-shell type elastic body (C) may be prepared by further performing heat treatment, dehydration, washing, drying steps, etc.
  • a water-soluble electrolyte or acid group-containing copolymer latex is added, and the particles are added before or during graft polymerization.
  • Methods for enlarging the Methods for enlarging cells using water-soluble electrolytes are disclosed in JP-A-4-170458 and JP-A-60-192754. Methods for enlarging the tissue using acid group-containing copolymer latex are disclosed in JP-A-10-245468 and JP-A-8-12704.
  • an enlarged product of such a core-shell type elastic body can also be used, and in particular, a core-shell type elastic body enlarged using an acid group-containing copolymer latex, that is, an enlarged acid latex product is preferably used. can do.
  • Examples of commercial products of the core-shell type elastic body (C) include Kane Ace (registered trademark) M724 (manufactured by Kaneka Corporation), Kane Ace (registered trademark) M711 (manufactured by Kaneka Corporation), and the like.
  • the blending amount of the core-shell type elastic body (C) in the polycarbonate resin composition according to the present embodiment is 1 to 1 to 100 parts by weight in total of the polycarbonate resin (A) and the amorphous polyester resin (B). It is 30 parts by weight.
  • the blending amount of the core-shell type elastic body (C) is within the above range, it is possible to provide a polycarbonate resin composition with a good balance of impact resistance, flame retardance, and fluidity during melting.
  • the blending amount is preferably 3 to 25 parts by weight, more preferably 5 to 20 parts by weight.
  • the polycarbonate resin composition according to the present disclosure contains a flame retardant.
  • the flame retardant (D) By blending the flame retardant (D) with the amorphous polyester resin (B), the flame retardancy of the polycarbonate resin composition can be significantly improved.
  • flame retardant various flame retardants known as flame retardants blended into thermoplastic resins can be used. Although not particularly limited, examples include flame retardants described in "Techniques and Applications of Polymer Flame Retardation" (pages 149 to 221) published by CMC Publishing.
  • brominated flame retardants such as tetrabromobisphenol A and decabromodiphenyl oxide
  • halogenated flame retardants such as chlorinated paraffin and chlorinated polyethylene
  • non-halogen phosphate flame retardants non-halogen phosphate flame retardants (monophosphates)
  • Phosphorus flame retardants such as halogen-containing phosphate flame retardants (monophosphate/condensation), inorganic phosphate flame retardants, red phosphorus flame retardants; antimony trioxide, aluminum hydroxide, hydroxide
  • inorganic flame retardants such as magnesium; organic salt flame retardants, silicone flame retardants, and the like. These may be used alone or in combination of two or more.
  • Preferred flame retardants include halogenated bisphenol A, halogenated polycarbonate oligomers, polycarbonate-type flame retardants of halogenated bisphenol A; halogen compounds that combine halogen compounds such as brominated epoxy compounds and flame retardant aids such as antimony oxide.
  • Organic salt flame retardants Phosphorus flame retardants such as aromatic phosphate ester flame retardants and halogenated aromatic phosphate ester flame retardants; Branched phenyl silicone compounds, phenyl silicone resins, etc. Examples include silicone flame retardants such as polysiloxane.
  • halogenated bisphenol A polycarbonate flame retardant examples include a tetrabromobisphenol A polycarbonate flame retardant, a copolymerized polycarbonate flame retardant of tetrabromobisphenol A and bisphenol A, and the like.
  • organic salt flame retardants examples include dipotassium diphenylsulfone-3,3'-disulfonate, potassium diphenylsulfone-3-sulfonate, sodium 2,4,5-trichlorobenzenesulfonate, and 2,4,5-dipotassium diphenylsulfone-3-disulfonate.
  • Potassium trichlorobenzenesulfonate potassium bis(2,6-dibromo-4-cumylphenyl)phosphate, sodium bis(4-cumylphenyl)phosphate, potassium bis(p-toluenesulfone)imide, potassium bis(diphenylphosphate)imide , potassium bis(2,4,6-tribromophenyl) phosphate, potassium bis(2,4-dibromophenyl) phosphate, potassium bis(4-bromophenyl) phosphate, potassium diphenyl phosphate, sodium diphenyl phosphate , potassium perfluorobutanesulfonate, sodium or potassium lauryl sulfate, sodium or potassium hexadecyl sulfate, and the like.
  • halogenated aromatic phosphate flame retardant examples include tris(2,4,6-tribromophenyl) phosphate, tris(2,4-dibromophenyl) phosphate, tris(4-bromophenyl) phosphate, etc. can be mentioned.
  • aromatic phosphate flame retardants examples include triphenyl phosphate, tris(2,6-xylyl) phosphate, tetrakis(2,6-xylyl)resorcin diphosphate, and tetrakis(2,6-xylyl)hydroquinone diphosphate.
  • Aromatic polyphosphates which are phenol and do not contain phenolic hydroxyl groups (OH groups), aromatic polyphosphates whose aromatic ring sources are resorcinol and phenol and which contain phenolic OH groups, aromatic polyphosphates whose aromatic ring sources are hydroquinone and phenol and which are phenolic OH groups.
  • Aromatic polyphosphates containing no groups, aromatic polyphosphates whose aromatic ring sources are hydroquinone and phenol and which contain phenolic OH groups aromatic polyphosphates whose aromatic ring sources are bisphenol A and phenol; aromatic polyphosphates whose aromatic ring sources are tetrabromobisphenol A and phenol; Aromatic polyphosphates whose ring sources are resorcin and 2,6-xylenol, aromatic polyphosphates whose aromatic ring sources are hydroquinone and 2,6-xylenol, aromatic whose aromatic ring sources are bisphenol A and 2,6-xylenol Examples include aromatic polyphosphates whose aromatic ring sources are tetrabromobisphenol A and 2,6-xylenol.
  • the blending amount of the flame retardant (D) is based on a total of 100 parts by weight of the polycarbonate resin (A) and the amorphous polyester resin (B). , preferably 1 to 80 parts by weight, more preferably 5 to 60 parts by weight, particularly preferably 10 to 40 parts by weight.
  • flame retardance can be improved compared to conventional compositions, so it is possible to reduce the amount of flame retardant blended.
  • further improvement in impact resistance can be expected by reducing the amount of flame retardant blended.
  • the polycarbonate resin composition according to this embodiment may contain an anti-drip agent for the purpose of preventing melt dripping during combustion.
  • the anti-drip agent include fluoroolefin resins containing fluoroolefin resin as a main component.
  • Fluoroolefin resins are polymers, copolymers, or composites that include fluoroethylene structures.
  • fluoroolefin resins include difluoroethylene polymers, tetrafluoroethylene polymers, tetrafluoroethylene-hexafluoropropylene copolymers, copolymers of tetrafluoroethylene and fluorine-free ethylene monomers, and tetrafluoroethylene.
  • polytetrafluoroethylene examples include composites of polymers and vinyl resins such as acrylic resins.
  • PTFE polytetrafluoroethylene
  • the weight average molecular weight of polytetrafluoroethylene is preferably 500,000 or more, particularly preferably 500,000 to 10,000,000.
  • polytetrafluoroethylene compounds having fibril-forming ability are preferred because they can provide even higher melt-drip prevention properties.
  • polytetrafluoroethylene having fibril-forming ability include compounds classified as Type 3 in ASTM standards.
  • polytetrafluoroethylene classified as type 3 include Teflon (registered trademark) 6-J (manufactured by DuPont Mitsui Fluorochemicals Co., Ltd.), Polyflon D-1, Polyflon F-103, and Polyflon F201 (manufactured by Daikin Industries, Ltd.). Co., Ltd.), CD1, CD076 (manufactured by Asahi ICI Fluoropolymers Co., Ltd.), and the like.
  • polytetrafluoroethylene other than compounds classified as type 3 examples include Hyflon F5 (manufactured by Montefluos Co., Ltd.), Polyflon MPA, Polyflon FA-100 (manufactured by Daikin Industries, Ltd.), and the like. These polytetrafluoroethylenes may be used alone or in combination of two or more.
  • the amount of anti-drip agent is 0 to 100 parts by weight in total of polycarbonate resin (A) and amorphous polyester resin (B) from the viewpoint of preventing melt dripping during combustion and achieving impact resistance.
  • the amount is preferably 0.05 to 5 parts by weight, more preferably 0.1 to 2 parts by weight.
  • the amount of anti-drip agent to be blended is determined based on the degree of flame retardancy required for the molded product, for example, UL94 V-0, V-1, V-2, etc., and also takes into consideration the amount of other components. It can be determined as appropriate.
  • the polycarbonate resin composition according to the present embodiment may or may not contain thermoplastic resins other than the polycarbonate resin (A) and the amorphous polyester resin (B).
  • the polycarbonate resin composition according to the present embodiment may contain a crystalline polyester resin in addition to the amorphous polyester resin (B), but it achieves good impact resistance and flame retardancy. From this point of view, it is preferable that the content is small.
  • the content of the crystalline polyester resin is preferably 0 to 15 parts by weight with respect to a total of 100 parts by weight of the polycarbonate resin (A) and the amorphous polyester resin (B),
  • the amount is more preferably 0 to 10 parts by weight, and even more preferably 0 to 5 parts by weight. Further, the amount may be 0 to 1 part by weight, or 0 to 0.1 part by weight.
  • the definition of the crystalline polyester resin is as described above, and specific examples thereof include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polypropylene naphthalate, polybutylene naphthalate, and the like.
  • the thermoplastic resin is examples include, but are not limited to, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyvinyl acetate, polyurethane, polytetrafluoroethylene, ABS resin, AS resin, acrylic resin, polyacetal, modified polyphenylene ether, polyamide, cyclic polyolefin, etc. It will be done.
  • the amount of the other thermoplastic resin is not particularly limited, but for example, 0 to 100 parts by weight, preferably 0 to 100 parts by weight in total of the polycarbonate resin (A) and the amorphous polyester resin (B).
  • the amount is preferably 0 to 50 parts by weight, more preferably 0 to 30 parts by weight, even more preferably 0 to 10 parts by weight, particularly preferably 0 to 5 parts by weight.
  • the polycarbonate resin composition according to the present embodiment can appropriately contain additives that can be blended into general thermoplastic resin compositions.
  • additives are not particularly limited, but include, for example, reinforcing materials, fillers, antioxidants, pigments, dyes, conductivity imparting agents, hydrolysis inhibitors, thickeners, plasticizers, lubricants, and ultraviolet absorbers. , antistatic agents, fluidity improvers, mold release agents, compatibilizers, heat stabilizers and the like.
  • the method for manufacturing the polycarbonate resin composition according to this embodiment is not particularly limited, and any known method can be used.
  • it can be produced by a known method of blending and melt-kneading each component using an apparatus such as a Henschel mixer, a Banbury mixer, a single-screw extruder, a twin-screw extruder, a two-roll machine, a kneader, a Brabender, or the like.
  • the melt-kneading temperature is preferably as low as possible.
  • a molded article can be obtained by molding the polycarbonate resin composition according to this embodiment into a predetermined shape. Specifically, by extrusion molding the polycarbonate resin composition, it can be formed into extrusion molded bodies having various shapes, extrusion sheets, films, and the like. Extrusion molding methods include cold runner or hot runner molding, injection compression molding, injection press molding, gas-assisted injection molding, foam molding (including injection of supercritical fluid), insert molding, Examples of injection molding methods include in-mold coating molding, adiabatic mold molding, rapid heating and cooling mold molding, two-color molding, sandwich molding, and ultrahigh-speed injection molding. In addition, an inflation method, a calendar method, a casting method, etc.
  • the molded body made of the polycarbonate resin composition according to this embodiment can be used in a wide range of applications such as various housings, hard coat products, glazing materials, light diffusion plates, optical disk substrates, light guide plates, medical materials, and miscellaneous goods. be able to.
  • various containers, miscellaneous goods such as personal computers, notebook computers, game consoles, display devices (CRT, liquid crystal, plasma, projector, organic EL, etc.), mice,
  • exterior materials for printers, copiers, scanners, faxes including these multifunction devices
  • keyboard keys switch molded products
  • PDAs personal digital assistants
  • mobile phones mobile books (dictionaries, etc.), and mobile phones.
  • TVs drives for recording media (CD, MD, DVD, Blu-ray discs, hard disks, etc.), reading devices for recording media (IC cards, smart media, memory sticks, etc.), optical cameras, digital cameras, parabolic antennas, power tools, VTRs, It can be used as resin products formed into irons, hair dryers, rice cookers, microwave ovens, audio equipment, lighting equipment, refrigerators, air conditioners, air purifiers, negative ion generators, typewriters, etc.
  • binding tape binding band
  • prepaid card balloon, pantyhose, hair cap, sponge, cellophane tape, umbrella, coat, plastic gloves, hair cap, rope, tube, foam tray, foam cushioning material, It may also be a cushioning material, a packaging material, a cigarette filter, etc.
  • the molded body may be a vehicle part such as a lamp socket, a lamp reflector, a lamp housing, an instrumental panel, a center console panel, a deflector part, a car navigation part, a car audio visual part, an automobile computer part, etc. .
  • the core-shell type elastic body (C) includes a core layer containing butadiene rubber or styrene/butadiene copolymer rubber, and at least one constituent monomer selected from the group consisting of methyl methacrylate, styrene, and butyl acrylate. 2.
  • volume average particle diameter of core-shell type elastic body was measured in the latex state using a particle size analyzer (Nanotracwave, manufactured by Nikkiso Co., Ltd.) using light scattering at a wavelength of 546 nm.
  • ⁇ Manufacture example 1> ⁇ Preparation of polybutadiene rubber latex>
  • 200 parts of pure water 0.002 parts of ethylenediaminetetraacetic acid disodium salt, 0.0012 parts of ferrous sulfate, 1.5 parts of sodium polyoxyethylene alkyl ether phosphate, and t-dodecyl mercaptan.
  • 100 parts of butadiene, 0.05 parts of sodium formaldehyde sulfoxylate, and 0.2 parts of para-menthane hydroperoxide were added, and the pH of the reaction solution was adjusted to 6.5 to 7. 5 and held at 50° C.
  • ⁇ Production example 2> ⁇ Preparation of polybutadiene rubber latex> 200 parts of water, 0.2 parts of potassium persulfate, and 0.2 parts of t-dodecyl mercaptan were placed in a 100 liter pressure polymerization vessel, stirred, and after sufficient nitrogen substitution to remove oxygen, oleic acid 1 part of sodium, 2 parts of sodium rosinate, and 100 parts of butadiene were charged into the system, and the temperature was raised to 60°C to start polymerization. Polymerization was completed in 12 hours. The conversion rate was 96%, and the volume average particle diameter of the rubber latex was 70 nm.
  • Examples 1 to 7 and Comparative Examples 1 to 7> According to the formulation shown in Table 1, using each component shown below, pellets and test pieces made of a resin composition containing polycarbonate resin were prepared, and Charpy strength (impact strength), tensile properties, bending properties, HDT, flame retardancy, and MFR were measured. Note that MFR is an index indicating fluidity during melting. The larger the MFR value, the higher the fluidity during melting.
  • (B) Component Amorphous polyester resin, blending amount (wt%) listed in Table 1 ⁇ b1-1: Glycol-modified polyethylene terephthalate (Eastman Chemical Company, Easter GN-001) ⁇ b1-2: Glycol modified polyethylene terephthalate (manufactured by Eastman Chemical Co., Tritan TX1501HF) ⁇ b2-1: Amorphous polyethylene terephthalate (manufactured by Teijin, TRN-MTJ)
  • B' Component: Comparative resin, blending amount (wt%) listed in Table 1
  • ⁇ B'-1 ABS resin (manufactured by FCFC, AF3510)
  • ⁇ B'-2 Acrylonitrile-styrene resin (manufactured by Technopolymer, SAN-R)
  • (C) or (C') component core-shell type elastic body, amount listed in Table 1 [parts by weight based on the total of 100 parts by weight of components (A) and (B) or (B')]
  • ⁇ C-1 Manufactured by Kaneka Corporation, Kane Ace M724, volume average particle diameter 120 nm, containing phosphoric acid emulsifier ⁇ C-2: Manufactured by Kaneka Corporation, Kane Ace M711, volume average particle diameter 200 nm, containing sulfonic acid emulsifier ⁇ C-3: Core-shell type elastic body (C-3) manufactured in Production Example 1, volume average particle diameter 300 nm, containing phosphoric acid emulsifier ⁇ C'-1: Manufactured by Kaneka Corporation, Kane Ace B513, volume average particle diameter 75 nm, contains fatty acid emulsifier - C'-2: Kane Ace M701, manufactured by Kaneka Corporation, volume average particle diameter 210 nm, contains fatty acid emul
  • Component (D) flame retardant (aromatic condensed phosphoric acid ester, manufactured by Daihachi Kagaku Kogyo Co., Ltd., PX200), blending amount listed in Table 1 [total of components (A) and (B) or (B') Parts by weight per 100 parts by weight]
  • Anti-drip agent manufactured by Asahi Glass Co., Ltd., PTFE G355, 0.1 part by weight per 100 parts by weight in total of components (A) and (B) or (B') Stabilizer: manufactured by ADEKA Co., Ltd., ADEKA STAB 2112, and 0.1 part by weight per 100 parts by weight of the total of Adekastab AO-60, (A), and (B) or (B') components.
  • HDT load deflection temperature
  • MFR MFR value of the pellets produced under the above conditions was measured according to JIS K7210 A method at a measurement temperature of 250° C. and a load of 5 kg. Table 1 shows the results of the above measurements.
  • Comparative Example 1 in which the amorphous polyester resin (B) was not blended and a general ABS resin was blended instead, and Comparative Example 1 in which the amorphous polyester resin (B) was not blended and a common ABS resin was blended instead. It can be seen that Comparative Example 2, in which acrylonitrile-styrene resin was blended, did not have sufficient flame retardancy. Furthermore, it can be seen that Comparative Example 3, which contains the amorphous polyester resin (B) but has a high content ratio, also does not have sufficient flame retardancy.
  • Comparative Example 4 in which only amorphous polyethylene terephthalate (b2) was blended without glycol-modified polyethylene terephthalate (b1) as the amorphous polyester resin (B), had low impact resistance and sufficient flame retardancy. However, it can be seen that the MFR value is small and the fluidity during melting is insufficient. It can be seen that Comparative Examples 5 to 7 in which core-shell type elastic bodies containing no phosphoric acid emulsifier or sulfonic acid emulsifier were used did not have sufficient flame retardancy.

Landscapes

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

Abstract

L'invention concerne une composition de résine contenant une résine de polycarbonate (A), une résine de polyester amorphe (B), un corps élastique cœur-écorce (C), et un retardateur de flamme (D). La teneur en (B) est de 15 à 35 % en poids du total de (A) et de (B). Le (B) comprend un polyéthylène téréphtalate modifié par glycol (b1). La teneur en (b1) est de 15 à 100 % en poids du (B). La teneur en (C) est de 1 à 30 parties en poids pour 100 parties en poids du total de (A) et de (B). La taille de particule moyenne en volume du (C) est d'au moins 100 nm. Le (C) comprend un émulsifiant d'acide phosphorique ou un émulsifiant d'acide sulfonique en tant qu'émulsifiant.
PCT/JP2023/020343 2022-06-03 2023-05-31 Composition de résine de polycarbonate et article façonné WO2023234367A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2022-090728 2022-06-03
JP2022090728 2022-06-03

Publications (1)

Publication Number Publication Date
WO2023234367A1 true WO2023234367A1 (fr) 2023-12-07

Family

ID=89024936

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2023/020343 WO2023234367A1 (fr) 2022-06-03 2023-05-31 Composition de résine de polycarbonate et article façonné

Country Status (1)

Country Link
WO (1) WO2023234367A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001180162A (ja) * 1999-12-27 2001-07-03 Tsutsunaka Plast Ind Co Ltd カード
JP2010070715A (ja) * 2008-09-22 2010-04-02 Teijin Chem Ltd 難燃性芳香族ポリカーボネート樹脂組成物
JP2013018864A (ja) * 2011-07-11 2013-01-31 Teijin Chem Ltd ポリカーボネート樹脂組成物およびその成形品
JP2015117376A (ja) * 2013-11-18 2015-06-25 コニカミノルタ株式会社 熱可塑性樹脂組成物の製造方法
CN114213827A (zh) * 2021-12-13 2022-03-22 广东顺威赛特工程塑料开发有限公司 一种耐溶剂无卤阻燃pc/petg合金及其制备方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001180162A (ja) * 1999-12-27 2001-07-03 Tsutsunaka Plast Ind Co Ltd カード
JP2010070715A (ja) * 2008-09-22 2010-04-02 Teijin Chem Ltd 難燃性芳香族ポリカーボネート樹脂組成物
JP2013018864A (ja) * 2011-07-11 2013-01-31 Teijin Chem Ltd ポリカーボネート樹脂組成物およびその成形品
JP2015117376A (ja) * 2013-11-18 2015-06-25 コニカミノルタ株式会社 熱可塑性樹脂組成物の製造方法
CN114213827A (zh) * 2021-12-13 2022-03-22 广东顺威赛特工程塑料开发有限公司 一种耐溶剂无卤阻燃pc/petg合金及其制备方法

Similar Documents

Publication Publication Date Title
US9803082B2 (en) Polyorganosiloxane-containing graft copolymer, resin composition, and molded article
JP5303027B2 (ja) 相溶性が改善された難燃性−耐スクラッチ性熱可塑性樹脂組成物
JP6221744B2 (ja) ポリオルガノシロキサン含有グラフト共重合体、樹脂組成物、成形体、摺動性改良剤及び摺動部材
JP5111458B2 (ja) 芳香族ポリカーボネート樹脂組成物の真珠光沢を低減させる方法
JP5150494B2 (ja) 樹脂組成物
JP2012140588A (ja) 離型性及び外観特性に優れたポリカーボネート系樹脂組成物、並びにこれを用いた成形品
KR100979927B1 (ko) 신규한 (메타)아크릴레이트계 공중합체 및 이를 이용한 내스크래치성 열가소성 수지 조성물
JP5371973B2 (ja) 難燃性ポリカーボネート樹脂組成物
JP2019123809A (ja) ポリカーボネート樹脂組成物及び成形品
JPWO2018116607A1 (ja) ポリカーボネート樹脂組成物及び成形品
WO2011110365A1 (fr) Composition polymère de type carbonate résistant à l'inflammation et ayant une résistance aux chocs modifiée
JP7386159B2 (ja) 熱可塑性樹脂組成物およびこれから形成された成形品
EP2542622A1 (fr) Composition de polymère de carbonate ignifuge à écoulement amélioré
JP5893848B2 (ja) 芳香族ポリカーボネート樹脂組成物およびその成形品
JP5204814B2 (ja) 熱可塑性樹脂組成物
JP3128187B2 (ja) 難燃性ポリカーボネート樹脂組成物
JP5111456B2 (ja) 芳香族ポリカーボネート樹脂組成物をｏａ機器若しくは家電製品の外装材に使用する方法
WO2023234367A1 (fr) Composition de résine de polycarbonate et article façonné
KR100966050B1 (ko) 상용성이 우수한 열가소성 수지 조성물
JP2986691B2 (ja) 樹脂組成物および成形品
JP3649611B2 (ja) 難燃性ポリカーボネート樹脂組成物および成形品
WO2023149409A1 (fr) Composition de résine à base de polycarbonate et objet moulé
JP6465079B2 (ja) 摺動部材用熱可塑性樹脂組成物及び摺動部材
JP4100734B2 (ja) 熱可塑性樹脂組成物
KR101447276B1 (ko) 외관특성이 우수한 고충격 난연 내스크래치 수지 조성물 및 그 성형품

Legal Events

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

Ref document number: 23816124

Country of ref document: EP

Kind code of ref document: A1