WO2002055604A1 - Composition a base de resine de polycarbonate ignifuge, son procede de production et article moule - Google Patents

Composition a base de resine de polycarbonate ignifuge, son procede de production et article moule Download PDF

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Publication number
WO2002055604A1
WO2002055604A1 PCT/JP2002/000140 JP0200140W WO02055604A1 WO 2002055604 A1 WO2002055604 A1 WO 2002055604A1 JP 0200140 W JP0200140 W JP 0200140W WO 02055604 A1 WO02055604 A1 WO 02055604A1
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flame
mass
polycarbonate resin
component
resin composition
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PCT/JP2002/000140
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English (en)
Japanese (ja)
Inventor
Akio Nodera
Masahiro Kitayama
Toshio Isozaki
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Idemitsu Petrochemical Co., Ltd.
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Publication of WO2002055604A1 publication Critical patent/WO2002055604A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates

Definitions

  • the present invention relates to a flame-retardant polycarbonate resin composition, a method for producing the same, and a molded article. More specifically, the present invention relates to a flame-retardant polycarbonate resin composition capable of obtaining a molded article having an excellent appearance, a method for producing the same, and a molded article thereof.
  • Polycarbonate resins are excellent in impact resistance, heat resistance, electrical properties, dimensional stability, etc., so they are used in OA (office automation) equipment, information and communication equipment, home appliances and other electrical and electronic equipment fields, and automobiles. It is widely used in various fields such as field and construction field.
  • This polycarbonate resin is a self-extinguishing resin itself, but when used as a material for OA equipment, information / communication equipment, electricity / electronic equipment, etc. It is requested that the degree be further increased.
  • halogen-based flame retardants such as halogenated bisphenol A and halogenated polycarbonate oligomers are used together with flame retardant aids such as antimony oxide due to their high flame retardant efficiency.
  • flame retardant aids such as antimony oxide due to their high flame retardant efficiency.
  • flame-retardant polycarbonate resins using these halogen-based flame retardants have a great impact on the environment when burning incineration of wastes.Therefore, flame retardants using halogen-free flame retardants are required. ing. Therefore, as this non-halogen flame retardant, an organic phosphorus flame retardant, especially an organic phosphoric acid ester compound has the effect of acting as a plasticizer at the same time as imparting flame retardancy. Flame retardant polycarbonate resin composition Has been proposed.
  • molded articles of the flame-retardant polycarbonate resin composition using the organophosphate compound have a problem that when used in a high-temperature or high-temperature, high-humidity environment, the impact strength is reduced or discoloration occurs. is there. Furthermore, since the molded article of the flame-retardant polycarbonate resin composition has insufficient heat stability, there remains a problem that it is inferior in recyclability for resource saving.
  • Japanese Patent Application Laid-Open No. 50-98546 discloses that a small amount of a metal salt of a polymeric aromatic sulfonic acid, for example, sodium polystyrene sulfonate is compounded. It is proposed to make polycarbonate resin flame-retardant by doing so. However, when the polystyrene resin is sulfonated in a usual manner and then neutralized with sodium hydroxide, the polystyrene carbonate sodium salt is used to make the polycarbonate resin flame-retardant. Due to the poor dispersibility of the sodium sulfonate salt, there is a drawback that the molded article has poor appearance.
  • a metal salt of a polymeric aromatic sulfonic acid for example, sodium polystyrene sulfonate
  • the present invention has high flame retardancy, excellent recycling properties and antistatic performance while maintaining the inherent physical properties of a polycarbonate resin by simply adding a small amount of a flame retardancy-imparting component.
  • An object of the present invention is to provide a flame-retardant polycarbonate resin composition capable of obtaining a molded article having excellent appearance and a method for producing the same, and a molded article thereof. Disclosure of the invention
  • the present inventors have conducted various studies in order to solve the above-mentioned problems, and as a result, have found that a polycarbonate resin containing an acid group-containing aromatic vinyl resin having an inorganic metal salt content of less than 5% by mass has a specific ratio. It has been found that the above-mentioned object can be achieved according to the flame-retardant polycarbonate resin composition blended in the above, and the present invention has been completed based on these findings.
  • the gist of the present invention is as follows.
  • a polytetrafluoroethylene resin is used as the component (C), and a total of 100 parts by mass of the components (A) and (B) described in the above [1] is used.
  • a core / shell type elastomer is used as the component (D), and the amount of the elastomer is 0 with respect to 100 parts by mass of the total of the components (A) and (B) described in the above [1]. 0.1 to 10 parts by mass of the flame-retardant polycarbonate resin composition according to any one of the above [1] to [3].
  • a phosphate ester-based flame retardant as the component (E) is used in an amount of 0.01 to 0.1 parts by mass based on 100 parts by mass of the total of the components (A) and (B) described in the above [1].
  • the flame-retardant polycarbonate resin composition according to any one of the above [1] to [4], which is added with 30 parts by mass.
  • the acid-base-containing aromatic vinyl-based resin as the component (B) has a concentration of 10 to A method for producing a flame-retardant polycarbonate resin composition, which comprises spraying a component other than the component (B) in a solution of 60% by mass and kneading the mixture.
  • the present invention uses 95 to 99.99 mass of the polycarbonate resin as the component (A). / 6, and (B) a flame-retardant polycarbonate composed of an acid-base-containing aromatic vinyl resin having an inorganic metal salt content of less than 5% by mass, 0.0'1 to 5% by mass.
  • a resin composition This flame retardant polycarbonate In the resin composition, the content of the inorganic metal salt of the component (B) is less than 5% by mass, and the content of the acid-base-containing aromatic vinyl resin is at least 0.01% by mass. When the content is less than 0.01% by mass, the flame retardancy of the flame-retardant polycarbonate resin composition obtained is insufficient.
  • the content is 5% by mass or less is that the mixing ratio of the component (B) is 5% by mass. Even if it is less than / 0 , flame retardancy can be sufficiently imparted, and if the blending ratio exceeds 5% by mass, the physical properties of the obtained flame retardant polycarbonate resin composition will be reduced. Because it becomes sick.
  • the flame-retardant polycarbonate resin composition of the present invention may be used, if necessary, with respect to 100 parts by mass of the resin composition having the basic structure composed of the components (A) and (B). 0.01 to 5 parts by mass of a polytetrafluoroethylene resin as the component (C), and 0.01 to 10 parts by mass of a core / chenore type elastomer as the component (D).
  • a phosphoric ester-based flame retardant can be added in a mixing ratio of 0.01 to 30 parts by mass.
  • the content of the polycarbonate resin of the component (A) and the content of the inorganic metal salt of the component (B) are 5% by mass.
  • the polycarbonate resin of the component (A) used as a raw material of the flame-retardant polycarbonate resin composition of the present invention is not particularly limited, and examples thereof include polycarbonate resins having various structural units. Normally, aromatic poly- lysates produced by the reaction of divalent phenols and carbonate precursors. Carbonate can be used. That is, a product produced by reacting a divalent phenol and a precursor of a carbonic acid by a solution method or a melting method can be used.
  • divalent phenol examples include 4,4, dihydroxybiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2— bis (4-arsenate Dorokishifu Eniru) Purono ⁇ 0 emissions, 2, 2 - bis (3 - Mechinore one 4-arsenide Dorokishifue two / Les) Puroha 0 emissions, 2, 2 _ bis (3, 5 - Jimechinore 4 - arsenide Dorokishi Phenyl) propane, 1, 1-bis (4-hydroxypheninole) hex Mouth hexane, bis (4-hydroxypheninole) athenole, bis (41hydroxydrenopheninole) snorveid, bis (4-hen) Droxifene) Snorehon, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) ketone, hydroquinone, rezonolecin And cate
  • divalent phenols bis (hydroxyphenyl) alpines are preferred, and those containing 2,2-bis (4-hydroxyphenyl) propane as a main raw material are particularly preferred.
  • the carbonate precursor include carbonyl halide, carbonyl ester, and haloformate. Specific examples thereof include phosgene, dihalo honolemate of divalent phenol, dipheninocarbonate, dimethyl carbonate, and getylcapbonate.
  • the polycarbonate resin may have a branched structure in addition to a molecular structure of a polymer chain having a linear structure.
  • molecular weight regulator phenol, p_t-butynolephenol, p-t-octylphenol, p-cumylphenol and the like can be used.
  • the polycarbonate resin used in the present invention in addition to the homopolymer produced using only the above divalent phenol, a copolymer having a polycarbonate structural unit and a polyorganosiloxane structural unit.
  • a resin composition comprising these homopolymer and copolymer may be used.
  • it may be a polyester-polycarbonate resin obtained by performing a polymerization reaction of polycarbonate in the presence of a bifunctional carboxylic acid such as terephthalic acid or an ester precursor such as an ester-forming derivative thereof.
  • resin compositions obtained by melt-kneading polycarbonate resins having various structural units can also be used.
  • the polycarbonate resin of the component (A) in the present invention those having substantially no halogen atom in the structural unit are preferably used.
  • the polycarbonate resin used as the component (A) preferably has a viscosity average molecular weight of 100,000 to 100,000. If the viscosity average molecular weight is less than 100,000, the resulting resin composition has insufficient thermal and mechanical properties, and the viscosity average molecular weight is less than 100,000. If the ratio exceeds the above, the moldability of the obtained resin composition will decrease.
  • the viscosity average molecular weight of the polycarbonate resin is more preferably from 11,000 to 40,000, and still more preferably from 12,000 to 30,000.
  • the acid-base-containing aromatic vinyl resin (B) used as a raw material of the flame retardant polycarbonate resin composition of the present invention is an aromatic vinyl thermoplastic resin.
  • the aromatic vinyl resin containing the acid base as the component (B) in the present invention, the content of the inorganic metal salt remaining in the aromatic vinyl resin containing the acid base is reduced to less than 5% by mass. Use the one that was made. More preferred as the component (B) is an acid-base-containing aromatic vinyl resin in which the content of the inorganic metal salt is reduced to less than 3% by mass.
  • the aromatic vinyl resin includes polystyrene, rubber-modified polystyrene, styrene-acrylonitrile copolymer, and acrylonitrile.
  • Thermoplastic resins that have at least peach ⁇ ⁇ that comes to styrene in the chain can be used.
  • a polystyrene resin is particularly preferably used.
  • Examples of the acid base substituted with a hydrogen atom of the aromatic ring in the aromatic vinyl resin include, for example, alkali metal salts such as a sulfonic acid group, a borate group and a phosphoric acid group, and alkaline earth metals. Metal salts, ammonium salts and the like. Further, the substitution ratio of these acid bases is not particularly limited, and can be appropriately selected, for example, within a range of 10 to 100%.
  • an acid-base-containing polystyrene resin suitable as the acid-base-containing aromatic vinyl resin is represented by the following general formula (1)
  • X represents an acid base
  • ⁇ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.
  • m represents an integer of 1 to 5
  • n represents a mole fraction of a structural unit derived from styrene substituted with an acid base, and 0 ⁇ n ⁇ 1.
  • the acid-base containing polystyrene resin represented by these is preferable.
  • the acid base represented by X is preferably a sulfonate group, a borate group or a phosphate group, and is preferably an alkali metal such as sodium or potassium of these acids. Salt, magnesium and calcium Alkaline earth metal salts, aluminum salts, lead salts, tin salts, ammonium salts and the like are preferred.
  • a hydrogen atom is preferable as Y in the general formula (1), and a methyl group is preferable as the hydrocarbon group.
  • an aromatic vinyl monomer having a sulfone group or the like as a monomer or a copolymerizable with them.
  • the mixture may be sulfonated, neutralized with a basic substance, and then purified.
  • aromatic vinyl polymer When the aromatic vinyl polymer is sulfonated, neutralized, and purified, for example, a polystyrene solution is added to a 1,2-dichloroethane solution of polystyrene resin by adding sulfuric anhydride to cause a reaction. Sulfonic acid is produced, then neutralized with a basic substance such as sodium hydroxide or potassium hydroxide, and then purified.
  • a method of recrystallization using a solvent may be employed, or sodium sulfate or potassium sulfate may be filtered.
  • a treatment method using an ion exchange agent, a chelating agent, or an adsorbent may be employed. Then, the content of the inorganic metal salt such as sodium sulfonate remaining in the sodium polystyrene sulfonate / polystyrene sulfonate after neutralization is reduced to less than 5% by mass, preferably less than 3% by mass. The reduced amount is used as the above (B) component.
  • the acid-base-containing aromatic vinyl resin as the component (B) those having a weight average molecular weight of 1,000 to 300,000 are preferable. Used for If the weight-average molecular weight of the acid-base-containing aromatic butyl resin is less than 1,000, the physical properties of the resin composition using this as a compounding component are not practically sufficient. If the weight-average molecular weight of the acid-base-containing aromatic vinyl resin exceeds 300,000, the fluidity of the resin composition using this as a compounding component is poor. This leads to a drop in productivity.
  • the flame-retardant polycarbonate resin composition of the present invention basically comprises the above (a)
  • A) (B) It may consist of both components, but depending on its use, it may be required to further suppress the melting and dripping.
  • a flame-retardant polycarbonate resin composition that satisfies such requirements, a polytetrafluoroethylene-based resin is further used as the component (C), and both the components (A) and (B) are used.
  • a flame-retardant polycarbonate resin composition obtained by adding 0.01 to 5 parts by mass to 100 parts by mass in total is suitably used.
  • the polytetrafluoroethylene resin of the component (C) includes, in addition to the homopolymer of tetrafluoronorethylene, this tetrafluoronorethylene, propylene and a hexofenole-containing propylene or a fluorine atom. Polymers and copolymers having no ethylene-based monomer and having a structural unit derived from fluorethylene in the polymer chain are used. These polytetrafluoroethylene resins may be used alone as the component (C), or two or more of them may be used as the component (C). Further, as these polytetrafluoroethylene resins, those having an average molecular weight of 500,000 or more are preferable.
  • the values are 500, 000 to 100, 0000, 0000.
  • those having a fibril forming ability can be used to obtain a higher effect of suppressing the dripping of the melt.
  • Such polytetrafluoroethylene resins having the ability to form bipril include those classified into Type 3 in the ASTM standard.
  • this polytetrafluoroethylene-based resin is prepared, for example, by adding tetrafluoroethylene to an aqueous solvent in the presence of sodium, potassium, and ammonium peroxydisulphide for 0.0! Those obtained by polymerization at a temperature of 0 to 200 ° C., preferably 20 to 100 ° C. under a pressure of IMPa are suitably used.
  • the flame-retardant polycarbonate resin composition there may be a case where a resin having excellent impact resistance properties, particularly excellent low-temperature impact properties, is required.
  • a flame-retardant polycarbonate resin composition that satisfies such demands core (Z) shell type elastomer is used as component (D), and both components (A) and (B) are used.
  • the flame-retardant polycarbonate resin composition obtained by adding 0.01 to 10 'parts by mass with respect to the total of 10'0 parts by mass is preferably used.
  • the core-shell type elastomer of the component (D) there is an elastomer having a two-layer structure composed of a core (core) and a shell (shell).
  • a master is preferably used.
  • the core part is in a soft rubber state
  • the shell part of its surface is in a hard resin state
  • the elastomer is itself in a powder state (particle state).
  • particle state can be Most of the core / shell type graphite elastomer retains its original shape after melt blending with polycarbonate resin. Therefore, this elastomer is uniformly dispersed in the polycarbonate resin, and is less likely to cause surface peeling.
  • the core Z-shell type graph elastomer is, for example, one or more rubbers obtained from a monomer mainly composed of alkyl acrylate, alkyl methacrylate, and dimethyl siloxane.
  • a polymer obtained by polymerizing one or more vinyl monomers such as styrene in the presence of a polymer is preferably used.
  • these alkyl acrylates and alkyl methacrylates include those having an alkyl group having 2 to 10 carbon atoms, such as ethyl acrylate, butyl acrylate, and 2-ethyl acrylate. Those obtained by using xinoleate acrylate, n-butane methacrylate are preferred.
  • Elastomers obtained by using these alkyl acrylate-based monomers include 70% by mass or more of an alkyl acrylate and a vinyl monomer copolymerizable therewith, for example, methyl methacrylate.
  • Li rate Accession Li Roni preparative drill, vinyl acetate, a copolymer obtained by reacting styrene and at a rate of 3 0 wt 0/0 or less is preferably used.
  • it may be cross-linked with a polyfunctional compound such as divinylbenzene or ethylenedimethacrylate, triaryl cyanurate, triaryl succinate, or the like.
  • aromatic vinyl compounds such as styrene, ⁇ '-methylstyrene, methyl acrylate, ethyl acrylate, etc. What is obtained by polymerizing or copolymerizing any methacrylate such as acrylate, methyl methacrylate, and methyl methacrylate may be used.
  • other vinyl-based monomers such as cyanided vinyl compounds such as acrylonitrile II and methacrylonitrile, and vinyl ester compounds such as vinyl acetate and vinyl propionate. It may be obtained by copolymerization.
  • these polymers and copolymers those obtained by various methods such as bulk polymerization, suspension polymerization, and emulsion polymerization are used, and among them, those obtained by emulsion polymerization are used. Those are particularly preferably used.
  • n - the Puchiruaku Li single preparative 6 0-8 0 weight 0/0, the ratio of 2 0-4 0% by weight of styrene and Metata methyl acrylic acid
  • An MAS resin elastic material that has been copolymerized in step (1) is used.
  • a flame-retardant polycarbonate resin composition that satisfies such demands further includes: (E) A phosphoric acid ester-based flame retardant is added in an amount of 0.01 to 30 parts by mass based on 100 parts by mass of the total of both components (A) and (B). A flame-retardant polycarbonate resin composition is preferably used.
  • a phosphoric ester compound having at least one ester oxygen atom directly bonded to a phosphorus atom is used.
  • Such a phosphate compound is, for example, represented by the following general formula (2)
  • R 1 , R 2 , R 3 , and R 4 each independently represent a hydrogen atom or an organic group ′, and X represents a divalent or higher valent organic group. Also, p represents 0 or 1, q represents an integer of 1 or more, and r represents an integer of 0 or more.
  • the phosphoric acid ester compound represented by the formula or a mixture thereof is preferably used.
  • examples of the organic group represented by R 1 to R 4 in the general formula (2) include an alkyl group, a cycloalkyl group, and an aryl group each of which may have a substituent.
  • the substituent is preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylthio group, or the like. Further, it may be an aryloxyalkyl group or the like which is a group obtained by combining these substituents, or an aryl- / resulfonyl aryl in which these substituents are bonded by an oxygen atom, a nitrogen atom, a zeolite atom or the like.
  • the organic group represented by X in two or more lungs may be, for example, a carbon atom derived from the organic group described above; r; (a hydrogen atom bonded to a child) Litis, excluding one or more I do.
  • an alkylene group which may have a substituent, a phenylene group, or a group may be a group derived from bisphenols which are polynuclear phenols.
  • Examples of the phosphate compound represented by the general formula (2) include, for example, trimethyl phosphate, trietinole phosphate, tributyl phosphate, trioctinole phosphate, and trioctinole phosphate.
  • phosphate ester compound examples include, for example, TPP (triphenyl phosphate), TXP (trixyleninole phosphate), CR733 manufactured by Daihachi Chemical Industry Co., Ltd. S [resorcinol (diphenyl phosphate)] CR 741 [bisphenol A (diphenyl phosphate)], PX 200 [1,3-phenylene-tetrakis (2,6-dimethylphosphate) Enyl) phosphoric acid ester, PX201 [1,4-phenylene thrakis (2,6-dimethylphenyl) phosphoric acid ester, PX202 [4,4'-biphenylene-tetrakis (2,6-Dimethylphenyl) phosphoric acid ester.
  • TPP triphenyl phosphate
  • TXP trixyleninole phosphate
  • CR733 manufactured by Daihachi Chemical Industry Co., Ltd.
  • the flame-retardant polycarbonate resin composition of the present invention contains various additive components, if necessary, in addition to the components (A) to (E). Can be made.
  • additives include antioxidants, antistatic agents, ultraviolet absorbers, light stabilizers (weathering agents), antibacterial agents, compatibilizers, and coloring U (dye, pigment). .
  • the acid-base-containing aromatic vinyl resin as the component (B) is used at a concentration of 10 to 60 mass. /.
  • the acid-base-containing aromatic vinyl resin (B) is used in a concentration of 10-60 mass. /.
  • all the components (A) to (E) may be kneaded.
  • the reason that the acid-base-containing aromatic vinyl resin of the component (B) is sprayed on other components in a solution state of a concentration of 10 to 60% by mass is that the concentration of the component (B) is 10%. mass.
  • the concentration of this component (B) is 60 mass. If the solution exceeds / 0 , the viscosity of the solution becomes too high, which may hinder uniform dispersion in other components.
  • the solvent for the component (B) water is preferable, and in addition, aromatic hydrocarbons such as methyl alcohol and the like, and aromatic hydrocarbons such as methyl and the like are also used. be able to.
  • the solution of the aromatic vinyl resin containing the acid base as the component (B) is sprayed on the mixture of the components (A) and (C) to (E)
  • the solution is preliminarily prepared with a ribbon blender or a drum tumbler.
  • the mixture is then melted and kneaded while removing the solvent using a single-screw or twin-screw extruder or the like equipped with a vent, and the obtained resin composition molded product is cut and pelletized. .
  • the resin temperature during melt kneading here can be appropriately selected in the range of 240 to 300 ° C.
  • the flame-retardant polycarbonate resin composition obtained in this manner is used for injection molding, injection compression molding, extrusion molding, professional molding, press molding, vacuum molding using the pellets. It can be molded into various molded articles by the foaming method or the foam molding method.
  • the acid-base-containing aromatic vinyl resin as the component (B) was sprayed on other components in a solution state having a concentration of 10 to 60% by mass.
  • the flame-retardant polycarbonate resin composition obtained by kneading later has a higher transparency in the resin composition comprising both components (A) and (B) than the generally employed mixing in the solid state.
  • a resin composition comprising a combination of the components (A) to (E) can improve various properties such as flame retardancy and impact resistance, and any of these molded products A molded article with excellent surface smoothness and good appearance can be obtained.
  • the molded article obtained by molding the flame-retardant polycarbonate resin composition of the present invention is a molded article of a resin composition comprising both components (A) and (B), such as a head lamp lens of an automobile. It is suitably used for parts of lighting equipment requiring high transparency. Further, in the molded article of the resin composition comprising the combination of (A) to (E) components, for example, a copier, a facsimile, a television, a radio, a tape recorder, a video deck, a personal computer, Printers, telephones, information terminals, cold It is widely used for housing parts for electric and electronic devices such as storages and microwave ovens, and also for parts in the fields of machinery, construction, and automobiles. Next, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.
  • the reaction product was aged at 40 ° C. for 30 minutes, and then neutralized to pH 7 with an aqueous sodium hydroxide solution ( and obtained here).
  • the crude product thus obtained was dissolved in ethanol, and sodium sulfate, which was an insoluble component, was separated by filtration.
  • the solvent ethanol was removed by drying to obtain a purified product, polystyrene.
  • the sodium sulfonate had a sodium sulfate content of 2% by mass and a snorefonation rate of 100%.
  • the component (A) of the raw material has a viscosity average molecular weight of 19,000 and under the conditions of 280 ° C and a load of 210 g according to JISK 720.
  • the melt flow rate was measured using a polycarbonate resin of 19 g / 10 min, and the content of the sodium sulfate obtained in the above (1) was used as the component (B). Is 2% by mass of polystyrene sulfonic acid sodium. Was used.
  • the mixing ratio of these two components is 99.9 mass of the () component. / 0 , the component (B) was 0.1 mass%.
  • both of these components (A) and (B), and octadecinole 3- (3,5-dibutyl-14-hydroxypheninole) propionate as an antioxidant [Ciba 'Specialty' Chemicals; (A) and (B) 0.2 parts by mass and 100 parts by mass of tris (2,4-di-t_butylbutyl) phosphite [100 parts by mass of both components] Asahi Denka Kogyo Co., Ltd .; Adekastab 2 111) was mixed with 0.1 parts by weight with respect to 100 parts by weight of (A) and (B), and a vent-type twin-screw extruder [Toshiba Machinery Co., Ltd .: TEM35], melted and kneaded at 280 ° C, and then pelletized.
  • the pellet of the flame-retardant polycarbonate resin composition thus obtained was dried at 120 ° C for 12 hours, and then subjected to a molding temperature of 2.7 ° C and a mold temperature of 8 ° C.
  • a test piece was obtained by injection molding at 0 ° C.
  • the parallel light transmittance was measured according to JIS K 705.
  • As the test piece a square plate with a thickness of 3.2 mm and a size of 25 x 35 mm was used.
  • Tensile strength test specimen (for weld test) The specimen was molded at a two-point gate using a molding die, and a tensile test was performed by molding a specimen having a ⁇ -eld.
  • test piece 80 X 40 X 3 mm was heated at a resin temperature of 320 ° C and a mold temperature of 80 ° C.
  • the test piece was molded after having been retained in the injection cylinder for 20 minutes, and the color tone change with the test specimen before the retention was measured.
  • the color difference ( ⁇ E) was determined in accordance with JISH7103 (yellowing degree test method).
  • a notebook computer housing (A4 type) was injection-molded under the conditions of a resin temperature of 320 ° C and a mold temperature of 80 ° C. Next, this molded product was pulverized and used as a 100% recycled raw material, and again injection-molded under the same conditions to form a test molded product. Then, the Izod impact strength of the recycled molded product was measured according to the above.
  • the molded article was treated for 1,000 hours at a temperature of 70 ° C. and a humidity of 90%.
  • the Izod impact strength after the treatment was measured according to the above.
  • Table 1 shows the evaluation results of these flame-retardant polycarbonate resin compositions.
  • the flame retardant polycarbonate resin composition obtained in the above (1) was evaluated in the same manner as in (3) of Example 1. Table 1 shows the results of these evaluations.
  • a sulfonation reaction of polystyrene with sulfuric anhydride was performed in the same manner as (1) of Example 1. Then, the reaction product obtained here is neutralized to pH 7 with an aqueous solution of sodium hydroxide, and then the solvent and water are removed under reduced pressure to give sodium polystyrene sulfonate. Obtained.
  • the sodium polystyrene sulfonate thus obtained had a sodium sulfate content of 6% by mass and a sulfonation ratio of 100%.
  • Example 2 The same procedure as in (2) of Example 1 was repeated except that the unpurified sodium polystyrenesulfonate obtained in (1) was used as the component (B) of the raw material. A flammable polycarbonate resin composition was produced.
  • the flame-retardant polycarbonate resin composition obtained in (2) was evaluated in the same manner as in (3) of Example 1. Table 1 shows the results of these evaluations.
  • a sulfonation reaction of polystyrene with sulfuric anhydride was carried out in the same manner as in (1) of Example 1. Then, the obtained reaction product was neutralized to pH 7 with an aqueous solution of potassium hydroxide, and the reaction product was purified in the same manner as (1) of Example 1 to obtain potassium polystyrene sulfonate. Um.
  • a flame-retardant polycarbonate resin composition was prepared in the same manner as in Example 1 (2) except that the polystyrene potassium sulfonate obtained in (1) was used as the component (B) of the raw material. Was manufactured.
  • the flame retardant polycarbonate resin composition obtained in the above (1) was evaluated in the same manner as in (3) of Example 1. Table 1 shows the results of these evaluations.
  • a sulfonation reaction of polystyrene with sulfuric anhydride was carried out in the same manner as in (1) of Example 1.
  • the reaction product obtained here was neutralized to pH 7 with an aqueous potassium hydroxide solution, and then the solvent and water were removed under reduced pressure to obtain potassium polystyrene sulfonate.
  • the polystyrene sulfonate thus obtained has a sulfuric acid content of 6% by mass. /. And the sulfonation ratio is 40. /. It was. (2) Production of flame-retardant polycarbonate resin composition
  • a flame-retardant polycarbonate was prepared in the same manner as in (2) of Example 1, except that the unpurified potassium polystyrenesulfonate obtained in (1) was used as the component (B) of the raw material. A resin composition was produced.
  • the flame-retardant polycarbonate resin composition obtained in (2) was evaluated in the same manner as in (3) of Example 1. Table 1 shows the results of these evaluations. '
  • the flame retardant polycarbonate resin composition obtained in the above (1) was evaluated in the same manner as in (3) of Example 1.
  • a test piece with a thickness of 1.5 mm was also performed. Table 1 shows the results of these evaluations.
  • an aqueous solution of sodium polystyrenesulfonate having a concentration of 35% by mass of the component (B) is sprayed on the solid components of (A), (C), (D) and (E). In this way, it was sprayed uniformly.
  • the kneading of these components (A) to (E) was performed in the same manner as in Example 1, (2).
  • the flame-retardant polycarbonate resin composition obtained in (1) was evaluated in the same manner as in (3) of Example 1. In the UL 94 combustion test, a 1.5 mm-thick test piece and a 0.8 mm-thick test piece were also tested. Table 1 shows the results of these evaluations.
  • Example 1 (2) The raw material resin used in Example 1 (2) as the component (A) of the raw material, and the polymer obtained in Example 1 (1) as the component (B)
  • the sodium (ethylene) sulfonate was composed of 94% by mass of the component (A) and 6% by mass of the component (B).
  • a flame-retardant polycarbonate resin composition was produced.
  • the flame retardant polycarbonate resin composition obtained in the above (1) was evaluated in the same manner as in (3) of Example 1. Table 1 shows the results of these evaluations.
  • Example 1 Example 2 Female Example 1 Example 3 Example 4 Breakthrough 2 Example 5 Example 6 Comparative Example 3 Comparative Example 4
  • the present invention provides high flame retardancy, excellent recycling characteristics and antistatic performance while maintaining the inherent physical properties of a polycarbonate resin by adding a small amount of a flame retardancy-imparting component, and
  • the present invention can provide a flame-retardant polycarbonate resin composition capable of obtaining a molded article having an excellent appearance, a method for producing the same, and a molded article.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

La présente invention concerne une composition à base de résine de polycarbonate ignifuge, qui comprend (A) de 95 à 99,99 % en poids d'une résine de polycarbonate et (B) de 0,01 à 5 % en poids d'une résine vinylique aromatique présentant un groupe de sel acide produit, par exemple, par neutralisation d'un groupe acide sur le noyau aromatique, et contenant un sel métallique inorganique, dans une quantité inférieure ou égale à 5 % en poids. La présente invention concerne également un procédé pour produire cette composition à base de résine. Ce procédé consiste à disposer d'une solution du composant (B), d'une concentration allant de 10 à 60 % en poids, à disperser la solution de (B) sur le composant (A), puis à malaxer le mélange résultant. En outre, cette invention concerne un article moulé, produit à partir de cette composition à base de résine. La composition à base de résine de polycarbonate ignifuge contient une quantité relativement faible de composant conférant des propriétés d'ignifugation. Cette composition à base de résine de polycarbonate est hautement ignifuge et présente une très bonne aptitude au recyclage, de très bonnes propriétés antistatiques et un très bel aspect, tout en conservant les propriétés physiques inhérentes à la résine de polycarbonate.
PCT/JP2002/000140 2001-01-12 2002-01-11 Composition a base de resine de polycarbonate ignifuge, son procede de production et article moule WO2002055604A1 (fr)

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CN109790368A (zh) * 2016-10-06 2019-05-21 索尼公司 透射型树脂组合物和透射型树脂成型制品

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JP5021122B2 (ja) * 2001-02-05 2012-09-05 出光興産株式会社 難燃性ポリカーボネート樹脂組成物及びその成形品
JP2003064229A (ja) * 2001-06-12 2003-03-05 Lion Corp 熱可塑性樹脂用難燃性付与剤及び難燃性熱可塑性樹脂
CN101906242A (zh) 2004-03-23 2010-12-08 索尼株式会社 阻燃剂、阻燃树脂组合物和生产该阻燃剂的方法
JP5436219B2 (ja) * 2007-11-08 2014-03-05 帝人株式会社 樹脂組成物
JP5647935B2 (ja) * 2011-04-18 2015-01-07 三菱エンジニアリングプラスチックス株式会社 電動自転車用バッテリー装置

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JP3461125B2 (ja) * 1998-08-18 2003-10-27 出光石油化学株式会社 難燃性ポリカーボネート樹脂組成物及びブロー成形品

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109790368A (zh) * 2016-10-06 2019-05-21 索尼公司 透射型树脂组合物和透射型树脂成型制品
US11434364B2 (en) 2016-10-06 2022-09-06 Sony Corporation Transparent resin composition and transparent resin molded article

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