WO2002059205A1 - Compositions de resines polycarbonates ignifuges et articles moules a partir de ces compositions - Google Patents

Compositions de resines polycarbonates ignifuges et articles moules a partir de ces compositions Download PDF

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Publication number
WO2002059205A1
WO2002059205A1 PCT/JP2002/000137 JP0200137W WO02059205A1 WO 2002059205 A1 WO2002059205 A1 WO 2002059205A1 JP 0200137 W JP0200137 W JP 0200137W WO 02059205 A1 WO02059205 A1 WO 02059205A1
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Prior art keywords
component
flame
polycarbonate resin
mass
resin composition
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PCT/JP2002/000137
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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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Priority claimed from JP2001017927A external-priority patent/JP5302486B2/ja
Priority claimed from JP2001027714A external-priority patent/JP5021122B2/ja
Application filed by Idemitsu Petrochemical Co., Ltd. filed Critical Idemitsu Petrochemical Co., Ltd.
Publication of WO2002059205A1 publication Critical patent/WO2002059205A1/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 and a molded article thereof. More specifically, a flame-retardant polycarbonate resin composition with excellent fluidity, solvent resistance, flame retardancy, and excellent durability of antistatic performance, and excellent rigidity and dimensional accuracy, and sustained antistatic performance
  • the present invention relates to a flame-retardant polycarbonate resin composition having excellent heat resistance and molded articles thereof.
  • Polycarbonate resins are excellent in impact resistance, heat resistance, electrical properties, dimensional stability, etc., and are used in the electrical and electronic equipment fields such as office automation (OA) equipment, information and communication equipment, and home appliances. It is widely used in various fields such as automobiles and construction. Polycarbonate resins have these excellent properties.However, in order to further improve mechanical strength and dimensional stability, reinforced polycarbonate resin compositions containing an inorganic filler such as glass fiber are used. Used. This polycarbonate resin is a self-extinguishing resin itself, but when used as a material for OA equipment, information, communication equipment, electric and electronic equipment, etc. Is required to be higher.
  • halogen-based flame retardants such as halogenated bisphenol / re A and halogenated polycarbonate ligomers increases the flame retardant efficiency. It has been used with auxiliaries.
  • auxiliaries there has been a demand for a flame retardant method using a halogen-free flame retardant because of its great impact on the environment during safety and waste incineration. Therefore,
  • an organic phosphorus-based flame retardant especially an organic phosphate compound
  • the organic phosphoric ester compound can be used because it has excellent flame retardancy and also acts as a plasticizer.
  • the flame-retardant polycarbonate resin composition used has been proposed.
  • polycarbonate resin has a high molding temperature and a high melt viscosity. Therefore, it is necessary to increase the molding temperature to increase the fluidity in order to cope with thinner and larger molded products. Therefore, this organophosphate compound contributes to flame retardancy, but it is not always sufficient in terms of the molding environment and appearance of the molded product, such as sticking to the mold and generating gas during molding of the polycarbonate resin. May not be available.
  • molded articles of the flame-retardant polycarbonate resin composition using the organic phosphate compound have a problem that the impact strength is reduced or the color is changed with the history of high temperature and the history of high temperature and high humidity.
  • 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, a sodium salt of polystyrene sulfonic acid is used. It is proposed to make the polycarbonate resin flame-retardant by blending. However, if the polycarbonate resin is flame-retarded using sodium polystyrenesulfonate obtained by sulfonating polystyrene by the usual method and neutralizing it with sodium hydroxide, the However, there is a drawback that molded articles have poor appearance due to poor dispersibility of sodium polystyrenesulfonate.
  • Japanese Patent Application Laid-Open No. Hei 8-176425 discloses a polycarbonate resin containing an organic alkali metal salt or an organic alkaline earth metal salt and an organopolysiloxane. Are proposed. Although this resin composition is excellent in flame retardancy and mechanical strength, a molded article obtained by molding the resin composition has a problem that dust adheres to the surface of the resin composition and the surface thereof is soaked.
  • Japanese Patent Application Laid-Open No. 11-172603 proposes a flame-retardant resin composition comprising a mixture of a metal salt of polystyrene sulfonic acid and various thermoplastic resins.
  • the resin composition mainly composed of polystyrene or polyphenylene ether a resin composition having excellent flame retardancy is indicated, but a polycarbonate resin which maintains the inherent properties of the polycarbonate resin is described. No mention is made of flame-retardant, flame-retardant resin compositions mainly composed of
  • the reinforced polycarbonate resin composition blended with an inorganic filler such as glass fiber maintains the excellent mechanical strength and dimensional stability of the resin, and maintains the antistatic performance without adhering dust.
  • Development of a flame-retardant polycarbonate resin composition capable of obtaining excellent molded articles has also been demanded.
  • the present invention relates to a flame-retardant polycarbonate resin composition which is excellent in fluidity, solvent resistance and flame retardancy, and which can obtain a molded article excellent in durability of antistatic performance without adhering dust.
  • the purpose is to provide such molded articles.
  • the present invention provides excellent mechanical strength and dimensional stability. It is an object of the present invention to provide a flame-retardant polycarbonate resin composition capable of obtaining a molded article excellent in persistence of antistatic performance to which dust does not adhere, and a molded article thereof.
  • the present inventors have identified (A) a polycarbonate resin, (B) a thermoplastic resin other than a polycarbonate resin, and (C) an aromatic vinyl resin containing an acid base. Flame-retardant polycarbonate resin composition and (A) polycarbonate resin, and (H) inorganic filler and (C) acid-base-containing aromatic vinyl resin blended at a specific composition ratio According to the flame-retardant polycarbonate resin composition thus obtained, the above-mentioned object can be achieved, and the present invention has been completed based on these findings.
  • the gist of the present invention is as follows.
  • the polycarbonate resin as the component (A) is a polycarbonate copolymer resin having a structural unit derived from an organosiloxane.
  • thermoplastic resin as the component (B) is a styrene-based resin or a polyester-based resin.
  • the core and shell type graft rubber-like elastic material as the component (F) is 0.5 to 10
  • a flame retardant of 0.1 to 30 parts by mass as a component (G) is added to the total of 100 parts by mass of the components (A), (B) and (C).
  • the flame-retardant polycarbonate resin composition according to any one of the above [1] to [8].
  • Polycarbonate resin 37 to 97.95% by mass as component (A), 2 to 60% by mass of inorganic filler as component (H) and acid-base-containing fragrance as component (C)
  • a flame-retardant polycarbonate resin composition comprising 0.5 to 3% by mass of an aromatic vinyl resin.
  • the inorganic filler of the component (H) is at least one filler selected from the group consisting of glass fiber, glass flake, glass beads, talc, myriki, and carbon fiber.
  • the component (F) is a core-shell type graphitic rubber-like elastic material 0.5 to 10
  • a total of 100 parts by mass of the components (A), (H) and (C) is blended with 0.1 to 30 parts by mass of a flame retardant as the component (G).
  • the flame-retardant polycarbonate resin composition according to any one of [10] to [16].
  • FIG. 1 is a perspective view of a jig for fixing a test piece used for evaluating the grease resistance of the flame-retardant polycarbonate resin composition of the present invention.
  • the flame-retardant polycarbonate resin composition of the present invention comprises 50 to 97.95% by mass of a polycarbonate resin as the component (A) and 2 to 47% by mass of a thermoplastic resin other than the polycarbonate resin as the component (B). And a flame-retardant polycarbonate resin composition comprising 0.05 to 3% by mass of an acid-base-containing aromatic vinyl resin as the component (C).
  • the flame-retardant polycarbonate resin composition of the present invention can be used as a component (D) for suppressing dripping, if necessary, in addition to the basic components (A), (B) and (C).
  • a silicone rubber compound containing a functional group as the component (E), a core-shell type rubber-like elastic material as the component (F), or a flame retardant as the component (G) is added at a specific ratio.
  • a flame-retardant polycarbonate resin composition contains 37 to 97.95% by mass of the polycarbonate resin (A), 2 to 60% by mass of the inorganic filler (H), (C)
  • a flame-retardant polycarbonate resin composition comprising from 0.05 to 3% by mass of an aromatic base resin containing an acid base as the component.
  • the flame-retardant polycarbonate resin composition of the present invention may further comprise, as necessary, a drip inhibitor as a component (D), in addition to the basic components (A), (H) and (C).
  • a drip inhibitor as a component (D)
  • a flame-retardant composition obtained by adding a functional group-containing silicone compound as the component (E), a core-shell type rubber-like elastic material as the component (F), or a flame retardant as the component (G) at a specific ratio. It is a reactive polycarbonate resin composition.
  • the polycarbonate resin of the component (A), the thermoplastic resin other than the polycarbonate resin of the component (B), and the inorganic filler of the component (H), which constitute the flame-retardant polycarbonate resin composition of the present invention Ingredient acid Base-containing aromatic vinyl resin, (D) component dripping inhibitor, (E) component functional group-containing silicone compound, (F) component core 'shell type graphitic rubber-like elastic material and (G) The component flame retardant is described in detail below.
  • the polycarbonate resin as the component (A) used as a raw material of the flame-retardant polycarbonate resin composition of the present invention is not particularly limited, and includes polycarbonate resins having various structural units.
  • an aromatic polycarbonate produced by reacting a divalent phenol with a carbonate precursor can be used. That is, a polycarbonate resin produced by reacting a divalent phenol with a polycarbonate precursor by a solution method or a melting method is suitably used.
  • divalent phenol examples include 4,4, dihydroxybiphenyl, bis (4-hydroxyphenyl) methane, 1,1,1-bis (4hydroxyphenyl) ethane, 2 , 2- bis (4-arsenate Dorokishifu Eninore) propane, 2, 2 - bis (3 - Mechinore one 4-arsenide Dorokishifue two Honoré) Purono ⁇ 0 emissions, 2, 2 - bis (3, 5 - dimethyl _ 4 - arsenide (Droxyphen) propane, 1,1-bis (4—hydroxyphenyl) cyclohexane, bis (4—hydroxyphenyl) athenole, bis (4—hydroxyphenyl) snorefide, bis (4-) (Hydroxy-phenol) snorehon, bis (4-hydroxyphenyl) snolefoxide, bis (4-hydroxyphenyl) ketone, hydroquinone, Zonoreshin, such as catheter call, and the like.
  • divalent phenols bis (hydroxyphenyl) alkanes are preferable, and those using 2,2-bis (4-hydroxyphenyl) propane as a main raw material are particularly preferable.
  • Carbonate precursors include carbonyl halides and carbohydrates. Nyl esters, haloformates and the like. Specific examples include phosgene, diphenol of divalent phenol, diphenyl carbonate, dimethyl carbonate, and getyl carbonate.
  • the polycarbonate resin may have a branched structure in addition to a molecular structure of a polymer chain having a linear structure.
  • (Droxypheninole)-1,3,5_triisopropyl 7-lebenzene, fluorodarucine, trimellitic acid, isatin bis ( ⁇ -cresol), etc. can be used. Then, it is possible to use phenol, ⁇ -t-puchinorenoenore, p-t-octylphenenole, ⁇ -cumylphenol, and the like.
  • 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, or a homopolymer thereof may be used. It may be a resin composition comprising a polymer and a copolymer. Further, it may be a polyester-polycarbonate resin obtained by performing a polymerization reaction of a polycarbonate in the presence of a bifunctional carboxylic acid such as terephthalic acid or an ester precursor such as an ester-forming derivative thereof. Further, resin compositions obtained by melt-kneading polycarbonate resins having various structural units can also be used. In addition, as the polycarbonate resin of the component (A) in the present invention, a resin that does not substantially contain a halogen atom in its structural unit is preferably used.
  • the polycarbonate resin used as the component (A) preferably has a viscosity-average molecular weight of 100,000 to 100,000. New 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 this polycarbonate resin is more preferably from 11,000 to 40,000, still more preferably from 12,000 to 30,000.
  • thermoplastic resin other than the polycarbonate resin as the component (B) used as a raw material of the flame-retardant polycarbonate resin composition of the present invention examples include, for example, general-purpose polystyrene ⁇ impact-resistant polystyrene, Gyrotics • Styrenes such as polystyrene, acrylonitrile-butadiene-styrene resin, acrylonitrile-styrene resin, methyl methacrylate butadiene styrene resin, and methyl methacrylate-styrene resin Resins: Polyester resins such as polyethylene terephthalate and polybutylene terephthalate; Polyolefin resins such as polyethylene and polypropylene; Polyamide resins such as Nylon 6, Nylon 66, and Nylon 12 Styrene-butadiene-styrene-based elastomer, styrene-ethylene Thermoplastic elastomers such as but
  • the styrene-based resin is particularly effective in improving the fluidity of the flame-retardant polycarbonate resin composition obtained when the styrene resin is used as the component (B). Since it is excellent, it is a preferable thermoplastic resin to be used as the component (B).
  • polyester Resins are flame-retardant poly resins obtained when they are used as the component (B). Molded articles that require solvent resistance because the effect of improving the solvent resistance of the carbonate resin composition are particularly excellent. This is a particularly preferred thermoplastic resin when producing styrene.
  • Examples of the inorganic filler of the (H) component used as a raw material of the flame-retardant polycarbonate resin composition of the present invention include, for example, glass fiber, glass flake, glass beads, glass nonane, tanolek, and clay. , Mai power, nor mai power, silica, alumina, calcium carbonate, calcium sulfate, calcium silicate, titanium oxide, zinc oxide, zinc sulfide, quartz powder, asbestos, graphite, carbon black, carbon fiber, titanate Mineral fibers such as potassium whiskers, aluminum borate whiskers, boron fibers, tetra-potted zinc oxide whiskers, rock wool, metal fibers such as stainless steel fibers, and metal foils such as aluminum foil.
  • glass fiber, glass flake, glass beads, talc, myriki, and carbon fiber are particularly preferable.
  • These inorganic fillers are preferably surface-treated in advance because of their good affinity for the resin component, but may be untreated.
  • the surface treatment agent include a silane coupling agent, a treatment agent such as a higher fatty acid, a fatty acid metal salt, an unsaturated organic acid, an organic titanate, a resin acid, and a polyethylene glycol. Can be used.
  • glass fibers suitable for use as the component (H) those produced using alkali-containing glass, low-alkali glass, or non-alkali glass as a material are preferable.
  • the form may be any form such as roving, milled fiber, chopped strand, and the like.
  • the diameter of this glass fiber is l ⁇ 20; um It is preferable to use one having a length of 1 to 6 mm.
  • the glass fiber supplied to the kneader breaks during kneading with the resin component, so that the fiber length in the resin composition pellet is 0.01 to 2 mm, preferably It is better to fill to 0.05 to 1 mm.
  • This glass fiber is treated with a surface treatment agent and then subjected to convergence treatment using a sizing agent in order to improve the adhesiveness to the resin component, and then the above components (A) and (C) are used. It is desirable to mix with the above resin components and melt knead them.
  • the surface treatment agent for this glass fiber include silane-based coupling agents such as aminosilane, epoxysilane, butylsilane, and acrylsilane, titanate, aluminum, chromium, zirconium, and boron. Coupling agents such as a system. Among them, a silane coupling agent and a titanate coupling agent are particularly preferably used.
  • the surface treatment method may be a general aqueous solution method, an organic solvent method, a spray method, or the like.
  • the sizing agent used in the sizing treatment after the surface treatment include sizing agents such as urethane-based, acryl-based, acrylonitrile-styrene-based copolymer, and epoxy-based sizing agents.
  • Known methods such as dip coating, roller coating, spray coating, flow coating, and spray coating can be used for the method of convergence treatment of glass fibers with these sizing agents.
  • the carbon fiber suitable for use as the component (H) cellulose fiber, acryl fiber, lignin, petroleum pitch or coal pitch fired as a raw material is preferably used.
  • Can be This carbon fiber also has a type such as flame-resistant, carbonaceous, or graphite, depending on the firing conditions, but any type may be used.
  • the form of carbon fiber is mouth-buffing, milled fiber, and tubing strand. It can be of any kind.
  • the fiber diameter is preferably 5 to 15 ⁇ m, and the fiber length is preferably in the range of 0.01 to 10 mm in the kneaded composition pellet with the resin component. .
  • the carbon fiber is previously surface-treated with an epoxy resin or a urethane resin because of its excellent affinity with a resin component.
  • the acid-base-containing aromatic vinyl-based resin (C) used as a raw material of the flame-retardant polycarbonate resin composition of the present invention is one of the hydrogen atoms of the aromatic ring in the polymer chain of the aromatic-vinyl-based resin.
  • An aromatic vinyl resin having a structure in which a part is substituted with an acid base is suitably used.
  • the aromatic vinyl resin includes at least styrene in a polymer chain such as polystyrene, rubber-modified polystyrene, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer resin.
  • An aromatic vinyl-based resin having a structural unit derived from styrene can be used. Among these, a polystyrene resin is particularly preferred.
  • Examples of the acid base to be substituted with a hydrogen atom of the aromatic ring in the aromatic vinyl resin include, for example, an alkali metal salt such as a sulfonic acid group, a borate group and a phosphoric acid group, and an alkaline earth metal. Salt and ammonium salt are available. Further, the substitution ratio of these acid bases is not particularly limited, and can be appropriately selected, for example, within the 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
  • Y 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 the following formula is preferably used.
  • 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. Suitable examples include salts, alkaline earth metal salts such as magnesium and potassium, aluminum salts, zinc salts, tin salts, and ammonium salts.
  • Y is preferably a hydrogen atom, and a hydrocarbon group is particularly preferably a methyl group.
  • an aromatic vinyl-based monomer having a sulfone group or the like as a monomer or other copolymerizable with these can be used.
  • neutralization with a basic substance can be performed.
  • a method can be employed in which an aromatic vinyl polymer or an aromatic vinyl copolymer, or a mixture thereof is sulfonated and neutralized with a salty substance.
  • aromatic vinyl polymer is sulfonated and then neutralized, for example, a polystyrene resin
  • 2-dichloroethane The solution is reacted with sulfuric anhydride to produce polystyrenesulfonic acid, which is then neutralized with a basic substance such as sodium hydroxide or potassium hydroxide, and purified to obtain an acid-base containing aromatic substance.
  • a group vinyl resin can be obtained.
  • the acid-base-containing aromatic vinyl-based resin as the component (C) is preferably less than 5% by mass, preferably less than 3% by mass of an inorganic metal salt contained in the acid-base-containing aromatic vinyl-based resin. It is more preferably used that has been reduced. If only the aromatic vinyl resin, for example, polystyrene is sulfonated and then neutralized with sodium hydroxide, the by-produced sodium sulfate will remain in the sodium polystyrene sulfonate. The content of sodium sulfate is 5 mass.
  • This sodium polystyrene sulfonate can be purified by recrystallization using a solvent, by filtering off sodium by-produced by filtration, or by treatment with an ion exchanger, chelating agent, or adsorbent. This can be done by:
  • the acid-base-containing aromatic vinyl resin (C) those having a weight average molecular weight of 1,000 to 300,000 are preferably used. If the acid-base-containing aromatic vinyl resin has a weight-average molecular weight of less than 1,000, the physical properties of the resin composition using this as a compounding component are reduced, and If the weight-average molecular weight of the acid-base-containing aromatic vinyl resin exceeds 300,000, the flowability of the resin composition using the resin as a component deteriorates, and the productivity decreases. It is the character that will be invited.
  • a fluororesin As the dripping inhibitor of the component (D), a fluororesin, a silicone resin, and a phenol resin are preferably used.
  • a fluororesin a fluorinated olefin-based resin is preferable, and a polymer or a copolymer having a polymer chain composed of fluorethylene units is more preferable.
  • fluorofluorinated resins include difluoroethylene resin, tetrafluoroethylene resin, tetrafluoroethylene-hexafluoropropylene copolymer resin, and tetrafluoroethylene and fluorine.
  • a copolymer resin with an atom-free ethylene-based monomer may be used.
  • polytetrafluoroethylene resin is particularly preferably used. In addition, these fluororesins may be used alone.
  • these fluororesins may be used as the component (D) or a combination of two or more types may be used as the component (D). Further, it is preferable that these fluororesins have an average molecular weight of 500,000 or more, and more preferably 500,000 to: 100,000,000.
  • polytetrafluoroethylene-based resins when a resin having a fibril forming ability is used, a higher melting dripping suppression effect can be obtained.
  • the polytetrafluoroethylene resin having such a fiprill-forming ability 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 in the range of 0.01 to lMP. Those obtained by polymerization at a temperature of 0 to 200 ° C., preferably 20 to 100 ° C. under the pressure of a, are suitably used.
  • Polytetrafluoroethylene having such bupryl forming ability Teflon 6-J manufactured by Mitsui 's DuPont Fluorochemicals
  • Polyflon D-1 and Polyflon F-1 are commercially available resins that are classified as Type 3 of the ASTM standard. 03, polyfluorocarbon F201 (manufactured by Daikin Industries, Ltd.) and CD076 (manufactured by Asahi Glass Fluoropolymers).
  • Argoflon F5 manufactured by Montefluos
  • Polyflon MPA manufactured by Polyflon MPA
  • Polyflon FA-100 manufactured by Daikin Industries.
  • silicone resin a polyorganosiloxane resin is preferable, and specifically, a polydimethylsiloxane resin, a polymethylphenylsiloxane resin, a polydiphenylsiloxane resin, a polymethylethylsiloxane resin, These mixtures are mentioned.
  • These silicone resins have a number-average molecular weight of 200 or more, preferably 500 to 5,000, and are in the form of oil, varnish, gum, and powder. Shape and pellet shape.
  • phenolic resins include phenols such as phenol, cresol, xylene, and ⁇ -IV kirphenol, and aldehydes such as formaldehyde and acetoaldehyde. Those obtained by reacting in the presence of a catalyst are preferably used.
  • the phenolic resin may be a resol type or a novolak type.
  • a functional group-containing silicone compound is used as the component (E) used as a raw material of the flame-retardant polycarbonate resin composition of the present invention.
  • This functional group-containing silicon corn compound (R ') a (R 2) b S i O _ a _ b) / 2
  • R 1 represents a functional group
  • R 2 is 1 to the number of carbon atoms 1 2 Represents a hydrocarbon group.
  • a and b are integers that satisfy 0 a3, 0 ⁇ b ⁇ 3, and 0 a + b ⁇ 3, respectively.
  • a polymer comprising the structural unit represented by It is a polymer.
  • Examples of the functional group represented by R 1 include an alkoxy group, an aryloxy group, a polyoxyalkylene group, a hydrogen group, a hydroxyl group, a carboxyl group, a silanol group, an amino group, a mercapto group, an epoxy group, and a vinyl group.
  • an alkoxy group, a hydrogen group, a hydroxyl group, an epoxy group, and a vinyl group are preferable, and a methoxy group and a vinyl group are more preferable.
  • Examples of the hydrocarbon group represented by R 2 include a methyl group, an ethyl group, and a phenyl group.
  • those particularly highly useful as the component (E) in the present invention are the hydrocarbon groups represented by R 2 in the above formula. It is a functional group-containing silicone compound consisting of a structural unit containing a fluorine group. Further, in the above formula, the functional group represented by R 1 may be one containing one kind of functional group or one containing a plurality of different kinds of functional groups. It may be a mixture. Those having a functional group (R 1 ) Z hydrocarbon group (R 2 ) value in the above formula of 0.1 to 3, preferably 0.3 to 2 are suitably used. Further, the silicone compound containing the functional group may be in a liquid form or a powder form. For liquids, those with a viscosity at room temperature of about 10 to 500, OOO cst are preferred.
  • a core-shell type graft rubber-like elastic material is suitably used as the component (F) used as a raw material of the flame-retardant polycarbonate resin composition of the present invention.
  • the core-shell type rubber-like elastic body has a two-layer structure consisting of a core and a shell.
  • the core part is in a soft rubber state
  • the seal part on the surface is in a hard resin state
  • the rubber-like elastic body itself is in a powder state (particle state).
  • a certain rubber-like elastic material is preferably used. After being melt-blended with the polycarbonate resin, the particle state of the core rubber elastic body of the core-shell type is mostly maintained in its original form. Therefore, this rubber-like elastic material is uniformly dispersed in the polycarbonate resin, and is less likely to cause surface layer peeling.
  • the core-shell type graft rubber-like elastic material is, for example, one or a kind obtained from a monomer mainly composed of butadiene, phenolic acrylate, dimethyl methacrylate, and dimethylsiloxane.
  • a polymer obtained by polymerizing one or more vinyl monomers such as styrene in the presence of two or more rubber-like polymers or ethylene-propylene-gen copolymer rubber is preferably used.
  • These alkyl acrylates / alkyl methacrylates have an alkyl group of 2 to 10 carbon atoms, such as ethyl acrylate, butyl acrylate, and 21-ethyl hexyl / reacrylate.
  • Elastomers obtained by using these monomers having alkyl acrylate as a main component include alkyl acrylate of 70% by weight or more, a vinyl monomer copolymerizable therewith, For example, a copolymer obtained by reacting methyl methacrylate, acrylonitrile, vinyl acetate, styrene and the like at a ratio of 30% by weight or less is suitably used. Further, it may be crosslinked with a polyfunctional compound such as divinylbenzene, ethylene dimethacrylate, triaryl cyanurate, triaryl cyanocyanate, or the like.
  • aromatic rubber compounds such as styrene and ⁇ -methylstyrene, acrylates / esters such as methyl acrylate, ethyl acrylate, methyl methacrylate, and methacrylate It is obtained by polymerizing or copolymerizing methacrylic acid esters such as ethyl acrylate. May be used.
  • these monomers are copolymerized with other vinyl monomers, for example, vinyl cyanide compounds such as atalylonitrile II and methacrylonitrile, and vinyl ester compounds such as vinyl acetate and vinyl propionate. It may be one obtained by performing the above.
  • vinyl cyanide compounds such as atalylonitrile II and methacrylonitrile
  • vinyl ester compounds such as vinyl acetate and vinyl propionate. It may be one obtained by performing the above.
  • these polymers and copolymers those obtained by various methods such as bulk polymerization, suspension polymerization, and emulsion polymerization are used, and among them, those
  • this core As a shell type graph Togomu like elastic body, n- Buchiruaku to re-rate 6 0-8 0 weight 0/0, styrene and Metaku methyl acrylic acid 2 0-4 in a proportion of 0 wt% A MAS resin elastic material that has been copolymerized is used.
  • the average particle diameter of 0.0 1 polysiloxane rubber component 5-9 5 wt% of poly (meth) and Atta Li Retogomu components 5-9 5 mass 0/0 has mutually entangled structure inseparably
  • a composite rubber-based graft copolymer obtained by subjecting at least one type of vinyl monomer to a composite rubber having a thickness of about 1 ⁇ m can be used.
  • Core-Schull type graft rubber-like elastic bodies having these various forms are commercially available as Hyprene B621 (manufactured by Zeon), KM-357P, EXL2602, EXL2 603 (manufactured by Kureha Chemical Industry Co., Ltd.), metaprene W529, methaprene S201, methaprene C223 (manufactured by Mitsubishi Rayon), and the like.
  • the component (G) used as a raw material of the flame-retardant polycarbonate resin composition of the present invention includes, for example, an organic phosphorus compound, a silicon compound, a nitrogen-containing compound, a metal hydroxide, a halogen compound, red phosphorus, and an oxidized compound.
  • Known flame retardants such as antimony and expandable graphite alone or in combination Can be used in appropriate combination.
  • examples of the nitrogen-containing compound include melamine and a melamine compound having an alkyl group or an aromatic group as a substituent.
  • the metal hydroxide include magnesium hydroxide and hydroxide. Aluminum and the like are preferred.
  • A, halogenated polycarbonate, decap-mouth modiphenyl ether, tetrapromobisphenol epoxy polyol, halogenated polystyrene, halogenated polyolefin, etc. have excellent flame retardant efficiency, but these are resins. It is preferable to use a halogen-free flame retardant because the mold may be corroded at the time of molding the composition and the natural environment may be adversely affected.
  • organic phosphorus compounds are mentioned as having excellent flame retarding efficiency, and among them, phosphoric acid ester flame retardants are preferred.
  • a phosphate ester flame retardant a phosphate compound having at least one ester oxygen atom directly bonded to a phosphorus atom is preferably 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.
  • p represents 0 or 1
  • q represents an integer of 1 or more
  • 1- represents an integer of 0 or more.
  • the phosphoric acid ester compound represented by 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 which may have a substituent, a cycloalkyl group, and an aryl group.
  • 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 arylalkoxyalkyl group or the like, which is a group obtained by combining these substituents, or an arylsulfonyl aryl group in which these substituents are bonded by an oxygen atom, a nitrogen atom, an io atom, or the like. It may be a group or the like.
  • the divalent or higher valent organic group represented by X means a divalent or higher valent group obtained by removing one or more hydrogen atoms bonded to a carbon atom from the above organic group.
  • it may be an alkylene group which may have a substituent, a phenylene group, or a group derived from bisphenols which are polynuclear phenols.
  • the polycarbonate resin of the component (A) has the following composition.
  • the proportion is 50 to 97.95% by mass.
  • the composition ratio of the component (A) is 50 mass. If it is less than / 0 , it is difficult to maintain the excellent physical properties inherent to the polycarbonate resin in the obtained resin composition, and the composition ratio is 97.95 mass. If the ratio exceeds / 0 , the resulting resin composition will not have sufficient fluidity ⁇ solvent resistance.
  • the composition ratio of the thermoplastic resin other than the polycarbonate resin as the component (B) is 2 to 47% by mass.
  • the composition ratio of this thermoplastic resin is 2 mass. If it is less than / 0 , the effect of improving the fluidity ⁇ solvent resistance of the resin composition obtained by blending the component (B) is not sufficient, and If the composition ratio exceeds 47% by mass, a high flame retardancy of V-2 or more in the UL standard cannot be obtained in the degree of flame retardancy of the obtained resin composition. Further, the composition ratio of the acid-base-containing aromatic vinyl-based resin as the component (C) is set to 0.05 to 3% by mass. When the composition ratio of the acid-base-containing aromatic vinyl resin is less than 0.05% by mass, the flame retardancy and antistatic performance of the resin composition obtained by blending the component (C) are considered.
  • composition ratio exceeds 3% by mass, physical properties such as impact strength of the obtained resin composition will be reduced. is there.
  • the more preferable mixing ratio of the component (C) is 0.1 to 2% by mass, and the more preferable mixing ratio is 0.5 to 2% by mass.
  • the flame-retardant polycarbonate resin composition of the present invention has a practically sufficiently high flame retardancy and antistatic property in a composition having a basic constitution comprising the components (A), (B) and (C).
  • the dripping of the (D) component is based on a total of 100 parts by mass of these basic components.
  • a flame-retardant polycarbonate resin composition containing 0.02 to 5 parts by mass of an inhibitor is preferably used. If the compounding ratio of the component (D) is less than 0.02 parts by mass, the effect of the compounding is not sufficient, and even if the compounding amount is increased beyond 5 parts by mass, an effect commensurate with it is obtained.
  • a more preferable mixing ratio of the component (D) is 0.1 to 1 part by mass.
  • a flame-retardant polycarbonate resin composition obtained by mixing 0.1 to 10 parts by mass of the functional group-containing silicone compound of the component (E) with respect to a total of 100 parts by mass of the basic constituent components If the compounding ratio of the component (E) is less than 0.1 part by mass, the effect of the compounding effect is exerted. This is because the effect is not sufficient, and even if the compounding amount is increased beyond 10 parts by mass, a corresponding effect cannot be obtained, and the mechanical strength of the obtained resin composition is rather lowered.
  • a more preferable mixing ratio of the component (E) is 0.1 to 5 parts by mass.
  • the total amount of the above-mentioned basic components is 100 parts by mass.
  • a flame-retardant polycarbonate resin composition obtained by blending 0.5 to 10 parts by mass of a core-shell type elastic rubber-like material of component F) is suitably used. If the compounding ratio of component (E) is less than 0.5 part by mass, the effect of the compounding is not sufficient, and even if the compounding amount is increased beyond 10 parts by mass, an effect commensurate with it is obtained. It is not possible.
  • a more preferable mixing ratio of the component (F) is 0.5 to 5 parts by mass.
  • the flame retardant of the component (G) is added in an amount of 0.1 parts by mass based on a total of 100 parts by mass of the above basic components. Flame-retardant polycarbonate resin compositions containing up to 30 parts by mass are suitably used. If the blending ratio of component (G) is less than 0.1 part by mass, the effect of the blending is not sufficient, and even if the blending amount is increased beyond 30 parts by mass, the effect corresponding thereto cannot be obtained. Because it is.
  • the polycarbonate resin of the component (A) is as follows.
  • the composition ratio is 37 to 97.95% by mass.
  • the composition ratio of the component (A) is less than 37% by mass, it is difficult to maintain excellent physical properties inherent to the polycarbonate resin in the obtained resin composition, and This composition ratio is 97.95 mass. If the ratio exceeds / o, the obtained resin composition will have insufficient rigidity and dimensional stability.
  • a more preferable composition ratio of the component (A) is 48 to 94.9% by mass.
  • the composition ratio of the inorganic filler (H) is 2 to 60% by mass.
  • composition ratio of the thermoplastic resin is less than 2% by mass, the effect of improving the rigidity and dimensional stability of the resin composition obtained by blending the component (H) is not sufficient. Also, if the composition ratio exceeds 60% by mass, the moldability of the obtained resin composition will be reduced. The more preferable composition ratio of the component (H) is 5 to 50% by mass.
  • the composition ratio of the acid-base-containing aromatic vinyl resin (C) is set to 0.05 to 3% by mass. If the composition ratio of the acid-base-containing aromatic vinyl resin is less than 0.05% by mass, the resin composition obtained by blending the component (C) has flame retardancy and antistatic properties. If the effect of improving the sustainability of performance is not sufficiently exhibited, and if the composition ratio exceeds 3% by mass, physical properties such as impact strength of the obtained resin composition will be reduced. It is.
  • a more preferable mixing ratio of the component (C) is 0.1 to 2% by mass, and a more preferable mixing ratio is 0.5 to 2% by mass.
  • the flame-retardant polycarbonate resin composition of the present invention is a composition having a basic constitution comprising the above components (A), (H) and (C), which has practically sufficiently high flame retardancy and antistatic property. Although sustainability of performance can be obtained, in applications where even higher flame retardancy is required, dripping of component (D) can be suppressed for a total of 100 parts by mass of these basic components.
  • a flame-retardant polycarbonate resin composition containing 0.02 to 5 parts by mass of an agent is suitably used.
  • the mixing ratio of the component (D) is 0.02 parts by mass. If the amount is less than 5, the effect of the compounding effect is not sufficiently exhibited, and even if the compounding amount is increased beyond 5 parts by mass, the effect corresponding thereto cannot be obtained.
  • the more preferable mixing ratio of the component (D) is 0.1 to 1 part by mass.
  • a total of 10% of the composition comprising each of the above basic components (A), (H) and (C) is used.
  • a flame-retardant polycarbonate resin composition obtained by mixing 0.1 to 10 parts by mass of the functional group-containing silicone compound (E) with respect to 0 parts by mass is preferably used. If the blending ratio of the component (E) is less than 0.1 part by mass, the effect of the blending is not sufficiently exhibited, and even if the blending amount exceeds 10 parts by mass, the effect corresponding thereto cannot be obtained. This is because the mechanical strength of the obtained resin composition is rather lowered.
  • a more preferable mixing ratio of the component (E) is 0.1 to 5 parts by mass.
  • the above basic components (A), (H) and (G (F) Flame retardant obtained by blending 0.5 to 10 parts by mass of a core / shell type graphitic elastic body of component (F) with respect to a total of 100 parts by mass of the composition comprising the components of A water-soluble polycarbonate resin composition is preferably used. If the blending ratio of the component (E) is less than 0.5 parts by mass, the effect of the blending is not sufficient, and even if the blending amount is increased beyond 10 parts by mass, the effect commensurate with it is obtained. It is not possible. A more preferable mixing ratio of the component (F) is 0.5 to 5 parts by mass.
  • the above basic constituents (A), (H) and (C) A flame-retardant polycarbonate resin composition comprising 0.1 to 30 parts by mass of the flame retardant of the component (G) based on a total of 100 parts by mass of the composition comprising Used for If the compounding ratio of the component (G) is less than 0.1 part by mass, the compounding effect is not sufficiently exhibited, and even if the compounding amount is increased beyond 30 parts by mass, the effect corresponding thereto cannot be obtained. Because.
  • the components (A), (B) or (H) and (C) are further added at the above-mentioned mixing ratios. Accordingly, the components (D) to (G) may be appropriately blended, mixed and melt-kneaded.
  • the compounding and kneading of each component here are performed by premixing with commonly used equipment, for example, a ribbon blender and a drum tumbler, and then a Banbury mixer, a single screw extruder, and a twin screw extruder. Melt kneading can be carried out using a rewind extruder, a multi-screw screw extruder, or a kneader.
  • the temperature at the time of melt-kneading may be appropriately selected usually in the range of 240 to 300 ° C.
  • the melt-kneaded product is preferably formed by a method of extruding into a strand by an extruder, particularly a vent-type extruder, followed by cooling, cutting and pelletizing.
  • various molded articles are formed by injection molding, injection compression molding, extrusion molding, blow molding, press molding, or the like. Can be manufactured.
  • the molded article obtained from the composition containing the component (A), the component (B) and the component (C) of the present invention thus obtained is excellent in flame retardancy and solvent resistance and has dust on the surface. Excellent durability of antistatic performance without adhesion.
  • the component (A), the component (H) and the component (C) of the present invention A molded article obtained from a composition containing styrene has excellent rigidity, dimensional stability, and flame retardancy, and also has excellent durability of antistatic performance without dust adhering to its surface.
  • composition of the present invention is highly useful in fields such as housings and internal parts of machines, refrigerators and microwave ovens, as well as in automobile parts.
  • each of the components (A), (B), (H), (C), (D), (E), (F) and (G) of the raw materials were mixed at the mixing ratios shown in Tables 1 and 2 [ However, each of the components (A), (B), (H) and (C) in the table represents% by mass, and each of the components (D), (E), (F) and (G) The parts by mass of each component are shown with respect to a total of 100 parts by mass of the components (A), ((B) or (H) ⁇ and (C). And supplied to a vent-type twin-screw extruder (TEM35, manufactured by Toshiba Machine Co., Ltd.), and melt-kneaded at 280 ° C. Then, the kneaded product was extruded into a strand, cooled, and cut to obtain a pellet of a flame-retardant polycarbonate resin composition.
  • TEM35 vent-type twin-screw extruder
  • Polycarbonate resin having a structural unit derived from (A-1) 2,2-bis (4-hydroxyphenyl) propane, having a linear structure and having a viscosity average molecular weight of 19,500 .
  • (A-2) contains 4% by mass of a block having 30 structural units derived from dimethylsiloxane, and the other comprises structural units derived from 2,2-bis (4-hydroxyphenyl) propane, A polycarbonate resin having a linear structure and a viscosity average molecular weight of 1500.
  • (B-1) Melt flow rate measured at 200 ° C and 5 kg load in accordance with JISK-7210, 8 g / l 0 min, and polybutadiene rubber content 1 0 mass 0/0 high impact polystyrene resin is [Idemitsu Petrochemical Co., Ltd.: IT 4 4].
  • (C-2) a polystyrene sulfonate having a weight average molecular weight of 20,000 and a sulfonation ratio of 40%.
  • the components of the raw materials are shown in Table 3 and Table 4. And supplied to a vented twin-screw extruder (TEM35, manufactured by Toshiba Machine Co., Ltd.) and melt-kneaded at 280 ° C. Next, the kneaded material was extruded into a strand, cooled, and cut to obtain a pellet of a flame-retardant polycarbonate resin composition.
  • TEM35 vented twin-screw extruder
  • the obtained pellets were dried at 120 ° C for 12 hours, and then injection-molded at a molding temperature of 270 ° C and a mold temperature of 80 ° C, to obtain a test piece and a molded product. did.
  • the Meltoff mouth rate was measured under the conditions of a temperature of 280 ° C and a load of 2.16 kg.
  • the measurement was performed according to JISK 7203.
  • Orientec Co., Ltd .; ⁇ -250 was used, and the measurement was performed under the conditions of a bending speed of 2.0 mm / min and a span of 60 mm. '
  • test piece was used to perform a vertical combustion test according to Underwriters Laboratory, Subject 94.
  • Example Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9
  • Example Considerd Example 10 Example 11
  • Example 12 Example 'J 1' 3 ⁇ Lung lJU Example 15 Room
  • Example 16 Example 17
  • Example 18 Example 19
  • a (A- 1) 9 9.0 0 9.0 0.0 44.5 8 6.08 8 8.5 8 8.5 8 8.5
  • a flame-retardant polycarbonate resin composition which is excellent in fluidity, solvent resistance and flame retardancy, and which can obtain a molded article excellent in durability of antistatic performance to which dust does not adhere.
  • Flame-retardant polycarbonate resin composition which is excellent in rigidity, dimensional stability and flame retardancy, and which can obtain a molded article excellent in durability of antistatic performance without adhering dust, and molded article thereof Can be provided.
  • a flame-retardant polycarbonate resin composition comprising 0.05 to 3% by mass.
  • thermoplastic resin (B) is a styrene resin or a polyester resin.
  • component (A), component (B) and component (C) are blended with 0.02 to 5 parts by mass of drip inhibitor as component (D).
  • a total of 100 parts by mass of the components (A), (B) and (C) is blended with 0.1 to 10 parts by mass of the functional group-containing silicone compound as the component (E).
  • the flame-retardant polycarbonate resin composition according to any one of claims 1 to 6.
  • component (F) 8. For a total of 100 parts by mass of component (A), component (B) and component (C), a core-shell type rubber-like rubber is used as component (F).

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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)

Abstract

L'invention concerne (1) une composition de résines polycarbonates ignifuge contenant 50 à 97,95 % en poids de résines polycarbonates, 2 à 47 % en poids de résines thermoplastiques différentes des résines polycarbonates, et 0,05 à 3 % en poids de résines vinyles aromatiques contenant des acides/bases ; (2) une composition de résines polycarbonates ignifuge contenant 37 à 97,95 % en poids de résines polycarbonates, 2 à 60 % en poids de charge inorganique, et 0,05 à 3 % en poids de résines vinyles aromatiques contenant des acides/bases ; et, (3) un élément destiné à des appareils électriques/électroniques obtenu par moulage d'une des compositions de résines selon l'invention.
PCT/JP2002/000137 2001-01-26 2002-01-11 Compositions de resines polycarbonates ignifuges et articles moules a partir de ces compositions WO2002059205A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2001-17927 2001-01-26
JP2001017927A JP5302486B2 (ja) 2001-01-26 2001-01-26 難燃性ポリカーボネート樹脂組成物及びその成形品
JP2001-27714 2001-02-05
JP2001027714A JP5021122B2 (ja) 2001-02-05 2001-02-05 難燃性ポリカーボネート樹脂組成物及びその成形品

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2133390A1 (fr) * 2008-06-10 2009-12-16 Sony Corporation Composition en résine de polycarbonate ignifuge
US7851529B2 (en) 2002-08-26 2010-12-14 Idemitsu Kosan Co., Ltd. Polycarbonate resin composition and molded article
US8003735B2 (en) 2004-12-08 2011-08-23 Idemitsu Kosan Co., Ltd. Polycarrbonate rubbery elastomer thermoplastic resin composition and molded body
CN106103589A (zh) * 2014-03-31 2016-11-09 出光兴产株式会社 被涂装用聚碳酸酯树脂成形材料、成形品及涂装成形品
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
US11286355B2 (en) 2017-09-22 2022-03-29 3M Innovative Properties Company Composite article

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11172063A (ja) * 1997-12-08 1999-06-29 Asahi Chem Ind Co Ltd 難燃性熱可塑性樹脂成形材料

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11172063A (ja) * 1997-12-08 1999-06-29 Asahi Chem Ind Co Ltd 難燃性熱可塑性樹脂成形材料

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7851529B2 (en) 2002-08-26 2010-12-14 Idemitsu Kosan Co., Ltd. Polycarbonate resin composition and molded article
US8003735B2 (en) 2004-12-08 2011-08-23 Idemitsu Kosan Co., Ltd. Polycarrbonate rubbery elastomer thermoplastic resin composition and molded body
EP2133390A1 (fr) * 2008-06-10 2009-12-16 Sony Corporation Composition en résine de polycarbonate ignifuge
US8748510B2 (en) 2008-06-10 2014-06-10 Sony Corporation Flame-retardant polycarbonate resin composition
CN106103589A (zh) * 2014-03-31 2016-11-09 出光兴产株式会社 被涂装用聚碳酸酯树脂成形材料、成形品及涂装成形品
CN106103589B (zh) * 2014-03-31 2019-09-06 出光兴产株式会社 被涂装用聚碳酸酯树脂成形材料、成形品及涂装成形品
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
US11286355B2 (en) 2017-09-22 2022-03-29 3M Innovative Properties Company Composite article

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