WO2019225558A1 - Composition ignifuge de résine de polycarbonate - Google Patents

Composition ignifuge de résine de polycarbonate Download PDF

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WO2019225558A1
WO2019225558A1 PCT/JP2019/019972 JP2019019972W WO2019225558A1 WO 2019225558 A1 WO2019225558 A1 WO 2019225558A1 JP 2019019972 W JP2019019972 W JP 2019019972W WO 2019225558 A1 WO2019225558 A1 WO 2019225558A1
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component
weight
parts
bis
acid
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健人 桝村
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帝人株式会社
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Priority to JP2020521228A priority Critical patent/JP7069306B2/ja
Priority to CN201980034315.9A priority patent/CN112189033A/zh
Publication of WO2019225558A1 publication Critical patent/WO2019225558A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/5399—Phosphorus bound to nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/04—Polyadducts obtained by the diene synthesis
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • 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 product thereof. More specifically, by adding an impact modifier, phosphazene, anti-drip agent and titanium oxide to a resin component comprising a polycarbonate resin and a polyester resin, mechanical properties, chemical resistance, flame resistance, high light reflectivity, The present invention relates to a polycarbonate resin composition having an improved appearance of a molded product.
  • Aromatic polycarbonate resins have excellent mechanical properties and thermal properties, and are used in various applications mainly in the OA equipment field and the electronic and electrical equipment field by imparting flame retardancy. .
  • resin materials having high impact, high flame retardancy, and excellent molded appearance.
  • a resin material having high impact and excellent molded appearance has been studied while satisfying the requirement of thin flame retardant in the required safety standard UL94 in aromatic polycarbonate resin.
  • Patent Document 1 As a method for imparting high flame retardancy to an aromatic polycarbonate resin, a combination of a halogen flame retardant such as a bromine compound and a flame retardant aid such as antimony trioxide has been generally used (Patent Document 1). reference).
  • Patent Document 3 As a prescription for improving the toughness of an aromatic polycarbonate resin, a method of adding an impact modifier such as a graft polymer is known (see Patent Document 3).
  • an impact modifier such as a graft polymer
  • the addition of a flame retardant causes a decrease in mechanical properties
  • the addition of an impact modifier causes a decrease in flame retardancy. Therefore, due to the balance between the amount of flame retardant and the amount of impact modifier, mechanical properties and difficulty within a certain range.
  • a resin composition having flammability has been provided (see Patent Document 4).
  • JP-A-2-1991162 Japanese Patent Laid-Open No. 2-115262 JP 2009-203269 A Japanese Patent Laid-Open No. 2001-123056
  • an object of the present invention is to provide a polycarbonate resin composition satisfying excellent mechanical properties, chemical resistance, flame retardancy, high light reflectivity, and appearance of a molded product at a high level.
  • the present inventor has added an impact modifier, a phosphazene, an anti-drip agent and titanium oxide to a resin component composed of a polycarbonate resin and a polyester resin.
  • the inventors have found a method for obtaining a polycarbonate resin composition having improved chemical properties, flame retardancy, high light reflectivity, and molded product appearance, and have completed the present invention.
  • the said subject is achieved by the flame-retardant polycarbonate resin composition of the following aspect.
  • a flame-retardant polycarbonate resin composition comprising (E) 0.05 to 2 parts by weight of an anti-drip agent (E component) and (F) 0.05 to 30 parts by weight of titanium oxide (F component) Stuff.
  • the flame-retardant polycarbonate resin composition of the present invention has improved mechanical properties, chemical resistance, flame retardancy, high light reflectivity, and appearance of molded products, the OA equipment field, the electronic / electronic equipment field, and other various types. Widely useful in the field. Therefore, the industrial effect exhibited by the present invention is extremely great.
  • the polycarbonate resin used in the present invention is obtained by reacting a dihydric phenol and a carbonate precursor.
  • the reaction method include an interfacial polymerization method, a melt transesterification method, a solid phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound.
  • dihydric phenol examples include hydroquinone, resorcinol, 4,4′-biphenol, 1,1-bis (4-hydroxyphenyl) ethane, and 2,2-bis (4-hydroxyphenyl).
  • Propane commonly called bisphenol A
  • 2,2-bis (4-hydroxy-3-methylphenyl) propane 2,2-bis (4-hydroxyphenyl) butane
  • 1,1-bis (4-hydroxyphenyl)- 1-phenylethane 1,1-bis (4-hydroxyphenyl) cyclohexane
  • 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane 2,2-bis (4-hydroxyphenyl) Pentane, 4,4 '-(p-phenylenediisopropylidene) diphenol, 4,4'-(m-phenylenediiso (Ropyridene) diphenol, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane
  • the general-purpose polycarbonate which is a bisphenol A-based polycarbonate
  • a special polycarbonate produced using other dihydric phenols can be used as the A component.
  • BPM 4,4 ′-(m-phenylenediisopropylidene) diphenol
  • Bis-TMC 1,1-bis (4-hydroxy Phenyl) cyclohexane
  • Bis-TMC 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane
  • BCF 9,9-bis (4-hydroxyphenyl) Polycarbonate (homopolymer or copolymer) using fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene
  • dihydric phenols other than BPA are preferably used in an amount of 5 mol% or more, particularly 10 mol% or more of the entire dihydric phenol component constituting the polycarbonate.
  • the component A constituting the resin composition is the following (1) to (3) copolymer polycarbonate.
  • BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, more preferably 45 to 65 mol%) in 100 mol% of the dihydric phenol component constituting the polycarbonate
  • BPA is 10 to 95 mol% (more preferably 50 to 90 mol%, more preferably 60 to 85 mol%) in 100 mol% of the dihydric phenol component constituting the polycarbonate
  • BCF I is a copolycarbonate having 5 to 90 mol% (more preferably 10 to 50 mol%, more preferably 15 to 40 mol%)
  • BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, more preferably 45 to 65 mol%) in 100 mol% of the dihydric phenol component constituting the polycarbonate, and Bis A copolymeric polycarbonate having a TMC of 20 to 80 mol% (more preferably 25 to 60 mol%, more preferably 35 to 55 mol%).
  • These special polycarbonates may be used alone or in combination of two or more. Moreover, these can also be mixed and used for the bisphenol A type polycarbonate generally used.
  • the water absorption rate of polycarbonate is a value obtained by measuring the moisture content after being immersed in water at 23 ° C. for 24 hours in accordance with ISO 62-1980 using a disc-shaped test piece having a diameter of 45 mm and a thickness of 3.0 mm. is there.
  • Tg glass transition temperature
  • DSC differential scanning calorimeter
  • carbonate precursor carbonyl halide, carbonic acid diester, haloformate or the like is used, and specific examples include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, and the like.
  • the aromatic polycarbonate resin of the present invention is a branched polycarbonate resin copolymerized with a trifunctional or higher polyfunctional aromatic compound, a polyester copolymerized with an aromatic or aliphatic (including alicyclic) difunctional carboxylic acid.
  • Carbonate resin, copolymer polycarbonate resin copolymerized with bifunctional alcohol (including alicyclic), and polyester carbonate resin copolymerized with such bifunctional carboxylic acid and bifunctional alcohol are included.
  • the mixture which mixed 2 or more types of the obtained aromatic polycarbonate resin may be sufficient.
  • Branched polycarbonate resin can impart anti-drip performance and the like to the resin composition of the present invention.
  • the trifunctional or higher polyfunctional aromatic compound used in the branched polycarbonate resin include phloroglucin, phloroglucid, or 4,6-dimethyl-2,4,6-tris (4-hydroxydiphenyl) heptene-2, , 4,6-trimethyl-2,4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) Ethane, 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, 4- ⁇ 4- [ Trisphenol such as 1,1-bis (4-hydroxyphenyl) ethyl] benzene ⁇ - ⁇ , ⁇ -dimethylbenzylphenol, tetra (4
  • the structural unit derived from the polyfunctional aromatic compound in the branched polycarbonate is preferably a total of 100 mol% of the structural unit derived from the dihydric phenol and the structural unit derived from the polyfunctional aromatic compound. It is 0.01 to 1 mol%, more preferably 0.05 to 0.9 mol%, still more preferably 0.05 to 0.8 mol%.
  • a branched structural unit may be generated as a side reaction, and the amount of the branched structural unit is preferably 100% by mole in total with the structural unit derived from dihydric phenol. It is preferably 0.001 to 1 mol%, more preferably 0.005 to 0.9 mol%, and still more preferably 0.01 to 0.8 mol%.
  • the ratio of the branched structure can be calculated by 1H-NMR measurement.
  • the aliphatic bifunctional carboxylic acid is preferably ⁇ , ⁇ -dicarboxylic acid.
  • Examples of the aliphatic difunctional carboxylic acid include sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, icosanedioic acid and other straight-chain saturated aliphatic dicarboxylic acids, and cyclohexanedicarboxylic acid.
  • alicyclic dicarboxylic acids such as As the bifunctional alcohol, an alicyclic diol is more preferable, and examples thereof include cyclohexanedimethanol, cyclohexanediol, and tricyclodecane dimethanol.
  • Reaction methods such as interfacial polymerization, melt transesterification, carbonate prepolymer solid phase transesterification, and ring-opening polymerization of cyclic carbonate compounds, which are methods for producing the polycarbonate resin of the present invention, include various documents and patent publications. This is a well-known method.
  • the viscosity average molecular weight (M) of the polycarbonate resin is not particularly limited, but is preferably 1.8 ⁇ 10 4 to 4.0 ⁇ 10 4 , more It is preferably 2.0 ⁇ 10 4 to 3.5 ⁇ 10 4 , more preferably 2.2 ⁇ 10 4 to 3.0 ⁇ 10 4 .
  • the viscosity average molecular weight is 1.8 ⁇ 10 4 or more, good mechanical properties may be brought about.
  • a resin composition obtained from a polycarbonate resin having a viscosity average molecular weight of 4.0 ⁇ 10 4 or less may be excellent in versatility in terms of good fluidity during injection molding.
  • the said polycarbonate resin may be obtained by mixing the thing whose viscosity average molecular weight is outside the said range.
  • a polycarbonate resin having a viscosity average molecular weight exceeding the above range (5 ⁇ 10 4 ) improves the entropy elasticity of the resin.
  • good moldability is exhibited in gas assist molding and foam molding which may be used when molding a reinforced resin material into a structural member. Such improvement in moldability is even better than that of the branched polycarbonate.
  • the component A is a polycarbonate resin A-1-1-1 component having a viscosity average molecular weight of 7 ⁇ 10 4 to 3 ⁇ 10 5 ), and a fragrance having a viscosity average molecular weight of 1 ⁇ 10 4 to 3 ⁇ 10 4
  • Polycarbonate resin (A-1-1 component) having a viscosity average molecular weight of 1.6 ⁇ 10 4 to 3.5 ⁇ 10 4 (hereinafter referred to as “A-1-1 component”).
  • a high molecular weight component-containing polycarbonate resin may also be used.
  • the molecular weight of the component A-1-1-1 is preferably 7 ⁇ 10 4 to 2 ⁇ 10 5 , more preferably 8 ⁇ 10 4 to 2 ⁇ . 10 5 , more preferably 1 ⁇ 10 5 to 2 ⁇ 10 5 , and particularly preferably 1 ⁇ 10 5 to 1.6 ⁇ 10 5 .
  • the molecular weight of the component A-1-1-2 is preferably 1 ⁇ 10 4 to 2.5 ⁇ 10 4 , more preferably 1.1 ⁇ 10 4 to 2.4 ⁇ 10 4 , and still more preferably 1.2 ⁇ 10 4 to 2.4 ⁇ 10 4 , particularly preferably 1.2 ⁇ 10 4 to 2.3 ⁇ 10 4 .
  • the high molecular weight component-containing polycarbonate resin (component A-1-1) is prepared by mixing the components A-1-1-1 and A-1-1-2 in various proportions to satisfy a predetermined molecular weight range. Can be obtained.
  • the A-1-1-1 component is 2 to 40% by weight in 100% by weight of the A-1-1 component, and more preferably 3 to 30% by weight of the A-1-1-1 component. More preferably, the A-1-1-1 component is 4 to 20% by weight, and particularly preferably the A-1-1-1 component is 5 to 20% by weight.
  • A-1-1 component (1) a method in which the A-1-1-1 component and the A-1-1-2 component are polymerized independently and mixed, ) Using such a method for producing an aromatic polycarbonate resin having a plurality of polymer peaks in a molecular weight distribution chart by the GPC method, represented by the method disclosed in JP-A-5-306336, in the same system, such an aromatic polycarbonate resin And (3) an aromatic polycarbonate resin obtained by such a production method (production method (2)) and A separately produced A Examples thereof include a method of mixing the 1-1-1 component and / or the A-1-1-2 component.
  • the viscosity average molecular weight M is calculated from the determined specific viscosity ( ⁇ SP ) by the following formula.
  • the viscosity average molecular weight of the polycarbonate resin in the flame retardant polycarbonate resin composition of the present invention is calculated as follows. That is, the composition is mixed with 20 to 30 times its weight of methylene chloride to dissolve soluble components in the composition. Such soluble matter is collected by Celite filtration. Thereafter, the solvent in the obtained solution is removed. The solid after removal of the solvent is sufficiently dried to obtain a solid component that dissolves in methylene chloride. A specific viscosity at 20 ° C. is determined from a solution obtained by dissolving 0.7 g of the solid in 100 ml of methylene chloride in the same manner as described above, and the viscosity average molecular weight M is calculated from the specific viscosity in the same manner as described above.
  • a polycarbonate-polydiorganosiloxane copolymer resin can also be used as the polycarbonate resin (component A) of the present invention.
  • the polycarbonate-polydiorganosiloxane copolymer resin is a copolymer prepared by copolymerizing a dihydric phenol represented by the following general formula (1) and a hydroxyaryl-terminated polydiorganosiloxane represented by the following general formula (3).
  • a polymerized resin is preferred.
  • R 1 and R 2 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or 6 to 6 carbon atoms.
  • E and f are each an integer of 1 to 4
  • W is a single bond or at least one group selected from the group consisting of groups represented by the following general formula (2). That. ]
  • R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, carbon Represents a group selected from the group consisting of an aryl group having 6 to 14 atoms and an aralkyl group having 7 to 20 carbon atoms, and R 19 and R 20 each independently represent a hydrogen atom, a halogen atom, or a carbon atom having 1 to 18 carbon atoms.
  • Alkyl groups alkoxy groups having 1 to 10 carbon atoms, cycloalkyl groups having 6 to 20 carbon atoms, cycloalkoxy groups having 6 to 20 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, and 6 carbon atoms.
  • R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a substituent having 6 to 12 carbon atoms.
  • R 9 and R 10 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and p is a natural number Q is 0 or a natural number, and p + q is a natural number of 10 to 300.
  • X is a divalent aliphatic group having 2 to 8 carbon atoms.
  • Examples of the dihydric phenol (I) represented by the general formula (1) include 4,4′-dihydroxybiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1 -Bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxy-3,3'-biphenyl) propane, 2,2-bis (4-hydroxy-3-isopropyl) Phenyl) propane, 2,2-bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2 2-bis (4-hydroxyphenyl) octane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-
  • 1,1-bis (4-hydroxyphenyl) -1-phenylethane 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4′-sulfonyldiphenol, 2,2′-dimethyl- 4,4′-sulfonyldiphenol, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,3-bis ⁇ 2- (4-hydroxyphenyl) propyl ⁇ benzene, 1,4-bis ⁇ 2- (4-hydroxyphenyl) propyl ⁇ benzene is preferred, especially 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis ( - hydroxyphenyl) cyclohexane (BPZ), 4,4'-sulfonyl diphenol, 9,9-bis (4-bis (4-bis
  • hydroxyaryl-terminated polydiorganosiloxane represented by the general formula (3) for example, the following compounds are preferably used.
  • the hydroxyaryl-terminated polydiorganosiloxane (II) is a phenol having an olefinically unsaturated carbon-carbon bond, preferably vinylphenol, 2-allylphenol, isopropenylphenol, 2-methoxy-4-allylphenol. It is easily produced by hydrosilylation reaction at the end of a polysiloxane chain having a degree of polymerization of.
  • (2-allylphenol) -terminated polydiorganosiloxane and (2-methoxy-4-allylphenol) -terminated polydiorganosiloxane are preferred, and (2-allylphenol) -terminated polydimethylsiloxane, especially (2-methoxy-4) -Allylphenol) terminated polydimethylsiloxane is preferred.
  • the hydroxyaryl-terminated polydiorganosiloxane (II) preferably has a molecular weight distribution (Mw / Mn) of 3 or less.
  • the molecular weight distribution (Mw / Mn) is more preferably 2.5 or less, and even more preferably 2 or less, in order to develop further excellent low outgassing properties and low temperature impact properties during high temperature molding. Within such a suitable range, the molecular weight distribution is sufficiently small, so that the amount of outgas generated during high temperature molding may be reduced, and the low temperature impact property may be excellent.
  • the degree of diorganosiloxane polymerization (p + q) of hydroxyaryl-terminated polydiorganosiloxane (II) is suitably 10 to 300.
  • the degree of polymerization (p + q) of the diorganosiloxane is preferably 10 to 200, more preferably 12 to 150, and still more preferably 14 to 100.
  • impact resistance which is characteristic of the polycarbonate-polydiorganosiloxane copolymer, is effectively exhibited when the degree of polymerization is sufficiently large, and a good appearance is obtained when the degree of polymerization is not too large. Is brought about.
  • the polydiorganosiloxane content in the total weight of the polycarbonate-polydiorganosiloxane copolymer resin used in the component A is preferably 0.1 to 50% by weight.
  • the polydiorganosiloxane component content is more preferably 0.5 to 30% by weight, still more preferably 1 to 20% by weight.
  • Above the lower limit of the preferred range the impact resistance and flame retardancy are excellent, and below the upper limit of the preferred range, a stable appearance that is hardly affected by the molding conditions is easily obtained.
  • Such polydiorganosiloxane polymerization degree and polydiorganosiloxane content can be calculated by 1H-NMR measurement.
  • hydroxyaryl-terminated polydiorganosiloxane (II) may be used alone or in combination of two or more.
  • other comonomer other than the dihydric phenol (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) is within a range of 10% by weight or less based on the total weight of the copolymer. It can also be used together.
  • a mixed solution containing an oligomer having a terminal chloroformate group is prepared in advance by a reaction of a dihydric phenol (I) and a carbonate-forming compound in a mixed solution of an organic solvent insoluble in water and an alkaline aqueous solution. To do.
  • the whole amount of the dihydric phenol (I) used in the method of the present invention may be converted into an oligomer at one time, or a part of the dihydric phenol (I) is used as a post-added monomer at the latter stage interface.
  • the post-added monomer is added to allow the subsequent polycondensation reaction to proceed rapidly, and it is not necessary to add it when it is not necessary.
  • the method of the oligomer production reaction is not particularly limited, but usually a method of performing in a solvent in the presence of an acid binder is preferable.
  • the proportion of carbonate ester-forming compound used may be appropriately adjusted in consideration of the stoichiometric ratio (equivalent) of the reaction. Moreover, when using gaseous carbonate ester-forming compounds, such as phosgene, the method of blowing this into a reaction system can be employ
  • the acid binder examples include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, and mixtures thereof.
  • the use ratio of the acid binder may be appropriately determined in consideration of the stoichiometric ratio (equivalent) of the reaction as described above. Specifically, it is preferable to use 2 equivalents or slightly more acid binder than the number of moles of dihydric phenol (I) used to form the oligomer (usually 1 mole corresponds to 2 equivalents). .
  • a solvent inert to various reactions such as those used for producing known polycarbonates may be used alone or as a mixed solvent.
  • Typical examples include hydrocarbon solvents such as xylene, halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene.
  • a halogenated hydrocarbon solvent such as methylene chloride is preferably used.
  • the reaction pressure for oligomer formation is not particularly limited, and any of normal pressure, pressurization and reduced pressure may be used, but it is usually advantageous to carry out the reaction under normal pressure.
  • the reaction temperature is selected from the range of ⁇ 20 to 50 ° C., and in many cases, heat is generated with the polymerization, so it is desirable to cool with water or ice.
  • the reaction time depends on other conditions and cannot be generally defined, but is usually 0.2 to 10 hours.
  • the pH range of the oligomer formation reaction is the same as the known interfacial reaction conditions, and the pH is always adjusted to 10 or more.
  • the molecular weight distribution (Mw / Mn) is up to 3 while stirring the mixed solution.
  • a highly purified hydroxyaryl-terminated polydiorganosiloxane (II) represented by the general formula (4) is added to the dihydric phenol (I), and the polyhydroxyorganosiloxane (II) and the oligomer are interfacially polycondensed. As a result, a polycarbonate-polydiorganosiloxane copolymer is obtained.
  • R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a substituent having 6 to 12 carbon atoms.
  • R 9 and R 10 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and p is a natural number Q is 0 or a natural number, and p + q is a natural number of 10 to 300.
  • X is a divalent aliphatic group having 2 to 8 carbon atoms.
  • an acid binder may be appropriately added in consideration of the stoichiometric ratio (equivalent) of the reaction.
  • the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, and mixtures thereof.
  • hydroxyaryl-terminated polydiorganosiloxane (II) to be used or a part of the dihydric phenol (I) as described above is added as a post-added monomer to this reaction stage, It is preferable to use 2 equivalents or an excess amount of alkali with respect to the total number of moles of monovalent phenol (I) and hydroxyaryl-terminated polydiorganosiloxane (II) (usually 1 mole corresponds to 2 equivalents).
  • the polycondensation by the interfacial polycondensation reaction between the dihydric phenol (I) oligomer and the hydroxyaryl-terminated polydiorganosiloxane (II) is carried out by vigorously stirring the above mixture.
  • a terminal terminator or a molecular weight modifier is usually used.
  • the terminator include compounds having a monovalent phenolic hydroxyl group.
  • the terminator include compounds having a monovalent phenolic hydroxyl group.
  • phenol p-tert-butylphenol, p-cumylphenol, tribromophenol, etc., long-chain alkylphenols, aliphatic carboxylic acids
  • examples include chloride, aliphatic carboxylic acid, hydroxybenzoic acid alkyl ester, hydroxyphenylalkyl acid ester, alkyl ether phenol and the like.
  • the amount used is in the range of 100 to 0.5 mol, preferably 50 to 2 mol, based on 100 mol of all dihydric phenol compounds used, and it is naturally possible to use two or more compounds in combination. is there.
  • a catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt may be added.
  • the reaction time of such a polymerization reaction is preferably 30 minutes or more, more preferably 50 minutes or more. If desired, a small amount of an antioxidant such as sodium sulfite or hydrosulfide may be added.
  • an antioxidant such as sodium sulfite or hydrosulfide
  • a branching agent can be used in combination with the above dihydric phenol compound to form a branched polycarbonate-polydiorganosiloxane.
  • Examples of the trifunctional or higher polyfunctional aromatic compound used in the branched polycarbonate-polydiorganosiloxane copolymer resin include phloroglucin, phloroglucid, or 4,6-dimethyl-2,4,6-tris (4-hydroxydiphenyl).
  • 1,1,1-tris (4-hydroxyphenyl) ethane is particularly preferable.
  • the ratio of the polyfunctional compound in the branched polycarbonate-polydiorganosiloxane copolymer resin is preferably 0.001 to 1 mol%, more preferably 0.005 to 0 in the total amount of the aromatic polycarbonate-polydiorganosiloxane copolymer resin. 0.9 mol%, more preferably 0.01 to 0.8 mol%, particularly preferably 0.05 to 0.4 mol%.
  • Such a branched structure amount can be calculated by 1 H-NMR measurement.
  • the reaction pressure can be any of reduced pressure, normal pressure, and increased pressure. Usually, it can be suitably carried out at normal pressure or about the pressure of the reaction system.
  • the reaction temperature is selected from the range of ⁇ 20 to 50 ° C., and in many cases, heat is generated with the polymerization, so it is desirable to cool with water or ice. Since the reaction time varies depending on other conditions such as the reaction temperature, it cannot be generally specified, but is usually 0.5 to 10 hours.
  • the obtained polycarbonate-polydiorganosiloxane copolymer resin is appropriately subjected to physical treatment (mixing, fractionation, etc.) and / or chemical treatment (polymer reaction, crosslinking treatment, partial decomposition treatment, etc.) to achieve the desired reduction. It can also be obtained as a polycarbonate-polydiorganosiloxane copolymer resin having a viscosity [ ⁇ SP / c].
  • the obtained reaction product (crude product) can be recovered as a polycarbonate-polydiorganosiloxane copolymer resin having a desired purity (purity) by performing various post-treatments such as a known separation and purification method.
  • the average size of the polydiorganosiloxane domain in the polycarbonate-polydiorganosiloxane copolymer resin molded article is preferably in the range of 1 to 60 nm.
  • the average size is more preferably 3 to 55 nm, and further preferably 5 to 50 nm.
  • impact resistance and flame retardancy may be sufficiently exerted when the average size of the domain is sufficiently large, and impact resistance is ensured when the average size of the domain is not too large. May be exhibited stably. Thereby, a flame retardant polycarbonate resin composition excellent in impact resistance and appearance is provided.
  • the polyester resin (component B) used in the thermoplastic resin composition of the present invention is a polymer or copolymer obtained by a condensation reaction mainly comprising an aromatic dicarboxylic acid or a reactive derivative thereof and a diol or an ester derivative thereof. A polymer is preferred.
  • aromatic dicarboxylic acid isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 4,4′-biphenyl ether Dicarboxylic acid, 4,4′-biphenylmethane dicarboxylic acid, 4,4′-biphenylsulfone dicarboxylic acid, 4,4′-biphenylisopropylidenedicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4′-dicarboxylic acid
  • Aromatic dicarboxylic acids such as acid, 2,5-anthracene dicarboxylic acid, 2,6-anthracene dicarboxylic acid, 4,4′-p-terphenylene dicarboxylic acid, 2,5-pyridinedicarboxylic acid are preferably used.
  • terephthalic acid isophthalic acid, ortho
  • Aromatic dicarboxylic acids may be used as a mixture of two or more. In addition, if the amount is small, it is also possible to use a mixture of one or more aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid and dodecanediic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, etc. together with the dicarboxylic acid. .
  • - contains an aromatic ring such as 2,2-bis ( ⁇ -hydroxyethoxyphenyl) propane, an aliphatic diol such as propanediol, diethylene glycol, triethylene glycol, an alicyclic diol such as 1,4-cyclohexanedimethanol, etc. Examples thereof include diols and mixtures thereof.
  • one or more long-chain diols having a molecular weight of 400 to 6,000 that is, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, etc. may be copolymerized.
  • the polyester resin of the present invention can be branched by introducing a small amount of a branching agent.
  • a branching agent A trimesic acid, a trimellitic acid, a trimethylol ethane, a trimethylol propane, a pentaerythritol, etc. are mentioned.
  • polyester resins include polyethylene terephthalate (PET), polypropylene terephthalate, polybutylene terephthalate (PBT), polyhexylene terephthalate, polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polyethylene-1,2-
  • PET polyethylene terephthalate
  • PBT polypropylene terephthalate
  • PEN polyethylene naphthalate
  • PBN polybutylene naphthalate
  • copolymer polyester resins such as polyethylene isophthalate / terephthalate, polybutylene terephthalate / isophthalate, and the like can be given.
  • polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate and mixtures thereof having a good balance of mechanical properties and the like can be preferably used.
  • the mixed use of polyethylene terephthalate and polybutylene terephthalate is impact. It is preferable in terms of strength and chemical resistance.
  • the use (weight) ratio of polyethylene terephthalate to polybutylene terephthalate is preferably in the range of 40/60 to 95/5 for polyethylene terephthalate / polybutylene terephthalate, in particular in the range of 50/50 to 90/10. Is preferred.
  • the terminal group structure of the obtained polyester resin is not particularly limited, and the ratio of the hydroxyl group and the carboxyl group in the terminal group may be a large amount other than the case where the ratio is large. Moreover, those terminal groups may be sealed by reacting a compound having reactivity with such terminal groups.
  • germanium-based polymerization catalysts include germanium oxides, hydroxides, halides, alcoholates, phenolates, and the like. More specifically, germanium oxide, germanium hydroxide, germanium tetrachloride, tetramethoxygermanium, etc. Can be illustrated.
  • compounds such as manganese, zinc, calcium, magnesium, etc. which are used in the transesterification reaction, which is a pre-stage of a conventionally known polycondensation, can be used together, and phosphoric acid or phosphorous acid after completion of the transesterification reaction It is also possible to deactivate the catalyst and perform polycondensation with the above compound.
  • the intrinsic viscosity measured at 25 ° C. using o-chlorophenol as a solvent is preferably 0.4 to 1.2, more preferably 0.65 to 1.15. .
  • the content of the B component is 60 to 5 parts by weight, preferably 50 to 10 parts by weight, more preferably 40 to 20 parts by weight, in a total of 100 parts by weight of the A component and the B component.
  • the content of component B is 5 parts by weight or more, sufficient chemical resistance can be obtained.
  • the amount is 60 parts by weight or less, good impact resistance and flame retardancy are ensured.
  • the flame retardant polycarbonate resin composition of the present invention contains an impact modifier as the C component.
  • the impact modifier preferably contains a rubber component, more preferably a polymer having a core-shell structure containing a rubber component in the core.
  • a graft polymer obtained by graft-polymerizing at least one compound containing a (meth) acrylic acid ester compound to one rubber selected from the group consisting of butadiene rubber, acrylic rubber, and silicone / acrylic composite rubber. More preferably, the graft polymer has a core-shell structure.
  • the core-shell type graft polymer is a monomer selected from vinyl compounds copolymerizable with a rubber component having a glass transition temperature of 10 ° C. or less, including a (meth) acrylate compound and an aromatic alkenyl compound. It is a graft copolymer copolymerized with a seed or two or more shells.
  • C component rubber components include butadiene rubber, butadiene-acrylic composite rubber, acrylic rubber, silicone / acrylic composite rubber, isobutylene-silicone composite rubber, isoprene rubber, styrene-butadiene rubber, chloroprene rubber, ethylene-propylene rubber, Nitrile rubber, ethylene-acrylic rubber, silicone rubber, epichlorohydrin rubber, fluororubber, and those in which hydrogen is added to these unsaturated bonds may be mentioned.
  • a rubber component containing no halogen atom is preferable in terms of environmental load.
  • the glass transition temperature of the rubber component is preferably ⁇ 10 ° C. or lower, more preferably ⁇ 30 ° C. or lower.
  • the rubber component is particularly preferably butadiene rubber or acrylic silicone / acrylic composite rubber.
  • the composite rubber is a rubber obtained by copolymerizing two kinds of rubber components or a rubber polymerized so as to have an IPN structure entangled with each other so as not to be separated.
  • the particle diameter of the core is preferably 240 to 300 nm, more preferably 250 to 290 nm, and further preferably 260 to 280 nm in terms of the weight average particle diameter. If it is in the range of 240 to 300 nm, better impact resistance is achieved.
  • the particle size distribution is preferably a bidisperse type having two peaks, particularly preferably a bidisperse type having two peaks in the vicinity of 100 nm and 300 nm, and better impact resistance is achieved than a monodisperse type having a single peak.
  • Examples of the aromatic vinyl in the vinyl compound copolymerized with the rubber component as the shell of the core-shell type graft polymer include styrene, ⁇ -methylstyrene, p-methylstyrene, alkoxystyrene, and halogenated styrene.
  • Examples of the acrylate ester include methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, octyl acrylate, and the like.
  • Examples of the methacrylate ester include methyl methacrylate, ethyl methacrylate, butyl methacrylate.
  • Cyclohexyl methacrylate, octyl methacrylate and the like, and methyl methacrylate is particularly preferable.
  • methacrylic acid esters such as methyl methacrylate are preferably contained as essential components, and from the viewpoint of mechanical properties and flame retardancy, it is more preferable not to contain an aromatic vinyl component. This is because the core-shell type graft polymer is excellent in affinity with the aromatic polycarbonate resin, so that more rubber components are present in the resin, and the good impact resistance of the aromatic polycarbonate resin is further increased. This is because it is effectively exhibited, and as a result, the impact resistance of the resin composition is improved.
  • the methacrylic acid ester is contained in 100% by weight of the graft component (in the case of the core-shell type polymer in 100% by weight of the shell), preferably 10% by weight or more, more preferably 15% by weight or more.
  • the elastic polymer containing a rubber component having a glass transition temperature of 10 ° C. or less may be produced by any polymerization method including bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. It can be a single-stage graft or a multi-stage graft. Moreover, the mixture with the copolymer of only the graft component byproduced in the case of manufacture may be sufficient.
  • examples of the polymerization method include a general emulsion polymerization method, a soap-free polymerization method using an initiator such as potassium persulfate, a seed polymerization method, and a two-stage swelling polymerization method.
  • the suspension polymerization method the aqueous phase and the monomer phase are individually maintained, both are accurately supplied to the continuous disperser, and the particle diameter is controlled by the rotation speed of the disperser, and the continuous production is performed.
  • a method may be used in which the monomer phase is supplied by passing it through a fine orifice having a diameter of several to several tens of ⁇ m or a porous filter in an aqueous liquid having dispersibility to control the particle size.
  • the reaction may be one stage or multistage for both the core and the shell.
  • Such a polymer is commercially available and can be easily obtained.
  • a rubber component those containing butadiene rubber as a main component are those of METABRENE E series manufactured by Mitsubishi Chemical Corporation (for example, E-875A whose shell component is methyl methacrylate as a main component and methyl methacrylate / styrene as a shell component).
  • E-870A as a component).
  • acrylic rubber as a main component include the W series (for example, W-600A whose shell component is methyl methacrylate as a main component) manufactured by Mitsubishi Chemical Corporation.
  • silicone / acrylic composite rubber as the main component include Methbrene S series manufactured by Mitsubishi Chemical Corporation (for example, S-2001, S-2030, etc. whose shell component is methyl methacrylate as a main component).
  • the content of component C is 1 to 10 parts by weight, preferably 1.5 to 9 parts by weight, more preferably 2 to 8 parts by weight, based on 100 parts by weight of the resin component comprising component A and component B. .
  • the content of component C is 1 part by weight or more, sufficient mechanical properties can be obtained.
  • the amount is 10 parts by weight or less, good flame retardancy and appearance of the molded product are ensured.
  • the flame-retardant polycarbonate resin composition of the present invention contains a phosphazene compound as the D component.
  • a phosphazene compound can impart an effect of suppressing a decrease in flame retardancy and a decrease in impact strength to the flame retardant polycarbonate resin composition by containing a phosphorus atom and a nitrogen atom in the molecule.
  • a compound other than a phosphazene compound such as a phosphate ester or a condensed phosphate ester, is used as the phosphorus-based flame retardant, the impact strength and flame retardancy are reduced due to plasticization of the polycarbonate resin. Arise.
  • the phosphazene compound is not particularly limited as long as it does not contain a halogen atom and has a phosphazene structure in the molecule.
  • the phosphazene structure represents a structure represented by the formula: —P (R2) ⁇ N— [wherein R2 is an organic group].
  • the phosphazene compound is represented by general formulas (5) and (6).
  • X 1 , X 2 , X 3 and X 4 represent hydrogen, a hydroxyl group, an amino group, or an organic group containing no halogen atom, and n represents an integer of 3 to 10).
  • examples of the organic group not containing a halogen atom represented by X 1 , X 2 , X 3 , or X 4 include an alkoxy group, a phenyl group, an amino group, and an allyl group. Is mentioned.
  • phosphazene compounds include SPS-100, SPE-100, SPR-100, SA-100, SPB-100, SPB-100L (above, manufactured by Otsuka Chemical Co., Ltd.), FP-100, FP -110 (above, manufactured by Fushimi Pharmaceutical). In the present invention, it is allowed to contain other components as long as the function of the phosphazene compound is not hindered.
  • the content of the D component is 1 to 20 parts by weight, preferably 5 to 15 parts by weight, and more preferably 8 to 12 parts by weight with respect to 100 parts by weight of the resin component composed of the A and B components.
  • the content of the D component is 1 part by weight or more, the effect of flame retardancy is obtained.
  • it is 20 parts by weight or less, good impact resistance is ensured.
  • the flame retardant polycarbonate resin composition of the present invention contains an anti-drip agent as the E component. By containing this anti-drip agent, good flame retardancy can be achieved without impairing the physical properties of the molded product.
  • Examples of the anti-drip agent for component E include a fluorinated polymer having a fibril-forming ability.
  • a fluorinated polymer having a fibril-forming ability examples include polytetrafluoroethylene and a tetrafluoroethylene copolymer (for example, a tetrafluoroethylene / hexafluoropropylene copolymer).
  • Polymer, etc. partially fluorinated polymers as shown in US Pat. No. 4,379,910, polycarbonate resins produced from fluorinated diphenols, and the like.
  • PTFE polytetrafluoroethylene
  • the molecular weight of PTFE having a fibril-forming ability has a very high molecular weight, and shows a tendency to bind PTFE to each other by an external action such as shearing force to form a fiber.
  • the molecular weight is 1 million to 10 million, more preferably 2 million to 9 million, in the number average molecular weight determined from the standard specific gravity.
  • Such PTFE can be used in solid form or in the form of an aqueous dispersion.
  • PTFE having such fibril forming ability can improve the dispersibility in the resin, and it is also possible to use a PTFE mixture in a mixed form with other resins in order to obtain better flame retardancy and mechanical properties. is there.
  • Examples of such commercially available PTFE having fibril forming ability include Teflon (registered trademark) 6J from Mitsui DuPont Fluorochemical Co., Ltd., Polyflon MPA FA500 and F-201L from Daikin Industries, Ltd., and the like.
  • Commercially available PTFE aqueous dispersions include Fullon AD-1 and AD-936 manufactured by Asahi IC Fluoropolymers Co., Ltd., Fullon D-1 and D-2 manufactured by Daikin Industries, Ltd., Mitsui DuPont Fluoro
  • a typical example is Teflon (registered trademark) 30J manufactured by Chemical Corporation.
  • a mixed form of PTFE As a mixed form of PTFE, (1) a method in which an aqueous dispersion of PTFE and an aqueous dispersion or solution of an organic polymer are mixed and co-precipitated to obtain a co-agglomerated mixture (JP-A-60-258263, (Method described in JP-A-63-154744), (2) Method of mixing an aqueous dispersion of PTFE and dried organic polymer particles (Method described in JP-A-4-272957) (3) A method in which an aqueous dispersion of PTFE and an organic polymer particle solution are uniformly mixed, and the respective media are simultaneously removed from the mixture (Japanese Patent Laid-Open Nos.
  • the proportion of PTFE in the mixed form is preferably 1 to 60% by weight, more preferably 5 to 55% by weight of PTFE in 100% by weight of the PTFE mixture.
  • the ratio of PTFE is within such a range, good dispersibility of PTFE can be achieved.
  • the ratio of the said F component shows the quantity of a net anti-drip agent, and in the case of PTFE of a mixed form, shows the amount of net PTFE.
  • the content of the E component is 0.05 to 2 parts by weight, preferably 0.1 to 1.5 parts by weight, and more preferably 0.1 to 1.5 parts by weight with respect to 100 parts by weight of the resin component composed of the A and B components. 2 to 1 part by weight.
  • the anti-drip agent is at least the above lower limit, sufficient flame retardancy can be obtained.
  • the anti-drip agent is not more than the above upper limit, PTFE is prevented from precipitating on the surface of the molded product and resulting in poor appearance, and further, the cost of the resin composition is reduced.
  • the styrenic monomer used in the organic polymer used in the polytetrafluoroethylene-based mixture of the present invention includes an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms and a halogen.
  • Styrene that may be substituted with one or more groups selected from the group consisting of, for example, ortho-methylstyrene, meta-methylstyrene, para-methylstyrene, dimethylstyrene, ethyl-styrene, para-tert-butylstyrene , Methoxystyrene, fluorostyrene, monobromostyrene, dibromostyrene, and tribromostyrene, vinylxylene, vinylnaphthalene, but are not limited thereto.
  • the styrenic monomer can be used alone or in combination of two or more.
  • the acrylic monomer used in the organic polymer used in the polytetrafluoroethylene-based mixture of the present invention includes a (meth) acrylate derivative that may be substituted. Specifically, the acrylic monomer is substituted with one or more groups selected from the group consisting of alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 8 carbon atoms, aryl groups, and glycidyl groups.
  • (Meth) acrylate derivatives such as (meth) acrylonitrile, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, hexyl ( (Meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate and glycidyl (meth) Acrylate, alkyl having 1 to 6 carbon atoms , Or maleimide which may be substituted by an aryl group, for example, maleimide, N- methyl - maleimide and N- phenyl - maleimide, maleic acid, phthalic acid
  • the amount of the acrylic monomer-derived unit contained in the organic polymer used for the coating layer is preferably 8 to 11 parts by weight, more preferably 8 to 10 parts by weight with respect to 100 parts by weight of the styrene monomer-derived unit. Parts, more preferably 8 to 9 parts by weight.
  • the acrylic monomer-derived unit is 8 parts by weight or more, good coating strength may be obtained.
  • the amount is 11 parts by weight or less, a good surface appearance of the molded product may be obtained.
  • the polytetrafluoroethylene-based mixture of the present invention preferably has a residual water content of 0.5% by weight or less, more preferably 0.2 to 0.4% by weight, still more preferably 0.1 to 0. 3% by weight. When the residual water content is 0.5% by weight or less, good flame retardancy may be secured.
  • the residual water content is dried to 0.5 wt% or less, preferably 0.2 to 0.4 wt%, more preferably 0.1 to 0.3 wt%.
  • a step is included.
  • the drying step can be performed using methods known in the art such as, for example, hot air drying or vacuum drying methods.
  • the initiator used in the polytetrafluoroethylene-based mixture of the present invention can be used without limitation as long as it is used for the polymerization reaction of styrene-based and / or acrylic monomers.
  • examples of the initiator include, but are not limited to, cumyl hydroperoxide, di-tert-butyl peroxide, benzoyl peroxide, hydrogen peroxide, and potassium peroxide.
  • one or more initiators can be used depending on the reaction conditions.
  • the amount of the initiator is freely selected within the range used in consideration of the amount of polytetrafluoroethylene and the type / amount of monomer, and is 0.15 to 0.005 based on the amount of the total composition. It is preferable to use 25 parts by weight.
  • the polytetrafluoroethylene-based mixture of the present invention was produced by the following procedure by suspension polymerization.
  • Such a suspension polymerization method does not require a polymerization step by emulsion dispersion in the emulsion polymerization method exemplified in Japanese Patent No. 3469391, and therefore does not require an emulsifier and an electrolyte salt for coagulating and precipitating the polymerized latex.
  • the emulsifier and the electrolyte salt in the mixture are easily mixed and difficult to remove. Therefore, the emulsifier, the sodium metal ion derived from the electrolyte salt, and the potassium metal ion are reduced. It ’s difficult.
  • the polytetrafluoroethylene-based mixture used in the present invention is produced by a suspension polymerization method, the use of such emulsifiers and electrolyte salts reduces the amount of sodium metal ions and potassium metal ions in the mixture. It is possible to improve thermal stability and hydrolysis resistance.
  • coated branched PTFE can be used as an anti-drip agent.
  • the coated branched PTFE is a polytetrafluoroethylene mixture composed of branched polytetrafluoroethylene particles and an organic polymer, and is derived from an organic polymer, preferably a styrene monomer, outside the branched polytetrafluoroethylene. It has a coating layer made of a polymer containing units and / or units derived from acrylic monomers. The coating layer is formed on the surface of branched polytetrafluoroethylene.
  • the coating layer preferably contains a copolymer of a styrene monomer and an acrylic monomer.
  • the polytetrafluoroethylene contained in the coated branched PTFE is branched polytetrafluoroethylene.
  • the branched polytetrafluoroethylene is in the form of particles, and preferably has a particle size of 0.1 to 0.6 ⁇ m, more preferably 0.3 to 0.5 ⁇ m, and still more preferably 0.3 to 0.4 ⁇ m.
  • the number average molecular weight of the polytetrafluoroethylene used in the present invention is preferably 1 ⁇ 10 4 to 1 ⁇ 10 7 , more preferably 2 ⁇ 10 6 to 9 ⁇ 10 6. Fluoroethylene is more preferred in terms of stability. Either powder or dispersion form may be used.
  • the content of branched polytetrafluoroethylene in the coated branched PTFE is preferably 20 to 60 parts by weight, more preferably 40 to 55 parts by weight, still more preferably 47 to 4 parts by weight based on 100 parts by weight of the total weight of the coated branched PTFE. 53 parts by weight, particularly preferably 48 to 52 parts by weight, most preferably 49 to 51 parts by weight. When the proportion of the branched polytetrafluoroethylene is within such a range, good dispersibility of the branched polytetrafluoroethylene can be achieved.
  • the flame-retardant polycarbonate resin composition of the present invention contains titanium oxide as the F component.
  • TiO 2 the titanium oxide component of the titanium oxide pigment
  • titanium oxide component of the titanium oxide pigment is expressed as “TiO 2 ”
  • the entire pigment containing the surface treatment agent is expressed as “titanium oxide”
  • TiO 2 in the F component has an anatase crystal form Any of the rutile type may be used, and they may be mixed and used as necessary. A rutile type is more preferable in terms of initial mechanical properties and long-term weather resistance. A rutile type crystal may contain an anatase type crystal.
  • TiO 2 production process is sulfuric acid method, chlorine method, but those which have been prepared by various other methods can be used, the chlorine method is more preferred.
  • the titanium oxide of the present invention is not particularly limited in its shape, but is preferably in the form of particles.
  • the average particle size of the titanium oxide of the present invention is preferably 0.10 to 0.50 ⁇ m, more preferably 0.20 to 0.30 ⁇ m. When the average particle size is 0.10 ⁇ m or more, appearance defects such as silver hardly occur even when the particles are highly filled. When it is 0.5 ⁇ m or less, a good appearance and mechanical properties may be secured.
  • the average particle size is calculated from the number average of individual single particle sizes measured by electron microscope observation.
  • the F component titanium oxide is surface-treated with an organic compound.
  • organically treated titanium oxide deterioration of the appearance due to yellowing is prevented, good reflectance of the molded body is ensured, and sufficient solar reflectance may be obtained, Suitable for outdoor use.
  • various treatment agents such as polyol, amine, and silicone can be used.
  • the polyol-based surface treatment agent include pentaerythritol, trimethylolethane, and trimethylolpropane.
  • the amine-based surface treatment agent include triethanolamine acetate and trimethylolamine acetate.
  • silicone-based surface treatment agent examples include alkylchlorosilanes (such as trimethylchlorosilane), alkylalkoxysilanes (such as methyltrimethoxysilane), and hydrogen polysiloxane.
  • hydrogen polysiloxane examples include alkyl hydrogen polysiloxane and alkylphenyl hydrogen polysiloxane. Such an alkyl group is preferably a methyl group or an ethyl group.
  • the titanium oxide surface-treated with such an alkylalkoxysilane and / or hydrogen polysiloxane gives good light reflectivity to the resin composition of the present invention.
  • the amount of the organic compound used for the surface treatment is preferably 0.05 to 5 parts by weight, more preferably 0.5 to 3 parts by weight, still more preferably 1.5 to 2.5 parts by weight per 100 parts by weight of the F component.
  • the range is parts by weight.
  • the surface treatment agent for the organic compound is preferably made in advance on titanium oxide (more preferably, titanium oxide coated with another metal oxide). However, it may be a method in which the surface treatment agent is separately added when the raw material of the resin composition is melt-kneaded, and the surface treatment of titanium oxide is performed in the melt-kneading step.
  • the content of the F component is 0.05 to 30 parts by weight, preferably 0.2 to 10 parts by weight, more preferably 1 to 5 parts by weight with respect to 100 parts by weight of the resin component composed of the A and B components. It is. When the content of the F component is 0.05 parts by weight or more, an impact modification effect is obtained. When it is 30 parts by weight or less, the molding of silver or the like is good and the physical properties are good.
  • the flame-retardant polycarbonate resin composition of the present invention can contain a silicate mineral as a G component.
  • a silicate mineral is a mineral composed of at least a metal oxide component and a SiO 2 component, and orthosilicate, disilicate, cyclic silicate, chain silicate, and the like are suitable.
  • the silicate mineral takes a crystalline state, and the shape of the crystal can take various shapes such as a fiber shape and a plate shape.
  • the silicate mineral may be a compound oxide, an oxyacid salt (consisting of an ionic lattice), or a solid solution, and the compound oxide may be a combination of two or more of a single oxide, and a single oxide and oxygen. Any of two or more combinations with acid salts may be used, and also in solid solution, any of solid solutions of two or more metal oxides and solid solutions of two or more oxyacid salts may be used.
  • the silicate mineral may be a hydrate.
  • the form of crystal water in the hydrate includes Si—OH as hydrogen silicate ions, ionic ions as hydroxide ions (OH—) with respect to metal cations, and H 2 O molecules in the gaps in the structure. Any form of entry may be used.
  • silicate mineral An artificial synthetic product corresponding to a natural product can be used as the silicate mineral.
  • silicate minerals obtained from various conventionally known methods, for example, various synthetic methods using solid reaction, hydrothermal reaction, ultrahigh pressure reaction, and the like can be used.
  • silicate mineral in each metal oxide component (MO) examples include the following.
  • the description in parentheses is the name of a mineral or the like mainly composed of such a silicate mineral, and means that the compound in parentheses can be used as the exemplified metal salt.
  • Na 2 O in the component Na 2 O ⁇ SiO 2, and its hydrates, Na 2 O ⁇ 2SiO 2, 2Na 2 O ⁇ SiO 2, Na 2 O ⁇ 4SiO 2, Na 2 O ⁇ 3SiO 2 ⁇ 3H 2 O, Na 2 O ⁇ Al 2 O 3 ⁇ 2SiO 2, Na 2 O ⁇ Al 2 O 3 ⁇ 4SiO 2 ( jadeite), 2Na 2 O ⁇ 3CaO ⁇ 5SiO 2, 3Na 2 O ⁇ 2CaO ⁇ 5SiO 2, and Na 2 O ⁇ Al 2 O 3 ⁇ 6SiO 2 ( albite), and the like.
  • Tobermorite group hydrates such as 2CaO ⁇ SiO 2 ⁇ H 2 O (Hillebrandite), and wollastonite group hydrates such as 6CaO ⁇ 6SiO 2 ⁇ H 2 O (zonotolite)
  • Gyrolite group hydrates such as 2CaO ⁇ SiO 2 ⁇ 2H 2 O (gyrolite), CaO ⁇ Al 2 O 3 ⁇ 2SiO 2 ⁇ H 2 O (lawsonite), CaO ⁇ FeO ⁇ 2SiO 2 (headenite), 3CaO ⁇ 2SiO 2 (Chirukoanaito), 3CaO ⁇ Al 2 O 3 ⁇ 3SiO 2 ( Guroshura), 3CaO ⁇ Fe 2 O3 ⁇ 3SiO 2 ( Andhra Daito), 6CaO ⁇ 4Al 2 O 3 ⁇ FeO ⁇ SiO 2 ( pleo black Ait) , As well as clinozoite
  • Portland cement can be mentioned as a silicate mineral containing CaO as its component.
  • the type of Portland cement is not particularly limited, and any of normal, early strength, ultra-early strength, moderate heat, sulfate resistance, white, and the like can be used.
  • various mixed cements such as blast furnace cement, silica cement, fly ash cement and the like can be used as the G component.
  • blast furnace slag and ferrite can be cited as silicate minerals containing other CaO as components.
  • ZnO.SiO 2 As what contains ZnO in its component, ZnO.SiO 2 , 2ZnO.SiO 2 (trothite), 4ZnO.2SiO 2 .H 2 O (heteropolar ore) and the like can be mentioned.
  • MnO As including MnO into its components, such as MnO ⁇ SiO 2, 2MnO ⁇ SiO 2, CaO ⁇ 4MnO ⁇ 5SiO 2 ( rhodonite) and Coe write the like.
  • FeO ⁇ SiO 2 (ferrosilite), 2FeO ⁇ SiO 2 (iron olivine), 3FeO ⁇ Al 2 O 3 ⁇ 3SiO 2 (almandin), and 2CaO ⁇ 5FeO ⁇ 8SiO 2 ⁇ H 2 O (Tetsuakuchinosene) and the like can be mentioned.
  • Examples of those containing CoO as a component include CoO.SiO 2 and 2CoO.SiO 2 .
  • MgO ⁇ SiO 2 (steatite, enstatite), 2MgO ⁇ SiO 2 (forsterite), 3MgO ⁇ Al 2 O 3 ⁇ 3SiO 2 (birop), 2MgO ⁇ 2Al 2 O 3 ⁇ 5SiO 2 (cordierite), 2MgO ⁇ 3SiO 2 ⁇ 5H 2 O, 3MgO ⁇ 4SiO 2 ⁇ H 2 O ( talc), 5MgO ⁇ 8SiO 2 ⁇ 9H 2 O ( attapulgite), 4MgO ⁇ 6SiO 2 ⁇ 7H 2 O (Sepiolite), 3MgO ⁇ 2SiO 2 ⁇ 2H 2 O (Chrysolite), 5MgO ⁇ 2CaO ⁇ 8SiO 2 ⁇ H 2 O (Translucentite), 5MgO ⁇ Al 2 O 3 ⁇ 3SiO 2 ⁇ 4H 2 O (Chlorite) , K 2
  • ZrO 2 ⁇ SiO 2 (zircon) and AZS refractory and the like As those containing ZrO 2 into its components, ZrO 2 ⁇ SiO 2 (zircon) and AZS refractory and the like.
  • Al 2 O 3 ⁇ SiO 2 sillimanite, under-leucite, kyanite
  • 2Al 2 O 3 ⁇ SiO 2, Al 2 O 3 ⁇ 3SiO 2, 3Al 2 O 3 2SiO 2 mullite
  • Al 2 O 3 ⁇ 2SiO 2 ⁇ 2H 2 O kaolinite
  • Al 2 O 3 ⁇ 4SiO 2 ⁇ H 2 O pyrophyllite
  • Al 2 O 3 ⁇ 4SiO 2 ⁇ H 2 O bentonite
  • K 2 O ⁇ 3Na 2 O ⁇ 4Al 2 O 3 ⁇ 8SiO 2 nepheline
  • K 2 O ⁇ 3Al 2 O 3 ⁇ 6SiO 2 ⁇ 2H 2 O muscovite, sericite
  • K 2 O.6MgO.Al 2 O 3 .6SiO 2 .2H 2 O various zeolites, fluorine
  • silicate minerals mica, talc, and wollastonite are particularly suitable.
  • talc is hydrous magnesium silicate in terms of chemical composition, generally represented by the chemical formula 4SiO 2 .3MgO.2H 2 O, and is usually scaly particles having a layered structure. Specifically, it is composed of about 56 to 65% by weight of SiO 2 , 28 to 35% by weight of MgO, and about 5% by weight of H 2 O. As other minor components, Fe 2 O 3 is 0.03 to 1.2% by weight, Al 2 O 3 is 0.05 to 1.5% by weight, CaO is 0.05 to 1.2% by weight, K 2 O. Is 0.2 wt% or less, Na 2 O is 0.2 wt% or less.
  • the talc has a particle size of 0.1 to 15 ⁇ m (more preferably 0.2 to 12 ⁇ m, still more preferably 0.3 to 10 ⁇ m, particularly preferably 0.5 to 5 ⁇ m) as measured by a sedimentation method. A range is preferable. Furthermore, it is particularly preferable to use talc having a bulk density of 0.5 (g / cm 3 ) or more as a raw material.
  • the average particle size of talc refers to D50 (median diameter of particle size distribution) measured by an X-ray transmission method which is one of liquid phase precipitation methods. As a specific example of an apparatus for performing such a measurement, Sedigraph 5100 manufactured by Micromeritics Inc. can be cited.
  • the manufacturing method when talc is crushed from raw stone there is no particular restriction on the manufacturing method when talc is crushed from raw stone, and the axial flow mill method, the annular mill method, the roll mill method, the ball mill method, the jet mill method, the container rotary compression shearing mill method, etc. are used. can do. Further, the talc after pulverization is preferably classified by various classifiers and having a uniform particle size distribution.
  • talc is preferably in an agglomerated state in view of its handleability and the like, and as such a production method, there are a method by deaeration compression, a method of compression using a sizing agent, and the like.
  • the degassing compression method is preferable in that the sizing agent resin component which is simple and unnecessary is not mixed into the resin composition of the present invention.
  • Mica having an average particle diameter of 10 to 100 ⁇ m as measured by a microtrack laser diffraction method can be preferably used. More preferably, the average particle size is 20 to 50 ⁇ m. When the average particle diameter of mica is 10 ⁇ m or more, the improvement effect on the rigidity is sufficient. Even when the thickness is 100 ⁇ m or less, the rigidity is sufficiently improved and the mechanical strength such as impact characteristics is also good.
  • Mica having a thickness measured by observation with an electron microscope of 0.01 to 1 ⁇ m can be preferably used. More preferably, the thickness is 0.03 to 0.3 ⁇ m.
  • the aspect ratio is preferably 5 to 200, more preferably 10 to 100.
  • the mica used is preferably mascobite mica, and its Mohs hardness is about 3.
  • Muscovite mica can achieve higher rigidity and strength than other mica such as phlogopite, and solves the problems of the present invention at a better level.
  • the mica may be pulverized by either dry pulverization or wet pulverization.
  • the dry pulverization method is more inexpensive and more general, but the wet pulverization method is effective for pulverizing mica more thinly and finely, and as a result, the effect of improving the rigidity of the resin composition becomes higher.
  • the fiber diameter of wollastonite is preferably 0.1 to 10 ⁇ m, more preferably 0.1 to 5 ⁇ m, still more preferably 0.1 to 3 ⁇ m.
  • the aspect ratio (average fiber length / average fiber diameter) is preferably 3 or more. The upper limit of the aspect ratio is 30 or less.
  • the fiber diameter is obtained by observing the reinforcing filler with an electron microscope, obtaining individual fiber diameters, and calculating the number average fiber diameter from the measured values. The electron microscope is used because it is difficult for an optical microscope to accurately measure the size of a target level.
  • the filler for which the fiber diameter is to be measured is randomly extracted, the fiber diameter is measured near the center, and the number average fiber is obtained from the obtained measured value. Calculate the diameter.
  • the observation magnification is about 1000 times, and the number of measurement is 500 or more (600 or less is suitable for work).
  • the measurement of average fiber length observes a filler with an optical microscope, calculates
  • the fiber length is calculated using a program for obtaining the maximum distance between two points of the image data using an image analysis device. Under such conditions, the size per pixel corresponds to a length of 1.25 ⁇ m, and the number of measurement is 500 or more (600 or less is suitable for work).
  • the wollastonite of the present invention is a magnetic separator that reflects the iron content mixed in the raw material ore and the iron content mixed due to equipment wear when pulverizing the raw material ore in order to sufficiently reflect the inherent whiteness in the resin composition. It is preferable to remove as much as possible. It is preferable that the iron content in wollastonite is 0.5% by weight or less in terms of Fe 2 O 3 by such magnetic separator processing.
  • Silicate minerals are preferably not surface-treated, but are surface-treated with various surface treatment agents such as silane coupling agents, higher fatty acid esters, and waxes. It may be. Furthermore, it may be granulated with a sizing agent such as various resins, higher fatty acid esters, and waxes.
  • the content of the G component is preferably 0.1 to 50 parts by weight, more preferably 0.15 to 40 parts by weight, and still more preferably 100 parts by weight of the resin component composed of the A and B components. 0.2 to 30 parts by weight.
  • As the G component is added flame retardancy and rigidity are improved.
  • Phosphorus stabilizer examples include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof, and tertiary phosphine.
  • phosphite compound for example, triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl Phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, tris (diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di -N-butylphenyl) phosphite, tris (2,4-di-ter
  • Still other phosphite compounds that react with dihydric phenols and have a cyclic structure can be used.
  • 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2,4-di-tert-butylphenyl) phosphite 2,2′-methylenebis (4,6-di-tert- Examples include butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite and 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite.
  • phosphate compound examples include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, Examples thereof include diisopropyl phosphate, and triphenyl phosphate and trimethyl phosphate are preferable.
  • Examples of the phosphonite compound include tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenylenedi.
  • Examples of the phosphonate compound include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate.
  • Tertiary phosphine includes triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, triamylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenylmethylphosphine, diphenyloctylphosphine, triphenylphosphine, tri-p-tolyl. Examples include phosphine, trinaphthylphosphine, and diphenylbenzylphosphine. A particularly preferred tertiary phosphine is triphenylphosphine.
  • the above phosphorus stabilizers can be used in a mixture of not only one but also two or more.
  • phosphonite compounds or phosphite compounds represented by the following general formula (7) are preferable.
  • R and R ′ represent an alkyl group having 6 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and may be the same or different from each other.
  • tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite is preferred as the phosphonite compound
  • the stabilizer containing phosphonite as a main component is Sandostab P-EPQ (trademark, manufactured by Clariant).
  • Irgafos P-EPQ trademark, CIBA SPECIALTY manufactured by CHEMICALS
  • more preferred phosphite compounds are distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-). -Tert-butyl-4-methylphenyl) pentaerythritol diphosphite and bis ⁇ 2,4-bis (1-methyl-1-phenylethyl) phenyl ⁇ pentaerythritol diphosphite.
  • Distearyl pentaerythritol diphosphite is commercially available as ADK STAB PEP-8 (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.) and JPP681S (trademark, manufactured by Johoku Chemical Industry Co., Ltd.), and any of them can be used.
  • Bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite is ADK STAB PEP-24G (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.), Alkanox P-24 (trademark, manufactured by Great Lakes), Ultranox P626 (trademark, manufactured by GE Specialty Chemicals), Doverphos S-9432 (trademark, manufactured by Dover Chemical), and Irgafos126 and 126FF (trademark, both manufactured by CIBA SPECIALTY CHEMICALS) are also available.
  • Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite is commercially available as ADK STAB PEP-36 (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.) and can be easily used.
  • Bis ⁇ 2,4-bis (1-methyl-1-phenylethyl) phenyl ⁇ pentaerythritol diphosphite is ADK STAB PEP-45 (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.) and Doverphos S-9228 (trademark). , Dover Chemical, Inc.) and any of them can be used.
  • the above phosphorus stabilizers can be used alone or in combination of two or more.
  • the content of the phosphorus stabilizer is preferably 0.01 to 1.0 part by weight, more preferably 0.03 to 0.8 part by weight, with respect to 100 parts by weight of the resin component composed of the A component and the B component. Parts, more preferably 0.05 to 0.5 parts by weight.
  • the content is 0.01 parts by weight or more, an effect of suppressing thermal decomposition during processing is exhibited, and good mechanical characteristics may be generated.
  • the amount is 1.0 part by weight or less, good mechanical properties can be ensured.
  • Phenol-based stabilizer The resin composition of the present invention may contain a phenol-based stabilizer.
  • Phenol stabilizers generally include hindered phenols, semi-hindered phenols, and less hindered phenol compounds. Particularly, hindered phenol compounds are more preferable from the viewpoint of applying a heat-stabilized formulation to polypropylene resins. Used for.
  • Such hindered phenol compounds include, for example, ⁇ -tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2-tert -Butyl-6- (3'-tert-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, 2,6-di-tert-butyl-4- (N, N-dimethylamino) Methyl) phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl) -6-tert-butylphenol), 4,4'-methylenebis (2,6 Di-tert-butylphenol), 2,2'-methylenebis (4-methyl-6
  • tetrakis [methylene-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] methane, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionate is preferably used, and it is represented by the following formula (8) (3, 3 ′, 3 ′′, 5, 5 ′, 5 as being excellent in suppressing deterioration of mechanical properties due to thermal decomposition during processing.
  • the above phenol stabilizers can be used alone or in combination of two or more.
  • the content of the phenol-based stabilizer is preferably 0.05 to 1.0 part by weight, more preferably 0.07 to 0.8 part by weight with respect to 100 parts by weight of the resin component comprising the A component and the B component. Parts, more preferably 0.1 to 0.5 parts by weight.
  • the content is 0.05 parts by weight or more, the effect of suppressing thermal decomposition during processing appears, and good mechanical properties may occur.
  • the amount is 1.0 part by weight or less, good mechanical properties may be secured.
  • Either a phosphorus stabilizer or a phenol stabilizer is preferably blended, and a combination thereof is more preferred.
  • 0.01 to 0.5 parts by weight of a phosphorus stabilizer and 0.01 to 0.5 parts by weight of a phenol stabilizer are blended with 100 parts by weight of the resin component comprising the A component and the B component. It is preferred that
  • the flame-retardant polycarbonate resin composition of the present invention may contain an ultraviolet absorber.
  • the ultraviolet absorber include those in the benzophenone series such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2- Hydroxy-4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydride benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2 ', 4,4' -Tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodiumsulfoxybenzophenone, bis (5-benzoyl-4- Hydroxy-2-methoxyphenyl) Examples include methane, 2-hydroxy
  • benzotriazole series for example, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3, 5-Dicumylphenyl) phenylbenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,2′-methylenebis [4- (1,1,3 , 3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- (2-hydroxy-3,5-di-tert-butylphenyl) benzotriazole, 2- (2- Hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3, -Di-tert-amylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octy
  • hydroxyphenyltriazine series for example, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol, 2- (4,6-diphenyl-1,3,5) -Triazin-2-yl) -5-methyloxyphenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-ethyloxyphenol, 2- (4,6-diphenyl) -1,3,5-triazin-2-yl) -5-propyloxyphenol and 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-butyloxyphenol Illustrated.
  • phenyl group of the above exemplary compounds such as 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hexyloxyphenol is Examples of the compound are phenyl groups.
  • cyclic imino ester system for example, 2,2′-p-phenylenebis (3,1-benzoxazin-4-one), 2,2′-m-phenylenebis (3,1-benzoxazin-4-one) And 2,2′-p, p′-diphenylenebis (3,1-benzoxazin-4-one) and the like.
  • cyanoacrylate for example, 1,3-bis-[(2′-cyano-3 ′, 3′-diphenylacryloyl) oxy] -2,2-bis [(2-cyano-3,3-diphenylacryloyl) oxy ] Methyl) propane, 1,3-bis-[(2-cyano-3,3-diphenylacryloyl) oxy] benzene and the like.
  • the ultraviolet absorber has a structure of a monomer compound capable of radical polymerization, so that the ultraviolet absorbent monomer and / or the light stable monomer and a single amount of alkyl (meth) acrylate or the like can be obtained. It may be a polymer type ultraviolet absorber copolymerized with a body.
  • Preferred examples of the UV-absorbing monomer include compounds containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic imino ester skeleton, and a cyanoacrylate skeleton in the ester substituent of (meth) acrylic acid ester.
  • a compound represented by any of the following formulas (10), (11) and (12) is more preferably used.
  • the said ultraviolet absorber can be used individually or in combination of 2 or more types.
  • the content of the ultraviolet absorber is preferably 0.1 to 3 parts by weight, more preferably 0.12 to 2 parts by weight, still more preferably 100 parts by weight of the resin component composed of the A component and the B component. 0.15 to 1 part by weight.
  • the content of the ultraviolet absorber is 0.1 parts by weight or more, sufficient light resistance may be exhibited, and when it is 3 parts by weight or less, poor appearance due to gas generation is prevented. From the viewpoint of good physical properties and the like.
  • the flame-retardant polycarbonate resin composition of the present invention may contain a hindered amine light stabilizer.
  • the hindered amine light stabilizer is generally called HALS (Hindered Amine Light Stabilizer) and is a compound having a 2,2,6,6-tetramethylpiperidine skeleton in the structure.
  • the hindered amine light stabilizers are roughly classified according to the binding partner of the nitrogen atom in the piperidine skeleton, the NH type (hydrogen is bonded to the nitrogen atom), the NR type (the alkyl group (R) is bonded to the nitrogen atom), There are three types of N-OR type (an alkoxy group (OR) is bonded to a nitrogen atom).
  • N—R is a low basicity from the viewpoint of the basicity of the hindered amine light stabilizer. More preferably, the N-OR type is used.
  • the hindered amine light stabilizers can be used alone or in combination of two or more.
  • the content of the hindered amine light stabilizer is preferably 0 to 1 part by weight, more preferably 0.05 to 1 part by weight, even more preferably 100 parts by weight of the resin component composed of the A component and the B component.
  • the amount is 0.08 to 0.7 parts by weight, particularly preferably 0.1 to 0.5 parts by weight.
  • the content of the hindered amine light stabilizer is 1 part by weight or less, it is preferable because an appearance defect due to gas generation or a decrease in physical properties due to decomposition of the polycarbonate resin may be prevented.
  • it is 0.05 weight part or more sufficient light resistance may express.
  • (V) Release agent It is preferable to mix
  • Known release agents can be used. For example, saturated fatty acid ester, unsaturated fatty acid ester, polyolefin wax (polyethylene wax, 1-alkene polymer, etc., which may be modified with a functional group-containing compound such as acid modification), silicone compound, fluorine compound ( And fluorine oil represented by polyfluoroalkyl ether), paraffin wax, beeswax and the like. Among these, fatty acid esters are preferable as a release agent.
  • Such fatty acid esters are esters of aliphatic alcohols and aliphatic carboxylic acids.
  • Such an aliphatic alcohol may be a monohydric alcohol or a dihydric or higher polyhydric alcohol.
  • the carbon number of the alcohol is in the range of 3 to 32, more preferably in the range of 5 to 30.
  • Examples of such monohydric alcohols include dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, tetracosanol, seryl alcohol, and triacontanol.
  • polyhydric alcohols examples include pentaerythritol, dipentaerythritol, tripentaerythritol, polyglycerol (triglycerol to hexaglycerol), ditrimethylolpropane, xylitol, sorbitol, and mannitol.
  • a polyhydric alcohol is more preferable.
  • the aliphatic carboxylic acid preferably has 3 to 32 carbon atoms, and more preferably an aliphatic carboxylic acid having 10 to 22 carbon atoms.
  • the aliphatic carboxylic acid include decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid, behenic acid, Mention may be made of saturated aliphatic carboxylic acids such as icosanoic acid and docosanoic acid, and unsaturated aliphatic carboxylic acids such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaenoic acid,
  • the above aliphatic carboxylic acids such as stearic acid and palmitic acid are usually produced from natural fats and oils such as animal fats such as beef tallow and lard and vegetable oils such as palm oil and sunflower oil. Therefore, these aliphatic carboxylic acids are usually a mixture containing other carboxylic acid components having different numbers of carbon atoms. Accordingly, in the production of the fatty acid ester of the present invention, aliphatic carboxylic acids produced from such natural fats and oils and in the form of a mixture containing other carboxylic acid components, particularly stearic acid and palmitic acid are preferably used.
  • the fatty acid ester of the present invention may be either a partial ester or a total ester (full ester). However, partial esters are more preferably full esters because they usually have a high hydroxyl value and tend to induce decomposition of the resin at high temperatures.
  • the acid value in the fatty acid ester of the present invention is preferably 20 or less, more preferably in the range of 4 to 20, and still more preferably in the range of 4 to 12, from the viewpoint of thermal stability.
  • the acid value can be substantially zero.
  • the hydroxyl value of the fatty acid ester is more preferably in the range of 0.1-30.
  • the iodine value is preferably 10 or less. The iodine value can be substantially zero.
  • the content of the release agent is preferably 0.005 to 2 parts by weight, more preferably 0.01 to 1 part by weight, still more preferably 0.001 parts by weight with respect to 100 parts by weight of the resin component composed of the A component and the B component. 05 to 0.5 parts by weight.
  • the flame retardant polycarbonate resin composition has good release properties and roll release properties.
  • such an amount of fatty acid ester provides a flame retardant polycarbonate resin composition having good mold release and roll release properties without impairing good hue.
  • the flame-retardant polycarbonate resin composition of the present invention can further provide a molded product containing various dyes / pigments and exhibiting various design properties. By blending a fluorescent brightening agent or other fluorescent dye that emits light, a better design effect that makes use of the luminescent color can be imparted. In addition, a flame retardant polycarbonate resin composition having coloring with a very small amount of dye and pigment and vivid color development can also be provided.
  • coumarin fluorescent dyes, benzopyran fluorescent dyes, and perylene fluorescent dyes are preferable because they have good heat resistance and little deterioration during molding of the polycarbonate resin.
  • dyes other than the above bluing agents and fluorescent dyes include perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as bitumen, perinone dyes, quinoline dyes, quinacridone And dyes such as dyes, dioxazine dyes, isoindolinone dyes, and phthalocyanine dyes.
  • the resin composition of this invention can mix
  • the metallic pigment those having a metal film or a metal oxide film on various plate-like fillers are suitable.
  • the content of the dye / pigment is preferably 0.00001 to 1 part by weight, more preferably 0.00005 to 0.5 part by weight, based on 100 parts by weight of the resin component composed of the A component and the B component.
  • the flame retardant polycarbonate resin composition of the present invention may contain other heat stabilizers other than the phosphorus stabilizers and phenol stabilizers. Such other heat stabilizers are preferably used in combination with any of these stabilizers and antioxidants, and particularly preferably used in combination with both. Examples of such other heat stabilizers include lactone stabilizers represented by reaction products of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene (such stabilizers). Details thereof are described in JP-A-7-233160). Such a compound is commercially available as Irganox HP-136 (trademark, manufactured by CIBA SPECIALTY CHEMICALS) and can be used.
  • a stabilizer obtained by mixing the compound with various phosphite compounds and hindered phenol compounds is commercially available.
  • Irganox HP-2921 manufactured by the above company is preferably exemplified.
  • a premixed stabilizer can also be used.
  • the blending amount of the lactone stabilizer is preferably 0.0005 to 0.05 parts by weight, more preferably 0.001 to 0.03 parts by weight with respect to 100 parts by weight of the component A.
  • stabilizers include sulfur-containing stabilizers such as pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), and glycerol-3-stearylthiopropionate. Illustrated. Such a stabilizer is particularly effective when the resin composition is applied to rotational molding.
  • the amount of the sulfur-containing stabilizer is preferably 0.001 to 0.1 parts by weight, more preferably 0.01 to 0.08 parts by weight, based on 100 parts by weight of the resin component composed of the A component and the B component. It is.
  • carbon fibers for example, calcium carbonate, glass fiber, glass bead, glass balloon, glass milled fiber, glass flake, carbon fiber, carbon flake, carbon bead, carbon milled fiber, graphite, vapor grown ultrafine carbon fiber (fiber diameter is 0.1 ⁇ m Carbon nanotubes (fiber diameter is less than 0.1 ⁇ m, hollow), fullerene, metal flakes, metal fibers, metal coated glass fibers, metal coated carbon fibers, metal coated glass flakes, silica, metal oxide particles, Examples include metal oxide fibers, metal oxide balloons, and various whiskers (such as potassium titanate whiskers, aluminum borate whiskers, and basic magnesium sulfate). These reinforcing fillers may be used alone or in combination of two or more.
  • whiskers such as potassium titanate whiskers, aluminum borate whiskers, and basic magnesium sulfate
  • the content of these fillers is preferably 0.1 to 60 parts by weight, more preferably 0.5 to 50 parts by weight with respect to 100 parts by weight of the resin component composed of the A component and the B component.
  • Such other resins include polyamide resins, polyimide resins, polyetherimide resins, polyurethane resins, silicone resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, polymethacrylate resins, phenol resins, and epoxy resins. It is done.
  • examples of the elastomer include isobutylene / isoprene rubber, ethylene / propylene rubber, acrylic elastomer, polyester elastomer, polyamide elastomer and the like.
  • additives In addition to the flame retardant polycarbonate resin composition of the present invention, a small proportion of additives known per se are added to the molded article to impart various functions and improve properties. Can do. These additives are used in usual amounts as long as the object of the present invention is not impaired.
  • additives include sliding agents (for example, PTFE particles), colorants (for example, pigments and dyes such as carbon black), light diffusing agents (for example, acrylic crosslinked particles, silicone crosslinked particles, ultrathin glass flakes, calcium carbonate particles).
  • sliding agents for example, PTFE particles
  • colorants for example, pigments and dyes such as carbon black
  • light diffusing agents for example, acrylic crosslinked particles, silicone crosslinked particles, ultrathin glass flakes, calcium carbonate particles.
  • Fluorescent dyes for example, inorganic phosphors (for example, phosphors with aluminate as a mother crystal), antistatic agents, crystal nucleating agents, inorganic and organic antibacterial agents, photocatalytic antifouling agents (for example, fine titanium oxide, fine particle oxidation) Zinc), radical generators, infrared absorbers (heat ray absorbers), and photochromic agents.
  • the form for carrying out the present invention is an aggregation of the preferable ranges of the above-mentioned requirements. For example, typical examples are described in the following examples. Of course, the present invention is not limited to these forms.
  • thermoplastic resin composition (I) Appearance of molded product A 2 mm thick molded plate (90 mm long ⁇ 50 mm wide) having an arithmetic average roughness (Ra) of 0.03 ⁇ m was applied to a cylinder temperature of 260 ° C., a mold temperature of 60 ° C., and an injection speed of 30 mm / s. The material was molded by injection molding under the conditions described above, and the hue and presence or absence of silver streaks were observed. In the evaluation, the 10th shot immediately after the purge was discarded, the 11th shot was used for hue evaluation, and the molded product up to 20th shot was then used for silver streak evaluation.
  • Examples 1 to 26, Comparative Examples 1 to 11 The mixture which consists of each component with the composition shown in Table 1 and Table 2 was supplied from the 1st supply port of the extruder. Such a mixture was obtained by mixing with a V-type blender. Extrusion was performed using a vent type twin screw extruder (Nippon Steel Works TEX30 ⁇ -38.5BW-3V) with a diameter of 30 mm ⁇ , melt kneading at a screw speed of 230 rpm, a discharge rate of 25 kg / h, and a vent vacuum of 3 kPa. Pellets were obtained. In addition, about extrusion temperature, it implemented at 260 degreeC from the 1st supply port to the die part.
  • C-2 butadiene-based core-shell type graft polymer (graft copolymer having a core-shell structure in which the core is 70 wt% mainly composed of butadiene rubber and the shell is 30 wt% mainly composed of methyl methacrylate and styrene, manufactured by Kaneka Corporation) Kane Ace M-701 (product name))
  • C-3 butadiene-based core-shell type graft polymer (graft copolymer having a core-shell structure in which the core is butadiene rubber as the main component and 60 wt% of the shell is methyl methacrylate as the main component, Kaneka Corporation) -711 (product name))
  • C-4 Acrylic core-shell type graft polymer (graft copolymer having a core-shell structure in which the core is composed of butadiene-acrylic composite rubber and butyl acrylate as main components and the shell is composed of methyl methacrylate as
  • D component Cyclic phenoxyphosphazene (Fushimi Pharmaceutical Co., Ltd .: FP-110T (trade name))
  • D-2 Phosphate ester mainly composed of resorcinol bis (di-2,6-xylyl phosphate) (manufactured by Daihachi Chemical Industry Co., Ltd .: PX200 (trade name))
  • E component E-1: PTFE (manufactured by Daikin Industries, Ltd., Polyflon MPA FA500H (trade name))
  • E-2 Coated PTFE (polytetrafluoroethylene coated with a styrene-acrylonitrile copolymer (polytetrafluoroethylene content 50% by weight), SN3307 (trade name) manufactured by Shine Polymer)
  • E-3 Coated PTFE (polytetrafluoroethylene coated with methyl methacrylate / butyl acryl
  • Typek PC-3 (trade name), the titanium dioxide is a rutile crystal produced by the chlorine method, and has a temperature of 23 ° C. to 100 ° C. using a thermogravimetric apparatus (TGA).
  • TGA thermogravimetric apparatus
  • thermogravimetric apparatus B)-(a) is 0.28 when the weight loss is (a) wt% and the weight loss at 23 to 300 ° C. is (b) wt%, and Al element / Ti element in fluorescent X-ray measurement
  • G component G component
  • G Talc (manufactured by Hayashi Kasei Co., Ltd .; HST 0.8 (trade name), average particle size 3.5 ⁇ m)
  • STB-1 Phenolic heat stabilizer (octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, molecular weight 531, Irganox 1076 (product name) manufactured by BASF Japan Ltd.)
  • STB-2 Phosphorus heat stabilizer (Tris (2,4-di-tert-butylphenyl) phosphite

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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

La présente invention concerne une composition de résine de polycarbonate qui présente des caractéristiques mécaniques, une résistance chimique, une ininflammabilité, une réflectivité de lumière élevée et un aspect d'article moulé très satisfaisants. L'invention concerne une composition de résine de polycarbonate ignifuge qui est caractérisée en ce qu'elle contient 1 à 10 parties en poids de (C) un modificateur d'impact (constituant (C)), 1 à 20 parties en poids de (D) un phosphazène (constituant (D)), 0,05 à 2 parties en poids de (E) un inhibiteur de goutte-à-goutte (constituant (E)) et 0,05 à 30 parties en poids de (F) oxyde de titane (constituant (F)) pour 100 parties en poids d'un constituant de résine qui est composé de 40 à 95 parties en poids de (A) une résine de polycarbonate (constituant (A)) et 60 à 5 parties en poids de (B) une résine de polyester (constituant (B)).
PCT/JP2019/019972 2018-05-22 2019-05-20 Composition ignifuge de résine de polycarbonate WO2019225558A1 (fr)

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WO2024024353A1 (fr) * 2022-07-28 2024-02-01 三菱エンジニアリングプラスチックス株式会社 Composition de résine de polycarbonate et article moulé
CN118126505A (zh) * 2024-05-08 2024-06-04 成都紫江包装有限公司 一种塑料瓶及其成型工艺

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WO2021181307A1 (fr) 2020-03-11 2021-09-16 Alcon Inc. Agents de réticulation vinyliques de polydiorganosiloxane photochromique
CN113214610A (zh) * 2021-05-12 2021-08-06 广东宇豪新材料科技有限公司 一种抗冲击复合材料及其制备方法

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