JP2018016756A - Polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition excellent in chemical resistance, flame retardancy, impact resistance, and heat resistance and also excellent in appearance, and to provide a molded article thereof.SOLUTION: A polycarbonate resin composition contains, based on 100 pts.wt. of a resin component comprising (A) 40-70 pts.wt. of an aromatic polycarbonate resin (component A) having a viscosity-average molecular weight of 27,500-32,000 and (B) 30-60 pts.wt. of a polyethylene terephthalate resin (component B), (C) 0.5-10 pts.wt. of a polyorganosiloxane-containing graft copolymer (component C), (D) 1-10 pts.wt. of a bromine-based flame retardant (component D), (E) 0.5-3 pts.wt. of an antimony-based flame retardant aid (component E), and (F) 0.1-1 pt.wt. of a fluorine-containing dripping inhibitor (component F).SELECTED DRAWING: None

Description

  The present invention relates to a thermoplastic resin composition and a molded article thereof. More specifically, the present invention relates to a thermoplastic resin composition having excellent chemical resistance, flame retardancy, impact resistance, heat resistance and excellent appearance, and a molded product thereof.

  Polycarbonate resin is a polymer in which aromatic or aliphatic dioxy compounds are linked by carbonic acid ester, and has excellent properties such as transparency, heat resistance, flame retardancy, and mechanical properties such as impact resistance. It is widely used in the fields of automobile interior and exterior parts, OA equipment, electrical and electronic equipment, and the like. However, the polycarbonate resin has excellent characteristics, but is inferior in chemical resistance, and has a problem that the use environment is limited in the above-mentioned applications. In particular, demands for fire resistance and chemical resistance due to recent hybridization and electrification of automobiles, high impact resistance due to thinning of office automation equipment and electrical and electronic equipment, and chemical resistance and heat resistance due to diversification of usage environments There is a growing demand for materials that combine chemical resistance, flame resistance, impact resistance, and heat resistance.

  In such a background, an example of improving the flame retardancy and impact properties of a polycarbonate resin is a composition in which a polyorganosiloxane-containing graft copolymer is mixed (Patent Document 1). However, the improvement in chemical resistance has not been sufficient. As an example of improving the chemical resistance of the polycarbonate resin, there is a resin composition made of polyethylene terephthalate resin (see Patent Documents 2, 3 and 4). However, both are not preferred because the polyethylene terephthalate resin is flammable and has a problem that the flame retardancy is greatly deteriorated.

  Further, as an example of improving impact resistance and heat resistance, there is a composition in which an acrylic resin and an impact reinforcing agent are added to a polycarbonate resin having a specific molecular weight and a polyester resin having a specific viscosity (Patent Document 5). However, the flame retardancy is not improved, and the improvement in heat resistance (tensile impact characteristics) after high temperature treatment required for the present invention is not mentioned, and the characteristics are insufficient, which is not preferable.

  Resin composition with improved notch impact resistance, chemical resistance and mechanical properties by adding aromatic polyester, graft copolymer with graft shell containing acrylic monomer, phosphorus flame retardant, and fluorinated polyolefin to specific polyester carbonate (Patent Document 6). However, since the heat resistance (tensile impact property) after high temperature treatment is significantly reduced by the plasticizing effect of the phosphorus flame retardant, it is not preferable.

  Examples of improved impact resistance and appearance include a graft copolymer based on a composite rubber of a polyorganosiloxane rubber and an alkyl (meth) acrylate rubber, a polycarbonate resin and a saturated polyester resin and / or a polyester-based elastomer. A composition is mentioned (patent document 7). However, this is not preferable because it does not satisfy the heat resistance (tensile impact characteristics) after the high temperature treatment required for the present invention.

A resin composition having improved thermal stability and mechanical strength by adding a polyester resin comprising a specific catalyst, a flame retardant, and a fluorine-containing anti-dripping agent to polycarbonate can be exemplified (Patent Document 8). Although this composition is excellent in flame retardancy, it is insufficient for the required heat resistance, and improvement has been demanded.
As described above, a thermoplastic resin composition having excellent chemical resistance, flame retardancy, impact resistance and excellent heat resistance capable of maintaining a high level of mechanical properties after high-temperature treatment has not been obtained. .

International Publication No. 2003/091342 Pamphlet Japanese Patent Publication No. 36-14035 Japanese Examined Patent Publication No. 39-20434 JP 59-176345 A JP 2010-144173 A JP 2005-534756 A Japanese Patent No. 2630414 Japanese Patent No. 5902409

  An object of the present invention is to provide a thermoplastic resin composition excellent in chemical resistance, flame retardancy, impact resistance, heat resistance and appearance, and a molded article comprising the same.

  As a result of intensive studies to achieve the above object, the inventors of the present invention have found that a polyethylene terephthalate resin, a specific proportion of a polyorganosiloxane-containing graft copolymer, a brominated flame retardant, an antimony-based resin are added to a polycarbonate resin having a specific molecular weight. It was found that a thermoplastic resin composition excellent in chemical resistance, flame retardancy, impact resistance, heat resistance and appearance can be obtained by adding a flame retardant aid and a fluorine-containing anti-dripping agent. Reached.

  According to the present invention, the above-mentioned problems are: (A) 40 to 70 parts by weight of an aromatic polycarbonate resin (component A) having a viscosity average molecular weight of 27,500 to 32,000 and (B) a polyethylene terephthalate resin (component B) 30. 0.5 to 10 parts by weight of (C) polyorganosiloxane-containing graft copolymer (component C) and (D) brominated flame retardant (component D) 1 to 100 parts by weight in total of -60 parts by weight 10 to 10 parts by weight, (E) 0.5 to 3 parts by weight of antimony flame retardant aid (E component) and (F) 0.1 to 1 part by weight of fluorine-containing anti-dripping agent (F component) This is achieved by the resin composition.

Details of the present invention will be described below.
(Component A: aromatic polycarbonate resin)
The aromatic polycarbonate resin used in the present invention is obtained by reacting a dihydric phenol and a carbonate precursor. Examples of 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.

  Representative examples of the dihydric phenol used here 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-phenylenediisopropyl Pyridene) diphenol, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) ester, bis (4-hydroxy-3-methylphenyl) sulfide, 9,9-bis (4-hydroxyphenyl) Examples include fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene. A preferred dihydric phenol is bis (4-hydroxyphenyl) alkane, and bisphenol A is particularly preferred from the viewpoint of impact resistance, and is widely used.

In the present invention, in addition to bisphenol A-based polycarbonate, which is a general-purpose polycarbonate, it is possible to use a special polycarbonate produced using other dihydric phenols as the A component.
For example, as part or all of the dihydric phenol component, 4,4 ′-(m-phenylenediisopropylidene) diphenol (hereinafter sometimes abbreviated as “BPM”), 1,1-bis (4-hydroxy) Phenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (hereinafter sometimes abbreviated as “Bis-TMC”), 9,9-bis (4-hydroxyphenyl) Polycarbonate (homopolymer or copolymer) using fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (hereinafter sometimes abbreviated as “BCF”) has dimensions due to water absorption. It is suitable for applications where the demands for change and shape stability are particularly severe. These 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.

In particular, when high rigidity and better hydrolysis resistance are required, it is particularly preferable that the component A constituting the resin composition is a copolymerized polycarbonate of the following (1) to (3). is there.
(1) 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 BCF Of 20 to 80 mol% (more preferably 25 to 60 mol%, more preferably 35 to 55 mol%).
(2) 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, and BCF Is 5 to 90 mol% (more preferably 10 to 50 mol%, more preferably 15 to 40 mol%).
(3) 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 -Copolymer polycarbonate in which TMC is 20 to 80 mol% (more preferably 25 to 60 mol%, still 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 production method and characteristics of these special polycarbonates are described in detail in, for example, JP-A-6-172508, JP-A-8-27370, JP-A-2001-55435, and JP-A-2002-117580. ing.

Of the various polycarbonates described above, those having a water absorption and Tg (glass transition temperature) adjusted within the following ranges by adjusting the copolymer composition, etc. have good hydrolysis resistance of the polymer itself, and Since it is remarkably excellent in low warpage after molding, it is particularly suitable in a field where form stability is required.
(I) polycarbonate having a water absorption of 0.05 to 0.15%, preferably 0.06 to 0.13% and Tg of 120 to 180 ° C, or (ii) Tg of 160 to 250 ° C, Polycarbonate which is preferably 170 to 230 ° C. and has a water absorption of 0.10 to 0.30%, preferably 0.13 to 0.30%, more preferably 0.14 to 0.27%.

Here, the water absorption of the 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. Moreover, Tg (glass transition temperature) is a value calculated | required by the differential scanning calorimeter (DSC) measurement based on JISK7121.
As the 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.

  In producing the aromatic polycarbonate resin by the interfacial polymerization method using the dihydric phenol and the carbonate precursor, a catalyst, a terminal terminator, and an antioxidant for preventing the dihydric phenol from being oxidized as necessary. Etc. may be used. 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. Moreover, the mixture which mixed 2 or more types of the obtained aromatic polycarbonate resin may be sufficient.

  The branched polycarbonate resin can impart anti-drip performance and the like to the polycarbonate resin composition of the present invention. Examples of 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, 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} -α, α-dimethylbenzylphenol, tetra (4-hydride) Loxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and their acids Among them, 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are preferable. 1-Tris (4-hydroxyphenyl) ethane is preferred.

  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 0.01-1 mol%, More preferably, it is 0.05-0.9 mol%, More preferably, it is 0.05-0.8 mol%.

  In particular, in the case of the melt transesterification method, 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. The content 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%. In addition, about the ratio of this branched structure, it is possible to calculate by 1H-NMR measurement.

  The aliphatic bifunctional carboxylic acid is preferably α, ω-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. Preferred are 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 aromatic polycarbonate resin of the present invention, include various documents and patents. This is a well-known method in gazettes.

In producing the polycarbonate resin composition of the present invention, the aromatic polycarbonate resin has a viscosity average molecular weight of 27,500 to 32,000, preferably 28,000 to 32,000, more preferably 28,000 to 31. , 000.
With an aromatic polycarbonate resin having a viscosity average molecular weight of less than 27,500, good mechanical properties cannot be obtained. On the other hand, a resin composition obtained from an aromatic polycarbonate resin having a viscosity average molecular weight exceeding 32,000 is inferior in flame retardancy.

The viscosity average molecular weight referred to in the present invention is first determined by using an Ostwald viscometer from a solution in which 0.7 g of polycarbonate is dissolved in 100 ml of methylene chloride at 20 ° C. with a specific viscosity (η _SP ) calculated by the following formula:
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀
[T ₀ is methylene chloride falling seconds, t is sample solution falling seconds]
The viscosity average molecular weight M is calculated from the determined specific viscosity (η _SP ) by the following formula.
η _SP /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ M ^0.83
c = 0.7

  The viscosity average molecular weight of the aromatic polycarbonate resin in the 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 the soluble component 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 aromatic polycarbonate resin 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). Polymeric resin.

[In General Formula (1), R ¹ and R ² are each independently 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. 20 cycloalkyl groups, cycloalkoxy groups having 6 to 20 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, aryl groups having 3 to 14 carbon atoms, aryloxy groups having 3 to 14 carbon atoms, carbon atoms Represents a group selected from the group consisting of an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. E and f are each an integer of 1 to 4, and W is a single bond or at least one group selected from the group consisting of groups represented by the following general formula (2). . ]

[In the general formula (2), 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 3 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 3 carbon atoms. -14 aryl group, aryloxy group having 6 to 10 carbon atoms, aralkyl group having 7 to 20 carbon atoms, aralkyloxy group having 7 to 20 carbon atoms, nitro group, aldehyde group, cyano group and It represents a group selected from the group consisting of carboxyl groups, and when there are a plurality thereof, they may be the same or different, g is an integer of 1 to 10, and h is an integer of 4 to 7. ]

[In General Formula (3), 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 substitution having 6 to 12 carbon atoms. Or an unsubstituted aryl group, 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 C2-C8 divalent aliphatic group. ]

  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, -Bis (4-hydroxyphenyl) octane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2- Bis (3-cyclohexyl-4-hydroxyphenyl) propane, 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) diphenylmethane, 9,9-bis (4-hydroxyphenyl) Fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 4,4 ′ -Dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldi Enyl ether, 4,4'-sulfonyldiphenol, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 4,4 '-Dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 2,2'-diphenyl-4,4'-sulfonyldiphenol, 4,4'- Dihydroxy-3,3′-diphenyldiphenyl sulfoxide, 4,4′-dihydroxy-3,3′-diphenyldiphenyl sulfide, 1,3-bis {2- (4-hydroxyphenyl) propyl} benzene, 1,4-bis {2- (4-hydroxyphenyl) propyl} benzene, 1,4-bis (4-hydro Xylphenyl) cyclohexane, 1,3-bis (4-hydroxyphenyl) cyclohexane, 4,8-bis (4-hydroxyphenyl) tricyclo [5.2.1.02,6] decane, 4,4 ′-(1, 3-adamantanediyl) diphenol, 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane, and the like.

  Among them, 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 (4 Hydroxyphenyl) cyclohexane (BPZ), 4,4'-sulfonyl diphenol, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene is preferred. Among them, 2,2-bis (4-hydroxyphenyl) propane having excellent strength and good durability is most preferable. Moreover, you may use these individually or in combination of 2 or more types.

  As the 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. Of these, (2-allylphenol) -terminated polydiorganosiloxane and (2-methoxy-4-allylphenol) -terminated polydiorganosiloxane are preferred, and (2-allylphenol) -terminated polydimethylsiloxane, particularly (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. When the upper limit of such a suitable range is exceeded, the amount of outgas generated during high temperature molding is large, and the low temperature impact property may be inferior.

  In order to achieve high impact resistance, the diorganosiloxane polymerization degree (p + q) of the hydroxyaryl-terminated polydiorganosiloxane (II) is suitably 10 to 300. The degree of diorganosiloxane polymerization (p + q) is preferably 10 to 200, more preferably 12 to 150, and still more preferably 14 to 100. If the amount is less than the lower limit of the preferable range, the impact resistance characteristic of the polycarbonate-polydiorganosiloxane copolymer is not effectively exhibited. If the upper limit of the preferable range is exceeded, poor appearance appears.

  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.

In the present invention, hydroxyaryl-terminated polydiorganosiloxane (II) may be used alone or in combination of two or more.
Further, within the range not hindering the present invention, 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.

In the present invention, 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.
In producing the oligomer of the dihydric phenol (I), 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. You may add to a polycondensation reaction as a reaction raw material. 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.

Although the method of this oligomer production | generation reaction is not specifically limited, Usually, the method performed in a solvent in presence of an acid binder is suitable.
The use ratio of the carbonate-forming compound 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 | adopted suitably.

  Examples of 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. 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). .

  As said solvent, what is necessary is just to use a solvent inert to various reaction, such as what is used for manufacture of a well-known polycarbonate, individually or as a mixed solvent. Typical examples include hydrocarbon solvents such as xylene, halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene. In particular, 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. Although the reaction time depends on other conditions and cannot be defined unconditionally, it is usually carried out in 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.

  In the present invention, after obtaining a mixed solution containing an oligomer of dihydric phenol (I) having a terminal chloroformate group in this way, 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 hydroxyaryl-terminated polydiorganosiloxane (II) and the oligomer are subjected to interfacial polycondensation. As a result, a polycarbonate-polydiorganosiloxane copolymer is obtained.

In (the general formula ^{(4), R 3, R} 4, R 5, R 6, R 7 and ^{R 8} are each independently a hydrogen atom, substituted 6-12 alkyl group carbon atoms or from 1 to 12 carbon atoms Or an unsubstituted aryl group, 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, p + q is a natural number of 10 to 300. X is a divalent aliphatic group having 2 to 8 carbon atoms.)

In performing the interfacial polycondensation reaction, an acid binder may be appropriately added in consideration of the stoichiometric ratio (equivalent) of the reaction. Examples of 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. Specifically, when the 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 interfacial polycondensation reaction between the oligomer of dihydric phenol (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) is carried out by vigorously stirring the above mixture.

  In such a polymerization reaction, a terminal terminator or a molecular weight modifier is usually used. Examples of the terminal terminator include compounds having a monohydric phenolic hydroxyl group. In addition to ordinary 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.

In order to accelerate the polycondensation reaction, 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.

  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). ) Heptene-2,2,4,6-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- [1,1-bis (4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol and the like Lisphenol, tetra (4-hydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, or trimellitic acid, pyromellitic acid, benzophenone Examples thereof include tetracarboxylic acid and acid chlorides thereof, among which 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are included. 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 1H-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 it is usually performed in 0.5 to 10 hours.

  In some cases, 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 obtain a desired reduction. It can also be obtained as a polycarbonate-polydiorganosiloxane copolymer resin having a viscosity [ηSP / c].

  The obtained reaction product (crude product) can be recovered as a polycarbonate-polydiorganosiloxane copolymer resin having a desired purity (purity) after 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 40 nm. The average size is more preferably 1 to 30 nm, still more preferably 5 to 25 nm. If it is less than the lower limit of such a suitable range, the impact resistance and flame retardancy are not sufficiently exhibited, and if it exceeds the upper limit of such a suitable range, the impact resistance may not be stably exhibited. Thereby, a polycarbonate resin composition excellent in impact resistance and appearance is provided.

  The average domain size and normalized dispersion of the polydiorganosiloxane domain of the polycarbonate-polydiorganosiloxane copolymer resin molded product in the present invention were evaluated by a small angle X-ray scattering method (SAXS). The small-angle X-ray scattering method is a method for measuring diffuse scattering / diffraction generated in a small-angle region within a scattering angle (2θ) <10 °. In this small-angle X-ray scattering method, if there are regions with different electron densities of about 1 to 100 nm in the substance, the X-ray diffuse scattering is measured by the difference in electron density. The particle diameter of the measurement object is obtained based on the scattering angle and the scattering intensity. In the case of a polycarbonate-polydiorganosiloxane copolymer resin having an aggregate structure in which a polydiorganosiloxane domain is dispersed in a polycarbonate polymer matrix, X-ray diffuse scattering occurs due to the difference in electron density between the polycarbonate matrix and the polydiorganosiloxane domain. The scattering intensity I at each scattering angle (2θ) in the range where the scattering angle (2θ) is less than 10 ° is measured, the small-angle X-ray scattering profile is measured, the polydiorganosiloxane domain is a spherical domain, and the particle size distribution varies. Assuming that there is a particle size, a simulation is performed using a commercially available analysis software from the temporary particle size and the temporary particle size distribution model to obtain the average size and particle size distribution (normalized dispersion) of the polydiorganosiloxane domain. According to the small-angle X-ray scattering method, the average size and particle size distribution of the polydiorganosiloxane domain dispersed in the polycarbonate polymer matrix, which cannot be accurately measured by observation with a transmission electron microscope, can be accurately, simply, and reproducibly reproduced. Can be measured. The average domain size means the number average of individual domain sizes. Normalized dispersion means a parameter in which the spread of the particle size distribution is normalized by the average size. Specifically, it is a value obtained by normalizing the dispersion of the polydiorganosiloxane domain size with the average domain size, and is represented by the following formula (1).

上記式（１）において、δはポリジオルガノシロキサンドメインサイズの標準偏差、Ｄａｖは平均ドメインサイズである。

In the above formula (1), δ is the standard deviation of the polydiorganosiloxane domain size, and Dav is the average domain size.

  The terms “average domain size” and “normalized dispersion” used in connection with the present invention are the measurement of the 1.0 mm thickness of the three-stage plate produced by the method described in the Examples by the small angle X-ray scattering method. The measured values obtained by In addition, the analysis was performed using an isolated particle model that does not take into account the interparticle interaction (interparticle interference).

(B component: Polyethylene terephthalate resin)
Polyethylene terephthalate resin (component B) is a saturated polyester polymer or copolymer obtained by a condensation reaction of terephthalic acid as a main component as an aromatic dicarboxylic acid component and ethylene glycol as a diol component. The thermoplastic polyester resin preferably contains 70 mol% or more, more preferably 80 mol% or more of ethylene terephthalate units as repeating units. According to a conventional method, the polyethylene terephthalate resin is produced by reacting the dicarboxylic acid component and the diol component with heating in the presence of a polycondensation catalyst containing titanium, germanium, antimony, etc. It is performed by discharging alcohol out of the system. For example, 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. At this time, either a batch method or a continuous polymerization method can be employed, and the degree of polymerization can be increased by solid phase polymerization.

  Moreover, the terminal group structure of the polyethylene terephthalate resin to be used is not particularly limited, and may be a case in which one of the terminal groups is large in addition to the case where the ratios of the hydroxyl groups and carboxyl groups in the terminal groups are substantially the same. Moreover, those terminal groups may be sealed by reacting a compound having reactivity with such terminal groups.

Further, in the present invention, compounds such as manganese, zinc, calcium, magnesium, etc., which are used in a transesterification reaction that is a prior stage of a conventionally known polycondensation, can be used in combination, and phosphoric acid or phosphorous after completion of the transesterification reaction. Such a catalyst can be deactivated and polycondensed with an acid compound or the like.
In particular, in accordance with a conventional method, a polymer produced by polymerizing the dicarboxylic acid component and the diol component while heating in the presence of a specific titanium-based catalyst and discharging by-product water or lower alcohol out of the system is used. Is preferred.

The titanium-based catalyst includes a reaction product of the following titanium compound component (A) and phosphorus compound component (B).
The titanium compound component (A) includes a titanium compound (1) represented by the following general formula (I), an aromatic polyvalent carboxylic acid represented by the titanium compound (1) and the following general formula (II), or anhydrous It is at least one titanium compound component selected from the group consisting of a titanium compound (2) obtained by reacting with a product.

[In the formula (I), R ¹ , R ² , R ³ and R ⁴ each independently represent an alkyl group having 2 to 10 carbon atoms, k represents an integer of 1 to 3, When k is 2 or 3, two or three R ² and R ³ may be the same or different from each other. ]

〔但し、式（ＩＩ）中、ｍは２〜４の整数を表す。〕

[However, in formula (II), m represents the integer of 2-4. ]

  The phosphorus compound component (B) is a phosphorus compound component composed of at least one of the phosphorus compounds (3) represented by the following general formula (III).

〔但し、式（ＩＩＩ）中、Ｒ^５は、未置換の又は置換された、６〜２０個の炭素原子を有するアリール基、又は１〜２０個の炭素原子を有するアルキル基を表す。〕

[In the formula (III), R ⁵ represents an unsubstituted or substituted aryl group having 6 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms. ]

  The polyethylene terephthalate resin produced by using the above specific titanium-based catalyst is superior in thermal stability and wet heat resistance as compared with the case of using germanium, antimony and other titanium-based catalysts. When the above specific titanium-based catalyst is used, the quality is stable even if the amount of additives such as hue stabilizer and heat stabilizer during production is less than when other catalysts are used. Since decomposition of the additive in a thermal environment or a moist heat environment is reduced, it is presumed that the thermal stability and the heat and humidity resistance are excellent.

  In the reaction product of the titanium compound component (A) and the phosphorus compound component (B), the titanium compound equivalent molar amount (mTi) of the titanium compound component (A) and the phosphorus atom equivalent molar amount of the phosphorus compound component (B) The reaction molar ratio (mTi / mP) with (mP) is preferably in the range of 1/3 to 1/1, and more preferably in the range of 1/2 to 1/1.

  The molar amount in terms of titanium atom of the titanium compound component (A) is the product of the molar amount of each titanium compound contained in the titanium compound component (A) and the number of titanium atoms contained in one molecule of the titanium compound. It is a total value, and the phosphorus atom equivalent molar amount of the phosphorus compound component (B) is the molar amount of each phosphorus compound contained in the phosphorus compound component (B) and the phosphorus atoms contained in one molecule of the phosphorus compound. It is the total value of the product with the number. However, since the phosphorus compound represented by the formula (III) contains one phosphorus atom per molecule, the phosphorus atom equivalent molar amount of the phosphorus compound is equal to the molar amount of the phosphorus compound.

  When the reaction molar ratio (mTi / mP) is larger than 1/1, that is, when the amount of the titanium compound component (A) becomes excessive, the color tone of the polyethylene terephthalate resin obtained using the resulting catalyst (b value is high). And the heat resistance may be reduced. Further, when the reaction molar ratio (mTi / mP) is less than 1/3, that is, when the amount of the titanium compound component (A) becomes too small, the catalyst activity of the resulting catalyst for the polyester formation reaction may be insufficient. is there.

  Examples of the titanium compound (1) represented by the general formula (I) used for the titanium compound component (A) include titanium tetrabutoxide, titanium tetraisopropoxide, titanium tetrapropoxide, and titanium tetraethoxide. Examples include tetraalkoxides, and alkyl titanates such as octaalkyltrititanates and hexaalkyldititanates, and among these, titanium having good reactivity with the phosphorus compound component used in the present invention. It is preferable to use tetraalkoxides, and it is particularly preferable to use titanium tetrabutoxide.

  The titanium compound (2) used for the titanium compound component (A) is obtained by reacting the titanium compound (1) with the aromatic polyvalent carboxylic acid represented by the general formula (II) or an anhydride thereof. The aromatic polyvalent carboxylic acid of the general formula (II) and its anhydride are preferably selected from the group consisting of phthalic acid, trimellitic acid, hemimellitic acid, pyromellitic acid and their anhydrides. In particular, it is more preferable to use trimellitic anhydride having good reactivity with the titanium compound (1) and high affinity with the polyester of the resulting polycondensation catalyst.

  The reaction between the titanium compound (1) and the aromatic polyvalent carboxylic acid of the general formula (II) or an anhydride thereof is carried out by mixing the aromatic polyvalent carboxylic acid or the anhydride thereof in a solvent and part or all of the mixture. Is dissolved in a solvent, and the titanium compound (1) is dropped into this mixed solution and heated at a temperature of 0 ° C. to 200 ° C. for 30 minutes or more, preferably at a temperature of 30 to 150 ° C. for 40 to 90 minutes. Is called. The reaction pressure at this time is not particularly limited, and normal pressure is sufficient. The catalyst can be appropriately selected from those capable of dissolving a required amount of the compound of formula (II) or a part or all of its anhydride, preferably ethanol, ethylene glycol, trimethylene. It is selected from glycol, tetramethylene glycol, benzene, xylene and the like.

  There is no limitation on the reaction molar ratio between the titanium compound (1) and the compound represented by the formula (II) or its anhydride. However, when the proportion of the titanium compound (1) is too high, the color tone of the obtained polyethylene terephthalate resin may be deteriorated or the softening point may be lowered. Conversely, when the proportion of the titanium compound (1) is too low. The polycondensation reaction may be difficult to proceed. For this reason, it is preferable that the reaction molar ratio of the titanium compound (1) to the compound of the formula (II) or an anhydride thereof is controlled within the range of 2/1 to 2/5. The reaction product obtained by this reaction may be directly subjected to the reaction with the above-described phosphorus compound (3) or recrystallized using a solvent comprising acetone, methyl alcohol and / or ethyl acetate. Then, this may be reacted with the phosphorus compound (3).

In the phosphorus compound (3) of the general formula (III) used for the phosphorus compound component (B), an aryl group having 6 to 20 carbon atoms represented by R ⁵ , or 1 to 20 carbon atoms The alkyl group possessed may be unsubstituted or substituted with one or more substituents. Examples of the substituent include a carboxyl group, an alkyl group, a hydroxyl group, and an amino group.

  The phosphorus compound (3) of the general formula (III) includes, for example, monomethyl phosphate, monoethyl phosphate, monotrimethyl phosphate, mono-n-butyl phosphate, monohexyl phosphate, monoheptyl phosphate, monooctyl phosphate, monononyl phosphate, Monodecyl phosphate, monododecyl phosphate, monolauryl phosphate, monooleyl phosphate, monotetradecyl phosphate, monophenyl phosphate, monobenzyl phosphate, mono (4-dodecyl) phenyl phosphate, mono (4-methylphenyl) phosphate, mono (4 -Ethylphenyl) phosphate, mono (4-propylphenyl) phosphate, mono (4-dodecylphenyl) phosphate, monotolylphosphate Monoalkyl phosphates and monoaryl phosphates, such as benzoyl, monoxyl phosphate, monobiphenyl phosphate, mononaphthyl phosphate, and monoanthryl phosphate, which may be used alone or in combination of two or more For example, a mixture of monoalkyl phosphate and monoaryl phosphate may be used. However, when the above phosphorus compound is used as a mixture of two or more kinds, it is preferable that the proportion of monoalkyl phosphate occupies 50% or more, more preferably 90% or more, particularly 100%. More preferably.

  In order to prepare a catalyst from the titanium compound component (A) and the phosphorus compound component (B), for example, a phosphorus compound component (B) comprising at least one phosphorus compound (3) of the formula (III) and a solvent are prepared. Mix and dissolve part or all of the phosphorus compound component (B) in a solvent, drop the titanium compound component (A) into this mixture, and usually react the reaction system preferably at 50 ° C to 200 ° C, more preferably Is carried out by heating at a temperature of 70 ° C. to 150 ° C., preferably for 1 minute to 4 hours, more preferably for 30 minutes to 2 hours. In this reaction, the reaction pressure is not particularly limited, and may be any of under pressure (0.1 to 0.5 MPa), normal pressure, or reduced pressure (0.001 to 0.1 MPa). Usually performed under normal pressure.

  The solvent for the phosphorus compound component (B) of the formula (III) used in the catalyst preparation reaction is not particularly limited as long as at least a part of the phosphorus compound component (B) can be dissolved. For example, ethanol, ethylene A solvent composed of at least one selected from glycol, trimethylene glycol, tetramethylene glycol, benzene, xylene and the like is preferably used. In particular, it is preferable to use, as a solvent, the same compound as the glycol component constituting the polyester to be finally obtained.

  The reaction product of the titanium compound component (A) and the phosphorus compound component (B) is separated from the reaction system by means such as centrifugal sedimentation or filtration, and then purified without being purified. It may be used as a catalyst for resin production, or the separated reaction product is purified by recrystallization from a recrystallization agent such as acetone, methyl alcohol and / or water, and the resulting purification The product may be used as a catalyst. Moreover, you may use the reaction product containing reaction mixture as a catalyst containing mixture as it is, without isolate | separating the said reaction product from the reaction system.

As a titanium-based catalyst, a titanium compound component (A) comprising at least one titanium compound (1) of the above formula (I) (where k represents 1), that is, titanium tetraalkoxide, and the above formula (III) It is preferable that the reaction product with the phosphorus compound component (B) comprising at least one phosphorus compound is used as a catalyst.
Furthermore, a compound represented by the following general formula (IV) is preferably used as the titanium-based catalyst.

〔上記式中Ｒ^６及びＲ^７は、それぞれ互いに独立に、２〜１２個の炭素原子を有するアルキル基、又は６〜１２個の炭素原子を有するアリール基を表す〕

[In the above formula, R ⁶ and R ⁷ each independently represent an alkyl group having 2 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms]

A catalyst containing a titanium / phosphorus compound represented by the formula (IV) has a high catalytic activity, and a polyethylene terephthalate resin produced using the catalyst has a good color tone (low b value) and is practically used. It has a sufficiently low content of acetaldehyde, residual metals and cyclic trimers of esters of aromatic dicarboxylic acids and alkylene glycols, and has practically sufficient polymer performance.
In the titanium-based catalyst, the titanium / phosphorus compound of the general formula (IV) is preferably contained in an amount of 50% by mass or more, and more preferably 70% by mass or more.

  The amount of the titanium-based catalyst used is preferably an amount such that the mmol amount in terms of titanium atom is 2 to 40% with respect to the total mmol amount of the aromatic dicarboxylic acid component contained in the polymerization starting material, It is more preferable that it is 35%, and it is still more preferable that it is 10 to 30%. When the content is less than 2%, the catalyst promoting effect on the polycondensation reaction of the polymerization starting material becomes insufficient, the production efficiency of the polyethylene terephthalate resin becomes insufficient, and a polyethylene terephthalate resin having a desired degree of polymerization is obtained. May not be possible. On the other hand, if it exceeds 40%, the color tone (b value) of the obtained polyethylene terephthalate resin becomes insufficient and becomes yellowish, and its practicality may be lowered.

  There is no limitation on the production method of the alkylene glycol ester of aromatic dicarboxylic acid and / or its low polymer, but usually, the aromatic dicarboxylic acid or its ester-forming derivative and the alkylene glycol or its ester-forming derivative are heated. Produced by reacting. For example, an ethylene glycol ester of terephthalic acid and / or a low polymer thereof used as a raw material for polyethylene terephthalate may be obtained by directly esterifying terephthalic acid and ethylene glycol, or by using a lower alkyl ester of terephthalic acid and ethylene glycol. It is produced by a method of transesterification or an addition reaction of terephthalic acid with ethylene oxide. In addition, the above-described aromatic dicarboxylic acid alkylene glycol ester and / or a low polymer thereof may contain other dicarboxylic acid ester copolymerizable therewith as an additional component, so that the effect of the method of the present invention is not substantially impaired. It may be contained in an amount within the range, specifically, 10 mol% or less, preferably 5 mol% or less, based on the total molar amount of the acid components.

  The copolymerizable additional component is preferably an acid component, for example, aliphatic and alicyclic dicarboxylic acids such as adipic acid, sebacic acid, 1,4-cyclohexanedicarboxylic acid, and hydroxycarboxylic acids such as One or more of β-hydroxyethoxybenzoic acid, p-oxybenzoic acid, and the like and a glycol component, for example, alkylene glycol having 2 or more carbon atoms, 1,4-cyclohexanedimethanol, neopentyl glycol, bisphenol A , An ester with one or more of aliphatic, cycloaliphatic, aromatic diol compounds such as bisphenol S and polyoxyalkylene glycol, or anhydrides thereof. The postscript component ester may be used alone or in combination of two or more thereof. However, the copolymerization amount is preferably within the above range.

  When terephthalic acid and / or dimethyl terephthalate is used as a starting material, recovered dimethyl terephthalate obtained by depolymerizing polyalkylene terephthalate or recovered terephthalic acid obtained by hydrolyzing this is used as polyester. 70 mass% or more can also be used on the basis of the mass of all the acid components to comprise. In this case, it is preferable that the target polyalkylene terephthalate is polyethylene terephthalate. In particular, recovered PET bottles, recovered fiber products, recovered polyester film products, polymer waste generated in the manufacturing process of these products, etc. It is preferable to use as a raw material source for producing polyester from the viewpoint of effective utilization of resources. Here, the method for depolymerizing the recovered polyalkylene terephthalate to obtain dimethyl terephthalate is not particularly limited, and any conventionally known method can be employed. For example, after the recovered polyalkylene terephthalate is depolymerized with ethylene glycol, the depolymerized product is subjected to a transesterification reaction with a lower alcohol such as methanol, and the reaction mixture is purified to recover the lower alkyl ester of terephthalic acid. The polyester resin can be obtained by subjecting this to an ester exchange reaction with alkylene glycol and polycondensing the resulting phthalic acid / alkylene glycol ester. Further, the method for recovering terephthalic acid from the recovered dimethyl terephthalate is not particularly limited, and any conventional method may be used. For example, dimethyl terephthalate can be recovered from the reaction mixture obtained by the transesterification by recrystallization and / or distillation, and then heated and hydrolyzed with water under high temperature and high pressure to recover terephthalic acid. In the impurities contained in terephthalic acid obtained by this method, the total content of 4-carboxybenzaldehyde, p-toluic acid, benzoic acid and dimethyl hydroxyterephthalate is preferably 1 ppm or less. Moreover, it is preferable that content of monomethyl terephthalate exists in the range of 1-5000 ppm. A polyester resin can be produced by directly esterifying the terephthalic acid recovered by the above-described method with an alkylene glycol and polycondensing the resulting ester.

  In the polyethylene terephthalate resin used in the present invention, the catalyst may be added to the polymerization starting material at any stage before the start of the polycondensation reaction of the aromatic dicarboxylic acid alkylene glycol ester and / or its low polymer. Further, there is no limitation on the addition method. For example, an aromatic dicarboxylic acid alkylene glycol ester may be prepared and a polycondensation reaction may be initiated by adding a catalyst solution or slurry to the reaction system, or the aromatic dicarboxylic acid alkylene glycol ester may be A catalyst solution or slurry may be added to the reaction system together with the starting materials during the preparation or after the charging.

  There are no particular restrictions on the production reaction conditions of the polyethylene terephthalate resin used in the present invention. In general, the polycondensation reaction is preferably performed at a temperature of 230 to 320 ° C. under normal pressure or reduced pressure (0.1 Pa to 0.1 MPa), or a combination of these conditions for 15 to 300 minutes. .

  In the polyethylene terephthalate resin used in the present invention, a reaction stabilizer, for example, trimethyl phosphate, may be added to the reaction system as needed at any stage in the production of the polyethylene terephthalate resin. You may mix | blend 1 or more types of an agent, a ultraviolet absorber, a flame retardant, a fluorescent whitening agent, a matting agent, a color adjusting agent, a defoaming agent, and other additives. In particular, the polyethylene terephthalate resin preferably contains an antioxidant containing at least one hindered phenol compound, but the content thereof is 1% by mass or less based on the mass of the polyethylene terephthalate resin. It is preferable. When the content exceeds 1% by mass, there may be a disadvantage that the quality of the obtained product is deteriorated due to thermal deterioration of the antioxidant itself.

  The hindered phenol compound for antioxidant used in the polyethylene terephthalate resin used in the present invention is pentaerythritol-tetra extract [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 3, 9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5 , 5] selected from undecane and the like, and it is also preferable to use these hindered phenolic antioxidants in combination with thioether secondary antioxidants. The method for adding the hindered phenol-based antioxidant to the polyethylene terephthalate resin is not particularly limited, but preferably any stage from the end of the ester exchange reaction or the esterification reaction to the completion of the polymerization reaction. Is added.

  Further, in order to finely adjust the color tone of the obtained polyethylene terephthalate resin, an organic blue pigment such as azo, triphenylmethane, quinoline, anthraquinone, phthalocyanine is used in the reaction system in the production stage of the polyethylene terephthalate resin. In addition, a color adjusting agent composed of one or more inorganic blue pigments can be added. In the production method of the present invention, as a matter of course, it is not necessary to use an inorganic blue pigment containing cobalt or the like which lowers the heat stability of melting of the polyethylene terephthalate resin as the color adjusting agent. Therefore, the polyethylene terephthalate resin used in the present invention is substantially free of cobalt.

  The polyethylene terephthalate resin used in the present invention preferably contains 0.001-50 ppm of titanium element derived from the catalyst, and more preferably contains 1-45 ppm. When the content of titanium element is more than 50 ppm, thermal stability and hue are deteriorated. When the content is less than 0.001 ppm, the catalyst remaining amount of the polyethylene terephthalate resin to be used is significantly lower, making it difficult to produce the polyethylene terephthalate resin. This means that good mechanical strength, heat stability and wet heat stability, which are the characteristics of this composition, cannot be obtained, which is not preferable.

  In the polyethylene terephthalate resin used in the present invention, it is usually preferable that the L value obtained from a hunter-type color difference meter is 80.0 or more and the b value is in the range of -2.0 to 5.0. If the L value of the polyethylene terephthalate resin is less than 80.0, the whiteness of the resulting polyethylene terephthalate resin will be low, and it may not be possible to obtain a high whiteness molded product that can be used practically. Further, when the b value is less than −2.0, the resulting polyethylene terephthalate resin has little yellowness, but the bluish color increases. When the b value exceeds 5.0, the resulting polyethylene terephthalate resin has a yellowness. However, it may not be possible to produce a practically useful molded product. The L value of the polyethylene terephthalate resin obtained by the method of the present invention is more preferably 82 or more, particularly preferably 83 or more, and a more preferable range of the b value is -1.0 to 4.5, particularly preferably 0. 0 to 4.0.

  The intrinsic viscosity of the polyethylene terephthalate resin obtained by the present invention is not limited, but is preferably in the range of 0.40 to 1.2. When the intrinsic viscosity is within this range, melt molding is easy and the strength of the molded product obtained therefrom is high. A more preferable range of the intrinsic viscosity is 0.45 to 1.1, and particularly preferably 0.50 to 1.0. The intrinsic viscosity of the polyethylene terephthalate resin is measured at a temperature of 35 ° C. by dissolving the polyethylene terephthalate resin in orthochlorophenol. The polyethylene terephthalate resin obtained by solid phase polycondensation is often used in general bottles and the like, and is therefore contained in the polyethylene terephthalate resin and has an intrinsic viscosity of 0.70 to 0.90. The cyclic trimer content of the ester of aromatic dicarboxylic acid and alkylene glycol is preferably 0.5 wt% or less, and the acetaldehyde content is preferably 5 ppm or less. The cyclic trimers include alkylene terephthalates such as ethylene terephthalate, trimethylene terephthalate, tetramethylene terephthalate, and hexamethylene terephthalate, and alkylene naphthalates such as ethylene naphthalate, trimethylene naphthalate, tetramethylene naphthalate and hexamethylene. Including methylene naphthalate.

  Content of B component is 30-60 weight part per 100 weight part in total of A component and B component, 35-60 weight part is preferable and 40-60 weight part is more preferable. When the content exceeds 60 parts by weight, impact resistance, flame retardancy, heat resistance and appearance are deteriorated. When the content is less than 30 parts by weight, chemical resistance and heat resistance are deteriorated.

(C component: polyorganosiloxane-containing graft copolymer)
The polyorganosiloxane-containing graft copolymer used as the component C of the present invention can be produced, for example, by the production method disclosed in JP-A No. 2003-238639.
That is, the polyorganosiloxane-containing graft copolymer polymerizes (Y) 0.5 to 10 parts by weight of the first vinyl monomer in the presence of (X) 40 to 90 parts by weight of polyorganosiloxane particles. Furthermore, (Z) it is preferable to be obtained by polymerizing 5 to 50 parts by weight of the second vinyl monomer.

  The (X) polyorganosiloxane particles have a toluene insoluble content (the amount of toluene insoluble when 0.5 g of the (X) polyorganosiloxane particles are immersed in 80 ml of toluene at room temperature for 24 hours) is 95% by weight or less, and further 50%. % Or less, particularly 20% by weight or less is preferable from the viewpoint of flame retardancy and impact resistance.

  Specific examples of (X) polyorganosiloxane particles include polydimethylsiloxane particles, polymethylphenylsiloxane particles, dimethylsiloxane-diphenylsiloxane copolymer particles, and the like. These may be used alone or in combination of two or more.

  (Y) The first vinyl monomer is (y-1) a polyfunctional monomer, that is, 100 to 50% by weight of a polyfunctional monomer containing two or more polymerizable unsaturated bonds in the molecule. And (y-2) a vinyl monomer composed of 0 to 50% by weight of other copolymerizable monomers. (Y) A 1st vinyl-type monomer is used in order to improve a flame-retardant effect and an impact-resistant improvement effect.

  (Y) The first vinyl monomer contains (y-1) a polyfunctional monomer, preferably 100 to 80% by weight, more preferably 100 to 90% by weight, (y-2) Other Is preferably 0 to 20% by weight, more preferably 0 to 10% by weight. (Y-1) By including a polyfunctional monomer in a proportion of 80% by weight or more, and (y-2) by including other copolymerizable monomers in a proportion of 80% by weight or less. The impact resistance improving effect of the finally obtained polyorganosiloxane-containing graft copolymer tends to be further improved, which is preferable.

  (Y-1) The polyfunctional monomer is a compound containing two or more polymerizable unsaturated bonds in the molecule, and specific examples thereof include allyl methacrylate, triallyl cyanurate, and divinylbenzene. . These may be used alone or in combination of two or more. Among these, the use of allyl methacrylate is particularly preferred from the viewpoint of economy and effects.

  (Y-2) Specific examples of other copolymerizable monomers include aromatic vinyl monomers such as styrene, vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, methyl acrylate, Examples thereof include (meth) acrylic acid ester monomers such as ethyl acrylate, methyl methacrylate and ethyl methacrylate, and carboxyl group-containing vinyl monomers such as (meth) acrylic acid and maleic acid. Two or more of these may be used in combination.

  (Z) The second vinyl monomer is a component constituting (C) a polyorganosiloxane-containing graft copolymer, and (C) the polyorganosiloxane-containing graft copolymer is blended with a thermoplastic resin. In order to improve the flame retardancy and impact resistance, the components used to ensure the compatibility of the graft copolymer and the thermoplastic resin and to uniformly disperse the graft copolymer in the thermoplastic resin But there is.

(Z) Examples of the second vinyl monomer include (y-2) other in the above (Y) first vinyl monomer such as methyl methacrylate, butyl methacrylate, styrene, acrylonitrile and the like. The same monomer as the copolymerizable monomer can be used, and two or more types may be used in combination.
(Z) The second vinyl monomer preferably has a polymer solubility parameter of 9.15 to 10.15 [(cal / cm ³ ) ^1/2 ], 9.17-10.10 [(cal / cm ³ ) ^1/2 ] is more preferable, and 9.20-10.05 [(cal / cm ³ ) ^1/2 ] is even more preferable. By setting the solubility parameter within the above range, the flame retardancy tends to be further improved, which is preferable.

  The polyorganosiloxane-containing graft copolymer used in the present invention comprises (X) polyorganosiloxane particles in the presence of 20 to 90% by weight, preferably 25 to 90% by weight, more preferably 30 to 90% by weight, (Y) 0.3 to 20% by weight, preferably 0.4 to 20% by weight, more preferably 0.5 to 20% by weight of the first vinyl monomer is polymerized; It is preferably obtained by polymerizing 2 to 60% by weight, preferably 4 to 60% by weight, and more preferably 5 to 50% by weight of the vinyl monomer 2.

(X) When the ratio of the polyorganosiloxane particles is too small or too large, the flame retarding effect is low.
In addition, when the amount of (Y) the first vinyl monomer is too small, the flame retarding effect and the impact resistance improving effect are lowered, and when it is too much, the impact resistance improving effect is lowered.
Furthermore, when (Z) the second vinyl monomer is too little or too much, the flame retarding effect is lowered in both cases.

  For the polyorganosiloxane-containing graft copolymer, known seed emulsion polymerization can be applied. For example, (X) radical polymerization of the first vinyl monomer in the latex of (X) polyorganosiloxane particles, (Z) It is obtained by performing radical polymerization of the second vinyl monomer. Further, both (Y) the first vinyl monomer and (Z) the second vinyl monomer may be polymerized in one stage or in two or more stages.

  The polyorganosiloxane-containing graft copolymer obtained by the above method may be used by separating the polymer from the latex, or may be used as it is. Examples of the method for separating the polymer include a usual method, for example, a method of coagulating, separating, washing, dehydrating and drying the latex by adding a metal salt such as calcium chloride, magnesium chloride, magnesium sulfate to the latex. . A spray drying method can also be used.

  Further, at least one vinyl monomer is graft-polymerized to the composite rubber having a structure in which the polysiloxane rubber component and the polyalkyl (meth) acrylate rubber component are intertwined with each other so that they cannot be separated as the C component of the present invention. A polyorganosiloxane-containing composite rubber-based graft copolymer can also be used.

  Among such rubber-based graft copolymers, at least one kind of vinyl monomer is present in the composite rubber having a structure in which the polysiloxane rubber component and the polyalkyl (meth) acrylate rubber component are intertwined so that they cannot be separated. The composite rubber-based graft copolymer obtained by graft polymerization is firstly composed of various cyclic organosiloxanes having three or more members, such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, a crosslinking agent, and the like. A latex of polyorganosiloxane rubber is prepared by emulsion polymerization using a graft crossing agent, and then the polyorganosiloxane rubber latex is impregnated with an alkyl (meth) acrylate monomer, a crosslinking agent and a graft crossing agent. Is obtained by polymerization from

  Examples of the alkyl (meth) acrylate monomer used herein include alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate, and alkyl methacrylates such as hexyl methacrylate and 2-ethylhexyl methacrylate. Among them, n-butyl acrylate is particularly preferable.

  Examples of vinyl monomers to be graft polymerized to the composite rubber include aromatic vinyl compounds such as styrene and α-methylstyrene, vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, and methacrylic compounds such as methyl methacrylate and 2-ethylhexyl methacrylate. Examples thereof include acrylic acid esters such as acid ester, methyl acrylate, ethyl acrylate, and butyl acrylate, and these are used alone or in combination of two or more. The composite rubber graft polymer may be a mixture of a vinyl monomer polymer or copolymer which is released without being grafted with the vinyl monomer to be graft polymerized. A polymer or copolymer of a series monomer may be mixed with a composite rubber graft polymer.

  In this composite rubber-based graft copolymer, the polyorganosiloxane rubber component and the polyalkyl (meth) acrylate rubber component have a structure in which the crosslinking network is entangled with each other. These organic solvents cannot be separated / extracted, and since they have such a structure, a molded product having excellent impact strength can be obtained by blending them. The ratio of the polyorganosiloxane rubber component to the polyalkyl (meth) acrylate rubber component is 10 to 90% by weight of the polyorganosiloxane rubber component and the polyalkyl (meth) acrylate rubber component, assuming that the total amount of both rubber components is 100% by weight. A range of 90 to 10% by weight can be taken. The average particle size of the composite rubber is usually about 0.08 to 0.6 μm. This composite rubber-based graft copolymer is a commercially available product such as METABRENE S-2001 manufactured by Mitsubishi Rayon Co., Ltd., and is easily available.

  The polyorganosiloxane-containing graft copolymer preferably contains 20% or more and 95% or less Si component, more preferably 25% or more and 90% or less, by area ratio in the Py-GC / MS method (600 ° C.). The Si component is included, and the Si component is particularly preferably 30% or more and 90% or less. When the Si component contained is higher than the lower limit, impact strength and flame retardancy are good, and when it is lower than the upper limit, the thermal stability is excellent and the appearance is not easily deteriorated due to a decrease in hue, which is preferable.

  Content of C component is 0.5-10 weight part with respect to a total of 100 weight part of A component and B component, Preferably it is 1-10 weight part, More preferably, it is 2-8 weight part. If the content is less than 0.5 parts by weight, sufficient impact properties, chemical resistance and heat resistance cannot be obtained, and if it exceeds 10 parts by weight, flame retardancy, appearance and heat resistance are deteriorated.

(D component: brominated flame retardant)
Examples of the brominated flame retardant used in the present invention include a brominated bisphenol A type polycarbonate flame retardant having a bromine content of 20% by weight or more, a brominated bisphenol A type epoxy resin, and a modification in which part or all of the terminal glycidyl groups are blocked. Products, brominated diphenyl ether flame retardant, brominated imide flame retardant, brominated polystyrene flame retardant and the like.

  Specific examples include decabromodiphenyl oxide, octabromodiphenyl oxide, tetrabromodiphenyl oxide, tetrabromophthalic anhydride, hexabromocyclododecane, bis (2,4,6-tribromophenoxy) ethane, ethylene bistetrabromophthalimide, Hexabromobenzene, 1,1-sulfonyl [3,5-dibromo-4- (2,3-dibromopropoxy)] benzene, polydibromophenylene oxide, tetrabromobisphenol S, tris (2,3-dibromopropyl-1) Isocyanurate, tribromophenol, tribromophenyl allyl ether, tribromoneopentyl alcohol, brominated polystyrene, brominated polyethylene, tetrabromobisphenol A, tetrabromobisphenol Abromide A derivatives, tetrabromobisphenol A-epoxy oligomer or polymer, tetrabromobisphenol A-carbonate oligomer or polymer, brominated epoxy resins such as brominated phenol novolac epoxy, tetrabromobisphenol A-bis (2-hydroxydiethyl ether) , Tetrabromobisphenol A-bis (2,3-dibromopropyl ether), tetrabromobisphenol A-bis (allyl ether), tetrabromocyclooctane, ethylenebispentabromodiphenyl, tris (tribromoneopentyl) phosphate, poly ( Pentabromobenzyl polyacrylate), octabromotrimethylphenylindane, dibromoneopentyl glycol, pentabromobenzyl polyacrylate Over DOO, dibromo cresyl glycidyl ether, N, N'ethylene - bis - such as tetrabromo phthalic imide. Among these, tetrabromobisphenol A-epoxy oligomer, tetrabromobisphenol A-carbonate oligomer, brominated epoxy resin and the like can be mentioned.

  As the brominated flame retardant of the present invention, brominated polycarbonate (including oligomer) is particularly suitable. Brominated polycarbonate has excellent heat resistance and can greatly improve flame retardancy. In the brominated polycarbonate used in the present invention, the structural unit represented by the following general formula (5) is at least 60 mol%, preferably at least 80 mol%, particularly preferably substantially the following general formula. A brominated polycarbonate compound composed of the structural unit represented by (5).

(In the formula (5), X is a bromine atom, R represents an alkylene group having 1 to 4 carbon atoms, an alkylidene group or -SO ₂ 1 to 4 carbon atoms - a.)
In the formula (5), R preferably represents a methylene group, an ethylene group, an isopropylidene group, —SO ₂ —, and particularly preferably an isopropylidene group.

  The brominated polycarbonate has a small number of remaining chloroformate groups and preferably has a terminal chlorine content of 0.3 ppm or less, more preferably 0.2 ppm or less. The amount of terminal chlorine is determined by dissolving a sample in methylene chloride, adding 4- (p-nitrobenzyl) pyridine and allowing it to react with terminal chlorine (terminal chloroformate). -3200). When the amount of terminal chlorine is 0.3 ppm or less, the thermal stability of the resin composition becomes better, and molding at a higher temperature becomes possible, and as a result, a resin composition having better molding processability is provided.

  The brominated polycarbonate preferably has a small number of remaining hydroxyl terminals. More specifically, the amount of terminal hydroxyl groups is preferably 0.0005 mol or less, more preferably 0.0003 mol or less with respect to 1 mol of the structural unit of brominated polycarbonate. The amount of terminal hydroxyl groups can be determined by dissolving a sample in deuterated chloroform and measuring it by 1H-NMR method. Such a terminal hydroxyl group amount is preferable because the thermal stability of the resin composition is further improved.

The specific viscosity of the brominated polycarbonate is preferably in the range of 0.015 to 0.1, more preferably in the range of 0.015 to 0.08. The specific viscosity of the brominated polycarbonate is calculated according to the above-described specific viscosity calculation formula used for calculating the viscosity average molecular weight of the polycarbonate resin which is the component A of the present invention.
Content of D component is 1-10 weight part with respect to 100 weight part in total of A component and B component, Preferably it is 1-9 weight part, More preferably, it is 1-8 weight part. If the content is less than 1 part by weight, the expected mechanical strength, flame retardancy, and appearance cannot be obtained, and if it exceeds 10 parts by weight, the appearance deteriorates.

(E component: antimony flame retardant aid)
As the antimony flame retardant aid (E component) used in the present invention, antimony trioxide, antimony tetroxide, and (NaO) _p · (Sb ₂ O ₅ ) · qH ₂ O (p = 0 to 1, q = 0-4) antimony pentoxide or sodium antimonate partially Na-chlorinated. As these antimony flame retardant aids, antimony pentoxide represented by (NaO) _p · (Sb ₂ O ₅ ) · qH ₂ O (p = 0 to 1, q = 0 to 4) or partly Na When chlorinated sodium antimonate is used, metal corrosivity becomes more preferable. Further, it is more preferable to use a solution having a pH of 6 to 9 when an ethanol solution of sodium antimonate is used, since the resin composition is hardly decomposed. The antimony flame retardant aid preferably has a particle size of 0.02 to 5 μm. Moreover, you may surface-treat with an epoxy compound, a silane compound, an isocyanate compound, a titanate compound etc. as needed.

  Content of E component is 0.5-3 weight part with respect to a total of 100 weight part of A component and B component, Preferably it is 0.7-3 weight part, More preferably, it is 1.0-3 weight Part. If the content is less than 0.5 parts by weight, the required flame retardancy cannot be obtained, and if it exceeds 3 parts by weight, the flame retardancy and appearance are deteriorated.

(F component: Fluorine-containing anti-dripping agent)
The resin composition of the present invention contains a fluorine-containing anti-dripping agent. By using such a fluorine-containing anti-drip agent in combination with the above flame retardant, better flame retardancy can be obtained. Examples of such a fluorine-containing anti-drip agent include a fluorine-containing polymer having a fibril-forming ability. Examples of such a polymer include polytetrafluoroethylene and tetrafluoroethylene copolymers (for example, 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, preferably polytetrafluoroethylene (hereinafter referred to as PTFE). May be called).

Polytetrafluoroethylene (fibrillated PTFE) having fibril-forming ability has a very high molecular weight, and exhibits a tendency to bind PTFE to each other by an external action such as shearing force to form a fiber. Its number average molecular weight ranges from 1.5 million to tens of millions. The lower limit is more preferably 3 million. The number average molecular weight is calculated based on the melt viscosity of polytetrafluoroethylene at 380 ° C. as disclosed in JP-A-6-145520. That is, the fibrillated PTFE has a melt viscosity at 380 ° C. measured by the method described in this publication in the range of 10 ⁷ to 10 ¹³ poise, preferably in the range of 10 ⁸ to 10 ¹² poise.

  Such PTFE can be used in solid form or in the form of an aqueous dispersion. In addition, 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. Further, as disclosed in JP-A-6-145520, those having a structure having such a fibrillated PTFE as a core and a low molecular weight polytetrafluoroethylene as a shell are also preferably used.

  Examples of commercially available fibrillated PTFE include Teflon (registered trademark) 6J from Mitsui DuPont Fluorochemical Co., Ltd., Polyflon MPA FA500, F-201L from Daikin Chemical Industries, Ltd., and the like. Commercially available aqueous dispersions of fibrillated PTFE include: Fluon AD-1, AD-936 manufactured by Asahi IC Fluoropolymers, Fluon D-1, D-2 manufactured by Daikin Industries, Ltd., Mitsui A representative example is Teflon (registered trademark) 30J manufactured by DuPont Fluorochemical Co., Ltd.

  As a mixed form of fibrillated PTFE, (1) a method in which an aqueous dispersion of fibrillated 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). (2) A method of mixing an aqueous dispersion of fibrillated PTFE and dried organic polymer particles (Japanese Patent Laid-Open No. 4-272957). Described method), (3) A method in which an aqueous dispersion of fibrillated 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. 06-220210, (Method described in Japanese Patent Application Laid-Open No. 08-188653), (4) A method of polymerizing monomers forming an organic polymer in an aqueous dispersion of fibrillated PTFE (Method described in JP-A-9-95583), and (5) an aqueous dispersion of PTFE and an organic polymer dispersion are uniformly mixed, and then a vinyl monomer is further polymerized in the mixed dispersion. Thereafter, those obtained by a method for obtaining a mixture (a method described in JP-A No. 11-29679) can be used. Commercial products of these mixed forms of fibrillated PTFE include “Metablene A3800” (trade name) manufactured by Mitsubishi Rayon Co., Ltd., “BLENDEX B449” (trade name) manufactured by GE Specialty Chemicals, and “Product of Pacific Interchem Corporation”. “POLY TS AD001” (product name) is exemplified.

The fibrillated PTFE is preferably finely dispersed as much as possible in order not to lower the mechanical strength. As a means of achieving such fine dispersion, the above mixed form of fibrillated PTFE is advantageous. A method of directly supplying an aqueous dispersion in a melt kneader is also advantageous for fine dispersion. However, in the case of the aqueous dispersion form, consideration is required in that the hue is slightly deteriorated. The proportion of fibrillated PTFE in the mixed form is preferably 10 to 80% by weight, more preferably 15 to 75% by weight, in 100% by weight of the mixture. When the ratio of fibrillated PTFE is in such a range, good dispersibility of fibrillated PTFE can be achieved.
Content of F component is 0.1-1 weight part with respect to a total of 100 weight part of A component and B component, Preferably it is 0.2-1 weight part, More preferably, it is 0.2-0. 8 parts by weight. If the content is less than 0.1 parts by weight, the flame retardancy is lowered, and if it exceeds 1 part by weight, the mechanical properties, flame retardancy and heat resistance are lowered.

(G component: UV absorber)
The resin composition of the present invention can contain an ultraviolet absorber as the G component. Since the resin composition of the present invention also has a good hue, such a hue can be maintained for a long time even when used outdoors by blending an ultraviolet absorber.
In the benzophenone series, for example, 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-sulfoxytrihydridolate benzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodiumsulfoxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) ) Methane, 2-hydroxy Examples include -4-n-dodecyloxybenzophenone and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.

  In the 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-3,5 Di-tert-amylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) benzotriazole, 2- ( 2-hydroxy-4-octoxyphenyl) benzotriazole, 2,2'-methylenebis (4-cumyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis (1,3-benzoxazine-4 -One), and 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimidomethyl) -5-methylphenyl] benzotriazole, and 2- (2'-hydroxy-5-methacryloxy) Copolymerization of ethylphenyl) -2H-benzotriazole with vinyl monomer copolymerizable with the monomer And 2- (2′-hydroxy-5-acryloxyethylphenyl) -2H-benzotriazole and a copolymer of vinyl monomer copolymerizable with the monomer, 2-hydroxyphenyl-2H-benzotriazole skeleton A polymer having

  In the hydroxyphenyl triazine 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. Furthermore, the 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 2,4-dimethyl. Examples of the compound are phenyl groups.

In the cyclic imino ester system, for example, 2,2′-p-phenylenebis (3,1-benzoxazin-4-one), 2,2 ′-(4,4′-diphenylene) bis (3,1-benzoxazine) -4-one), 2,2 ′-(2,6-naphthalene) bis (3,1-benzoxazin-4-one), and the like.
In the case of 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.

  Further, the ultraviolet absorber has a structure of a monomer compound capable of radical polymerization, whereby the ultraviolet-absorbing monomer and / or the light-stable monomer having a hindered amine structure, and an alkyl (meth) acrylate. A polymer type ultraviolet absorber obtained by copolymerization with a monomer such as may be used. 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) acrylate. The

Among them, benzotriazole and hydroxyphenyltriazine are preferable from the viewpoint of ultraviolet absorption ability, and cyclic imino ester and cyanoacrylate are preferable from the viewpoint of heat resistance and hue. You may use the said ultraviolet absorber individually or in mixture of 2 or more types.
The content of the ultraviolet absorber is preferably 0.05 to 1 part by weight, more preferably 0.05 to 0.8 part by weight, and still more preferably 0. 05 to 0.7 parts by weight, most preferably 0.1 to 0.7 parts by weight.

(Other additives)
In the resin composition of the present invention, various stabilizers, mold release agents, colorants, fillers, flame retardants and the like for stabilizing the molecular weight reduction and hue at the time of molding can be used.

(I) Stabilizer Various well-known stabilizers can be mix | blended with the resin composition of this invention. Examples of the stabilizer include phosphorus stabilizers, hindered phenol antioxidants, and light stabilizers.

(I-1) Phosphorus stabilizer Examples of the phosphorous stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof, and tertiary phosphine. Among these, phosphorous acid, phosphoric acid, phosphonous acid, and phosphonic acid, triorganophosphate compounds, and acid phosphate compounds are particularly preferable. The organic group in the acid phosphate compound includes any of mono-substituted, di-substituted, and mixtures thereof. Any of the following exemplified compounds corresponding to the compound is similarly included.

  Triorganophosphate compounds include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tridecyl phosphate, tridodecyl phosphate, trilauryl phosphate, tristearyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, diphenyl Examples include cresyl phosphate, diphenyl monoorthoxenyl phosphate, and tributoxyethyl phosphate. Among these, trialkyl phosphate is preferable. The carbon number of the trialkyl phosphate is preferably 1 to 22, more preferably 1 to 4. A particularly preferred trialkyl phosphate is trimethyl phosphate.

  Examples of the acid phosphate compound include methyl acid phosphate, ethyl acid phosphate, butyl acid phosphate, butoxyethyl acid phosphate, octyl acid phosphate, decyl acid phosphate, lauryl acid phosphate, stearyl acid phosphate, oleyl acid phosphate, behenyl acid phosphate, behenyl acid phosphate Nonylphenyl acid phosphate, cyclohexyl acid phosphate, phenoxyethyl acid phosphate, alkoxy polyethylene glycol acid phosphate, bisphenol A acid phosphate, and the like. Among these, long-chain dialkyl acid phosphates having 10 or more carbon atoms are effective for improving thermal stability, and the acid phosphate itself is preferable because of high stability.

  Examples of the phosphite compound include 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-butyl) Phenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, distearyl Taerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis ( 2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, bis {2,4-bis (1-methyl-1-phenylethyl) phenyl} pentaerythritol diphosphite, phenylbisphenol A penta Examples include erythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, and dicyclohexylpentaerythritol diphosphite.

  Further, as other phosphite compounds, those which react with dihydric phenols and have a cyclic structure can be used. For example, 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.

  Examples of the phosphonite compound include tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenylenedi. Phosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3′-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite Tetrakis (2,6-di-tert-butylphenyl) -4,3′-biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3′-biphenylene diphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di tert-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-n-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl)- 4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, and the like, and tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite, bis (Di-tert-butylphenyl) -phenyl-phenylphosphonite is preferred, tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl)- More preferred is phenyl-phenylphosphonite. Such a phosphonite compound is preferable because it can be used in combination with a phosphite compound having an aryl group in which two or more alkyl groups are substituted.

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.

  Suitable phosphorus stabilizers are a triorganophosphate compound, an acid phosphate compound, and a phosphite compound represented by the following general formula (6). It is particularly preferable to add a triorganophosphate compound.

（式（６）中、ＲおよびＲ’は炭素数６〜３０のアルキル基または炭素数６〜３０のアリール基を表し、互いに同一であっても異なっていてもよい。）

(In Formula (6), 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.)

As described above, tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite is preferable as the phosphonite compound, and the stabilizer containing phosphonite as a main component is Sandostab P-EPQ (trademark, manufactured by Clariant). ) And Irgafos P-EPQ (trademark, manufactured by CIBA SPECIALTY CHEMICALS) and both can be used.
Among the above formulas (6), 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.

(I-2) Hindered phenolic antioxidant As the hindered phenolic compound, various compounds that are usually blended in resins can be used. Examples of such hindered phenol compounds include α-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-cyclohexylphenol), 2,2′-dimethylene-bis (6-α-methyl-benzyl-p-cresol), 2,2 ′ -Ethylidene-bis (4,6-di-tert-butylphenol), 2,2'-butylidene-bis (4-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert) -Butylphenol), triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1,6-hexanediol bis [3- (3,5-di- tert-butyl-4-hydroxyphenyl) propionate], bis [2-tert-butyl-4-methyl 6- (3-tert-butyl) Ru-5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1, -Dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, 4,4'-thiobis (6-tert-butyl-m-cresol), 4,4'-thiobis (3- Methyl-6-tert-butylphenol), 2,2′-thiobis (4-methyl-6-tert-butylphenol), bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4 ′ -Di-thiobis (2,6-di-tert-butylphenol), 4,4'-tri-thiobis (2,6-di-tert-butylphenol), 2,2-thiodie Renbis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-tert- Butylanilino) -1,3,5-triazine, N, N′-hexamethylenebis- (3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N, N′-bis [3- (3 , 5-Di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl -2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl-4-hydroxyphenyl) iso Cyanurate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 1,3,5-tris2 [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate, tetrakis [methylene-3- (3,5-di-tert-butyl- 4-hydroxyphenyl) propionate] methane, triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, triethylene glycol-N-bis-3- (3- tert-butyl-4-hydroxy-5-methylphenyl) acetate, 3,9-bis [2 {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) acetyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, tetrakis [Methylene-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] methane, 1,3,5-trimethyl-2,4,6-tris (3-tert-butyl-4-hydroxy Examples include -5-methylbenzyl) benzene and tris (3-tert-butyl-4-hydroxy-5-methylbenzyl) isocyanurate.

  Among the above compounds, tetrakis [methylene-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] methane, octadecyl-3- (3,5-di-tert-butyl-) is used in the present invention. 4-hydroxyphenyl) propionate, and 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4 , 8,10-Tetraoxaspiro [5,5] undecane is preferably used. In particular, 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxa Spiro [5,5] undecane is preferred. The said hindered phenolic antioxidant can be used individually or in combination of 2 or more types.

  It is preferable that either a phosphorus stabilizer or a hindered phenol antioxidant is blended. In particular, a phosphorus stabilizer is preferably blended, and a triorganophosphate compound is more blended. The content of the phosphorus-based stabilizer and the hindered phenol-based antioxidant is preferably 0.005 to 1 part by weight, more preferably 0.01 to 0, with respect to 100 parts by weight in total of the component A and the component B, respectively. .3 parts by weight.

(I-3) Other Heat Stabilizers The resin composition of the present invention may contain other heat stabilizers other than the phosphorus stabilizers and hindered phenol antioxidants. 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 the reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene (such stabilizers). Is described in detail 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. Furthermore, a stabilizer obtained by mixing the compound with various phosphite compounds and hindered phenol compounds is commercially available. For example, Irganox HP-2921 manufactured by the above company is preferably exemplified. In the present invention, such a premixed stabilizer can also be used. The content of the lactone-based 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 total of the A component and the B component.

  Other 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 total of the component A and the component B. .

(Ii) Mold Release Agent The resin composition of the present invention is further made of a fatty acid ester, a polyolefin wax, a silicone compound, a fluorine compound (polyfluoroethylene) for the purpose of improving productivity during molding and improving dimensional accuracy of a molded product. Fluorine oil represented by alkyl ether, etc.), known release agents such as paraffin wax and beeswax can also be blended. Since the resin composition of the present invention has good fluidity, the pressure propagation is good and a molded article with uniform strain can be obtained. On the other hand, in the case of a molded product having a complicated shape that increases the mold release resistance, the molded product may be deformed at the time of mold release. The compounding of the specific component solves such a problem without impairing the properties of the resin composition.

  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. Moreover, carbon number of this alcohol becomes like this. Preferably it is 3-32, More preferably, it is 5-30. On the other hand, the aliphatic carboxylic acid is preferably an aliphatic carboxylic acid having 3 to 32 carbon atoms, more preferably 10 to 30 carbon atoms. Of these, saturated aliphatic carboxylic acids are preferred. The fatty acid ester of the present invention is preferable in that all esters (full esters) are excellent in thermal stability at high temperatures. The acid value in the fatty acid ester of the present invention is preferably 20 or less (can take substantially 0). The hydroxyl value of the fatty acid ester is more preferably in the range of 0.1-30. Further, the iodine value of the fatty acid ester is preferably 10 or less (can take substantially 0). These characteristics can be obtained by a method defined in JIS K 0070.

As the polyolefin wax, an ethylene homopolymer having a molecular weight of 1,000 to 10,000, a homopolymer or copolymer of an α-olefin having 3 to 60 carbon atoms, or ethylene and a carbon atom having 3 to 3 carbon atoms. A copolymer with 60 α-olefins is exemplified. The molecular weight is a number average molecular weight measured in terms of standard polystyrene by GPC (gel permeation chromatography) method. The upper limit of the number average molecular weight is more preferably 6,000, and still more preferably 3,000. The carbon number of the α-olefin component in the polyolefin wax is preferably 60 or less, more preferably 40 or less. More preferred specific examples include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene and the like. A suitable polyolefin wax is an ethylene homopolymer or a copolymer of ethylene and an α-olefin having 3 to 60 carbon atoms. The proportion of the α-olefin having 3 to 60 carbon atoms is preferably 20 mol% or less, more preferably 10 mol% or less. What is marketed as what is called polyethylene wax is used suitably.
The content of the release agent is preferably 0.005 to 5 parts by weight, more preferably 0.01 to 4 parts by weight, and still more preferably 0.005 parts by weight with respect to 100 parts by weight of the total of the component A and the component B. 02 to 3 parts by weight.

(Iii) Dye and Pigment The resin composition of the present invention can further provide a molded product containing various dyes and pigments and exhibiting various design properties. As dyes and pigments used in the present invention, perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as bitumen, perinone dyes, quinoline dyes, quinacridone dyes, Examples thereof include dioxazine dyes, isoindolinone dyes, and phthalocyanine dyes. Furthermore, the resin composition of this invention can mix | blend a metallic pigment, and can also obtain a better metallic color. As the metallic pigment, aluminum powder is suitable. Further, by blending a fluorescent brightening agent or other fluorescent dye that emits light, a better design effect utilizing the luminescent color can be imparted.

Examples of the fluorescent dye (including a fluorescent brightening agent) used in the present invention include a coumarin fluorescent dye, a benzopyran fluorescent dye, a perylene fluorescent dye, an anthraquinone fluorescent dye, a thioindigo fluorescent dye, and a xanthene fluorescent dye. And xanthone fluorescent dyes, thioxanthene fluorescent dyes, thioxanthone fluorescent dyes, thiazine fluorescent dyes, and diaminostilbene fluorescent dyes. Among these, coumarin fluorescent dyes, benzopyran fluorescent dyes, and perylene fluorescent dyes are preferable because they have good heat resistance and little deterioration during resin molding.
The content of the dye / pigment is preferably 0.00001 to 1 part by weight, and more preferably 0.00005 to 0.5 part by weight, based on 100 parts by weight of the total of the A component and the B component.

(Iv) Compound having heat absorption ability The resin composition of the present invention may contain a compound having heat absorption ability. Such compounds include phthalocyanine-based near-infrared absorbers, metal oxide-based near-infrared absorbers such as ATO, ITO, iridium oxide, ruthenium oxide and imonium oxide, and metal borides such as lanthanum boride, cerium boride and tungsten boride. Preferable examples include various metal compounds having excellent near-infrared absorptivity such as a system and tungsten oxide near-infrared absorber, and carbon filler. As such a phthalocyanine-based near infrared absorber, for example, MIR-362 manufactured by Mitsui Chemicals, Inc. is commercially available and easily available. Examples of the carbon filler include carbon black, graphite (including both natural and artificial) and fullerene, and carbon black and graphite are preferable. These can be used alone or in combination of two or more. The content of the phthalocyanine-based near infrared absorber is preferably 0.0005 to 0.2 parts by weight, more preferably 0.0008 to 0.1 parts by weight, with respect to 100 parts by weight of the total of the A component and the B component. 0.001-0.07 weight part is further more preferable. The content of the metal oxide near-infrared absorber, the metal boride-based near infrared absorber, and the carbon filler is preferably in the range of 0.1 to 200 ppm (weight ratio) in the resin composition of the present invention. A range of ˜100 ppm is more preferable.

(V) Light diffusing agent The resin composition of the present invention can be provided with a light diffusing effect by blending a light diffusing agent. Examples of such light diffusing agents include polymer fine particles, inorganic fine particles having a low refractive index such as calcium carbonate, and composites thereof. Such polymer fine particles are fine particles already known as light diffusing agents for thermoplastic resins. More preferably, acrylic crosslinked particles having a particle size of several μm, silicone crosslinked particles represented by polyorganosilsesquioxane, and the like are exemplified. Examples of the shape of the light diffusing agent include a spherical shape, a disk shape, a column shape, and an indefinite shape. Such spheres need not be perfect spheres, but include deformed ones, and such columnar shapes include cubes. A preferred light diffusing agent is spherical, and the more uniform the particle size is. The content of the light diffusing agent is preferably 0.005 to 20 parts by weight, more preferably 0.01 to 10 parts by weight, and still more preferably 0.01 to 100 parts by weight with respect to a total of 100 parts by weight of the component A and the component B. 3 parts by weight. Two or more light diffusing agents can be used in combination.

(Vi) White pigment for high light reflection The resin composition of the present invention can be provided with a light reflection effect by blending a white pigment for high light reflection. As such a white pigment, a titanium dioxide (particularly titanium dioxide treated with an organic surface treating agent such as silicone) pigment is particularly preferred. The content of the white pigment for high light reflection is preferably 3 to 30 parts by weight, more preferably 8 to 25 parts by weight, based on 100 parts by weight of the total of the A component and the B component. Two or more kinds of white pigments for high light reflection can be used in combination.

(Vii) Antistatic agent The resin composition of the present invention may require antistatic performance, and in such a case, it is preferable to include an antistatic agent. Examples of the antistatic agent include (1) aryl sulfonic acid phosphonium salts represented by dodecylbenzenesulfonic acid phosphonium salts, organic sulfonic acid phosphonium salts such as alkyl sulfonic acid phosphonium salts, and tetrafluoroboric acid phosphonium salts. Examples thereof include phosphonium borate salts. The content of the phosphonium salt is suitably 5 parts by weight or less, preferably 0.05 to 5 parts by weight, more preferably 1 to 3.5 parts by weight, based on 100 parts by weight of the total of component A and component B. More preferably, it is in the range of 1.5 to 3 parts by weight.

  Examples of the antistatic agent include: (2) lithium organic sulfonate, organic sodium sulfonate, organic potassium sulfonate, cesium organic sulfonate, rubidium organic sulfonate, calcium organic sulfonate, magnesium organic sulfonate, and barium organic sulfonate. And organic sulfonate alkali (earth) metal salts. Such metal salts are also used as flame retardants as described above. More specific examples of such metal salts include metal salts of dodecylbenzene sulfonic acid and metal salts of perfluoroalkane sulfonic acid. The content of the organic sulfonic acid alkali (earth) metal salt is suitably 0.5 parts by weight or less, preferably 0.001 to 0.3 parts by weight, based on 100 parts by weight of the total of component A and component B. More preferably, it is 0.005-0.2 weight part. In particular, alkali metal salts such as potassium, cesium, and rubidium are preferable.

  Examples of the antistatic agent include (3) organic sulfonic acid ammonium salts such as alkyl sulfonic acid ammonium salt and aryl sulfonic acid ammonium salt. The ammonium salt is suitably 0.05 parts by weight or less based on 100 parts by weight of the total of the A component, B component and C component. Examples of the antistatic agent include (4) a polymer containing a poly (oxyalkylene) glycol component such as polyether ester amide as a constituent component. The polymer is suitably 5 parts by weight or less based on a total of 100 parts by weight of the A component and the B component.

(Viii) Filler The resin composition of the present invention can contain various known fillers as reinforcing fillers. As such a filler, various fibrous fillers, plate-like fillers, and granular fillers can be used. Here, the fibrous filler has a fibrous shape (including a rod shape, a needle shape, a flat shape, or a shape whose axes extend in a plurality of directions), and the plate-shaped filler has a plate shape. It is a filler which has a shape (including those having irregularities on the surface and those having a curved surface). The granular filler is a filler having a shape other than these including an indefinite shape.
The fiber-like and plate-like shapes are often clear from the observation of the shape of the filler. For example, a difference from a so-called indeterminate shape can be said to be a fiber-like or plate-like one having an aspect ratio of 3 or more.

  As plate-like fillers, glass-flake, talc, mica, kaolin, metal flakes, carbon flakes, and graphite, and these fillers are coated with different materials such as metals and metal oxides. A material etc. are illustrated preferably. The particle size is preferably in the range of 0.1 to 300 μm. The particle size is about 10 μm in terms of the median diameter (D50) of the particle size distribution measured by the X-ray transmission method, which is one of the liquid phase precipitation methods. In the region of 10-50 μm, laser diffraction is performed. -The value by the median diameter (D50) of the particle size distribution measured by the scattering method is referred to, and in the region of 50 to 300 μm, the value is by the vibration sieving method. Such a particle size is a particle size in the resin composition. The plate-like filler may be surface-treated with various coupling agents such as silane, titanate, aluminate, and zirconate, and olefin resin, styrene resin, acrylic resin, polyester resin. Further, it may be a granulated product that has been subjected to a bundling treatment or compression treatment with various resins such as epoxy resins and urethane resins, higher fatty acid esters, and the like.

The fiber diameter of the fibrous filler is preferably in the range of 0.1 to 20 μm. The upper limit of the fiber diameter is preferably 13 μm, more preferably 10 μm. On the other hand, the lower limit of the fiber diameter is preferably 1 μm.
The fiber diameter here refers to the number average fiber diameter. The number average fiber diameter is obtained by scanning the residue collected after dissolving the molded product in a solvent, or decomposing the resin with a basic compound, and the ash residue collected after ashing with a crucible. It is a value calculated from an image observed with an electron microscope.

  Examples of the fibrous filler include glass fiber, flat cross-section glass fiber, glass milled fiber, glass flake, carbon fiber, flat cross-section carbon fiber, carbon milled fiber, metal fiber, basalt fiber, asbestos, rock wool, and ceramic fiber. , Slag fiber, potassium titanate whisker, boron whisker, aluminum borate whisker, calcium carbonate whisker, titanium oxide whisker, wollastonite, zonotolite, palygorskite (attapulgite), sepiolite and other fibrous inorganic fillers, aramid fiber, polyimide Fibrous heat-resistant organic fillers typified by heat-resistant organic fibers such as fibers and polybenzthiazole fibers, vegetable fibers such as hemp hemp and bamboo, and Such as a fibrous filler with different materials and surface coatings, such as with respect to those of fillers such as metal or metal oxide are exemplified. Examples of the filler whose surface is coated with a different material include metal-coated glass fibers, metal-coated glass flakes, titanium oxide-coated glass flakes, and metal-coated carbon fibers. The surface coating method of different materials is not particularly limited. For example, various known plating methods (for example, electrolytic plating, electroless plating, hot-dip plating, etc.), vacuum deposition methods, ion plating methods, CVD methods ( For example, thermal CVD, MOCVD, plasma CVD, etc.), PVD method, sputtering method, etc. can be mentioned.

Here, the fibrous filler means a fibrous filler having an aspect ratio of 3 or more, preferably 5 or more, more preferably 10 or more. The upper limit of the aspect ratio is about 10,000, preferably 200. The aspect ratio of such a filler is a value in the resin composition. The flat cross-section glass fiber has an average value of the major axis of the fiber cross section of 10 to 50 μm, preferably 15 to 40 μm, more preferably 20 to 35 μm, and an average value of the ratio of major axis to minor axis (major axis / minor axis) of 1. .5-8, preferably 2-6, more preferably 2.5-5 glass fiber. The fibrous filler may be surface-treated with various coupling agents in the same manner as the plate-like filler, may be converged with various resins, and may be granulated by compression.
The content of the filler is preferably 200 parts by weight or less, more preferably 100 parts by weight or less, still more preferably 50 parts by weight or less, and particularly preferably 30 parts by weight with respect to 100 parts by weight of the total of the component A and the component B. Or less.

(Ix) Other Additives The resin composition of the present invention may contain other flow modifiers, antibacterial agents, dispersants such as liquid paraffin, photocatalytic antifouling agents, and photochromic agents.

(Manufacture of resin composition)
Arbitrary methods are employ | adopted for preparation of the resin composition of this invention. For example, there can be mentioned a method in which the A component, B component, C component, D component, E component, F component and optionally other components are premixed and then melt-kneaded and pelletized. Examples of the premixing means include a Nauter mixer, a V-type blender, a Henschel mixer, a mechanochemical apparatus, and an extrusion mixer. In the premixing, granulation can be performed by an extrusion granulator or a briquetting machine as necessary. As another method, for example, when a component having a powder form is included as the component B, a master batch of an additive diluted with powder by blending a part of the powder and an additive to be blended is manufactured. A method using a batch is mentioned. After the preliminary mixing, the mixture is melt-kneaded by a melt-kneader represented by a vent type twin-screw extruder and pelletized by a device such as a pelletizer. Other examples of the melt kneader include a Banbury mixer, a kneading roll, and a constant temperature stirring vessel, but a vent type twin screw extruder is preferred.

  In addition, a method of supplying each component independently to a melt kneader represented by a twin screw extruder without premixing each component can also be employed. Moreover, after premixing some components, the method of supplying to a melt-kneader independently of the remaining components is mentioned. In particular, when an inorganic filler is blended, the inorganic filler is preferably supplied from a supply port in the middle of the extruder into the molten resin using a supply device such as a side feeder. The premixing means and granulation are the same as described above. In addition, when there exists a liquid thing in the component to mix | blend, what is called a liquid injection apparatus or a liquid addition apparatus can be used for supply to a melt kneader.

As the extruder, one having a vent capable of degassing moisture in the raw material and volatile gas generated from the melt-kneaded resin can be preferably used. From the vent, a vacuum pump is preferably installed for efficiently discharging generated moisture and volatile gas to the outside of the extruder. It is also possible to remove a foreign substance from the resin composition by installing a screen for removing the foreign substance mixed in the extrusion raw material in the zone in front of the extruder die. Examples of such a screen include a wire mesh, a screen changer, a sintered metal plate (such as a disk filter), and the like.
Examples of the melt kneader include a banbury mixer, a kneading roll, a single screw extruder, a multi-screw extruder having three or more axes, in addition to a twin screw extruder.

  Furthermore, it is preferable that the moisture contained in the A component and the B component is small before melt kneading. Therefore, it is more preferable to melt-knead after drying either A component or B component, or both by methods, such as various hot air drying, electromagnetic wave drying, and vacuum drying. The vent suction during melt-kneading is preferably in the range of 1 to 60 kPa, preferably 2 to 30 kPa. The prepared resin composition preferably contains 0.001 to 50 ppm, more preferably 0.001 to 45 ppm of titanium element derived from the catalyst. When the amount of Ti remaining is more than 50 ppm, the appearance is deteriorated and the heat and humidity resistance is lowered due to a decrease in thermal stability and hue.

  The resin extruded as described above is directly cut into pellets, or after forming strands, the strands are cut with a pelletizer to be pelletized. When it is necessary to reduce the influence of external dust during pelletization, it is preferable to clean the atmosphere around the extruder. Furthermore, in the manufacture of such pellets, various methods already proposed for polycarbonate resin for optical discs are used to narrow the shape distribution of pellets, reduce miscuts, and reduce fine powder generated during transportation or transportation. In addition, it is possible to appropriately reduce bubbles (vacuum bubbles) generated inside the strands and pellets. By these prescriptions, it is possible to increase the molding cycle and reduce the occurrence rate of defects such as silver. Moreover, although the shape of a pellet can take common shapes, such as a cylinder, a prism, and a spherical shape, it is a cylinder more suitably. The diameter of such a cylinder is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, and still more preferably 2 to 3.3 mm. On the other hand, the length of the cylinder is preferably 1 to 30 mm, more preferably 2 to 5 mm, and still more preferably 2.5 to 3.5 mm.

The resin composition of the present invention preferably has a characteristic retention of 50% or more, more preferably 55% or more, more preferably 60% or more at 150 ° C. as evaluated by a method defined in ISO8256. Is more preferable.
The resin composition of the present invention is preferably evaluated by a method defined by UL94V and preferably has an ability equivalent to V-0 at 1.5 mmt.

  The resin composition of the present invention can be produced in various products by usually injection-molding the pellets produced as described above to obtain molded products. In such injection molding, not only ordinary molding methods but also injection compression molding, injection press molding, gas assist injection molding, foam molding (including a method of injecting a supercritical fluid), insert molding, in-mold coating molding, heat insulation Examples thereof include mold molding, rapid heating / cooling mold molding, two-color molding, multicolor molding, sandwich molding, and ultrahigh-speed injection molding. In addition, either a cold runner method or a hot runner method can be selected for molding.

  Moreover, the resin composition of this invention can also be used in the form of various profile extrusion molded products, a sheet | seat, a film, etc. by extrusion molding. For forming sheets and films, an inflation method, a calendar method, a casting method, or the like can also be used. It is also possible to form a heat-shrinkable tube by applying a specific stretching operation. The resin composition of the present invention can be formed into a molded product by rotational molding, blow molding or the like.

  Thereby, a thermoplastic resin composition and a molded product excellent in chemical resistance, flame retardancy, impact resistance, heat resistance and excellent in appearance are provided. That is, according to the present invention, the viscosity average molecular weight of 27,500-32,000 aromatic polycarbonate resin (component A) 40-70 parts by weight and (B) polyethylene terephthalate resin (component B) 30-60 parts by weight (C) 0.5-10 parts by weight of (C) polyorganosiloxane-containing graft copolymer (C component), (D) 1-10 parts by weight of brominated flame retardant (D component), with respect to 100 parts by weight in total. (E) Polycarbonate resin composition containing 0.5 to 3 parts by weight of antimony flame retardant aid (E component) and (F) 0.1 to 1.0 part by weight of fluorine-containing anti-dripping agent (F component) A molded product obtained by melt molding is provided.

  Molded articles in which the resin composition of the present invention is used include various electronic / electric equipment parts, camera parts, OA equipment parts, precision machine parts, machine parts, vehicle parts (particularly interior and exterior parts for vehicles), other agricultural materials, It is useful for various applications such as transport containers, playground equipment, and miscellaneous goods, and the industrial effects that it plays are exceptional.

  Furthermore, various surface treatments can be performed on the molded article made of the resin composition of the present invention. Surface treatment here refers to a new layer on the surface of resin molded products such as vapor deposition (physical vapor deposition, chemical vapor deposition, etc.), plating (electroplating, electroless plating, hot dipping, etc.), painting, coating, printing, etc. A method used for ordinary thermoplastic resins is applicable. Specific examples of the surface treatment include various surface treatments such as hard coat, water / oil repellent coat, ultraviolet absorption coat, infrared absorption coat, and metalizing (evaporation). Hard coat is a particularly preferred and required surface treatment. In addition, since the resin composition of the present invention has improved metal adhesion, application of vapor deposition and plating is also preferable. The molded product thus provided with the metal layer can be used for electromagnetic wave shielding parts, conductive parts, antenna parts, and the like. Such parts are particularly preferably sheet-like and film-like.

  Specific examples of the molded article in which the resin composition of the present invention is used are suitable for application to living materials, building materials, interior goods, OA equipment, home appliances, internal parts, housings, and the like. These products include, for example, personal computers, notebook computers, CRT displays, printers, mobile terminals, mobile phones, copiers, fax machines, recording media (CD, CD-ROM, DVD, PD, FDD, etc.) drives, parabolic antennas, electric motors. Tools, VTRs, TVs, irons, hair dryers, rice cookers, microwave ovens, audio equipment, audio equipment such as audio / laser discs (registered trademark) / compact discs, lighting equipment, refrigerators, air conditioners, typewriters, word processors, suitcases And household materials such as cleaning tools, etc., and resin products formed from the thermoplastic resin composition of the present invention can be used for various parts such as these casings. Examples of other resin products include vehicle parts such as deflector parts, car navigation parts, car stereo parts, charging infrastructure parts, and automobile interior and exterior parts.

  The polycarbonate resin composition of the present invention is excellent in chemical resistance, flame retardancy, impact resistance, heat resistance and appearance, so that it is not limited to the outdoors / indoors, but is used for automobiles, infrastructure facilities, housing facilities, and building materials. It is widely useful in various fields such as applications, household materials applications, OA / EE applications, outdoor equipment applications, and others. Therefore, the industrial effect exhibited by the present invention is extremely great.

  The form of the invention that the present inventor considers to be the best is an aggregation of the preferable ranges of the above requirements. For example, typical examples are described in the following examples. Of course, the present invention is not limited to these forms.

  The following examples further illustrate the present invention. Unless otherwise specified, parts in the examples are parts by weight, and% is% by weight. Evaluation was carried out by the following method.

(Evaluation of thermoplastic resin composition)
(I) Charpy impact strength Various pellets obtained from the compositions of the examples were dried in a hot air circulation dryer at 120 ° C. for 6 hours, and then the cylinder temperature was 270 ° C. and the mold temperature was 70 using an injection molding machine. A test piece for evaluation (ISO bending test piece (based on ISO 179) was molded at ° C. Using the obtained ISO bending test piece, Charpy impact strength with a notch was measured according to ISO 179.

(Ii) Notch bending strength Using the ISO bending test piece obtained by the method described in (i) above, the notch described in ISO 179 was provided. The evaluation was carried out by a method based on ISO178 from the opposite side of the notch, and the bending strength was measured.

(Iii) Chemical resistance Various pellets obtained from each composition of the examples were dried at 120 ° C. for 5 hours, and then the cylinder temperature was 270 ° C. and the mold was made by an injection molding machine (SG-150U manufactured by Sumitomo Heavy Industries, Ltd.). A flat plate molded product having a length of 150 mm, a width of 150 mm, and a thickness of 2 mmt was formed at a temperature of 70 ° C. After applying strain to this flat molded product and applying commercially available regular gasoline for 10 minutes in an environment of a temperature of 23 ° C. and a relative humidity of 50%, the appearance is visually observed and evaluated. Asked.

(Iv) Flame retardancy The pellets obtained from the respective compositions of the examples were dried at 120 ° C. for 6 hours in a hot air circulating dryer, and the cylinder temperature was 270 using an injection molding machine [Toshiba Machine Co., Ltd. IS150EN-5Y]. A test piece for flame retardancy evaluation was molded at a temperature of 70 ° C and a mold temperature of 70 ° C. The vertical combustion test of UL standard 94 was conducted at a thickness of 1.5 mm, and the grade was evaluated. When the determination fails to satisfy any of the criteria of V-0, V-1, and V-2, “notV” is indicated.

(V) Heat resistance Various pellets obtained from each composition of the examples were dried at 120 ° C. for 5 hours and then cylinder temperature 270 ° C. and mold temperature by an injection molding machine (SG-150U manufactured by Sumitomo Heavy Industries, Ltd.). Molded pieces were molded at 70 ° C, and untreated molded products (a) and molded products (b) treated at 150 ° C for 500 hours were measured for tensile impact strength according to ISO8256. The rate was determined.
Tensile impact strength retention rate (%) = [tensile impact strength of (b) / tensile impact strength of (a)] × 100

(Vi) Appearance The appearance of an ISO tensile test piece obtained by the following method was visually evaluated. The evaluation was performed according to the following criteria.
○: Appearance defects are not observed ×: Appearance defects such as flow marks and silver from the gate side are strongly generated

[Examples 1 to 10, Comparative Examples 1 to 13]
The mixture which consists of all components 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 is performed using a vent type twin screw extruder (Nippon Steel Works TEX30α-38.5BW-3V) with a diameter of 30 mmφ and melt kneading at a screw rotation speed of 230 rpm, a discharge rate of 25 kg / h, and a vacuum degree of the vent of 3 kPa. Pellets were obtained. In addition, about extrusion temperature, it implemented at 270 degreeC from the 1st supply port to the die part. The above-mentioned test piece was molded using the obtained pellets.
The results are shown in Tables 1 and 2. In addition, each component of the symbol description in Table 1 and Table 2 is as follows.

(A component)
A-1: Aromatic polycarbonate resin (polycarbonate resin powder having a viscosity average molecular weight of 28,000 made from bisphenol A and phosgene by a conventional method, manufactured by Teijin Limited)
A-2: Aromatic polycarbonate resin (polycarbonate resin powder having a viscosity average molecular weight of 31,000 made by a conventional method from bisphenol A and phosgene, manufactured by Teijin Limited)
A-3: Aromatic polycarbonate resin (polycarbonate resin powder having a viscosity average molecular weight of 22,400 made by a conventional method from bisphenol A and phosgene, Panlite L-1225WPWQ (product name) manufactured by Teijin Ltd.)
A-4: Aromatic polycarbonate resin (polycarbonate resin powder having a viscosity average molecular weight of 35,000 made from bisphenol A and phosgene by a conventional method, manufactured by Teijin Limited)
(B component)
B-1: Polyethylene terephthalate resin polymerized using a titanium-based catalyst obtained by reacting titanium tetrabutoxide and monolauryl phosphate (intrinsic viscosity = 0.77, remaining amount of titanium 25 ppm)
B-2: Polyethylene terephthalate resin polymerized using a titanium-based catalyst obtained by reacting titanium tetrabutoxide and monolauryl phosphate (intrinsic viscosity = 0.53, remaining amount of titanium 25 ppm)
B-3: Polybutylene terephthalate resin (Intrinsic viscosity = 0.875 DURANEX 500FP (product name) manufactured by Wintech Polymer Co., Ltd.)

(C component)
C-1: Polymethyl methacrylate is graft-polymerized to 70% by weight of a composite rubber having a structure in which a polyorganosilicon rubber component and a polyalkyl (meth) acrylate rubber component are intertwined so that they cannot be separated. Organosiloxane-containing graft copolymer (Metbrene S-2001 (trade name) manufactured by Mitsubishi Rayon Co., Ltd.)
C-2: Polyorganosiloxane-containing graft copolymer having a polyorganosiloxane rubber component of 60 to 70% by weight (manufactured by Kaneka Corporation: KANEACE MR-01)
(D component)
D-1: Brominated flame retardant composed of carbonate oligomer of tetrabromobisphenol A (Fireguard FG7000 manufactured by Teijin Limited)
D-2: Phosphate ester mainly composed of bisphenol A bis (diphenyl phosphate) (manufactured by Daihachi Chemical Industry Co., Ltd .: CR-741 (trade name))
(E component)
E-1: Antimony trioxide (Nippon Seiko Co., Ltd. PATOX-K (trade name))
(F component)
F-1: Polytetrafluoroethylene having fibril forming ability (manufactured by Daikin Industries, Ltd .: Polyflon MPAFA500 (trade name))
(G component)
G-1: Benzotriazole-based ultraviolet absorber (Ciba Specialty Chemicals: Tinuvin 234)
(Other ingredients)
P-1: Trimethyl phosphate P-2: Bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite

  From the above Tables 1 and 2, it can be seen that a polycarbonate resin composition satisfying the chemical resistance, flame retardancy, impact resistance, heat resistance and appearance in a high dimension can be obtained by the blending of the present invention.

Claims (10)

  (A) A resin component consisting of 40 to 70 parts by weight of an aromatic polycarbonate resin (component A) having a viscosity average molecular weight of 27,500 to 32,000 and (B) 30 to 60 parts by weight of a polyethylene terephthalate resin (component B) (C) 0.5-10 parts by weight of the polyorganosiloxane-containing graft copolymer (C component), (D) 1-10 parts by weight of brominated flame retardant (D component), (E) A polycarbonate resin composition containing 0.5 to 3 parts by weight of an antimony flame retardant aid (E component) and 0.1 to 1 part by weight of (F) a fluorine-containing anti-dripping agent (F component). B component reacts the titanium compound (1) represented by the following general formula (I) and the titanium compound (1) with the aromatic polycarboxylic acid represented by the following general formula (II) or an anhydride thereof. At least one titanium compound component selected from the group consisting of the titanium compound (2) obtained in the above, and a phosphorus compound component consisting of at least one phosphorus compound (3) represented by the following general formula (III): 2. The polycarbonate resin composition according to claim 1, which is a polyethylene terephthalate resin polymerized by using a compound containing the reaction product as a catalyst.

[In the formula (I), R ¹ , R ² , R ³ and R ⁴ each independently represent an alkyl group having 2 to 10 carbon atoms, k represents an integer of 1 to 3, And when k is 2 or 3, two or three R ² and R ³ may be the same or different from each other.

[In the formula (II), m represents an integer of 2 to 4]

[In the formula (III), R ⁵ represents an unsubstituted or substituted aryl group having 6 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms.]   The polycarbonate resin composition according to claim 1 or 2, which contains 0.001 to 50 ppm of titanium element derived from the catalyst. The polycarbonate resin composition in any one of Claims 1-3 whose catalyst containing a titanium element is a compound represented by following formula (IV).

[In the above formula, R ⁶ and R ⁷ each independently represent an alkyl group having 2 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms]   Graft polymerization of one or more alkyl (meth) acrylate monomers having 1 to 3 carbon atoms and optionally an aromatic vinyl monomer on a rubber core containing a polyorganosiloxane as component C The polycarbonate resin composition according to any one of claims 1 to 4, which is a core-shell elastic polymer.   Bromine selected from the group consisting of a brominated bisphenol A type polycarbonate flame retardant having a bromine content of 20% by weight or more, a brominated bisphenol A type epoxy resin and a modified product in which part or all of the terminal glycidyl groups are blocked. The polycarbonate resin composition according to claim 1, which is a flame retardant.   The polycarbonate resin composition according to any one of claims 1 to 6, comprising 0.05 to 1 part by weight of (G) ultraviolet absorber (G component) with respect to 100 parts by weight of the resin component.   An injection-molded article formed from the polycarbonate resin composition according to any one of claims 1 to 7.   The injection-molded product according to claim 8, wherein the injection-molded product is a vehicle interior / exterior member.   The injection-molded product according to claim 8, wherein the injection-molded product is an interior / exterior member for OA / electrical electronics.