JP5204795B2 - Polycarbonate resin composition - Google Patents

Description

  The present invention relates to a polycarbonate resin composition having improved thermal stability and heat-and-moisture resistance. More specifically, the present invention relates to a polycarbonate resin composition containing a polyester resin produced using a catalyst composed of a characteristic element, excellent in mechanical strength and fluidity, and having both good thermal stability and wet heat resistance.

  Resin compositions composed of aromatic polycarbonate resins and aromatic polyester resins are widely used in various industrial fields because of their high level of appearance and excellent mechanical properties, dimensional stability, and chemical resistance. Yes. In particular, a resin composition comprising an aromatic polycarbonate resin and a polyethylene terephthalate resin (hereinafter sometimes referred to as PC / PET alloy) has been studied and disclosed as various resin compositions (see Patent Documents 1, 2, and 3). ). PC / PET alloys have the characteristics of adding the chemical resistance of polyethylene terephthalate resin to the excellent impact resistance, mechanical properties, dimensional stability, etc. of aromatic polycarbonate resins. It is effectively used in the field and the field of OA equipment.

  In recent years, in the automobile field and the OA field, parts are being made thinner and lighter, and so on. For example, in the field of automobiles, technology development that uses large parts typified by body panels such as fenders as resin materials has become active again for weight reduction. The demand for heat resistance and heat and humidity resistance is increasing. In addition, a reduction in the number of parts is also required for cost reduction, and there is a need for integration of parts and molding processability that can cope with more complicated and large shapes, that is, better thermal stability. It has become like this.

Under such circumstances, an alloy material using PET produced with a specific polymerization catalyst has been proposed as a means for PC / PET alloy to satisfy the above requirements (see Patent Documents 4 and 5). In Patent Document 4, the decrease in color tone, melt stability, appearance, and moldability observed in PET produced with a general antimony compound or titanium compound as a polymerization catalyst is improved by using a germanium catalyst. However, it is not satisfactory with respect to the wet heat and thermal stability required for current automotive applications, and further improvements are required. In Patent Document 5, a resin composition comprising a polyester resin and a polycarbonate resin produced using 1-30 ppm of a titanium-containing catalyst compound has improved color tone, thermal stability, and melt stability. Although the thermal stability and melt stability are improved by reducing the amount of the catalyst, the thermal stability tends to decrease as the amount of the polyester resin increases, and further improvement is required. In addition, no knowledge about wet heat properties, which are increasing the demand for PC / polyester materials, is taught.
As described above, a PC / PET alloy is desired to have a material having high moist heat resistance while maintaining good thermal stability and excellent chemical resistance, impact strength, heat resistance and rigidity.

Japanese Patent Publication No. 36-14035 Japanese Examined Patent Publication No. 39-20434 JP 59-176345 A Japanese Patent Laid-Open No. 51-102043 JP-T-2005-521772

  In view of the above, an object of the present invention is to provide a resin composition comprising an aromatic polycarbonate resin and a polyester resin, which is excellent in mechanical strength, fluidity and thermal stability, and also has good wet heat resistance. There is. As a result of intensive investigations to achieve the above object, the present inventor has found that such an object can be achieved by using a polyester resin produced by a titanium-based polymerization catalyst having a specific structure, and further intensive investigations are advanced. The present invention has been completed.

According to the present invention, the above problem is a resin composition comprising (A) 50 to 99 parts by weight of an aromatic polycarbonate resin (component A) and (B) 1 to 50 parts by weight of a polyester resin (component B), 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. and at least one titanium compound component selected from the group consisting of titanium compound (2) was collected using a phosphorus compound component comprising at least one phosphorus compound (3) represented by the following formula (III) And a reaction molar ratio (mTi / mP) of the titanium compound component molar amount (mTi) of the titanium compound component and the phosphorus atom component molar amount (mP) of the phosphorus compound component is within a range of 1/3 to 1/1. reaction product that had been A compound containing a polyester resin which is polymerized using as a catalyst, the polyester resin is achieved by the following (i) and the resin composition characterized by satisfying the requirements of (ii).
(I) the intrinsic viscosity is 0.40 to 1.2,
(Ii) The amount of the titanium-based catalyst used is 2 to 40 mm% with respect to the total millimolar amount of the aromatic dicarboxylic acid component contained in the polymerization starting material in terms of millimolar amount in terms of titanium atom.

〔但し、式（Ｉ）中、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は、それぞれ互いに独立に２〜１０個の炭素原子を有するアルキル基を表し、ｋは１〜３の整数を表し、かつｋが２又は３の場合、２個又は３個のＲ^２及びＲ^３は、それぞれ互いに同一であってもよく、或いは異なっていてもよい。〕

[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. ]

〔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. ]

Hereinafter, the details of the present invention will be described.
(Component A: aromatic polycarbonate resin)
The aromatic polycarbonate resin used as the component A of 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 polycarbonate resin composition is a copolymerized polycarbonate of the following (1) to (3). It is.
(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 0.1% in 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 01 to 1 mol%, preferably 0.05 to 0.9 mol%, particularly preferably 0.05 to 0.8 mol%.

In particular, in the case of the melt transesterification method, a branched structural unit may be generated as a side reaction. However, the amount of the branched structural unit is also 0.1% in a total of 100 mol% with a structural unit derived from a dihydric phenol. Those having a ratio of 001 to 1 mol%, preferably 0.005 to 0.9 mol%, particularly preferably 0.01 to 0.8 mol% are preferred. The ratio of the branched structure can be calculated by ¹ H-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.
Further, a polycarbonate-polyorganosiloxane copolymer obtained by copolymerizing polyorganosiloxane units can also be used.

The reaction forms such as interfacial polymerization, melt transesterification, solid phase transesterification of carbonate prepolymer, and ring-opening polymerization of cyclic carbonate compounds, which are methods for producing the polycarbonate resin of the present invention, are various documents and patent publications. This is a well-known method.
Although it does not specifically limit, Preferably it is 10,000-50,000, More preferably, it is 14,000-30,000, More preferably, it is 14,000-26,000.

  With an aromatic polycarbonate resin having a viscosity average molecular weight of less than 10,000, 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 50,000 is inferior in versatility in that it is inferior in fluidity during injection molding.

  The aromatic polycarbonate resin may be obtained by mixing those having a viscosity average molecular weight outside the above range. In particular, an aromatic polycarbonate resin having a viscosity average molecular weight exceeding the range (50,000) improves the entropy elasticity of the resin. As a result, good moldability is exhibited in gas assist molding and foam molding which may be used when molding a reinforced resin material into a structural member. Such improvement in moldability is even better than that of the branched polycarbonate. As a more preferred embodiment, the A component is an aromatic polycarbonate resin having a viscosity average molecular weight of 70,000 to 300,000 (component A-1-1), and an aromatic polycarbonate resin having a viscosity average molecular weight of 10,000 to 30,000. An aromatic polycarbonate resin (A-1 component) (hereinafter referred to as “high molecular weight component-containing aromatic polycarbonate resin”) having a viscosity average molecular weight of 16,000 to 35,000. May also be used.

  In such a high molecular weight component-containing aromatic polycarbonate resin (A-1 component), the molecular weight of the A-1-1 component is preferably 70,000 to 200,000, more preferably 80,000 to 200,000, still more preferably. 100,000 to 200,000, particularly preferably 100,000 to 160,000. The molecular weight of the A-1-2 component is preferably 10,000 to 25,000, more preferably 11,000 to 24,000, still more preferably 12,000 to 24,000, and particularly preferably 12,000 to 23. , 000.

  The high molecular weight component-containing aromatic polycarbonate resin (component A-1) is obtained by mixing the components A-1-1 and A-1-2 at various ratios and adjusting them so as to satisfy a predetermined molecular weight range. Can do. Preferably, in 100% by weight of the A-1 component, the A-1-1 component is 2 to 40% by weight, more preferably the A-1-1 component is 3 to 30% by weight, and still more preferably The A-1-1 component is 4 to 20% by weight, and particularly preferably the A-1-1 component is 5 to 20% by weight.

  As the preparation method of the component A-1, (1) a method in which the components A-1-1 and A-1-2 are independently polymerized and mixed, and (2) JP-A-5-306336. The method of producing an aromatic polycarbonate resin showing a plurality of polymer peaks in a molecular weight distribution chart by GPC method, represented by the method shown in Japanese Patent Publication No. Gazette, in the same system, the aromatic polycarbonate resin of the present invention A- A method of producing so as to satisfy the conditions of one component, and (3) an aromatic polycarbonate resin obtained by the production method (production method of (2)), a separately produced A-1-1 component and / or Examples thereof include a method of mixing the A-1-2 component.

The viscosity average molecular weight referred to in the present invention is first determined by using an Ostwald viscometer from a solution obtained by dissolving 0.7 g of aromatic polycarbonate 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 calculation of the viscosity average molecular weight of the aromatic polycarbonate resin in the glass fiber reinforced resin composition of the present invention is performed 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.

(B component: polyester resin).
The polyester resin used as the component B of the present invention is a polymer or copolymer obtained by a condensation reaction mainly comprising an aromatic dicarboxylic acid or a reactive derivative thereof and a diol or an ester derivative thereof.

  As the aromatic dicarboxylic acid here, terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 4,4′-biphenyl ether Dicarboxylic acid, 4,4′-biphenylmethane dicarboxylic acid, 4,4′-biphenylsulfone dicarboxylic acid, 4,4′-biphenylisopropylidenedicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4′-dicarboxylic acid Acid, 2,5-anthracene dicarboxylic acid, 2,6-anthracene dicarboxylic acid, 4,4'-p-terphenylene dicarboxylic acid, aromatic dicarboxylic acid such as 2,5-pyridinedicarboxylic acid, diphenylmethane dicarboxylic acid, diphenyl ether Dicarboxylic acid and β-hydroxyethoxybenzoate It is preferably used selected from the acid, particularly terephthalic acid, 2,6-naphthalenedicarboxylic acid can be preferably used. Aromatic dicarboxylic acids may be used as a mixture of two or more. In addition, if the amount is small, it is also possible to use a mixture of one or more aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid and dodecanediic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, etc. together with the dicarboxylic acid. .

  Examples of the diol that is a component of the polyester resin of the present invention include ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, pentamethylene glycol, hexamethylene glycol, decamethylene glycol, 2-methyl-1,3. -It contains an aromatic ring such as 2,2-bis (β-hydroxyethoxyphenyl) propane, an aliphatic diol such as propanediol, diethylene glycol, or triethylene glycol; an alicyclic diol such as 1,4-cyclohexanedimethanol; Examples thereof include diols and mixtures thereof. If the amount is even smaller, one or more long-chain diols having a molecular weight of 400 to 6,000, that is, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, and the like may be copolymerized.

  The polyester resin of the present invention can be branched by introducing a small amount of a branching agent. Although there is no restriction | limiting in the kind of branching agent, A trimesic acid, a trimellitic acid, a trimethylol ethane, a trimethylol propane, a pentaerythritol, etc. are mentioned.

  Specific polyester resins include polyethylene terephthalate (PET), polypropylene terephthalate, polybutylene terephthalate (PBT), polyhexylene terephthalate, polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polyethylene-1,2- In addition to bis (phenoxy) ethane-4,4′-dicarboxylate, a copolymer polyester resin such as polyethylene isophthalate / terephthalate, polybutylene terephthalate / isophthalate, and the like can be given. Among these, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate and a mixture thereof having a good balance of mechanical properties and the like can be preferably used.

Further, the terminal group structure of the obtained aromatic polyester resin is not particularly limited, and may be a case where the ratio of one of the hydroxyl groups and the carboxyl group in the terminal group is large in addition to the case where the ratio is almost the same. . Moreover, those terminal groups may be sealed by reacting a compound having reactivity with such terminal groups.
Such a polyester resin is produced by polymerizing a 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 according to a conventional method. .

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.

〔但し、式（Ｉ）中、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は、それぞれ互いに独立に２〜１０個の炭素原子を有するアルキル基を表し、ｋは１〜３の整数を表し、かつｋが２又は３の場合、２個又は３個のＲ^２及びＲ^３は、それぞれ互いに同一であってもよく、或いは異なっていてもよい。〕

[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。〕
リン化合物成分（Ｂ）は、下記一般式（ＩＩＩ）で表されるリン化合物（３）の少なくとも１種からなるリン化合物成分である。

[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 polyester resin produced by using the above specific titanium-based catalyst is superior in thermal stability and wet heat resistance compared to the case where germanium, antimony and other titanium-based catalysts are used. 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) is excessive, the color tone of the polyester resin obtained using the resulting catalyst (b value is too high). ) And its 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 catalytic 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, if the proportion of the titanium compound (1) is too high, the color tone of the resulting polyester resin may be deteriorated or the softening point may be lowered. On the contrary, if the proportion of the titanium compound (1) is too low, it is heavy. The condensation 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 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.

  After 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, the polyester resin is purified without purification. It may be used as a production catalyst, or the separated reaction product is purified by recrystallization from a recrystallization agent such as acetone, methyl alcohol and / or water, and the purified product obtained thereby. 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]

The catalyst containing the titanium / phosphorus compound represented by the formula (IV) has high catalytic activity, and the polyester resin produced using the catalyst has a good color tone (low b value) and is practically sufficient. In addition, it has a low content of acetaldehyde, a residual metal and a cyclic trimer of an ester of an aromatic dicarboxylic acid and an alkylene glycol, 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 mm % 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 mm %, and it is still more preferable that it is 10-30 mm %. If it is less than 2 mm %, the catalyst's promotion effect on the polycondensation reaction of the polymerization starting material becomes insufficient, the polyester production efficiency becomes insufficient, and a polyester resin having a desired degree of polymerization cannot be obtained. There is. On the other hand, if it exceeds 40 mm %, the color tone (b value) of the resulting polyester 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 polyester resin used in the present invention, the timing of adding the catalyst to the polymerization starting material is any stage before the start of the polycondensation reaction of the aromatic dicarboxylic acid alkylene glycol ester and / or its low polymer. Moreover, 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 is no special restriction | limiting also in the manufacturing reaction conditions of the polyester resin used for this 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 polyester resin used in the present invention, if necessary, a reaction stabilizer such as trimethyl phosphate may be added to the reaction system at any stage in the production of the polyester. One or more of an agent, a flame retardant, a fluorescent brightening agent, a matting agent, a color adjusting agent, an antifoaming agent, and other additives may be blended. In particular, the polyester 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 polyester resin. 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 an antioxidant used in the polyester 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] It is also preferably practiced to use these hindered phenolic antioxidants in combination with thioether secondary antioxidants selected from undecane and the like. The method for adding the hindered phenolic antioxidant to the polyester resin is not particularly limited, but preferably at any stage between the completion of the ester exchange reaction or the esterification reaction and the completion of the polymerization reaction. Added.

  Further, in order to finely adjust the color tone of the obtained polyester resin, in the production stage of the polyester resin, organic blue pigments such as azo, triphenylmethane, quinoline, anthraquinone, phthalocyanine and the like are included in the reaction system. A color adjusting agent composed of one or more 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 melt heat stability of the polyester resin as a color adjusting agent. Therefore, the polyester resin used in the present invention is substantially free of cobalt.

The resin composition of 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 remaining amount of catalyst of the polyester resin used is significantly lower, making it difficult to produce the polyester resin. This means that the good mechanical strength, thermal stability and wet heat stability, which are the characteristics of this composition, cannot be obtained, which is not preferable.

  In the polyester resin used in the present invention, it is usually preferred 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 polyester resin is less than 80.0, the whiteness of the resulting polyester 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 polyester resin has little yellowness, but the bluishness increases. When the b value exceeds 5.0, the resulting polyester resin has a strong yellowness. Therefore, it may not be possible to produce a practically useful molded product. The L value of the polyester 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. ~ 4.0.

  Although there is no restriction | limiting in the intrinsic viscosity of the polyester resin obtained by this invention, It is preferable to exist in the range of 0.40-1.2. 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 polyester resin is measured at a temperature of 35 ° C. by dissolving the polyester resin in orthochlorophenol. In addition, the polyester resin obtained by solid phase polycondensation is often used for a general bottle or the like, and is therefore contained in the polyester 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.

  The content of the polyester resin is 1 to 50 parts by weight, preferably 5 to 45 parts by weight, more preferably 15 to 35 parts by weight, per 100 parts by weight of the total of component A and component B. If it is 1 part by weight or less, the chemical resistance improving effect is not observed, and if it exceeds 50 parts by weight, the appearance is deteriorated and the heat and humidity resistance is lowered, which is not preferable.

(Other additives)
In the polycarbonate resin composition of the present invention, various stabilizers, mold release agents, colorants, impact modifiers, fillers, flame retardants and the like for stabilizing molecular weight reduction and hue during molding processing should be used. Can do.

(I) Flame retardant Various compounds known as flame retardants are blended in the polycarbonate resin composition of the present invention. The compounding of the compound used as a flame retardant not only improves the flame retardancy but also provides, for example, an improvement in antistatic properties, fluidity, rigidity, and thermal stability based on the properties of each compound.
Examples of such flame retardants include (1) organometallic salt flame retardants (for example, alkali (earth) organic sulfonate metal salts, borate metal salt flame retardants, stannate metal salt flame retardants, etc.), (2) Organophosphorous flame retardants (for example, monophosphate compounds, phosphate oligomer compounds, phosphonate oligomer compounds, phosphonitrile oligomer compounds, and phosphonic acid amide compounds), (3) silicone flame retardants comprising silicone compounds, and (4) halogens And flame retardant (for example, brominated epoxy resin, brominated polystyrene, brominated polycarbonate (including oligomers), brominated polyacrylate, chlorinated polyethylene, etc.).

(1) Organometallic salt-based flame retardant An organic metal salt-based flame retardant is advantageous in that heat resistance is substantially maintained and antistatic properties can be imparted. The organometallic salt flame retardant most advantageously used in the present invention is a fluorine-containing organometallic salt compound. The fluorine-containing organometallic salt compound of the present invention refers to a metal salt compound comprising an anion component composed of an organic acid having a fluorine-substituted hydrocarbon group and a cation component composed of a metal ion. More preferred specific examples include metal salts of fluorine-substituted organic sulfonic acids, metal salts of fluorine-substituted organic sulfates, and metal salts of fluorine-substituted organic phosphates. Fluorine-containing organometallic salt compounds can be used alone or in combination of two or more. Among them, a metal salt of a fluorine-substituted organic sulfonic acid is preferable, and a metal salt of a sulfonic acid having a perfluoroalkyl group is particularly preferable. Here, the carbon number of the perfluoroalkyl group is preferably in the range of 1-18, more preferably in the range of 1-10, and still more preferably in the range of 1-8.

  The metal constituting the metal ion of the organometallic salt flame retardant is an alkali metal or an alkaline earth metal. Examples of the alkali metal include lithium, sodium, potassium, rubidium and cesium. Examples of the alkaline earth metal include beryllium. , Magnesium, calcium, strontium and barium. More preferred is an alkali metal. Accordingly, a preferred organometallic salt flame retardant is an alkali metal perfluoroalkyl sulfonate. Among such alkali metals, rubidium and cesium are suitable when transparency requirements are higher, but these are not general-purpose and difficult to purify, resulting in disadvantages in terms of cost. is there. On the other hand, although lithium and sodium are advantageous in terms of cost and flame retardancy, they may be disadvantageous in terms of transparency. In consideration of these, the alkali metal in the perfluoroalkylsulfonic acid alkali metal salt can be properly used, but perfluoroalkylsulfonic acid potassium salt having an excellent balance of properties is most suitable in any respect. Such potassium salts and alkali metal salts of perfluoroalkylsulfonic acid composed of other alkali metals can be used in combination.

  Such alkali metal perfluoroalkylsulfonates include potassium trifluoromethanesulfonate, potassium perfluorobutanesulfonate, potassium perfluorohexanesulfonate, potassium perfluorooctanesulfonate, sodium pentafluoroethanesulfonate, perfluorobutanesulfone. Acid sodium, sodium perfluorooctane sulfonate, lithium trifluoromethane sulfonate, lithium perfluorobutane sulfonate, lithium perfluoroheptane sulfonate, cesium trifluoromethane sulfonate, cesium perfluorobutane sulfonate, cesium perfluorooctane sulfonate, Cesium perfluorohexane sulfonate, rubidium perfluorobutane sulfonate, and perful B hexane sulfonate rubidium and the like, and these can be used in combination with more than one or two. Of these, potassium perfluorobutanesulfonate is particularly preferred.

  The fluorine-containing organometallic salt preferably has a fluoride ion content as measured by ion chromatography of 50 ppm or less, more preferably 20 ppm or less, and even more preferably 10 ppm or less. The lower the fluoride ion content, the better the flame retardancy and light resistance. The lower limit of the fluoride ion content can be substantially zero, but is practically preferably about 0.2 ppm in view of the balance between the refining man-hour and the effect. Such alkali metal salt of perfluoroalkylsulfonic acid having a fluoride ion content is purified, for example, as follows. The perfluoroalkylsulfonic acid alkali metal salt is dissolved in 2 to 10 times by weight of the metal salt in ion-exchanged water in the range of 40 to 90 ° C. (more preferably 60 to 85 ° C.). The alkali metal salt of perfluoroalkylsulfonic acid is a method of neutralizing perfluoroalkylsulfonic acid with an alkali metal carbonate or hydroxide, or perfluoroalkylsulfonyl fluoride with an alkali metal carbonate or hydroxide. It is produced by a neutralizing method (more preferably by the latter method). The ion-exchanged water is particularly preferably water having an electric resistance value of 18 MΩ · cm or more. The solution in which the metal salt is dissolved is stirred at the above temperature for 0.1 to 3 hours, more preferably 0.5 to 2.5 hours. Thereafter, the liquid is cooled to 0 to 40 ° C, more preferably in the range of 10 to 35 ° C. Crystals precipitate upon cooling. The precipitated crystals are removed by filtration. This produces a suitable purified perfluoroalkylsulfonic acid alkali metal salt.

  The content of the fluorine-containing organometallic salt compound is preferably 0.005 to 0.6 parts by weight, more preferably 0.005 to 0.2 parts by weight, based on the total of 100 parts by weight of component A and component B, Preferably it is 0.008-0.13 weight part. The more preferable range is, the effects (for example, flame retardancy and antistatic properties) expected by the blending of the fluorine-containing organic metal salt are exhibited, and the adverse effect on the light resistance of the polycarbonate resin composition is reduced.

  In addition, as an organic metal salt flame retardant other than the above-mentioned fluorine-containing organic metal salt compound, a metal salt of an organic sulfonic acid not containing a fluorine atom is suitable. Examples of the metal salt include an alkali metal salt of an aliphatic sulfonic acid, an alkaline earth metal salt of an aliphatic sulfonic acid, an alkali metal salt of an aromatic sulfonic acid, and an alkaline earth metal salt of an aromatic sulfonic acid (any Also does not contain a fluorine atom).

  Preferable examples of the aliphatic sulfonic acid metal salt include an alkali (earth) metal salt of an alkyl sulfonate, and these can be used alone or in combination of two or more (here, alkali The (earth) metal salt is used to include both alkali metal salts and alkaline earth metal salts). Preferred examples of the alkane sulfonic acid used for the alkali (earth) metal salt of the alkyl sulfonate include methane sulfonic acid, ethane sulfonic acid, propane sulfonic acid, butane sulfonic acid, methyl butane sulfonic acid, hexane sulfonic acid, and heptane. Examples thereof include sulfonic acid and octanesulfonic acid, and these can be used alone or in combination of two or more.

  The aromatic sulfonic acid used in the aromatic (earth) metal salt of aromatic sulfonate includes monomeric or polymeric aromatic sulfide sulfonic acid, aromatic carboxylic acid and ester sulfonic acid, monomeric or polymeric sulfonic acid. Aromatic ether sulfonic acid, aromatic sulfonate sulfonic acid, monomeric or polymeric aromatic sulfonic acid, monomeric or polymeric aromatic sulfonic acid, aromatic ketone sulfonic acid, heterocyclic sulfonic acid, Examples include at least one acid selected from the group consisting of sulfonic acids of aromatic sulfoxides and condensates of methylene type bonds of aromatic sulfonic acids, and these are used alone or in combination of two or more. be able to.

  Specific examples of the aromatic (earth) metal salt of an aromatic sulfonate include, for example, disodium diphenyl sulfide-4,4′-disulfonate, dipotassium diphenyl sulfide-4,4′-disulfonate, potassium 5-sulfoisophthalate, Sodium 5-sulfoisophthalate, polysodium polyethylene terephthalate polysulfonate, calcium 1-methoxynaphthalene-4-sulfonate, disodium 4-dodecylphenyl ether disulfonate, polysodium poly (2,6-dimethylphenylene oxide) polysulfonate Poly (1,3-phenylene oxide) polysulfonic acid polysodium, poly (1,4-phenylene oxide) polysulfonic acid polysodium, poly (2,6-diphenylphenylene oxide) polysulfonic acid poly Lithium, poly (2-fluoro-6-butylphenylene oxide) polysulfonate, potassium sulfonate of benzenesulfonate, sodium benzenesulfonate, strontium benzenesulfonate, magnesium benzenesulfonate, dipotassium p-benzenedisulfonate, naphthalene-2 , 6-disulfonic acid dipotassium, biphenyl-3,3'-disulfonic acid calcium, diphenylsulfone-3-sulfonic acid sodium, diphenylsulfone-3-sulfonic acid potassium, diphenylsulfone-3,3'-disulfonic acid dipotassium, diphenylsulfone Α, α, α-trifluoroacetophenone sodium 4-sulfonate, dipotassium benzophenone-3,3′-disulfonate, Nene-2,5-disulfonate, dipotassium thiophene-2,5-disulfonate, calcium thiophene-2,5-disulfonate, sodium benzothiophenesulfonate, potassium diphenylsulfoxide-4-sulfonate, naphthalene Examples thereof include a formalin condensate of sodium sulfonate and a formalin condensate of sodium anthracene sulfonate.

  On the other hand, the alkali (earth) metal salt of sulfate ester may include, in particular, the alkali (earth) metal salt of sulfate ester of monovalent and / or polyhydric alcohols. Alcohol sulfates include methyl sulfate, ethyl sulfate, lauryl sulfate, hexadecyl sulfate, polyoxyethylene alkylphenyl ether sulfate, pentaerythritol mono, di, tri, tetrasulfate, and lauric acid monoglyceride. And sulfuric acid esters of palmitic acid monoglyceride and stearic acid monoglyceride sulfate. The alkali (earth) metal salts of these sulfates are preferably alkali (earth) metal salts of lauryl sulfate.

  Examples of other alkali (earth) metal salts include alkali (earth) metal salts of aromatic sulfonamides such as saccharin, N- (p-tolylsulfonyl) -p-toluenesulfonimide, N Examples include-(N'-benzylaminocarbonyl) sulfanilimide and alkali (earth) metal salts of N- (phenylcarboxyl) sulfanilimide.

  Among the above, preferable metal salts of organic sulfonic acids not containing fluorine atoms are aromatic (earth) metal salts of aromatic sulfonates, and potassium salts are particularly preferable. When blending such an alkali (earth) sulfonate metal salt, its content is preferably 0.001 to 1 part by weight, more preferably 0, based on a total of 100 parts by weight of component A and component B. 0.005 to 0.5 parts by weight, more preferably 0.01 to 0.1 parts by weight.

(2) Organophosphorous flame retardant As the organophosphorous flame retardant of the present invention, an aryl phosphate compound is suitable. This is because such a phosphate compound is generally excellent in hue and hardly adversely affects high light reflectivity. Moreover, since the phosphate compound has a plasticizing effect, it is advantageous in that the moldability of the polycarbonate resin composition of the present invention can be improved. As the phosphate compound, various known phosphate compounds as conventional flame retardants can be used, and more preferably, one or more phosphate compounds represented by the following general formula (5) can be mentioned.

（但し上記式中のＸは、ハイドロキノン、レゾルシノール、ビス（４−ヒドロキシジフェニル）メタン、ビスフェノールＡ、ジヒドロキシジフェニル、ジヒドロキシナフタレン、ビス（４−ヒドロキシフェニル）スルホン、ビス（４−ヒドロキシフェニル）ケトン、ビス（４−ヒドロキシフェニル）サルファイドから誘導される二価の基が挙げられ、ｊ、ｋ、ｌ、ｍはそれぞれ独立して０または１であり、ｎは０〜５の整数であり、またはｎ数の異なるリン酸エステルの混合物の場合は０〜５の平均値であり、Ｒ^１、Ｒ^２、Ｒ^３、およびＲ^４はそれぞれ独立して１個以上のハロゲン原子を置換したもしくは置換していないフェノール、クレゾール、キシレノール、イソプロピルフェノール、ブチルフェノール、ｐ−クミルフェノールから誘導される一価フェノール残基である。）

(However, X in the above formula is hydroquinone, resorcinol, bis (4-hydroxydiphenyl) methane, bisphenol A, dihydroxydiphenyl, dihydroxynaphthalene, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis And a divalent group derived from (4-hydroxyphenyl) sulfide, wherein j, k, l and m are each independently 0 or 1, n is an integer of 0 to 5, or n number In the case of a mixture of phosphoric acid esters having different values, the average value is 0 to 5, and R ¹ , R ² , R ³ , and R ⁴ are each independently substituted or not substituted with one or more halogen atoms From phenol, cresol, xylenol, isopropylphenol, butylphenol, p-cumylphenol This is a derived monohydric phenol residue.)

  The phosphate compound of the above formula may be a mixture of compounds having different n numbers, in which case the average n number is preferably 0.5 to 1.5, more preferably 0.8 to 1. 2, More preferably, it is 0.95-1.15, Most preferably, it is the range of 1-1.14.

Preferred specific examples of the dihydric phenol for deriving X are resorcinol, bisphenol A, and dihydroxydiphenyl.
Preferred specific examples of the monohydric phenol for deriving the above R ¹ , R ² , R ³ , and R ⁴ are phenol and 2,6-dimethylphenol.
The monohydric phenol may be substituted with a halogen atom. Specific examples of the phosphate compound having a group derived from the monohydric phenol include tris (2,4,6-tribromophenyl) phosphate and tris. Examples include (2,4-dibromophenyl) phosphate, tris (4-bromophenyl) phosphate, and the like.

On the other hand, specific examples of the phosphate compound not substituted with a halogen atom include monophosphate compounds such as triphenyl phosphate and tri (2,6-xylyl) phosphate, and resorcinol bisdi (2,6-xylyl) phosphate). Preferred are phosphate oligomers mainly composed of phosphate oligomers, phosphate oligomers mainly composed of 4,4-dihydroxydiphenyl bis (diphenyl phosphate), and phosphate oligomers mainly composed of bisphenol A bis (diphenyl phosphate). Indicates that a small amount of other components having different degrees of polymerization may be included, and more preferably, the component of n = 1 in the formula (1) is 80% by weight or more, more preferably 85% by weight or more, and still more preferably Contains over 90% by weight Are shown.).
The content of the organophosphorous flame retardant is preferably 1 to 20 parts by weight, more preferably 2 to 10 parts by weight, still more preferably 2 to 7 parts by weight, based on a total of 100 parts by weight of component A and component B. It is.

(3) Silicone-based flame retardant The silicone compound used as the silicone-based flame retardant of the present invention improves flame retardancy by a chemical reaction during combustion. As the compound, various compounds conventionally proposed as flame retardants for aromatic polycarbonate resins can be used. The silicone compound binds itself during combustion or binds to a component derived from the resin to form a structure, or gives a flame retardant effect to the polycarbonate resin by a reduction reaction during the structure formation. It is considered. Therefore, it is preferable that a group having high activity in such a reaction is contained, and more specifically, a predetermined amount of at least one group selected from an alkoxy group and a hydrogen (ie, Si—H group) is contained. preferable. As a content rate of this group (alkoxy group, Si-H group), the range of 0.1-1.2 mol / 100g is preferable, the range of 0.12-1 mol / 100g is more preferable, 0.15-0. The range of 6 mol / 100 g is more preferable. Such a ratio can be determined by measuring the amount of hydrogen or alcohol generated per unit weight of the silicone compound by the alkali decomposition method. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, and particularly preferably a methoxy group.

Generally, the structure of a silicone compound is constituted by arbitrarily combining the following four types of siloxane units. That is,
M units: (CH ₃ ) ₃ SiO _1/2 , H (CH ₃ ) ₂ SiO _1/2 , H ₂ (CH ₃ ) SiO _1/2 , (CH ₃ ) ₂ (CH ₂ = CH) SiO _1/2 Monofunctional siloxane units such as (CH ₃ ) ₂ (C ₆ H ₅ ) SiO _1/2 , (CH ₃ ) (C ₆ H ₅ ) (CH ₂ ═CH) SiO _1/2 ,
D unit: (CH ₃ ) ₂ SiO, H (CH ₃ ) SiO, H ₂ SiO, H (C ₆ H ₅ ) SiO, (CH ₃ ) (CH ₂ ═CH) SiO, (C ₆ H ₅ ) ₂ SiO Bifunctional siloxane units such as
T unit: (CH ₃ ) SiO _3/2 , (C ₃ H ₇ ) SiO _3/2 , HSiO _3/2 , (CH ₂ ═CH) SiO _3/2 , (C ₆ H ₅ ) SiO _3/2 etc. A trifunctional siloxane unit of
Q unit: a tetrafunctional siloxane unit represented by SiO ₂ .

Specifically, the structure of the silicone compound used in the silicone-based flame retardant is represented by the following formulas: D _n , T _p , M _m D _n , M _m T _p , M _m Q _q , M _m D _n T _{p , M m D n Q q,} M m T p Q q, M m D n T p Q q, D n T p, D n Q q, include _{D n} T p _{Q q.} Among these, preferable structures of the silicone compound are M _m D _n , M _m T _p , M _m D _n T _p , and M _m D _n Q _q , and more preferable structures are M _m D _n or M _m D _n. T _p .

  Here, the coefficients m, n, p, and q in the above formulas are integers of 1 or more representing the degree of polymerization of each siloxane unit, and the sum of the coefficients in each formula is the average degree of polymerization of the silicone compound. . This average degree of polymerization is preferably in the range of 3 to 150, more preferably in the range of 3 to 80, still more preferably in the range of 3 to 60, and particularly preferably in the range of 4 to 40. The better the range, the better the flame retardancy. Further, as described later, a silicone compound containing a predetermined amount of an aromatic group is excellent in transparency and hue.

  When any of m, n, p, and q is a numerical value of 2 or more, the siloxane unit with the coefficient can be two or more types of siloxane units having different hydrogen atoms or organic residues to be bonded. .

  The silicone compound may be linear or have a branched structure. The organic residue bonded to the silicon atom is preferably an organic residue having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms. Specific examples of such an organic residue include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and a decyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, And aralkyl groups such as tolyl groups. More preferably, they are a C1-C8 alkyl group, an alkenyl group, or an aryl group. As the alkyl group, an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, and a propyl group is particularly preferable.

  Further, the silicone compound used as the silicone flame retardant preferably contains an aryl group. More preferably, the ratio (aromatic group amount) of the aromatic group represented by the following general formula (6) is 10 to 70% by weight (more preferably 15 to 60% by weight).

（式（６）中、Ｘはそれぞれ独立にＯＨ基、炭素数１〜２０の一価の有機残基を示す。ｎは０〜５の整数を表わす。さらに式（６）中においてｎが２以上の場合はそれぞれ互いに異なる種類のＸを取ることができる。）

(In formula (6), each X independently represents an OH group or a monovalent organic residue having 1 to 20 carbon atoms. N represents an integer of 0 to 5. Further, in formula (6), n is 2) In these cases, different types of X can be taken.)

The silicone compound used as the silicone-based flame retardant may contain a reactive group in addition to the Si-H group and the alkoxy group. Examples of the reactive group include an amino group, a carboxyl group, an epoxy group, and a vinyl group. Examples thereof include a group, a mercapto group, and a methacryloxy group.
As a silicone compound which has Si-H group, the silicone compound containing at least 1 or more types of the structural unit shown by the following general formula (7) and (8) is illustrated suitably.

（式（７）および式（８）中、Ｚ^１〜Ｚ^３はそれぞれ独立に水素原子、炭素数１〜２０の一価の有機残基、または下記一般式（９）で示される化合物を示す。α^１〜α^３はそれぞれ独立に０または１を表わす。ｍ１は０もしくは１以上の整数を表わす。さらに式（７）中においてｍ１が２以上の場合の繰返し単位はそれぞれ互いに異なる複数の繰返し単位を取ることができる。）

(In formula (7) and formula (8), Z ^{1 to} Z ³ each independently represent a hydrogen atom, a monovalent organic residue having 1 to 20 carbon atoms, or a compound represented by the following general formula (9). Α ^{1 to} α ³ each independently represents 0 or 1. m1 represents 0 or an integer greater than or equal to 1. Further, in formula (7), when m1 is 2 or more, the repeating unit is a plurality of different repeating units. Can take units.)

（式（９）中、Ｚ^４〜Ｚ^８はそれぞれ独立に水素原子、炭素数１〜２０の一価の有機残基を示す。α^４〜α^８はそれぞれ独立に０または１を表わす。ｍ２は０もしくは１以上の整数を表わす。さらに式（９）中においてｍ２が２以上の場合の繰返し単位はそれぞれ互いに異なる複数の繰返し単位を取ることができる。）

(In formula (9), Z ^{4 to} Z ⁸ each independently represents a hydrogen atom or a monovalent organic residue having 1 to 20 carbon atoms. Α ^{4 to} α ⁸ each independently represents 0 or 1. m 2 Represents 0 or an integer greater than or equal to 1. Further, in formula (9), when m2 is 2 or more, the repeating unit may take a plurality of repeating units different from each other.

  Examples of the silicone compound having an alkoxy group in the silicone compound used for the silicone-based flame retardant include at least one compound selected from the compounds represented by the general formula (10) and the general formula (11).

（式（１０）中、β^１はビニル基、炭素数１〜６のアルキル基、炭素数３〜６のシクロアルキル基、並びに炭素数６〜１２のアリール基およびアラルキル基を示す。γ^１、γ^２、γ^３、γ^４、γ^５、およびγ^６は炭素数１〜６のアルキル基およびシクロアルキル基、並びに炭素数６〜１２のアリール基およびアラルキル基を示し、少なくとも１つの基がアリール基またはアラルキル基である。δ^１、δ^２、およびδ^３は炭素数１〜４のアルコキシ基を示す。）

(In the formula (10), β ¹ represents a vinyl group, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group or aralkyl group having 6 to 12 carbon atoms. Γ ¹ , γ ² , γ ³ , γ ⁴ , γ ⁵ , and γ ⁶ represent an alkyl group and a cycloalkyl group having 1 to ⁶ carbon atoms, and an aryl group and an aralkyl group having 6 to 12 carbon atoms, and at least one group is aryl. And δ ¹ , δ ² , and δ ³ are each an alkoxy group having 1 to 4 carbon atoms.)

（式（１１）中、β^２およびβ^３はビニル基、炭素数１〜６のアルキル基、炭素数３〜６のシクロアルキル基、並びに炭素数６〜１２のアリール基およびアラルキル基を示す。γ^７、γ^８、γ^９、γ^１０、γ^１１、γ^１２、γ^１３およびγ^１４は炭素数１〜６のアルキル基、炭素数３〜６のシクロアルキル基、並びに炭素数６〜１２のアリール基およびアラルキル基を示し、少なくとも１つの基がアリール基またはアラルキルである。δ^４、δ^５、δ^６、およびδ^７は炭素数１〜４のアルコキシ基を示す。）

(In formula (11), β ² and β ³ represent a vinyl group, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group and an aralkyl group having 6 to 12 carbon atoms. γ ⁷ , γ ⁸ , γ ⁹ , γ ¹⁰ , γ ¹¹ , γ ¹² , γ ^13, and γ ¹⁴ are each an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and 6 to 12 carbon atoms. An aryl group and an aralkyl group, and at least one group is an aryl group or an aralkyl group, and δ ⁴ , δ ⁵ , δ ⁶ , and δ ⁷ represent an alkoxy group having 1 to 4 carbon atoms.

  The content of the above components is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, still more preferably 0.1 to 5 parts, based on 100 parts by weight of the total of the A component and the B component. Parts by weight.

(4) Halogen flame retardant As the halogen flame retardant of the present invention, brominated polycarbonate (including oligomers) 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 (12) is at least 60 mol%, preferably at least 80 mol%, particularly preferably substantially the following general formula. A brominated polycarbonate compound comprising the structural unit represented by (12).

（式（１２）中、Ｘは臭素原子、Ｒは炭素数１〜４のアルキレン基、炭素数１〜４のアルキリデン基または−ＳＯ_２−である。）

(In the formula (12), 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 (12), 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 polycarbonate resin composition becomes better, and molding at a higher temperature becomes possible. As a result, a polycarbonate resin composition that is superior in 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 ¹ H-NMR method. Such a terminal hydroxyl group amount is preferable because the thermal stability of the polycarbonate 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.
The content of the above component is preferably 0.01 to 10 parts by weight, more preferably 0.01 to 8 parts by weight, and still more preferably 0.05 to 7 parts by weight, based on the total of 100 parts by weight of component A and component B. Parts by weight.

(Ii) Fluorine-containing anti-dripping agent The polycarbonate resin composition of the present invention may contain a fluorine-containing anti-drop 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.
The content of the above components is preferably 0.01 to 3 parts by weight, more preferably 0.01 to 2 parts by weight, and still more preferably 0.05 to 1 based on 100 parts by weight of the total of component A and component B. .5 parts by weight.

(Iii) Stabilizer Various known stabilizers can be blended in the polycarbonate resin composition of the present invention. Examples of the stabilizer include phosphorus stabilizers, hindered phenol antioxidants, ultraviolet absorbers, and light stabilizers.

(Iii-1) Phosphorous 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 triorganophosphate compounds, acid phosphate compounds, and phosphite compounds represented by the following general formula (13). It is particularly preferable to add a triorganophosphate compound.

（式（１３）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 (13), 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 as 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 (13), 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.

(Iii-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, based on 100 parts by weight of the total of component A and component B, respectively. .3 parts by weight.

(Iii-3) Ultraviolet Absorber The polycarbonate resin composition of the present invention can contain an ultraviolet absorber. Since the polycarbonate resin composition of the present invention also has a good hue, the hue can be maintained for a long time even in outdoor use by incorporating 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- Dorokishi -4-n-dodecyloxy benzoin phenone, and such as 2-hydroxy-4-methoxy-2'-carboxy benzophenone may be exemplified.

  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.

  Further, as the ultraviolet absorber, specifically, for cyanoacrylate, for example, 1,3-bis-[(2′-cyano-3 ′, 3′-diphenylacryloyl) oxy] -2,2-bis [(2- Examples include cyano-3,3-diphenylacryloyl) oxy] methyl) propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl) oxy] benzene.

  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 0.01 to 2 parts by weight, more preferably 0.02 to 2 parts by weight, still more preferably 0.03 to 1 based on the total of 100 parts by weight of component A and component B. Parts by weight, most preferably 0.05 to 0.5 parts by weight.

(Iii-4) Other Heat Stabilizers The polycarbonate 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, based on 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 polycarbonate 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 component A and component B.

(Iv) Mold Release Agent The polycarbonate resin composition of the present invention is further prepared with a fatty acid ester, a polyolefin wax, a silicone compound, a fluorine compound (polyester) for the purpose of improving productivity during molding and improving dimensional accuracy of a molded product. Known release agents such as fluoro oil represented by fluoroalkyl ether), paraffin wax, beeswax and the like can also be blended. Since the polycarbonate 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 polycarbonate 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 above releasing agent is preferably 0.005 to 5 parts by weight, more preferably 0.01 to 4 parts by weight, and still more preferably 0.02 based on a total of 100 parts by weight of component A and component B. ~ 3 parts by weight.

(V) Dye / pigment The polycarbonate resin composition of the present invention can further contain various dyes / pigments and can provide a molded product exhibiting various design properties. Examples of dyes used in the present invention include 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 polycarbonate resin composition of the present invention can be blended with a metallic pigment to obtain a better metallic color. As the metallic pigment, aluminum powder is suitable. In addition, by blending a fluorescent brightening agent or other fluorescent dyes that emit 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 molding of the polycarbonate resin.
The content of the dye / pigment is preferably 0.00001 to 1 part by weight, more preferably 0.00005 to 0.5 part by weight based on 100 parts by weight of the total of the A component and the B component.

(Vi) Compound having heat ray absorbing ability The polycarbonate resin composition of the present invention may contain a compound having heat ray absorbing 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, based on the total of 100 parts by weight of the component A and the component B. 0.001 to 0.07 part by weight is 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.

(Vii) Light diffusing agent The polycarbonate 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 that are already known as light diffusing agents for polycarbonate 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, still more preferably 0.01 to 3 parts by weight based on the total of 100 parts by weight of the component A and the component B. Parts by weight. Two or more light diffusing agents can be used in combination.

(Viii) White pigment for high light reflection The polycarbonate 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 a total of 100 parts by weight of the component A and the component B. Two or more kinds of white pigments for high light reflection can be used in combination.

(Ix) Antistatic agent The polycarbonate 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 0.00, based on the total of 100 parts by weight of the component A, the component B and the component C. 3 parts by weight, more preferably 0.005 to 0.2 parts by weight. 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.

(X) Filler
Various known fillers can be blended in the polycarbonate resin composition of the present invention as a reinforcing filler. 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, particularly preferably 30 parts by weight based on 100 parts by weight of the total of the A component and the B component. It is as follows.

(Xi) Other additives The polycarbonate resin composition of the present invention includes A component, thermoplastic resin other than B component, elastomer, other flow modifiers, antibacterial agents, dispersants such as liquid paraffin, photocatalyst protection A soiling agent, a photochromic agent, etc. can be mix | blended.
Examples of such other resins include polyamide resins, polyimide resins, polyetherimide resins, polyurethane resins, silicone resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, polyolefin resins such as polyethylene and polypropylene, polystyrene resins, acrylonitrile / styrene. Copolymer (AS resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), polymethacrylate resin, phenol resin, epoxy resin, cyclic polyolefin resin, polylactic acid resin, polycaprolactone resin, and thermoplastic fluororesin (for example, And the like (represented by polyvinylidene fluoride resin).

As the elastomer, for example, isobutylene / isoprene rubber, styrene / butadiene rubber, ethylene / propylene rubber, acrylic elastomer, polyester elastomer, polyamide elastomer, MBS (methyl methacrylate / sterene / butadiene) which is a core-shell type elastomer. Examples thereof include rubber and MAS (methyl methacrylate / acrylonitrile / styrene) rubber.
The content of the other thermoplastic resin is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, based on the total of 100 parts by weight of component A and component B.

(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, the B 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 A, a master batch of an additive diluted with powder by blending a part of the powder and an additive to be blended is manufactured, and the master 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 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 polycarbonate 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.

  The polycarbonate resin composition of the present invention can also be used in the form of various shaped extruded products, sheets, films, 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. Further, the polycarbonate resin composition of the present invention can be formed into a molded product by rotational molding or blow molding.

  As a result, a polycarbonate resin composition and a molded product having both mechanical strength, chemical resistance, thermal stability, and good wet heat resistance are provided. That is, according to the present invention, there is provided a resin composition comprising (A) 50 to 99 parts by weight of an aromatic polycarbonate resin (component A) and (B) 1 to 50 parts by weight of a polyester resin (component B). Obtained by reacting the titanium compound (1) represented by the above general formula (I) and the titanium compound (1) with the aromatic polycarboxylic acid represented by the above general formula (II) or an anhydride thereof. Reaction of at least one titanium compound component selected from the group consisting of the obtained titanium compound (2) and a phosphorus compound component consisting of at least one phosphorus compound (3) represented by the general formula (III) There is provided a molded article obtained by melt-molding a resin composition, which is a polyester resin polymerized using a compound containing a product as a catalyst.

  Molded articles in which the polycarbonate 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), and other agricultural materials. It is useful for various uses such as transport containers, playground equipment, and miscellaneous goods, and its industrial effects are exceptional.

  Furthermore, various surface treatments can be performed on the molded article made of the polycarbonate 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 polycarbonate resin 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 polycarbonate resin composition of the present invention has improved metal adhesion, application of vapor deposition and plating is also preferred. 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.

  The polycarbonate resin composition of the present invention is excellent in mechanical strength, chemical resistance, thermal stability, and also has good moisture and heat resistance. Therefore, as described above, the building, building material, agricultural material, marine material, vehicle It is useful in a wide range of fields such as electrical / electronic equipment, machinery, and others. Therefore, the industrial effect exhibited by the present invention is extremely great.

  The form of the present invention considered to be the best by the present inventor is a collection 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.

(I) Evaluation of polycarbonate resin composition (i) Ti elemental analysis: Measurement was performed using an ICP mass spectrometer Agilent 7500cs manufactured by Agilent Technologies. In addition, after adding the sulfuric acid to the weighed sample and ashing the resin by microwave decomposition, the sample was further added with nitric acid and the residue metal obtained by microwave decomposition was fixed in ultrapure water. The amount was measured.
(Ii) Charpy impact strength measurement: After drying the various pellets obtained at 120 ° C. for 5 hours, the cylinder temperature was 280 ° C. and the mold temperature was 70 ° C. using an injection molding machine (SG-150U, manufactured by Sumitomo Heavy Industries, Ltd.). The molded piece was molded, and the Charpy impact strength with a notch was measured according to ISO179.
(Iii) MVR measurement: The various pellets obtained were dried at 120 ° C. for 5 hours, and then an injection molding machine (SG-150U, manufactured by Sumitomo Heavy Industries, Ltd.) was used. The cylinder temperature was 270 ° C. and the mold temperature was 70. A test piece having a thickness of 2 mm was molded at 50 ° C. and a molding cycle of 50 seconds. The test piece was left in a constant temperature and humidity tester at a temperature of 80 ° C. and a relative humidity of 95% for 500 hours, and then left for 24 hours in an environment at a temperature of 23 ° C. and a relative humidity of 50% (after wet heat treatment). MVR measurement value measured under the load condition of 280 ° C. and 2.16 kg using a test piece) and a test piece (test piece before wet heat treatment) left for 24 hours in an environment of a temperature of 23 ° C. and a relative humidity of 50%. The MVR measurement value measured under the same conditions was calculated according to the following formula, and the rate of change (ΔMVR) before and after the wet heat treatment was calculated. A larger ΔMVR means that the resin deterioration of the molded product is larger, and ΔMVR needs to be 300 or less.
ΔMVR = 100 × (MVR of test piece after wet heat treatment) / (MVR of test piece before wet heat treatment) (iv) Appearance of molded product: After drying various pellets obtained at 120 ° C. for 5 hours, an injection molding machine ( Sumitomo Heavy Industries, Ltd. SG-150U) is visually evaluated by visually observing the appearance of a molded product of 150mm length x 150mm width x 2mm thickness at a cylinder temperature of 280 ° C and a mold temperature of 70 ° C. went. The evaluation was performed according to the following criteria.
○: No abnormality is observed Δ: Silver is seen only at the gate part ×: Silver is seen throughout the molded product

[Examples 1-7, Comparative Examples 1-5]
A polycarbonate resin, a polyester resin, and various additives shown in Tables 1 and 2 were mixed at blending amounts in blenders, and then melt-kneaded using a vent type twin screw extruder to obtain pellets. Various additives to be used were prepared in advance by premixing with a polycarbonate resin with a concentration of 10 to 100 times the blending amount as a guide, and then the whole was mixed by a blender. A vent type twin screw extruder (manufactured by Nippon Steel Works, Ltd .: TEX30α (completely meshing, rotating in the same direction, two-thread screw)) was used. Extrusion conditions were a discharge rate of 20 kg / h, a screw rotation speed of 150 rpm, a vent vacuum of 3 kPa, and an extrusion temperature of 270 ° C. from the first supply port to the die part. The obtained pellets were dried with a hot air circulation dryer at 120 ° C. for 5 hours, and then a test piece for evaluation was molded using an injection molding machine. The evaluation results are shown in Tables 1 and 2.

Each component of the symbol notation in Table 1 and Table 2 is as follows.
(A component)
PC-1: Linear aromatic polycarbonate resin powder having a viscosity average molecular weight of 16,000 PC-2: Linear aromatic polycarbonate resin powder having a viscosity average molecular weight of 25,000 (component B)
PET-1: Polyethylene terephthalate resin polymerized using a titanium-based catalyst obtained by reacting titanium tetrabutoxide and monolauryl phosphate (IV = 0.83)
PET-2: Polyethylene terephthalate resin polymerized using a titanium-based polymerization catalyst obtained by reacting titanium tetrabutoxide and monolauryl phosphate (IV = 0.53)
PET-3: Polyethylene terephthalate resin polymerized using an acetyltriisopropyl titanate polymerization catalyst (IV = 0.80)
(Other ingredients)
P-1: Trimethyl phosphate P-2: Bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite

Claims (6)

(A) A resin composition comprising 50 to 99 parts by weight of an aromatic polycarbonate resin (component A) and (B) 1 to 50 parts by weight of a polyester resin (component B), wherein the component B is represented by the following general formula (I) A titanium compound (1), and a titanium compound (2) obtained by reacting the titanium compound (1) with an aromatic polyvalent carboxylic acid represented by the following general formula (II) or an anhydride thereof At least one titanium compound component selected from the group consisting of and a phosphorus compound component consisting of at least one phosphorus compound (3) represented by the following general formula (III): A compound containing a reaction product obtained by reacting an amount (mTi) and a reaction molar ratio (mTi / mP) of the phosphorus compound component in terms of phosphorus atom equivalent (mP) within a range of 1/3 to 1/1 Used as Te is a polymerized polyester resin, the resin composition characterized satisfying the requirements of the polyester resin is below (i) and (ii).
(I) the intrinsic viscosity is 0.40 to 1.2,
(Ii) The amount of the titanium-based catalyst used is 2 to 40 mm% with respect to the total millimolar amount of the aromatic dicarboxylic acid component contained in the polymerization starting material in terms of millimolar amount in terms of titanium atom.

[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. ]

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

[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 resin composition according to claim 1, wherein the component B is a polyester resin polymerized using a compound represented by the following formula (IV) as a catalyst.

[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] The resin composition according to any one of claims. 1 to 2 B component is polyethylene terephthalate. An injection-molded article formed from the resin composition according to any one of claims 1 to 3 . The injection-molded article according to claim 4 , wherein the injection-molded article is a vehicle interior / exterior member. The injection molded product according to claim 4 , wherein the injection molded product is an interior / exterior member for OA / electrical electronics.