JP2008101117A - Aromatic polycarbonate resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aromatic polycarbonate resin composition excellent in low temperature impact strength. <P>SOLUTION: The aromatic polycarbonate resin composition comprises an aromatic polycarbonate resin (A component) and a core-shell type conjugate rubber (B component) of a conjugated rubber-based graft copolymer obtained by forming a shell on a core, wherein the shell is formed by graft-polymerizing at least one vinyl monomer and the core is a conjugate rubber comprising a polyorganosiloxane rubber component and at least one polyalkyl (meth)acrylate rubber component, and wherein, when the B component content is d pts.wt. per 100 pts.wt. total of the A component and the B component, the maximum strength of absorption peak of the B component appears in a range from 2,700-3,000 cm<SP>-1</SP>is (a) and maximum strength of the absorption peak appears in a range of 830-780 cm<SP>-1</SP>is b, (b/a) is within a range of 0.2-3.5 and relation formula (1): 200<d<SP>4</SP>×(b/a)<800 (1) is satisfied. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an aromatic polycarbonate resin composition and an aromatic polycarbonate resin composition excellent in low-temperature impact strength comprising a specific core-shell type composite rubber.

Aromatic polycarbonate resins are widely used industrially because of their excellent heat resistance, mechanical strength, and electrical properties.
However, the aromatic polycarbonate resin has a drawback that the low-temperature impact strength of the member having a notch is low. Therefore, a method for improving the low temperature impact strength by adding an impact modifier is known, but only by using those techniques, that is, by using a conventionally known impact modifier, There was a problem that sufficient effects or stable effects could not be obtained, and the excellent impact strength, deflection temperature under load, and other mechanical strength of the aromatic polycarbonate resin were sacrificed. .

  For example, in JP-A-1-230664 (Patent Document 1), a vinyl monomer is graft-polymerized onto a polycarbonate resin, a polyester resin, and a composite rubber composed of a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate rubber component. There has been proposed a resin composition comprising a composite rubber-based graft copolymer. Although this resin composition is improved in low temperature impact strength and weather resistance, it is assumed that a polyester resin is an essential component, so that the original mechanical properties of an aromatic polycarbonate resin such as a deflection temperature under load are maintained. Have difficulty.

  Japanese Patent Application Laid-Open No. 2004-359889 (Patent Document 2) mentions an impact modifier effective for improving low-temperature impact strength and defines the addition amount. However, since the addition amount described is wide, When a molded product having a notch was evaluated, the amount of addition more effective for improving the low temperature impact strength and suppressing the deterioration of various mechanical properties was unclear.

  JP 2002-030210 (Patent Document 3) refers to excellent low temperature impact strength, but presupposes that a rubbery polymer not containing a polyorganosiloxane rubber component is an essential component unlike the present invention. In Examples, it is difficult to maintain the original mechanical properties of the aromatic polycarbonate resin such as the deflection temperature under load by using 5% or more of a thermoplastic resin other than the aromatic PC such as the rubber polymer.

  Japanese Patent Application Laid-Open No. 8-134277 (Patent Document 4) refers to excellent low temperature impact strength, but assumes that a polyester resin is an essential component, and is an original machine of an aromatic polycarbonate resin such as a deflection temperature under load. It is not only difficult to maintain the physical properties, but the low-temperature impact strength itself is not sufficient.

Japanese Patent Laid-Open No. 1-230664 JP 2004-359889 A JP 2002-030210 A JP-A-8-134277

  In view of the above, an object of the present invention is to provide an aromatic polycarbonate resin that is excellent in low-temperature impact strength when a molded product having a notch is evaluated, and that maintains the original impact strength and other mechanical properties of the polycarbonate resin at ordinary temperatures. There is.

  As a result of intensive studies aimed at achieving the above object, the present inventor has obtained a specific impact modifier, that is, a composite rubber composed of a polyorganosiloxane rubber component and one or more polyalkyl (meth) acrylate rubber components. It is possible to add a core-shell type composite rubber, which is a composite rubber-type graft copolymer obtained by graft-polymerizing one or more vinyl monomers to the core of the core, to form a shell. It is found that the range of the amount of additive that exerts an effect on strength improvement and the effect is manifested is a very limited range derived from a specific relational expression using the infrared absorption spectrum intensity unique to the impact modifier. It was.

According to the present invention, at least one of the above-mentioned problems is present in the core of a composite rubber composed of an aromatic polycarbonate resin (component A) and a polyorganosiloxane rubber component and at least one polyalkyl (meth) acrylate rubber component. An aromatic polycarbonate resin composition comprising a core-shell type composite rubber (component B), which is a composite rubber-based graft copolymer obtained by graft polymerization of a vinyl monomer of d parts by weight and the content of the B component of the total amount 100 parts by weight of B component, the maximum intensity of the absorption peak appearing from 2700 cm ^-1 in the range of 3000 cm ^-1 in the infrared absorption spectrum of the B component a, 830 cm ^-1 To 780 cm ⁻¹ , where b is the maximum intensity of the absorption peak, and the ratio of both absorption peak intensities (b / a) Is in the range of 0.2 to 3.5, and the following relational expression (1)
200 <d ⁴ × (b / a) <800 (1)
It is achieved by an aromatic polycarbonate resin composition characterized by satisfying

Hereinafter, the details of the present invention will be described.
(Component A: aromatic polycarbonate resin)
The aromatic polycarbonate resin (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 polycondensation 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 (hereinafter sometimes abbreviated as “BPA”) is particularly preferred because of its excellent toughness, and is widely used.

  In the present invention, in addition to the general-purpose polycarbonate bisphenol A-based polycarbonate, a special polycarbonate produced using other dihydric phenols can be used as the A component.

  For example, as part or all of the dihydric phenol component, 4,4 ′-(m-phenylenediisopropylidene) diphenol (hereinafter sometimes abbreviated as “BPM”), 1,1-bis (4-hydroxy Phenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (hereinafter sometimes abbreviated as “Bis-TMC”), 9,9-bis (4-hydroxyphenyl) Polycarbonate (homopolymer or copolymer) using fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (hereinafter sometimes abbreviated as “BCF”) has dimensions due to water absorption. It is suitable for applications where the demands for change and shape stability are particularly severe. These dihydric phenols other than BPA are preferably used in an amount of 5 mol% or more, particularly 10 mol% or more of the entire dihydric phenol component constituting the polycarbonate.

In particular, when high rigidity and better hydrolysis resistance are required, it is particularly preferable that the component A constituting the resin composition is a copolymerized polycarbonate of the following (1) to (3). is there.
(1) BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, more preferably 45 to 65 mol%) in 100 mol% of the dihydric phenol component constituting the polycarbonate, and BCF Of 20 to 80 mol% (more preferably 25 to 60 mol%, more preferably 35 to 55 mol%).
(2) BPA is 10 to 95 mol% (more preferably 50 to 90 mol%, more preferably 60 to 85 mol%) in 100 mol% of the dihydric phenol component constituting the polycarbonate, and BCF Is 5 to 90 mol% (more preferably 10 to 50 mol%, more preferably 15 to 40 mol%).
(3) BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, more preferably 45 to 65 mol%) in 100 mol% of the dihydric phenol component constituting the polycarbonate, and Bis -Copolymer polycarbonate in which TMC is 20 to 80 mol% (more preferably 25 to 60 mol%, still more preferably 35 to 55 mol%).

  These special polycarbonates may be used alone or in combination of two or more. Moreover, these can also be mixed and used for the bisphenol A type polycarbonate generally used.

  The production method and characteristics of these special polycarbonates are described in detail in, for example, JP-A-6-172508, JP-A-8-27370, JP-A-2001-55435, and JP-A-2002-117580. ing.

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

  Here, the water absorption of the polycarbonate is a value obtained by measuring the moisture content after being immersed in water at 23 ° C. for 24 hours in accordance with ISO 62-1980 using a disc-shaped test piece having a diameter of 45 mm and a thickness of 3.0 mm. is there. Moreover, Tg (glass transition temperature) is a value calculated | required by the differential scanning calorimeter (DSC) measurement based on JISK7121.

  As the carbonate precursor, carbonyl halide, carbonic acid diester, haloformate or the like is used, and specific examples include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, and the like.

  In producing a polycarbonate resin by interfacial polymerization of the above dihydric phenol and carbonate precursor, a catalyst, a terminal terminator, an antioxidant for preventing the dihydric phenol from being oxidized, etc., as necessary. May be used. The polycarbonate resin of the present invention includes a branched polycarbonate resin copolymerized with a trifunctional or higher polyfunctional aromatic compound, and a polyester carbonate resin copolymerized with an aromatic or aliphatic (including alicyclic) difunctional carboxylic acid. , A copolymer polycarbonate resin copolymerized with a bifunctional alcohol (including alicyclic), and a polyester carbonate resin copolymerized with the bifunctional carboxylic acid and the bifunctional alcohol together. Moreover, the mixture which mixed 2 or more types of the obtained polycarbonate resin may be sufficient.

  The branched polycarbonate resin increases the melt tension of the resin composition of the present invention, and can improve the molding processability in extrusion molding, foam molding and blow molding based on such properties. As a result, a molded product by these molding methods, which is superior in dimensional accuracy, is obtained.

  Examples of the trifunctional or higher polyfunctional aromatic compound used in the branched polycarbonate resin include 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, and 4- {4- [1,1- Trisphenol such as bis (4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol is preferably exemplified. Other polyfunctional aromatic compounds include phloroglucin, phloroglucid, tetra (4-hydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene. And trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, and acid chlorides thereof. Of these, 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are preferable, and 1,1,1-tris (4- Hydroxyphenyl) ethane is preferred.

  The structural unit derived from the polyfunctional aromatic compound in the branched polycarbonate resin is 0 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. 0.03 to 1 mol%, preferably 0.07 to 0.7 mol%, particularly preferably 0.1 to 0.4 mol%.

Further, such a branched structural unit is not only derived from a polyfunctional aromatic compound but also derived without using a polyfunctional aromatic compound, such as a side reaction during a melt transesterification reaction. Also good. The ratio of such a branched structure can be calculated by ¹ H-NMR measurement.

  On the other hand, the aliphatic bifunctional carboxylic acid is preferably α, ω-dicarboxylic acid, and specific examples thereof include sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, icosane diacid. Examples thereof include linear saturated aliphatic dicarboxylic acids such as acids and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. As the bifunctional alcohol, an alicyclic diol is suitable, and examples thereof include cyclohexanedimethanol, cyclohexanediol, and tricyclodecane dimethanol. Further, a polycarbonate-polyorganosiloxane copolymer obtained by copolymerizing polyorganosiloxane units can also be used.

  The component A may be a mixture of two or more of polycarbonates having different dihydric phenol components, polycarbonates containing branched components, various polyester carbonates, polycarbonate-polyorganosiloxane copolymers, and the like. Furthermore, what mixed 2 or more types of polycarbonates from which a manufacturing method differs, a polycarbonate from which a terminal terminator differs, etc. 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.

  As the A component aromatic polycarbonate of the present invention, not only virgin raw materials but also polycarbonate resins regenerated from used products, so-called material-recycled aromatic polycarbonates, can be used. Used products include soundproof walls, glass windows, translucent roofing materials, various glazing materials represented by automobile sunroofs, transparent members such as windshields and automobile headlamp lenses, containers such as water bottles, and optical recording media Etc. are preferable. These do not contain a large amount of additives or other resins, and the desired quality is easily obtained stably. In particular, an automotive headlamp lens, an optical recording medium, and the like are preferred as preferred embodiments because they satisfy the more preferable conditions of the viscosity average molecular weight. In addition, said virgin raw material is a raw material which is not yet used in the market after the manufacture.

The viscosity average molecular weight of the aromatic polycarbonate is preferably 1 × 10 ^{4 to} 5 × 10 ⁴ , more preferably 1.4 × 10 ^{4 to} 3 × 10 ⁴ , and still more preferably 1.8 × 10 ^{4 to} 2.5 ×. 10 is ^4. In the range of 1.8 × 10 ^{4 to} 2.5 × 10 ⁴ , both excellent impact resistance and fluidity are particularly excellent. Most preferably, it is 2.1 × 10 ^{4 to} 2.4 × 10 ⁴ . The viscosity average molecular weight may be satisfied as the whole component A, and includes those satisfying such a range by a mixture of two or more kinds having different molecular weights.

In particular, a polycarbonate resin having a viscosity average molecular weight exceeding the above range (5 × 10 ⁴ ) increases the melt tension of the resin composition of the present invention, and molding in extrusion molding, foam molding and blow molding based on such characteristics. Processability can be improved. Such an improvement effect is even better than the branched polycarbonate.

As a more suitable aspect, the A component is a polycarbonate resin (A-3-1 component) having a viscosity average molecular weight of 7 × 10 ⁴ to 2 × 10 ^{6, and} a polycarbonate resin having a viscosity average molecular weight of 1 × 10 ^{4 to} 3 × 10 ⁴ Polycarbonate resin (A-3 component) consisting of (A-3-2 component) and having a viscosity average molecular weight of 1.6 × 10 ^{4 to} 3.5 × 10 ⁴ (hereinafter, “high molecular weight component-containing polycarbonate resin”) May also be used).

In such a high molecular weight component-containing polycarbonate resin (A-3 component), the molecular weight of the A-3-1 component is preferably 7 × 10 ^{4 to} 3 × 10 ⁵ , more preferably 8 × 10 ⁴ to 2 × 10 ⁵ , preferably ^{1 × 10 5 ~2 × 10 5} , particularly preferably ^{1 × 10 5 ~1.6 × 10 5} . The molecular weight of the A-3-2 component is preferably 1 × 10 ^{4 to} 2.5 × 10 ⁴ , more preferably 1.1 × 10 ^{4 to} 2.4 × 10 ⁴ , and still more preferably 1.2 × 10 ^4. to 2.4 × 10 ^4, particularly preferably ^{1.2 × 10 4 ~2.3 × 10 4} .

  The high molecular weight component-containing polycarbonate resin (component A-3) can be obtained by mixing the components A-3-1 and A-3-2 in various proportions and adjusting them so as to satisfy a predetermined molecular weight range. . Preferably, in 100% by weight of the A-3 component, the A-3-1 component is 2 to 40% by weight and the A-3-2 component is 60 to 98% by weight, more preferably the A-3-1 component is 5 to 20% by weight and the A-3-2 component is 80 to 95% by weight. Usually, the molecular weight distribution of the polycarbonate resin is in the range of 2-3. Therefore, it is preferable that the A-3-1 component and the A-3-2 component of the present invention satisfy the molecular weight distribution range. The molecular weight distribution is represented by the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) calculated by GPC (gel permeation chromatography) measurement. And Mw is based on standard polystyrene conversion.

  In addition, as a method for preparing the A-3 component, (1) a method in which the A-3-1 component and the A-3-2 component 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 for producing the composition so as to satisfy the conditions of one component, and (3) an aromatic polycarbonate resin obtained by the production method (the production method of (2)), a separately produced A-3-1 component and / or Examples thereof include a method of mixing the A-3-2 component.

The viscosity average molecular weight referred to in the present invention is first determined by using an Ostwald viscometer from a solution in which 0.7 g of aromatic polycarbonate is dissolved in 100 ml of methylene chloride at 20 ° C., and the specific viscosity 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 obtained specific viscosity is inserted by the following equation to determine the viscosity average molecular weight M.
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

(B component: core-shell type composite rubber)
The core-shell type composite rubber (component B) of the present invention comprises at least one vinyl in a composite rubber core composed of a specific polyorganosiloxane rubber component and at least one polyalkyl (meth) acrylate rubber component. systems monomer graft polymerized core is a composite rubber-based graft copolymer comprising to form a shell - a shell type composite rubber, absorption appears from 2700 cm ^-1 in its infrared absorption spectrum in the range of 3000 cm ^-1 to the maximum intensity a peak ratio of the maximum intensity b of the absorption peak appearing from 830 cm ^-1 in the range of 780 cm ^-1 (b / a) is in the range of 0.2 to 3.5, preferably 1.3 More preferably, it is 1.4 to 3.1.

Absorption peak appearing from 2700 cm ^-1 in the range of 3000 cm ^-1 is meant the presence of hydrocarbon groups in the component B (alkyl group, alkylene group), the absorption peak appearing from 830 cm ^-1 in the range of 780 cm ^-1 is It means the presence of siloxane bond. Therefore, if the value of b / a is large, it means that the ratio of the siloxane component in the B component is large.

  When the value of b / a is smaller than 0.2, it is impossible to satisfy both a sufficient low temperature impact strength and a sufficient normal temperature impact strength when a molded product having a notch is evaluated. If the value exceeds 3.5, not only will it not be possible to achieve both a sufficient low temperature impact strength and a sufficient impact strength at room temperature when evaluating a molded product having a notch, but also produce itself. However, it becomes difficult due to the structure.

  We have found that b / a in the core-shell type composite rubber (component B) is an important factor in determining the effective addition amount for improving the low temperature impact strength with respect to the aromatic polycarbonate resin. ing.

The ratio of the A component and the B component in the aromatic polycarbonate resin composition of the present invention is such that the content of the B component is d parts by weight with respect to a total of 100 parts by weight of the A component and the B component, and 2700 cm in the infrared absorption spectrum of the B component. ^When the maximum intensity of the absorption peak appearing in the range of ⁻¹ to 3000 cm ⁻¹ is a and the maximum intensity of the absorption peak appearing in the range of 830 cm ⁻¹ to 780 cm ⁻¹ is b, the following relational expression (1)
200 <d ⁴ × (b / a) <800 (1)
Satisfying the following relational expression (2)
200 <d ⁴ × (b / a) <500 (2)
More preferably, the following relational expression (3)
200 <d ⁴ × (b / a) <400 (3)
The most preferable range is the following relational expression (4).
200 <d ⁴ × (b / a) <300 (4)
It is the range which satisfies.

When d ⁴ × (b / a) shows a small value, sufficient low temperature impact strength is not exhibited when a molded product having a notch is evaluated. When d ⁴ × (b / a) shows a large value, when a molded product having a notch is evaluated, sufficient impact strength at normal temperature cannot be obtained, or sufficient low temperature impact strength and sufficient impact strength at normal temperature. Cannot be achieved.

In addition, the measurement of said infrared absorption spectrum was implemented with the following method.
The sample (core-shell type composite rubber) was sandwiched between two KBr plates and pressed with a tablet molding machine. Next, the sample site | part in the plate obtained by pressing was measured with the transmission method using the microscopic infrared absorption spectrum measuring device (Spectrum Spotlight 300 by PerkinElmer Japan Co., Ltd.).

The maximum intensity a of the absorption peak appearing from 2700 cm ^-1 in the infrared absorption spectrum in the range of 3000 cm ^-1, the maximum intensity b ratio of the absorption peak appearing from 830 cm ^-1 in the range of 780 cm ^-1 (b / a ) Is considered to have some relation to the content of the polyorganosiloxane rubber component in the core-shell type composite rubber. Therefore, b / a can be adjusted by increasing or decreasing the content of the polyorganosiloxane rubber component in the core-shell type composite rubber (component B). That is, b / a tends to increase when the content of the polyorganosiloxane rubber component in the core-shell type composite rubber (component B) is increased and decrease when the content is decreased.

When an additive manufacturer develops a resin composition, since the type and amount of additive raw material are known, the information can be reflected in the amount of additive added to the composition.
On the other hand, in the case of a resin producer who develops or produces a product by purchasing an additive or using a modified product, the type and amount of the additive material are often not disclosed. Therefore, there is less information available about the additive than the additive manufacturer, which is disadvantageous in the development of the resin composition. As a countermeasure, the present invention showing a method for increasing the information on the additive by characterizing the additive using the infrared absorption spectrum intensity that can be measured relatively easily and reflecting it in the blending amount, etc. It can be said that it is very useful as a blending technique in the composition.

  The 5% weight reduction temperature of the core-shell type composite rubber (component B) is preferably 280 to 350 ° C, more preferably 290 to 340 ° C, still more preferably 300 to 335 ° C. When the 5% weight loss temperature is outside this range, the performance as an impact modifier becomes insufficient. Such a 5% weight loss temperature is determined by measurement conditions in which the temperature is increased from 23 ° C. in a nitrogen gas atmosphere to 600 ° C. at a temperature increase rate of 20 ° C./min in a TGA measuring apparatus. Although the reason why the 5% weight reduction temperature affects the performance as an impact modifier is not clear in the above, the sample with a too low 5% weight reduction temperature has a molding heat resistance due to the influence of volatile components. It is considered that the degree of crosslinking is insufficient, that is, the rubber elasticity is insufficient, the performance as an impact modifier is considered insufficient, and when the 5% weight loss temperature is too high, the degree of crosslinking is too high. Therefore, the rubber elasticity as an impact modifier is insufficient, and the organic property of the entire sample including the shell is lowered, so the dispersibility in polycarbonate resin is reduced, and the performance as an impact modifier is reduced. Is considered to be insufficient.

  The composite rubber preferably has a structure in which the polyorganosiloxane rubber and the polyalkyl (meth) acrylate rubber are intertwined with each other so that they cannot be separated. When a simple mixture of polyorganosiloxane rubber and polyalkyl (meth) acrylate rubber is used, the effect of improving impact resistance is not sufficient.

  The average particle size of the composite rubber is preferably 0.08 to 0.6 μm. When the average particle size of the composite rubber is less than 0.08 μm, the impact resistance of the resulting resin composition is reduced, and when the average particle size exceeds 0.6 μm, the surface appearance of the molded product of the resin composition is deteriorated. To do. In order to obtain the composite rubber-based graft copolymer used in the present invention, first, various cyclic organosiloxanes having three or more members, for example, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, etc. The polyorganosiloxane rubber latex is prepared by emulsion polymerization using a cross-linking agent and / or a graft crossing agent, and then the alkyl (meth) acrylate monomer, the cross-linking agent and the graft crossing agent are added to the polyorganosiloxane rubber latex. It is obtained by impregnating and polymerizing. Examples of the alkyl (meth) acrylate monomer used herein include alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate, and alkyl acrylates such as hexyl methacrylate and 2-ethylhexyl methacrylate. Although methacrylate is mentioned, it is particularly preferable to use n-butyl acrylate.

  Examples of vinyl monomers to be graft-polymerized on the composite rubber include aromatic vinyl compounds such as styrene and α-methylstyrene; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; methyl methacrylate, 2-ethylxyl methacrylate, and the like. Methacrylic acid ester; acrylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, and the like. These may be used alone or in combination of two or more.

  The ratio of the composite rubber and the vinyl monomer in the core-shell type composite rubber (component B) used in the present invention is based on the weight of the core-shell type composite rubber (component B). It is within the range of 30 to 95% by weight of the synthetic rubber, preferably 40 to 95% by weight and 5 to 70% by weight of the vinyl monomer, preferably 5 to 60% by weight. If the vinyl monomer is less than 5% by weight, poor dispersion of the graft copolymer in the resin composition will occur, and if it exceeds 70% by weight, the effect of improving the impact strength will be reduced.

  The polyorganosiloxane constituting the core-shell type composite rubber (component B) used in the present invention is a polymer containing dimethylsiloxane units as constituent units. Examples of the dimethylsiloxane constituting the polyorganosiloxane include a dimethylsiloxane-based cyclic body having a 3-membered ring or more, and a 3- to 7-membered ring is preferable. Specific examples include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane. These may be used alone or in combination of two or more. Among these, the main component is preferably octamethylcyclotetrasiloxane because the particle size distribution can be easily controlled.

  The polyorganosiloxane preferably contains a vinyl polymerizable functional group-containing siloxane as a constituent component. Here, the vinyl polymerizable functional group-containing siloxane contains a vinyl polymerizable functional group and can be bonded to dimethylsiloxane via a siloxane bond. Among the vinyl polymerizable functional group-containing siloxanes, various alkoxysilane compounds containing vinyl polymerizable functional groups are preferable in consideration of reactivity with dimethylsiloxane. Specifically, β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylethoxydiethylsilane, γ-methacryloyloxypropylethoxydiethoxymethylsilane and δ-methacryloyloxybutyldiethoxymethylsilane and other methacryloyloxysilane, tetramethyltetravinylcyclotetrasiloxane and other vinylsiloxanes, p-vinylphenyldimethoxymethylsilane and other vinylphenylsilanes And γ-mercaptopropyldimethoxymethylsilane, γ-mercaptopropyltrimethoxysilane, etc. Script siloxanes. These vinyl polymerizable functional group-containing siloxanes can be used alone or as a mixture of two or more.

  The polyorganosiloxane may be crosslinked with a siloxane-based crosslinking agent. Examples of the siloxane crosslinking agent include trifunctional or tetrafunctional silane crosslinking agents such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, and tetrabutoxysilane.

There is no restriction | limiting in particular as a manufacturing method of polyorganosiloxane, For example, the following manufacturing methods are employable.
First, a latex is prepared by emulsifying a mixture containing dimethylsiloxane and, if necessary, a vinyl-polymerizable functional group-containing siloxane, or a mixture containing a siloxane-based crosslinking agent with an emulsifier and water. Polymerization is performed at a high temperature using an acid catalyst, and then the acid is neutralized with an alkaline substance to obtain a polyorganosiloxane latex.

  In this production method, as a method for preparing latex, a method using a homomixer that makes fine particles by shearing force by high-speed rotation, a method that mixes by high-speed stirring using a homogenizer that makes fine particles by jet output by a high-pressure generator, etc. Is mentioned. Among these, the method using a homogenizer is a preferable method because the particle size distribution of the polyorganosiloxane latex becomes narrow.

  As a method of mixing the acid catalyst during the polymerization, a method of adding and mixing together with a siloxane mixture, an emulsifier and water, and a method in which latex in which the siloxane mixture is finely divided are dropped into a high-temperature acid aqueous solution at a constant rate. Although the method of mixing etc. is mentioned, Since it is easy to control the particle diameter of polyorganosiloxane, the method of adding and mixing the acid aqueous solution which does not have a micelle formation ability is preferable.

The polymerization temperature is preferably 50 ° C. or higher, and more preferably 70 ° C. or higher. The polymerization time is usually 2 hours or longer, preferably 5 hours or longer when the acid catalyst is mixed with a siloxane mixture, an emulsifier and water to form fine particles for polymerization.
Examples of the alkaline substance added when the polymerization is stopped include caustic soda, caustic potash, sodium carbonate, and the like.

  The emulsifier used in the above production method is not particularly limited as long as it can emulsify dimethylsiloxane, but an anionic emulsifier is preferable. Examples of the anionic emulsifier include sodium alkylbenzene sulfonate and sodium polyoxyethylene nonylphenyl ether sulfate. Among these, sodium alkylbenzene sulfonate and sodium lauryl sulfonate are preferable.

  Examples of the acid catalyst used for polymerization of polyorganosiloxane include sulfonic acids such as aliphatic sulfonic acid, aliphatic substituted benzenesulfonic acid, and aliphatic substituted naphthalenesulfonic acid, and mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid. These acid catalysts are used alone or in combination of two or more. Among these, the use of mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid that do not form micelles can narrow the particle size distribution of the polyorganosiloxane latex, which is further attributed to the emulsifier component in the polyorganosiloxane latex. This is preferable in that the appearance defect of the molded product can be reduced.

  In addition, as the component B in the composition of the present invention, a mixture of the above composite rubber graft copolymer and vinyl polymer may be used. In this case, the vinyl copolymer is graft polymerized as described above. 70 to 100% by weight of one or more monomers selected from the group consisting of aromatic vinyl monomers, vinyl cyanide monomers and (meth) acrylic acid ester monomers similar to vinyl monomers And vinyl monomers copolymerizable therewith, such as those obtained by copolymerizing 30 to 0% by weight of ethylene, vinyl acetate or the like. Two or more of these vinyl copolymers may be used in combination. Particularly preferred as such a composite rubber graft copolymer or a mixture (A) of the composite rubber graft copolymer and vinyl polymer is composite rubber graft copolymer described in JP-A-1-230664. Examples thereof include a polymer or a mixture of the graft copolymer and a vinyl polymer.

(About other additives)
If necessary, the polycarbonate resin composition of the present invention contains, in addition to the polycarbonate resin and the core-shell type composite rubber, 1.0 wt% or less of other additives as a whole, for example, Various flame retardants, anti-drip agents, reinforcing fillers, mold release agents, various stabilizers and coloring materials are added to impart flame retardancy, mechanical strength, and releasability, and to stabilize the molecular weight and hue during molding. Can be used. Examples of such stabilizers include phosphorus stabilizers, hindered phenol stabilizers, ultraviolet absorbers, and light stabilizers.

  However, in order to maintain the original properties of the polycarbonate resin, it is preferable not to add more additives than necessary. In parts where even better mechanical properties are required, it is preferable that the release agent is 0.3% or less and the stabilizer is 0.1% or less as an additive other than the component B. More preferably, the release agent is 0.2% or less, and the stabilizer is 0.05% or less. Even more preferably, the stabilizer is 0.02% or less.

(Flame retardants)
As the flame retardant of the present invention, various compounds conventionally known as flame retardants for aromatic polycarbonate resins can be applied. More preferably, (i) organophosphorous flame retardants (for example, monophosphate compounds, phosphate oligomer compounds, (Ii) Organometallic salt flame retardants (for example, alkali (earth) organic sulfonate metal salts, boric acid metal salt flame retardants, stannic acid metal salt flame retardants, etc.), phosphonate oligomer compounds, phosphonitrile oligomer compounds, And (iii) a silicone flame retardant comprising a silicone compound, and (iv) a halogen flame retardant (eg, brominated epoxy resin, brominated polystyrene, brominated polycarbonate (including oligomers), bromine Polyacrylate, chlorinated polyethylene, etc.) . 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.

  Among these flame retardants, (i) organophosphorous flame retardants, (ii) organometallic salt flame retardants, and (iii) silicone flame retardants composed of silicone compounds are preferred.

(I) Organophosphorus Flame Retardant As the organophosphorus flame retardant of the present invention, an aryl phosphate compound is suitable. Such a phosphate compound is effective in improving flame retardancy, and since the phosphate compound has a plasticizing effect, it is advantageous in that the molding processability of the resin composition of the present invention can be improved although the heat resistance is lowered. is there. As the phosphate compound, various phosphate compounds known as conventional flame retardants can be used, and more preferably, one or more phosphate compounds represented by the following general formula (1) can be mentioned.

（但し上記式中のＸは、二価フェノールから誘導される二価の有機基を表し、Ｒ^１、Ｒ^２、Ｒ^３、およびＲ^４はそれぞれ一価フェノールから誘導される一価の有機基を表し、ｎは０〜５の整数を表す。）

(However, X in the above formula represents a divalent organic group derived from a dihydric phenol, and R ¹ , R ² , R ³ and R ⁴ are each a monovalent organic group derived from a monohydric phenol. And n represents an integer of 0 to 5.)

  The phosphate compound of formula (1) may be a mixture of compounds having different n numbers, and in the case of such a mixture, the average n number is preferably 0.5 to 1.5, more preferably 0.8. To 1.2, more preferably 0.95 to 1.15, and particularly preferably 1 to 1.14.

  Preferable specific examples of the dihydric phenol for deriving X include hydroquinone, resorcinol, bis (4-hydroxydiphenyl) methane, bisphenol A, dihydroxydiphenyl, dihydroxynaphthalene, bis (4-hydroxyphenyl) sulfone, bis (4 -Hydroxyphenyl) ketone and bis (4-hydroxyphenyl) sulfide are exemplified, among which resorcinol, bisphenol A, and dihydroxydiphenyl are preferable.

Preferable specific examples of the monohydric phenol for deriving R ¹ , R ² , R ³ , and R ⁴ include phenol, cresol, xylenol, isopropylphenol, butylphenol, and p-cumylphenol. Are phenol and 2,6-dimethylphenol.

  Such a monohydric phenol may substitute 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 phosphate compounds not substituted with halogen atoms 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 contained, and more preferably, the component of n = 1 in the above formula (4) is 80% by weight or more, more preferably 85% by weight or more, still more preferably Containing 90% by weight or more Show.).

(Ii) 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 these may be used in combination of at least 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 compounding amount 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 100 parts by weight of the total of component A and component B. More preferably, it is 0.008-0.13 weight part. The effect (for example, flame retardancy, antistatic property, etc.) expected by blending the fluorine-containing organic metal salt is exhibited as the preferable range is reached.

  In addition, as an organic metal salt flame retardant other than the 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 such an aromatic sulfonate alkali (earth) metal salt is blended, its content is preferably 0.001 to 1 part by weight, more preferably based on 100 parts by weight of the total of component A and component B, more preferably 0.005 to 0.5 part by weight, more preferably 0.01 to 0.1 part by weight.

(Iii) Silicone Flame Retardant The silicone compound used as the silicone 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 (2) is 10 to 70% by weight (more preferably 15 to 60% by weight).

（式（２）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（２）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 (2), each X independently represents an OH group and a monovalent organic residue having 1 to 20 carbon atoms. N represents an integer of 0 to 5. Further, in formula (2), 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 the silicone compound having a Si—H group, a silicone compound containing at least one of structural units represented by the following general formulas (3) and (4) is preferably exemplified.

（式（３）および式（４）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（５）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（３）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 (3) and formula (4), 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 (5). Α ^{1 to} α ³ each independently represents 0 or 1. m1 represents 0 or an integer of 1 or more, and in formula (3), when m1 is 2 or more, the repeating unit is a plurality of different repeating units. Can take units.)

（式（５）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（５）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 (5), 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 the formula (5), when m2 is 2 or more, the repeating unit may take a plurality of different repeating units.

  In the silicone compound used for the silicone-based flame retardant, examples of the silicone compound having an alkoxy group include at least one compound selected from compounds represented by the general formula (6) and the general formula (7).

（式（６）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 Formula (6), 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 and an 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（７）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 (7), 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. 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 amount of the silicone-based flame retardant is preferably 0.1 to 7 parts by weight, more preferably 0.5 to 4 parts by weight, and still more preferably 1 based on the total of 100 parts by weight of the component A and the component B. ~ 2 parts by weight.

(Fluorine-containing anti-dripping agent)
The fluorine-containing anti-drip agent used in the present invention is a polytetrafluoroethylene having a fibril-forming ability, which prevents melting and dropping during combustion and further improves flame retardancy, and has a fibril-forming ability. Polytetrafluoroethylene is preferably used. Hereinafter, polytetrafluoroethylene may be simply referred to as PTFE. PTFE having a fibril forming ability has a very high molecular weight, and tends to be bonded to each other by an external action such as shearing force to form a fiber. The molecular weight is 1 million to 10 million, more preferably 2 million to 9 million in the number average molecular weight determined from the standard specific gravity. Such PTFE can be used in solid form or in the form of an aqueous dispersion. 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.

  Examples of commercially available PTFE having such fibril forming ability include Teflon (registered trademark) 6J from Mitsui DuPont Fluorochemical Co., Ltd., Polyflon MPA FA500 from Daikin Chemical Industries, and F-201L. . Commercially available aqueous dispersions of PTFE include: Fullon AD-1, AD-936 manufactured by Asahi IC Fluoropolymers Co., Ltd. Fullon D-1, D-2 manufactured by Daikin Industries, Ltd., Mitsui DuPont Fluoro A typical example is Teflon (registered trademark) 30J manufactured by Chemical Corporation.

  As a mixed form of PTFE, (1) a method in which an aqueous dispersion of PTFE and an aqueous dispersion or solution of an organic polymer are mixed and co-precipitated to obtain a co-aggregated mixture (Japanese Patent Application Laid-Open No. 60-258263; (Method described in JP-A-63-154744), (2) A method of mixing an aqueous dispersion of PTFE and dried organic polymer particles (method described in JP-A-4-272957), (3) A method in which an aqueous dispersion of PTFE and an organic polymer particle solution are uniformly mixed, and each medium is simultaneously removed from the mixture (described in JP-A-06-220210, JP-A-08-188653, etc.) And (4) a method of polymerizing monomers forming an organic polymer in an aqueous dispersion of PTFE (a method described in JP-A-9-95583), and (5) A method in which an aqueous dispersion of TFE and an organic polymer dispersion are uniformly mixed, and then a vinyl monomer is further polymerized in the mixed dispersion, and then a mixture is obtained (described in JP-A-11-29679, etc.). Those obtained by (Method) can be used. Commercially available products of PTFE in these mixed forms include “Metablene A3800” (trade name) manufactured by Mitsubishi Rayon Co., Ltd. and “BLENDEX B449” (trade name) manufactured by GE Specialty Chemicals.

  As a ratio of PTFE in the mixed form, 1 to 60% by weight of PTFE is preferable in 100% by weight of the PTFE mixture, and more preferably 5 to 55% by weight. When the ratio of PTFE is within such a range, good dispersibility of PTFE can be achieved.

  The content of the fluorine-containing anti-dripping agent is preferably 0.01 to 2 parts by weight, more preferably 0.05 to 1 part by weight, and still more preferably 0.00 based on the total of 100 parts by weight of the component A and the component B. 1 to 0.6 parts by weight.

(Reinforced filler)
In the present invention, various reinforcing fillers can be included as the F component. Such reinforcing fillers include, for example, talc, wollastonite, mica, clay, montmorillonite, smectite, kaolin, calcium carbonate, glass fiber, glass beads, glass balloon, glass milled fiber, glass flake, carbon fiber, carbon flake. , Carbon beads, carbon milled fiber, metal flake, metal fiber, metal coated glass fiber, metal coated carbon fiber, metal coated glass flake, silica, ceramic particle, ceramic fiber, ceramic balloon, aramid particle, aramid fiber, polyarylate fiber, Examples of the whisker include graphite, potassium titanate whisker, aluminum borate whisker, and basic magnesium sulfate. Of these, silicate fillers such as talc, wollastonite, mica, glass fiber, and glass milled fiber are preferably used. Of these, talc, wollastonite and mica are particularly preferred. These reinforcing fillers may be used alone or in combination of two or more.

  In the present invention, wollastonite having a number average fiber diameter of 0.5 to 5 μm is preferable. The number average fiber diameter is obtained by measuring a total of 1000 fiber diameters randomly extracted from an image observed with an electron micrograph and calculating the number average value. Moreover, the aspect ratio L / D (L: number average fiber length, D: number average fiber diameter) is preferably 5 or more, and more preferably 6 or more. The number average fiber length is calculated by observing wollastonite with an optical microscope or an electron microscope at a magnification at which the entire image of wollastonite can be observed almost completely, and inputting the image into an image analyzer. be able to. Examples of the image analysis apparatus include PIAS-III system manufactured by Pierce. As wollastonite used in the present invention, the loss on ignition at 1000 ° C. is preferably 2% by weight or less, more preferably 1.5% by weight or less, and further preferably 1% by weight or less.

  Furthermore, examples of talc suitable in the present invention include those having an average particle diameter of 5 μm or less. More preferred are those having an average particle size of 3 μm or less, particularly preferably 2 μm or less. An example of the lower limit is 0.05 μm. Here, the average particle diameter of talc refers to D50 (median diameter of particle diameter distribution) measured by an X-ray transmission method which is one of liquid phase precipitation methods. As a specific example of an apparatus for performing such a measurement, Sedigraph 5100 manufactured by Micromeritics Inc. can be cited.

  Talc is preferably used in a granulated form. As a granulation method, there are a case where a binder is used and a case where it is not substantially used. What does not use a binder is more suitable. As a granulation method when a binder is not used, a deaeration compression method (for example, a roller compression with a briquetting machine while deaeration in a vacuum state), a rolling granulation method or an agglomeration granulation method Etc.

  Suitable mica in the present invention may be in the form of a powder having an average particle size of 1 to 80 μm. More preferably, an average particle diameter of 2-50 micrometers can be mentioned. The average particle diameter is a value measured by a laser diffraction / scattering method. When the average particle size is 1 to 80 μm, the flame retardancy is better and the fine dispersion condition in the resin is satisfied. As the thickness of mica, one having a thickness measured by observation with an electron microscope of 0.01 to 1 μm can be used. The thickness is preferably 0.03 to 3 μm. Further, such mica may be surface-treated with a silane coupling agent or the like, and further granulated with a binder such as epoxy, urethane or acrylic, and may be granulated.

  When the reinforcing filler is blended, the thermoplastic resin composition of the present invention can include a surface coating lubricant for suppressing the breakage of the reinforcing filler and improving the thermal stability of the resin composition. The folding inhibitor inhibits adhesion between the matrix resin and the reinforcing filler, reduces stress acting on the reinforcing filler during melt kneading, and suppresses filler folding. The effects of the surface coating lubricant include (I) improved rigidity (increases the filler aspect ratio), (II) improved toughness (easily exerting the toughness of the matrix resin, especially an aromatic polycarbonate resin with particularly good toughness) And (III) improved thermal stability, and (IV) improved conductivity (in the case of a conductive filler). Such a surface coating lubricant includes (i) a lubricant containing a functional group having reactivity with a silicate mineral, and (ii) a lubricant whose surface has been previously coated on a silicate mineral. Accordingly, among the above-mentioned surface treatment agents for silicate minerals, those having a lubricant effect act as a surface coating lubricant. A suitable surface coating lubricant is an acidic group-containing lubricant or an alkylalkoxysilane or alkylhydrogensilane having an alkyl group having 60 or less carbon atoms.

  The number of carbon atoms in the alkyl group of such a silane compound is preferably 4 or more. Furthermore, such carbon number is preferably 20 or less, more preferably 18 or less, and still more preferably 16 or less. The alkyl group in such a silane compound is preferably 1 or 2, particularly preferably 1. Further, preferred examples of the alkoxy group include a methoxy group and an ethoxy group.

  On the other hand, examples of the acidic group in the acidic group-containing lubricant include a carboxyl group, a carboxylic anhydride group, a sulfonic acid group, a sulfinic acid group, a phosphonic acid group, and a phosphinic acid group. Suitable acidic groups are at least one of carboxyl groups, carboxylic anhydride groups, sulfonic acid groups, sulfinic acid groups, phosphonic acid groups and phosphinic acid groups. In particular, a lubricant having at least one acidic group selected from a carboxyl group, a carboxylic acid anhydride group and a phosphonic acid group is preferable, and a lubricant having a carboxyl group and / or a carboxylic acid anhydride group is particularly preferable. In the acidic group-containing lubricant, the concentration of the acidic group is in the range of 0.05 to 10 meq / g, more preferably in the range of 0.1 to 6 meq / g, and still more preferably in the range of 0.5 to 4 meq / g.

  Here, the lubricant is a compound widely known for reducing friction with an apparatus or a mold in plastic molding and obtaining a good mold release, and specifically includes olefin wax, higher fatty acid (for example, Examples thereof include aliphatic carboxylic acids having 16 to 60 carbon atoms, polyalkylene glycols having a polymerization degree of about 10 to 200, silicone oils, and fluorocarbon oils. Examples of olefin waxes include paraffin wax, microcrystalline wax, Fischer-Tropsch wax, and α-olefin polymer as paraffin wax. Examples of polyethylene wax include polyethylene having a molecular weight of about 1,000 to 15,000. Examples include polypropylene. This molecular weight is a weight average molecular weight calculated based on a calibration curve obtained from standard polystyrene in GPC (gel permeation chromatography).

  Examples of a method for bonding carboxyl groups to such a lubricant (excluding higher fatty acids) include, for example, (a) a method of copolymerizing a monomer having a carboxyl group and an α-olefin monomer, and (b) the above The method etc. which couple | bond or copolymerize the compound or monomer which has carboxyl groups with respect to a lubricant can be mentioned.

  In the method (a), a living polymerization method can be employed in addition to radical polymerization methods such as solution polymerization, emulsion polymerization, suspension polymerization, and bulk polymerization. Furthermore, a method of once forming a macromonomer and then polymerizing is also possible. The form of the copolymer can be used as a copolymer of various forms such as an alternating copolymer, a block copolymer, and a tapered copolymer in addition to the random copolymer. In the method (b), a radical generator such as peroxide or 2,3-dimethyl-2,3-diphenylbutane (commonly called “dicumyl”) is added to a lubricant, particularly an olefinic wax, if necessary, and a high temperature. A method of reacting or copolymerizing under the above can be adopted. In this method, a reactive site is thermally generated in the lubricant, and a compound or monomer that reacts with the active site is reacted. Other methods for generating active sites required for the reaction include irradiation with radiation and electron beam, and application of external force by mechanochemical technique. Furthermore, a method in which a monomer that generates an active site required for the reaction is copolymerized in advance in the lubricant. Examples of the active site for the reaction include an unsaturated bond and a peroxide bond, and a method for obtaining the active site includes a nitroxide-mediated radical polymerization method represented by TEMPO.

  Examples of the compound or monomer having a carboxyl group include acrylic acid, methacrylic acid, maleic acid, fumaric acid, maleic anhydride, and citraconic anhydride, and maleic anhydride is particularly preferable.

  As the acidic group-containing lubricant, the carboxyl group is preferably 0.05 to 10 meq / g, more preferably 0.1 to 6 meq / g, still more preferably 0.5 to 4 meq / g per gram of the carboxyl group-containing lubricant. Carboxy group-containing olefin waxes contained in a concentration are preferred. Furthermore, the molecular weight of the olefin wax is preferably 1,000 to 10,000. Furthermore, a copolymer of an α-olefin and maleic anhydride that satisfies the conditions of such concentration and molecular weight is preferable. Such a copolymer can be produced by melt polymerization or bulk polymerization in the presence of a radical catalyst according to a conventional method. Here, as the α-olefin, those having 10 to 60 carbon atoms as an average value can be preferably exemplified. More preferable examples of the α-olefin include those having an average carbon number of 16 to 60, and more preferably 25 to 55.

  Such a surface coating lubricant is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 3 parts by weight, and further 0.05 to 1 part by weight based on 100 parts by weight of the total of component A and component B. preferable.

(About various stabilizers and coloring materials)
In the polycarbonate resin composition of the present invention, various stabilizers and coloring materials can be used to stabilize the molecular weight and hue at the time of molding. Examples of such stabilizers include phosphorus stabilizers, hindered phenol stabilizers, ultraviolet absorbers, and light stabilizers.

(I) Phosphorus stabilizer Examples of the phosphorous stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof, and tertiary phosphine.

  Specifically, as the phosphite compound, for example, triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl Phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, tris (diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di -N-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, dis Allyl pentaerythritol 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 Examples include pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, and dicyclohexyl pentaerythritol 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 phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, Examples thereof include diisopropyl phosphate, and triphenyl phosphate and trimethyl phosphate are preferable.

  Examples of the phosphonite compound include tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenylenedi. 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.

  The phosphorus stabilizers can be used alone or in combination of two or more. Among the phosphorus stabilizers, phosphonite compounds or phosphite compounds represented by the following general formula (8) are preferable.

（式（８）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 (8), 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 (8), more preferred phosphite compounds are distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di). -Tert-butyl-4-methylphenyl) pentaerythritol diphosphite, and bis {2,4-bis (1-methyl-1-phenylethyl) phenyl} pentaerythritol diphosphite.

  Distearyl pentaerythritol diphosphite is commercially available as ADK STAB PEP-8 (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.) and JPP681S (trademark, manufactured by Johoku Chemical Industry Co., Ltd.), and any of them can be used. Bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite is ADK STAB PEP-24G (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.), Alkanox P-24 (trademark, manufactured by Great Lakes), Ultranox. P626 (trademark, manufactured by GE Specialty Chemicals), Doverphos S-9432 (trademark, manufactured by Dover Chemical), and Irgafos126 and 126FF (trademark, manufactured by CIBA SPECIALTY CHEMICALS) are also available. Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite is commercially available as ADK STAB PEP-36 (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.) and can be easily used. Further, bis {2,4-bis (1-methyl-1-phenylethyl) phenyl} pentaerythritol diphosphite is produced by ADK STAB PEP-45 (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.) and Doverphos S-9228 (trademark). , Manufactured by Dober Chemical Co.) and any of them can be used.

  In the present invention, among these phosphorus stabilizers, trimethyl phosphate, which has a high phosphorus content and is effective in molding heat resistance when added in a small amount, is excellent in effect for improving molding heat resistance, and has a relatively low decrease in hydrolysis resistance. 2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite is preferred.

(Ii) Hindered phenolic antioxidant As the hindered phenolic compound, various compounds that are usually blended in a resin 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 compounding amount of the phosphorus stabilizer and the hindered phenol antioxidant is 0.005 to 1 part by weight, preferably 0.01 to 0.3 part by weight, based on the total of 100 parts by weight of component A and component B, respectively. Part.

(Iii) Mold Release Agent The polycarbonate resin composition of the present invention preferably further contains a mold release agent for the purpose of improving productivity during molding and reducing distortion of the molded product. Known release agents can be used. For example, saturated fatty acid ester, unsaturated fatty acid ester, polyolefin wax (polyethylene wax, 1-alkene polymer, etc., which may be modified with a functional group-containing compound such as acid modification), silicone compound, fluorine compound ( And fluorine oil represented by polyfluoroalkyl ether), paraffin wax, beeswax and the like.

  Among these, fatty acid esters are preferable as a release agent. Such fatty acid esters are esters of aliphatic alcohols and aliphatic carboxylic acids. Such an aliphatic alcohol may be a monohydric alcohol or a dihydric or higher polyhydric alcohol. Moreover, as carbon number of this alcohol, it is the range of 3-32, More preferably, it is the range of 5-30. Examples of such monohydric alcohols include dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, tetracosanol, seryl alcohol, and triacontanol. Examples of such polyhydric alcohols include pentaerythritol, dipentaerythritol, tripentaerythritol, polyglycerol (triglycerol to hexaglycerol), ditrimethylolpropane, xylitol, sorbitol, and mannitol. In the fatty acid ester of the present invention, a polyhydric alcohol is more preferable.

  On the other hand, the aliphatic carboxylic acid preferably has 3 to 32 carbon atoms, and particularly preferably an aliphatic carboxylic acid having 10 to 22 carbon atoms. Examples of the aliphatic carboxylic acid include decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid, behenic acid, Mention may be made of saturated aliphatic carboxylic acids such as icosanoic acid and docosanoic acid, and unsaturated aliphatic carboxylic acids such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaenoic acid, and cetreic acid . Among the above, aliphatic carboxylic acids having 14 to 20 carbon atoms are preferable. Of these, saturated aliphatic carboxylic acids are preferred. In particular, stearic acid and palmitic acid are preferred.

  The above aliphatic carboxylic acids such as stearic acid and palmitic acid are usually produced from natural fats and oils such as animal fats such as beef tallow and lard and vegetable oils such as palm oil and sunflower oil. Therefore, these aliphatic carboxylic acids are usually a mixture containing other carboxylic acid components having different numbers of carbon atoms. Accordingly, in the production of the fatty acid ester of the present invention, aliphatic carboxylic acids produced from such natural fats and oils and in the form of a mixture containing other carboxylic acid components, particularly stearic acid and palmitic acid are preferably used.

  The fatty acid ester of the present invention may be either a partial ester or a total ester (full ester). However, partial esters are more preferably full esters because they usually have a high hydroxyl value and tend to induce decomposition of the resin at high temperatures. The acid value in the fatty acid ester of the present invention is preferably 20 or less, more preferably 4 to 20 and even more preferably 4 to 12 from the viewpoint of thermal stability. The acid value can be substantially zero. The hydroxyl value of the fatty acid ester is more preferably in the range of 0.1-30. Further, the iodine value is preferably 10 or less. The iodine value can be substantially zero. These characteristics can be obtained by a method defined in JIS K 0070.

  The content of the release agent is preferably 0.005 to 2 parts by weight, more preferably 0.01 to 1 part by weight, and still more preferably 0.05 to 0 based on the total of 100 parts by weight of the component A and the component B. .5 parts by weight. In such a range, the polycarbonate resin composition has good release properties and release properties. In particular, such an amount of fatty acid ester provides a polycarbonate resin composition having good release properties and roll release properties without impairing good hue.

(Iv) Ultraviolet absorber The polycarbonate resin composition of the present invention may contain an ultraviolet absorber. Since the resin composition of the present invention may be inferior in weather resistance due to the influence of a rubber component or a flame retardant, the incorporation of an ultraviolet absorber is effective to prevent such deterioration.

  Specific examples of the ultraviolet absorber of the present invention include, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4 in the benzophenone series. -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′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxy-5-sodiumsulfoxybenzophenone, bis (5-benzoyl-4-hydro Shi-2-methoxyphenyl) methane, 2-hydroxy -4-n-dodecyloxy benzoin phenone, and 2-hydroxy-4-methoxy-2'-carboxy benzophenone may be exemplified.

  Specific examples of the ultraviolet absorber include, for example, 2- (2-hydroxy-5-methylphenyl) benzotriazole and 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole in the benzotriazole series. 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-chlorobenzotriazol 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-benzoxazin-4-one), and 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimidomethyl) -5-methylphenyl] benzotriazole, and 2- (2'-Hydroxy-5-methacryloxyethylphenyl) -2H-benzotriazole and co-polymerized with the monomer 2 such as a copolymer with a possible vinyl monomer and a copolymer of 2- (2′-hydroxy-5-acryloxyethylphenyl) -2H-benzotriazole with a vinyl monomer copolymerizable with the monomer Examples include polymers having a -hydroxyphenyl-2H-benzotriazole skeleton.

  Specific examples of the ultraviolet absorber include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol and 2- (4) in hydroxyphenyltriazine series. , 6-Diphenyl-1,3,5-triazin-2-yl) -5-methyloxyphenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-ethyloxy Phenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-propyloxyphenol, and 2- (4,6-diphenyl-1,3,5-triazine-2- Yl) -5-butyloxyphenol and the like. 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.

  As the ultraviolet absorber, specifically, in the cyclic imino ester type, for example, 2,2′-p-phenylenebis (3,1-benzoxazin-4-one), 2,2 ′-(4,4′-diphenylene) ) Bis (3,1-benzoxazin-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

  Of these, benzotriazoles and hydroxyphenyltriazines are preferred from the viewpoint of ultraviolet absorbing ability, and cyclic iminoesters and cyanoacrylates are preferred from the viewpoint of heat resistance and hue (transparency). You may use the said ultraviolet absorber individually or in mixture of 2 or more types.

  The content of the ultraviolet absorber is 0.01 to 2 parts by weight, preferably 0.03 to 2 parts by weight, more preferably 0.02 to 1 part by weight, based on a total of 100 parts by weight of component A and component B. More preferably, it is 0.05-0.5 weight part.

(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 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.

Examples of dyes other than the above bluing agents and fluorescent dyes include perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as bitumen, perinone dyes, quinoline dyes, quinacridone And dyes such as dyes, dioxazine dyes, isoindolinone dyes, and phthalocyanine dyes. Furthermore, the resin composition of this invention can mix | blend a metallic pigment, and can also obtain a better metallic color. As the metallic pigment, those having a metal film or a metal oxide film on various plate-like fillers are suitable.
The content of the dye / pigment is preferably 0.00001 to 1 part by weight, more preferably 0.00005 to 0.5 part by weight, based on 100 parts by weight of the total of component A and component B.

(Vi) 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 blending amount of the lactone stabilizer is preferably 0.0005 to 0.05 parts by weight, more preferably 0.001 to 0.03 parts by weight 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 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 the total of 100 parts by weight of the component A and the component B.

(Vii) 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 the 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.

(Viii) 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 such antistatic agents include (1) organic sulfonic acid phosphonium salts such as (1) aryl sulfonic acid phosphonium salts represented by dodecylbenzene sulfonic acid phosphonium salts, and 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 a total of 100 parts by weight of component A and component B. More preferably, it is the range of 1.5-3 weight part.

  Antistatic agents include, for example: (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 sulfonate alkali (earth) metal salt is suitably 0.5 parts by weight or less based on the total of 100 parts by weight of the component A and the component B, preferably 0.001 to 0.3 parts by weight, More preferably, it is 0.005-0.2 weight part. In particular, alkali metal salts such as potassium, cesium, and rubidium are preferable.

  Examples of the antistatic agent include (3) organic sulfonic acid ammonium salts such as alkylsulfonic acid ammonium salt and arylsulfonic acid ammonium salt. The ammonium salt is suitably 0.05 parts by weight or less based on a total of 100 parts by weight of component A and component B. 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 component A and component B.

(Ix) Other Additives The polycarbonate resin composition of the present invention includes thermoplastic resins other than the A and B components, other flow modifiers, antibacterial agents, dispersants such as liquid paraffin, and photocatalytic antifouling agents. Further, a heat ray absorbent and a photochromic agent can be blended.

  As thermoplastic resins other than A component and B component, aromatic polyester resin (polyethylene terephthalate resin (PET resin), polybutylene terephthalate resin (PBT resin), cyclohexanedimethanol copolymerized polyethylene terephthalate resin (so-called PET-G resin), Polyethylene naphthalate resin, polybutylene naphthalate resin, etc.), polymethyl methacrylate resin (PMMA resin), cyclic polyolefin resin, polylactic acid resin, polycaprolactone resin, thermoplastic fluororesin (for example, represented by polyvinylidene fluoride resin) And polyolefin resins (polyethylene resin, ethylene- (α-olefin) copolymer resin, polypropylene resin, propylene- (α-olefin) copolymer resin, etc.). The other thermoplastic resin and rubbery polymer are preferably 20 parts by weight or less, more preferably 10 parts by weight or less, based on the total of 100 parts by weight of component A and component B.

(Manufacture of polycarbonate resin composition)
Arbitrary methods are employ | adopted in order to manufacture the polycarbonate resin composition of this invention. For example, component A, component B and optionally other additives are thoroughly mixed using premixing means such as a V-type blender, Henschel mixer, mechanochemical apparatus, extrusion mixer, etc., and then extruded granulated as necessary. There is a method of granulating such a premixed mixture using a vessel or a briquetting machine, then melt-kneading with a melt-kneader represented by a vent type twin screw extruder, and then pelletizing with a pelletizer.

  In addition, each component can be independently supplied to a melt kneader represented by a vented twin screw extruder, or a part of each component can be premixed and then supplied to the melt kneader independently of the remaining components. The method of doing is also mentioned. Examples of the method of premixing a part of each component include a method in which components other than the component A are premixed in advance and then mixed with the polycarbonate resin of the component A or directly supplied to the extruder.

  As a premixing method, for example, when a component having a powder form is included as the component A, a part of the powder and an additive to be blended are mixed to produce a master batch of the additive diluted with the powder. A method using a master batch can be mentioned. Furthermore, the method etc. which supply one component independently from the middle of a melt extruder are mentioned. 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 extruder.

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.

  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.

  In addition, a master pellet is prepared by previously melting and kneading the A component and the B component with a melt kneader so as to contain the high concentration B component of the present invention, and the master pellet is added to the remaining A component and other additions. The method of mixing with an agent and pelletizing with a melt kneader is mentioned.

  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, sandwich molding, and ultra-high 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.
This provides a molded article of an aromatic polycarbonate resin composition with improved low-temperature impact strength without deteriorating mechanical properties typified by heat resistance and impact strength.

That is, according to the present invention, at least one type of compound is added to the core of the composite rubber composed of the A aromatic polycarbonate resin (component A) and the polyorganosiloxane rubber component and at least one polyalkyl (meth) acrylate rubber component. An aromatic polycarbonate resin composition containing a core-shell type composite rubber (component B), which is a composite rubber-based graft copolymer obtained by graft polymerization of a vinyl monomer to form a shell, comprising component A d parts by weight and the content of the B component to the total 100 parts by weight of B component, the maximum intensity of the absorption peak appearing from 2700 cm ^-1 in the range of 3000 cm ^-1 in the infrared absorption spectrum of the B component a, from 830 cm ^-1 and When the maximum intensity of the absorption peak appearing in the range of 780 cm ⁻¹ is b, the ratio (b / a) between the absorption peak intensities is 0. In the range of 2 to 3.5 and the following relational expression (1)
200 <d ⁴ × (b / a) <800 (1)
A molded article with improved impact strength obtained by melt-molding an aromatic polycarbonate resin composition characterized by satisfying the above requirements is provided.

The impact strength at 23 ° C. of the molded product is preferably 50 kJ / m ² or more, more preferably 53 kJ / m ² or more, and further preferably 55 kJ / m ² or more. The impact strength at −30 ° C. is preferably 40 kJ / m ² or more, more preferably 43 kJ / m ² or more, and still more preferably 45 kJ / m ² or more.

  Specific examples of the molded product in which the resin composition of the present invention is used are suitable for application to internal parts and housings of OA equipment and home appliances. These products include, for example, personal computers, notebook computers, CRT displays, printers, mobile terminals, mobile phones, copiers, fax machines, recording media (CD, CD-ROM, DVD, PD, FDD, etc.) drives, parabolic antennas, electric motors. Tools, VTRs, TVs, irons, hair dryers, rice cookers, microwave ovens, audio equipment, audio equipment such as audio / laser discs / compact discs, lighting equipment, refrigerators, air conditioners, typewriters, word processors, etc. Resin products formed from the thermoplastic resin composition of the present invention can be used for various parts such as these cases. Other resin products include vehicle parts such as lamp sockets, lamp reflectors, lamp housings, instrument panels, center console panels, deflector parts, car navigation parts, and car stereo parts.

  Furthermore, various surface treatments can be performed on the molded article made of the resin composition of the present invention. Surface treatment here refers to a new layer on the surface of resin molded products such as vapor deposition (physical vapor deposition, chemical vapor deposition, etc.), plating (electroplating, electroless plating, hot dipping, etc.), painting, coating, printing, etc. A method used for ordinary 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).

  The aromatic polycarbonate resin composition of the present invention has improved low temperature impact strength of notched members without deteriorating mechanical properties represented by impact strength at normal temperature, heat resistance and surface impact strength. , OA, electrical / electronic devices, automobiles, and other various fields. 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) Impact Strength According to ISO 179, the measurement was performed at 23 ° C. and −30 ° C.
Regarding measurement at −30 ° C., a test piece to be measured was left in a thermostat set at −30 ° C. for 6 hours or more, and immediately after taking out from the thermostat, measurement was performed immediately with a measuring instrument. The measurement was performed in a room adjusted to 23 ° C. and humidity 50%.
(Ii) Deflection temperature under load Deflection temperature under load was measured according to ISO 75-1 and 75-2. The measurement load was 1.80 MPa.

[Examples 1 to 13, Comparative Examples 1 to 12]
Using a vent type twin screw extruder (Kobe Steel Works KTX30) having a diameter of 30 mmφ, the mixture uniformly mixed by shaking the entire bag in a polyethylene bag so as to have the composition shown in Table 1, Pellets were obtained by melting and kneading at a screw rotation speed of 120 rpm, a discharge rate of 15 kg / h, and a vent vacuum of 3 kPa, followed by extrusion. The extrusion temperature was 280 ° C.
The obtained pellets were dried in a hot air circulation dryer at 120 ° C. for 6 hours, and then the cylinder temperature was 320 ° C. and the mold temperature was 60 ° C. by an injection molding machine (Sumitomo Heavy Industries, Ltd .; SG-150U). Under the conditions, a predetermined test specimen for evaluation was obtained.

Each component indicated by symbols in Table 1 is as follows.
(A component)
PC-1 :: aromatic polycarbonate resin [polycarbonate resin powder having a viscosity average molecular weight of 22,500 made from bisphenol A and phosgene by a conventional method, Panlite L-1225WP manufactured by Teijin Chemicals Ltd.]
PC-2: Aromatic polycarbonate resin [polycarbonate resin powder having a viscosity average molecular weight of 19,700 made from bisphenol A and phosgene by a conventional method, Panlite L-1225WX manufactured by Teijin Chemicals Ltd.]

(B component)
MBS-1: Core-shell graft copolymer (Metbrene S-2001 (trade name) manufactured by Mitsubishi Rayon Co., Ltd.); a composite having a structure in which a dimethylsiloxane polymer and an (n-butyl acrylate) polymer are intertwined with each other from 830 cm ^-1 to the maximum intensity a of the absorption peak appearing graft copolymer consisting of a shell 20 wt% of a core 80 wt% of methyl methacrylate is rubber. from 2700 cm ^-1 in an infrared absorption spectrum in the range of 3000 cm ^-1 The ratio (b / a) of the maximum intensity b of the absorption peak appearing in the range of 780 cm ⁻¹ (hereinafter abbreviated as “IR peak ratio”) is 0.39.
MBS-2: Core-shell graft copolymer (S-2100 manufactured by Mitsubishi Rayon Co., Ltd., IR peak ratio 0.43)
MBS-3: Core-shell graft copolymer (SRK-200 manufactured by Mitsubishi Rayon Co., Ltd., IR peak ratio 1.36)
MBS-4: Core-shell graft copolymer (Mitsubishi Rayon Co., Ltd. SRK-120, IR peak ratio 1.51)
MBS-5: Core-shell graft copolymer (SX-005 manufactured by Mitsubishi Rayon Co., Ltd., IR peak ratio 3.00)

(For comparison of B component)
MBS-6: Core-shell graft copolymer (Metbrene C-223A (trade name) manufactured by Mitsubishi Rayon Co., Ltd.); Graft copolymer having a core of 70% by weight of polybutadiene and a shell of styrene and methyl methacrylate, IR peak ratio 0.02)

(Other ingredients)
21 JP: Polyolefin containing no carboxyl group or carboxylic anhydride group (polyethylene “2100JP” manufactured by Mitsui Chemicals, Inc.)
HW: Low molecular weight polyethylene (High wax HW405MP (trade name) manufactured by Mitsui Chemicals, Inc.)
SL: Saturated fatty acid ester release agent (Rikemar SL900 manufactured by Riken Vitamin Co., Ltd.)
TMP: Trimethyl phosphate (Dahachi Chemical Industry Co., Ltd. TMP)
PEP: Phosphite stabilizer comprising bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite (Asahi Denka Kogyo Co., Ltd .: ADK STAB PEP-36, initial acid value 0.9 mgKOH / G, acid value increase value 0 mgKOH / g)

  By adding specific amounts of specific core-shell type composite rubbers according to the present invention from the above table, low temperature impact strength can be increased without deteriorating mechanical properties such as impact strength at normal temperature and deflection temperature under load. You can see that it can be improved.

Claims (8)

Graft polymerization of one or more vinyl monomers on the core of a composite rubber composed of an aromatic polycarbonate resin (component A) and a polyorganosiloxane rubber component and one or more polyalkyl (meth) acrylate rubber components An aromatic polycarbonate resin composition containing a core-shell type composite rubber (component B), which is a composite rubber-based graft copolymer formed by forming a shell, with respect to a total of 100 parts by weight of component A and component B d parts by weight and the content of the B component, the absorption peaks appearing the maximum intensity of the absorption peak appearing from 2700 cm ^-1 in the range of 3000 cm ^-1 in the infrared absorption spectrum of the B component a, from 830 cm ^-1 in the range of 780 cm ^-1 When the maximum intensity of b is b, the ratio of the absorption peak intensities (b / a) is in the range of 0.2 to 3.5. And the following relational expression (1)
200 <d ⁴ × (b / a) <800 (1)
An aromatic polycarbonate resin composition characterized by satisfying: The following relational expression (2)
200 <d ⁴ × (b / a) <500 (2)
The aromatic polycarbonate resin composition according to claim 1, wherein:   The aromatic polycarbonate resin composition according to claim 1 or 2, wherein the ratio (b / a) of both absorption peak intensities is in the range of 1.3 to 3.3.   The B-component is a core-shell type composite rubber comprising a core of a composite rubber having a structure in which a dimethylsiloxane polymer and an (n-butyl acrylate) polymer are intertwined with each other, and a shell of methyl methacrylate. The aromatic polycarbonate resin composition according to any one of the above. The aromatic polycarbonate resin composition according to claim 1, wherein the impact strength at 23 ° C. is 50 kJ / m ² or more, and the impact strength at −30 ° C. is 40 kJ / m ² or more.   The aromatic polycarbonate resin composition according to any one of claims 1 to 5, comprising 5 to 70 parts by weight of a vinyl polymer per 100 parts by weight of the aromatic polycarbonate resin.   The aromatic polycarbonate resin composition according to any one of claims 1 to 6, comprising 0.001 to 0.1 part by weight of a phosphorus stabilizer per 100 parts by weight of the aromatic polycarbonate resin.   A molded article having improved low-temperature impact strength formed from the aromatic polycarbonate resin composition according to any one of claims 1 to 7.