JP2020147709A - Polycarbonate resin composition and molding having dot-like appearance - Google Patents

Abstract

To provide a polycarbonate resin composition having a good molding appearance, and a molding having a dot-like appearance.SOLUTION: A polycarbonate resin composition contains, based on (A) a polycarbonate resin (component A) 100 pts.wt., (B) a synthetic mica powder surface-coated with a silicone binder resin containing a colorant (component B) of 0.01-8 pts.wt. A molding having a dot-like good design is obtained by using the composition.SELECTED DRAWING: None

Description

The present invention relates to a polycarbonate resin composition and a molded article having a dot-like appearance. More specifically, by blending a polycarbonate resin with synthetic mica powder whose surface is coated with a silicone-based binder resin containing a colorant, a polycarbonate resin composition having an excellent appearance of a molded product and molding having an excellent dot-like design can be obtained. It is about goods.

Aromatic polycarbonate resins have excellent mechanical properties, moldability, and thermal properties, and are therefore used in various applications mainly in the fields of OA equipment and electronic and electrical equipment. In recent years, with the thinning and weight reduction in applications such as OA equipment and home appliances, there is an increasing demand for resin materials having high impact, high flame retardancy, and excellent molded appearance. As such a material, Patent Document 1 proposes a resin composition in which a rubber-reinforced styrene resin, talc, and wallastnite are blended with aromatic polycarbonate.

On the other hand, in applications such as OA equipment and home appliances, there is an increasing demand for resin materials that are molded products having an appearance excellent in design. As such a material, Patent Document 2 proposes a thermoplastic resin composition having a stone-grained appearance in which synthetic mica powder whose surface is coated with a resin containing a colorant is blended and dispersed in a thermoplastic resin.

However, at present, an aromatic polycarbonate resin has not been obtained as a polycarbonate resin composition having an excellent appearance of a molded product while maintaining excellent mechanical properties, moldability, and thermal properties.

Japanese Unexamined Patent Publication No. 2006-342199 JP-A-2009-120637

An object of the present invention is to provide a polycarbonate resin composition having an excellent appearance of a molded product and a molded product having a dot-like appearance.

As a result of diligent studies to solve the above problems, the present inventors have formed a polycarbonate resin composition containing a synthetic mica powder whose surface is coated with a silicone-based binder resin containing a colorant. The present invention has been completed by finding that the polycarbonate resin composition has an excellent product appearance, and that the molded product formed from the resin composition has a dot-like appearance.

That is, according to the present invention, the following (configuration 1) to (configuration 9) are provided.
(Structure 1)
(A) Polycarbonate resin (Component A) 100 parts by weight, (B) Polycarbonate resin containing 0.01 to 8 parts by weight of synthetic mica powder (component B) surface-coated with a silicone-based binder resin containing a colorant. Composition.
(Structure 2)
The polycarbonate resin composition according to Composition 1, wherein the synthetic mica powder of component B has an average particle size of 100 to 5000 μm.
(Structure 3)
The polycarbonate resin composition according to Composition 1, which contains 1 to 100 parts by weight of the rubber-reinforced styrene resin (C component) with respect to 100 parts by weight of the polycarbonate resin (A component).
(Structure 4)
The polycarbonate resin composition according to Configuration 1, which contains 1 to 100 parts by weight of an inorganic filler (component D) other than (D) synthetic mica powder with respect to 100 parts by weight of the polycarbonate resin (component A).
(Structure 5)
The polycarbonate resin composition according to Composition 4, wherein the inorganic filler of the D component is at least one inorganic filler selected from the group consisting of talc and wallastonite.
(Structure 6)
The polycarbonate resin composition according to Composition 1, which contains (E) 1 to 100 parts by weight of the flame retardant (E component) with respect to 100 parts by weight of the polycarbonate resin (A component).
(Structure 7)
The polycarbonate resin composition according to Composition 1, which contains 0.01 to 10 parts by weight of the (F) drip inhibitor (F component) with respect to 100 parts by weight of the polycarbonate resin (A component).
(Structure 8)
The polycarbonate resin composition according to Constituent 1, which contains 0.01 to 10 parts by weight of the release agent (G component) with respect to 100 parts by weight of the polycarbonate resin (A component).
(Structure 9)
A molded product having a dot-like appearance formed from the polycarbonate resin composition according to any one of configurations 1 to 8.

The polycarbonate resin composition of the present invention has an excellent appearance of a molded product, and the molded product formed from the resin composition has a dot-like appearance with excellent design. Therefore, the field of OA equipment, the field of electronic and electrical equipment, etc. It is preferably used as a housing material for polycarbonate, and is particularly suitable for housing applications such as mobile phones and tablets.

It is a photograph which shows an example of the dot-like appearance in the molded article of this invention.

The details of the present invention will be described below.
(Component A: Polycarbonate resin)
The polycarbonate resin used in the present invention is obtained by reacting a divalent phenol with a carbonate precursor. Examples of the reaction method include an interfacial polymerization method, a melt transesterification method, a solid phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound.

Typical examples of the dihydric phenol used here are hydroquinone, resorcinol, 4,4'-biphenol, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl). ) Propane (commonly known as 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) Pentan, 4,4'-(p-phenylenediisopropyridene) diphenol, 4,4'-(m-phenylenediisopropyriden) 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) ketone Hydroxyphenyl) ester, bis (4-hydroxy-3-methylphenyl) sulfide, 9,9-bis (4-hydroxyphenyl) fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene. Be done. A preferable divalent phenol is a bis (4-hydroxyphenyl) alkane, and among them, bisphenol A is particularly preferable from the viewpoint of impact resistance, and is widely used.

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

In producing an aromatic polycarbonate resin by interfacial polymerization of the divalent phenol and the carbonate precursor, if necessary, a catalyst, a terminal terminator, and an antioxidant for preventing the dihydric phenol from being oxidized. Etc. may be used. The aromatic polycarbonate resin of the present invention is a branched polycarbonate resin obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound, or a polyester obtained by copolymerizing an aromatic or aliphatic (including alicyclic) bifunctional carboxylic acid. It includes a carbonate resin, a copolymerized polycarbonate resin obtained by copolymerizing a bifunctional alcohol (including an alicyclic type), and a polyester carbonate resin obtained by copolymerizing both the bifunctional carboxylic acid and the bifunctional alcohol. Further, it may be a mixture of two or more of the obtained aromatic polycarbonate resins.

The branched polycarbonate resin can impart drip prevention performance and the like to the resin composition of the present invention. Examples of the trifunctional or higher polyfunctional aromatic compound used in such a branched polycarbonate resin include fluoroglusin, fluorogluside, or 4,6-dimethyl-2,4,6-tris (4-hydrokidiphenyl) hepten-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) Etan, 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, 4- {4-[ 1,1-bis (4-hydroxyphenyl) ethyl] benzene} -α, trisphenol such as α-dimethylbenzylphenol, tetra (4-hydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone, 1, Examples thereof include 4-bis (4,4-dihydroxytriphenylmethyl) benzene, or trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid and their acid chlorides, among which 1,1,1-tris (4-hydroxy) Phenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are preferable, and 1,1,1-tris (4-hydroxyphenyl) ethane is particularly preferable.

The structural unit derived from the polyfunctional aromatic compound in the branched polycarbonate is preferably a total of 100 mol% of the structural unit derived from divalent phenol and the structural unit derived from such a polyfunctional aromatic compound. It is 0.01 to 1 mol%, more preferably 0.05 to 0.9 mol%, still more preferably 0.05 to 0.8 mol%.

Further, particularly in the case of the molten transesterification method, branched structural units may be generated as a side reaction, and the amount of such branched structural units is preferably 100 mol% in total including the structural units derived from divalent phenol. It is preferably 0.001 to 1 mol%, more preferably 0.005 to 0.9 mol%, still more preferably 0.01 to 0.8 mol%. The ratio of such a branched structure can be calculated by 1H-NMR measurement.

The aliphatic bifunctional carboxylic acid is preferably α, ω-dicarboxylic acid. Examples of the aliphatic bifunctional carboxylic acid include linear saturated aliphatic dicarboxylic acids such as sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, and icosandioic acid, and cyclohexanedicarboxylic acid. Such as alicyclic dicarboxylic acid is preferably mentioned. As the bifunctional alcohol, an alicyclic diol is more preferable, and examples thereof include cyclohexanedimethanol, cyclohexanediol, and tricyclodecanedimethanol.

Further, a polycarbonate-polydiorganosiloxane copolymer resin can be used as the polycarbonate resin (component A).

Reaction formats such as the interfacial polymerization method, the molten transesterification method, the carbonate prepolymer solid phase transesterification method, and the ring-opening polymerization method of the cyclic carbonate compound, which are the methods for producing the polycarbonate resin of the present invention, are described in various documents and patent publications. This is a well-known method.

In producing the polycarbonate resin composition of the present invention, the viscosity average molecular weight (M) of the polycarbonate resin is not particularly limited, but is preferably 1.8 × 10 ^{4 to} 4.0 × 10 ⁴ , and more preferably 2. It is 0.0 × 10 ^{4 to} 3.5 × 10 ⁴ , and more preferably 2.2 × 10 ^{4 to} 3.0 × 10 ⁴ . The viscosity-average molecular weight of 1.8 × 10 ⁴ less than the polycarbonate resin may not good mechanical properties are obtained. On the other hand, the resin composition obtained from a polycarbonate resin having a viscosity-average molecular weight exceeds 4.0 × 10 ⁴ is inferior in versatility in that poor flowability during injection molding.

The viscosity average molecular weight referred to in the present invention is first determined by using an Ostwald viscometer from a solution of 0.7 g of polycarbonate in 100 ml of methylene chloride at 20 ° C. for the specific viscosity (η _SP ) calculated by the following formula.
Specific viscosity (η _SP ) = (t-t ₀ ) / t ₀
[T ₀ is the number of seconds for methylene chloride to fall, t is the number of seconds for the sample solution to fall]
From the obtained specific viscosity (η _SP ), the viscosity average molecular weight M is calculated by the following formula.
η _SP / c = [η] + 0.45 × [η] ² c (where [η] is the ultimate viscosity)
[Η] = 1.23 × 10 ^-4 M ^0.83
c = 0.7
The viscosity average molecular weight of the polycarbonate resin in the polycarbonate resin composition of the present invention is calculated as follows. That is, the composition is mixed with 20 to 30 times the weight of methylene chloride to dissolve the soluble component in the composition. Such soluble matter is collected by Celite filtration. The solvent in the resulting solution is then removed. The solid after removing the solvent is sufficiently dried to obtain a solid having a component that dissolves in methylene chloride. From a solution prepared by dissolving 0.7 g of such a solid in 100 ml of methylene chloride, the specific viscosity at 20 ° C. is obtained in the same manner as above, and the viscosity average molecular weight M is calculated from the specific viscosity in the same manner as above.

(Component B: Synthetic mica powder surface-coated with a silicone-based binder resin containing a colorant)
The synthetic mica powder used in the present invention is surface-coated with a silicone-based binder resin containing a colorant.

By using synthetic mica powder surface-coated with a silicone-based binder resin, yellowing is suppressed as compared with the case of using synthetic mica powder surface-coated with an epoxy-based binder resin, so that the color tone is excellent and good. It is possible to obtain a molded product having a dot-like appearance.

Examples of the colorant include inorganic pigments and organic dyes, and there are no particular restrictions as long as they can be colored.

Examples of inorganic pigments include oxide pigments such as carbon black, titanium oxide, zinc white, petals, chromium oxide, iron black, titanium yellow, zinc-iron brown, copper-chromium black, and copper-iron black. Can be mentioned.

Examples of organic dyes such as organic pigments and organic dyes include phthalocyanine dyes; azo-based, thioindigo-based, perylene-based, perylene-based, quinacridone-based, dioxazine-based, isoindolinone-based, and quinophthalone-based condensed polycyclic pigments. Examples thereof include anthraquinone-based, perinone-based, perylene-based, methine-based, quinoline-based, heterocyclic, and methyl-based dyes. These colorants may be used alone or in combination of two or more.

The average particle size of the synthetic mica powder surface-coated with the silicone-based binder resin is preferably 100 to 5000 μm, more preferably 200 to 3000 μm, further preferably 300 to 2000 μm, and even more preferably 400 to 1500 μm. Is particularly preferred. In the above range, the synthetic mica powder is uniformly dispersed in the resin composition, and a molded product having a good dot-like appearance can be obtained. The average particle size is measured by the microtrack laser diffraction method.

The content of synthetic mica powder (component B) surface-coated with a silicone-based binder resin containing (B) a colorant is 0.01 to 8 parts by weight with respect to 100 parts by weight of the polycarbonate resin (component A). Yes, 0.1 to 6 parts by weight is preferable, 0.3 to 5 parts by weight is more preferable, and 0.5 to 4 parts by weight is further preferable. If it is less than the lower limit, a dot-like appearance cannot be obtained, and if it exceeds the upper limit, the color tone and appearance deteriorate.

The polycarbonate resin composition of the present invention can further provide a molded product containing various dyes and pigments and exhibiting various design properties. By blending a fluorescent whitening agent or a fluorescent dye that emits light other than that, it is possible to impart a better design effect that makes the best use of the emitted color. Further, it is also possible to provide a polycarbonate resin composition which is colored with a very small amount of dyeing pigment and has a vivid color development property.

(C component: rubber reinforced styrene resin)
The rubber-reinforced styrene resin preferably used in the present invention is a copolymer obtained by copolymerizing an aromatic vinyl compound with one or more selected from other vinyl monomers and rubbery polymers. .. The proportion of the aromatic vinyl compound in the component is preferably 10% by weight or more, more preferably 30% by weight or more, still more preferably 40 to 90% by weight, and particularly preferably 50 to 80% by weight. The ratio of the aromatic vinyl compound is a ratio in 100% by weight of the total amount of the C component, and when a plurality of polymers are mixed as the C component, it is not necessary to satisfy the suitable conditions for all the polymers. However, the proportion of the aromatic vinyl compound in any of the polymers is preferably 10% by weight or more. Next, a typical monomer compound contained in the styrene resin will be described.

Examples of aromatic vinyl compounds include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, vinylxylene, ethylstyrene, dimethylstyrene, p-tert-butylstyrene, vinylnaphthalene, methoxystyrene, and monobromstyrene. Examples thereof include dibromstyrene, fluorostyrene, tribromstyrene and the like, and styrene is particularly preferable.

As other vinyl monomers copolymerizable with the aromatic vinyl compound, vinyl cyanide compounds and (meth) acrylic acid ester compounds can be preferably mentioned. Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile, and acrylonitrile is particularly preferable.

Specific examples of the (meth) acrylic acid ester compound include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and amyl (meth) acrylate. Hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, etc. Can be mentioned. The notation of (meth) acrylate indicates that it contains both methacrylate and acrylate, and the notation of (meth) acrylic acid ester indicates that it includes both methacrylic acid ester and acrylic acid ester. Methyl methacrylate can be mentioned as a particularly suitable (meth) acrylic acid ester compound.

Examples of other vinyl monomers copolymerizable with aromatic vinyl compounds other than vinyl cyanide compounds and (meth) acrylic acid ester compounds include epoxy group-containing methacrylic acid esters such as glycidyl methacrylate, maleimide, and N-methylmaleimide. Examples thereof include maleimide-based monomers such as N-phenylmaleimide, α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, phthalic acid, and itaconic acid, and their anhydrides.

Examples of the rubbery polymer include polybutadiene, polyisoprene, diene copolymers (for example, random copolymers and block copolymers of styrene / butadiene, acrylonitrile / butadiene copolymers, and (meth) acrylic acid alkyl esters. And butadiene copolymers, etc.), ethylene and α-olefin copolymers (eg, ethylene-propylene random copolymers and block copolymers, ethylene-butene random copolymers and block copolymers, etc.) , Copolymers of ethylene and unsaturated carboxylic acid esters (eg, ethylene-methacrylate copolymers, and ethylene-butyl acrylate copolymers), Copolymers of ethylene and aliphatic vinyl (eg, ethylene-vinyl acetate) Copolymers, etc.), ethylene and propylene and non-conjugated dienter polymers (eg, ethylene, propylene, hexadiene copolymers, etc.), acrylic rubbers (eg, polybutyl acrylate, poly (2-ethylhexyl acrylate), and butyl acrylate) IPN type rubber consisting of a copolymer of and 2-ethylhexyl acrylate), and a silicone-based rubber (for example, polyorganosiloxane rubber, polyorganosiloxane rubber component and polyalkyl (meth) acrylate rubber component; that is, two rubbers. Examples thereof include rubber having a structure in which the components are intertwined with each other so that the components cannot be separated, and IPN type rubber composed of a polyorganosiloxane rubber component and a polyisobutylene rubber component. Of these, polybutadiene, polyisoprene, or a diene-based copolymer in which the effect is more likely to be exhibited is more preferable, and polybutadiene is particularly preferable.

Specific examples of the rubber-reinforced styrene resin include HIPS resin, ABS resin, AES resin, ASA resin, MBS resin, MABS resin, MAS resin, SIS resin, and SBS resin, all of which are easily available. It is possible. Of these, HIPS resin, ABS resin, AES resin, ASA resin, and MBS resin are more preferable.

Among these, ABS resin and MBS resin are particularly preferable. ABS resin has excellent molding processability for thin-walled molded products and also has good impact resistance. MBS resin also has good impact resistance to thin-walled molded products. Particularly favorable properties are exhibited in combination with an aromatic polycarbonate resin.

Here, the AES resin is a copolymer resin mainly composed of acrylonitrile, ethylene-propylene rubber, and styrene, the ASA resin is a copolymer resin mainly composed of acrylonitrile, styrene, and acrylic rubber, and the MABS resin is methyl methacrylate, acrylonitrile, and so on. Copolymer resin mainly composed of butadiene and styrene, MAS resin is copolymer resin mainly composed of methyl methacrylate, acrylic rubber, and styrene, and SIS resin is a block copolymer resin composed mainly of polystyrene and polyisoprene (more than di-block). The SBS resin represents a block copolymer composed of polystyrene and polybutadiene (which may be di-block or higher, and also includes hydrogenated ones).

The rubber-reinforced styrene resin can be used alone or in combination of two or more. For example, the combination of ABS resin and MBS resin is also preferably used in the present invention.

In the ABS resin, the ratio of the diene rubber component in 100% by weight of the ABS resin component (that is, in the total of 100% by weight of the ABS polymer and the AS polymer) is preferably 5 to 80% by weight, more preferably 7 to 70%. By weight%, particularly preferably 10-60% by weight.

In the ABS resin, the rubber particle diameter is preferably 0.05 to 5 μm, more preferably 0.1 to 2.0 μm, still more preferably 0.1 to 1.5 μm in terms of weight average particle diameter. As for the distribution of the rubber particle diameter, either one having a single distribution or one having a plurality of peaks of two or more can be used, and further, in the morphology, the rubber particles form a single phase. Alternatively, it may have a salami structure by containing an occlude phase around the rubber particles.

Further, it has been well known that the ABS resin contains a copolymer of a vinyl cyanide compound and an aromatic vinyl compound that are not grafted on the diene rubber component. The ABS resin may contain a free polymer component generated during such polymerization as described above, and is also a blend of a vinyl compound polymer obtained by separately copolymerizing an aromatic vinyl compound and a vinyl cyanide compound. It may be a polymer.

As described above, the rubber-reinforced styrene resin includes an embodiment in which a rubber component-containing copolymer and a separately polymerized rubber component-free polymer are blended. Such blending may be performed when producing the resin composition of the present invention, or may be performed prior to blending.

Examples of the thermoplastic copolymer (AS copolymer) obtained by copolymerizing a vinyl cyanide compound and an aromatic vinyl compound include those mentioned above, and acrylonitrile is particularly preferable. Examples of the aromatic vinyl compound include the above-mentioned compounds, but styrene and α-methylstyrene are preferable. As the ratio of each component in the AS copolymer, when the whole is 100% by weight, the vinyl cyanide compound is preferably 5 to 50% by weight, more preferably 15 to 35% by weight, and the aromatic vinyl compound is preferable. Is 95 to 50% by weight, more preferably 85 to 65% by weight. Further, these vinyl compounds may be copolymerized with the other copolymerizable vinyl compound, and the content ratio thereof is preferably 15% by weight or less in the AS copolymer. Further, as the initiator, chain transfer agent and the like used in the reaction, various conventionally known ones can be used as needed.

The AS copolymer may be produced by any method such as bulk polymerization, solution polymerization, suspension polymerization, suspension bulk polymerization, and emulsion polymerization, but it is preferably bulk polymerization. Further, the copolymerization method may be either one-stage copolymerization or multi-stage copolymerization. The reduction viscosity of the AS copolymer is such that the reduction viscosity (30 ° C.) determined by the method described below is 0.2 to 1.0 dl / g, more preferably 0.3 to 0.7 dl / g. Is.

The reduced viscosity was measured by precisely weighing 0.25 g of the AS copolymer and dissolving it in 50 ml of dimethylformamide over 2 hours in an environment of 30 ° C. using an Ubbelohde viscometer. The viscometer used has a solvent flow time of 20 to 100 seconds. The reduced viscosity is calculated by the following formula from the number of seconds of solvent flowing down (t ₀ ) and the number of seconds of solution flowing down (t).
Reduced viscosity (η _sp / C) = {(t / t ₀ ) -1} / 0.5

The ratio of the free AS copolymer can be obtained by dissolving the ABS copolymer in a good solvent of the AS copolymer such as acetone and collecting the ABS copolymer from the soluble component. On the other hand, the insoluble matter (gel) becomes a net ABS copolymer.

The ratio of vinyl cyanide compound and aromatic vinyl compound grafted to the diene rubber component in the ABS copolymer (ratio of the weight of the graft component to the weight of the diene rubber component), that is, the graft ratio (% by weight) is 20. It is preferably ~ 200%, more preferably 20-80%.

Such ABS resin may be produced by any method such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. More preferred is an ABS resin produced by the massive polymerization method. Further, as such a massive polymerization method, the continuous massive polymerization method (so-called Toray method) described in Chemical Engineering Vol. 48, No. 6, p. 415 (1984) and Chemical Engineering Vol. 53, No. 6, p. 423 (1989) are typically used. ) Is exemplified by the continuous massive polymerization method (so-called Mitsui Toatsu method). Any ABS resin is preferably used as the ABS resin. Further, the copolymerization method may be one-step copolymerization or multi-step copolymerization.

In the MBS resin, the ratio of the diene rubber component to 100% by weight of the MBS resin component is preferably 30 to 90% by weight, more preferably 40 to 85% by weight, and particularly preferably 50 to 80% by weight.

In the MBS resin, the rubber particle diameter is preferably 0.05 to 2 μm, more preferably 0.1 to 1.0 μm, still more preferably 0.1 to 0.5 μm in terms of weight average particle diameter. As the distribution of the rubber particle size, either one having a single distribution or one having a plurality of peaks of two or more peaks can be used. As the MBS resin, those produced by emulsion polymerization can be preferably used.

It is preferable to contain 1 to 100 parts by weight of the rubber-reinforced styrene resin (C component) with respect to 100 parts by weight of the polycarbonate resin (A component), and more preferably 5 to 80 parts by weight. It is more preferably contained in an amount of 10 to 50 parts by weight, particularly preferably 15 to 40 parts by weight. When the content of the rubber-reinforced styrene resin is in the above range, it has good impact resistance and excellent molding processability.

(Component D: Inorganic filler other than synthetic mica powder)
In the present invention, an inorganic filler other than synthetic mica powder can be preferably used. Inorganic fillers include talc, wallastonite, calcium carbonate, glass fiber, glass beads, glass balloons, glass milled fiber, glass flakes, carbon fibers, carbon flakes, carbon beads, carbon milled fibers, graphite, carbon nanotubes, metals. Flake, metal fiber, metal coated glass fiber, metal coated carbon fiber, metal coated glass flake, silica, metal oxide particles, metal oxide fiber, metal oxide balloon, and various whiskers (potassium titanate whisker, aluminum borate whisker) , And basic magnesium sulfate, etc.) are exemplified. Among them, at least one inorganic filler selected from the group consisting of talc and wallastonite is preferably used from the viewpoint of mechanical strength and appearance of the molded product.

The talc, the chemical compositional a hydrated magnesium silicate, is generally represented by the chemical formula _{4SiO 2 · 3MgO · 2H 2 O} , is usually scaly particles having a layered structure and compositionally the the SiO ₂ 56 to 65 wt%, the MgO 28 to 35 wt%, and a _{H 2} O about 5 wt%. Fe ₂ O ₃ is 0.03 to 1.2% by weight, Al ₂ O ₃ is 0.05 to 1.5% by weight, Ca O is 0.05 to 1.2% by weight, and K ₂ O is other small amount components. Contains 0.2% by weight or less, Na ₂ O contains 0.2% by weight or less, and the like. The particle size of talc has an average particle size of 0.1 to 15 μm (more preferably 0.2 to 12 μm, still more preferably 0.3 to 10 μm, particularly preferably 0.5 to 5 μm) measured by the precipitation method. It is preferably in the range. Further, it is particularly preferable to use talc having a bulk density of 0.5 (g / cm ³ ) or more as a raw material. The average particle size of talc refers to D50 (median diameter of particle size distribution) measured by the X-ray transmission method, which is one of the liquid phase precipitation methods. Specific examples of the device for performing such measurement include Sedigrap 5100 manufactured by Micromeritix.

There are no particular restrictions on the manufacturing method for crushing talc from rough stones, and axial flow milling methods, annular milling methods, roll milling methods, ball milling methods, jet milling methods, container rotary compression shear milling methods, etc. are used. can do. Further, the talc after crushing is preferably classified by various classifiers and has a uniform particle size distribution. There are no particular restrictions on the classifiers, including impactor-type inertial force classifiers (variable impactors, etc.), Coanda effect-based inertial force classifiers (elbow jets, etc.), and centrifugal field classifiers (multi-stage cyclone, microplex, dispersion separator, etc.). , Accucut, turboclassifier, turboplex, micron separator, superseparator, etc.) and the like. Further, the talc is preferably in an aggregated state in terms of its handleability and the like, and such a production method includes a method by degassing compression, a method of compressing using a sizing agent and the like. In particular, the degassing compression method is preferable because it is simple and does not mix unnecessary sizing agent resin components into the resin composition of the present invention.

The fiber diameter of wallastonite is preferably 0.1 to 10 μm, more preferably 0.1 to 5 μm, and even more preferably 0.1 to 3 μm. The aspect ratio (average fiber length / average fiber diameter) is preferably 3 or more. The upper limit of the aspect ratio is 30 or less. Here, the fiber diameter is determined by observing the reinforcing filler with an electron microscope, determining the individual fiber diameters, and calculating the number average fiber diameter from the measured values. An electron microscope is used because it is difficult for an optical microscope to accurately measure the size of a target level. For the fiber diameter, the filler to be measured for the fiber diameter is randomly extracted from the image obtained by observation with an electron microscope, the fiber diameter is measured near the center, and the number average fiber is obtained from the obtained measured value. Calculate the diameter. The magnification of observation is about 1000 times, and the number of measurements is 500 or more (600 or less is suitable for work). On the other hand, in the measurement of the average fiber length, the filler is observed with an optical microscope, the individual lengths are obtained, and the number average fiber length is calculated from the measured values. Observation with a light microscope begins with preparing a sample that is dispersed so that the fillers do not overlap very much. The observation is performed under the condition of 20 times the objective lens, and the observed image is captured as image data in a CCD camera having about 250,000 pixels. The fiber length of the obtained image data is calculated by using an image analyzer and using a program for obtaining the maximum distance between two points of the image data. Under such conditions, the size per pixel corresponds to a length of 1.25 μm, and the number of measurements is 500 or more (600 or less is suitable for work).

In order to fully reflect the original whiteness of wallastnite in the resin composition, iron mixed in the raw material ore and iron mixed in due to wear of the equipment when crushing the raw material ore are removed as much as possible by a magnetic separator. Is preferable. By such magnetic separator treatment, the iron content in wallastnite is preferably 0.5% by weight or less in terms of Fe ₂ O ₃ .

Silicate minerals (more preferably mica, talc, wallastonite) are preferably not surface treated, but are surface treated with various surface treatment agents such as silane coupling agents, higher fatty acid esters, and waxes. May be. Further, it may be granulated with a sizing agent such as various resins, higher fatty acid esters, and waxes to form granules.

It is preferable that 1 to 100 parts by weight of an inorganic filler (D component) other than (D) synthetic mica powder is contained with respect to 100 parts by weight of the polycarbonate resin (A component), and 5 to 80 parts by weight is contained. More preferably, it is further preferably contained in an amount of 10 to 60 parts by weight, and particularly preferably 20 to 50 parts by weight. When the content of the inorganic filler other than the synthetic mica powder is in the above range, it has good mechanical properties and a molded product appearance.

(E component: flame retardant)
A flame retardant can be preferably used in the present invention. As the flame retardant, a phosphoric acid ester, an alkali sulfonic acid (earth) metal salt, a silicone compound or the like, which are known to exhibit flame retardancy with respect to aromatic polycarbonate, can be used.

As the phosphoric acid ester used as a flame retardant, various phosphoric acid esters known to exhibit flame retardancy with respect to aromatic polycarbonate can be used. Above all, it is more preferably represented by the following general formula (III). In the following general formula (III), the aryl group means a residue excluding one hydrogen atom of the benzene ring of the aromatic compound. It is preferably a residue obtained by removing one hydrogen atom from the benzene ring of the aromatic hydrocarbon. Examples of the aryl group include a phenyl group, a tolyl group, a xsilyl group, a biphenylyl group, and a naphthyl group.

(Here, R1, R2, R3 and R4 are each independently an aryl group having 6 to 12 carbon atoms, R5 and R6 each independently represent a methyl group or a hydrogen atom, and R7 and R8 represent a methyl group, m1. And m2 independently represent integers 0 to 2, a, b, c and d are independently 0 or 1, and n is an integer from 1 to 5 respectively.)

As the phosphoric acid ester, preferably in general formula (III), m1 and m2 are 0, a, b, c, and d are 1, R1, R2, R3, and R4 are phenyl groups, and R5 and R6 are methyl groups. It is an aspect. Since the phosphoric acid ester containing bisphenol A bis (diphenyl phosphate) as a main component has a high phosphorus content, the resin composition containing the phosphoric acid ester has good flame retardancy and good fluidity during molding. Further, since such a phosphoric acid ester has good hydrolysis resistance due to its structure, the resin composition containing it is also excellent in long-term quality retention.

A more suitable phosphoric acid ester as a flame retardant is the above general formula (III) having an acid value of 0.2 mgKOH / g or less, and a phosphoric acid ester compound represented by the following general formula (IV) (hereinafter referred to as “”. The content (sometimes referred to as "half ester") is 1.5% by weight or less.

(Here, R1 and R2 are independently aryl groups having 6 to 12 carbon atoms, R5 and R6 each independently represent a methyl group or a hydrogen atom, R7 and R8 represent a methyl group, and m1 and m2 are respectively. It independently indicates an integer of 0 to 2, and a and b are independently 0 or 1, respectively.)

The acid value of the phosphoric acid ester is more preferably 0.15 mgKOH / g or less, further preferably 0.1 mgKOH / g or less, and particularly preferably 0.05 mgKOH / g or less. The lower limit of the acid value can be substantially 0, and practically 0.01 mgKOH / g or more is preferable. On the other hand, the content of the half ester is more preferably 1.1% by weight or less, further preferably 0.9% by weight or less. As the lower limit, 0.1% by weight or more is practically preferable, and 0.2% by weight or more is more preferable. When the acid value exceeds 0.2 mgKOH / g, or when the half ester content exceeds 1.5% by weight, the thermal stability during molding becomes inferior, and the resin composition accompanies the decomposition of the aromatic polycarbonate. The hydrolysis resistance of the product is reduced.

The phosphate ester is preferably a component having a degree of condensation n in 100% by weight of 0.1 to 3% by weight, more preferably 0.5 to 2.5% by weight, and n = 1. Component 85-98.5% by weight, more preferably 89.5-98.5% by weight, n = 2 component 1-9% by weight, more preferably 1-7% by weight, and n ≧ 3 component 1. The weight average degree of condensation N is 1.01 to 1.10, preferably 1.01 to 1, which comprises 5% by weight or less, more preferably 1% by weight or less, and is calculated by excluding the component of n = 0. It is .09, more preferably 1.01 to 1.07. The B component having such a distribution is excellent in both heat resistance and impact resistance of the resin composition. In addition, each of the above n components means a component synthesized from a predetermined divalent phenol and monovalent phenol, and does not include reaction by-products and the like. For example, when phenol is used as monovalent phenol, the component of n = 0 is triphenyl phosphate.

The alkali sulfonic acid (earth) metal salt used as a flame retardant is a metal salt of perfluoroalkyl sulfonic acid and alkali metal or alkaline earth metal, or aromatic sulfonic acid and alkali metal or alkaline earth metal salt. Refers to the metal salt of.

Examples of the alkali metal constituting the metal salt include lithium, sodium, potassium, rubidium and cesium, and examples of the alkaline earth metal include beryllium, magnesium, calcium, strontium and barium. More preferably, it is an alkali metal. Among such alkali metals, rubidium and cesium are preferable when the demand for transparency is higher, but they are not versatile and difficult to purify, which may result in a disadvantage in terms of cost. is there. On the other hand, although it is advantageous in terms of cost and flame retardancy, lithium and sodium may be disadvantageous in terms of transparency. In consideration of these, the alkali metal in the alkali metal sulfonic acid salt can be used properly, but in all respects, the potassium sulfonic acid salt having an excellent balance of characteristics is the most suitable. Such potassium salt and sulfonic acid alkali metal salt composed of other alkali metals can also be used in combination.

Specific examples of the alkali metal salt of perfluoroalkyl sulfonic acid include potassium trifluoromethanesulfonate, potassium perfluorobutanesulfonate, potassium perfluorohexanesulfonate, potassium perfluorooctanesulfonate, sodium pentafluoroethanesulfonate, and perfluoro. Sodium butane sulfonate, sodium perfluorooctane sulfonate, lithium trifluoromethanesulfonate, lithium perfluorobutane sulfonate, lithium perfluoroheptane sulfonate, cesium trifluoromethanesulfonate, cesium perfluorobutane sulfonate, perfluorooctane sulfonic acid Examples thereof include cesium, cesium perfluorohexanesulfonate, rubidium perfluorobutanesulfonate, and rubidium perfluorohexanesulfonate, and these can be used alone or in combination of two or more. Here, the number of carbon atoms of the perfluoroalkyl group is preferably in the range of 1 to 18, more preferably in the range of 1 to 10, and even more preferably in the range of 1 to 8. Of these, potassium perfluorobutane sulfonate is particularly preferable.

Specific examples of the aromatic sulfonic acid alkali (earth) metal salt include, for example, diphenylsulfide-4,4'-disodium disulfonate, diphenylsulfide-4,4'-dipotassium disulfonate, potassium 5-sulfoisophthalate, and the like. Sodium 5-sulfoisophthalate, polysodium polyethylene terephthalate polysulfonate, calcium 1-methoxynaphthalene-4-sulfonate, disodium 4-dodecylphenyl ether disulfonate, poly (2,6-dimethylphenylene oxide) polysodium polysulfonate , Poly (1,3-phenylene oxide) poly sulfonate polysodium, poly (1,4-phenylene oxide) poly sulfonate polysodium, poly (2,6-diphenylphenylene oxide) poly sulfonate polypotassium, poly (2-fluoro-) 6-Butylphenylene oxide) Lithium polysulfonate, potassium benzenesulfonate sulfonate, sodium benzenesulfonate, strontium benzenesulfonate, magnesium benzenesulfonate, dipotassium p-benzenedisulfonate, dipotassium naphthalene-2,6-disulfonate, biphenyl -3,3'-Calcium disulfonate, sodium diphenylsulfon-3-sulfonate, potassium diphenylsulfon-3-sulfonate, diphenylsulfon-3,3'-dipotassium disulfonate, diphenylsulfon-3,4'-disulfonic acid Dipotassium, α, α, α-sodium trifluoroacetophenone-4-sulfonate, dipotassium benzophenone-3,3′-disulfonate, disophene-2,5-disulfonate, dipotassium thiophene-2,5-disulfonate , Calcium thiophene-2,5-disulfonate, sodium benzothiophene sulfonate, potassium diphenylsulfoxide-4-sulfonate, formalin condensate of sodium naphthalene sulfonate, formalin condensate of sodium anthracene sulfonate, etc. Can be done. Among these aromatic sulfonic acid alkali (earth) metal salts, potassium salts are particularly preferable.

Silicone compounds used as flame retardants are compounds that have a siloxane bond and improve flame retardancy through a chemical reaction during combustion, and various compounds that have been conventionally proposed as flame retardants for aromatic polycarbonate resins. Can be used. The silicone compound imparts a flame-retardant effect to the polycarbonate resin by forming a structure by itself or by combining with a component derived from the resin at the time of combustion, or by a reduction reaction at the time of forming the structure. It is considered. Therefore, it preferably contains a highly active group in such a reaction, and more specifically, it contains a predetermined amount of at least one group selected from an alkoxy group and a hydrogen (that is, Si—H group). preferable. The content ratio of such groups (alkoxy group, Si—H group) is preferably in the range of 0.1 to 1.2 mol / 100 g, more preferably in the range of 0.12 to 1 mol / 100 g, and 0.15 to 0. The range of 6 mol / 100 g is more preferable. Such a ratio can be obtained by measuring the amount of hydrogen or alcohol generated per unit weight of the silicone compound by the alkaline 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 formed by arbitrarily combining four types of siloxane units shown below. That is,
M unit: (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 , (CH ₃ ) ₂ (C ₆ H ₅ ) SiO _1/2 , (CH ₃ ) (C ₆ H ₅ ) (CH ₂ = CH) SiO _{1/2 and} other monofunctional siloxane units,
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 unit, 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. Trifunctional siloxane unit,
O unit: A tetrafunctional siloxane unit represented by SiO ₂ .

Specifically, the structure of the silicone-based compound is expressed as 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 , D _n T _p Q _q . Among these, the preferred structures of the silicone compounds are M _m D _n , M _m T _p , M _m D _n T _p , M _m D _n Q _q , and more preferable structures are M _m D _n or M _m D _n. It is T _p .

Here, the coefficients m, n, p, and q in the demonstrative formula are integers of 1 or more representing the degree of polymerization of each siloxane unit, and the total of the coefficients in each demonstrative formula is the average degree of polymerization of the silicone compound. .. The 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 more suitable the range, the better the flame retardancy. Further, as will be described later, the silicone compound containing a predetermined amount of aromatic groups is also excellent in transparency. 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. ..

Further, the silicone compound may be linear or have a branched structure. The organic residue bonded to the silicone atom is preferably an organic residue having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms. Specific examples of such organic residues include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group and decyl group, cycloalkyl groups such as cyclohexyl group, and aryl groups such as phenyl group and tolyl group. Groups and aralkyl groups can be mentioned. More preferably, it is an alkyl group having 1 to 8 carbon atoms, 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, it is preferable that the silicone compound contains an aryl group because it can provide an aromatic polycarbonate resin composition having excellent flame retardancy and more transparency. More preferably, the proportion (amount of aromatic group) containing the aromatic group represented by the following general formula (V) is preferably 10 to 70% by weight (more preferably 15 to 60% by weight).

(In formula (V), 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, n is 2 in formula (V). In the above cases, different types of X can be taken.)

The silicone-based compound may contain a reactive group in addition to the Si—H group and the alkoxy group, and the reactive groups include, for example, an amino group, a carboxyl group, an epoxy group, a vinyl group, a mercapto group, and a methacryloxy. Examples include groups.

It is preferable to contain 1 to 100 parts by weight, and more preferably 5 to 70 parts by weight of the (E) flame retardant (E component) with respect to 100 parts by weight of the polycarbonate resin (A component). It is more preferably contained in an amount of about 50 parts by weight, particularly preferably 20 to 40 parts by weight. When the content of the flame retardant is in the above range, it has good flame retardancy and mechanical properties.

(F component: anti-drip agent)
The polycarbonate resin composition of the present invention can contain a drip inhibitor as the F component. By containing this drip inhibitor, good flame retardancy can be achieved without impairing the physical properties of the molded product.

Examples of the drip inhibitor include fluoropolymers having a fibril-forming ability, and examples of such polymers include polytetrafluoroethylene and tetrafluoroethylene-based copolymers (for example, tetrafluoroethylene / hexafluoropropylene copolymers, etc.). Etc.), partially fluorinated polymers as shown in US Pat. No. 4,379,910, polycarbonate resins produced from fluorinated diphenols, and the like. Of these, polytetrafluoroethylene (hereinafter sometimes referred to as PTFE) is preferable.

The molecular weight of PTFE having a fibril-forming ability has an extremely high molecular weight, and exhibits a tendency to bond PTFE to each other to form a fibrous form due to an external action such as shearing force. Its molecular weight is 1 million to 10 million, more preferably 2 million to 9 million in the number average molecular weight obtained from the standard specific gravity. As the PTFE, not only a solid form but also an aqueous dispersion form can be used. Further, the PTFE having such a fibril-forming ability improves the dispersibility in the resin, and it is also possible to use a PTFE mixture in a mixed form with another resin in order to obtain better flame retardancy and mechanical properties. is there.

Examples of commercially available PTFE products having such a fibril-forming ability include Teflon (registered trademark) 6J of Mitsui-DuPont Fluorochemical Co., Ltd., Polyflon MPA FA500 and F-201L of Daikin Industries, Ltd. and the like. Commercially available aqueous dispersions of PTFE include Fluon AD-1, AD-936 manufactured by Asahi Icy Fluoropolymers Co., Ltd., Fluon D-1 and D-2 manufactured by Daikin Industries, Ltd., and Mitsui DuPont Fluoro. Teflon (registered trademark) 30J manufactured by Chemical Co., Ltd. can be mentioned as a representative.

Examples of the mixed form of PTFE include (1) a method of mixing an aqueous dispersion of PTFE and an aqueous dispersion or solution of an organic polymer and co-precipitating to obtain a coaggregating mixture (Japanese Patent Laid-Open No. 60-258263). (Method described in JP-A-63-154744, etc.), (2) Method of mixing an aqueous dispersion of PTFE and dried organic polymer particles (method described in JP-A-4-272957). , (3) A method of uniformly mixing an aqueous dispersion of PTFE and an organic polymer particle solution and simultaneously removing each medium from such a mixture (Japanese Patent Laid-Open No. 06-220210, Japanese Patent Application Laid-Open No. 08-188653, etc.). The method described), (4) a method for polymerizing a monomer forming an organic polymer in an aqueous dispersion of PTFE (method described in JP-A-9-95583), and (5) PTFE. A method of uniformly mixing an aqueous dispersion and an organic polymer dispersion, further polymerizing a vinyl-based monomer in the mixed dispersion, and then obtaining a mixture (method described in JP-A-11-29679). Can be used as obtained by. Examples of commercially available products of these mixed forms of PTFE include "Metabrene A3800" (trade name) manufactured by Mitsubishi Rayon Co., Ltd. and "BLENDEX B449" (trade name) manufactured by GE Specialty Chemicals.

The proportion of PTFE in the mixed form is preferably 1 to 60% by weight, more preferably 5 to 55% by weight, based on 100% by weight of the PTFE mixture. When the proportion of PTFE is in such a range, good dispersibility of PTFE can be achieved. The ratio of the F component indicates the amount of the net anti-drip agent, and in the case of the mixed form of PTFE, it indicates the net amount of PTFE.

It is preferable that 0.01 to 10 parts by weight of (F) drip inhibitor (F component) is contained with respect to 100 parts by weight of (A) polycarbonate resin (A component), and 0.1 to 5 parts by weight is contained. Is more preferable, and it is more preferably contained in an amount of 0.3 to 3 parts by weight, and particularly preferably contained in an amount of 0.5 to 2 parts by weight. When the content of the drip inhibitor is in the above range, excellent flame retardancy and surface appearance of the molded product are good.

The styrene-based monomer used in the organic polymer used in the polytetrafluoroethylene-based mixture is composed of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a halogen. Styrene that may be substituted with one or more groups selected from the group, such as ortho-methylstyrene, meta-methylstyrene, para-methylstyrene, dimethylstyrene, ethyl-styrene, para-tert-butylstyrene, methoxy Examples include, but are not limited to, styrene, fluorostyrene, monobromostyrene, dibromostyrene, and tribromostyrene, vinylxylene, vinylnaphthalene. The styrene-based monomer can be used alone or in combination of two or more types.

The acrylic monomer used in the organic polymer used in the polytetrafluoroethylene-based mixture contains a (meth) acrylate derivative which may be substituted. Specifically, the acrylic monomer is composed of one or more groups selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group, and a glycidyl group. May be substituted (meth) acrylate derivatives such as (meth) acrylonitril, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, hexyl. (Meta) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate and glycidyl (meth) ) Maleimides which may be substituted with an acrylate, an alkyl group having 1 to 6 carbon atoms, or an aryl group, for example, maleimide, N-methyl-maleimide and N-phenyl-maleimide, maleic acid, phthalic acid and itaconic acid are exemplified. However, it is not limited to these. The acrylic monomer can be used alone or in combination of two or more types. Of these, (meth) acrylonitrile is preferred.

The amount of the acrylic monomer-derived unit contained in the organic polymer used for the coating layer is preferably 8 to 11 parts by weight, more preferably 8 to 10 parts by weight, based on 100 parts by weight of the styrene-based monomer-derived unit. Parts, more preferably 8-9 parts by weight. If the amount of the acrylic monomer-derived unit is less than 8 parts by weight, the coating strength may be lowered, and if it is more than 11 parts by weight, the surface appearance of the molded product may be deteriorated.

The residual water content of the polytetrafluoroethylene-based mixture is preferably 0.5% by weight or less, more preferably 0.2 to 0.4% by weight, still more preferably 0.1 to 0.3% by weight. Is. If the residual water content is more than 0.5% by weight, the flame retardancy may be adversely affected.

In the process of producing a polytetrafluoroethylene-based mixture, a coating layer containing one or more monomers selected from the group consisting of styrene-based monomers and acrylic monomers is branched in the presence of an initiator. It involves forming on the outside of polytetrafluoroethylene. Further, after the step of forming the coating layer, the residual water content is dried to 0.5% by weight or less, preferably 0.2 to 0.4% by weight, more preferably 0.1 to 0.3% by weight. It is preferable to include steps. The drying step can be performed using methods known in the art, such as hot air drying or vacuum drying methods.

The initiator used in the polytetrafluoroethylene-based mixture can be used without limitation as long as it is used in the polymerization reaction of styrene-based and / or acrylic-based monomers. Examples of the initiator include, but are not limited to, cumyl hydroperoxide, di-tert-butyl peroxide, benzoyl peroxide, hydrogen peroxide, and potassium peroxide. In the polytetrafluoroethylene-based mixture of the present invention, one or more of the initiators can be used depending on the reaction conditions. The amount of the initiator is freely selected within the range used in consideration of the amount of polytetrafluoroethylene and the type / amount of the monomer, and is 0.15 to 0. Based on the amount of the total composition. It is preferable to use 25 parts by weight.

In addition, coated branched PTFE can be used as a drip inhibitor. The coated branched PTFE is a polytetrafluoroethylene-based mixture composed of branched polytetrafluoroethylene particles and an organic polymer, and is derived from an organic polymer, preferably a styrene-based monomer, outside the branched polytetrafluoroethylene. It has a coating layer made of a polymer containing units and / or units derived from an acrylic monomer. The coating layer is formed on the surface of branched polytetrafluoroethylene. Further, the coating layer preferably contains a copolymer of a styrene-based monomer and an acrylic-based monomer.

The polytetrafluoroethylene contained in the coated branched PTFE is branched polytetrafluoroethylene. When the contained polytetrafluoroethylene is not branched polytetrafluoroethylene, the effect of preventing dropping becomes insufficient when the addition of polytetrafluoroethylene is small. The branched polytetrafluoroethylene is in the form of particles, preferably having a particle size of 0.1 to 0.6 μm, more preferably 0.3 to 0.5 μm, and even more preferably 0.3 to 0.4 μm. When the particle size is smaller than 0.1 μm, the surface appearance of the molded product is excellent, but it is difficult to commercially obtain polytetrafluoroethylene having a particle size smaller than 0.1 μm. If the particle size is larger than 0.6 μm, the surface appearance of the molded product may deteriorate. The number average molecular weight of the polytetrafluoroethylene used in the present invention is preferably 1 × 10 ⁴ to 1 × 10 ⁷ , more preferably 2 × 10 ^{6 to} 9 × 10 ⁶ , and generally has a high molecular weight of polytetra. Fluoroethylene is more preferred in terms of stability. Either powder or dispersion can be used. The content of branched polytetrafluoroethylene in the coated branched PTFE is preferably 20 to 60 parts by weight, more preferably 40 to 55 parts by weight, still more preferably 47 to 47 to 100 parts by weight based on the total weight of the coated branched PTFE. It is 53 parts by weight, particularly preferably 48 to 52 parts by weight, and most preferably 49 to 51 parts by weight. When the proportion of branched polytetrafluoroethylene is in such a range, good dispersibility of branched polytetrafluoroethylene can be achieved.

(G component: mold release agent)
A mold release agent can be preferably used in the present invention. It is preferable that the polycarbonate resin composition of the present invention further contains a mold release agent for the purpose of improving productivity at the time of molding and reducing distortion of the molded product. As such a release agent, a known one can be used. For example, saturated fatty acid esters, unsaturated fatty acid esters, polyolefin waxes (polyethylene wax, 1-alkene polymer, etc. those modified with functional group-containing compounds such as acid modification can also be used), silicone compounds, fluorine compounds ( Fluorooil represented by polyfluoroalkyl ether), paraffin wax, beeswax and the like can be mentioned.

Among them, a fatty acid ester is mentioned as a preferable release agent. Such fatty acid esters are esters of fatty alcohols and aliphatic carboxylic acids. Such an aliphatic alcohol may be a monohydric alcohol or a divalent or higher polyhydric alcohol. The carbon number of the alcohol is in the range of 3 to 32, more preferably in the range of 5 to 30. Examples of such monohydric alcohols include dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, tetracosanol, ceryl alcohol, triacontanol and the like. 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), nonadecanic acid, bechenic acid, and the like. Saturated aliphatic carboxylic acids such as icosanoic acid and docosanoic acid, and unsaturated aliphatic carboxylic acids such as palmitic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaenoic acid, and sethaic acid can be mentioned. .. Among the above, the aliphatic carboxylic acid preferably has 14 to 20 carbon atoms. Of these, saturated aliphatic carboxylic acids are preferable. Particularly stearic acid and palmitic acid are preferred.

The above-mentioned aliphatic carboxylic acids such as stearic acid and palmitic acid are usually produced from animal fats and oils such as beef tallow and pork fat and natural fats and oils such as palm oil and sunflower oil. Therefore, these aliphatic carboxylic acids are usually mixtures containing other carboxylic acid components having different carbon atom numbers. Therefore, also in the production of the fatty acid ester of the present invention, an aliphatic carboxylic acid 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 may be either a partial ester or a total ester (full ester). However, a partial ester usually has a high hydroxyl value and easily induces decomposition of the resin at a high temperature, so that it is more preferably a full ester. The acid value of the fatty acid ester is preferably 20 or less, more preferably 4 to 20, and further preferably 4 to 12 from the viewpoint of thermal stability. The acid value can be substantially 0. The hydroxyl value of the fatty acid ester is more preferably in the range of 0.1 to 30. Further, the iodine value is preferably 10 or less. The iodine value can be substantially 0. These characteristics can be obtained by the method specified in JIS K 0070.

It is preferable to contain 0.01 to 10 parts by weight of the release agent (G component) with respect to 100 parts by weight of the polycarbonate resin (A component), and 0.05 to 5 parts by weight. It is more preferable to contain 0.1 to 4 parts by weight, and it is particularly preferable to contain 0.5 to 3 parts by weight. When the content of the release agent is in the above range, the mold release property is excellent at the time of molding, and the surface appearance of the molded product becomes good.

(Other additives)
(I) Phosphorus-based stabilizer The resin composition of the present invention can contain a phosphorus-based stabilizer. Examples of phosphorus-based stabilizers include phosphorous acid, phosphoric acid, phosphonic acid, phosphonic acid and esters thereof, and tertiary phosphine.

Specifically, examples of the phosphite compound include triphenylphosphite, tris (nonylphenyl) phosphite, tridecylphosphite, trioctylphosphite, trioctadecylphosphite, didecylmonophenylphosphite, and dioctylmonophenyl. Phosphite, diisopropylmonophenylphosphite, monobutyldiphenylphosphite, monodecyldiphenylphosphite, monooctyldiphenylphosphite, tris (diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di-iso-propylphenyl) -N-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, distearylpentaerythritol 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 pentaerythritol diphosphite, bis ( Nonylphenyl) pentaerythritol diphosphite, dicyclohexylpentaerythritol diphosphite and the like.

Further, as another phosphite compound, a compound which reacts with divalent phenols and has a cyclic structure can also 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 thereof include butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite and 2,2-methylenebis (4,6-di-tert-butylphenyl) octylphosphite.

Phosphate compounds include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, Examples thereof include diisopropyl phosphate, preferably triphenyl phosphate and trimethyl phosphate.

Phenylnite compounds include tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite and tetrakis (2,4-di-tert-butylphenyl) -4,3'-biphenylenedi. Phenylonite, tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite , Tetrax (2,6-di-tert-butylphenyl) -4,3'-biphenylenediphosphonite, Tetrax (2,6-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di) -N-Phenylphenyl) -3-Phenyl-Phenylphosphonite, bis (2,6-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) Examples thereof include -3-phenyl-phenylphosphonite, tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite and bis (di-tert-butylphenyl) -phenyl-phenylphosphonite are preferable, and tetrakis (2, 4-Di-tert-butylphenyl) -biphenylenediphosphonite and bis (2,4-di-tert-butylphenyl) -phenyl-phenylphosphonite are more preferred. Such a phosphonite compound is preferable because it can be used in combination with a phosphite compound having an aryl group in which the alkyl group is substituted by 2 or more.

Examples of the phosphonate compound include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate.

Tertiary phosphines include triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, triamylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenylmethylphosphine, diphenyloctylphosphine, triphenylphosphine, and tri-p-tolyl. Examples include phosphine, triphenylphosphine, and diphenylbenzylphosphine. A particularly preferred tertiary phosphine is triphenylphosphine.

Tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite is preferable as the phosphonite compound, and the stabilizers containing the phosphonite as a main component are Sandostab P-EPQ (trademark, manufactured by Clariant) and Irgafos P. -It is commercially available as EPQ (trademark, manufactured by CIBA SPECIALTY CHEMICALS), and any of them can be used.

More suitable 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.

Disteallyl pentaerythritol diphosphite is commercially available as Adecastab PEP-8 (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.) and JPP681S (trademark, manufactured by Johoku Chemical Industry Co., Ltd.), and both can be used. Bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite is Adecastab 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 Chemicals), and Irgaofos 126 and 126FF (trademark, manufactured by CIBA SPECIALTY CHEMICALS) are commercially available. Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite is commercially available as Adecaster PEP-36 (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.) and can be easily used. Bis {2,4-bis (1-methyl-1-phenylethyl) phenyl} pentaerythritol diphosphite is Adecaster PEP-45 (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.) and Doverphos S-9228 (trademark). , Made by Dover Chemical), and any of them can be used.

The phosphorus-based stabilizer can be used alone or in combination of two or more. The content of the phosphorus-based stabilizer is preferably 0.01 to 1.0 parts by weight, more preferably 0.03 to 0.8 parts by weight, still more preferably 0. parts by weight, based on 100 parts by weight of the polycarbonate resin. It is 05 to 0.5 parts by weight. When the content of the phosphorus-based stabilizer is within the above range, the effect of suppressing thermal decomposition during molding is exhibited, and deterioration of mechanical properties is less likely to occur.

(Ii) Phenolic stabilizer The resin composition of the present invention can contain a phenol stabilizer. Examples of phenol-based stabilizers generally include hindered phenols, semi-hindered phenols, and less hindered phenol compounds, but hindered phenol compounds are particularly preferable from the viewpoint of applying a heat-stable formulation to a polycarbonate resin. Used. Examples of such hindered phenol compounds include α-tocopherol, butylhydroxytoluene, cinapyl alcohol, vitamin E, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, and 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) -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-butylphenyl) , 2,2-thiodiethylenebis- [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-hydroxy) Phenyl) isocyanurate, 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-5-methylbenzyl) benzene, and tris (3-tert-butyl-4-hydroxy-5-methyl) Benzyl) isocyanurate and the like are exemplified. Among the above compounds, tetrakis [methylene-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] methane and octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionate is preferably used, and (3,3', 3'', 5,5', 5''-hexa-tert-butyl-is excellent in suppressing deterioration of mechanical properties due to thermal decomposition during processing. a, a', a''- (mesitylen-2,4,6-triyl) tri-p-cresol, and 1,3,5-tris- (3,5-di-tert-butyl-4-hydroxybenzyl) ) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trion is more preferably used.

The above phenolic stabilizers can be used alone or in combination of two or more. The content of the phenolic stabilizer is preferably 0.05 to 1.0 parts by weight, more preferably 0.07 to 0.8 parts by weight, still more preferably 0. parts by weight, based on 100 parts by weight of the polycarbonate resin. 1 to 0.5 parts by weight. When the content of the phenolic stabilizer is within the above range, the effect of suppressing thermal decomposition during molding is exhibited, and deterioration of mechanical properties is less likely to occur.

It is preferable that either a phosphorus-based stabilizer or a phenol-based stabilizer is blended, and the combined use of these is even more preferable. In the case of combined use, it is preferable that 0.01 to 0.5 parts by weight of a phosphorus-based stabilizer and 0.01 to 0.5 parts by weight of a phenol-based stabilizer are blended with 100 parts by weight of the polycarbonate resin.

(Iii) Ultraviolet absorber The polycarbonate resin composition of the present invention can contain an ultraviolet absorber. Examples of benzophenone-based UV absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, and 2-. Hydroxy-4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxitrihydrate benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2', 4,4' -Tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodium sulfoxybenzophenone, bis (5-benzoyl-4-) Examples thereof include hydroxy-2-methoxyphenyl) methane, 2-hydroxy-4-n-dodecyloxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.

In the benzotriazole system, for example, 2- (2-hydroxy-5-methylphenyl) benzotriazol, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3, 5-Dicumylphenyl) phenylbenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,2'-methylenebis [4- (1,1,3) , 3-Tetramethylbutyl) -6- (2H-benzotriazole-2-yl) phenol], 2- (2-hydroxy-3,5-di-tert-butylphenyl) benzotriazol, 2- (2- (2-) Hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-di-tert-amylphenyl) benzotriazole, 2- (2-hydroxy-5) -Tert-octylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) benzotriazole, 2- (2-hydroxy-4-octoxyphenyl) benzotriazole, 2,2'- Methylenebis (4-cumyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis (1,3-benzoxazine-4-one), and 2- [2-hydroxy-3- (3,4) 5,6-Tetrahydrophthalimidemethyl) -5-methylphenyl] benzotriazol, and 2- (2'-hydroxy-5-methacryloxyethylphenyl) -2H-benzotriazole and vinyl-based monomers copolymerizable with the monomer. 2-Hydroxyphenyl-2H, such as a copolymer of 2- (2'-hydroxy-5-acryloxyethylphenyl) -2H-benzotriazole and a vinyl-based monomer copolymerizable with the monomer. -A polymer having a benzotriazole skeleton is exemplified.

In the hydroxyphenyltriazine system, for example, 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-hexyloxyphenol, 2- (4,6-diphenyl-1,3,5) -Triazine-2-yl) -5-methyloxyphenol, 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-ethyloxyphenol, 2- (4,6-diphenyl) -1,3,5-triazine-2-yl) -5-propyloxyphenol, and 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-butyloxyphenol, etc. Illustrated. Further, the phenyl group of the above-exemplified compound such as 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine-2-yl) -5-hexyloxyphenol is 2,4-dimethyl. A compound that has become a phenyl group is exemplified.

In the cyclic iminoester system, for example, 2,2'-p-phenylenebis (3,1-benzoxazine-4-one), 2,2'-m-phenylenebis (3,1-benzoxazine-4-one) , And 2,2'-p, p'-diphenylenebis (3,1-benzoxazine-4-one) and the like.

In the cyanoacrylate system, for example, 1,3-bis-[(2'-cyano-3', 3'-diphenylacryloyl) oxy] -2,2-bis [(2-cyano-3,3-diphenylacryloyl) oxy] ] Methyl) propane, 1,3-bis-[(2-cyano-3,3-diphenylacryloyl) oxy] benzene and the like are exemplified.

Further, the above-mentioned ultraviolet absorber has a structure of a monomer compound capable of radical polymerization, so that such an ultraviolet-absorbing monomer and / or a photostable monomer and a single amount of an alkyl (meth) acrylate or the like are used. It may be a polymer-type ultraviolet absorber copolymerized with a body. Preferable examples of the ultraviolet 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 the (meth) acrylic acid ester. To.
The above-mentioned ultraviolet absorbers can be used alone or in combination of two or more.

The content of the ultraviolet absorber is preferably 0.1 to 10 parts by weight, more preferably 0.12 to 5 parts by weight, still more preferably 0.15 to 3 parts by weight, based on 100 parts by weight of the polycarbonate resin. Is. When the content of the ultraviolet absorber is within the above range, sufficient light resistance is exhibited, and poor appearance and deterioration of physical properties due to gas generation during molding are prevented, which is preferable.

(Iv) Hindered Amine-based Light Stabilizer The polycarbonate resin composition of the present invention can contain a Hindered Amine-based light stabilizer. The hindered amine-based light stabilizer is generally called HALS (Hindered Amine Light Stabilizer) and is a compound having a 2,2,6,6-tetramethylpiperidine skeleton in its structure, for example, 4-acetoxy-2,2,6. , 6-Tetramethylpiperidin, 4-stearoyloxy-2,2,6,6-tetramethylpiperidin, 4-acryloyloxy-2,2,6,6-tetramethylpiperidin, 4- (phenylacetoxy) -2, 2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-methoxy-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2, 2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6,6-tetramethylpiperidin, 4-benzyloxy-2,2,6,6-tetramethylpiperidin, 4-phenoxy-2, 2,6,6-tetramethylpiperidine, 4- (ethylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (cyclohexylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (Phenylcarbamoyloxy) -2,2,6,6-tetramethylpiperidin, bis (2,2,6,6-tetramethyl-4-piperidyl) carbonate, bis (2,2,6,6-tetra Methyl-4-piperidyl) oxalate, bis (2,2,6,6-tetramethyl-4-piperidyl) malonate, bis (2,2,6,6-tetramethyl-4-piperidyl) sevacate, bis (2, 2,6,6-Tetramethyl-4-piperidyl) adipate, bis (2,2,6,6-tetramethyl-4-piperidyl) terephthalate, bis (1,2,2,6,6-pentamethyl-4- Piperidyl) carbonate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) oxalate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) malonate, bis (1,2, 2,6,6-pentamethyl-4-piperidyl) sevacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) adipate, bis (1,2,2,6,6-pentamethyl-4- Piperidyl) terephthalate, N, N'-bis-2,2,6,6-tetramethyl-4-piperidinyl-1,3-benzenedicarboxyamide, 1,2-bis (2,2,6,6-tetra) Methyl-4-pi Peridyloxy) ethane, α, α'-bis (2,2,6,6-tetramethyl-4-piperidyloxy) -p-xylene, bis (2,2,6,6-tetramethyl-4-piperidyltrilen) -2,4-dicarbamate, bis (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylene-1,6-dicarbamate, tris (2,2,6,6-tetramethyl-4) -Piperidyl) -benzene-1,3,5-tricarboxylate, N, N', N'', N'''-tetrakis- (4,6-bis- (butyl- (N-methyl-2,2)) , 6,6-tetramethylpiperidine-4-yl) amino) -triazine-2-yl) -4,7-diazadecan-1,10-diamine, dibutylamine, 1,3,5-triazine, N, N' Polycondensate of −bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine , Poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-diyl} Piperidine) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3 , 4-Butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, Tris (2,2,6,6- Tetramethyl-4-piperidyl) -benzene-1,3,4-tricarboxylate, 1- [2- {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy} butyl]- With 4- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] 2,2,6,6-tetramethylpiperidine, and 1,2,3,4-butanetetracarboxylic acid 1,2,2,6,6-pentamethyl-4-piperidinol and β, β, β', β'-tetramethyl-3,9- [2,4,5,10-tetraoxaspiro (5,5)) Undecane] Examples thereof include a condensate with diethanol.

Hindered amine-based photostabilizers are roughly classified according to the bond partner of the nitrogen atom in the piperidine skeleton, NH type (hydrogen is bonded to the nitrogen atom), NR type (alkyl group (R) is bonded to the nitrogen atom), There are three types, N-OR type (alkoxy group (OR) bonded to nitrogen atom), but when applied to polycarbonate resin, N-R is low basic from the viewpoint of basicity of hindered amine light stabilizer. It is more preferable to use a mold or N-OR mold.

The hindered amine-based light stabilizer can be used alone or in combination of two or more. The content of the hindered amine-based light stabilizer is preferably 0.01 to 2 parts by weight, more preferably 0.05 to 1 part by weight, still more preferably 0.08 to 0.08 to 100 parts by weight with respect to 100 parts by weight of the polycarbonate resin. It is 0.7 parts by weight, particularly preferably 0.1 to 0.5 parts by weight. When the content of the hindered amine-based light stabilizer is within the above range, sufficient light resistance is exhibited, and it is preferable that poor appearance due to gas generation during molding and deterioration of physical properties due to decomposition of the polycarbonate resin are suppressed.

(V) Other Additives In addition, the polycarbonate resin composition of the present invention may contain a small proportion of additives known per se in order to impart various functions and improve properties to the molded product. These additives are in the usual blending amount as long as the object of the present invention is not impaired.

Examples of such additives include sliding agents (for example, PTFE particles), light diffusing agents (for example, acrylic crosslinked particles, silicone crosslinked particles, ultrathin glass flakes, calcium carbonate particles), fluorescent dyes, and inorganic phosphors (for example, aluminate). Antistatic agent, crystal nucleating agent, inorganic and organic antibacterial agent, photocatalytic antifouling agent (for example, fine particle titanium oxide, fine particle zinc oxide), radical generator, infrared absorber (heat ray absorption) Agents), and photochromic agents and the like.

The present invention will be further described below with reference to examples. Unless otherwise specified, the parts in the examples are parts by weight, and% is by weight%. The evaluation was carried out by the following method.
(I) Appearance of molded product (design)
Using the obtained pellets, a molded plate (length 90 mm × width 50 mm) having a thickness of 2 mm and an arithmetic mean roughness (Ra) of 0.03 μm was formed at a cylinder temperature of 260 ° C., a mold temperature of 60 ° C., and an injection speed. It was molded by injection molding under the condition of 30 mm / s, and the appearance (design) of the molded product was observed.
The appearance of the molded product was confirmed to have a dot-like design, and when the dot-like design was confirmed, it was marked as "○", and the dot-like appearance was confirmed, but metal foreign matter was observed and it was not suitable for the appearance of the molded product. The case is indicated by "x", and the case where the dot tone is not confirmed is indicated by "XX".
(Ii) Flame retardancy A V test was carried out according to UL94 using UL test pieces obtained by the following method. In addition, the case where the judgment could not satisfy any of the criteria of V-0, V-1, and V-2 was indicated as "HB".

[Examples 1 to 4, Comparative Examples 1 to 9]
With the composition shown in Table 1, a method was performed in which a mixture composed of each component was supplied by dividing the supply port of the extruder into two stages. The mixer for adding the mixture to each supply port was sufficiently mixed using a premixing means such as a V-type blender, a Henschel mixer and an extrusion mixer. A mixture of components A and D to G was supplied from the first supply port, a mixture of components B and C was supplied from the second supply port, and melt-kneaded with a bent twin-screw extruder. For extrusion, a vent type twin-screw extruder with a diameter of 44 mmφ (Japan Steel Works, Ltd. TEX44αII-25AW-3V) is used, and the pellets are melt-kneaded at a screw rotation speed of 230 rpm, a discharge rate of 150 kg / h, and a vent vacuum degree of 3 kPa. Obtained. The extrusion temperature was 260 ° C. from the first supply port to the die portion. A part of the obtained pellets is dried at 80 to 100 ° C. for 6 hours in a hot air circulation type dryer, and then a UL test piece is prepared at a cylinder temperature of 250 ° C. and a mold temperature of 60 ° C. using an injection molding machine. Molded. The evaluation results are shown in Table 2. In addition, FIG. 1 shows the appearance of a molded product which was injection-molded from the pellet obtained in Example 1 under the condition of (i) above.

Each component of the symbol notation in Table 1 is as follows.
(Component A)
A-1: Aromatic polycarbonate resin (polycarbonate resin powder having a viscosity average molecular weight of 22,400 made from bisphenol A and phosgene by a conventional method, Panlite L-1225WP (product name) manufactured by Teijin Limited)
(B component)
B-1: Synthetic mica powder surface-coated with a silicone-based binder resin containing a colorant B-1-1; Titanium dioxide (Ishihara) as a colorant for 100% synthetic mica powder surface-coated with a silicone-based binder resin. Industrial type PC-3) 5.0%, carbon black (Mitsubishi CB950) 0.4%, yellow baking pigment (Tokan Material Technology 42-118A) 0.28%, red oxidation Contains 0.2% of iron (R180M manufactured by Biferrox), average particle size 500 μm
B-1-2; 5.0% titanium dioxide (Type PC-3 manufactured by Ishihara Sangyo Co., Ltd.) and carbon black (manufactured by Mitsubishi) as colorants for 100% synthetic mica powder surface-coated with silicone-based binder resin. CB950) 0.05%, yellow baking pigment (42-118A manufactured by Tokan Material Technology Co., Ltd.) 0.1%, red iron oxide (R180M manufactured by Biferrox Co., Ltd.) 0.2%, average particles Diameter 1000 μm
B-2 (Comparison): Natural mica powder surface-coated with a silicone-based binder resin containing a colorant B2-11: Dioxide as a colorant for 100% of natural mica powder surface-coated with a silicone-based binder resin Titanium (Ishihara Sangyo Type PC-3) 5.0%, Carbon Black (Mitsubishi CB950) 0.4%, Yellow Fired Pigment (Tokan Material Technology 42-118A) 0.28% , Red iron oxide (R180M manufactured by Biferrox) containing 0.2%, average particle size 500 μm
B-2-2: Titanium dioxide (Type PC-3 manufactured by Ishihara Sangyo Co., Ltd.) 5.0% and carbon black (manufactured by Mitsubishi) as colorants for 100% natural mica powder surface-coated with silicone-based binder resin. CB950) 0.05%, yellow baking pigment (42-118A manufactured by Tokan Material Technology Co., Ltd.) 0.1%, red iron oxide (R180M manufactured by Biferrox Co., Ltd.) 0.2%, average particles Diameter 1000 μm
B-3 (Comparison): Synthetic mica powder surface-coated with an epoxy-based binder resin containing a colorant B-3-1: Dioxide as a colorant for 100% of synthetic mica powder surface-coated with an epoxy-based binder resin Titanium (Ishihara Sangyo Epoxy PC-3) 5.0%, Carbon Black (Mitsubishi CB950) 0.4%, Yellow Fired Pigment (Tokan Material Technology 42-118A) 0.28% , Red iron oxide (R180M manufactured by Biferrox) containing 0.2%, average particle size 500 μm
B-3-2: Titanium dioxide (Type PC-3 manufactured by Ishihara Sangyo Co., Ltd.) 5.0% and carbon black (manufactured by Mitsubishi) as colorants against 100% synthetic mica powder surface-coated with epoxy binder resin. CB950) 0.05%, yellow baking pigment (42-118A manufactured by Tokan Material Technology Co., Ltd.) 0.1%, red iron oxide (R180M manufactured by Biferrox Co., Ltd.) 0.2%, average particles Diameter 1000 μm
(C component)
C-1: ABS-1: ABS resin [Toray 700-314 (trade name), butadiene rubber component about 12% by weight, average rubber particle diameter 350 nm]
(D component)
D-1: Talc (manufactured by Hayashi Kasei Co., Ltd .; HST0.8 (trade name), average particle size 3.5 μm)
D-2: Wallastnite (manufactured by Shimizu Kogyo Co., Ltd .; H-1250F (trade name) number average fiber diameter 2.1 μm, weighted average fiber length 26 μm)
(E component)
E-1: Phosphate ester containing bisphenol A bis (diphenyl phosphate) as the main component (manufactured by Daihachi Chemical Industry Co., Ltd .: CR-741 (trade name))
(F component)
F-1: PTFE (Polyflon MPA FA500H (trade name) manufactured by Daikin Industries, Ltd.)
(G component)
G-1: Olefin wax by copolymerization of α-olefin and maleic anhydride (manufactured by Mitsubishi Chemical Corporation; Diacarna 30M (trade name))
G-2: Fatty acid ester-based release agent (Rikemar SL900 (product name) manufactured by RIKEN Vitamin Co., Ltd.)

The polycarbonate resin composition of the present invention has an excellent appearance of a molded product, and the molded product formed from the resin composition has a dot-like appearance with excellent design. Therefore, the field of OA equipment, the field of electronic and electrical equipment, etc. It is preferably used as a housing material for polycarbonate, and is particularly useful for housing applications such as mobile phones and tablets.

Claims (9)

(A) Polycarbonate resin (Component A) 100 parts by weight, (B) Polycarbonate resin containing 0.01 to 8 parts by weight of synthetic mica powder (component B) surface-coated with a silicone-based binder resin containing a colorant. Composition. The polycarbonate resin composition according to claim 1, wherein the synthetic mica powder of component B has an average particle size of 100 to 5000 μm. The polycarbonate resin composition according to claim 1, which contains 1 to 100 parts by weight of the rubber-reinforced styrene resin (C component) with respect to 100 parts by weight of the polycarbonate resin (A component). The polycarbonate resin composition according to claim 1, which contains 1 to 100 parts by weight of an inorganic filler (component D) other than (D) synthetic mica powder with respect to 100 parts by weight of the polycarbonate resin (component A). The polycarbonate resin composition according to claim 4, wherein the inorganic filler of the D component is at least one inorganic filler selected from the group consisting of talc and wallastonite. The polycarbonate resin composition according to claim 1, which contains (E) 1 to 100 parts by weight of the flame retardant (component E) with respect to 100 parts by weight of the polycarbonate resin (component A). The polycarbonate resin composition according to claim 1, which contains 0.01 to 10 parts by weight of the (F) drip inhibitor (F component) with respect to 100 parts by weight of the polycarbonate resin (A component). The polycarbonate resin composition according to claim 1, which contains 0.01 to 10 parts by weight of the (G) release agent (G component) with respect to 100 parts by weight of the polycarbonate resin (A component). A molded product having a dot-like appearance formed from the polycarbonate resin composition according to any one of claims 1 to 8.