JP2011140545A - Fiber-reinforced resin composition and resin molded article produced by molding the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fiber-reinforced resin composition which is based on a resin composition comprising an aromatic polycarbonate resin reinforced with basalt fibers, is excellent in mechanical strength and flame-retarding characteristics, and uses a reinforcing material comprising a natural substance. <P>SOLUTION: The fiber-reinforcing resin composition includes (A) 100 pts.wt. of a thermoplastic resin (component A), (B) 1 to 100 pts.wt. of fibers (component B) comprising basalt, and (C) 0.01 to 30 pts.wt. of a flame retardant (component C). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a fiber reinforced resin composition and a resin molded body formed by molding the same. More specifically, the present invention relates to a fiber reinforced resin composition that uses a thermoplastic resin containing an aromatic polycarbonate resin reinforced with fibers made of basalt as a base and is excellent in mechanical strength and flame retardancy and uses a reinforcing material made of a natural substance.

  Thermoplastic resins reinforced with a reinforcing filler such as glass fiber are widely used because of their excellent mechanical strength and processability. In particular, polycarbonate resins are used in many applications such as mechanical parts, automobile parts, electrical / electronic parts, and office equipment parts because of their excellent properties such as mechanical strength, dimensional stability and flame retardancy.

In recent years, with the reduction in thickness and weight of these applications, resin materials are required to have higher strength and flame retardancy. However, if the filling amount of the glass fiber is increased to improve the mechanical strength, the flame retardancy is impaired, and it is difficult to obtain desired characteristics.
In addition, the use of natural substances is also desired for reinforcing fillers to be added to materials due to the growing awareness of reducing environmental impact. Under such circumstances, the reinforcing materials obtained by refining and classifying natural minerals such as mica and wollastonite are inferior in the effect of improving rigidity or impact resistance compared to glass fibers, and have mechanical characteristics. Have a problem.

  In patent document 1, it is proposed to mix | blend the fiber which consists of basalt as a natural substance with a thermoplastic resin. However, this document only mentions design properties, and does not mention its excellent mechanical strength and flame retardancy. Patent Document 2 proposes a thermoplastic resin composition having excellent mechanical strength and laser marking properties by using a filler made of basalt. Patent Document 3 proposes a resin composition that has good mechanical strength and color tone by using basalt fibers and that is easy for thermal recycling. However, none of the above patents mentions the compatibility between strength and flame retardancy required for thin-walled molded articles.

Japanese Patent No. 3603097 JP 2008-45051 A JP 2007-291226 A

  In view of the above, an object of the present invention is to provide a fiber reinforced resin using a reinforcing material made of a natural substance, which is excellent in mechanical strength and flame retardancy, using a resin composition containing an aromatic polycarbonate resin reinforced with basalt fibers as a base. It is to provide a composition. As a result of intensive studies to achieve the above object, the present inventor has found that such an object can be achieved by using basalt fibers, and further studies have been made to complete the present invention.

  According to the present invention, the above-mentioned problems are (A) 100 parts by weight of thermoplastic resin (A component), (B) 1 to 100 parts by weight of fiber (B component) made of basalt, and (C) flame retardant ( C component) achieved by a fiber reinforced resin composition containing 0.01 to 30 parts by weight.

Hereinafter, the details of the present invention will be described.
(Component A: thermoplastic resin)
(A-1 component: aromatic polycarbonate resin)
The aromatic polycarbonate resin used as the A component thermoplastic resin in the present invention is obtained by reacting a dihydric phenol and a carbonate precursor. Examples of the reaction method include an interfacial polymerization method, a melt transesterification method, a solid phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound.

  Representative examples of the dihydric phenol used here include hydroquinone, resorcinol, 4,4′-biphenol, 1,1-bis (4-hydroxyphenyl) ethane, and 2,2-bis (4-hydroxyphenyl). ) Propane (commonly called bisphenol A), 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl)- 1-phenylethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxyphenyl) Pentane, 4,4 ′-(p-phenylenediisopropylidene) diphenol, 4,4 ′-(m-phenylenediisopropyl Pyridene) diphenol, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) ester, bis (4-hydroxy-3-methylphenyl) sulfide, 9,9-bis (4-hydroxyphenyl) Examples include fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene. A preferred dihydric phenol is bis (4-hydroxyphenyl) alkane, and bisphenol A is particularly preferred from the viewpoint of impact resistance, and is widely used.

  In the present invention, in addition to the bisphenol A-based aromatic polycarbonate, which is a general-purpose aromatic polycarbonate, a special aromatic polycarbonate produced using other dihydric phenols can be used as the A-1 component. Is possible.

  For example, as part or all of the dihydric phenol component, 4,4 ′-(m-phenylenediisopropylidene) diphenol (hereinafter sometimes abbreviated as “BPM”), 1,1-bis (4-hydroxy) Phenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (hereinafter sometimes abbreviated as “Bis-TMC”), 9,9-bis (4-hydroxyphenyl) Aromatic polycarbonate (homopolymer or copolymer) using fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (hereinafter sometimes abbreviated as “BCF”) It is suitable for applications that require particularly strict dimensional changes and form stability requirements. These dihydric phenols other than BPA are preferably used in an amount of 5 mol% or more, particularly 10 mol% or more of the entire dihydric phenol component constituting the aromatic polycarbonate.

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

These special aromatic polycarbonates may be used alone or in combination of two or more. These can also be used by mixing with a widely used bisphenol A type aromatic polycarbonate.
The production method and characteristics of these special aromatic polycarbonates are described in detail, for example, in JP-A-6-172508, JP-A-8-27370, JP-A-2001-55435, and JP-A-2002-117580. Are listed.

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

  Here, the water absorption of the aromatic polycarbonate was measured by using a disk-shaped test piece having a diameter of 45 mm and a thickness of 3.0 mm, and immersing it in water at 23 ° C. for 24 hours in accordance with ISO 62-1980. Value. Moreover, Tg (glass transition temperature) is a value calculated | required by the differential scanning calorimeter (DSC) measurement based on JISK7121.

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

  In producing the aromatic polycarbonate resin by the interfacial polymerization method using the dihydric phenol and the carbonate precursor, a catalyst, a terminal terminator, and an antioxidant for preventing the dihydric phenol from being oxidized as necessary. Etc. may be used. The aromatic polycarbonate resin of the present invention is a branched polycarbonate resin copolymerized with a trifunctional or higher polyfunctional aromatic compound, a polyester copolymerized with an aromatic or aliphatic (including alicyclic) difunctional carboxylic acid. Carbonate resins, copolymerized aromatic polycarbonate resins copolymerized with bifunctional alcohols (including alicyclic), and polyester carbonate resins copolymerized together with such bifunctional carboxylic acids and difunctional alcohols are included. Moreover, the mixture which mixed 2 or more types of the obtained aromatic polycarbonate resin may be sufficient.

  The branched polycarbonate resin can impart anti-drip performance and the like to the fiber reinforced resin composition of the present invention. Examples of the trifunctional or higher polyfunctional aromatic compound used in the branched polycarbonate resin include phloroglucin, phloroglucid, or 4,6-dimethyl-2,4,6-tris (4-hydroxydiphenyl) heptene-2, 2 , 4,6-trimethyl-2,4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) Ethane, 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, 4- {4- [ Trisphenol such as 1,1-bis (4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol, tetra (4-hydride) Loxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and their acids Among them, 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are preferable. 1-Tris (4-hydroxyphenyl) ethane is preferred.

  The structural unit derived from the polyfunctional aromatic compound in the branched polycarbonate is preferably a total of 100 mol% of the structural unit derived from the dihydric phenol and the structural unit derived from the polyfunctional aromatic compound. It is 0.01-1 mol%, More preferably, it is 0.05-0.9 mol%, Most preferably, it is 0.05-0.8 mol%.

In particular, in the case of the melt transesterification method, a branched structural unit may be generated as a side reaction. However, the amount of the branched structural unit is also 0.1% in a total of 100 mol% with a structural unit derived from a dihydric phenol. 001-1 mol% is preferable, 0.005-0.9 mol% is more preferable, and what is 0.01-0.8 mol% is especially preferable. The ratio of the branched structure can be calculated by ¹ H-NMR measurement.

The aliphatic bifunctional carboxylic acid is preferably α, ω-dicarboxylic acid. Examples of the aliphatic difunctional carboxylic acid include sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, icosanedioic acid and other straight-chain saturated aliphatic dicarboxylic acids, and cyclohexanedicarboxylic acid. Preferred are alicyclic dicarboxylic acids such as As the bifunctional alcohol, an alicyclic diol is more preferable, and examples thereof include cyclohexanedimethanol, cyclohexanediol, and tricyclodecane dimethanol.
Further, a polycarbonate-polyorganosiloxane copolymer obtained by copolymerizing polyorganosiloxane units can also be used.

  Reaction methods such as interfacial polymerization, melt transesterification, carbonate prepolymer solid phase transesterification, and ring-opening polymerization of cyclic carbonate compounds, which are methods for producing the aromatic polycarbonate resin of the present invention, include various documents and patents. This is a well-known method in gazettes.

In producing the glass fiber reinforced resin composition of the present invention, the viscosity average molecular weight (M) of the aromatic polycarbonate resin is not particularly limited, but is preferably 1 × 10 ^{4 to} 5 × 10 ⁴ , more preferably 1 4 × 10 ^{4 to} 3 × 10 ⁴ , more preferably 1.4 × 10 ^{4 to} 2.4 × 10 ⁴ .
With an aromatic polycarbonate resin having a viscosity average molecular weight of less than 1 × 10 ⁴ , good mechanical properties cannot be obtained. On the other hand, a resin composition obtained from an aromatic polycarbonate resin having a viscosity average molecular weight exceeding 5 × 10 ⁴ is inferior in versatility in that it is inferior in fluidity during injection molding.

The aromatic polycarbonate resin may be obtained by mixing those having a viscosity average molecular weight outside the above range. In particular, an aromatic polycarbonate resin having a viscosity average molecular weight exceeding the above range (5 × 10 ⁴ ) improves the entropy elasticity of the resin. As a result, good moldability is exhibited in gas assist molding and foam molding which may be used when molding a reinforced resin material into a structural member. Such improvement in moldability is even better than that of the branched polycarbonate. As a more suitable aspect, A-1 component is an aromatic polycarbonate resin (A-1-1-1 component) with a viscosity average molecular weight of 7 × 10 ^{4 to} 3 × 10 ⁵ , and a viscosity average molecular weight of 1 × 10 ^{4 to} 3 × consisted of 10 ⁴ of the aromatic polycarbonate resin (a-1-1-2 component), the aromatic polycarbonate resin (a-1-a viscosity-average molecular weight of 1.6 × ¹⁰ 4 to 3.5 × 10 ⁴ 1 component) (hereinafter sometimes referred to as “high molecular weight component-containing aromatic polycarbonate resin”) can also be used.

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

  The high molecular weight component-containing aromatic polycarbonate resin (component A-1-1) is a mixture of the components A-1-1-1 and A-1-1-2 in various proportions and satisfies a predetermined molecular weight range. It can be obtained by adjusting as follows. Preferably, in 100% by weight of the A-1-1 component, the A-1-1-1 component is 2 to 40% by weight, and more preferably, the A-1-1-1 component is 3 to 30% by weight. More preferably, the A-1-1-1 component is 4 to 20% by weight, and particularly preferably the A-1-1-1 component is 5 to 20% by weight.

  Moreover, as a preparation method of A-1-1 component, (1) The method of superposing | polymerizing each A-1-1-1 component and A-1-1-2 component independently, and mixing these, (2 ) A method for producing an aromatic polycarbonate resin showing a plurality of polymer peaks in a molecular weight distribution chart by GPC method represented by the method disclosed in Japanese Patent Application Laid-Open No. 5-306336 in the same system. And (3) an aromatic polycarbonate resin obtained by the production method (production method (2)) and A separately produced A. Examples thereof include a method of mixing the 1-1-1 component and / or the A-1-1-2 component.

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

In addition, calculation of the viscosity average molecular weight of aromatic polycarbonate resin in the fiber reinforced resin composition of this invention is performed in the following way. That is, the composition is mixed with 20 to 30 times its weight of methylene chloride to dissolve the soluble component in the composition. Such soluble matter is collected by Celite filtration. Thereafter, the solvent in the obtained solution is removed. The solid after removal of the solvent is sufficiently dried to obtain a solid component that dissolves in methylene chloride. A specific viscosity at 20 ° C. is determined from a solution obtained by dissolving 0.7 g of the solid in 100 ml of methylene chloride in the same manner as described above, and the viscosity average molecular weight M is calculated from the specific viscosity in the same manner as described above.
The content of the component A-1 in the component A is preferably 50% by weight or more, more preferably 55% by weight or more, and further preferably 60% by weight or more.

(A-2 component: styrene resin)
In the present invention, a styrene resin (component A-2) can be used as the thermoplastic resin of the component A. Since this styrenic resin has good moldability, moderate heat resistance and flame retardancy, it is a preferred thermoplastic resin in order to maintain a balance between these properties.
Such a styrenic resin is a copolymer or copolymer of an aromatic vinyl compound, and, if necessary, at least one selected from other vinyl monomers and rubbery polymers copolymerizable therewith. It is a polymer obtained by polymerization.

  As the aromatic vinyl compound, styrene is particularly preferable. Preferable examples of the other vinyl monomer copolymerizable with the aromatic vinyl compound include a vinyl cyanide compound and a (meth) acrylic acid ester compound. A particularly preferred vinyl cyanide compound is acrylonitrile, and a particularly preferred (meth) acrylic acid ester compound is methyl methacrylate.

  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, N-methylmaleimide, Examples thereof include maleimide 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 anhydrides thereof.

  Examples of the rubbery polymer copolymerizable with the aromatic vinyl compound include polybutadiene, polyisoprene, and diene copolymers (eg, styrene / butadiene random copolymers and block copolymers, acrylonitrile / butadiene copolymers). , And (meth) acrylic acid alkyl ester and butadiene copolymers), ethylene and α-olefin copolymers (eg, ethylene / propylene random copolymers and block copolymers, ethylene / butene random copolymers). Polymers and block copolymers), copolymers of ethylene and unsaturated carboxylic acid esters (for example, ethylene / methacrylate copolymers and ethylene / butyl acrylate copolymers), copolymers of ethylene and aliphatic vinyl. Polymer (for example, ethylene / vinyl acetate copolymer) ), Ethylene, propylene and non-conjugated diene terpolymers (eg, ethylene / propylene / hexadiene copolymer), acrylic rubbers (eg, polybutyl acrylate, poly (2-ethylhexyl acrylate), and butyl acrylate 2 A copolymer with ethylhexyl acrylate, etc.), and a silicone rubber (for example, polyorganosiloxane rubber, IPN type rubber comprising a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate rubber component; that is, two rubber components And rubbers having a structure in which they are entangled with each other so that they cannot be separated, and an IPN type rubber composed of a polyorganosiloxane rubber component and a polyisobutylene rubber component.

  Specific examples of the styrene resin include styrene resins such as polystyrene resin, HIPS resin, MS resin, ABS resin, AS resin, AES resin, ASA resin, MBS resin, MABS resin, MAS resin, and SMA resin. And (hydrogenated) styrene-butadiene-styrene copolymer resin, (hydrogenated) styrene-isoprene-styrene copolymer resin, and the like. In addition, the notation of (hydrogenated) means that both non-hydrogenated resin and hydrogenated resin are included. Here, the MS resin is a copolymer resin mainly composed of methyl methacrylate and styrene, the AES resin is a copolymer resin mainly composed of acrylonitrile, ethylene-propylene rubber, and styrene, and the ASA resin is mainly composed of acrylonitrile, styrene, and acrylic rubber. MABS resin is a copolymer resin mainly composed of methyl methacrylate, acrylonitrile, butadiene and styrene, MAS resin is a copolymer resin mainly composed of methyl methacrylate, acrylic rubber and styrene, and SMA resin is styrene and A copolymer resin mainly composed of maleic anhydride (MA) is shown.

  Such a styrenic resin may have a high stereoregularity such as syndiotactic polystyrene by using a catalyst such as a metallocene catalyst during the production thereof. Further, in some cases, polymers and copolymers having a narrow molecular weight distribution, block copolymers, and polymers and copolymers having high stereoregularity obtained by methods such as anion living polymerization and radical living polymerization are used. It is also possible.

  Among these, acrylonitrile / styrene copolymer resin (AS resin) and acrylonitrile / butadiene / styrene copolymer resin (ABS resin) are preferable. It is also possible to use a mixture of two or more styrenic polymers.

  The AS resin used in the present invention is a thermoplastic copolymer obtained by copolymerizing a vinyl cyanide compound and an aromatic vinyl compound. As such a vinyl cyanide compound, acrylonitrile can be particularly preferably used. As the aromatic vinyl compound, styrene and α-methylstyrene can be preferably used. The proportion of each component in the AS resin is preferably 5 to 50% by weight of vinyl cyanide compound, more preferably 15 to 35% by weight, and preferably 95% of aromatic vinyl compound when the total is 100% by weight. -50% by weight, more preferably 85-65% by weight. Further, these vinyl compounds may be used in combination with other copolymerizable vinyl compounds described above, and the content ratio thereof is preferably 15% by weight or less in the AS resin component. Moreover, conventionally well-known various things can be used for the initiator, chain transfer agent, etc. which are used by reaction as needed.

  Such an AS resin may be produced by any of bulk polymerization, suspension polymerization, and emulsion polymerization, but is preferably bulk polymerization. The copolymerization method may be either one-stage copolymerization or multistage copolymerization. The reduced viscosity of the AS resin is preferably 0.2 to 1.0 dl / g, more preferably 0.3 to 0.5 dl / g. The reduced viscosity is a value obtained by precisely weighing 0.25 g of AS resin and measuring a solution obtained by dissolving in 50 ml of dimethylformamide over 2 hours in an environment of 30 ° C. using an Ubbelohde viscometer. When the reduced viscosity is less than 0.2 dl / g, the impact is lowered, and when it exceeds 1.0 dl / g, the fluidity is deteriorated.

  The ABS resin used in the present invention is a mixture of a thermoplastic graft copolymer obtained by graft polymerization of a vinyl cyanide compound and an aromatic vinyl compound to a diene rubber component, and a copolymer of a vinyl cyanide compound and an aromatic vinyl compound. It is. As the diene rubber component forming the ABS resin, for example, rubber having a glass transition temperature of −30 ° C. or less such as polybutadiene, polyisoprene and styrene-butadiene copolymer is used, and the proportion thereof is 100% by weight of the ABS resin component. The content is preferably 5 to 80% by weight, more preferably 8 to 50% by weight, and particularly preferably 10 to 30% by weight. As the vinyl cyanide compound grafted on the diene rubber component, acrylonitrile is particularly preferably used. As the aromatic vinyl compound grafted on the diene rubber component, styrene and α-methylstyrene are particularly preferably used. The ratio of the component grafted to the diene rubber component is preferably 95 to 20% by weight, particularly preferably 50 to 90% by weight, based on 100% by weight of the ABS resin component. Furthermore, it is preferable that the vinyl cyanide compound is 5 to 50% by weight and the aromatic vinyl compound is 95 to 50% by weight with respect to 100% by weight of the total amount of the vinyl cyanide compound and the aromatic vinyl compound. Further, methyl (meth) acrylate, ethyl acrylate, maleic anhydride, N-substituted maleimide and the like can be mixed and used for a part of the components grafted to the diene rubber component, and the content ratio thereof is in the ABS resin component. What is 15 weight% or less is preferable. Furthermore, conventionally known various initiators, chain transfer agents, emulsifiers and the like can be used as necessary.

  In the ABS resin of the present invention, the rubber particle diameter is preferably 0.1 to 5.0 μm, more preferably 0.15 to 1.5 μm, and particularly preferably 0.2 to 0.8 μm. As the distribution of the rubber particle diameter, either a single distribution or a rubber particle having two or more peaks can be used, and the rubber particles form a single phase in the morphology. Alternatively, it may have a salami structure by containing an occluded phase around the rubber particles.

  In addition, it is well known that the ABS resin contains a vinyl cyanide compound and an aromatic vinyl compound that are not grafted to the diene rubber component, and the ABS resin of the present invention is free of the occurrence of such polymerization. The polymer component may be contained. The reduced viscosity of the copolymer comprising such a free vinyl cyanide compound and aromatic vinyl compound is preferably a reduced viscosity (30 ° C.) determined by the above-described method of 0.2 to 1.0 dl / g. Preferably it is 0.3-0.7 dl / g.

  The ratio of the grafted vinyl cyanide compound and aromatic vinyl compound is preferably 20 to 200%, more preferably 20 to 70% in terms of graft ratio (% by weight) with respect to the diene rubber component. is there.

  Such an ABS resin may be produced by any of bulk polymerization, suspension polymerization, and emulsion polymerization, but is preferably bulk polymerization. Further, as such bulk polymerization method, typically, continuous bulk polymerization method (so-called Toray method) described in Chemical Engineering Vol. 48, No. 6, page 415 (1984), and Chemical Engineering Vol. 53, No. 6, page 423 ( 1989), a continuous bulk polymerization method (so-called Mitsui Toatsu method) is exemplified. Any ABS resin is preferably used as the ABS resin of the present invention. Further, the copolymerization may be carried out in one step or in multiple steps. Moreover, what blended the vinyl compound polymer obtained by copolymerizing an aromatic vinyl compound and a vinyl cyanide component separately to the ABS resin obtained by this manufacturing method can also be used preferably.

As the AS resin and the ABS resin, those having a reduced amount of alkali (earth) metal are more preferable from the viewpoint of good thermal stability and hydrolysis resistance. The amount of alkali (earth) metal in the styrenic resin is preferably less than 100 ppm, more preferably less than 80 ppm, still more preferably less than 50 ppm, and particularly preferably less than 10 ppm. Also from this point, AS resin and ABS resin by a bulk polymerization method are preferably used. Furthermore, in relation to such good thermal stability and hydrolysis resistance, when an emulsifier is used in the AS resin and ABS resin, the emulsifier is preferably a sulfonate salt, more preferably an alkyl sulfonic acid. It is salt. When a coagulant is used, the coagulant is preferably sulfuric acid or an alkaline earth metal salt of sulfuric acid.
1-100 weight part is preferable with respect to 100 weight part of A-1 component, as for the compounding quantity of a styrene-type resin, 5-80 weight part is more preferable, and 10-70 weight part is further more preferable.

(Other thermoplastic resins)
In the present invention, a thermoplastic resin other than the A-1 component and the A-2 component can be used as the A component thermoplastic resin. Examples of thermoplastic resins other than the components A-1 and A-2 include aromatic polyester resins (polyethylene terephthalate resin (PET resin), polybutylene terephthalate resin (PBT resin), polyphenylene sulfide resin (PPS resin), and cyclohexanedimethanol. Polymerized polyethylene terephthalate resin (so-called PET-G resin), polyethylene naphthalate resin, and polybutylene naphthalate resin), polymethyl methacrylate resin (PMMA resin), cyclic polyolefin resin, polylactic acid resin, and polyolefin resin (polyethylene resin, And ethylene- (α-olefin) copolymer resin, polypropylene resin, and propylene- (α-olefin) copolymer resin). Examples of the rubbery polymer include various core-shell type graft copolymers and thermoplastic elastomers. The content of the other thermoplastic resin and rubber polymer is preferably 100 parts by weight or less, more preferably 80 parts by weight or less, based on 100 parts by weight of the component A-1.

(B component: fiber made of basalt)
The fiber made of basalt used as the component B of the present invention is obtained by melt spinning basalt made of lava. Here, the basalt is a kind of volcanic rock, SiO ₂ classified by bulk chemical composition (especially wt% of SiO ₂₎ is one having a patchy tissue 45 to 52%. If the raw material of the basalt fiber used for this invention is a basalt, there will be no restriction | limiting in particular in the composition. In the present invention, when an aromatic polycarbonate resin or a polyester resin is used as the thermoplastic resin, it is preferable from the viewpoint of the thermal stability of the resin that the basalt fiber has less alkali components. The method for producing the basalt fiber used in the present invention is arbitrary, and specifically, for example, conditions relating to the melting temperature, spinning, etc. when melt spinning the basalt as a raw material may be appropriately selected and determined. The average fiber diameter of the basalt fiber used in the present invention is preferably 7 to 25 μm. If the average fiber diameter is too small, the impact resistance will be low, and conversely if it is too large, the effect of improving the rigidity will be insufficient, and the fibers will easily float on the surface layer of the molded product, resulting in a decrease in glossiness. Color unevenness may be caused, and 9 to 22 μm is particularly preferable. The basalt fiber used in the present invention preferably has an average fiber length of 50 to 2,000 μm when dispersed in the fiber reinforced resin composition of the present invention. If the average fiber length is shorter than 50 μm, the effect of improving the rigidity is insufficient, and if it exceeds 2,000 μm, the appearance is deteriorated. Therefore, the average fiber length is more preferably 100 to 1,000 μm, and further preferably 150 to 800 μm. In addition, an average fiber length means the number average fiber length in the fiber reinforced resin composition of this invention. The number average fiber length is a value calculated by an image analyzer from an image obtained by observing the residue of the filler collected by processing such as high-temperature ashing of a molded product, dissolution with a solvent, and decomposition with a chemical, using an optical microscope. . Further, when calculating such a value, the fiber diameter is used as a guide and the length is less than that.

  The basalt fiber used in the present invention has, among other things, known techniques and additives for the purpose of handling, dispersibility in resin, and improvement in adhesion strength with the resin, sizing agent, sizing agent, and adhesion improvement. Surface treatment may be performed with an agent or the like. If the surface treatment method of basalt fiber and the surface treatment agent used therefor are any conventionally known surface treatment agent, specifically, for example, a known surface treatment agent or method used for glass fiber or carbon fiber. It may be determined in consideration of suitability with the component A used in the present invention. For example, a surface treated with a silane coupling agent, a titanate coupling agent, an aluminate coupling agent or the like is preferable from the viewpoint of improving mechanical strength. In addition, those that have been subjected to bundling treatment with olefin resin, styrene resin, acrylic resin, polyester resin, epoxy resin, urethane resin, etc. are preferable. From the viewpoint of mechanical strength, epoxy resin and urethane resin are preferred. Particularly preferred. The amount of the sizing agent attached is preferably 0.1 to 3% by weight, more preferably 0.2 to 2% by weight, in 100% by weight of the component B. In this invention, content of B component is 1-100 weight part with respect to 100 weight part of A component, Preferably it is 3-90 weight part, More preferably, it is 5-80 weight part. When the amount is less than 1 part by weight, the rigidity is not substantially improved, and when it exceeds 100 parts by weight, the extrudability and the appearance are deteriorated, which is not preferable.

(C component: flame retardant)
The fiber reinforced resin composition of the present invention contains various compounds known as flame retardants. The compounding of the compound used as a flame retardant not only improves the flame retardancy but also provides, for example, an improvement in antistatic properties, fluidity, rigidity, and thermal stability based on the properties of each compound.
Examples of such flame retardants include (1) organometallic salt flame retardants (for example, alkali (earth) organic sulfonate metal salts, borate metal salt flame retardants, stannate metal salt flame retardants, etc.), (2) Organophosphorous flame retardants (for example, monophosphate compounds, phosphate oligomer compounds, phosphonate oligomer compounds, phosphonitrile oligomer compounds, and phosphonic acid amide compounds), (3) silicone flame retardants comprising silicone compounds, and (4) halogens And flame retardant (for example, brominated epoxy resin, brominated polystyrene, brominated polycarbonate (including oligomers), brominated polyacrylate, chlorinated polyethylene, etc.). Content of C component is 0.01-30 weight part with respect to 100 weight part of A component, 0.02-25 weight part is preferable, and 0.03-20 weight part is more preferable. When the amount is less than 0.01 part by weight, flame retardancy cannot be ensured, and when it exceeds 30 parts by weight, the extrudability is deteriorated.

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

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

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

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

  The amount of the fluorine-containing organometallic salt compound is preferably 0.01 to 0.6 parts by weight, more preferably 0.015 to 0.2 parts by weight, and still more preferably 0.005 parts by weight with respect to 100 parts by weight of the component A. 02 to 0.15 parts by weight. The more preferable range is, the effects (for example, flame retardancy and antistatic property) expected from the blending of the fluorine-containing organic metal salt are exhibited, and the adverse effect on the light resistance of the resin composition is reduced.

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

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

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

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

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

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

  Among the above, preferable metal salts of organic sulfonic acids not containing fluorine atoms are aromatic (earth) metal salts of aromatic sulfonates, and potassium salts are particularly preferable. When blending such an aromatic sulfonic acid alkali (earth) metal salt, its content is preferably 0.01-1 part by weight, more preferably 0.02-0, per 100 parts by weight of component A. 0.5 part by weight, more preferably 0.03 to 0.3 part by weight.

(2) Organophosphorus Flame Retardant As the organophosphorus flame retardant of the present invention, various phosphate compounds known as conventional flame retardants can be used, and more preferably one type represented by the following general formula (1). Or 2 or more types of phosphate ester can be mentioned. Further, in order to cope with the recent thinning of electric / electronic parts, phosphate compounds are advantageous in that they have a plasticizing effect and can improve the moldability of the resin composition of the present invention.

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

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

The average n number is preferably 0.5 to 1.5, more preferably 0.8 to 1.2, still more preferably 0.95 to 1.15, and particularly preferably 1 to 1.14.
Preferable specific examples of the dihydric phenol for deriving X include resorcinol, bisphenol A, and dihydroxydiphenyl.

Preferable specific examples of the monohydric phenol for deriving R ¹ , R ² , R ³ and R ⁴ include phenol and 2,6-dimethylphenol.
Specific examples of phosphate compounds having a monohydric phenol-derived group substituted with such a halogen atom include tris (2,4,6-tribromophenyl) phosphate and tris (2,4-dibromophenyl) phosphate, tris. Examples include (4-bromophenyl) phosphate.

On the other hand, specific examples of the phosphate compound not substituted with a halogen atom include monophosphate compounds such as triphenyl phosphate and tri (2,6-xylyl) phosphate, and resorcinol bisdi (2,6-xylyl) phosphate). Preferred are phosphate oligomers mainly composed of phosphate oligomers, phosphate oligomers mainly composed of 4,4-dihydroxydiphenyl bis (diphenyl phosphate), and phosphate oligomers mainly composed of bisphenol A bis (diphenyl phosphate). Indicates that a small amount of other components having different degrees of polymerization may be included, and more preferably, the component of n = 1 in the formula (1) is 80% by weight or more, more preferably 85% by weight or more, and still more preferably Contains over 90% by weight Are shown.).
The content of the organophosphorus flame retardant is preferably 1 to 30 parts by weight, more preferably 2 to 25 parts by weight, and further preferably 3 to 15 parts by weight with respect to 100 parts by weight of the component A.

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

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

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

Here, the coefficients m, n, p, and q in the above formulas are integers of 1 or more representing the degree of polymerization of each siloxane unit, and the sum of the coefficients in each formula is the average degree of polymerization of the silicone compound. . This average degree of polymerization is preferably in the range of 3 to 150, more preferably in the range of 3 to 80, still more preferably in the range of 3 to 60, and particularly preferably in the range of 4 to 40. The better the range, the better the flame retardancy. Further, as described later, a silicone compound containing a predetermined amount of an aromatic group is excellent in transparency and hue.
When any of m, n, p, and q is a numerical value of 2 or more, the siloxane unit with the coefficient can be two or more types of siloxane units having different hydrogen atoms or organic residues to be bonded. .

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

  Further, the silicone compound used as the silicone flame retardant preferably contains an aryl group. More preferably, the ratio (aromatic group amount) of the aromatic group represented by the following general formula (2) is 10 to 70% by weight (more preferably 15 to 60% by weight).

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

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

The silicone compound used as the silicone-based flame retardant may contain a reactive group in addition to the Si-H group and the alkoxy group. Examples of the reactive group include an amino group, a carboxyl group, an epoxy group, and a vinyl group. Examples thereof include a group, a mercapto group, and a methacryloxy group.
As the silicone compound having a Si—H group, a silicone compound containing at least one of structural units represented by the following general formulas (3) and (4) is preferably exemplified.

（式（３）および式（４）中、Ｚ^１〜Ｚ^３はそれぞれ独立に水素原子、炭素数１〜２０の一価の有機残基、または下記一般式（５）で示される化合物を示す。α^１〜α^３はそれぞれ独立に０または１を表わす。ｍ１は０もしくは１以上の整数を表わす。さらに式（３）中においてｍ１が２以上の場合の繰返し単位はそれぞれ互いに異なる複数の繰返し単位を取ることができる。）

(In formula (3) and formula (4), Z ^{1 to} Z ³ each independently represent a hydrogen atom, a monovalent organic residue having 1 to 20 carbon atoms, or a compound represented by the following general formula (5). Α ^{1 to} α ³ each independently represents 0 or 1. m1 represents 0 or an integer of 1 or more, and in formula (3), when m1 is 2 or more, the repeating unit is a plurality of different repeating units. Can take units.)

（式（５）中、Ｚ^４〜Ｚ^８はそれぞれ独立に水素原子、炭素数１〜２０の一価の有機残基を示す。α^４〜α^８はそれぞれ独立に０または１を表わす。ｍ２は０もしくは１以上の整数を表わす。さらに式（５）中においてｍ２が２以上の場合の繰返し単位はそれぞれ互いに異なる複数の繰返し単位を取ることができる。）

(In formula (5), Z ^{4 to} Z ⁸ each independently represents a hydrogen atom or a monovalent organic residue having 1 to 20 carbon atoms. Α ^{4 to} α ⁸ each independently represents 0 or 1. m 2 Represents 0 or an integer greater than or equal to 1. Further, in the formula (5), when m2 is 2 or more, the repeating unit may take a plurality of different repeating units.

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

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

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

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

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

  The content of the silicone flame retardant is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 8 parts by weight, still more preferably 0.5 to 6 parts by weight with respect to 100 parts by weight of the component A. Part.

(4) Halogen flame retardant As the halogen flame retardant of the present invention, brominated polycarbonate (including oligomers) is particularly suitable. Brominated polycarbonate has excellent heat resistance and can greatly improve flame retardancy. In the brominated polycarbonate used in the present invention, the structural unit represented by the following general formula (8) is at least 60 mol%, preferably at least 80 mol%, particularly preferably substantially the following general formula. It is a brominated polycarbonate compound consisting of the structural unit represented by (8).

（式（８）中、Ｘは臭素原子、Ｒは炭素数１〜４のアルキレン基、炭素数１〜４のアルキリデン基または−ＳＯ_２−である。）

(In the formula (8), X is a bromine atom, R represents an alkylene group having 1 to 4 carbon atoms, an alkylidene group or -SO ₂ 1 to 4 carbon atoms - a.)

In the formula (8), R preferably represents a methylene group, an ethylene group, an isopropylidene group, —SO ₂ —, and particularly preferably an isopropylidene group.
The brominated polycarbonate has a small number of remaining chloroformate groups and preferably has a terminal chlorine content of 0.3 ppm or less, more preferably 0.2 ppm or less. The amount of terminal chlorine is determined by dissolving a sample in methylene chloride, adding 4- (p-nitrobenzyl) pyridine and allowing it to react with terminal chlorine (terminal chloroformate). -3200). When the amount of terminal chlorine is 0.3 ppm or less, the thermal stability of the resin composition becomes better, and molding at a higher temperature becomes possible, and as a result, a resin composition having better molding processability is provided.

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

The specific viscosity of the brominated polycarbonate is preferably in the range of 0.015 to 0.1, more preferably in the range of 0.015 to 0.08. The specific viscosity of the brominated polycarbonate is calculated according to the above-described specific viscosity calculation formula used in calculating the viscosity average molecular weight of the aromatic polycarbonate resin which is the component A of the present invention.
The content of the halogen-based flame retardant is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 15 parts by weight, still more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the component A. Part.

(D component: fluorine-containing anti-drip agent)
The fiber reinforced resin composition of the present invention can contain a fluorine-containing dripping inhibitor. By using such a fluorine-containing anti-drip agent in combination with the above flame retardant, better flame retardancy can be obtained. Examples of such a fluorine-containing anti-drip agent include a fluorine-containing polymer having a fibril-forming ability. Examples of such a polymer include polytetrafluoroethylene and tetrafluoroethylene copolymers (for example, tetrafluoroethylene / hexafluoropropylene copolymer). Polymer, etc.), partially fluorinated polymers as shown in US Pat. No. 4,379,910, polycarbonate resins produced from fluorinated diphenols, and the like, preferably polytetrafluoroethylene (hereinafter referred to as PTFE). May be called).

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

  Such PTFE can be used in solid form or in the form of an aqueous dispersion. In addition, PTFE having such fibril-forming ability can improve the dispersibility in the resin, and it is also possible to use a PTFE mixture in a mixed form with other resins in order to obtain better flame retardancy and mechanical properties. is there. Further, as disclosed in JP-A-6-145520, those having a structure having such a fibrillated PTFE as a core and a low molecular weight polytetrafluoroethylene as a shell are also preferably used.

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

  As a mixed form of fibrillated PTFE, (1) a method in which an aqueous dispersion of fibrillated PTFE and an aqueous dispersion or solution of an organic polymer are mixed and co-precipitated to obtain a co-agglomerated mixture (JP-A-60-258263). (2) A method of mixing an aqueous dispersion of fibrillated PTFE and dried organic polymer particles (Japanese Patent Laid-Open No. 4-272957). Described method), (3) A method in which an aqueous dispersion of fibrillated PTFE and an organic polymer particle solution are uniformly mixed, and the respective media are simultaneously removed from the mixture (Japanese Patent Laid-Open Nos. 06-220210, (Method described in Japanese Patent Application Laid-Open No. 08-188653), (4) A method of polymerizing monomers forming an organic polymer in an aqueous dispersion of fibrillated PTFE (Method described in JP-A-9-95583), and (5) an aqueous dispersion of PTFE and an organic polymer dispersion are uniformly mixed, and then a vinyl monomer is further polymerized in the mixed dispersion. Thereafter, those obtained by a method for obtaining a mixture (a method described in JP-A-11-29679, etc.) can be used. Commercial products of these mixed forms of fibrillated PTFE include “Metablene A3800” (trade name) manufactured by Mitsubishi Rayon Co., Ltd., “BLENDEX B449” (trade name) manufactured by GE Specialty Chemicals, and “Products manufactured by Pacific Interchem Corporation” “POLY TS AD001” (product name) is exemplified.

  In order to more effectively utilize the good mechanical strength of the fiber reinforced resin composition of the present invention, the fibrillated PTFE is preferably finely dispersed as much as possible. As a means of achieving such fine dispersion, the above mixed form of fibrillated PTFE is advantageous. A method of directly supplying an aqueous dispersion in a melt kneader is also advantageous for fine dispersion. However, in the case of the aqueous dispersion form, consideration is required in that the hue is slightly deteriorated. The proportion of fibrillated PTFE in the mixed form is preferably 10 to 80% by weight, more preferably 15 to 75% by weight, in 100% by weight of the mixture. When the ratio of fibrillated PTFE is in such a range, good dispersibility of fibrillated PTFE can be achieved.

  The content of the D component of the present invention is preferably 0.01 to 3 parts by weight, more preferably 0.01 to 2 parts by weight, and still more preferably 0.05 to 1.5 parts by weight with respect to 100 parts by weight of the A component. Parts by weight. When the D component exceeds 3 parts by weight, the appearance of the molded product deteriorates, and when it is less than 0.01 parts by weight, an effective drip prevention effect cannot be obtained.

(Other additives)
In the fiber reinforced resin composition of the present invention, various stabilizers, release agents, coloring materials, and the like can be used to stabilize the molecular weight and hue at the time of molding.

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

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

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

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

  Examples of the phosphite compound include triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl Monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, tris (diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di-n-butyl) Phenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, distearyl Taerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis ( 2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, bis {2,4-bis (1-methyl-1-phenylethyl) phenyl} pentaerythritol diphosphite, phenylbisphenol A penta Examples include erythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, and dicyclohexylpentaerythritol diphosphite.

  Further, as other phosphite compounds, those which react with dihydric phenols and have a cyclic structure can be used. For example, 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2,4-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-tert- Examples include butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite and 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite.

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

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

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

  Suitable phosphorus stabilizers are a triorganophosphate compound, an acid phosphate compound, and a phosphite compound represented by the following general formula (9). It is particularly preferable to add a triorganophosphate compound.

（式（９）中、ＲおよびＲ’は炭素数６〜３０のアルキル基または炭素数６〜３０のアリール基を表し、互いに同一であっても異なっていてもよい。）

(In Formula (9), R and R ′ represent an alkyl group having 6 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and may be the same or different from each other.)

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

  Among the above formulas (9), more preferred phosphite compounds are distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di). -Tert-butyl-4-methylphenyl) pentaerythritol diphosphite, and bis {2,4-bis (1-methyl-1-phenylethyl) phenyl} pentaerythritol diphosphite.

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

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

  It is preferable that either a phosphorus stabilizer or a hindered phenol antioxidant is blended. In particular, a phosphorus stabilizer is preferably blended, and a triorganophosphate compound is more blended. The amount of phosphorus stabilizer and hindered phenol antioxidant is preferably 0.005 to 1 part by weight, more preferably 0.01 to 0.3 part by weight per 100 parts by weight of component A. is there.

(I-3) Ultraviolet Absorber The fiber-reinforced resin composition of the present invention can contain an ultraviolet absorber. Since the resin composition of the present invention also has a good hue, such a hue can be maintained for a long time even when used outdoors by blending an ultraviolet absorber.

  As the ultraviolet absorber of the present invention, in the benzophenone series, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydridolate benzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2 ′, 4 , 4′-tetrahydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxy-5-sodiumsulfoxybenzophenone, bis (5-benzoyl) -4-hydroxy-2- Tokishifeniru) methane, 2-hydroxy -4-n-dodecyloxy benzoin phenone, and 2-hydroxy-4-methoxy-2'-carboxy benzophenone may be exemplified.

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

  In the hydroxyphenyl triazine series, for example, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol, 2- (4,6-diphenyl-1,3,5) -Triazin-2-yl) -5-methyloxyphenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-ethyloxyphenol, 2- (4,6-diphenyl) -1,3,5-triazin-2-yl) -5-propyloxyphenol and 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-butyloxyphenol Illustrated. Furthermore, the phenyl group of the above exemplary compounds such as 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hexyloxyphenol is 2,4-dimethyl. Examples of the compound are phenyl groups.

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

  In the case of cyanoacrylate, for example, 1,3-bis-[(2′-cyano-3 ′, 3′-diphenylacryloyl) oxy] -2,2-bis [(2-cyano-3,3-diphenylacryloyl) Examples include oxy] methyl) propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl) oxy] benzene.

  Further, the ultraviolet absorber has a structure of a monomer compound capable of radical polymerization, whereby the ultraviolet-absorbing monomer and / or the light-stable monomer having a hindered amine structure, and an alkyl (meth) acrylate. A polymer type ultraviolet absorber obtained by copolymerization with a monomer such as may be used. Preferred examples of the UV-absorbing monomer include compounds containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic imino ester skeleton, and a cyanoacrylate skeleton in the ester substituent of (meth) acrylate. The

  Among them, benzotriazole and hydroxyphenyltriazine are preferable from the viewpoint of ultraviolet absorption ability, and cyclic imino ester and cyanoacrylate are preferable from the viewpoint of heat resistance and hue. You may use the said ultraviolet absorber individually or in mixture of 2 or more types.

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

(I-4) Other Heat Stabilizers The fiber reinforced resin composition of the present invention may contain other heat stabilizers other than the phosphorus stabilizers and hindered phenol antioxidants. Such other heat stabilizers are preferably used in combination with any of these stabilizers and antioxidants, and particularly preferably used in combination with both. Such other heat stabilizers include sulfur-containing stabilizers such as pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), and glycerol-3-stearylthiopropionate. Agents are exemplified. Such a stabilizer is particularly effective when the resin composition is applied to rotational molding. The amount of the sulfur-containing stabilizer is preferably 0.001 to 0.1 parts by weight, more preferably 0.01 to 0.08 parts by weight, with respect to 100 parts by weight of component A.

(Ii) Release agent The fiber-reinforced resin composition of the present invention is a fatty acid ester, a polyolefin wax, a silicone compound, a fluorine compound, for the purpose of improving productivity during molding and improving the dimensional accuracy of a molded product. Known release agents such as paraffin wax and beeswax can also be blended. Since the fiber reinforced resin composition used in the present invention has a low molding shrinkage ratio, the mold release resistance tends to increase, and as a result, the molded product tends to be deformed during mold release. The blending of the specific component solves such a problem without impairing the properties of the fiber reinforced resin composition.

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

Examples of the polyolefin wax include an ethylene homopolymer having a molecular weight of 1,000 to 10,000, or a copolymer of ethylene and an α-olefin having 3 to 60 carbon atoms. The molecular weight is a number average molecular weight measured in terms of standard polystyrene by GPC (gel permeation chromatography) method. The upper limit of the number average molecular weight is more preferably 6,000, and still more preferably 3,000. The carbon number of the α-olefin component in the polyolefin wax is preferably 60 or less, more preferably 40 or less. More preferred specific examples include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene and the like. The proportion of the α-olefin having 3 to 60 carbon atoms is preferably 20 mol% or less, more preferably 10 mol% or less. What is marketed as what is called polyethylene wax is used suitably.
The content of the release agent is preferably 0.005 to 5 parts by weight, more preferably 0.01 to 4 parts by weight, and still more preferably 0.02 to 3 parts by weight with respect to 100 parts by weight of the component A. It is.

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

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

(Iv) Compound having heat ray absorbing ability The fiber-reinforced resin composition of the present invention may contain a compound having heat ray absorbing ability. Such compounds include phthalocyanine-based near-infrared absorbers, metal oxide-based near-infrared absorbers such as ATO, ITO, iridium oxide and ruthenium oxide, and metal boride-based near infrared rays such as lanthanum boride, cerium boride and tungsten boride. Preferred examples include various metal compounds having excellent near-infrared absorption ability such as an absorber, and carbon filler. As such a phthalocyanine-based near infrared absorber, for example, MIR-362 manufactured by Mitsui Chemicals, Inc. is commercially available and easily available. Examples of the carbon filler include carbon black, graphite (including both natural and artificial) and fullerene, and carbon black and graphite are preferable. These can be used alone or in combination of two or more. The content of the phthalocyanine near infrared absorber is preferably 0.0005 to 0.2 parts by weight, more preferably 0.0008 to 0.1 parts by weight, and 0.001 to 0 parts per 100 parts by weight of the component A. 0.07 part by weight is more preferable. The content of the metal oxide near-infrared absorber, the metal boride-based near infrared absorber, and the carbon filler is preferably in the range of 0.1 to 200 ppm (weight ratio) in the resin composition of the present invention. A range of ˜100 ppm is more preferable.

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

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

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

  Examples of the antistatic agent include: (2) lithium organic sulfonate, organic sodium sulfonate, organic potassium sulfonate, cesium organic sulfonate, rubidium organic sulfonate, calcium organic sulfonate, magnesium organic sulfonate, and barium organic sulfonate. And organic sulfonate alkali (earth) metal salts. Such metal salts are also used as flame retardants as described above. More specific examples of such metal salts include metal salts of dodecylbenzene sulfonic acid and metal salts of perfluoroalkane sulfonic acid. The content of the organic sulfonate alkali (earth) metal salt is suitably 0.01 to 0.5 parts by weight, preferably 0.01 to 0.3 parts by weight, relative to 100 parts by weight of component A. Preferably it is 0.02-0.2 weight part. In particular, alkali metal salts such as potassium, cesium, and rubidium are preferable.

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

(Viii) Other reinforcing fillers The present invention may include a plate-like filler or a fibrous filler other than the B component depending on the required characteristics. Examples of the plate-like filler used in the present invention include mica, talc, clay, graphite, glass flake, and smectite minerals such as montmorillonite. Such plate-like fillers include those coated with metal or metal oxide. The plate-like filler of the present invention is preferably at least one plate-like filler selected from the group consisting of mica, talc, glass flakes, and graphite, and glass flakes are particularly preferred. Glass flake is a plate-like glass filler manufactured by a method such as a cylindrical blow method or a sol-gel method. Various kinds of glass flake raw materials can be selected depending on the degree of pulverization and classification. The average particle size of the glass flakes used for the raw material is preferably 10 to 1000 μm, more preferably 20 to 500 μm, and still more preferably 30 to 300 μm. This is because the above range is excellent in both handleability and moldability. Usually, a plate-like glass filler is cracked by melt-kneading with a resin, and its average particle size is reduced. The number average particle size of the glass flakes in the resin composition is preferably 10 to 200 μm, more preferably 15 to 100 μm, and still more preferably 20 to 80 μm. The number average particle size is calculated by an image analyzer from an image obtained by observing the residue of the sheet glass filler collected by high temperature ashing of the molded product, dissolution with a solvent, decomposition with chemicals, etc. with an optical microscope. Is the value to be Further, when calculating such a value, the flake thickness is used as a guide and the length of the flake is not counted. Moreover, as thickness, 0.4-10 micrometers is preferable, 1-8 micrometers is more preferable, 1.5-6 micrometers is still more preferable. The glass flakes having the above number average particle diameter and thickness achieve good strength and rigidity.

  The mica used in the present invention is preferably in the form of a powder having an average particle size of 10 to 700 μm from the viewpoint of securing rigidity. Mica is a pulverized product of silicate mineral containing aluminum, potassium, magnesium, sodium, iron and the like. Mica includes muscovite, phlogopite, biotite, and artificial mica. Any mica can be used in the present invention, but muscovite is more rigid than phlogopite or biotite. Yes, muscovite is preferable in terms of rigidity. In addition, since phlogopite and biotite contain a larger amount of Fe in the main component than muscovite, their own hue becomes blackish, and muscovite is also suitable for various coloring. In addition, muscovite is advantageous in that artificial mica (natural phlogopite with OH group substituted by F) is expensive. Accordingly, muscovite is preferred in the present invention from various points of view.

  In addition, as a pulverization method in the production of mica, a dry pulverization method of pulverizing raw mica ore with a dry pulverizer, and coarsely pulverizing mica ore with a dry pulverizer, followed by adding a grinding aid such as water to a slurry state There is a wet pulverization method in which the main pulverization is performed with a wet pulverizer, followed by dehydration and drying. The lower limit of the average particle size of mica is preferably 10 μm or more as measured by the microtrack laser diffraction method, while the upper limit is 700 μm or less as the average particle size measured by the vibration screening method. preferable. It is preferable that the microtrack laser diffraction method is performed by using a vibration sieving method with a 325 mesh pass for 95% by weight or more of mica. For mica having a larger particle size, the vibration sieving method is generally used. In the vibration sieving method of the present invention, first, sieving is carried out for 10 minutes using a JIS standard standard sieve in which 100 g of mica powder to be used is stacked in the order of openings using a vibration sieve device. In this method, the particle size distribution is obtained by measuring the weight of the powder remaining on each sieve. The weight average particle diameter measured by the vibration sieving method is preferably in the range of 50 to 700 μm, and more preferably in the range of 50 to 400 μm because the impact strength is excellent. Such an effect of the particle size is particularly preferably exhibited in mica obtained using muscovite as a raw material. Those exceeding 700 μm are rare, and molding defects such as gate clogging during molding tend to occur, which is not preferable. On the other hand, pulverization of less than 10 μm is not economical because it requires an extremely large number of man-hours. As the thickness of mica, one having a thickness measured by observation with an electron microscope of 0.01 to 10 μm can be used. Further, such mica may be surface-treated with a silane coupling agent or the like, or may be granulated with a sizing agent such as various resins such as urethane resins or higher fatty acid esters.

Talc used in the present invention is a scaly particle having a layered structure, and is chemically hydrous magnesium silicate, generally represented by the chemical formula 4SiO ₂ · 3MgO · 2H ₂ O, usually the SiO ₂ 56-65 wt%, the MgO 28 to 35 wt%, and a _{H 2} O about 5 wt%. As other minor components, Fe ₂ O ₃ is 0.03 to 1.2% by weight, Al ₂ O ₃ is 0.05 to 1.5% by weight, CaO is 0.05 to 1.2% by weight, K ₂ O. Is 0.2 wt% or less, Na ₂ O is 0.2 wt% or less, and the specific gravity is about 2.7. The particle size of talc shown here is the particle size at a 50% stacking rate determined from the particle size distribution measured by the Andreazen pipette method measured according to JIS M8016. The particle diameter is preferably 0.3 to 15 μm, more preferably 0.5 to 10 μm. In addition, there is no particular limitation on the production method for pulverizing such talc from raw stone, and axial flow mill method, annular mill method, roll mill method, ball mill method, jet mill method, container rotary compression shearing mill method, etc. Can be used. Furthermore, the talc after pulverization is preferably classified by various classifiers and has a uniform particle size distribution. There are no particular restrictions on the classifier, impactor type inertial force classifier (variable impactor, etc.), Coanda effect type inertial force classifier (elbow jet, etc.), centrifugal field classifier (multistage cyclone, microplex, dispersion separator) , Accucut, Turbo Classifier, Turboplex, Micron Separator, and Super Separator). Further, such talc is preferably in an agglomerated state in terms of its handleability and the like, and as such a production method, there are a method by deaeration compression, a method of compression using a sizing agent, and the like. In particular, the method by deaeration and compression is preferred because it is simple and does not include unnecessary sizing agent resin components in the composition of the present invention.

  The graphite used in the present invention is scaly graphite. A resin composition containing such flaky graphite has good electrical conductivity, good mechanical strength, and low anisotropy. The particle size of the graphite of the present invention is preferably in the range of 5 to 300 μm. The particle size is more preferably 5 to 70 μm, further preferably 7 to 40 μm, and most preferably 7 to 35 μm. By satisfying such a range, good flame retardancy is achieved. On the other hand, if the average particle size is less than 5 μm, the effect of improving the dimensional accuracy tends to be lowered, and if the average particle size exceeds 300 μm, the impact resistance is slightly lowered and so-called graphite floats on the surface of the molded product. It is not preferable. This is because the float on the surface may cause graphite to fall off the surface of the molded product and cause electrical damage to the electronic component. In addition, the above preferable average particle diameter has an advantage that the appearance of the molded product is improved and good slidability is easily obtained. The fixed carbon content of the graphite of the present invention is preferably 80% by weight or more, more preferably 90% by weight or more, and still more preferably 98% by weight or more. The volatile content of the graphite of the present invention is preferably 3% by weight or less, more preferably 1.5% by weight or less, and still more preferably 1% by weight or less. The average particle diameter of graphite in the present invention refers to the particle diameter of graphite itself before becoming a composition, and the particle diameter is determined by a laser diffraction method. Further, the surface of graphite is subjected to surface treatment such as epoxy treatment, urethane treatment, silane coupling treatment, and oxidation treatment in order to increase the affinity with the thermoplastic resin as long as the characteristics of the composition of the present invention are not impaired. It may be given.

  As the fibrous filler other than the component B, glass milled fiber, wollastonite, carbon filler, glass fiber, and modified cross-section glass fiber are preferably exemplified. As such a fibrous filler, a filler whose surface is coated with a metal oxide such as titanium oxide, zinc oxide, cerium oxide, and silicon oxide can also be used. Examples of the carbon-based filler include carbon fiber, metal-coated carbon fiber, carbon milled fiber, vapor-grown carbon fiber, carbon nanotube, and carbon black. The carbon nanotube may be any one of a fiber diameter of 0.003 to 0.1 μm, a single layer, a double layer, and a multilayer, and a multilayer (so-called MWCNT) is preferable. Among these, carbon fiber and metal-coated carbon fiber are preferable in that they are excellent in mechanical strength and can impart good electrical conductivity.

  The fibrous filler may be surface-treated with various surface treatment agents in advance. Such surface treatment agents include silane coupling agents (including alkylalkoxysilanes and polyorganohydrogensiloxanes), higher fatty acid esters, acid compounds (for example, phosphorous acid, phosphoric acid, carboxylic acid, and carboxylic acid anhydrides). Etc.) and various surface treatment agents such as wax. Furthermore, it may be granulated with a sizing agent such as various resins, higher fatty acid esters, and waxes.

  The content of the reinforcing filler of the present invention is preferably 1 to 100 parts by weight, more preferably 5 to 70 parts by weight, and still more preferably 10 to 50 parts by weight with respect to 100 parts by weight of the component B. If the B component is less than 1 part by weight, the reinforcing effect is insufficient, and if it exceeds 100 parts by weight, the ratio of the reinforcing material made of a natural substance is undesirably reduced.

(Ix) Other additives The fiber reinforced resin composition of the present invention may contain a flow modifier, an antibacterial agent, a dispersant such as liquid paraffin, a photocatalytic antifouling agent and a photochromic agent.

(Manufacture of fiber reinforced resin composition)
Arbitrary methods are employ | adopted in order to manufacture the fiber reinforced resin composition of this invention. For example, component A, component B, component C, and optionally other additives are thoroughly mixed using premixing means such as a V-type blender, Henschel mixer, mechanochemical device, extrusion mixer, etc. In this method, the pre-mixture is granulated with an extrusion granulator or a briquetting machine, then melt-kneaded with a melt-kneader represented by a vent type twin-screw extruder, and then pelletized with a pelletizer. .

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

  As a premixing method, for example, when a component having a powder form is included as the component A, a part of the powder and an additive to be blended are mixed to produce a master batch of the additive diluted with the powder. A method using a master batch can be mentioned. Furthermore, the method etc. which supply one component independently from the middle of a melt extruder are mentioned. In addition, when there exists a liquid thing in the component to mix | blend, what is called a liquid injection apparatus or a liquid addition apparatus can be used for supply to a melt extruder.

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

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

  The molded product of the present invention can be obtained by injection molding the pellets produced by the above method. In such injection molding, not only ordinary molding methods but also injection compression molding, injection press molding, gas assist injection molding, foam molding (including a method of injecting a supercritical fluid), insert molding, in-mold coating molding, heat insulation Examples thereof include mold molding, rapid heating / cooling mold molding, two-color molding, sandwich molding, and ultra-high speed injection molding. In addition, either a cold runner method or a hot runner method can be selected for molding. Thus, a molded article made of a fiber reinforced resin composition using a reinforcing material made of a natural substance and having excellent mechanical strength and flame retardancy is provided. That is, according to the present invention, according to the present invention, the problem is that (A) 100 parts by weight of the thermoplastic resin (A component), (B) 1 to 100 weights of fibers (B component) made of basalt. And (C) a flame retardant (component C) 0.01 to 30 parts by weight of a fiber reinforced resin composition is contained. Furthermore, various surface treatments can be performed on the molded article made of the resin composition of the present invention. Surface treatment here refers to a new layer on the surface of resin molded products such as vapor deposition (physical vapor deposition, chemical vapor deposition, etc.), plating (electroplating, electroless plating, hot dipping, etc.), painting, coating, printing, etc. A method used for ordinary polycarbonate resin is applicable. Specific examples of the surface treatment include various surface treatments such as hard coat, water / oil repellent coat, ultraviolet absorption coat, infrared absorption coat, and metalizing (evaporation).

  The fiber reinforced resin composition of the present invention is useful in a wide range of fields because it is excellent in mechanical strength and flame retardancy and uses a reinforcing material made of a natural substance. Is useful for applications where Therefore, the industrial effect exhibited by the present invention is extremely great.

  The form of the present invention considered to be the best by the present inventor is a collection of the preferable ranges of the above requirements. For example, typical examples are described in the following examples. Of course, the present invention is not limited to these forms.

(I) Evaluation of fiber reinforced resin composition (i) Flexural strength, flexural modulus: measured in accordance with ISO 178 (measurement condition 23 ° C.). In addition, the test piece was shape | molded by the cylinder temperature of 300 degreeC and the mold temperature of 90 degreeC with the injection molding machine (Sumitomo Heavy Industries, Ltd. SG-150U).
(Ii) Flame-retardant properties: UL94 rank was evaluated based on the UL94 standard at thicknesses of 0.6 mm and 1.2 mm. In addition, the test piece was shape | molded by the cylinder temperature of 300 degreeC and the mold temperature of 90 degreeC with the injection molding machine (Sumitomo Heavy Industries, Ltd. SG-150U).
(Iii) Extrusion stability: The case where the strand at the time of extrusion is stable and easy to be pelletized is indicated by ◯, and the case where the strand is largely out of control and difficult to be pelletized is indicated by ×.

[Examples 1-6, Comparative Examples 1-6]
Polycarbonate resin, fiber made of basalt, flame retardant and various additives listed in Table 1 and Table 2 are mixed in blenders in each blending amount, and then melt-kneaded using a vent type twin screw extruder to obtain pellets It was. The flame retardant and various additives to be used were preliminarily prepared with a polycarbonate resin in advance with a concentration of 10 to 100 times the blending amount as a guide, and then the whole was mixed by a blender. The vent type twin-screw extruder used was TEX-30XSST (completely meshing, rotating in the same direction, two-thread screw) manufactured by Nippon Steel Works. The extrusion conditions were a discharge rate of 20 kg / h, a screw rotation speed of 150 rpm, and a vent vacuum of 3 kPa. The extrusion temperature was 290 ° C. from the first supply port to the second supply port, and 300 ° C. from the second supply port to the die part. did. In addition, the fiber and glass fiber which consist of basalt were supplied from the 2nd supply port using the side feeder of the said extruder, and the remaining polycarbonate resin, the flame retardant, and the additive were supplied to the extruder from the 1st supply port. The first supply port here is a supply port farthest from the die, and the second supply port is a supply port located between the die of the extruder and the first supply port. The obtained pellets were dried in a hot air circulation dryer at 100 ° C. for 5 hours, and then a test piece for evaluation was molded using an injection molding machine. The evaluation results are shown in Tables 1 and 2.

Each component of the symbol notation in Table 1 and Table 2 is as follows.
(A component)
PC: Linear aromatic polycarbonate resin powder having a viscosity average molecular weight of 22400 (manufactured by Teijin Chemicals Ltd .: Panlite L-1225WP)
ABS: Acrylonitrile-styrene-butadiene copolymer (“Santac UT-61” (trade name) manufactured by Nippon Air and L Co., Ltd., bulk polymer, about 80% by weight of free AS polymer component and ABS polymer component ( Acetone insoluble gel content) about 20 wt%, butadiene rubber component content is about 15 wt% of the total)
(B component)
BF: Basalt fiber (manufactured by Gold Basalt Fiber Co., Ltd .: GBF Basalt chopped sland, fiber diameter: 11 μm, cut length 4.5 mm, epoxy-based focusing material)
(Other ingredients)
GF: Circular cross-section chopped glass fiber (manufactured by Nippon Electric Glass Co., Ltd .; ECS-03T-511, diameter 13 μm, cut length 3 mm, surface treatment with aminosilane and urethane sizing agent)
(C component)
FR-1: Resorcinol bis (dixylenyl phosphate) (PX-200, manufactured by Daihachi Chemical Industry Co., Ltd.)
FR-2: potassium perfluorobutane sulfonate (Dainippon Ink Chemical Co., Ltd. MegaFuck F-114P)
(D component)
PTFE: Polytetrafluoroethylene having fibril-forming ability (Polyflon MPA FA500 manufactured by Daikin Industries, Ltd.)

  As is apparent from Tables 1 and 2, the resin composition containing basalt fibers is superior in bending strength and flexural modulus to the resin composition containing glass fibers and exhibits high flame retardancy. Recognize. That is, it can be seen that the present invention provides a resin composition that is excellent in mechanical strength and flame retardancy and uses a reinforcing material made of a natural substance.

Claims (10)

  (A) 1-100 parts by weight of fiber (B component) made of basalt (B) and (C) flame retardant (C component) 0.01-30 parts by weight with respect to 100 parts by weight of thermoplastic resin (A component) A fiber-reinforced resin composition comprising:   The fiber-reinforced resin composition according to claim 1, wherein the component A contains 50% by weight or more of an aromatic polycarbonate resin (component A-1).   The fiber reinforced resin composition according to claim 1 or 2, wherein the B component has an average fiber diameter of 7 to 25 µm and an average fiber length of 50 to 2,000 µm.   The fiber reinforced resin composition according to any one of claims 1 to 3, wherein the component C is at least one flame retardant selected from the group consisting of an organic metal salt flame retardant and an organic phosphorus flame retardant.   The fiber reinforced resin composition according to claim 4, wherein the organic metal salt flame retardant is an alkali (earth) metal sulfonate.   6. The fiber-reinforced resin composition according to claim 5, wherein the organic sulfonic acid alkali (earth) metal salt is a perfluoroalkylsulfonic acid alkali (earth) metal salt. The fiber-reinforced resin composition according to claim 4, wherein the organophosphorus flame retardant is a flame retardant represented by the following general formula (1).

(However, X in the above formula is hydroquinone, resorcinol, bis (4-hydroxydiphenyl) methane, bisphenol A, dihydroxydiphenyl, dihydroxynaphthalene, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis And a divalent group derived from (4-hydroxyphenyl) sulfide, wherein j, k, l and m are each independently 0 or 1, n is an integer of 0 to 5, or n number In the case of a mixture of phosphoric acid esters having different values, the average value is 0 to 5, and R ¹ , R ² , R ³ , and R ⁴ are each independently substituted or not substituted with one or more halogen atoms From phenol, cresol, xylenol, isopropylphenol, butylphenol, p-cumylphenol A monovalent group that is derived.)   The fiber-reinforced resin composition according to any one of claims 1 to 7, comprising 0.01 to 3 parts by weight of (D) a fluorine-containing anti-dripping agent (D component) with respect to 100 parts by weight of the A component.   The fiber-reinforced resin composition according to any one of claims 1 to 8, wherein the component A contains 1 to 100 parts by weight of a styrene resin (component A-2) with respect to 100 parts by weight of the component A-1.   The resin molded product formed by injection-molding the fiber reinforced resin composition in any one of Claims 1-9.