JP2007314766A - Thermoplastic resin composition and resin molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition which is excellent in extrusion moldability, stiffness, flame retardancy, impact resistance and thermal stability and show excellent balance among physical properties, and to provide a resin molded article produced by molding the same. <P>SOLUTION: The thermoplastic resin composition comprises: 40 to 99 pts.wt. of an aromatic polycarbonate resin (component A) which comprises 50 to 100 wt.% of an aromatic polycarbonate resin (component A1) and 50 to 0 wt.% of a thermoplastic resin (component A2) other than an aromatic polycarbonate resin; 1 to 60 pts.wt. of a granulated talc (component B) which comprises a talc having an average particle diameter of 0.1 to 10 μm, wherein the talc is so granulated as to have a bulk density of 0.4 to 1.5 g/ml; based on the total amount of the components A and B being 100 pts.wt., 0.01 to 40 pts.wt. of a flame retardant (component C) selected from an organic alkali(ine earth) metal salt (component C1), an organic phosphorous flame retardant (component C2), and a silicone-based flame retardant (component C3); and 0.01 to 5 pts.wt. of a fluorinated polyolefin (component D), wherein the component B has such a grain size that the ratio of granules trapped on a 500 μm-mesh sieve is 55 wt.% or more. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a thermoplastic resin composition and a resin molded article, and more specifically, extrudability, rigidity, difficulty, and the like comprising a resin component containing an aromatic polycarbonate resin and a specific granular talc and a specific flame retardant. The present invention relates to a thermoplastic resin composition having improved flammability, impact resistance and thermal stability, and excellent physical property balance, and a resin molded product comprising the thermoplastic resin composition.

  Aromatic polycarbonate resin is a general-purpose engineering plastic with excellent transparency, impact resistance, heat resistance, dimensional stability, etc., and its excellent characteristics make it a wide range of electrical, electronic, OA equipment parts, machine parts, vehicle parts, etc. Used in the field. Among these fields, electrical / electronic / OA equipment parts are particularly demanded to be flame retardant, and techniques for making them flame retardant by incorporating various flame retardants are widely used.

  As flame retardants, resin compositions containing halogen-based flame retardants such as bromine compounds have been used for a long time, but they have high flame retardancy but have a problem of environmental impact, and are non-halogen-based flame retardants. Many resin compositions containing a flame retardant have been proposed.

  Furthermore, since the aromatic polycarbonate resin itself generally has low fluidity, an organic phosphate ester flame retardant is used as a polymer alloy with a styrene resin such as acrylonitrile-butadiene-styrene copolymer (ABS resin). Etc. are widely used mainly for OA equipment casings such as personal computers and printers.

  In recent years, in electric / electronic / OA equipment parts, the thickness of resin molded products to be used has been reduced, and materials having good appearance and high rigidity are required. And the flame-retardant resin composition containing the inorganic filler of small particle diameters, such as a talc, is proposed (for example, refer patent document 1). However, the aromatic polycarbonate resin composition containing talc can provide a good molded article surface appearance, but because of the strong basicity of talc, the aromatic polycarbonate resin decomposes and is inferior in thermal stability and impact resistance. There was a problem. Furthermore, in the resin composition containing a non-halogen flame retardant, there is also a problem that the flame retardancy decreases as the talc content increases.

  On the other hand, a technique using an inorganic filler after surface treatment has been proposed (see, for example, Patent Documents 2 to 4). However, with the techniques described in these patent documents, the flame retardancy and thermal stability of the obtained resin molded product are not always sufficient, and if a large amount of talc with a small particle size is contained, hopper clogging and biting into the extruder There were also problems such as poor extrudability and poor impact resistance due to poor talc dispersion.

  As described above, in a thermoplastic resin composition containing an aromatic polycarbonate resin containing talc having a small particle size and a non-halogen flame retardant, the extrusion processability, rigidity, flame retardancy, impact resistance, and thermal stability are improved. There was a strong demand for superior technology.

  As means for solving this problem, a resin composition using talc that has been mechanically compressed to increase bulk specific gravity (see, for example, Patent Document 5), or a resin composition that uses talc that defines electrical conductivity (for example, a patent) Reference 6) is proposed. However, although Patent Document 6 describes that talc is compressed and granulated, it is described that it can be granulated using a binder, but no specific examples are found, and further extrusion processing is performed. The flame resistance, flame resistance, impact resistance, and thermal stability were insufficient.

  On the other hand, a technique using an inorganic filler granulated with a binder (see, for example, Patent Document 7) or an aromatic polycarbonate resin containing granular talc granulated with a specific amount of bentonite. A thermoplastic resin composition has also been proposed (see, for example, Patent Document 8). Although these patent documents describe that a flame retardant can be blended, the aromatic polycarbonate resin contains granular talc and a non-halogen flame retardant, and is excellent in flame retardancy and thermal stability. The aromatic polycarbonate resin composition has not been described or suggested.

Japanese Patent Application No. 2003-134304 Japanese Patent Laid-Open No. 10-338805 JP 2005-48072 A JP 2005-220216 A JP-A-8-176339 JP 2002-60637 A JP 2002-220549 A JP 2006-77176 A

  The object of the present invention is to eliminate the above-mentioned disadvantages of the prior art, improve the extrusion processability, rigidity, flame retardancy, impact resistance, and thermal stability, and provide a thermoplastic resin composition having an excellent balance of physical properties and It is providing the resin molded product which consists of the said thermoplastic resin composition.

  As a result of intensive studies to achieve the above object, the present inventors have made a thermoplastic resin composition containing a specific granular talc and a specific flame retardant in a resin component containing an aromatic polycarbonate resin. (Hereinafter, it may be simply referred to as “resin composition”) improves all of extrudability, rigidity, flame retardancy, impact resistance, and thermal stability, resulting in a resin composition with an excellent balance of physical properties. As a result, the present invention has been completed.

  That is, the first gist of the present invention consists of 100 to 100% by weight in total of aromatic polycarbonate resin (A1 component) 50 to 100% by weight and thermoplastic resin (A2 component) other than aromatic polycarbonate resin 50 to 0% by weight. Resin component (component A) 40 to 99 parts by weight Granular talc (component B) granulated from talc having an average particle size of 0.1 to 10 μm and a bulk density of 0.4 to 1.5 g / ml It consists of an organic alkali metal salt and / or an organic alkaline earth metal salt (C1 component), an organic phosphorus flame retardant (C2 component), and a silicone resin (C3 component) with respect to a total of 100 parts by weight of 1 to 60 parts by weight. A thermoplastic fat composition containing 0.01 to 40 parts by weight of at least one flame retardant (C component) selected from the group, and 0.01 to 5 parts by weight of a fluorinated polyolefin (D component), Granular powder In the particle size of the click (B component), the proportion of the 500μm sieve opening eye lies in the thermoplastic resin composition characterized in that it is 55 wt% or more.

  And the 2nd summary of this invention exists in the resin molded product formed by shape | molding a thermoplastic resin composition.

  The thermoplastic resin composition of the present invention is characterized in that all of extrusion processability, rigidity, flame retardancy, impact resistance, and thermal stability are improved and the balance of physical properties is excellent. The thermoplastic resin composition of the present invention having such features can be used in a wide range of fields, such as electrical / electronic equipment parts, OA equipment, machine parts, vehicle parts, building members, various containers, and leisure. It is useful for various applications such as goods / miscellaneous goods, information terminal equipment parts such as mobile phones, and is particularly suitable for electrical / electronic equipment parts, OA equipment parts, information terminal equipment parts.

  Electrical / electronic equipment parts, OA equipment parts, and information terminal equipment parts include personal computers, game machines, television display devices, printers, copy machines, scanners, fax machines, electronic notebooks and PDAs, battery packs, Examples include housing members and internal parts such as cameras, video cameras, mobile phones, recording medium drives and readers.

  Hereinafter, the present invention will be described in more detail. The “group” of various compounds may have a substituent without departing from the spirit of the present invention.

Aromatic polycarbonate resin (A1 component)
The aromatic polycarbonate resin which is the A1 component of the present invention (hereinafter sometimes abbreviated as “A1 component”) includes, for example, an aromatic dihydroxy compound and a carbonate precursor, or a small amount of A linear or branched thermoplastic aromatic polycarbonate polymer or copolymer obtained by reacting a hydroxy compound or the like.

  The aromatic polycarbonate resin in the present invention is not particularly limited and can be produced by a known method, for example, an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, Examples thereof include a solid phase transesterification method of a prepolymer.

  As aromatic dihydroxy compounds used as raw materials, 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A), 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane (= Tetrabromobisphenol A), bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2- Bis (4-hydroxyphenyl) octane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2- (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, , 1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane, 2,2-bis (4-hydroxyphenyl) -1,1,1-trichloropropane, 2,2- Bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexachloropropane, 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane Bis (hydroxyaryl) alkanes exemplified by the above;

  Exemplified by 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, etc. Bis (hydroxyaryl) cycloalkanes; 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, etc. Bisphenols; dihydroxydiaryl ethers exemplified by 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether, etc .;

  Dihydroxydiaryl sulfides exemplified by 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide, etc .; 4,4′-dihydroxydiphenyl sulfoxide, 4,4′- Dihydroxydiaryl sulfoxides exemplified by dihydroxy-3,3′-dimethyldiphenyl sulfoxide, etc .; exemplified by 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfone, etc. Dihydroxydiaryl sulfones; hydroquinone, resorcin, 4,4′-dihydroxydiphenyl and the like.

  Among these, bis (4-hydroxyphenyl) alkanes are preferable, and 2,2-bis (4-hydroxyphenyl) propane [= bisphenol A] is particularly preferable from the viewpoint of impact resistance. . These aromatic dihydroxy compounds may be used alone or in combination of two or more.

  As the carbonate precursor to be reacted with the aromatic dihydroxy compound, carbonyl halide, carbonate ester, haloformate, etc. are used. Specifically, phosgene; diaryl carbonates such as diphenyl carbonate and ditolyl carbonate; dimethyl carbonate, diethyl carbonate And dialkyl carbonates such as divalent phenols. These carbonate precursors may also be used alone or in combination of two or more.

The aromatic polycarbonate resin may be a branched aromatic polycarbonate resin obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound. Examples of the trifunctional or higher polyfunctional aromatic compound include phloroglucin, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-2, 4,6-dimethyl-2,4,6- Tri (4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-3, 1,3,5-tri (4-hydroxyphenyl) benzene, 1, Polyhydroxy compounds exemplified by 1,1-tri (4-hydroxyphenyl) ethane or the like, or 3,3-bis (4-hydroxyaryl) oxyindole (= isatin bisphenol) , 5-chloroisatin, 5,7-dichloroisatin, 5-bromoisatin and the like. Among these, 1,1,1-tri (4-hydroxyphenyl) ethane is preferable. The polyfunctional aromatic compound can be used by replacing a part of the aromatic dihydroxy compound, and the amount used is preferably in the range of 0.01 to 10 mol% with respect to the aromatic dihydroxy compound. The range of .1 to 2 mol% is more preferable.

  Next, the manufacturing method of the aromatic polycarbonate resin used for this invention is demonstrated. Of the methods for producing an aromatic polycarbonate resin, the interfacial polymerization method will be described first. The polymerization reaction in this production method is usually carried out in the presence of an organic solvent inert to the reaction, an aqueous alkaline solution, and the pH is usually kept at 9 or higher. The aromatic dihydroxy compound and, if necessary, a molecular weight modifier (terminal terminator). And by reacting with phosgene using an antioxidant for preventing oxidation of aromatic dihydroxy compounds, adding a polymerization catalyst such as a tertiary amine or a quaternary ammonium salt, and conducting interfacial polymerization to produce polycarbonate. obtain. The addition of the molecular weight regulator is not particularly limited as long as it is from the time of phosgenation to the start of the polymerization reaction. The reaction temperature is, for example, 0 to 40 ° C., and the reaction time is, for example, several minutes (for example, 10 minutes) to several hours (for example, 6 hours).

  Here, examples of the organic solvent inert to the reaction include chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, monochlorobenzene and dichlorobenzene, and aromatic hydrocarbons such as benzene, toluene and xylene. . Examples of the alkali compound used in the alkaline aqueous solution include hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide.

  Examples of the molecular weight regulator include compounds having a monovalent phenolic hydroxyl group. Examples of the compound having a monovalent phenolic hydroxyl group include m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, p-tert-butylphenol and p-. Long chain alkyl substituted phenols and the like. The amount of the molecular weight regulator used is preferably 50 to 0.5 mol, more preferably 30 to 1 mol, per 100 mol of the aromatic dihydroxy compound.

  As a polymerization catalyst, tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine, trihexylamine and pyridine: quaternary ammonium salts such as trimethylbenzylammonium chloride, tetramethylammonium chloride, triethylbenzylammonium chloride Etc.

Next, the melt transesterification method will be described. The polymerization reaction in this production method is, for example, a transesterification reaction between a carbonic acid diester and an aromatic dihydroxy compound. Examples of the carbonic acid diester include dialkyl carbonate compounds such as dimethyl carbonate, diethyl carbonate and di-tert-butyl carbonate, substituted diphenyl carbonates such as diphenyl carbonate and ditolyl carbonate, and the like. The carbonic acid diester is preferably diphenyl carbonate or substituted diphenyl carbonate, more preferably diphenyl carbonate.

  In the aromatic polycarbonate resin, the amount of terminal hydroxyl groups greatly affects the thermal stability, hydrolysis stability, color tone and the like of the product polycarbonate, and may be appropriately adjusted by any conventionally known method. In the melt transesterification reaction, usually, the mixing ratio of the carbonic acid diester and the aromatic dihydroxy compound and the degree of pressure reduction during the transesterification reaction are adjusted to obtain an aromatic polycarbonate having the desired molecular weight and terminal hydroxyl group content adjusted. Can do.

  Usually, in the melt transesterification reaction, the diester carbonate is used in an equimolar amount or more with respect to 1 mol of the aromatic dihydroxy compound, and it is preferably used in an amount of 1.01-1.30 mol. Further, as a more aggressive adjustment method, there is a method of adding a terminal terminator separately at the time of reaction, and examples of the terminal terminator in this case include monohydric phenols, monovalent carboxylic acids, and carbonic acid diesters. It is done.

  When producing polycarbonate by the melt transesterification method, a transesterification catalyst is usually used. The transesterification catalyst is not particularly limited, but an alkali metal compound and / or an alkaline earth metal compound is preferable. In addition, a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine compound may be used in combination. As the transesterification reaction using the above raw materials, the reaction is carried out at a temperature of 100 to 320 ° C., and finally a melt polycondensation reaction is performed under reduced pressure of 2 mmHg or less while removing by-products such as aromatic hydroxy compounds. Just do it.

  The melt polycondensation can be performed by either a batch method or a continuous method. Among these, in consideration of the stability of the aromatic polycarbonate resin used in the present invention and the resin composition of the present invention, it is preferable to carry out in a continuous manner. As the catalyst deactivator used in the melt transesterification method, it is preferable to use a compound that neutralizes the transesterification reaction catalyst, such as a sulfur-containing acidic compound or a derivative formed therefrom. The compound that neutralizes such a catalyst is preferably added in an amount of 0.5 to 10 equivalents, more preferably 1 to 5 equivalents, relative to the alkali metal contained in the catalyst. In addition, the compound that neutralizes such a catalyst is preferably added in an amount of 1 to 100 ppm, more preferably 1 to 20 ppm, based on the polycarbonate.

  The molecular weight of the aromatic polycarbonate resin used in the present invention may be appropriately selected and determined, but the viscosity average molecular weight [Mv] converted from the solution viscosity is preferably in the range of 10,000 to 50,000. By setting the viscosity average molecular weight of the aromatic polycarbonate to 10,000 or more, the mechanical strength tends to be further improved, and it is more preferable when used for applications requiring high mechanical strength. On the other hand, when the viscosity average molecular weight is less than 50000, it tends to be possible to further improve the decrease in fluidity, which is more preferable from the viewpoint of easy molding processability.

  The viscosity average molecular weight is more preferably 12000 to 40000, and further preferably 14000 to 30000. Moreover, you may mix 2 or more types of aromatic polycarbonate resin from which a viscosity average molecular weight differs. Of course, you may mix the aromatic polycarbonate resin whose viscosity average molecular weight is outside the said suitable range.

Here, the viscosity average molecular weight [Mv] is obtained by using methylene chloride as a solvent and obtaining an intrinsic viscosity [η] (unit: dl / g) at a temperature of 20 ° C. using an Ubbelohde viscometer. , Η = 1.23 × 10 ⁻⁴ M ^0.83 . Here, the intrinsic viscosity [η] is a value calculated from the following equation by measuring the specific viscosity [ηsp] at each solution concentration [C] (g / dl).

  The terminal hydroxyl group concentration of the aromatic polycarbonate resin used in the present invention is usually 1000 ppm or less, preferably 800 ppm or less, more preferably 600 ppm or less, particularly 10 ppm or more for the aromatic polycarbonate resin produced by the transesterification method. Of these, it is preferably 30 ppm or more, more preferably 40 ppm or more.

  By setting the terminal hydroxyl group concentration to 10 ppm or more, a decrease in molecular weight can be suppressed, and the mechanical properties of the resin composition tend to be further improved. Moreover, it is preferable for the terminal group hydroxyl group concentration to be 1000 ppm or less because the residence heat stability and color tone of the resin composition tend to be further improved.

The terminal hydroxyl group unit is the weight of the terminal hydroxyl group expressed in ppm with respect to the weight of the aromatic polycarbonate resin, and the measurement method is colorimetric determination (Macromol. Chem. 88 215) by the titanium tetrachloride / acetic acid method. (Method of (1965)).

  Moreover, the aromatic polycarbonate resin used in the present invention may contain an aromatic polycarbonate oligomer in order to improve the appearance of the resin molded product and the fluidity. The viscosity average molecular weight [Mv] of the aromatic polycarbonate oligomer is preferably 1500 to 9500, particularly 2000 to 9000, and the content thereof is preferably 30% by weight or less in the aromatic polycarbonate resin component.

  Further, as the aromatic polycarbonate resin used in the present invention, not only virgin raw materials but also aromatic polycarbonate resins regenerated from used products, so-called material recycled aromatic polycarbonate resins may be used. Used products include optical recording media such as optical disks, light guide plates, vehicle window glass, vehicle headlamp lenses, windshields, and other vehicle transparent members, water bottle containers, glasses lenses, soundproof walls, glass windows, waves, etc. A building member such as a plate is preferred. Also, non-conforming products, pulverized products obtained from sprues, runners, etc., or pellets obtained by melting them can be used. The regenerated aromatic polycarbonate resin is preferably 80% by weight or less, more preferably 50% by weight or less of the aromatic polycarbonate resin component.

Thermoplastic resins other than aromatic polycarbonate resin (A2 component)
As the thermoplastic resin other than the aromatic polycarbonate resin which is the A2 component of the present invention (hereinafter sometimes abbreviated as “A2 component”), various known arbitrary thermoplastic resins can be used. Specifically, for example, thermoplastic polyester resins such as polyethylene terephthalate resin, polytrimethylene terephthalate, polybutylene terephthalate resin; polystyrene resin, high impact polystyrene resin (HIPS), acrylonitrile-styrene copolymer (AS resin), acrylonitrile. -Styrene resins such as butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), acrylonitrile-ethylenepropylene rubber-styrene copolymer (AES resin); polyethylene resin, Polyolefin resins such as polypropylene resins; Polyamide resins; Polyimide resins; Polyetherimide resins; Polyurethane resins; Polyphenylene ether resins; Polyphenylene sulfide resins; Sulfone resins; polymethacrylate resins, and the like. These may be used in combination of two or more types may be used alone. Among these, styrene resins are particularly preferable from the viewpoints of flame retardancy and impact resistance.

  In the presence of a styrene-based resin, a styrene-based polymer composed of a styrene-based monomer, a copolymer of the styrene-based monomer and another copolymerizable vinyl-based monomer, or a rubbery polymer. This refers to at least one polymer selected from the group consisting of the styrene monomer or a copolymer of the styrene monomer and another copolymerizable vinyl monomer. Among these, it is preferable to use the styrene monomer in the presence of a rubbery polymer or a copolymer of the styrene monomer and another copolymerizable vinyl monomer.

  Specific examples of the styrene monomer include styrene derivatives such as styrene, α-methylstyrene, P-methylstyrene, divinylbenzene, ethylvinylbenzene, dimethylstyrene, pt-butylstyrene, bromostyrene, and dibromostyrene. Among them, styrene is preferable. In addition, these can also be used individually or in mixture of 2 or more types.

  As vinyl monomers copolymerizable with the above styrenic monomers, vinylcyan compounds such as acrylonitrile and methacrylonitrile, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, Acrylic acid alkyl esters such as 2-ethylhexyl acrylate, octyl acrylate and cyclohexyl acrylate, methacrylic acid such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate and cyclohexyl methacrylate Acrylic such as alkyl ester, phenyl acrylate, benzyl acrylate Methacrylic acid aryl esters such as aryl esters, phenyl methacrylate and benzyl methacrylate, epoxy group-containing acrylic acid esters or methacrylic acid esters such as glycidyl acrylate and glycidyl methacrylate, maleimides such as N, N-methylmaleimide and N-phenylmaleimide Examples thereof include α, β-unsaturated carboxylic acids such as monomers, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid and itaconic acid, or anhydrides thereof.

  Further, rubbery polymers copolymerizable with styrene monomers include polybutadiene, polyisoprene, styrene-butadiene random copolymers and block copolymers, acrylonitrile-butadiene random copolymers and block copolymers, acrylonitrile. -Butadiene copolymer, copolymer of alkyl acrylate or alkyl methacrylate and butadiene, polybutadiene-polyisoprene diene copolymer, ethylene-isoprene random copolymer and block copolymer, ethylene-butene random Copolymers of ethylene and α-olefins such as copolymers and block copolymers, ethylene-methacrylate copolymers, ethylene-butyl acrylate copolymers and the like of ethylene and α, β-unsaturated carboxylic acid esters Copolymer, D Examples include ethylene-propylene-nonconjugated diene terpolymers such as len-vinyl acetate copolymer, ethylene-propylene-hexadiene copolymer, acrylic rubber, and composite rubber composed of polyorganosiloxane rubber and polyalkyl acrylate or methacrylate rubber. Can be mentioned.

  Such styrene resins include, for example, high impact polystyrene (HIPS), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), methyl methacrylate-acrylonitrile-butadiene-styrene copolymer. Polymer (MABS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), acrylonitrile-ethylenepropylene rubber-styrene copolymer (AES resin), styrene-methyl methacrylate copolymer (MS resin), styrene -Maleic anhydride copolymer etc. are mentioned.

  Among these, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), acrylonitrile-ethylenepropylene rubber-styrene A copolymer (AES resin) is preferred, more preferably an acrylonitrile-butadiene-styrene copolymer (ABS resin), an acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), an acrylonitrile-ethylenepropylene rubber-styrene copolymer It is a combination (AES resin), and an acrylonitrile-butadiene-styrene copolymer (ABS resin) is particularly preferable. These can be used alone or in admixture of two or more.

  The styrene resin is produced by a method such as emulsion polymerization, solution polymerization, bulk polymerization, suspension polymerization or bulk / suspension polymerization. In the present invention, a so-called styrene polymer or styrene random copolymer is used. In the case of a polymer or block copolymer, those produced by bulk polymerization, suspension polymerization or bulk / suspension polymerization are suitable, and in the case of a styrene-based graft copolymer, bulk polymerization, bulk / suspension polymerization or Those produced by emulsion polymerization are preferred.

  In the present invention, an acrylonitrile-butadiene-styrene copolymer (ABS resin) that is particularly preferably used is a thermoplastic graft copolymer obtained by graft polymerization of acrylonitrile and styrene to a butadiene rubber component, and a copolymer of acrylonitrile and styrene. It is a mixture. The butadiene rubber component is preferably 5 to 40% by weight, more preferably 10 to 35% by weight, and particularly preferably 13 to 25% by weight, in 100% by weight of the ABS resin component. The rubber particle diameter is preferably 0.1 to 5 μm, more preferably 0.2 to 3 μm, further 0.3 to 1.5 μm, and particularly preferably 0.4 to 0.9 μm. The rubber particle size distribution may be either a single distribution or a plurality of distributions of two or more peaks.

Granular talc (component B)
The granular talc which is the B component of the present invention (hereinafter sometimes abbreviated as “B component”) is a talc having an average particle size of 0.1 to 10 μm and a bulk density of 0.4 to 1.5 g / It is granulated so as to be ml, and its particle size is characterized in that the proportion on a sieve having an opening of 500 μm is 55% by weight or more.

Granular talc used in the present invention is a hydrous magnesium silicate having a layered structure, the chemical formula is represented by _{4SiO 2 · 3MgO · H 2 O} , 28~ usually a SiO ₂ 58 to 66 wt%, of MgO 35% by weight and about 5% by weight of H ₂ O. 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, and K ₂ O is It contains 0.2% by weight or less, Na ₂ O is 0.2% by weight or less, and the specific gravity is about 2.7.

  The granular talc used in the present invention is obtained by granulating talc having an average particle size of 0.1 to 10 μm (hereinafter sometimes referred to as “raw material talc”). The average particle size of the raw material talc is: Of these, it is preferably 0.3 to 8 μm, more preferably 0.7 to 5 μm. When the average particle size is 0.1 μm or more, the thermal stability of the resin composition tends to be further improved. On the other hand, when the average particle size is less than 10 μm, the appearance and rigidity of the molded product of the resin composition are more improved. It tends to improve.

Here the average particle diameter refers to the D ₅₀ as measured in the liquid phase precipitation method using X-ray transmission. As an apparatus capable of performing such measurement, a Sedigraph particle size analyzer (“Model 5100” manufactured by Micromeritics Instruments) can be mentioned.

  Further, the granular talc used in the present invention is preferably subjected to a surface treatment in order to increase the affinity of the (component A) with the resin. Specific examples of the surface treatment agent include alcohols such as trimethylolethane, trimethylolpropane, and pentaerythritol, alkanolamines such as triethylamine, higher fatty acids such as stearic acid, and fatty acid metal salts such as calcium stearate and magnesium stearate. Coupling of hydrocarbon lubricants such as polyethylene wax and liquid paraffin, basic amino acids such as lysine and arginine, polyglycerin and their derivatives, silane coupling agents, titanate coupling agents, aluminum coupling agents, etc. At least one selected from agents.

  Next, the bulk density of the granular talc used in the present invention is usually 0.4 to 1.5 g / ml, particularly 0.5 to 1.3 g / ml, particularly 0.6 to 1.1 g / ml. Preferably there is. When the bulk density is 0.4 g / ml or more, the extrudability, flame retardancy, impact resistance, and thermal stability of the resin composition tend to be further improved, while the bulk density is 1.5 g / ml. By making it less than, it exists in the tendency which the molded article external appearance and impact resistance of a resin composition improve more.

Here, the bulk density is a value obtained by the following method.
(1) Place the granular talc on a sieve with an aperture of 1.4 mm, and pass through the sieve while sweeping lightly with a brush.
(2) The granular talc passed through the sieve is put into a receiver attached to the bulk density measuring device specified in JIS K5101 until it reaches a heap.
(3) Scrap off the granular talc that is piled up from the inlet of the receiver with a spatula, measure the weight of the granular talc in the receiver, and calculate the bulk density using the following equation.

    Bulk density (g / ml) = weight of granular talc in the receiver (g) / capacity of receiver (ml)

  The particle size of the granular talc used in the present invention is such that the ratio on the sieve having a mesh opening of 500 μm is 55% by weight or more, especially 60% by weight or more, more preferably 70% by weight or more, particularly 90% by weight or more. preferable. In the granular talc particle size, the flame retardancy and thermal stability of the resin composition of the present invention tend to be further improved by setting the ratio on the sieve having an opening of 500 μm to 55% by weight or more.

Here, the particle size of the granular talc is a value obtained by the following method in accordance with JIS Z8801.
(1) Place the granular talc on a sieve having an opening of 2 mm, and pass the sieve while sweeping lightly with a brush.
(2) The above granular talc passed through a sieve was put into a 200 ml beaker, and reduced to about 30 ml using a sample reducer “1305 6” (groove width 6 mm) manufactured by Yoshida Seisakusho. .
(3) The above-mentioned granular talc was sieved using a sieve having an opening of 500 μm, and the weight of the granular talc that did not pass through the 500 μm sieve (on the sieve) was determined, and the ratio from the total amount was determined. The sieving was carried out for 10 minutes at a vibration frequency of 120 times / second using an “electromagnetic vibration sieve M-100 type” manufactured by Tsutsui Rika Kagakuki.

  The manufacturing method (granulation method) of the granular talc used for this invention using raw material talc is arbitrary, and conventionally well-known arbitrary granulation methods can be used. Specifically, for example, those granulated using a binder are preferable from the viewpoint of flame retardancy, thermal stability, impact resistance and rigidity of the resin composition.

  The binder used when producing the granular talc used in the present invention is highly granulated with raw material talc, is colorless or nearly white, is an inert and stable substance, and does not deteriorate the physical properties of the resin molded body. Anything is desirable. Specific examples include clay minerals such as bentonite that exhibit high caking properties under wet conditions, colloidal silica, gypsum, water-soluble polymers, waxes, higher fatty acids, and resin powders. Of these, clay minerals and water-soluble polymers are preferred, and water-soluble polymers are particularly preferred from the viewpoint of thermal stability, impact resistance, and rigidity of the resin composition.

  Specific examples of the water-soluble polymer include water-soluble polyester resins, polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, sodium polyacrylate, sodium alginate, agar, polysaccharides (methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose). , Cellulose derivatives such as sodium carboxymethyl cellulose (hereinafter sometimes abbreviated as “CMC”) and starch, and proteins (gelatin, glue, etc.).

  Of these, water-soluble polyester resins, polysaccharides and proteins having high caking properties and high adsorptivity to talc are preferable, and water-soluble polyester resins and CMCs are preferred from the viewpoint of flame retardancy and impact resistance of the resin composition. Are preferable, and a water-soluble polyester resin is particularly preferable.

  In the present invention, the water-soluble polyester resin preferably used as a binder includes a dicarboxylic acid component comprising a dicarboxylic acid or a reactive derivative thereof, a diol component comprising a diol or an ester derivative thereof, and a water-solubilizing component. Is a copolymer obtained by subjecting these components to a condensation reaction and having solubility in water. The solubility in water may be appropriately selected and determined, and can be adjusted by the content of the water-solubilizing component.

  The dicarboxylic acid as a raw material for the water-soluble polyester resin may be either an aromatic dicarboxylic acid or an aliphatic dicarboxylic acid, but an aromatic dicarboxylic acid is preferable from the viewpoint of the heat resistance of the resin composition. Specific examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, and 4,4. '-Biphenyl terdicarboxylic acid, 4,4'-biphenylmethane dicarboxylic acid, 4,4'-biphenylsulfone dicarboxylic acid, 4,4'-biphenylisopropylidenedicarboxylic acid, 1,2-bis (phenoxy) ethane- 4,4′-dicarboxylic acid, 2,5-anthracene dicarboxylic acid, 2,6-anthracene dicarboxylic acid, 4,4′-p-ter-phenylene dicarboxylic acid, 2,5-pyridinedicarboxylic acid, and the like. (For example, alkyl group-substituted products such as 5-methylisophthalic acid) and reactive derivatives (for example, terephthalate) Alkyl ester derivatives such as dimethyl phosphate and diethyl terephthalate) can also be used.

  Among these, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, and alkyl ester derivatives thereof are preferable. These aromatic dicarboxylic acids may be used alone or in combination of two or more, and together with the aromatic dicarboxylic acid, an aliphatic dicarboxylic acid such as adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, You may use together 1 or more types, such as alicyclic dicarboxylic acids, such as cyclohexane dicarboxylic acid.

  Diols which are raw materials for water-soluble polyester resins include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol. 1,4-pentanediol, 1,6-hexanediol, decamethylene glycol, aliphatic diols such as 2,2-dimethyl-1,3-propanediol; 1,4 Cycloaliphatic diethanolol, 1,3-cyclohexanedimethanol, cyclohexanediol, trans- or cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol Aromatic diols; aromatic diols such as p-xylene diol, bisphenol A, tetrabromobisphenol A, tetrabromobisphenol A-bis (2-hydroxyethyl ether) It can be exemplified Le, and the like, can also be used these substituents.

  Among these, ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,4-cyclohexanedimethanol are preferable from the viewpoint of heat resistance of the resin composition, and ethylene glycol is more preferable. -L, 1,3-propanediol, 1,4-butanediol, particularly ethylene glycol is preferred. These may be used alone or in combination of two or more. Further, as the diol component, one or more kinds of long chain diols having a molecular weight of 400 to 6000, that is, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, etc. Copolymerization may also be carried out in combination with ruthels.

  Examples of the water-solubilizing component that is a raw material for the water-soluble polyester resin include dicarboxylic acids having a metal sulfonate group, polyethylene glycol, and the like. Among these, dicarboxylic acids having a metal sulfonate group are preferable from the viewpoint of heat resistance.

  Examples of the dicarboxylic acid having a metal sulfonate group include sodium, potassium such as 5-sulfoisophthalic acid, 2-sulfoisophthalic acid, 4-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfonaphthalene-2,6-dicarboxylic acid, etc. Alkali metal salts or ester-forming derivatives thereof, and 5-sodium sulfoisophthalic acid or an ester derivative thereof is preferred from the viewpoint of water solubility.

  If the content of the dicarboxylic acid having a metal sulfonate group is too small, the water solubility of the resulting polyester resin will be insufficient, and conversely if too large, the heat resistance of the water soluble polyester resin may be insufficient. Therefore, this content is preferably 1 to 40 mol%, more preferably 5 to 35 mol%, based on the total carboxylic acid component that is the raw material of the water-soluble polyester resin.

  Preferable specific examples of the water-soluble polyester resin that is a binder of the granular inorganic filler (component B) used in the present invention include a copolymer composed of terephthalic acid, ethylene glycol, and 5-sodium sulfoisophthalic acid. “Plus coat Z-221”, “plus coat Z-561”, “plus coat Z-446”, etc., manufactured by Chemical Industry Co., Ltd. may be mentioned.

  The CMC used as the binder in the present invention is, for example, natural pulp made from sodium hydroxide as alkali cellulose and etherified with monochloroacetic acid. Production methods include a solvent method and an aqueous medium method. The properties of CMC vary depending on the degree of polymerization and the degree of etherification in units of anhydrous glycol. The CMC used in the present invention includes an average degree of polymerization of 100 to 500, an etherification degree of 0.5 to 1.7, and a viscosity of an aqueous 1% solution (25 (° C., B-type viscometer) of 10 to 500 mPa · s is preferable.

  The binder content in the granular talc used in the present invention is preferably 0.01 to 5% by weight, more preferably 0.05 to 3.5% by weight, particularly 0.1% in 100% by weight of the granular talc. It is preferably ˜3% by weight. By setting the binder content to 0.01% by weight or more, the granular talc is not easily broken, and the flame retardancy, thermal stability, and impact resistance of the resin composition tend to be further improved. On the other hand, when the binder content is less than 5% by weight, the dispersion in the resin composition becomes good, and the appearance of the molded article and the impact resistance of the resin composition tend to be improved.

  The method for producing the granular talc used in the present invention is arbitrary and is not particularly limited, while enhancing the kneadability of talc and binder, giving plasticity to the kneaded product during granule production, facilitating production, and It is preferred to add a wetting agent to reduce the wear of the granulator and to further adjust the hardness of the granulate. Usually, a lubricant is added to talc and a binder, and if necessary, a dispersant and other additives are added to obtain a mixture while stirring with a mixer such as a Henschel mixer or a super mixer.

  This mixture is kneaded with a single-screw or twin-screw extruder, etc., extruded into strands, cut and granulated, and dried using a fluid dryer or band heater to produce granular talc. To do. Classification can also be performed after drying.

  The size and shape of the granular talc are not particularly limited, such as rod-like, columnar, needle-like, spherical, granular, flake-like, and irregular shape, and various types can be produced depending on the molding conditions and sizing conditions. For example, when producing rod-shaped or cylindrical particles, the shaft diameter can be appropriately set by changing the size of the screen opening of the screen-type extruder, and after shaping, the particles can be sized and cut to the desired shaft length. it can.

  The size is not particularly limited as long as it is within the range of the above bulk density and particle size, but smaller than the resin pellet used for melt kneading and molding is more advantageous when dispersed in a melt kneader or molding machine. . For example, in a rod-like or columnar granular talc, the average axial diameter is preferably 0.2 to 6 mm and the average axial length is preferably 2 to 6 mm, and the ratio of average axial diameter to average axial length is 1: 0.5. Those within the range of ˜2 are more preferred.

  The lubricant used in the present invention includes water, an organic solvent, etc., but water is preferable from the viewpoint of cost and workability, and alcohols may be mixed with water. It is possible to dissolve or suspend the binder in water, which is a wetting agent. Additives required for granules, such as dispersants, surfactants, and various synthetic resin additives The uniformity can be further improved by dissolving or suspending the dye or pigment. Further, when water is used as the lubricant, it is preferable to dry the moisture contained using a fluid dryer or the like so that the moisture content is 1% or less, particularly 0.3% or less. The drying temperature is usually 80 to 150 ° C, and preferably 80 to 110 ° C.

  The blending ratio of the lubricant is usually 10 to 150 parts by weight, preferably 15 to 100 parts by weight, particularly preferably 20 to 60 parts by weight, based on 100 parts by weight of the total of talc and binder. If the blending ratio of the lubricant is less than 10 parts by weight, the effect is small, and if it exceeds 150 parts by weight, it may take too much time and energy to remove the lubricant.

  In the present invention, if the dispersant is added to the granular talc in an amount of 0.05 to 2.0% by weight, preferably 0.1 to 0.5% by weight, the dispersibility of the granular talc in the resin composition molded product Is preferable. Dispersants used may be generally known, for example, alcohols, alkanolamines, organic silicone compounds, higher fatty acids, fatty acid metal salts, hydrocarbon lubricants, basic amino acids, polyglycerols and their derivatives as described above. Can be mentioned. In this invention, 1 type, or 2 or more types chosen from these can be used, You may granulate using the talc which performed the above-mentioned surface treatment, and also adding a dispersing agent.

  Furthermore, in the granular talc used in the present invention, various additives may be blended in addition to the dispersant, as long as the characteristics of the present invention are not impaired. Specific examples of such additives include various antioxidants such as hindered phenols, various heat stabilizers such as phosphites, various ultraviolet absorbers such as benzotriazoles, benzophenones, and triazines, and phosphoric acid. Various flame retardants such as ester, silicone and metal salt, various release agents such as olefin wax and fatty acid ester, antibacterial and antifungal agents such as phenol, anionic, cationic and nonionic Antistatic agents, colorants, fillers other than talc, light stabilizers, plasticizers, foaming agents and the like can be mentioned. Of course, a plurality of these additives can be blended.

Flame retardant (C component)
The flame retardant which is the C component used in the present invention (hereinafter sometimes abbreviated as “C component”) is an organic alkali metal salt and / or an organic alkaline earth metal salt (C1 component), an organic phosphorus flame retardant. (C2 component) and at least one flame retardant selected from the group consisting of silicone resins (C3 component).

  The organic alkali metal salt and / or organic alkaline earth metal salt (hereinafter sometimes abbreviated as “C1 component”), which is the C1 component used in the present invention, is used for flame-retarding an aromatic polycarbonate resin. Various known ones can be used, and in particular, alkali metal salts and / or alkaline earth metal salts of organic sulfonic acids can be preferably used. As the organic sulfonic acid of the present invention, various known ones can be used, and perfluoroalkylsulfonic acid and / or aromatic sulfonic acid is particularly preferable from the viewpoint of flame retardancy.

  Specific examples of the perfluoroalkylsulfonic acid include trifluoromethanesulfonic acid, perfluorobutanesulfonic acid, perfluorohexanesulfonic acid, perfluorooctanesulfonic acid, and the like. You may use together. Among them, the perfluoroalkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and particularly preferably perfluorobutanesulfonic acid.

  Specific examples of the aromatic sulfonic acid include, for example, diphenyl sulfide-4,4′-disulfonic acid, 5-sulfoisophthalic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, naphthalene-2,6-disulfonic acid, biphenyl-3, Examples include 3′-disulfonic acid, diphenylsulfone-3-sulfonic acid, diphenylsulfone-3,3′-disulfonic acid, potassium diphenylsulfoxide-4-sulfonate, naphthalenesulfonic acid, and the like. More than one species can be used in combination. Among these, diphenyl sulfide-4,4′-disulfonic acid, benzenesulfonic acid, and dodecylbenzenesulfonic acid are preferable.

  Examples of the alkali metal include lithium, sodium, potassium, rubidium, and cesium, and examples of the alkaline earth metal include beryllium, magnesium, calcium, strontium, and barium. Of these, lithium, sodium, potassium and cesium are preferred.

  Preferred specific examples of the organic alkali metal salt and / or the organic alkaline earth metal salt include potassium perfluorobutanesulfonate, cesium perfluorobutanesulfonate, potassium diphenylsulfide-4,4′-disulfonate, dodecylbenzenesulfonic acid. Examples thereof include sodium and potassium dodecylbenzenesulfonate, and among these, potassium perfluorobutanesulfonate is particularly preferable.

  The organophosphorus flame retardant (hereinafter sometimes abbreviated as “C2 component”), which is the C2 component used in the present invention, is an organic compound containing phosphorus in the molecule, and flame retardants the aromatic polycarbonate resin. Various known compounds used in the above can be used, and an organic phosphate compound represented by the following general formula (1) and / or general formula (2) is preferable.

(In General Formula (1), R ¹ , R ² and R ³ each independently represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms which may be substituted with an alkyl group. , H, i and j each independently represent 0 or 1.)
The organophosphate compound represented by the general formula (1) can be produced from phosphorus oxychloride or the like by a known method. Specific examples of the phosphorus compound represented by the general formula (1) include triphenyl phosphate, tricresyl phosphate, diphenyl 2-ethylcresyl phosphate, tri (isopropylphenyl) phosphate, methylphosphonic acid diphenyl ester, and phenylphosphonic acid. Examples include diethyl ester, diphenyl cresyl phosphate, and tributyl phosphate.

(In General Formula (2), R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently an alkyl group having 1 to 6 carbon atoms or an aryl having 6 to 20 carbon atoms which may be substituted with an alkyl group. And p, q, r and s are each independently 0 or 1, t is an integer of 1 to 5, and X is an arylene group.)

  The organophosphate compound represented by the above general formula (2) is a condensed phosphate ester in which t is 1 to 5. However, in the case of a mixture of plural types of condensed phosphate esters having different t, t is It is calculated as an average value of the mixture. X represents an arylene group, and is a divalent group derived from a dihydroxy compound such as resorcinol, hydroquinone, bisphenol A, and the like.

As specific examples of the organic phosphate compound represented by the general formula (2), when resorcinol is used as the dihydroxy compound, phenyl resorcinol polyphosphate, cresyl resorcinol polyphosphate, phenyl cresyl resorcinol poly Phosphate, xylyl resorcin polyphosphate, phenyl-pt-butylphenyl resorcin polyphosphate, phenyl isopropylphenyl resorcin polyphosphate, cresyl xylyl resorcin polyphosphate, phenyl isopropylphenyl diisopropylphenyl resorcin Examples include polyphosphate.

  Examples of the organic phosphorus flame retardant used in the present invention include a phosphazene compound in addition to the organic phosphate compound, specifically, at least one selected from a cyclic phenoxyphosphazene compound, a chain phenoxyphosphazene compound, and a crosslinked phenoxyphosphazene compound. Compounds.

  Among the organophosphorus flame retardants, in the present invention, an organophosphate compound represented by the general formula (2) is preferable, and the acid value is 0.5 mgKOH / g or less, particularly 0.2 mgKOH / g or less. Some are preferred. Here, the acid value is a value obtained by dissolving an organic phosphorus flame retardant in alcohol-ether and titrating with 0.5N potassium hydroxide using phenolphthalein as an indicator.

  The silicone-based resin that is the C3 component used in the present invention (hereinafter sometimes abbreviated as “C3 component”) is usually any conventionally known arbitrary resin that is used for flame retardant purposes of aromatic polycarbonate resins. Things can be used. Generally, a silicone resin in which a substituent bonded to a silicon atom is composed of an aromatic hydrocarbon group and an aliphatic hydrocarbon group having 2 or more carbon atoms, preferably an aromatic carbon in the substituent bonded to silicon. This is a silicone resin having a hydrogen ratio of 40 mol% or more.

  Examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group, and a phenyl group is preferable. An epoxy group, amino group, hydroxyl group, vinyl group or the like may be bonded to the aromatic hydrocarbon group as a substituent. Examples of the aliphatic hydrocarbon group having 2 or more carbon atoms include an unsubstituted alkyl group such as an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group, and an epoxy group, an amino group, a hydroxyl group, and a vinyl group as substituents. Examples thereof include substituted alkyl groups. The number of carbon atoms of the aliphatic hydrocarbon group is preferably 2-12.

Silicone resins are mainly bifunctional (R ^a ₂ SiO) and trifunctional (R ^a ₂ SiO) and trifunctional (R ^a ₂ SiO) when each silicon atom in the molecule is made to have 1-4 functional types depending on the number of oxygen atoms directly bonded to silicon atoms. It is a silicone resin made of R ^a SiO _3/2 ), and can include a monofunctional type (R ^a ₃ SiO _1/2 ) or a tetrafunctional type (SiO ₂ ). Here, the substituent R ^a directly bonded to the silicon atom is an aromatic hydrocarbon group and / or an aliphatic hydrocarbon group having 2 or more carbon atoms. Thus, the ratio of the aromatic hydrocarbon group in the substituent R ^a which bind to these silicon atoms is 40 mol% or more is preferable in terms of the flame retardancy of the resin composition.

  Silicone resins can be produced by various known methods. For example, manufactured by hydrolyzing alkyltrialkoxysilane, aryltrialkoxysilane, dialkyldialkoxysilane, alkylaryldiakoxysilane, trialkylalkoxysilane, dialkylarylalkoxysilane, alkyldiarylalkoxysilane, tetraalkoxysilane, etc. can do. The molecular structure (crosslinking degree) and molecular weight can be controlled by adjusting the molar ratio of these silane compound raw materials, the hydrolysis rate, and the like. Furthermore, alkoxysilane remains depending on the production conditions, but if alkoxysilane remains in the resin composition, it may cause a decrease in hydrolysis resistance of the resin composition, so there may be little or no residual alkoxysilane. preferable.

Fluorinated polyolefin (component D)
Examples of the fluorinated polyolefin (hereinafter, may be abbreviated as “D component”) as the D component used in the present invention include fluorinated polyolefins such as polyfluoroethylene. Tetrafluoroethylene is preferred. This shows the tendency to disperse | distribute easily in a polymer and to make a fibrous material by couple | bonding polymers.

  Polytetrafluoroethylene having fibril-forming ability is classified as type 3 according to the ASTM standard. Polytetrafluoroethylene can be used in solid form or in the form of an aqueous dispersion. Examples of polytetrafluoroethylene having fibril-forming ability include “Teflon (registered trademark) 6J”, “Teflon (registered trademark) 30J” manufactured by Mitsui DuPont Fluorochemical Co., Ltd. and “Polyflon (trade name)” manufactured by Daikin Industries, Ltd. Can do.

Rubber polymer (E component)
The thermoplastic resin composition of the present invention further contains a rubber polymer (hereinafter sometimes abbreviated as “E component”) as the E component for the purpose of improving the impact resistance of the resin composition. It is preferable. The rubbery polymer used in the present invention has a glass transition temperature of 0 ° C. or lower, particularly −20 ° C. or lower, and is a polymer obtained by copolymerizing a rubbery polymer with a monomer component copolymerizable therewith. Is also included. As the E component used in the present invention, any conventionally known E component that can be blended in an aromatic polycarbonate resin and improve its mechanical properties can be used.

  Examples of rubber polymers include polybutadiene, polyisoprene, diene copolymers (styrene / butadiene copolymers, acrylonitrile / butadiene copolymers, acrylic / butadiene rubbers, etc.), ethylene and α-olefin copolymer Copolymers (ethylene / propylene copolymer, ethylene / butene copolymer, ethylene / octene copolymer, etc.), copolymers of ethylene and unsaturated carboxylic acid ester (ethylene / methacrylate copolymer, ethylene / butyl acrylate) Copolymer of ethylene and aliphatic vinyl compound, terpolymer of ethylene, propylene and non-conjugated diene, acrylic rubber (polybutyl acrylate, poly (2-ethylhexyl acrylate) Butyl acrylate, 2-ethylhexyl acrylate copolymer, etc.), Co - emissions based rubber (a polyorganosiloxane rubber; polyorganosiloxane rubber and a polyalkyl (meth) acrylate - Togomu consisting of IPN type composite rubber and the like) and the like. These may be used alone or in combination of two or more. “(Meth) acrylate” means “acrylate” and “methacrylate”, and “(meth) acrylic acid” described later means “acrylic acid” and “methacrylic acid”.

  Preferred examples of the monomer component copolymerized with such a rubbery polymer include aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, (meth) acrylic acid compounds, and the like. . As other monomer components, epoxy group-containing (meth) acrylic acid ester compounds such as glycidyl (meth) acrylate; maleimide compounds such as maleimide, N-methylmaleimide, N-phenylmaleimide; maleic acid, phthalic acid And α, β-unsaturated carboxylic acid compounds such as itaconic acid and their anhydrides such as maleic anhydride. These monomer components may be used alone or in combination of two or more.

  In order to improve the impact resistance of the thermoplastic resin composition of the present invention, it is preferable to use a core / shell type graft copolymer type rubber polymer. Among them, a core layer of at least one rubber polymer selected from butadiene-containing rubber, butyl acrylate-containing rubber, 2-ethylhexyl acrylate-containing rubber, and silicone rubber is used. A core / shell type graft copolymer comprising a shell layer formed by copolymerizing at least one monomer component selected from a methacrylic acid ester and an aromatic vinyl compound is particularly preferred. More specifically, methyl methacrylate-butadiene-styrene polymer (MBS), methyl methacrylate-butadiene polymer (MB), methyl methacrylate-acrylic rubber polymer (MA), methyl methacrylate Rate-acrylic-butadiene rubber copolymer, methylmethacrylate-acrylic-butadiene rubber-styrene copolymer, methylmethacrylate- (acrylic silicone IPN (interpenetrating polymer network) rubber) polymer Etc. Such rubbery polymers may be used alone or in combination of two or more.

  Examples of such core / shell type graft copolymers include Rohm and Haas Japan's Paraloid EXL2315, EXL2602, EXL2603 and other EXL series, KM330, KM336P and other KM series, KCZ201 and other KCZ series, Mitsubishi Examples include Metablene S-2001 and SRK-200 manufactured by Rayon.

  Other specific examples of the rubbery polymer obtained by copolymerizing a rubbery polymer with a monomer component copolymerizable therewith include polybutadiene rubber, styrene-butadiene copolymer (SBR), and styrene-butadiene-styrene. Block copolymer (SBS), styrene-ethylene / butylene-styrene block copolymer (SEBS), styrene-ethylene / propylene-styrene block copolymer (SEPS), ethylene-ethyl acrylate copolymer (EEA), ethylene -Methyl acrylate copolymer (EMA), ethylene-butene copolymer (EBR), ethylene-octene copolymer (EOR), etc. are mentioned.

Phosphorus compounds (F component)
The thermoplastic resin composition of the present invention further includes an organic phosphate compound represented by the following general formula (3) as the F component in order to improve thermal stability within a range not impairing the effects of the present invention, the following general formula ( It is preferable to contain at least one phosphorus compound selected from the group consisting of the organic phosphite compounds represented by 4) (hereinafter sometimes abbreviated as “F component”).

O = P (OH) _m (OR) _3-m (3)
(In general formula (3), R is an alkyl group or an aryl group, and may be the same or different. M is an integer of 0-2.)

（式中、Ｒ'はアルキル基又はアリール基であり、各々同一でも異なっていてもよい。）

(In the formula, R ′ is an alkyl group or an aryl group, and each may be the same or different.)

  In the general formula (3), R is preferably an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, more preferably an alkyl group having 2 to 25 carbon atoms. is there. M is preferably 1 and / or 2.

  In the general formula (4), R ′ is preferably an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms. Preferable specific examples of the phosphite represented by the general formula (4) include distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis ( Mention may be made of 2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite.

Content Ratio In the thermoplastic resin composition of the present invention, the content ratio of the A to D components constituting this is 50 to 100% by weight of the aromatic polycarbonate resin (A1 component) and a thermoplastic resin other than the aromatic polycarbonate ( (A2 component) 50 to 0% by weight of resin component (component A) 40 to 99 parts by weight and granular talc (component B) 1 to 60 parts by weight in total 100 parts by weight of flame retardant ( C component) 0.01 to 40 parts by weight, and fluorinated polyolefin (D component) 0.01 to 5 parts by weight.

  When the A2 component is contained, the content ratio of the A1 component and the A2 component is preferably 50 to 95% by weight of the A1 component in the total of 100% by weight of the A1 component and the A2 component. It is preferable that it is 60 to 85 weight%. Moreover, it is preferable that A2 component is 50 to 5 weight%, and it is preferable that it is 45 to 10 weight% especially 40 to 15 weight%. When the A1 component is 50% by weight or more, flame retardancy and impact resistance tend to be improved, and when it is less than 95% by weight, fluidity tends to be improved.

  Moreover, B component is 1-60 weight part in the total 100 weight part of A component and B component, It is preferable that it is 3-50 weight part especially 5-40 weight part. If it is less than 1 part by weight, the rigidity is not sufficient, and if it exceeds 60 parts by weight, impact resistance and thermal stability are lowered.

  As C component, it is preferable that C1 component is 0.02-1 weight part with respect to a total of 100 weight part of A component and B component, Especially 0.03-0.5 weight part, Especially 0.05- The amount is preferably 0.3 parts by weight. If it is 0.02 parts by weight or more, flame retardancy tends to be improved, and if it is less than 1 part by weight, flame retardancy and thermal stability tend to be improved.

  Moreover, C2 component becomes like this. Preferably it is 1-35 weight part with respect to a total of 100 weight part of A component and B component, More preferably, it is 3-30 weight part, Especially preferably, it is 5-25 weight part. When the C2 component is 1 part by weight or more, flame retardancy tends to be improved, and when it is less than 35 parts by weight, heat resistance and thermal stability tend to be improved.

  Further, the C3 component is preferably 0.1 to 5 parts by weight, more preferably 0.2 to 4 parts by weight, and particularly preferably 0.3 to 3 parts by weight with respect to 100 parts by weight of the total of the A component and the B component. Part. When the C3 component is 0.1 parts by weight or more, flame retardancy tends to be improved, and when it is less than 5 parts by weight, flame retardancy and impact resistance tend to be improved.

  The D component is 0.01 to 5 parts by weight, preferably 0.05 to 3.5 parts by weight, particularly preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the total of the A component and the B component. Part. If the D component is less than 0.01 part by weight, the flame retardancy may not be sufficient, and if it is 5 parts by weight or more, the appearance of the molded product may be deteriorated.

  Next, the content of the rubber polymer (component E) is preferably 1 to 30 parts by weight, more preferably 3 to 25 parts by weight, particularly preferably 5 to 100 parts by weight of the total of component A and component B. ~ 20 parts by weight. When 1 part by weight or more of E component is blended, impact resistance tends to be good, and when it is less than 30 parts by weight, rigidity and thermal stability tend to be good.

  Moreover, it is preferable that content of a phosphorus compound (F component) is 0.1-5 weight part with respect to 100 weight part of granular talc (B component), Especially 0.3-4 weight part, It is preferable that it is 0.5-3 weight part. When 0.1 part by weight or more of the F component is blended, impact resistance, thermal stability, and hue tend to be good, and when it exceeds 5 parts by weight, thermal stability may be inferior.

Other Components The thermoplastic resin composition of the present invention may contain various resin additives as long as the purpose of the present invention is not impaired. Various resin additives include antioxidants, mold release agents, UV absorbers, dyes and pigments, inorganic fillers other than talc, antistatic agents, antifogging agents, lubricants / antiblocking agents, fluidity improvers, plasticizers, Dispersing agents, antibacterial agents and the like can be mentioned. Two or more of these may be used in combination. Hereinafter, an example of an additive suitable for the thermoplastic resin composition of the present invention will be specifically described.

  Examples of the antioxidant include hindered phenol antioxidants. Specific examples thereof include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl). ) Propionate, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexane-1,6-diylbis [3- (3,5-di-) tert-butyl-4-hydroxyphenylpropionamide), 2,4-dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl ] Methyl] phosphoate, 3,3 ', 3 ", 5,5', 5" -hexa-tert-butyl-a, a ', a "- (Mesitylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4 -Hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-tert) -Butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4,6-bis (Octylthio) -1,3,5-triazin-2-ylamino) phenol, etc. These may be used in combination of two or more.

  Among the above, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) Propionate is preferred. These two phenolic antioxidants are commercially available from Ciba Specialty Chemicals under the names “Irganox 1010” and “Irganox 1076”.

  Content of antioxidant is 0.001-1 weight part normally with respect to a total of 100 weight part of A component and B component, and it is preferable that it is 0.01-0.5 weight part especially. If it is less than 0.001 part by weight, the antioxidant effect is insufficient, and if it exceeds 1 part by weight, the effect reaches a peak and is not economical.

  The release agent includes at least one compound selected from the group consisting of aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15000, and polysiloxane silicone oil. Can be mentioned.

  Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monovalent, divalent or trivalent carboxylic acid. Here, the aliphatic carboxylic acid includes alicyclic carboxylic acid. Among these, preferable aliphatic carboxylic acids are monovalent or divalent carboxylic acids having 6 to 36 carbon atoms, and aliphatic saturated monovalent carboxylic acids having 6 to 36 carbon atoms are more preferable. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, melissic acid, tetrariacontanoic acid, montanic acid, Examples include adipic acid and azelaic acid.

  As the aliphatic carboxylic acid in the ester of an aliphatic carboxylic acid and an alcohol, the same one as the aliphatic carboxylic acid can be used. On the other hand, examples of the alcohol include saturated or unsaturated monovalent or polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, a monovalent or polyvalent saturated alcohol having 30 or less carbon atoms is preferable, and an aliphatic saturated monohydric alcohol or polyhydric alcohol having 30 or less carbon atoms is more preferable. Here, aliphatic includes alicyclic compounds. Specific examples of such alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol. Etc.

  In addition, said ester compound may contain aliphatic carboxylic acid and / or alcohol as an impurity, and may be a mixture of a some compound.

  Specific examples of esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture based on myricyl palmitate), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostearate Examples thereof include rate, glycerol distearate, glycerol tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate and the like.

  Examples of the aliphatic hydrocarbon having a number average molecular weight of 200 to 15000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomer having 3 to 12 carbon atoms. Here, as the aliphatic hydrocarbon, alicyclic hydrocarbon is also included. Moreover, these hydrocarbon compounds may be partially oxidized. Among these, paraffin wax, polyethylene wax, or a partial oxide of polyethylene wax is preferable, and paraffin wax and polyethylene wax are more preferable. The number average molecular weight is preferably 200 to 5,000. These aliphatic hydrocarbons may be a single substance or a mixture of various constituent components and molecular weights as long as the main component is within the above range.

  Examples of the polysiloxane silicone oil include dimethyl silicone oil, phenylmethyl silicone oil, diphenyl silicone oil, and fluorinated alkyl silicone. Two or more of these may be used in combination.

  Content of a mold release agent is 0.001-2 weight part normally with respect to a total of 100 weight part of A component and B component, and it is preferable that it is 0.01-1 weight part especially. If the amount is less than 0.001 part by weight, the mold release effect may be insufficient. If the amount exceeds 2 parts by weight, degradation of hydrolysis resistance and mold contamination during injection molding may occur.

  Specific examples of the ultraviolet absorber include organic ultraviolet absorbers such as benzotriazole compounds, benzophenone compounds, and triazine compounds in addition to inorganic ultraviolet absorbers such as cerium oxide and zinc oxide. Of these, organic ultraviolet absorbers are preferred. In particular, benzotriazole compounds, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2- [4,6-bis (2, 4-Dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol, 2,2 ′-(1,4-phenylene) bis [4H-3,1-benzoxazine-4- ON], [(4-methoxyphenyl) -methylene] -propanedioic acid-dimethyl ester is preferred.

  Specific examples of the benzotriazole compound include condensates of methyl-3- [3-tert-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate-polyethylene glycol. Specific examples of other benzotriazole compounds include 2-bis (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- (3 ′, 5′-di-tert-butyl-2′-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chloro Benzotriazole, 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- (3,5-di-tert-amyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy- 3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2,2′-methylene- [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol] [methyl-3- [3-tert-butyl-5- (2H-benzotriazole) -2-yl) -4-hydroxyphenyl] propionate-polyethylene glycol] condensate. Two or more of these may be used in combination.

  Of the above, preferably 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl]- 2H-benzotriazole, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2- [4,6-bis (2,4 -Dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol, 2,2'-methylene-bis [4- (1,1,3,3-tetramethylbutyl)- 6- (2N-benzotriazol-2-yl) phenol].

  Content of a ultraviolet absorber is 0.01-3 weight part normally with respect to a total of 100 weight part of A component and B component, and it is preferable that it is 0.1-1 weight part especially. If it is less than 0.01 part by weight, the effect of improving weather resistance may be insufficient, and if it exceeds 3 parts by weight, mold deposits and the like may occur.

  Examples of the dye / pigment include inorganic pigments, organic pigments, and organic dyes. Examples of inorganic pigments include sulfide pigments such as carbon black, cadmium red, and cadmium yellow; silicate pigments such as ultramarine; titanium oxide, zinc white, petal, chromium oxide, iron black, titanium yellow, Oxide pigments such as zinc-iron brown, titanium cobalt green, cobalt green, cobalt blue, copper-chromium black, copper-iron black; chrome such as chrome, molybdate orange Acid pigments: ferrocyan pigments such as bitumen. Organic pigments and organic dyes include phthalocyanine dyes such as copper phthalocyanine blue and copper phthalocyanine; azo dyes such as nickel azo yellow; thioindigo, perinone, perylene, quinacridone, dioxazine And condensed polycyclic dyes such as isoindolinone and quinophthalone; anthraquinone, heterocyclic, and methyl dyes. Two or more of these may be used in combination. Of these, titanium oxide, carbon black, cyanine-based, quinoline-based, anthraquinone-based, and phthalocyanine-based compounds are preferable from the viewpoint of thermal stability.

  The dye / pigment content is usually 5 parts by weight or less, more preferably 3 parts by weight or less, and particularly preferably 2 parts by weight or less based on 100 parts by weight of the total of the A component and B component. If it exceeds 5 parts by weight, the impact resistance may be insufficient.

  Specific examples of inorganic fillers other than talc include glass fibers such as glass fibers (chopped strands), short glass fibers (milled fibers), glass flakes and glass beads; carbon fibers, short carbon fibers, carbon Nanotubes, carbon-based fillers such as graphite; whiskers such as potassium titanate and aluminum borate; silicate compounds such as mica, wollastonite, kaolinite, zonotolite, sepiolite, attabalgite, montmorillonite, bentonite, smectite Silica, alumina, calcium carbonate and the like. Among these, mica, wollastonite, and kaolinite are preferable. Two or more of these may be used in combination.

  The content of the inorganic filler is usually 1 to 60 parts by weight, particularly 3 to 50 parts by weight, particularly 5 to 30 parts by weight, based on 100 parts by weight of the total of component A and component B. If the amount is less than 1 part by weight, the reinforcing effect may not be sufficient. If the amount exceeds 60 parts by weight, the appearance and impact resistance may be reduced, and the fluidity may be insufficient.

Production of thermoplastic resin composition The thermoplastic resin composition of the present invention is not particularly defined as long as it contains the above-mentioned components A to D, and the production method thereof is also appropriately determined according to the resin composition. be able to. For example, the manufacturing method of a well-known thermoplastic resin composition can be employ | adopted widely. Specifically, the above-mentioned components A to D and E component, F component and other additive components blended as necessary are mixed in advance using various mixers such as a tumbler and a Henschel mixer, and then a Banbury mixer. The resin composition can be produced by melt-kneading with a roll, a roll, a brabender, a single-screw kneading extruder, a twin-screw kneading extruder, a kneader or the like.

  In addition, it is possible to produce a resin composition without mixing each component in advance, or by mixing only a part of the components and supplying them to an extruder using a feeder and melt-kneading them. It is possible to reduce the deterioration of the working environment due to the scattering of granular talc and the generation of dust by supplying resin to the extruder using a feeder without mixing other ingredients and then melt-kneading to produce a resin composition. This is a preferable method in terms of properties. Furthermore, when the C component is in a liquid state at room temperature, the method of adding all the components other than the C component to the upstream portion, adding the C component in the middle stream and thereafter, and melt-kneading with the resin component is also a flame retardant property of the resulting resin composition. In some cases, it is preferable.

Production of resin molded product The method for producing a resin molded product from the thermoplastic resin composition of the present invention is not particularly limited, and a molding method generally employed for thermoplastic resins, that is, a general injection molding method, High-speed injection molding method, injection compression molding method, two-color molding method, hollow molding method such as gas assist, molding method using heat insulating mold, molding method using rapid heating mold, foam molding (including supercritical fluid) ), Insert molding, IMC (in-mold coating molding) molding method, extrusion molding method, sheet molding method, thermoforming method, rotational molding method, laminate molding method, press molding method, etc. I can do it. A molding method using a hot runner method can also be adopted.

  In addition, in the present invention, from the viewpoint of reducing environmental burden such as waste reduction and cost reduction, when manufacturing a resin molded product from a resin composition, such as a product nonconforming product, sprue, runner, used product, etc. Recycled raw materials can be mixed with virgin materials for recycling (so-called material recycling). At this time, it is preferable to use the recycled raw material because it can be used after being pulverized, since it is possible to reduce inconvenience when the molded product is manufactured. The content ratio of the recycled material is usually 70% by weight or less, preferably 50% by weight or less, and more preferably 30% by weight or less with respect to the total amount of the recycled material and the virgin material.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist. In the following examples and comparative examples, the blending amount means parts by weight.

  In obtaining each resin composition of Examples and Comparative Examples, the following raw materials were prepared.

<Aromatic polycarbonate resin>
Aromatic polycarbonate resin (1): Bisphenol A type aromatic polycarbonate produced by an interfacial polymerization method (“Iupilon S-3000FN” manufactured by Mitsubishi Engineering Plastics, viscosity average molecular weight 22500, terminal hydroxyl group concentration = 150 ppm)

Aromatic polycarbonate resin (2): Bisphenol A type aromatic polycarbonate produced by interfacial polymerization (“Iupilon H-4000FN” manufactured by Mitsubishi Engineering Plastics, viscosity average molecular weight 15500, terminal hydroxyl group concentration = 150 ppm)

Aromatic polycarbonate resin (3): Bisphenol A type aromatic polycarbonate produced by an interfacial polymerization method (“Iupilon E-2000FN” manufactured by Mitsubishi Engineering Plastics, viscosity average molecular weight 28000, terminal hydroxyl group concentration = 150 ppm)

<Thermoplastic resin other than aromatic polycarbonate resin>
ABS resin (1): acrylonitrile-butadiene-styrene copolymer, “Santac AT-08” manufactured by Nippon A & L, butadiene rubber content 18% by weight

ABS resin (2): acrylonitrile-butadiene-styrene copolymer, “DP-611” manufactured by Technopolymer, butadiene rubber content 40% by weight

<Granular talc>
Granular talc (1): “MTB-12” manufactured by Matsumura Sangyo Co., Ltd., talc average particle size 1.8 μm, bulk density 0.74 g / ml, particle size / mesh size 500 μm Cylindrical shape, average shaft diameter 1.2 mm, average shaft length 1.5 mm, binder type / CMC (Dell Daiichi Kogyo Seiyaku, Selogen 7A), binder content / 0.3 wt%, lubricant / water, moisture content /0.11%

Granular talc (2): 4000 g of talc (manufactured by Matsumura Sangyo Co., Ltd., High Filler # 5000PJ) having an average particle diameter of 1.8 μm is placed in a 20 liter Henschel mixer, and stirring blades are stirred at high speed of 1500 rpm while terephthalic acid, 200 g of a water-soluble polyester aqueous solution containing 20% by weight of a water-soluble polyester resin composed of ethylene glycol and 5-sodium sulfoisophthalic acid (“Plus Coat Z-221” manufactured by Kyoyo Chemical Industry Co., Ltd.) and 1440 g of tap water are added over 2 minutes. did. Further, after addition of the aqueous solution, the mixture was stirred for 3 minutes to obtain a clay-like kneaded product.

  Next, the kneaded product was extruded and granulated with a roll basket type granulator equipped with a screen having an opening of 1.2 mm, and dried with a fluidized bed dryer having a hot air temperature of 100 ° C. for about 60 minutes to obtain granular talc. Further, the particles were aligned by a granulator to obtain cylindrical granules (hereinafter abbreviated as granular talc (2)) having an average axial diameter of 1.2 mm and an average axial length of 1.5 mm. The obtained granular talc (2) has a water-soluble polyester resin content of 1% by weight, a bulk density of 0.70 g / ml, a particle size / aperture on the 500 μm sieve of 98% by weight, and a water content / 0.4. %Met.

<Talc for comparative example>
Powdered talc: “High filler # 5000PJ” manufactured by Matsumura Sangyo Co., Ltd., average particle size 1.8 μm, bulk density 0.12 g / ml, particle size / aperture 500 μm

Compression talc: “UPN HS-T0.8” manufactured by Hayashi Kasei Co., Ltd., deaerated compressed product, average particle size 2 μm, bulk density 0.8 g / ml, particle size / mesh size 500 μm The ratio on the sieve is 32% by weight

Granular talc (3): “HiTalc HTP ultra5C” manufactured by IMI-FABI, average particle size 0.5 μm, bulk density 0.9 g / ml, particle size / aperture 500 μm

<Flame Retardant>
Organic alkali metal salt: potassium perfluorobutanesulfonate, “KFBS” manufactured by Mitsubishi Materials Corporation

Organic phosphorus flame retardant: organic condensed phosphate ester compound (in the general formula (2), X = 1,3-phenylene, R ^{4 to} R ⁷ = 2,6-xylyl, acid value 0.12 mgKOH / g), “ADK STAB FP-500” manufactured by Asahi Denka Kogyo Co., Ltd.

Silicone resin: organosiloxane polymer that is solid at room temperature with propyl and phenyl substituents bonded to silicon atoms, "SH6018" manufactured by Toray Dow Corning

<Fluorinated polyolefin>
Fluorinated polyolefin: Polytetrafluoroethylene, “Polyflon F-201L” manufactured by Daikin Industries, Ltd.

<Rubber polymer>
Rubber polymer: Core / shell type graft copolymer comprising polybutadiene (core) / alkyl acrylate / alkyl methacrylate copolymer (shell), “EXL2603” manufactured by Rohm and Haas Japan

<Phosphorus compounds>
Phosphorus compound (1): bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, “Adeka Stub PEP-24G” manufactured by Asahi Denka Kogyo Co., Ltd.

Phosphorus compound (2): Chemical formula O = P (OH) _{n ′} (OC ₁₈ H ₃₇ ) _{3-n ′} (n ′ is a mixture of 1 and 2), “ADK STAB AX-71” manufactured by Asahi Denka Kogyo Co., Ltd.

<Other ingredients>
Antioxidant: Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (“Irganox 1010” manufactured by Ciba Specialty Chemicals)

Mold release agent: Pentaerythritol tetrastearate ("Yunistar H476" manufactured by NOF Corporation)

<Preparation of resin composition and preparation of test piece>
Examples 1-4 and Comparative Examples 1-3
After each component shown in Table 1 is uniformly mixed with a tumbler-mixer at the ratio shown in the same table, a twin screw extruder (“TEX30XCT” manufactured by Nippon Steel Works, L / D = 42, number of barrels 12) is used. The pellets of the resin composition were prepared by supplying the extruder from the barrel 1 at a cylinder temperature of 270 ° C. and a screw rotation speed of 300 rpm, and melt-kneading them.

  After drying the pellet of the resin composition obtained above at 120 ° C. for 6 hours or more, using a M150AII-SJ type injection molding machine manufactured by Meiki Seisakusho, cylinder temperature 280 ° C., mold temperature 80 ° C., molding cycle Under the condition of 55 seconds, an ASTM test piece and a 100 mmφ disk-shaped molded product (thickness 3 mmt) were prepared. Also, using a J50 type injection molding machine manufactured by Nippon Steel, using a cylinder temperature of 280 ° C., a mold temperature of 80 ° C., and a molding cycle of 50 seconds, a length of 127 mm × width of 12.7 mm × 1.6 mm and a thickness of 1. A UL94 standard vertical combustion test piece having a thickness of 2 mm was prepared.

Examples 5-7 and Comparative Examples 4-6
After each component shown in Table 2 is uniformly mixed with a tumbler-mixer at the ratio shown in the table, a twin screw extruder (“TEX30XCT” manufactured by Nippon Steel Works, L / D = 42, number of barrels 12) is used. The pellets of the resin composition were prepared by supplying them to the extruder from the barrel 1 at a cylinder temperature of 260 ° C. and a screw rotation speed of 300 rpm, followed by melt kneading.

  After the pellets of the resin composition obtained above were dried at 100 ° C. for 6 hours or longer, a M150AII-SJ type injection molding machine manufactured by Meiki Seisakusho was used, cylinder temperature 270 ° C., mold temperature 80 ° C., molding cycle An ASTM test piece and a 100 mmφ disk-shaped molded product (thickness: 3 mmt) were prepared under the condition of 55 seconds. Furthermore, the retention molding was performed in 5 minutes per cycle, and the disk-shaped molded products after the fifth shot were evaluated. In addition, using a J50 type injection molding machine manufactured by Nippon Steel, under the conditions of a cylinder temperature of 270 ° C., a mold temperature of 80 ° C., and a molding cycle of 50 seconds, a length of 127 mm × width 12.7 mm × 1.2 mm thickness UL94 standard A vertical burning specimen was prepared.

Examples 8, 9 and Comparative Examples 7-9
After each component shown in Table 3 is uniformly mixed with a tumbler-mixer at the ratio shown in the same table, a twin screw extruder (“TEX30XCT” manufactured by Nippon Steel Works, L / D = 42, number of barrels 12) is used. The pellets of the resin composition were prepared by supplying the extruder 1 from the barrel 1 at a cylinder temperature of 250 ° C. and a screw speed of 300 rpm, and melt-kneading them.

  After the pellets of the resin composition obtained above were dried at 80 ° C. for 6 hours or more, a M150AII-SJ type injection molding machine manufactured by Meiki Seisakusho was used, cylinder temperature 250 ° C., mold temperature 60 ° C., molding cycle An ASTM test piece and a 100 mmφ disk-shaped molded product (thickness: 3 mmt) were prepared under the condition of 55 seconds. Furthermore, the retention molding was performed in 5 minutes per cycle, and the disk-shaped molded products after the fifth shot were evaluated. In addition, using a J50 type injection molding machine manufactured by Nippon Steel, under the conditions of a cylinder temperature of 250 ° C., a mold temperature of 60 ° C., and a molding cycle of 50 seconds, a UL94 standard of 127 mm long × 12.7 mm wide × 1.2 mm thick A vertical burning specimen was prepared.

<Evaluation method>
(1) Extrudability In the adjustment of the resin composition, there is no problem such as clogging of the hopper or poor biting into the extruder, and the one that can be easily stranded and pelletized at a discharge rate of 40 kg / h or more is ○, discharge amount A hopper clogged or a poor bite into the extruder was generated at 40 kg / h, and the discharge amount was reduced to make it possible to somehow form a strand or pellet.

(2) Rigidity (flexural modulus)
In accordance with ASTM D790, a flexural modulus (unit: MPa) was measured at 23 ° C. using a test piece having a thickness of 6.4 mm.

(3) Flame retardancy (UL94 standard vertical combustion test)
Using the 1.6 mm thick and 1.2 mm thick combustion test pieces produced as described above, a vertical combustion test was performed in accordance with the UL94 standard to evaluate the combustibility.

(4) Impact resistance (surface impact strength)
Using the high-rate impact tester (manufactured by Shimadzu Corporation), the punched impact test was performed on the disk-shaped molded product produced above with a punch diameter of 1/2 inch, a support diameter of 3 inches, and a punching speed of 1 m / s. Went. The greater the surface impact strength (fracture energy, unit: J), the better the impact resistance.

(5) Thermal stability a. Surface appearance Visually observe the surface appearance of the disk-shaped molded product (normal molded product and staying molded product) prepared above, and the surface with almost no roughening due to the silver stroke, ○, the roughness due to the silver stroke The thing with was evaluated as x.

b. Surface impact strength For the disk-shaped molded product (residual molded product) produced above, using a high-rate impact tester (manufactured by Shimadzu Corporation), punch diameter 1/2 inch, support diameter 3 inch, punching speed 1 m / s A punching impact test was performed. The greater the surface impact strength (fracture energy, unit: J), the better the impact resistance.

<Examples 1-9 and Comparative Examples 1-9>
Each resin composition described in Tables 1 to 3 was produced and evaluated by the method described above. The results are shown in Tables 1 to 3.

  The following can be understood from the results of Examples and Comparative Examples shown in Tables 1 to 3. The resin compositions described in Examples 1 to 4 of the present invention are excellent in extrusion processability, rigidity, flame retardancy, impact resistance, and thermal stability. On the other hand, the resin composition described in Comparative Examples 1 to 3 in which the B component is outside the range specified in this patent is inferior in extrusion processability, flame retardancy, impact resistance, and thermal stability.

  The resin compositions described in Examples 5 to 7 are excellent in extrusion processability, rigidity, flame retardancy, impact resistance, and thermal stability. On the other hand, the resin compositions described in Comparative Examples 4 to 6 in which the B component is outside the range specified in this patent are inferior in flame retardancy, impact resistance, and thermal stability.

  The resin compositions described in Examples 8 and 9 are excellent in extrusion processability, rigidity, flame retardancy, impact resistance, and thermal stability. On the other hand, the resin compositions described in Comparative Examples 7 to 9 in which the B component is outside the range specified in this patent are inferior in extrusion processability, flame retardancy, impact resistance, and thermal stability.

Claims (9)

  Resin component (A component) 40 comprising a total of 100 wt% of aromatic polycarbonate resin (A1 component) 50-100 wt% and thermoplastic resin other than aromatic polycarbonate resin (A2 component) 50-0 wt% Total of 1 to 60 parts by weight of granular talc (component B) obtained by granulating talc having an average particle diameter of 0.1 to 10 μm and a bulk density of 0.4 to 1.5 g / ml At least one selected from the group consisting of an organic alkali metal salt and / or an organic alkaline earth metal salt (C1 component), an organic phosphorus flame retardant (C2 component), and a silicone resin (C3 component) with respect to 100 parts by weight. A flame retardant (component C) 0.01 to 40 parts by weight and a fluorinated polyolefin (component D) 0.01 to 5 parts by weight, a thermoplastic fat composition comprising granular talc (component B) In the granularity of Ratio on sieve opening 500μm sieve is characterized in that 55 wt% or more, the thermoplastic resin composition.   2. The thermoplastic resin composition according to claim 1, wherein the granular talc (component B) is granulated using a binder.   The thermoplastic resin composition according to claim 2, wherein the binder content in the granular talc (component B) is 0.01 to 5% by weight.   The thermoplastic resin composition according to claim 2 or 3, wherein the binder in the granular talc (component B) is a water-soluble polymer.   The thermoplastic resin composition according to any one of claims 1 to 4, wherein a ratio of the granular talc (component B) on the sieve having an opening of 500 µm is 75% by weight or more.   The thermoplastic resin composition according to any one of claims 1 to 5, wherein the A2 component is a styrene resin.   The thermoplastic resin according to any one of claims 1 to 6, further comprising 1 to 30 parts by weight of a rubbery polymer (E component) based on 100 parts by weight of the total of the A component and the B component. Composition.   8. The thermoplastic resin composition according to claim 7, wherein the rubber polymer (component E) is a core / shell type graft copolymer.   A resin molded product obtained by molding the thermoplastic resin composition according to any one of claims 1 to 8.