JP2009051989A - Thermoplastic resin composition and resin molded product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition which has well-balanced excellent fluidity, rigidity and residence thermal stability, and further excellent extrusion processability, and can provide a molded product with a good appearance. <P>SOLUTION: The thermoplastic resin composition comprises 40-99 pts.wt. of an aromatic polycarbonate resin (component A) which consists of a total of 100 wt.% of 5-95 wt.% of an aromatic polycarbonate resin (component A1) and 95-5 wt.% of a polylactide resin (component A2); 1-60 pts.wt. of a granulated silicate compound (component B); and 0-35 pts.wt. of a rubber-like polymer (component C), 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)2009,JPO&INPIT

Description

  The present invention relates to a thermoplastic resin composition containing an aromatic polycarbonate resin, a polylactic acid-based resin and a granular silicate compound, and a resin molded article comprising the thermoplastic resin composition. Specifically, a thermoplastic resin composition having excellent balance in terms of fluidity, rigidity, impact resistance, and residence heat stability, and excellent extrudability, and a good appearance when formed into a molded product, and the thermoplastic resin composition The present invention relates to a resin molded product made of a product.

  Aromatic polycarbonate resin is a general-purpose engineering plastic that excels in transparency, impact resistance, heat resistance, dimensional stability, etc., and its excellent characteristics make it a wide range of parts such as electrical / electronic / OA equipment parts, machine parts, and automotive parts. Used in the field. However, aromatic polycarbonate resins have a problem of high melt viscosity and inferior molding processability, and there is a strong demand for improving molding processability (fluidity) as the molded product becomes thinner and larger. ing.

  As means for solving the above problems, a polymer alloy comprising an aromatic polycarbonate resin and an aromatic polyester resin (polybutylene terephthalate, polyethylene terephthalate, etc.) has been developed, and the fluidity, which is a drawback of the aromatic polycarbonate resin, has been improved. It is used in a wide range of fields as a material with excellent chemical properties. However, there is a problem in that impact resistance is sacrificed by blending an aromatic polyester resin with an aromatic polycarbonate resin, and a material having an excellent balance between fluidity and impact resistance has been demanded.

  On the other hand, a resin composition excellent in fluidity in which a polylactic acid resin is blended with an aromatic polycarbonate resin has been proposed (see, for example, Patent Document 1). In addition, polylactic acid-based resins are capable of synthesizing polymers based on plant resources, and carbon dioxide circulates as a non-petroleum resource (carbon neutral), and thus has attracted attention as an environmentally friendly material. .

  However, in accordance with the above proposal, simply blending an aromatic polycarbonate resin with a polylactic acid resin is not satisfactory in compatibility, and the extrudability (strandization or pelletization) is insufficient, such as the strands cannot be pulled off. In addition, there was a problem that in the appearance of the surface of the molded article of the resin composition, pearly luster and uneven mixing were seen, resulting in poor appearance.

  A resin composition composed of an aromatic polycarbonate resin, a polylactic acid-based resin, and an inorganic filler has been proposed as a resin composition having an improved surface appearance of a molded product of the above-described resin composition (see, for example, Patent Documents 2 to 4). However, as proposed here, a resin composition simply containing an inorganic filler has insufficient impact resistance and stagnant heat stability.

  On the other hand, resin compositions excellent in extrusion productivity, workability, and mechanical properties in which granular talc is blended with engineer plastics such as aromatic polycarbonate resin have been proposed (see, for example, Patent Documents 5 and 6). However, the above-mentioned patent document does not disclose a resin composition comprising an aromatic polycarbonate resin or a polylactic acid resin, and the resin composition comprising an aromatic polycarbonate resin, a polylactic acid resin or granular talc is fluid, rigid, There was no suggestion or mention that the impact resistance and the residence heat stability were excellent in a balanced manner, further excellent in extrusion processability, and had a good appearance when formed into a molded product.

JP-A-7-109413 JP-A-2005-48066 JP 2006-188651 A JP 2006-182994 A JP 2006-77176 A JP 2006-111822 A

  The purpose of the present invention is to eliminate the above-mentioned drawbacks of the prior art, and to have a good balance in terms of fluidity, rigidity, impact resistance and residence heat stability, and excellent extrudability and good appearance when formed into a molded product. It is providing the thermoplastic resin composition which has these, and 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 obtained a thermoplastic resin composition (hereinafter referred to as “a thermoplastic resin composition”) containing an aromatic polycarbonate resin, a polylactic acid resin and a granular silicate compound. In some cases, it may be simply referred to as “resin composition”.) In the granular silicate compound (component B), the particle size on the sieve having a mesh size of 500 μm is 55% by weight or more, so that fluidity, rigidity and impact resistance are achieved. The present invention has been completed by finding that the resin composition is excellent in balance in terms of stability and residence heat stability, and surprisingly has excellent extrudability and has a good appearance when formed into a molded product.

  That is, the gist of the present invention is that a resin component (A) comprising a total of 100 wt% of an aromatic polycarbonate resin (A1 component) 5 to 95 wt% and a polylactic acid resin (A2 component) 95 to 5 wt%. Component) 40 to 99 parts by weight, 1 to 60 parts by weight of a granular silicate compound (B component), and 0 to 35 parts by weight of a rubbery polymer (component C), which is a granular composition. In the particle size of the silicate compound (component B), the ratio on the sieve having a mesh size of 500 μm is 55% by weight or more.

The thermoplastic resin composition of the present invention is excellent in balance in terms of fluidity, rigidity, impact resistance, and residence heat stability, and further has excellent extrudability and a good appearance when formed into a molded product. .
The thermoplastic resin composition of the present invention having such features can be used in a wide range of fields. Electric / electronic devices and parts thereof, OA equipment, information terminal equipment, machine parts, home appliances, vehicle parts It is useful for various applications such as construction materials, various containers, recreational goods, miscellaneous goods, lighting equipment, etc., especially housing members for electric / electronic equipment, OA equipment, information terminal equipment, vehicle exterior / skin parts, vehicle interior Application to parts can be expected.

  As housing members for electrical / electronic equipment, office automation equipment, and information terminal equipment, display devices such as personal computers, game machines, televisions, printers, copy machines, scanners, fax machines, electronic notebooks, PDAs, cameras, and video Examples of the housing member include a camera, a mobile phone, a drive for a recording medium, and a reading device.

  Vehicle exterior / outer parts include outer door handles, bumpers, fenders, door panels, trunk lids, front panels, rear panels, roof panels, bonnets, pillars, side malls, garnishes, wheels. Caps, food bulges, fuel lids, various spoilers, motorbike cowls and the like.

  Examples of the vehicle interior parts include an inner door handle, a center panel, an instrument panel, a console box, a luggage floor board, and a display housing such as car navigation.

  Hereinafter, the present invention will be described in more detail. In the present specification, “to” means that the numerical values described before and after that are included as the lower limit value and the upper limit value, and the “group” possessed by various compounds is within the scope of the present invention. It includes that it may have a substituent.

[1] Aromatic polycarbonate resin (A1 component)
The aromatic polycarbonate resin used in the present invention (hereinafter sometimes abbreviated as “A1 component”) uses, as raw materials, an aromatic dihydroxy compound and a carbonate precursor, or a small amount of them together. A linear or branched thermoplastic polymer or copolymer obtained using a polyhydroxy compound.

  Examples of the aromatic dihydroxy compound include 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A), 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane (= tetra Bromobisphenol 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-bis ( , 5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 1,1- 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, bis such as 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane And (hydroxyaryl) alkanes.

  Moreover, as aromatic dihydroxy compounds other than the above, for example, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxy) Bis (hydroxyaryl) cycloalkanes exemplified by phenyl) -3,3,5-trimethylcyclohexane and the like; 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3- Cardo structure-containing bisphenols exemplified by methylphenyl) fluorene; dihydroxydiaryl ethers exemplified by 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether; '-Dihydroxydiphenyl sulfide, 4,4'-dihydride Dihydroxy diaryl sulfides exemplified by xy-3,3′-dimethyldiphenyl sulfide; dihydroxy exemplified by 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfoxide, etc. Diaryl sulfoxides; dihydroxy diaryl sulfones exemplified by 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfone, etc .; hydroquinone, resorcin, 4,4′-dihydroxydiphenyl, etc. Is mentioned.

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

  Examples of the carbonate precursor include carbonyl halide, carbonate ester, haloformate and the like. Specific examples thereof include phosgene; diaryl carbonates such as diphenyl carbonate and ditolyl carbonate; dialkyl such as dimethyl carbonate and diethyl carbonate. Carbonates; dihaloformates of dihydric phenols and the like. Two or more of these carbonate precursors may be used in combination.

  The aromatic polycarbonate resin used in the present invention 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, In addition to polyhydroxy compounds such as 1,1,1-tri (4-hydroxyphenyl) ethane, 3,3-bis (4-hydroxyaryl) oxindole (= isatin bisphenol), 5-chloroisatin, 5,7 -Dichloro isatin, 5-bromo isatin and the like.

  Of these, 1,1,1-tri (4-hydroxyphenyl) ethane is preferred. The polyfunctional aromatic compound can be used by substituting a part of the aromatic dihydroxy compound, and the amount used is usually 0.01 to 10 mol%, preferably based on the aromatic dihydroxy compound. 0.1 to 2 mol%.

  Examples of the method for producing the aromatic polycarbonate resin include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer. Industrially, an interfacial polymerization method or a melt transesterification method is advantageous, and typical examples of these two methods will be described below.

  The reaction by the interfacial polymerization method can be performed, for example, as follows. First, in the presence of an organic solvent inert to the reaction and an aqueous alkaline solution, the pH is usually maintained at 9 or higher, and the aromatic dihydroxy compound and phosgene are reacted. At this time, if necessary, a molecular weight modifier (terminal terminator) or an antioxidant of an aromatic dihydroxy compound can be present in the reaction system. Next, a polymerization catalyst such as tertiary amine or quaternary ammonium salt is added to carry out interfacial polymerization.

  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. Moreover, as an alkali compound used for preparation of aqueous alkali solution, alkali metal hydroxides, such as sodium hydroxide and potassium hydroxide, are mentioned.

  Examples of the molecular weight regulator include compounds having a monovalent phenolic hydroxyl group, and specific examples thereof include m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, p-tert-butylphenol. , P-long chain alkyl-substituted phenol and the like. The usage-amount of a molecular weight regulator is 0.5-50 mol normally with respect to 100 mol of aromatic dihydroxy compounds, Preferably it is 1-30 mol.

  Polymerization catalysts include tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine, trihexylamine and pyridine; quaternary ammonium salts such as trimethylbenzylammonium chloride, tetramethylammonium chloride and triethylbenzylammonium chloride Etc.

  The temperature of the phosgenation reaction is usually 0 to 40 ° C., and the reaction time is several minutes (for example, 10 minutes) to several hours (for example, 6 hours). Further, the addition timing of the molecular weight regulator can be appropriately selected between the phosgenation reaction and the start of the polymerization reaction.

  The reaction by the melt transesterification method is performed, for example, by an ester exchange 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, and substituted diphenyl carbonates such as diphenyl carbonate and ditolyl carbonate. Among these, diphenyl carbonate or substituted diphenyl carbonate is preferable, and diphenyl carbonate is particularly preferable.

  In general, a transesterification catalyst is used in the melt transesterification process. 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. The temperature of the transesterification reaction is usually 100 to 320 ° C. Then, the subsequent melt polycondensation reaction is finally performed under reduced pressure of 2 mmHg or less while removing byproducts such as aromatic hydroxy compounds.

  The melt polycondensation can be performed by either a batch method or a continuous method, but it is preferably performed by a continuous method. As the catalyst deactivator used in the melt transesterification method, it is preferable to use a compound that neutralizes the transesterification reaction catalyst, for example, a sulfur-containing acidic compound or a derivative formed therefrom. The used amount (addition amount) of the catalyst deactivator is usually 0.5 to 10 equivalents, preferably 1 to 5 equivalents with respect to the alkali metal contained in the catalyst, and usually 1 to 100 ppm, preferably with respect to the polycarbonate. Is 1-20 ppm.

  In addition, the terminal hydroxyl group amount of the aromatic polycarbonate resin that greatly affects the thermal stability, hydrolysis stability, color tone and the like of the resin can be appropriately adjusted by any conventionally known method. In the case of the melt transesterification method, an aromatic polycarbonate having a desired molecular weight and terminal hydroxyl group can be obtained by adjusting the mixing ratio of the carbonic acid diester and the aromatic dihydroxy compound and the degree of pressure reduction during the melt polycondensation reaction. . In the case of the melt transesterification method, the ratio of the carbonic acid diester to 1 mol of the aromatic dihydroxy compound is usually an equimolar amount or more, preferably 1.01 to 1.30 mol. As a method for positively adjusting the amount of terminal hydroxyl groups, there may be mentioned a method in which a terminal terminator is added separately during the reaction. Examples of the terminal terminator include monohydric phenols, monovalent carboxylic acids, and carbonic acid diesters.

  The molecular weight of the aromatic polycarbonate resin used in the present invention is usually 10,000 to 50, as viscosity average molecular weight [Mv] converted from solution viscosity, from the viewpoint of mechanical strength and fluidity (ease of moldability). 000, preferably 12,000 to 40,000, more preferably 14,000 to 35,000, and particularly preferably 16,000 to 32,000. Moreover, you may mix 2 or more types of aromatic polycarbonate resin from which a viscosity average molecular weight differs. Furthermore, you may mix the aromatic polycarbonate resin whose viscosity average molecular weight is outside said suitable range as needed.

Here, the viscosity average molecular weight [Mv] is obtained by using methylene chloride as a solvent, using an Ubbelohde viscometer, and determining the intrinsic viscosity [η] (unit dl / g) at a temperature of 20 ° C. : Means a value calculated from the equation of 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 700 ppm or less, more preferably 400 ppm or less, and particularly preferably 300 ppm or less. The lower limit is preferably 10 ppm or more, more preferably 20 ppm or more, further 30 ppm or more, and particularly 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 heat resistance and residence heat stability 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)).

  In addition, the aromatic polycarbonate resin used in the present invention may contain an aromatic polycarbonate oligomer in order to improve the appearance of the molded product and the fluidity. The aromatic polycarbonate oligomer has a viscosity average molecular weight [Mv] of usually 1,500 to 9,500, preferably 2,000 to 9,000. The amount of the aromatic polycarbonate oligomer used is usually 30% by weight or less based on the aromatic polycarbonate resin.

  Furthermore, in the present invention, not only virgin resins but also aromatic polycarbonate resins regenerated from used products, so-called material recycled aromatic polycarbonate resins, may be used as the aromatic polycarbonate resin. Used products include, for example, optical recording media such as optical discs, light guide plates, vehicle window glass, vehicle headlamp lenses, windshields and other vehicle transparent members, water bottle containers, glasses lenses, soundproof walls, glass windows, etc.・ Construction materials such as corrugated sheet. Also, non-conforming products, pulverized products obtained from sprues, runners, etc., or pellets obtained by melting them can be used. The ratio of the recycled aromatic polycarbonate resin is usually 80% by weight or less, preferably 50% by weight or less based on the virgin resin.

[2] Polylactic acid resin (A2 component)
The polylactic acid resin (hereinafter, may be abbreviated as “A2 component”), which is the A2 component used in the present invention, is a polymer or copolymer mainly composed of L-lactic acid and / or D-lactic acid. In addition, the copolymerization component other than lactic acid is usually 50 mol% or less, preferably 35 mol% or less, more preferably 20 mol% or less, and particularly preferably 10 mol% or less. A particularly preferred polylactic acid-based resin in the present invention is a poly-L-lactic acid resin containing 80 mol% or more of L-form.

  The components copolymerizable with lactic acid include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,2-butanediol, 1,5-pentanediol, 1, 6-hexanediol, 1,8-octanediol, 1,10-decandiol, 1,12-dodecandiol, 1,14-tetradecandiol, 1,16-hexadecandiol, 1, Aliphatic diols such as 18-octadecandiol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanediethanol, 1,4-cyclohexanedimethano Alicyclic diols such as oxalic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, undecadicarboxylic acid, dodecadicarboxylic acid, 1,14-te Aliphatic dicarboxylic acids such as radecane dicarboxylic acid, aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid, glycolic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, hydroxybenzoic acid And lactones such as caprolactone, valerolactone, propiolactone, undecalactone, 1,5-oxepan-2-one, and the like. These may be used alone or as a mixture of two or more.

  Furthermore, in the present invention, aliphatic polyhydric alcohols such as glycerin and trimethylolpropane, aliphatic polybasic acids such as butanetetracarboxylic acid, polyhydric alcohols such as polysaccharides, It may be partially copolymerized, and the molecular weight may be increased using a binder (polymer chain extender) such as diisocyanate.

  As a method for producing a polylactic acid-based resin, a known polymerization method can be used, such as a method for direct dehydration polycondensation (for example, a method disclosed in JP-A-6-65360), a cyclic dimer of lactic acid. An indirect polymerization method (for example, a production method disclosed in US Pat. No. 2,758,987) in which a body (lactide) is melt-polymerized can be used.

  When a polylactic acid resin is produced by directly dehydrating polycondensation of raw materials, the raw material lactic acids or lactic acids and other copolymerization components are preferably co-polymerized in the presence of an organic solvent, particularly a phenyl ether solvent. High molecular weight having a strength suitable for the present invention is obtained by polymerizing by a method in which water is removed from a solvent distilled off by boiling dehydration condensation, particularly preferably by azeotropic distillation, and returned to a reaction system. Can be obtained.

  The intrinsic viscosity of the polylactic acid-based resin may be appropriately selected and determined, but is usually 0.7 to 3.0 dL / g, particularly 1.0 to 2.5 dL / g, particularly 1.5 to 2.3 dL / g. It is preferable that it is g. By setting the intrinsic viscosity to 0.7 dL / g or more, mechanical properties and residence heat stability in the resin composition of the present invention tend to be improved. On the contrary, when the intrinsic viscosity is less than 3.0 dL / g, the fluidity of the resin composition tends to be improved. The intrinsic viscosity is a value obtained by using a mixed solvent of phenol / tetrachloroethane (weight ratio 1/1), measured at 30 ° C., and a Haggins constant of 0.33.

  Furthermore, the polylactic acid resin used in the present invention can be not only a virgin raw material but also a polylactic acid resin regenerated from a used product, that is, a so-called material recycled polylactic acid resin. Used products include containers, films, sheets, fibers, non-conforming products, sprues, runners, etc., and pulverized products obtained from them or pellets obtained by melting them can also be used. .

[3] Granular talc (component B)
The granular silicate compound (hereinafter, may be abbreviated as “B component”) which is the B component of the present invention is characterized in that the particle size is 55% by weight or more on a sieve having a mesh size of 500 μm. To do.

The granular silicate compound used in the present invention are those comprising at least a metal oxide component and SiO ₂ component, Orutoshirike - DOO, Jishirike - DOO, cyclic silicate - DOO, chain silicate - DOO layered silicate - Any form such as G may be used. Further, the granular silicate compound of the present invention takes a crystalline state, and may be in any form that the silicate compound can take, and the shape of the crystal may be various shapes such as a fiber shape and a plate shape. It may be selected and determined as appropriate. As a granular silicate compound which is B component of this invention, what is represented by a following formula is especially preferable.

xMO _· ySiO 2 _{· zH} 2 O
(Here, x and y represent natural numbers, z represents an integer of 0 or more, MO represents a metal oxide component, and may be a plurality of metal oxide components.)

  Examples of the metal M in the metal oxide MO include potassium, sodium, lithium, barium, calcium, zinc, manganese, iron, cobalt, magnesium, zirconium, aluminum, and titanium. Preferred examples of the metal oxide MO include CaO. Or MgO.

  Specific examples of the granular silicate compound preferably used as the component B used in the present invention include granular silicates such as wollastonite, talc, mica, zonotlite, sepiolite, attabalgite, kaolinite, montmorillonite, bentonite, smectite, etc. More preferable are compounds such as granular wollastonite, granular talc, granular mica and granular kaolinite from the viewpoints of rigidity, impact resistance, appearance, and residence heat stability. This is particularly preferable from the viewpoint of the balance of rigidity, impact resistance, appearance, and residence heat stability.

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} , the normal SiO ₂ 58 to 66 wt%, the MgO 28 to 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 silicate compound used in the present invention is usually obtained by granulating a raw silicate compound of 0.05 to 50 μm, and the average particle size of the raw silicate compound is preferably 0.07 to 20 μm. Among these, 0.1 to 10 μm is preferable, and 0.7 to 5 μm is particularly preferable. When the average particle diameter is 0.05 μm or more, the thermal stability of the resin composition tends to be further improved. On the other hand, when the average particle diameter is less than 50 μm, the appearance and rigidity of the molded product of the resin composition are 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.

  Next, the bulk density of the granular silicate compound used in the present invention may be appropriately selected and determined, but is 0.4 to 1.5 g / ml, more preferably 0.5 to 1.3 g / ml. ml, particularly preferably 0.6 to 1.1 g / ml. When the bulk density is 0.4 g / ml or more, the thermal stability and impact resistance of the resin composition tend to be further improved. On the other hand, when the bulk density is less than 1.5 g / ml, the resin composition There is a tendency that the appearance and impact resistance of the molded product are further improved.

Here, the bulk density is a value obtained by the following method.
(1) Place the granular silicate compound on a sieve having an aperture of 1.4 mm, and pass through the sieve while sweeping lightly with a brush.

  (2) The granular silicate compound passed through the sieve is charged into a receiver attached to the bulk density measuring device specified in JIS K5101 until it reaches a heap.

  (3) The upper part of the granular silicate compound from the receiving port is scraped off with a spatula, the weight of the granular silicate compound in the receiver is measured, and the bulk density is calculated by the following equation.

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

  The granular silicate compound used in the present invention has a particle size of 55% by weight or more, more preferably 60% by weight or more, still more preferably 70% by weight or more, and particularly preferably 90% on a sieve having an opening of 500 μm. % By weight or more. In the particle size of the granular silicate compound, the thermal stability of the resin composition of the present invention tends 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 silicate compound is a value determined by the following method in accordance with JIS Z8801.

  (1) Place the granular silicate compound on a sieve having an opening of 2 mm, and pass through the sieve while sweeping lightly with a brush.

  (2) Put the above granular silicate compound passed through a sieve into a 200 ml beaker, and reduce it to about 30 ml using Yoshida Seisakusho's sample reducer “1305 6” (groove width 6 mm). went.

  (3) Using a sieve having a mesh opening of 500 μm, screening the above-mentioned granular silicate compound is performed, and the weight of the one that does not pass through the 500 μm sieve (on the sieve) is determined, and the ratio from the total amount is determined. It was. 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 silicate compound used for this invention using a raw material silicate compound is arbitrary, A conventionally well-known arbitrary granulation method can be used. Specifically, for example, those granulated using a binder are preferable from the viewpoint of thermal stability, impact resistance, and rigidity of the resin composition.

  The binder used when producing the granular silicate compound used in the present invention is highly granulated with the raw material silicate compound, is colorless or white, is an inert and stable substance, and is a resin molded body. Any material that does not degrade the physical properties 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 preferable, and water-soluble polymers are more preferable from the viewpoint of thermal stability, impact resistance, and rigidity of the resin composition.

  Examples of the water-soluble polymer include polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, sodium polyacrylate, sodium alginate, agar, and polysaccharides (celluloses such as methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropulosecellulose, sodium carboxymethylcellulose) Derivatives and starch), proteins (gelatin, glue, etc.) and the like.

  Among these, polysaccharides and proteins having high caking properties and high adsorptivity with silicate compounds are more preferable, among which sodium carboxymethylcellulose (hereinafter sometimes abbreviated as “CMC”) and gelatin are preferable. CMC is particularly preferable.

  In the present invention, CMC particularly preferably used as the water-soluble polymer binder 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 preferred CMC used in the present invention is an average polymerization degree of 100 to 500, an etherification degree of 0.5 to 1.7, and a 1% aqueous solution viscosity (25 ° C., type B) from the viewpoint of solubility in water and aqueous solution viscosity. Viscometer) is in the range of 10 to 500 mPa · s, and those outside these ranges may cause problems in terms of granulation.

  The binder content in the granular silicate compound used in the present invention is preferably 0.01 to 5% by weight, more preferably 0.05 to 3.5% by weight, in 100% by weight of the granular silicate compound. Particularly preferred is 0.1 to 2% by weight. By making the binder content 0.01% by weight or more, the granular silicate compound is less likely to collapse, and the thermal stability and impact resistance of the resin composition tend to be further improved, while the binder content is reduced. When the content is less than 5% by weight, the dispersion of the granular silicate compound in the resin composition becomes better, and the appearance of the molded article and impact resistance of the resin composition tend to be further improved.

  The method for producing the granular silicate compound used in the present invention is arbitrary, and there is no particular limitation. However, the kneadability between the silicate compound and the binder is improved, and the kneaded product at the time of granule production is given plasticity to facilitate production. It is preferable to add a wetting agent to reduce the wear of the granulator and to further adjust the hardness of the granule. Usually, a lubricant is added to the silicate compound and the 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 a strand, cut and granulated, dried using a fluid dryer, band heater, etc., and a granular silicate compound Manufacturing. Classification can also be performed after drying.

  The size and shape of the granular silicate compound is not particularly limited, such as rod-shaped, cylindrical, needle-shaped, spherical, granular, flake-shaped, and irregular-shaped, and various types can be manufactured depending on the molding conditions and sizing conditions. it can. 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 silicate compound, 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. More preferably within the range of 5-2.

  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, and more preferably 0.3% or less. 80-150 degreeC is suitable for drying temperature, Preferably it is 80-110 degreeC.

  The blending ratio of the lubricant is 10 to 150 parts by weight, preferably 15 to 100 parts by weight, particularly preferably 20 to 60 parts by weight with respect to 100 parts by weight of the total of the silicate compound and the 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 takes too much time and energy to remove the lubricant.

  In the present invention, if a dispersant is added to the granular silicate compound in an amount of 0.05 to 2.0% by weight, preferably 0.1 to 0.5% by weight, the resin composition molded product of the granular silicate compound In some cases, the dispersibility is improved. Dispersants to be used may be those 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. There is at least one selected.

  In addition, the granular silicate compound used in the present invention may be subjected to a surface treatment in order to enhance the affinity with the resin (component A). Specific examples of the surface treatment agent include alcohols such as trimethylolethane, trimethylolpropane, and pentaerythritol, alkanolamines such as triethylamine, organosilicone compounds such as organopolysiloxane, higher fatty acids such as stearic acid, Fatty acid metal salts such as calcium stearate and magnesium stearate, polyethylene wax, hydrocarbon lubricants such as liquid paraffin, basic amino acids such as lysine and arginine, polyglycerin and their derivatives, silane coupling agents, titanate couplings And at least one selected from coupling agents such as an agent and an aluminum-based coupling agent.

  Furthermore, you may mix | blend various additives other than a dispersing agent with the granular silicate compound used by this invention in the range which does not impair the characteristic of this invention as needed. 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 Examples thereof include antistatic agents, colorants, fillers other than silicate compounds, light stabilizers, plasticizers, and foaming agents. Of course, a plurality of these additives can be blended.

[4] Rubber polymer (component C)
The thermoplastic resin composition of the present invention preferably contains a rubber polymer (hereinafter sometimes abbreviated as “C component”) for the purpose of improving impact resistance. The rubbery polymer indicates a glass transition temperature of 0 ° C. or lower, particularly −20 ° C. or lower, and includes a polymer obtained by copolymerizing a rubbery polymer with a monomer component copolymerizable therewith. . As the rubbery polymer used in the present invention, any conventionally known polymer which is generally blended with an aromatic polycarbonate resin and can improve its impact resistance can be used.

  Specific examples of the rubbery polymer include polybutadiene rubber, polyisoprene rubber, polybutyl acrylate, poly (2-ethylhexyl acrylate), polyalkyl acrylate rubber such as butyl acrylate / 2-ethylhexyl acrylate copolymer; polyorganosiloxane rubber In addition to silicone rubber such as butadiene-acrylic composite rubber, IPN composite rubber comprising polyorganosiloxane rubber and polyalkyl acrylate rubber, styrene-butadiene rubber, ethylene-α olefin rubber (ethylene-propylene rubber, ethylene- Butene rubber, ethylene-octene rubber, etc.), ethylene-acrylic rubber, fluorine rubber and the like. Two or more of these may be used in combination. Among these, in terms of impact resistance, any one selected from the group of polybutadiene rubber, polyalkyl acrylate rubber, IPN type composite rubber composed of polyorganosiloxane rubber and polyalkyl acrylate rubber, and styrene-butadiene rubber. Species are preferred.

  Specific examples of monomer components copolymerizable with the rubber polymer include aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, (meth) acrylic acid compounds, glycidyl (meth) acrylates, etc. Epoxy group-containing (meth) acrylic acid ester compounds; maleimide compounds such as maleimide, N-methylmaleimide and N-phenylmaleimide; α, β-unsaturated carboxylic acid compounds such as maleic acid, phthalic acid and itaconic acid and their An anhydride (for example, maleic anhydride etc.) etc. are mentioned. Two or more of these monomer components may be used in combination. Among these, from the viewpoint of impact resistance, it is preferably any one selected from the group of aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, and (meth) acrylic acid compounds. Yes, and more preferably a (meth) acrylic acid ester compound. Specific examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, and the like. It is done.

  The rubbery polymer used in the present invention is preferably of the core / shell type graft copolymer type from the viewpoint of impact resistance. In this case, the core layer is at least one rubber component selected from the group of IPN (interpolating polymer network) type composite rubber composed of polybutadiene-containing rubber, polybutyl acrylate-containing rubber, polyorganosiloxane rubber and polyalkyl acrylate rubber. The shell layer is preferably formed of (meth) acrylic acid ester and acrylonitrile-styrene copolymer.

  Preferred examples of the above core / shell type graft copolymer include methyl methacrylate-butadiene-styrene copolymer (MBS), methyl methacrylate-butadiene copolymer (MB), methyl methacrylate-acrylonitrile-butadiene-styrene copolymer. Polymer (MABS), methyl methacrylate-acrylic rubber copolymer (MA), acrylonitrile-styrene-acrylic rubber copolymer (ASA), methyl methacrylate-acrylic rubber-styrene copolymer (MAS), methyl methacrylate-acrylic Examples thereof include a butadiene rubber copolymer, a methyl methacrylate-acrylic butadiene rubber-styrene copolymer, and a methyl methacrylate- (acrylic silicone IPN rubber) copolymer. Two or more of these may be used in combination.

  Examples of the above-mentioned core / shell type graft copolymer include “STAPHYLOID MG1011” manufactured by Gantz Kasei Co., Ltd., “PARALLOID EXL2315”, “EXL2602” manufactured by Rohm and Haas Japan Co., Ltd., “ Examples include the EXL series such as EXL2603, the KM series such as “KM330” and “KM336P”, the KCZ series such as “KCZ201”, “Metablene S-2001” and “SRK-200” manufactured by Mitsubishi Rayon Co., Ltd.

  Specific examples of other rubbery polymers include styrene-butadiene copolymer (SBR), styrene-butadiene-styrene block copolymer (SBS), styrene-ethylene / butylene-styrene block copolymer (SEBS), Examples thereof include styrene-ethylene / propylene-styrene block copolymer (SEPS), acrylonitrile-butadiene rubber-styrene copolymer (ABS), and acrylonitrile-ethylenepropylene rubber-styrene copolymer (AES).

[5] Content Ratio In the thermoplastic resin composition of the present invention, the content ratio of the component A to component C constituting the component is 5 to 95 weights of aromatic polycarbonate resin (component A1). %, And a resin component (component A) consisting of 95 to 5% by weight of polylactic acid resin (component A2) 40 to 99 parts by weight, granular silicate compound (component B) 1 to 60 parts by weight, And 0 to 35 parts by weight of a rubbery polymer (component C).

  The content ratio of the A1 component and the A2 component is 5 to 95% by weight, preferably 40 to 90% by weight, more preferably 50 to 85% by weight in the total of 100% by weight of the A1 component and the A2 component. The A2 component is 95 to 5% by weight, preferably 60 to 10% by weight, and more preferably 50 to 15% by weight. When the A1 component is less than 5% by weight, the impact resistance is not sufficient, and when it exceeds 95% by weight, the residence heat stability and the impact resistance are inferior.

The B component is 1 to 60 parts by weight, preferably 2 to 50 parts by weight, more preferably 3 to 35 parts by weight, in 100 parts by weight of the total of A, B and C components. If the component B is less than 1 part by weight, the rigidity, the molded product surface appearance and the extrusion processability tend to be inferior, and if it exceeds 60 parts by weight, the impact resistance and thermal stability are inferior.
Moreover, C component is 0-35 weight part, Preferably it is 1-30 weight part, More preferably, it is 3-25 weight part. When the component C is blended in an amount of 1 part by weight or more, impact resistance tends to be good, and when it exceeds 35 parts by weight, thermal stability and rigidity may be inferior.

[6] Phosphorus compound (component D)
The thermoplastic resin composition of the present invention contains a phosphorus compound (hereinafter sometimes abbreviated as “D component”) in order to improve the residence heat stability within a range that does not impair the effects of the present invention. It is preferable. Various known compounds can be used as the phosphorus compound, and the organic phosphate compound (D1 component) represented by the following general formula (I) and / or the following general formula (II) is represented. A phosphite compound (D2 component) is preferred.

O = P (OH) _m (OR) _3-m (I)
(In the general formula (I), R is an alkyl group or an aryl group, and when there are a plurality of R, each R may be the same or different. Indicates an integer of 2.)

（式中、Ｒ’はアルキル基またはアリ−ル基を示し、各々、同一であっても異なっていてもよい。）

(In the formula, R ′ represents an alkyl group or an aryl group, which may be the same or different.)

In the above general formula (I) as the component D1, R is preferably an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, more preferably 2 to 2 carbon atoms. 25 alkyl groups. M is preferably 1 or 2. Preferable specific examples of the organic phosphate compound represented by the general formula (I) include a mixture of monostearyl acid phosphate and distearyl acid phosphate.
In the general formula (II) as the component D2, 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 compound represented by the general formula (II) include distearyl pentaerythritol diphosphite and bis (2,4-di-tert-butylphenyl) pentaerythritol. Mention may be made of phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite.

  As content of a phosphorus compound (D component), it is preferable that it is 0.001-2 weight part with respect to a total of 100 weight part of A component, B component, and C component, and 0.01-1.5 among these is preferable. Part by weight, particularly 0.03 to 1 part by weight is preferred. It is preferable to add 0.001 part by weight or more of component D because the residence heat stability is good, and when it is less than 2 parts by weight, impact resistance tends to be further improved.

[7] Other ingredients
The thermoplastic resin composition of the present invention may contain other resins and various resin additives in addition to the above A, B, C, D, and components as long as the purpose of the present invention is not impaired as required. . Other resins include, for example, styrene resins such as acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, polystyrene resin, and thermoplastics other than polylactic acid resins such as polybutylene terephthalate resin and polyethylene terephthalate resin. Polyolefin resin such as polyester resin, polyethylene resin, polypropylene resin, polyamide resin, polyimide resin, polyetherimide resin, polyurethane resin, polyphenylene ether resin, polyphenylene sulfide resin, polysulfone resin, polymethacrylate resin, phenol resin, epoxy resin, etc. It is done.

  In addition, as various resin additives, antioxidants, heat stabilizers, mold release agents, dyes and pigments, inorganic fillers other than granular silicate compounds, flame retardants, weather resistance improvers, antistatic agents, antifogging agents, Examples include lubricants / anti-blocking agents, fluidity improvers, plasticizers, dispersants, antibacterial agents, and the like. Two or more of these may be used in combination. Hereinafter, an example of an additive suitable for the resin composition of the present invention will be specifically described.

  Examples of the antioxidant include hindered phenolic 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 aromatic polycarbonate resin and polylactic acid-type resin, Preferably it is 0.01-0.5 weight part. When the content of the antioxidant is less than 0.001 part by weight, the effect as an antioxidant is insufficient, and when it exceeds 1 part by weight, the effect reaches a peak and is not economical.

  The heat stabilizer used in the present invention includes a phosphite compound (a) in which at least one ester in the molecule is esterified with phenol and / or phenol having at least one alkyl group having 1 to 25 carbon atoms. ), Phosphorous acid (b) and tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylene-di-phosphonite (c).

  Specific examples of the phosphite compound (a) include trioctyl phosphite, tridecyl phosphite, triphenyl phosphite, trisnonylphenyl phosphite, tris (octylphenyl) phosphite, tris (2,4 -Di-tert-butylphenyl) phosphite, tridecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl Examples thereof include phosphite and 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite. These may be used alone or in combination of two or more. Among the above, tris (2,4-di-tert-butylphenyl) phosphite is particularly preferable.

  Content of a heat stabilizer is 0.001-1 weight part normally with respect to a total of 100 weight part of aromatic polycarbonate resin and polylactic acid-type resin, Preferably it is 0.01-0.5 weight part. When the content of the heat stabilizer is less than 0.001 part by weight, the effect as the heat stabilizer is insufficient, and when it exceeds 1 part by weight, the hydrolysis resistance may deteriorate.

  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 give.

  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 may be 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 aromatic polycarbonate resin and polylactic acid-type resin, Preferably it is 0.01-1 weight part. When the content of the release agent is less than 0.001 part by weight, the effect of the release property may not be sufficient. When the content exceeds 2 parts by weight, the hydrolysis resistance is deteriorated and the mold is contaminated during injection molding. There are problems such as.

  Specific examples of inorganic fillers other than granular silicate compounds include glass fillers such as glass fibers (chopped strands), short glass fibers (milled fibers), glass flakes, and glass beads; carbon fibers, carbon short fibers, and carbon nanotubes. And carbon-based fillers such as graphite; whiskers such as potassium titanate and aluminum borate; silica, alumina, calcium carbonate and the like. Among these, glass fibers (chopped strands), short glass fibers (milled fibers), and glass flakes are preferable. Two or more of these may be used in combination.

  The content of the inorganic filler other than the granular silicate compound is usually 1 to 150 parts by weight, preferably 3 to 100 parts by weight, more preferably 5 to 100 parts by weight in total of the aromatic polycarbonate resin and the polylactic acid resin. ~ 60 parts by weight. When the content of the inorganic filler is less than 1 part by weight, the reinforcing effect may not be sufficient, and when it exceeds 150 parts by weight, the appearance and impact resistance may be inferior and the fluidity may not be sufficient.

  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′-methyl Ren-bis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol] [methyl-3- [3-tert-butyl-5- (2H- Benzotriazol-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 aromatic polycarbonate resin and polylactic acid-type resin, Preferably it is 0.1-1 weight part. When the content of the ultraviolet absorber is less than 0.01 parts by weight, the effect of improving weather resistance may be insufficient, and when it exceeds 3 parts by weight, problems such as mold deposit may occur.

  Examples of the dye / pigment include inorganic pigments, organic pigments, and organic dyes. Examples of inorganic pigments include, for example, sulfide pigments such as carbon black, cadmium red, and cadmium yellow; silicate pigments such as ultramarine blue; zinc white, petal, chromium oxide, titanium oxide, iron black, titanium yellow, and zinc- Oxide pigments such as iron brown, titanium cobalt green, cobalt green, cobalt blue, copper-chromium black and copper-iron black; chromic pigments such as chrome lead and molybdate orange; Examples include Russian pigments.

  Examples of organic pigments and organic dyes include phthalocyanine dyes such as copper phthalocyanine blue and copper phthalocyanine green; azo dyes such as nickel azo yellow; thioindigo, perinone, perylene, quinacridone, dioxazine, and isoindolinone. And condensed polycyclic dyes such as quinophthalone; anthraquinone, heterocyclic, and methyl dyes and the like. Two or more of these may be used in combination. Among these, carbon black, titanium oxide, cyanine-based, quinoline-based, anthraquinone-based, and phthalocyanine-based compounds are preferable from the viewpoint of thermal stability.

  The content of the dye / pigment is usually 5 parts by weight or less, preferably 3 parts by weight or less, and more preferably 2 parts by weight or less with respect to 100 parts by weight of the total of the aromatic polycarbonate resin and the polylactic acid resin. When the content of the dye / pigment exceeds 5 parts by weight, the impact resistance may not be sufficient.

  Examples of the flame retardant include halogenated bisphenol A polycarbonate, brominated bisphenol epoxy resin, brominated bisphenol phenoxy resin, halogenated flame retardant such as brominated polystyrene, phosphate ester flame retardant, diphenylsulfone-3,3 ′. -Organic metal salt flame retardants such as dipotassium disulfonate, potassium diphenylsulfone-3-sulfonate, potassium perfluorobutanesulfonate, and polyorganosiloxane flame retardants are preferable, but phosphate ester flame retardants are particularly preferable. .

  Specific examples of the phosphate ester flame retardant include triphenyl phosphate, resorcinol bis (dixylenyl phosphate), hydroquinone bis (dixylenyl phosphate), 4,4′-biphenol bis (dixylenyl phosphate), bisphenol A Examples thereof include bis (dixylenyl phosphate), resorcinol bis (diphenyl phosphate), hydroquinone bis (diphenyl phosphate), 4,4′-biphenol bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate), and the like. Two or more of these may be used in combination. In these, resorcinol bis (dixylenyl phosphate) and bisphenol A bis (diphenyl phosphate) are preferable.

  The content of the flame retardant is usually 1 to 30 parts by weight, preferably 3 to 25 parts by weight, and more preferably 5 to 20 parts by weight with respect to 100 parts by weight as the total of the aromatic polycarbonate resin and the polylactic acid resin. When the content of the flame retardant is less than 1 part by weight, the flame retardancy may not be sufficient, and when it exceeds 30 parts by weight, the heat resistance may decrease.

  Examples of the anti-dripping agent include fluorinated polyolefins such as polyfluoroethylene, and polytetrafluoroethylene having fibril forming ability is particularly preferable. This shows the tendency to disperse | distribute easily in a polymer and to couple | bond together polymers and to make a fibrous material. 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” or “Teflon (registered trademark) 30J” from Mitsui DuPont Fluorochemical Co., Ltd. and “Polyflon (trade name) from Daikin Industries, Ltd. Is commercially available.

  The content of the anti-dripping agent is usually 0.02 to 4 parts by weight, preferably 0.03 to 3 parts by weight, based on 100 parts by weight of the total of the aromatic polycarbonate resin and the polylactic acid resin. When the compounding amount of the dripping inhibitor exceeds 5 parts by weight, the appearance of the molded product may be deteriorated.

[8] Manufacturing method of resin composition and manufacturing method of molded product
Since the thermoplastic resin composition of the present invention is not particularly defined as long as it contains the specified components A to C, its production method can also be appropriately determined according to the resin composition. For example, the manufacturing method of a well-known thermoplastic resin composition is employable widely.

  Specifically, the components A to C, the component D blended as necessary, and other additive components are mixed in advance using various mixers such as a tumbler and a Henschel mixer, and then the Banbury mixer, A resin composition can be produced by melt-kneading with a kneading machine, brabender, single-screw kneading extruder, twin-screw kneading extruder, 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 silicate compounds and the generation of dust by supplying resin to the extruder using a feeder without mixing other components and then melt-kneading to produce a resin composition. This is a preferable method in terms of properties. Furthermore, in the case of a silicate compound in which the B component is easily crushed, a method of adding other than the B component to the upstream portion and melting and kneading, and then adding the B component in the middle stream and then melt-kneading with the resin component is also obtained. It is preferable from the viewpoint of mechanical properties of the resin composition.

  The method for producing a molded product from the thermoplastic resin composition of the present invention is not particularly limited, and is a molding method generally employed for thermoplastic resins, that is, a general injection molding method, an ultra-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), inserter It is possible to employ a molding method, an IMC (in-mold coating molding) molding method, an extrusion molding method, a sheet molding method, a thermoforming method, a rotational molding method, a laminate molding method, a press molding method and the like. A molding method using a hot runner method can also be selected.

  In addition, in the present invention, from the viewpoint of reducing environmental load such as waste reduction and cost reduction, when manufacturing a molded product from a thermoplastic resin composition, non-conforming product, sprue, runner, used product, etc. Recycled raw materials can be mixed with virgin materials for recycling, so-called material recycling. In this case, it is preferable to use the recycled raw material because it can be used after being pulverized, since it can reduce problems when producing a molded product. The content ratio of the recycled material is preferably 70% by weight or less, more preferably 50% by weight or less, and further preferably 30% by weight or less, out of a total of 100% by weight 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 (A1 component)>
Aromatic polycarbonate resin (1): Bisphenol A type aromatic polycarbonate produced by interfacial polymerization ("Iupilon S-3000FN" manufactured by Mitsubishi Engineering Plastics, viscosity average molecular weight 21000)

Aromatic polycarbonate resin (2): Bisphenol A type aromatic polycarbonate produced by an interfacial polymerization method ("Iupilon H-4000FN" manufactured by Mitsubishi Engineering Plastics, viscosity average molecular weight 15000)

Aromatic polycarbonate resin (3): Bisphenol A type aromatic polycarbonate produced by interfacial polymerization ("Iupilon E-2000FN" manufactured by Mitsubishi Engineering Plastics, viscosity average molecular weight 28000)

<Polylactic acid resin (A2 component)>
Polylactic acid resin (1): Polylactic acid (“Lacia H-400” manufactured by Mitsui Chemicals, Inc., intrinsic viscosity 1.75 dL / g)

Polylactic acid resin (2): Polylactic acid (“Lacia H-100” manufactured by Mitsui Chemicals, Inc., intrinsic viscosity 1.36 dL / g)

<Thermoplastic polyester resin for comparative example>
Polybutylene terephthalate resin: “Duranex 2002” manufactured by Polyplastics Co., Ltd. (intrinsic viscosity 1.03 dL / g)

Polyethylene terephthalate resin: “Novapex GG500” manufactured by Mitsubishi Chemical Corporation (inherent viscosity 0.76 dl / g)

In addition, the intrinsic viscosity of the polylactic acid-based resin and the thermoplastic polyester resin for the comparative example was determined in the following manner using an Ubbelohde viscometer. That is, using a mixed solvent of phenol / tetrachloroethane (weight ratio 1/1), at 30 ° C., the number of falling seconds of only the polymer solution having a concentration of 1.0 g / dL and the solvent was measured and determined from the following formula.
_{IV = ((1 + 4K H} η sp) 0.5 -1) / (2K H C)
(Where η _sp = η / η ₀ −1, η is the polymer solution falling seconds, η ₀ is the solvent dropping seconds, C is the polymer solution concentration (g / dL), and K _H is the Huggins constant. 0.33)

<Granular silicate compound (component B)>
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): 4992.5 g of talc having an average particle size of 1.8 μm (manufactured by Matsumura Sangyo Co., Ltd., High Filler # 5000PJ) was placed in a 20 liter Henschel mixer, and the CMC was stirred while stirring at a high speed of 1500 rpm. (Daiichi Kogyo Seiyaku Co., Ltd., Cellogen 7A) An aqueous solution in which 7.5 g of water was previously dissolved in 2000 g of water was added over 2 minutes. 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 had a bulk density of 0.68 g / ml, a particle size / aperture on the 500 μm sieve of 68% by weight, and a water content of 0.3%.

<Silicate compound 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

  In addition, the particle size of the granular silicate compound and the comparative silicate compound was determined by the following method in accordance with JIS Z8801.

(1) The granular silicate compound and the silicate compound for comparative examples were placed on a sieve having an opening of 2 mm, and passed through the sieve while being evenly lightly swept with a brush.

(2) The silicate compound passed through a sieve was placed in 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 sieved silicate compound was sieved using a sieve having an opening of 500 μm, and the weight of the substance 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.

<Rubber polymer (component C)>
Rubber polymer (1): Core / shell type graft copolymer comprising poly (alkyl acrylate) (core) / alkyl acrylate / alkyl methacrylate copolymer (shell), Rohm and Hearth “Paraloid EXL2315” manufactured by Japan

Rubber polymer (2): Core / shell type graft copolymer consisting of polybutadiene (core) / alkyl acrylate / alkyl methacrylate copolymer (shell), manufactured by Rohm and Haas Japan "Paraloid EXL2603"

<Phosphorus compound (component D)>
Phosphorus compound (1): 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.

Phosphorus compound (2): distearyl pentaerythritol diphosphite, “Adeka Stub PEP-8” manufactured by Asahi Denka Kogyo Co., Ltd.

<Other ingredients>
Thermal stabilizer: Tris (2,4-di-tert-butylphenyl) phosphite (Adeka Stub AS2112 manufactured by Asahi Denka Kogyo Co., Ltd.)

[Preparation of resin composition]
After each component shown in Table 1 to Table 4 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, barrel number 12 ) Was supplied to the extruder from the barrel 1 at a cylinder temperature of 260 ° C. and a screw rotation speed of 250 rpm, and melt-kneaded to prepare pellets of the resin composition.

[Preparation of test piece]
After the pellets obtained by the above method are dried at 120 ° C. for 6 hours or longer, using a M150AII-SJ type injection molding machine manufactured by Meiki Seisakusho, cylinder temperature 270 ° C., mold temperature 80 ° C., molding cycle An ASTM test piece and a 100 mmφ disk-shaped molded article (thickness 3 mmt) were prepared under the condition of 55 seconds. In addition, the retention molding was performed in 4 minutes per cycle, and the disk-shaped molded product (retention molded product) after the fifth shot was evaluated.

[Evaluation methods]
(1) Extrudability:
When preparing the resin composition, those that can be easily formed into a strand and pelletized at a discharge rate of 30 k / h or more, and those that can be stranded and pelletized at a discharge rate of 30 k / h because the strand cannot be pulled and the discharge amount is reduced. Was evaluated as x.

(2) Fluidity (Q value)
The pellets of the resin composition are dried at 120 ° C. for 4 hours or longer, and using a high load type flow tester, the effluent Q value per unit time of the composition under the conditions of 280 ° C. and load 160 kgf / cm ² (unit: ml / s) was measured to evaluate the fluidity. An orifice having a diameter of 1 mm and a length of 10 mm was used. It shows that it is excellent in fluidity | liquidity, so that Q value is high.

(3) Rigidity (flexural modulus)
Based on ASTM D790, the bending elastic modulus (unit: MPa) was measured at 23 ° C. using a test piece having a thickness of 6.4 mm.

(4) Impact resistance (Izod impact strength)
In accordance with ASTM D256, Izod impact strength (unit: J / m) was measured at 23 ° C. using a notched specimen having a thickness of 3.2 mm.

(5) Appearance:
The surface appearance of the disk-shaped molded product prepared with the molding cycle of 55 seconds was visually observed, and evaluation was made with ○ having no mixing unevenness (color unevenness) and x having mixing unevenness (color unevenness). .

(6) Stability heat stability The surface appearance of the disk-shaped molded product (residual molded product) prepared in the molding cycle of 4 minutes was visually observed, and ◎, Silva was found to have no rough skin due to silver stroke. -Evaluation was made with ○ indicating that there was almost no rough skin due to the streak, and X indicating rough skin due to the silver streak.

[Examples 1 to 10, Comparative Examples 1 to 12]
Resin compositions were produced at the composition ratios shown in Tables 1 to 4, and the above-described evaluation was performed. The results are shown in Tables 1 to 4.

  The following can be understood from the results of Examples and Comparative Examples shown in Tables 1 to 4. The resin compositions described in Examples 1 to 10 of the present invention have an excellent balance of fluidity, rigidity, impact resistance, and residence heat stability, and are excellent in extrusion processability and have a good surface appearance. .

  On the other hand, the resin composition described in Comparative Example 1 containing no B component is inferior in extrudability and surface appearance as compared to the resin composition described in the Examples, and the B component The resin compositions described in Comparative Examples 2 to 4 and Comparative Examples 8 to 10, which are outside the range, are inferior in impact resistance and residence heat stability as compared to the resin compositions described in the Examples.

  In addition, the resin composition described in Comparative Example 5 in which the content of the A2 component is outside the range specified in this patent is inferior in impact resistance and residence heat stability as compared to the resin composition described in the Examples. Furthermore, the resin compositions described in Comparative Examples 6 and 7 and Comparative Examples 11 to 12 in which the A2 component is outside the scope of this patent provision are more fluid and impact resistant than the resin compositions described in the Examples. Inferior to sex.

Claims (13)

  40 to 99 parts by weight of resin component (component A) consisting of 5 to 95% by weight of aromatic polycarbonate resin (component A1) and 95% to 5% by weight of polylactic acid resin (component A2) A thermoplastic fat composition containing 1 to 60 parts by weight of a granular silicate compound (component B) and 0 to 35 parts by weight of a rubbery polymer (component C), wherein the granular silicate compound (component B) The thermoplastic resin composition is characterized in that, in the particle size, the ratio on a sieve having an opening of 500 μm is 55% by weight or more.   The thermoplastic resin composition according to claim 1, wherein the bulk density of the granular silicate compound (component B) is 0.4 to 1.5 g / ml.   3. The thermoplastic resin composition according to claim 1, wherein the granular silicate compound (component B) has an average particle size of 0.05 to 50 μm.   The thermoplastic resin composition according to any one of claims 1 to 3, wherein the granular silicate compound (component B) is granulated using a binder.   The thermoplastic resin composition according to claim 4, wherein the binder content in the granular silicate compound (component B) is 0.01 to 5% by weight.   The thermoplastic resin composition according to claim 4 or 5, wherein the binder in the granular silicate compound (component B) is a water-soluble polymer.   The thermoplastic resin composition according to any one of claims 1 to 6, wherein the granular silicate compound (component B) is granular talc.   The thermoplastic resin composition according to any one of claims 1 to 7, wherein the ratio of the granular silicate compound (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 8, wherein the polylactic acid resin (component A2) has an intrinsic viscosity of 1.5 to 2.3 dL / g.   The resin component (component A) is composed of 100% by weight in total of 50 to 85% by weight of aromatic polycarbonate resin (component A1) and 50 to 15% by weight of polylactic acid resin (component A2). The thermoplastic resin composition according to any one of claims 1 to 9.   The thermoplastic resin according to any one of claims 1 to 10, wherein the content of the rubber polymer (C component) in the total 100 parts by weight of the A to C components is 1 to 30 parts by weight. Composition.   The thermoplastic resin composition according to any one of claims 1 to 11, wherein the rubber polymer (component C) 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 12.