JP2012136716A - Thermoplastic resin composition and resin-molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition, particularly an aromatic polycarbonate resin composition, excellent in flowability, impact resistance and stiffness.SOLUTION: The thermoplastic resin composition comprises the total 100 pts.wt. consisting of: 30-95 pts.wt. of an aromatic polycarbonate resin (component A); 1-50 pts.wt. of a styrenic resin (component B); and 1-50 pts.wt. of polylactic acid-based resin (component C), wherein the rubber ingredient content in the component B is 0-39 wt.%. The thermoplastic resin-molded article made by molding the above composition is also provided.

Description

  The present invention relates to a thermoplastic resin composition comprising an aromatic polycarbonate resin, a styrene resin, and a polylactic acid resin. More specifically, the present invention relates to a thermoplastic resin composition excellent in fluidity and impact resistance and excellent in rigidity, and a resin molded product formed by molding the same.

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.
However, aromatic polycarbonate resins have the problem of high melt viscosity and inferior moldability, and there is a strong demand to improve moldability (fluidity) as the thickness and size of molded products increase. It has been.

As a means to improve the fluidity of aromatic polycarbonate resin, polymer alloying with acrylonitrile / butadiene / styrene resin (ABS resin), acrylonitrile / styrene resin (AS resin), etc. has been proposed and put into practical use. There is a need for improved fluidity.
In addition, in order to improve the fluidity of the aromatic polycarbonate resin, several techniques for adding a low molecular weight polymer have been proposed (for example, see Patent Documents 1 and 2). However, a resin composition that is not always satisfactory in the balance between fluidity and impact resistance has not been found.

On the other hand, a resin composition excellent in fluidity in which an aromatic polycarbonate resin is blended with polylactic acid has been proposed (see, for example, Patent Document 3). In addition, the aliphatic polyester can synthesize polymers based on plant resources, and since carbon dioxide circulates as a non-petroleum resource (carbon neutral), it attracts attention as an environmentally friendly material.
However, simply adding polylactic acid to an aromatic polycarbonate resin as disclosed in the above-mentioned patent document has a problem that the fluidity is improved but the impact resistance is low.

Also disclosed is a resin composition excellent in fluidity and impact resistance, in which polylactic acid and an impact modifier are blended with an aromatic polycarbonate resin (see, for example, Patent Document 4). However, this resin composition is intended to improve impact resistance by incorporating an impact modifier with a high rubber component content, but it is not always satisfactory in terms of fluidity and rigidity. There has been a demand for a material having excellent properties and rigidity.
Furthermore, a biodegradable pearly luster plastic including a biodegradable polyester resin and at least one member selected from the group consisting of a polycarbonate resin, an AS resin, and a methacrylic resin is disclosed (for example, see Patent Document 5). However, this resin composition is a technique aiming to achieve both mechanical strength and biodegradability. In a resin composition composed of a polycarbonate resin, a styrene resin and a polylactic acid resin, it has fluidity, impact resistance, and rigidity. There was no suggestion about improvement at the same time.

Japanese Patent Laid-Open No. 11-181198 JP 2000-239477 A JP-A-7-109413 JP-A-2005-48067 JP-A-11-279380

  An object of the present invention is to provide a thermoplastic resin composition that eliminates the above-mentioned disadvantages of the prior art, is excellent in fluidity and impact resistance, and is excellent in rigidity.

  As a result of intensive studies to achieve the above object, the present inventors have made a thermoplastic resin composition (hereinafter simply referred to as “resin composition”) comprising an aromatic polycarbonate resin, a styrene resin, and a polylactic acid resin. ), The use of a styrene-based resin having a rubber component content of a specific amount or less finds that the resin composition is excellent in fluidity, impact resistance and rigidity, The present invention has been completed.

  That is, the gist of the present invention is that the aromatic polycarbonate resin (component A) 30 to 95 parts by weight, the styrene resin (component B) 1 to 50 parts by weight, and the polylactic acid resin (component C) 1 to 50 parts by weight in total 100 The present invention resides in a thermoplastic resin composition consisting of parts by weight, wherein the rubber component content in the B component is 0 to 39 weights, and a resin molded product formed by molding the same.

The thermoplastic resin composition of the present invention is a resin composition excellent in fluidity and impact resistance and excellent in rigidity.
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 building materials, various containers, leisure goods / miscellaneous goods, lighting equipment, etc., especially housing members for electric / electronic equipment, OA equipment, information terminal equipment, vehicle exterior / skin parts, vehicle interior parts Application to can be expected.

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

Vehicle exterior / skin parts include outer door handles, bumpers, fenders, door panels, trunk lids, front panels, rear panels, roof panels, bonnets, pillars, side moldings, garnishes, wheel caps, hood bulges, fuel lids, and various spoilers. Motorbike cowl.
Examples of 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 for 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 (component A)
The aromatic polycarbonate resin which is the A component used in the present invention (hereinafter sometimes abbreviated as “A component”) includes, for example, an aromatic dihydroxy compound and a carbonate precursor, or a small amount of them together. A linear or branched thermoplastic aromatic polycarbonate polymer or copolymer obtained by reacting a polyhydroxy compound or the like.

  As the aromatic polycarbonate resin (component A) used in the present invention, those obtained by any conventionally known production method can be used. Specific examples 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. Among them, it is advantageous in the chemical industry to use an interfacial polymerization method or a melt transesterification method. Hereinafter, these two methods will be described as examples of the method for producing an aromatic polycarbonate resin.

  Specific examples of the aromatic dihydroxy compound used as a raw material include 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A) and 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) Lopan, 2,2-bis (3,5-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-tri Chloropropane, 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexachloropropane, 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3 Bis (hydroxyaryl) alkanes exemplified by 3-hexafluoropropane and the like;

  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 to be prepared;

  Cardostructure-containing bisphenols exemplified by 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, and the like; 4,4′-dihydroxydiphenyl ether, Dihydroxydiaryl ethers exemplified by 4′-dihydroxy-3,3′-dimethyldiphenyl ether and the like;

  Dihydroxydiaryl sulfides exemplified by 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide, and the like; 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxy- Dihydroxydiaryl sulfoxides exemplified by 3,3′-dimethyldiphenyl sulfoxide and the like; dihydroxydiaryl sulfones exemplified by 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfone and the like And the like; 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 dihalophenolate of divalent phenol. These carbonate precursors may also be used alone or in combination of two or more.

  The aromatic polycarbonate resin (component A) 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, 1, Polyhydroxy compounds exemplified by 1,1-tri (4-hydroxyphenyl) ethane, etc., or 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 preferable. The polyfunctional aromatic compound can be used by substituting a part of the aromatic dihydroxy compound, and the amount used is preferably 0.01 to 10 mol% with respect to the aromatic dihydroxy compound. ~ 2 mol% is preferred.

  The reaction by the interfacial polymerization method is, for example, in the presence of an organic solvent inert to the reaction and an aqueous alkali solution, usually maintaining the pH at 9 or higher, and adding an aromatic dihydroxy compound as necessary to a molecular weight modifier (terminal terminator). Reacting with phosgene together with an antioxidant of an aromatic dihydroxy compound. Next, a method of obtaining a polycarbonate by adding a polymerization catalyst such as a tertiary amine or a quaternary ammonium salt and performing interfacial polymerization can be mentioned. 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 may be appropriately selected and determined between the phosgenation reaction and the start of the polymerization reaction.

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 alkali metal hydroxides 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 phenol.

  The amount of the molecular weight regulator used is preferably 0.5 to 50 mol, more preferably 1 to 30 mol, per 100 mol of the aromatic dihydroxy compound. 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 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. Of these, diphenyl carbonate and substituted diphenyl carbonate are preferable, and diphenyl carbonate is particularly preferable.

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 (component A) 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. Further, the lower limit thereof is preferably 10 ppm or more, particularly 30 ppm or more, and more preferably 40 ppm or more in the aromatic polycarbonate resin produced by the transesterification method.
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 unit of terminal hydroxyl group concentration is the weight of the terminal hydroxyl group expressed in ppm relative to the weight of the aromatic polycarbonate resin, and the measuring method is colorimetric determination (Macromol. Chem. 88 215) by the titanium tetrachloride / acetic acid method. (Method of (1965)).

  Moreover, in order to improve the appearance of the molded product and the fluidity, the aromatic polycarbonate resin (component A) used in the present invention may contain an aromatic polycarbonate ligomer. The viscosity average molecular weight [Mv] of this aromatic polycarbonate ligomer is preferably 1500 to 9500, more preferably 2000 to 9000. The aromatic polycarbonate ligomer is preferably used in the range of 30% by weight or less of the component A.

  Further, as the aromatic polycarbonate resin (component A) 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 component A.

[2] Styrenic resin (component B)
The styrene resin that is the B component used in the present invention (hereinafter sometimes abbreviated as “B component”) is a styrene polymer composed of a styrene monomer, a styrene monomer and other co-polymers. Contains a rubber component formed by copolymerizing a styrene monomer in the presence of a copolymer with a polymerizable vinyl monomer and a rubbery polymer (hereinafter sometimes referred to as "rubber component"). One or more types selected from a rubber component-containing copolymer obtained by copolymerizing a styrene monomer and another copolymerizable vinyl monomer in the presence of a copolymer or a rubbery polymer The rubber component content in the B component is 0 to 39% by weight.
Although these production methods are arbitrary, a copolymer obtained by copolymerizing a styrene monomer and another copolymerizable vinyl monomer in the presence of a rubber polymer is preferable. The component content is preferably 5 to 39% by weight, more preferably 10 to 35% by weight, and particularly preferably 13 to 25% by weight.

  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, cyclohexyl acrylate; methacrylic acid such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, cyclohexyl methacrylate Alkyl esters; acrylics such as phenyl acrylate and benzyl acrylate Aryl ester; Methacrylic acid aryl ester such as phenyl methacrylate and benzyl methacrylate; Epoxy group-containing acrylic acid ester or methacrylic acid ester such as glycidyl acrylate and glycidyl methacrylate; Maleimide type such as maleimide, N, N-methylmaleimide and N-phenylmaleimide Monomers; α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid or anhydrides thereof; and the like.

  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.

Specific examples of the styrene resin (component B) used in the present invention include high impact polystyrene (HIPS), acrylonitrile-styrene copolymer (AS resin), and acrylonitrile-butadiene-styrene copolymer (ABS resin). , Methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), acrylonitrile-ethylenepropylene rubber-styrene copolymer (AES resin), styrene-methyl Examples thereof include a methacrylate copolymer (MS resin) and a styrene-maleic anhydride copolymer.
Among these, acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), and acrylonitrile-ethylenepropylene rubber-styrene copolymer (AES resin) are particularly preferable. An acrylonitrile-butadiene-styrene copolymer (ABS resin) is preferable. These can be used alone or in admixture of two or more.

  The styrene resin used in the present invention 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 resin is used. In the case of a random copolymer or block copolymer, those produced by bulk polymerization, suspension polymerization, or bulk / suspension polymerization are suitable. In the case of a styrene-based graft copolymer, bulk polymerization, bulk / suspension is preferred. Those produced by polymerization or 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 0 to 39% by weight, preferably 5 to 39% 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 as the B component. is there.
The rubber particle diameter is preferably 0.1 to 5 μm, more preferably 0.2 to 3 μm, still more preferably 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.
In addition, when using a thermoplastic graft polymer as described above as the B component used in the present invention, even if one rubber content exceeds 39% by weight, the total rubber content in the B component is It may be 39% by weight or less.

[3] Polylactic acid resin (component C)
A polylactic acid-based resin (hereinafter, may be abbreviated as “C component”), which is a C 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, Aliphatic diols such as 8-octanediol, 1,10-decanediol, 1,12-dodecanediol, 1,14-tetradecanediol, 1,16-hexadecanediol, 1,18-octadecanediol, 1,2- Cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,4-cyclohexanedimethanol and other alicyclic diols, 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, naphthalenedicarboxylic acid, glycolic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, hydroxybenzoic acid, etc. Examples include lactones such as hydroxycarboxylic acids, caprolactone, valerolactone, propiolactone, undecalactone, and 1,5-oxepan-2-one. These may be used alone or as a mixture of two or more.

  Further, in the present invention, aliphatic polyhydric alcohols such as glycerin and trimethylolpropane, aliphatic polybasic acids such as butanetetracarboxylic acid, and polyhydric alcohols such as polysaccharides are partially copolymerized. The molecular weight may be increased by 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.
In the case of producing a polylactic acid resin by directly dehydrating polycondensation of raw materials, the raw material lactic acid or lactic acid and other copolymer components are preferably azeotroped in the presence of an organic solvent, particularly a phenyl ether solvent. Polymerization is carried out by a method of dehydrating condensation and, particularly preferably, removing water from the solvent distilled off azeotropically to make it substantially anhydrous, and returning it to the reaction system. A polylactic acid resin can be obtained.

  The molecular weight of the polylactic acid-based resin is usually 10,000 or more, preferably 40,000 or more, and more preferably 80,000 or more as a weight average molecular weight. The weight average molecular weight refers to a molecular weight in terms of polymethyl methacrylate (PMMA) measured by gel permeation chromatography (GPC).

[4] Content ratio In the thermoplastic resin composition of the present invention, the content ratios of the components A, B, and C constituting this are aromatic polycarbonate resin in a total of 100 parts by weight of the components A, B, and C. (A component) 30-95 weight part, Styrenic resin (B component) 1-50 weight part, Polylactic acid-type resin (C component) 1-50 weight part.
Among the total 100 parts by weight of the A to C components, the A component is preferably 30 to 95 parts by weight, particularly 40 to 90 parts by weight, more preferably 45 to 85 parts by weight, and particularly preferably 50 to 80 parts by weight. When the A component is 30 parts by weight or more, impact resistance tends to be improved, and when it is less than 95 parts by weight, fluidity tends to be improved.

Further, in 100 parts by weight of the total of A, B and C components, the B component is preferably 1 to 50 parts by weight, particularly 5 to 40 parts by weight, and more preferably 10 to 35 parts by weight. When the B component is 1 part by weight or more, fluidity and impact resistance tend to be improved, and when it is less than 50 parts by weight, rigidity tends to be improved.
Next, the C component is preferably 1 to 50 parts by weight, particularly 3 to 40 parts by weight, and more preferably 5 to 30 parts by weight, out of a total of 100 parts by weight of the A, B and C components. When the C component is 1 part by weight or more, the fluidity tends to be improved, and when it is 50 parts by weight or less, the impact resistance tends to be improved.
Furthermore, the content ratio (B part by weight / C part by weight) of the content (B part by weight) of the styrene resin (B part) and the content (C part by weight) of the polylactic acid resin (C part) is A range of 0.5 to 4 is preferable, a range of 0.7 to 3 is more preferable, and a range of 0.9 to 2.5 is particularly preferable. When (B part by weight / C part by weight) is 0.5 or more, impact resistance tends to be improved, and conversely, when it is 4 or less, rigidity and impact resistance tend to be improved.

[5] Other components The thermoplastic resin composition of the present invention contains other resins and various resin additives in addition to the above-mentioned components A, B and C, as long as the object of the present invention is not impaired as required. May be.
Other resins include, for example, thermoplastic aromatic polyester resins such as polyethylene terephthalate resin, polytrimethylene terephthalate resin, polybutylene terephthalate resin, polyolefin resins such as polyethylene resin and polypropylene resin, polyamide resin, polyimide resin, and polyetherimide. Examples thereof include resins, polyurethane resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, polymethacrylate resins, phenol resins, and epoxy resins. These may be used alone or in combination of two or more.

  Various resin additives include antioxidants, mold release agents, dyes and pigments, heat stabilizers, reinforcing agents, flame retardants, impact resistance improvers, weather resistance improvers, antistatic agents, antifogging agents, and lubricants. -Antiblocking agents, fluidity improvers, plasticizers, dispersants, antibacterial agents, and the like. These may be used alone or in combination of two or more. Among these, the thermoplastic resin composition of the present invention is applied with an antioxidant, a thermal stabilizer, a release agent, an inorganic filler, an ultraviolet absorber, an impact modifier, a dye / pigment, a flame retardant and an anti-dripping agent. It is preferable to use it appropriately for the purpose.

Antioxidant In the present invention, the antioxidant preferably used includes a hindered phenol antioxidant. Specific examples 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 ″-(mesitile -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 and the like.

These may be used alone or in combination of two or more. Among the above, in particular 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.
The content of the phenolic antioxidant is preferably 0.001 to 1 part by weight, more preferably 0.01 to 0.5 part by weight, with respect to 100 parts by weight of the total of A, B and C components. is there. If the content of the phenolic antioxidant is less than 0.001 part by weight, the effect as an antioxidant is insufficient, and if it exceeds 1 part by weight, no further effect as an antioxidant can be obtained.

Thermal stabilizer The thermal stabilizer preferably used in the present invention is phosphorous acid 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. It is at least one selected from an ester compound, phosphorous acid and tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylene-di-phosphonite.
Specific examples of the phosphite compound 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 phosphite, distearyl Pentaerythritol diphosphite, diphenylpentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol di Examples thereof include phosphite and bis (2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite. These may be used alone or in combination of two or more. Among the above, tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert) -Butyl-4-methylphenyl) pentaerythritol diphosphite is preferred.
The content of the heat stabilizer is preferably 0.001 to 1 part by weight and more preferably 0.01 to 0.5 part by weight with respect to 100 parts by weight of the total of components A, B and C. If the content of the heat stabilizer is less than 0.001 part by weight, the effect as a heat stabilizer is insufficient, and if it exceeds 1 part by weight, the hydrolysis resistance may deteriorate.

Release Agent The release agent preferably used in the present invention includes 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. It is at least one compound selected.
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 , Adipic acid, azelaic acid and the like.
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. Examples of the alcohol that reacts with the aliphatic carboxylic acid to form an ester include saturated or unsaturated monohydric alcohol, saturated or unsaturated polyhydric alcohol, and the like. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these alcohols, monovalent or polyvalent saturated alcohols having 30 or less carbon atoms are preferable, and aliphatic saturated monovalent alcohols or polyhydric alcohols having 30 or less carbon atoms are more preferable.
Here, aliphatic includes alicyclic compounds. Specific examples of these alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol. Etc. These ester compounds of aliphatic carboxylic acids and alcohols may contain aliphatic carboxylic acids and / or alcohols as impurities, or may be a mixture of a plurality of compounds.

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, and pentaerythritol tetrastearate.
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, an alicyclic hydrocarbon is also included. Moreover, these hydrocarbon compounds may be partially oxidized. Among these, paraffin wax, polyethylene wax, and partial oxides of polyethylene wax are preferable, and paraffin wax and polyethylene wax are more preferable.
The number average molecular weight is 200 to 15,000, 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. These may be used alone or in combination of two or more.

  The content of the release agent is preferably 0.001 to 2 parts by weight, more preferably 0.01 to 1 part by weight with respect to 100 parts by weight of the total of the components A, B and C. If the content of the release agent is less than 0.001 part by weight, the effect of releasability may not be sufficient. On the other hand, if the content exceeds 2 parts by weight, hydrolysis resistance decreases, mold contamination during injection molding, etc. There is a problem. One type of release agent can be used, but a plurality of release agents can be used in combination.

Inorganic filler In the thermoplastic resin composition of the present invention, an inorganic filler can be contained for the purpose of improving rigidity and strength. Specific examples of inorganic fillers include glass fillers such as glass fibers (chopped strands), short glass fibers (milled fibers), glass flakes, and glass beads, carbon fillers such as carbon fibers, carbon short fibers, carbon nanotubes, and graphite. , Whiskers such as potassium titanate and aluminum borate, talc, mica, wollastonite, kaolinite, zonotlite, sepiolite, attabalgite, montmorillonite, bentonite, smectite and other silicate compounds, silica, alumina, calcium carbonate, etc. . These may be used alone or in combination of two or more. Among these, glass fiber (chopped strand), short glass fiber (milled fiber), glass flake, talc, mica, wollastonite, and kaolinite are particularly preferable.
The content of the inorganic filler is preferably 1 to 150 parts by weight, more preferably 3 to 100 parts by weight, and particularly preferably 5 to 60 parts by weight with respect to a total of 100 parts by weight of the components A, B and C. If the content of the inorganic filler is less than 1 part by weight, the reinforcing effect may not be sufficient. Conversely, if it exceeds 150 parts by weight, the appearance, impact resistance, and fluidity may not be sufficient.

Ultraviolet absorber In the present invention, an ultraviolet absorber may be further added. Examples of the ultraviolet absorber used here include organic ultraviolet absorbers such as benzotriazole compounds, benzophenone compounds, and triazine compounds, in addition to inorganic ultraviolet absorbers such as titanium oxide, cerium oxide, and zinc oxide. In the present invention, among these, organic ultraviolet absorbers are preferred, and 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 It is preferably at least one selected from -phenylene) bis [4H-3,1-benzoxazin-4-one] and [(4-methoxyphenyl) -methylene] -propanedioic acid-dimethyl ester.

  As a specific example of the benzotriazole compound, a condensate with methyl-3- [3-tert-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate-polyethylene glycol is preferable. 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 Renbis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol] [methyl-3- [3-tert-butyl-5- (2H-benzo] And triazol-2-yl) -4-hydroxyphenyl] propionate-polyethylene glycol] condensate. These may be used alone or in combination of two or more.

  Among these, 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole and 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl are particularly preferable. ] -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].

  The content of the ultraviolet absorber is preferably 0.01 to 3 parts by weight, more preferably 0.1 to 1 part by weight with respect to 100 parts by weight of the total of components A, B and C. If it exceeds 3 parts by weight, there may be a problem such as mold deposit, and if it is less than 0.01 part by weight, the effect of improving weather resistance may be insufficient.

In the present invention, coloring components such as dyes and pigments may be further added. Examples of the dye / pigment used at this time include inorganic pigments, organic pigments, and organic dyes. Examples of inorganic pigments include carbon black; sulfide pigments such as cadmium red and cadmium yellow; silicate pigments such as ultramarine blue; titanium oxide, zinc white, petal, chromium oxide, iron black, titanium yellow, and zinc-iron. Oxide pigments such as chrome brown, titanium cobalt green, cobalt green, cobalt blue, copper-chromium black, copper-iron black; chromic pigments such as yellow lead and molybdate orange; ferrocyans such as bitumen And the like.
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, isoindolinone, Examples include condensed polycyclic dyes such as quinophthalone; anthraquinone, heterocyclic, and methyl dyes. These may be used alone or in combination of two or more. Among these, titanium oxide, carbon black, 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 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 components A, B, and C. If the content of the dye / pigment exceeds 5 parts by weight, the impact resistance may not be sufficient.

Flame retardant and anti-dripping agent In the present invention, a flame retardant may be further added. Examples of the flame retardant used here include halogenated bisphenol A polycarbonate, brominated bisphenol-based epoxy resins, brominated bisphenol-based phenoxy resins, halogenated flame retardants such as brominated polystyrene, phosphate ester-based flame retardants, and diphenylsulfone-3. , 3′-disulfonic acid dipotassium, diphenylsulfone-3-sulfonic acid potassium, potassium perfluorobutanesulfonic acid, and other organic metal salt flame retardants, polyorganosiloxane flame retardants, and the like. Particularly preferred.
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. These may be used alone or in combination of two or more. Among these, resorcinol bis (dixylenyl phosphate) and bisphenol A bis (diphenyl phosphate) are preferable.
The content of the phosphate ester flame retardant is preferably 1 to 30 parts by weight, more preferably 3 to 25 parts by weight, and particularly preferably 5 to 20 parts by weight with respect to 100 parts by weight of the total of A, B and C components. It is. If the content of the phosphate ester flame retardant is less than 1 part by weight, the flame retardancy may not be sufficient, whereas if it exceeds 30 parts by weight, the heat resistance may not be sufficient.

Examples of the anti-dripping agent used in the present invention include fluorinated polyolefins such as polyfluoroethylene, and polytetrafluoroethylene having fibril-forming ability is preferable. 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 are commercially available from Mitsui / Dupont Fluoro Chemical Co., Ltd. as Teflon (registered trademark) 6J or Teflon (registered trademark) 30J, or from Daikin Industries, Ltd. as polyflon (trade name). Yes.
The content of the anti-dripping agent is preferably 0.02 to 4 parts by weight, more preferably 0.03 to 3 parts by weight, with respect to 100 parts by weight of the total of components A, B and C. When the blending amount of the dripping inhibitor exceeds 5 parts by weight, the appearance of the molded product may be deteriorated.

[6] Method for adjusting thermoplastic resin composition The thermoplastic resin composition of the present invention is obtained by appropriately selecting any conventionally known method for the resin, additives and the like in addition to the components A, B and C. Can be manufactured.
Specifically, for example, A, B, C components and additive components blended as necessary are mixed in advance using various mixers such as a tumbler and a Henschel mixer, and then Banbury mixer, roll, Brabender, uniaxial A resin composition can be produced by melt-kneading with a kneading extruder, a twin-screw kneading extruder, a kneader or the like. Further, the resin composition can be produced 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.

[7] Molding method of thermoplastic resin composition The method for producing a molded product from the thermoplastic resin composition of the present invention is not particularly limited, and a molding method generally employed for thermoplastic resins, ie, general Injection molding method, 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 insulation mold, molding method using rapid heating mold, foaming Adopt 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. Can do. Moreover, the shaping | molding method using a hot runner system can also be selected.

In addition, in the present invention, from the viewpoint of reducing environmental burden such as waste reduction and cost reduction, when manufacturing molded products from resin compositions, non-conforming products, sprues, runners, used products, etc. are recycled. The raw material can be mixed with the virgin material 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.
<A component: aromatic polycarbonate resin>
PC-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)
PC-2: Bisphenol A type aromatic polycarbonate produced by an interfacial polymerization method (“Iupilon H-4000FN” manufactured by Mitsubishi Engineering Plastics, viscosity average molecular weight 15500, terminal hydroxyl group concentration = 150 ppm)
PC-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)
<B component: Styrenic resin>
ABS-1: Acrylonitrile-butadiene-styrene copolymer (“Santac AT-08” manufactured by Nippon A & L Co., butadiene rubber content 18% by weight)
ABS-2: Acrylonitrile-butadiene-styrene copolymer (“Santac UT-61” manufactured by Nippon A & L Co., butadiene rubber content 17% by weight)
<Other than B component>
MBS: Methyl methacrylate-butadiene-styrene copolymer ("Maybrene C-223A" manufactured by Mitsubishi Rayon Co., Ltd., butadiene rubber content 70% by weight)

<C component: polylactic acid resin>
PLA: Polylactic acid (“Lacia H-400” manufactured by Mitsui Chemicals, Inc.)
<Other ingredients>
Thermal stabilizer: Tris (2,4-di-tert-butylphenyl) phosphite (Adeka Stub AS2112 manufactured by Asahi Denka Kogyo Co., Ltd.)
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]
A component, B component, C component and other components were uniformly mixed with a tumbler mixer in the ratio shown in Table 1, and then a twin screw extruder (manufactured by Nippon Steel Works, TEX30XCT, L / D = 42, barrel number 12). ) Was fed to the extruder from the barrel 1 at a cylinder temperature of 260 ° C. and a screw rotation speed of 200 rpm, and melt-kneaded to prepare pellets of the resin composition.

[Preparation of test piece]
The pellets obtained by the above method were dried at 100 ° C. for 6 hours or more, and then, using a M150AII-SJ type injection molding machine manufactured by Meiki Seisakusho, the cylinder temperature was 270 ° C., the mold temperature was 80 ° C., and the molding cycle was 55 An ASTM test piece and a 100 mmφ disk-shaped product (thickness 3 mm) were prepared under the conditions of seconds.

[Evaluation methods]
(1) Fluidity (Q value)
Using a high load flow tester, the flow rate Q value (unit: cc / s) per unit time of the composition was measured under the conditions of 280 ° C. and a load of 160 kgf / cm ² 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.
(2) 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.
(3) Rigidity (flexural modulus)
In accordance with ASTM D790, measurement was performed at 23 ° C. using a test piece having a thickness of 6.4 mm.

[Examples 1-6, Comparative Examples 1-5]
Each resin composition described in Tables 1 and 2 was produced and evaluated by the method described above. The results are shown in Tables 1 and 2.

From the results shown in Tables 1 and 2, the following can be understood. The resin compositions described in Examples 1 to 6 of the present invention are excellent in fluidity and impact resistance and excellent in rigidity. On the other hand, since the resin composition described in Comparative Example 1 does not contain the B component and the C component, it is inferior in fluidity as compared with the composition of the example.
Since the resin composition described in Comparative Example 2 does not contain a C component, the resin composition is inferior in fluidity and rigidity as compared with the compositions of Examples. Moreover, since the resin composition of Comparative Examples 3 and 4 does not contain B component, it is inferior to fluidity | liquidity and impact resistance compared with the composition of an Example. And as for the resin composition of the comparative example 5, B component is outside the range of prescription | regulation of this patent, and it is inferior to fluidity | liquidity and rigidity compared with the composition of an Example.

That is, the gist of the present invention is a total of 100 to 95 parts by weight of aromatic polycarbonate resin (component A), 1 to 50 parts by weight of styrene resin (component B), and 1 to 50 parts by weight of polylactic acid resin (component C). The rubber component content in the B component is 0 to 39% by weight , the terminal hydroxyl group concentration of the aromatic polycarbonate resin (A component) is 40 to 800 ppm, and the styrenic resin (B component) is It is at least one selected from acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), and acrylonitrile-ethylenepropylene rubber-styrene copolymer (AES resin), heat, wherein a, B, by containing a releasing agent 0.001 parts by weight per 100 parts by weight of component C It consists in plastic resin compositions, and resin molded article obtained by molding the same.

The content of the release agent is 0 .0 to 100 parts by weight of the total of A, B, and C components. 001-2 parts by weight, good Mashiku is 0.01 to 1 part by weight. If the content of the release agent is less than 0.001 part by weight, the effect of releasability may not be sufficient. On the other hand, if the content exceeds 2 parts by weight, hydrolysis resistance decreases, mold contamination during injection molding, etc. There is a problem. One type of release agent can be used, but a plurality of release agents can be used in combination.

Claims (5)

  It consists of 30 to 95 parts by weight of aromatic polycarbonate resin (component A), 1 to 50 parts by weight of styrene resin (component B), and 1 to 50 parts by weight of polylactic acid resin (component C). A thermoplastic resin composition characterized in that the rubber component content therein is 0 to 39% by weight.   2. The thermoplastic resin composition according to claim 1, wherein the content of the rubber component in the styrene-based resin (component B) is 10 to 35 wt%.   Styrene resin (component B) is acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), acrylonitrile-ethylenepropylene rubber-slen copolymer (AES resin) The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition is at least one selected from the group consisting of   The content ratio (B parts by weight / C parts by weight) of the content (B parts by weight) of the styrene resin (component B) and the content (C parts by weight) of the polylactic acid resin (component C) is 0. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition is in the range of 5-4.   The resin molded product formed by shape | molding the thermoplastic resin composition in any one of Claims 1 thru | or 4.