JP5166699B2 - Aromatic polycarbonate resin composition - Google Patents

Description

  The present invention relates to an aromatic polycarbonate resin composition for obtaining a molded article containing a polymer obtained from biomass resources and having excellent heat resistance, mechanical properties, and durability stability. More specifically, the present invention relates to an aromatic polycarbonate resin composition for obtaining a molded product excellent in heat resistance, mechanical properties, and hydrolysis resistance obtained by blending a specific polylactic acid with an aromatic polycarbonate.

  Aromatic polycarbonate has excellent heat resistance, mechanical properties, impact resistance, dimensional stability, etc., and is widely used in applications such as OA equipment field, automobile field, and electric / electronic parts field. On the other hand, aromatic polycarbonates also have an aspect that most of the raw materials depend on petroleum resources.

  In recent years, due to concerns about the depletion of petroleum resources and the problem of increased carbon dioxide in the air that causes global warming, biomass resources that do not depend on petroleum as a raw material and that do not increase carbon dioxide even when burned are formed. In the polymer field, biomass plastics produced from biomass resources are actively developed.

  A representative example of biomass plastic is polylactic acid, which has relatively high heat resistance and mechanical properties among biomass plastics, so its application is expanding to tableware, packaging materials, general merchandise, etc. Sexuality has also been considered.

  However, when polylactic acid is used as an industrial material in the field where aromatic polycarbonate is used, not only the properties such as mechanical properties and heat resistance are insufficient, but also polylactic acid is biodegradable. In addition, the property of having a combination of the above is a restriction that the hydrolysis resistance is remarkably low with respect to the use under wet heat conditions, and the application development is not progressing.

  In addition, optical isomers exist in polylactic acid. When poly-L-lactic acid and poly-D-lactic acid, which are polymers of L-lactic acid and D-lactic acid, are mixed, a stereocomplex crystal is formed. Or it is known that it becomes a material which shows higher melting | fusing point than the crystal | crystallization of poly-D-lactic acid alone (refer patent document 1, nonpatent literature 1), and this stereocomplex polylactic acid is utilized for an automotive component, utilizing the heat resistance. Attempts have been made to use it for industrial applications such as home appliance parts (see Patent Document 2).

  However, when this stereocomplex polylactic acid is to be produced by an industrially advantageous melt extrusion process, it is very difficult to sufficiently make a stereocomplex, and the good heat resistance characteristic of it is exhibited. In addition, although stereocomplex polylactic acid tends to have a higher crystallization rate than poly-L-lactic acid or poly-D-lactic acid, it is still insufficient for efficient production by injection molding. There are still many issues for development.

  Amidst such movements, with regard to plastics that depend on petroleum as a raw material, as a measure to reduce its environmental impact, there has recently been an increase in the movement to introduce biomass plastics in part. In addition, proposals for blending natural polymers such as corn starch (see Patent Document 3), compositions in combination with polylactic acid (see Patent Documents 4 to 6), and the like have been made.

As for polylactic acid, an attempt has been made to introduce a resin such as an aromatic polycarbonate and a flame retardant and use it as an industrial material (see Patent Document 7).
However, in any case, when it is used as an industrial material, the problem of degradation of hydrolysis resistance due to the properties of polylactic acid has not been solved, and the current situation is that it is an obstacle to application development.

JP 63-24014 A Japanese Patent No. 3583097 JP 7-506863 A Japanese Patent No. 3279768 JP-A-2005-48066 JP-A-2005-48067 JP 2004-190026 JP Macromolecules, 24, 5651 (1991)

Therefore, the main object of the present invention is to provide an aromatic polycarbonate resin composition for obtaining a molded product containing a polymer obtained from biomass resources and having excellent heat resistance, mechanical properties and durability stability. .
As a result of diligent research to achieve such an object, the present inventors have found that a molded article comprising an aromatic polycarbonate resin composition obtained by blending a specific polylactic acid with an aromatic polycarbonate has heat resistance, mechanical properties. The present invention has been completed by finding that the molded article has excellent hydrolysis resistance.

  That is, the present invention comprises (A) 100 parts by weight of an aromatic polycarbonate resin (component A) and (B) 1 to 200 parts by weight of polylactic acid (component B), and polystyrene in the GPC measurement of polylactic acid (component B). It is an aromatic polycarbonate resin composition characterized by having a reduced weight average molecular weight of 120,000 or more.

  The present invention is a composition comprising an aromatic polycarbonate resin and a high molecular weight polylactic acid unit component mainly composed of L-lactic acid units, a high molecular weight polylactic acid unit component composed of D-lactic acid units, or a mixture thereof. Resin composition that has excellent heat resistance, mechanical properties, and hydrolysis resistance, and also has reduced environmental impact, so various electronic / electric equipment, OA equipment, vehicle parts, machine parts, and other agricultural materials It is useful for various uses such as fishing materials, transport containers, packaging containers, playground equipment, and sundries, and the industrial effects that it plays are exceptional.

  Hereinafter, each component in the resin composition of the present invention, a blending ratio thereof, a preparation method, and the like will be specifically described sequentially.

<About component A>
The component A in the resin composition of the present invention is an aromatic polycarbonate resin that is a main component of the resin composition. A typical aromatic polycarbonate resin (hereinafter sometimes simply referred to as “polycarbonate”) is obtained by reacting a dihydric phenol and a carbonate precursor, and as a reaction method, an interfacial polycondensation method, Examples thereof include a melt transesterification method, a solid phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound.

  Specific examples of the dihydric phenol include hydroquinone, resorcinol, 4,4′-biphenol, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane (commonly referred to as “bisphenol”). A ″), 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxyphenyl) pentane, 4, 4 ′-(p-phenylenediisopropylidene) diphenol, 4,4 ′-(m-phenylenediisopropylidene) Phenol, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide, bis (4- Hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) ester, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, bis (3,5-dibromo- 4-hydroxyphenyl) sulfone, bis (4-hydroxy-3-methylphenyl) sulfide, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, etc. Is mentioned. Among these, bis (4-hydroxyphenyl) alkane, especially bisphenol A (hereinafter sometimes abbreviated as “BPA”) is widely used.

  In the present invention, in addition to bisphenol A-based polycarbonate, which is a general-purpose polycarbonate, it is possible to use a special polycarbonate produced using other dihydric phenols as the A component.

  For example, as part or all of the dihydric phenol component, 4,4 ′-(m-phenylenediisopropylidene) diphenol (hereinafter sometimes abbreviated as “BPM”), 1,1-bis (4-hydroxy Phenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (hereinafter sometimes abbreviated as “Bis-TMC”), 9,9-bis (4-hydroxyphenyl) Polycarbonate (homopolymer or copolymer) using fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (hereinafter sometimes abbreviated as “BCF”) has dimensions due to water absorption. It is suitable for applications where the demands for change and shape stability are particularly severe. These dihydric phenols other than BPA are preferably used in an amount of 5 mol% or more, particularly 10 mol% or more of the entire dihydric phenol component constituting the polycarbonate.

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

  These special polycarbonates may be used alone or in combination of two or more. Moreover, these can also be mixed and used for the bisphenol A type polycarbonate generally used.

  The production methods and characteristics of these special polycarbonates are described in detail in, for example, JP-A-6-172508, JP-A-8-27370, JP-A-2001-55435, and JP-A-2002-117580. ing.

Of the various polycarbonates described above, those having a water absorption and Tg (glass transition temperature) adjusted within the following ranges by adjusting the copolymer composition and the like have good hydrolysis resistance of the polymer itself, and Since it is remarkably excellent in low warpage after molding, it is particularly suitable in a field where form stability is required.
(I) polycarbonate having a water absorption of 0.05 to 0.15% by weight, preferably 0.06 to 0.13% by weight, and Tg of 120 to 180 ° C., or (ii) Tg of 160 to 250 ° C, preferably 170-230 ° C, and the water absorption is 0.10-0.30% by weight, preferably 0.13-0.30% by weight, more preferably 0.14-0.27% by weight. Some polycarbonate.

  Here, the water absorption of the polycarbonate is a value obtained by measuring the moisture content after being immersed in water at 23 ° C. for 24 hours in accordance with ISO 62-1980 using a disc-shaped test piece having a diameter of 45 mm and a thickness of 3.0 mm. is there. Moreover, Tg (glass transition temperature) is a value calculated | required by the differential scanning calorimeter (DSC) measurement based on JISK7121.

  On the other hand, as the carbonate precursor, carbonyl halide, carbonate ester, haloformate or the like is used, and specific examples thereof include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, and the like.

  In producing a polycarbonate from such a dihydric phenol and a carbonate precursor by an interfacial polymerization method, a catalyst, a terminal terminator, and an antioxidant for preventing the dihydric phenol from being oxidized as necessary. Etc. may be used. The polycarbonate may be a branched polycarbonate copolymerized with a trifunctional or higher polyfunctional aromatic compound. Examples of the trifunctional or higher polyfunctional aromatic compound used here include 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,1-tris (3,5-dimethyl-4-hydroxy). Phenyl) ethane and the like.

  When the polyfunctional compound which produces a branched polycarbonate is included, the ratio is 0.001-1 mol% in the total amount of polycarbonate, preferably 0.005-0.9 mol%, particularly preferably 0.01-0.8. Mol%. In particular, in the case of the melt transesterification method, a branched structure may occur as a side reaction. The amount of the branched structure is also 0.001 to 1 mol%, preferably 0.005 to 0.9% in the total amount of the polycarbonate. Those having a mol%, particularly preferably 0.01 to 0.8 mol% are preferred. Note that the ratio of the branched structure can be calculated by 1H-NMR measurement.

  In addition, the aromatic polycarbonate resin as the component A in the resin composition of the present invention is a polyester carbonate obtained by copolymerizing an aromatic or aliphatic (including alicyclic) bifunctional carboxylic acid, a bifunctional alcohol (fatty acid). It may be a copolymerized polycarbonate copolymerized with a cyclic group) and a polyester carbonate copolymerized with such a bifunctional carboxylic acid and a bifunctional alcohol. Moreover, the mixture which blended 2 or more types of the obtained polycarbonate may be used.

  The aliphatic bifunctional carboxylic acid used here is preferably an α, ω-dicarboxylic acid. Examples of the aliphatic difunctional carboxylic acid include, for example, sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, icosanedioic acid and the like, and saturated aliphatic dicarboxylic acid and cyclohexanedicarboxylic acid. Preferred are alicyclic dicarboxylic acids such as As the bifunctional alcohol, an alicyclic diol is more preferable, and examples thereof include cyclohexanedimethanol, cyclohexanediol, and tricyclodecane dimethanol.

  Furthermore, in the present invention, a polycarbonate-polyorganosiloxane copolymer obtained by copolymerizing polyorganosiloxane units can be used as the component A.

  The aromatic polycarbonate resin as component A is a mixture of two or more of polycarbonates such as polycarbonates having different dihydric phenols, polycarbonates containing branched components, polyester carbonates, and polycarbonate-polyorganosiloxane copolymers. There may be. Furthermore, what mixed 2 or more types of polycarbonates from which a manufacturing method differs, a polycarbonate from which a terminal terminator differs, etc. can also be used.

  The reaction forms such as interfacial polymerization, melt transesterification, solid phase transesterification of carbonate prepolymer, and ring-opening polymerization of cyclic carbonate compounds, which are methods for producing the polycarbonate resin of the present invention, are various documents and patent publications. This is a well-known method.

  The viscosity average molecular weight of the aromatic polycarbonate resin to be the component A is not limited. However, when the viscosity average molecular weight is less than 10,000, the strength and the like are lowered, and when it exceeds 50,000, the molding process characteristics are lowered. Therefore, the range of 10,000 to 50,000 is preferable. The range of 3,000 to 30,000 is more preferable, and the range of 14,000 to 28,000 is more preferable. In this case, it is also possible to mix a polycarbonate having a viscosity average molecular weight outside the above range within a range in which moldability and the like are maintained. For example, a high molecular weight polycarbonate component having a viscosity average molecular weight exceeding 50,000 can be blended.

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

In addition, when measuring the viscosity average molecular weight in the resin composition of this invention, it carries out in the following way. That is, the resin composition is dissolved in 20 to 30 times its weight of methylene chloride, and the soluble component is collected by Celite filtration, and then the solution is removed and dried sufficiently to obtain a solid component soluble in methylene chloride. . A specific viscosity (η _SP ) at 20 ° C. is determined from a solution obtained by dissolving 0.7 g of the solid in 100 ml of methylene chloride using an Ostwald viscometer, and the viscosity average molecular weight M is calculated by the above formula.

  The aromatic polycarbonate resin which is the component A of the present invention can be reused. In that case, the proportion of components having a small environmental load increases together with the B component of the non-petroleum resource material, which is a more preferable material in terms of the environmental load reduction effect. The recycled aromatic polycarbonate resin means a resin recovered without obtaining a polymer decomposition step from a resin molded product formed by at least a processing step for producing a target product. For example, a used product Typical examples are resin molded products that are separated and collected from plastic, resin molded products that are separated and collected from defective products during product manufacturing, and resin molded products that include unnecessary parts such as spools and runners that occur during molding. Is done. The decomposition step refers to a step aimed at decomposing the bonds forming the main chain of the aromatic polycarbonate and recovering the monomers and oligomers produced by the decomposition, and is intended for kneading, pulverization, processing, etc. It does not mean thermal decomposition in the process.

  The reused aromatic polycarbonate resin preferably contains 90% by weight or more of the aromatic polycarbonate component in 100% by weight of the resin material, more preferably 95% by weight or more, and still more preferably 98% by weight. What is contained above is used.

  The used products include soundproof walls, glass windows, translucent roofing materials, various glazing materials represented by automobile sunroofs, transparent members such as windshields and automobile headlamp lenses, containers such as water bottles, and light. A recording medium is preferred. These do not contain a large amount of additives or other resins, and the desired quality is easily obtained stably. In particular, a preferable example is a molded product in which a hard coat film is laminated on the surface of a transparent polycarbonate resin molded product. This is because such molded articles are often colored by the influence of the hard coat agent while having good transparency. Specific examples of such molded articles include various glazing materials, transparent members such as windshields and automobile headlamp lenses.

  Moreover, the recycled aromatic polycarbonate resin can use either the pulverized product of the resin molded product which has become unnecessary or pellets produced by remelting and extruding the pulverized product. In addition, if the resin molded product has a printed coating film, seal, label, decorative coating film, conductive coating, conductive plating, metal deposition, etc., the pulverized product from which such portions have been removed (after pulverization and pulverization after removal) Any of the pellets produced by remelting and extruding the pulverized product can be used. When the printed coating film is included, the effect of the present invention is not sufficiently exhibited because it is easy to be colored due to these influences. Therefore, it is preferable in the present invention to remove the printed coating film. As a method of removing such a printed coating film or plating, a method of rolling between two rolls, a method of contacting with heated / pressurized water, various solvents, an acid / alkaline aqueous solution, or the like, a method of mechanically scraping off the removed portion , A method of irradiating ultrasonic waves, a method of blasting, and the like, and a combination of these can also be used.

  On the other hand, in a molded product in which a hard coat film is laminated on the surface of a transparent polycarbonate resin molded product, it is possible to achieve a good hue, so it is more efficient to blend the pulverized product as it is, and environmental impact Contributes to the reduction of The pulverized product can be produced by pulverizing a resin molded product using a known pulverizer.

  The recycled aromatic polycarbonate resin can be contained preferably in an amount of 5% by weight or more, more preferably 10% by weight or more, and still more preferably 15% by weight or more in 100% by weight of the aromatic polycarbonate resin of component A. The upper limit can be 100% by weight, but practically it is preferably 50% by weight or less because a resin composition with more stable characteristics can be obtained.

<About B component>
The B component in the resin composition of the present invention is polylactic acid having an L-lactic acid unit and a D-lactic acid unit as basic components, represented by the following formula (i).

  The polylactic acid (component B) in the resin composition of the present invention has a weight average molecular weight of 120,000 or more in terms of standard polystyrene by gel permeation chromatography (GPC) measurement using chloroform as an eluent. To do. The weight average molecular weight is more preferably 130,000 or more, still more preferably 140,000 or more. The factors that improve hydrolysis resistance by increasing the molecular weight of polylactic acid (component B) are not clear, but the following matters are considered to be one factor.

  A carboxyl group is present at the molecular chain terminal of polylactic acid produced by a conventionally known method. In the resin composition of the present invention, when such polylactic acid having a high carboxyl end group content is used, not only the decomposition / degradation of the aromatic polycarbonate resin is promoted, but also the molding comprising the resin composition of the present invention. It causes the hydrolysis resistance of the product to decrease. In the polylactic acid having a high molecular weight, the carboxyl end group content per unit weight of the polylactic acid is reduced as compared with the low molecular weight polylactic acid. Therefore, in the resin composition of the present invention, by using such a high molecular weight polylactic acid, the hydrolysis resistance of a molded product comprising the polylactic acid is improved.

In addition, the carboxyl end group content of the polylactic acid in the present invention is preferably 20 equivalents / 10 ³ kg or less, and more preferably 15 equivalents / 10 ³ kg or less.

  The polylactic acid (component B) in the resin composition of the present invention is a polylactic acid unit consisting mainly of a B-2 component, a B-3 component, and / or a D-lactic acid unit mainly consisting of L-lactic acid units. B-5 component and B-6 component.

The B-2 component is a polylactic acid unit composed of 90 to 99 mol% of L-lactic acid units and 1 to 10 mol% of copolymer component units other than D-lactic acid units and / or lactic acid.
The B-3 component is a polylactic acid composed of more than 99 mol% of L-lactic acid units and 100 mol% or less, and D-lactic acid units and / or copolymer component units other than lactic acid of 0 mol% or more and less than 1 mol%. Unit.

The B-5 component is a polylactic acid unit composed of 90 to 99 mol% of D-lactic acid units and 1 to 10 mol% of copolymer component units other than L-lactic acid units and / or lactic acid.
The B-6 component is a polylactic acid composed of more than 99 mol% of D-lactic acid units and not more than 100 mol% and L-lactic acid units and / or copolymer component units other than lactic acid of 0 mol% or more and less than 1 mol%. Unit.

The polylactic acid (B component) in the resin composition of the present invention is also a polylactic acid unit mainly composed of B-2 component and B-3 component which are polylactic acid units mainly composed of L-lactic acid units, and a D-lactic acid unit. It consists of a specific combination with a certain B-5 component and B-6 component . It is preferable to form a stereocomplex by combining such specific polylactic acid units in order to further improve the hydrolysis resistance of a molded article comprising the resin composition of the present invention.

  Particularly preferred polylactic acid (component B) is composed of component B-2 and component B-5, and the weight ratio of component B-2 to component B-5 (component B-2 / component B-5) is 10/90. It consists of polylactic acid (combination 1), B-3 component, and B-5 component in the range of ~ 90/10, and the weight ratio of B-3 component to B-5 component (B-3 component / B-5 component) ) Consisting of polylactic acid (combination 2), B-6 component, and B-2 component in the range of 10/90 to 90/10, and the weight ratio of B-6 component to B-2 component (B-6 component) / B-2 component) is polylactic acid (combination 3) in the range of 10/90 to 90/10.

The above particularly preferable combinations are summarized as follows.

  As described above, in the combination of polylactic acid (component B), the combination of the component B-3 and the component B-6 is excluded from the particularly preferable range.

In polylactic acid (component B), polylactic acid units mainly composed of L-lactic acid units ( components B-2 to B-3 ) and polylactic acid units mainly composed of D-lactic acid units ( components B-5 to B-6) ) Is 10/90 to 90/10, but in order to form more stereocomplexes, it is preferably 25/75 to 75/25, more preferably 40/60 to 60 / 40. If the weight ratio of one polymer is less than 10 or exceeds 90, homocrystallization is prioritized and it is difficult to form a stereo complex, which is not preferable.

  The copolymer component unit other than lactic acid in the polylactic acid unit in the polylactic acid (component B) is derived from dicarboxylic acid, polyhydric alcohol, hydroxycarboxylic acid, lactone, etc. having a functional group capable of forming two or more ester bonds. Units and units derived from various polyesters, various polyethers, various polycarbonates and the like composed of these various components can be used alone or as a mixture.

  Examples of the dicarboxylic acid include succinic acid, adipic acid, azelaic acid, sebacic acid, terephthalic acid, and isophthalic acid. Examples of polyhydric alcohols include aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, glycerin, sorbitan, neopentyl glycol, diethylene glycol, triethylene glycol, polyethylene glycol, and polypropylene glycol. Or aromatic polyhydric alcohol etc., such as what added ethylene oxide to bisphenol, etc. are mentioned. Examples of the hydroxycarboxylic acid include glycolic acid and hydroxybutylcarboxylic acid. Examples of the lactone include glycolide, ε-caprolactone glycolide, ε-caprolactone, β-propiolactone, δ-butyrolactone, β- or γ-butyrolactone, pivalolactone, δ-valerolactone, and the like.

<About the production method of polylactic acid (component B)>
Each polylactic acid unit ( B-2 to B-6 component) constituting the polylactic acid (component B) in the resin composition of the present invention can be produced by any known polylactic acid polymerization method, for example, lactide. Can be produced by a ring-opening polymerization of lactic acid, a dehydration condensation of lactic acid, and a method combining these with solid phase polymerization.

When each polylactic acid unit (components B-2 to B-6 ) is produced by any known polymerization method, lactide, which is a cyclic dimer of lactic acid, may be produced as a by-product. Each polylactic acid unit may contain such a lactide as long as it does not impair the thermal stability of the resin.

  The lactide contained in each polylactic acid unit can be removed from the polylactic acid unit by a method of removing the polylactic acid unit after the polymerization of each polylactic acid unit under a melt pressure or a method of extracting and removing using a solvent. It is preferable for improving the thermal stability. The lactide contained in each polylactic acid unit is 2% or less, preferably 1% or less, more preferably 0.5% or less with respect to each polylactic acid unit.

The copolymer component unit other than lactic acid used for each polylactic acid unit (components B-2 to B-6 ) constituting the polylactic acid (component B) is a dicarboxylic acid having a functional group capable of forming two or more ester bonds. Examples thereof include acids, polyhydric alcohols, hydroxycarboxylic acids, lactones, and the like, and various polyesters, various polyethers, and various polycarbonates composed of these various components.

  Examples of the dicarboxylic acid include succinic acid, adipic acid, azelaic acid, sebacic acid, terephthalic acid, and isophthalic acid. Examples of polyhydric alcohols include aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, glycerin, sorbitan, neopentyl glycol, diethylene glycol, triethylene glycol, polyethylene glycol, and polypropylene glycol. Or aromatic polyhydric alcohol etc., such as what added ethylene oxide to bisphenol, etc. are mentioned. Examples of the hydroxycarboxylic acid include glycolic acid and hydroxybutylcarboxylic acid. Examples of the lactone include glycolide, ε-caprolactone glycolide, ε-caprolactone, β-propiolactone, δ-butyrolactone, β- or γ-butyrolactone, pivalolactone, δ-valerolactone, and the like.

Each of the polylactic acid units (components B-2 to B6 ) constituting the polylactic acid (component B) may contain a catalyst involved in polymerization as long as the thermal stability of the resin is not impaired. Examples of such catalysts include various tin compounds, aluminum compounds, titanium compounds, zirconium compounds, calcium compounds, organic acids, and inorganic acids. Such catalysts include tin, aluminum, zirconium and titanium fatty acid salts, carbonates, sulfates, phosphates, oxides, hydroxides, halides, alcoholates, or the metals themselves. Specific examples include tin octylate, aluminum acetylacetonate, aluminum alkoxide, titanium alkoxide, and zirconium alkoxide.

The catalyst involved in the polymerization contained in each of the polylactic acid units (components B-2 to B-6 ) is a method of extracting and removing using a solvent after the polymerization reaction of each polylactic acid unit, or inactivating the catalyst. In order to improve the thermal stability of the resin, it is preferable to remove or deactivate it by a method in which a known stabilizer to be coexisted.

As polylactic acid (B component) of the resin composition of the present invention, polylactic acid units ( B-2 to B-3 components ) mainly composed of L-lactic acid units and polylactic acid units ( B- ) mainly composed of D-lactic acid units. In order to improve the hydrolysis resistance by forming a stereo complex using a combination of 5 to B-6 components ), the resin composition is mixed with an aromatic polycarbonate resin (component A) and other components. However, before mixing together with the aromatic polycarbonate resin (component A) and other components, it is possible to produce a stereo complex efficiently by using a method of heat treatment in the presence of both in advance. Is preferable.

Specifically, a polylactic acid unit mainly composed of L-lactic acid units ( components B-2 to B-3 ) and a polylactic acid unit mainly composed of D-lactic acid units ( components B-5 to B-6 ) coexist. A method of heat-treating the prepared product at 245 to 300 ° C. is particularly preferable in order to efficiently generate a stereocomplex.

In the heat treatment, polylactic acid units mainly composed of L-lactic acid units ( components B-2 to B-3 ) and polylactic acid units mainly composed of D-lactic acid units ( components B-5 to B-6 ) Is preferably mixed as uniformly as possible. The mixing can be any method as long as they are uniformly mixed when heat-treated.

As such a mixing method, a polylactic acid unit mainly composed of L-lactic acid units ( components B-2 to B-3 ) and a polylactic acid unit mainly composed of D-lactic acid units ( components B-5 to B-6 ) Are mixed in the presence of a solvent and then reprecipitated to obtain a mixture, or a method of removing the solvent by heating to obtain a mixture.

  When mixing in the presence of a solvent, prepare a solution in which the components B-2 to B-3 and the components B-5 to B-6 are separately dissolved in a solvent and mix them, or both It is preferable to carry out by dissolving together in a solvent and mixing.

The solvent is not particularly limited as long as polylactic acid units ( B-2 to B -3 components and B-5 to B-6 ) are dissolved. For example, chloroform, methylene chloride, dichloroethane, Preferred are tetrachloroethane, phenol, tetrahydrofuran, N-methylpyrrolidone, N, N-dimethylformamide, butyrolactone, trioxane, hexafluoroisopropanol, or a mixture of two or more.

  Even in the presence of a solvent, the solvent evaporates by heating and can be heat-treated in a solvent-free state. The rate of temperature increase after evaporation of the solvent (heat treatment) is preferably, but not limited to, a short time since there is a possibility of decomposition when heat treatment is performed for a long time.

In addition, mixing of a polylactic acid unit mainly composed of L-lactic acid units ( components B-2 to B-3 ) and a polylactic acid unit mainly composed of D-lactic acid units ( components B-5 to B-6 ) It can also be performed in the presence. That is, a method in which B-2 to B-3 components and B-5 to B-6 components previously powdered or chipped are mixed after mixing a predetermined amount and then melted, or after melting, kneaded and mixed, Alternatively, it is possible to employ a method in which any one of the B-2 to B -3 components or the B-5 to B-6 components is melted, and the remaining one is added and kneaded and mixed.

Therefore, the present invention comprises a polylactic acid unit mainly composed of L-lactic acid units ( components B-2 to B-3 ) and a polylactic acid unit mainly composed of D-lactic acid units ( components B-5 to B-6 ). It is a resin composition produced by employing a method for producing polylactic acid which is mixed and heat-treated in the absence of a solvent or in the presence of a solvent.

Here, the size of the powder or chip is particularly limited as long as the powder or chip of each polylactic acid unit ( components B-2 to B- 3 and B-5 to B-6 ) is uniformly mixed. However, it is preferably 3 mm or less, and more preferably 1 to 0.25 mm. When melting and mixing, a stereocomplex crystal is formed regardless of the size. However, when the powder or chip is simply melted after being uniformly mixed, if the diameter of the powder or chip becomes 3 mm or more, the Since crystals also precipitate, it is not preferable.

In the method of heat-treating a polylactic acid unit (component B), a polylactic acid unit mainly composed of L-lactic acid units ( components B-2 to B-3 ) and a polylactic acid unit mainly composed of D-lactic acid units ( B-5 to B-5) As a mixing apparatus used for mixing the B-6 component ), in the case of mixing by melting, in addition to a reactor with a batch type stirring blade, a continuous reactor, a biaxial or uniaxial extruder, In the case of mixing with powder, a tumbler type powder mixer, a continuous powder mixer, various milling devices, and the like can be suitably used.

The heat treatment in the present invention is a polylactic acid unit mainly composed of L-lactic acid units ( components B-2 to B-3 ) and a polylactic acid unit mainly composed of D-lactic acid units ( B-5 to B-6). Component ) is allowed to coexist so that the weight ratio is in the range of 10/90 to 90/10, and is maintained in the temperature range of 245 to 300 ° C. The temperature of the heat treatment is preferably 270 to 300 ° C, more preferably 280 to 290 ° C. If it exceeds 300 ° C., it is difficult to suppress the decomposition reaction, which is not preferable. The heat treatment time is not particularly limited, but is 0.2 to 60 minutes, preferably 1 to 20 minutes. As an atmosphere during the heat treatment, either an inert atmosphere at normal pressure or a reduced pressure can be applied.

  The apparatus and method used for the heat treatment can be any apparatus and method that can be heated while adjusting the atmosphere. For example, a batch reactor, a continuous reactor, a biaxial or uniaxial extruder, etc. Alternatively, it is possible to adopt a method of processing while molding using a press machine or a flow tube type extruder.

<About component C>
The crystal nucleating agent which is the C component used in the present invention is mainly a known compound generally used as a crystal nucleating agent for crystalline resins such as polylactic acid and aromatic polyester.

  For example, inorganic fine particles such as talc, silica, graphite, carbon powder, pyroferrite, gypsum, neutral clay, metal oxides such as magnesium oxide, aluminum oxide, titanium dioxide, sulfate, phosphate, phosphonate, Examples thereof include oxalate, oxalate, stearate, benzoate, salicylate, tartrate, sulfonate, montan wax salt, montan wax ester salt, terephthalate, benzoate, carboxylate and the like.

  Among these compounds used as the crystal nucleating agent, talc is particularly effective, and those having an average particle size of 20 μm or less are preferably used, but those having an average particle size of 5 μm or less are more preferable. .

  The blending amount of these crystal nucleating agents cannot be uniformly defined because the amount of the crystal nucleating agent to express its effect varies depending on the type and shape of the crystal nucleating agent. However, the blending amount is 0.1 per 100 parts by weight of the polylactic acid component (B component). 01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, more preferably 0.1 to 2 parts by weight. If the amount of the crystal nucleating agent is too small, the effect as a crystal nucleating agent will not be exhibited, and conversely, if it is too much, the effect as a crystal nucleating agent will not be increased. May give bad results.

Although there is no restriction | limiting in particular in the compounding method of the crystal nucleating agent of C component used in this invention, It consists mainly of the polylactic acid unit ( B-2-B-3 component ) which consists of L-lactic acid units, and mainly D-lactic acid units. If polylactic acid units ( components B-5 to B-6 ) are mixed in advance before mixing with the aromatic polycarbonate resin (component A), they are mixed with the aromatic polycarbonate and other components. The method to be added is preferable because the adverse effect on the formation of the stereo complex is small.

<About D component>
When the inorganic filler (component D) is further blended in the resin composition of the present invention, a molded product having excellent mechanical properties, dimensional properties, and the like can be obtained.

  As inorganic fillers, various inorganic emphasis commonly known such as glass fiber, carbon fiber, glass flake, wollastonite, kaolin clay, mica, talc and various whiskers (potassium titanate whisker, aluminum borate whisker, etc.) Materials can be mentioned. The shape of the inorganic filler can be freely selected from fibrous, flaky, spherical and hollow shapes, and fibrous and flaky materials are suitable for improving the strength and impact resistance of the resin composition.

  Among them, the inorganic filler is preferably an inorganic filler made of a pulverized product of natural mineral, more preferably an inorganic filler made of a pulverized product of a natural mineral of silicate, and from the point of its shape. Are preferably mica, talc, and wollastonite.

  On the other hand, since these inorganic fillers are non-petroleum resource materials compared to petroleum resource materials such as carbon fibers, raw materials with a lower environmental load are used. There exists an effect that the significance which uses C component is raised more. Furthermore, the above-mentioned more preferable inorganic filler has an advantageous effect that good flame retardancy is exhibited as compared with carbon fiber and the like.

  The average particle size of mica that can be used in the present invention is a number average particle size calculated by a number average of a total of 1000 particles observed with a scanning electron microscope and extracted those having a size of 1 μm or more. The number average particle diameter is preferably 10 to 500 μm, more preferably 30 to 400 μm, still more preferably 30 to 200 μm, and most preferably 35 to 80 μm. When the number average particle diameter is less than 10 μm, the impact strength may be lowered. On the other hand, if it exceeds 500 μm, the impact strength is improved, but the appearance tends to deteriorate.

  As the thickness of mica, one having a thickness measured by electron microscope observation of 0.01 to 10 μm can be used. Preferably 0.1-5 micrometers thing can be used. An aspect ratio of 5 to 200, preferably 10 to 100 can be used. The mica used is preferably mascobite mica, and its Mohs hardness is about 3. Muscovite mica can achieve higher rigidity and strength than other mica such as phlogopite, and a more suitable molded product is provided.

  In addition, as a method for pulverizing mica, a dry pulverization method of pulverizing raw mica ore with a dry pulverizer, and coarsely pulverizing mica rough ore with a dry pulverizer, followed by adding a grinding aid such as water in a slurry state There is a wet pulverization method in which main pulverization is performed by a wet pulverizer, followed by dehydration and drying. The mica of the present invention can be produced by any pulverization method, but the dry pulverization method is generally lower in cost. On the other hand, the wet pulverization method is effective for pulverizing mica more thinly and finely, but is expensive. Mica may be surface-treated with various surface treatment agents such as silane coupling agents, higher fatty acid esters, and waxes, and further granulated with sizing agents such as various resins, higher fatty acid esters, and waxes to form granules. May be.

Talc that can be used in the present invention is a scaly particle having a layered structure, which is a hydrous magnesium silicate in terms of chemical composition, and is generally represented by the chemical formula 4SiO ₂ .3MgO.2H ₂ O. the SiO ₂ 56-65 wt%, the MgO 28 to 35 wt%, and a H ₂ O about 5 wt%. As other minor components, Fe ₂ O ₃ is 0.03 to 1.2% by weight, Al ₂ O ₃ is 0.05 to 1.5% by weight, CaO is 0.05 to 1.2% by weight, K ₂ O. Is 0.2 wt% or less, Na ₂ O is 0.2 wt% or less, the specific gravity is about 2.7, and the Mohs hardness is 1.

  The average particle diameter of the talc of the present invention is preferably 0.5 to 30 μm. The average particle size is a particle size at a 50% stacking rate obtained from the particle size distribution measured by the Andreazen pipette method measured according to JIS M8016. The particle diameter of talc is more preferably 2 to 30 μm, further preferably 5 to 20 μm, and most preferably 10 to 20 μm. Talc in the range of 0.5 to 30 μm imparts good surface appearance and flame retardancy to the aromatic polycarbonate resin composition in addition to rigidity and low anisotropy.

  In addition, there is no particular restriction on the manufacturing method when talc is crushed from raw stone, and the axial flow mill method, the annular mill method, the roll mill method, the ball mill method, the jet mill method, the container rotary compression shearing mill method, etc. are used. can do. Further, the talc after pulverization is preferably classified by various classifiers and having a uniform particle size distribution. There are no particular restrictions on classifiers, impactor type inertial force classifiers (variable impactors, etc.), Coanda effect type inertial force classifiers (elbow jets, etc.), centrifugal field classifiers (multistage cyclone, microplex, dispersion separator) , Accucut, Turbo Classifier, Turboplex, Micron Separator, and Super Separator).

  Further, talc is preferably in an agglomerated state in view of its handleability and the like, and as such a production method, there are a method by deaeration compression, a method of compression using a sizing agent, and the like. In particular, the method by deaeration and compression is preferable because it is simple and does not include unnecessary sizing agent resin components in the molded article of the present invention.

The wollastonite that can be used in the present invention is substantially represented by the chemical formula CaSiO ₃ , usually SiO ₂ is about 50 wt% or more, CaO is about 47 wt% or more, and other Fe ₂ O ₃ , Al ₂ O _3. Etc. Wollastonite is a white acicular powder obtained by crushing and classifying raw wollastonite, and has a Mohs hardness of about 4.5. The average fiber diameter of wollastonite used is preferably 0.5 to 20 μm, more preferably 0.5 to 10 μm, and most preferably 1 to 5 μm. The average fiber diameter is observed by a scanning electron microscope, and is calculated by a number average of a total of 1000 samples having a diameter of 0.1 μm or more extracted.

  Some of these inorganic fillers also function as a crystal nucleating agent which is a C component, but when used as an inorganic filler for the purpose of improving mechanical properties and the like, the blending amount thereof is an aromatic polycarbonate resin (A component). The amount is preferably 0.3 to 200 parts by weight, more preferably 1 to 100 parts by weight, and most preferably 3 to 50 parts by weight per 100 parts by weight. When the blending amount is less than 0.3 parts by weight, the reinforcing effect on the mechanical properties of the molded product of the present invention is not sufficient, and when it exceeds 200 parts by weight, the molding processability and hue deteriorate, which is not preferable. .

  In addition, in the resin composition of this invention, when using a fibrous inorganic filler and a flaky inorganic filler, the folding inhibitor for suppressing those folding can be included. The folding inhibitor inhibits adhesion between the matrix resin and the inorganic filler, reduces stress acting on the inorganic filler during melt kneading, and suppresses the folding of the inorganic filler. Examples of the effect of the folding inhibitor include (1) improvement of rigidity (increase in aspect ratio of inorganic filler), (2) improvement of toughness, and (3) improvement of conductivity (in the case of conductive inorganic filler). Can do. Specifically, the crease suppressor has (i) a compound having a low affinity with the resin, and (ii) a structure having a low affinity with the resin when the surface of the inorganic filler is directly coated with the compound. It is a compound having a functional group capable of reacting with the surface of the inorganic filler.

  Representative examples of the compound having a low affinity for the resin include various lubricants. Examples of the lubricant include mineral oil, synthetic oil, higher fatty acid ester, higher fatty acid amide, polyorganosiloxane (silicone oil, silicone rubber, etc.), olefinic wax (paraffin wax, polyolefin wax, etc.), polyalkylene glycol, fluorinated fatty acid. Fluorine oils such as esters, trifluorochloroethylene, and polyhexafluoropropylene glycol are listed.

  As a method of directly coating the surface of the inorganic filler with a compound having a low affinity for the resin, (1) a method of directly immersing the compound or a solution or emulsion of the compound in the inorganic filler; A method of passing an inorganic filler in the vapor or powder of a compound, (3) a method of irradiating the inorganic filler with the powder of the compound at high speed, and (4) a mechanochemical that rubs the inorganic filler and the compound. And the like.

  Examples of the compound having a structure having a low affinity with the resin and having a functional group capable of reacting with the surface of the inorganic filler include the above-described lubricants modified with various functional groups. Examples of such functional groups include a carboxyl group, a carboxylic acid anhydride group, an epoxy group, an oxazoline group, an isocyanate group, an ester group, an amino group, and an alkoxysilyl group.

  One suitable folding inhibitor is an alkoxysilane compound in which an alkyl group having 5 or more carbon atoms is bonded to a silicon atom. The number of carbon atoms of the alkyl group bonded to the silicon atom is preferably 5 to 60, more preferably 5 to 20, still more preferably 6 to 18, and particularly preferably 8 to 16. The alkyl group is preferably 1 or 2, particularly preferably 1. Further, preferred examples of the alkoxy group include a methoxy group and an ethoxy group. Such alkoxysilane compounds are preferred in that they have high reactivity with the inorganic filler surface and excellent coating efficiency. Therefore, it is suitable for a finer inorganic filler.

  One suitable folding inhibitor is a polyolefin wax having at least one functional group selected from a carboxyl group and a carboxylic anhydride group. The molecular weight is preferably 500 to 20,000, more preferably 1,000 to 15,000 in terms of weight average molecular weight. In such a polyolefin wax, the amount of carboxyl group and carboxylic anhydride group is in the range of 0.05 to 10 meq / g per gram of lubricant having at least one functional group selected from carboxyl group and carboxylic anhydride group. Is preferable, more preferably 0.1 to 6 meq / g, and still more preferably 0.5 to 4 meq / g. It is preferable that the ratio of the functional group in the folding inhibitor is the same as the ratio of the carboxyl group and the carboxylic anhydride group in the functional group other than the carboxyl group.

  A particularly preferred example of the folding inhibitor is a copolymer of an α-olefin and maleic anhydride. Such a copolymer can be produced by melt polymerization or bulk polymerization in the presence of a radical catalyst according to a conventional method. Here, as the α-olefin, those having 10 to 60 carbon atoms as an average value can be preferably exemplified. More preferable examples of the α-olefin include those having an average carbon number of 16 to 60, and more preferably 25 to 55.

  The folding inhibitor is preferably 0.01 to 2 parts by weight, more preferably 0.05 to 1.5 parts by weight, more preferably 0.1 to 0.8 parts by weight per 100 parts by weight of the aromatic polycarbonate resin (component A) of the present invention. Part by weight is more preferred.

<About E component>
In the resin composition of the present invention, when a terminal blocking agent (E component) is further blended, a molded product having further improved hydrolysis resistance can be obtained.

  The E component end-capping agent indicates a function of blocking by reacting with part or all of the carboxyl group ends of polylactic acid (B component) in the resin composition of the present invention. Examples include condensation reaction type compounds such as amide compounds, and addition reaction type compounds such as carbodiimide compounds, epoxy compounds, oxazoline compounds, oxazine compounds, and aziridine compounds. If the latter addition reaction type compound is used, there is no need to discharge an extra by-product out of the reaction system as in the case of end-capping by dehydration condensation reaction of alcohol and carboxyl group. Therefore, in producing the resin composition of the present invention, before mixing with the aromatic polycarbonate resin (component A), the polylactic acid units (B-1 to B-3 components) mainly composed of L-lactic acid units, When using a method in which polylactic acid units consisting of D-lactic acid units (components B-4 to B-6) are mixed in advance, a by-product is obtained by adding, mixing, and reacting an addition reaction type end-capping agent. While suppressing the decomposition of the resin by the product, a sufficient carboxyl group end-capping effect can be obtained, and a molded product having practically sufficient hydrolysis resistance can be obtained.

  As the carbodiimide compounds (including polycarbodiimide compounds) among the end-capping agents that can be used in the present invention, those synthesized by a generally well-known method can be used. A compound that can be synthesized by subjecting various polyisocyanates to a decarboxylation condensation reaction in a solvent-free or inert solvent at a temperature of about 70 ° C. or higher is used. .

  Examples of the monocarbodiimide compound contained in the carbodiimide compound include dicyclohexylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, t-butylisopropylcarbodiimide, diphenylcarbodiimide, di-t-butylcarbodiimide, di-β-naphthylcarbodiimide and the like. Of these, dicyclohexylcarbodiimide or diisopropylcarbodiimide is preferred from the viewpoint of easy industrial availability.

  In addition, as the polycarbodiimide compound contained in the carbodiimide compound, those produced by various methods can be used. Basically, conventional polycarbodiimide production methods (US Pat. No. 2,941,956, No. 47-33279, J.0rg.Chem.28, 2069-2075 (1963), Chemical Review 981, Vol.81 No.4, p619-621) can be used.

  Examples of the organic diisocyanate that is a synthetic raw material in the production of the polycarbodiimide compound include aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, and mixtures thereof. Specifically, 1,5-naphthalene diisocyanate. 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2, , 4-tolylene diisocyanate and 2,6-tolylene diisocyanate, hexamethylene diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophor Diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, methylcyclohexane diisocyanate, tetramethylxylylene diisocyanate, 2,6-diisopropylphenyl isocyanate, 1,3,5-triisopropylbenzene-2,4-diisocyanate, etc. be able to.

  Moreover, in the case of the said polycarbodiimide compound, it can also control to a suitable polymerization degree using the compound which reacts with the terminal isocyanate of polycarbodiimide compound, such as monoisocyanate.

  Examples of the monoisocyanate for sealing the end of such a polycarbodiimide compound and controlling the degree of polymerization thereof include phenyl isocyanate, tolyl isocyanate, dimethylphenyl isocyanate, cyclohexyl isocyanate, butyl isocyanate, naphthyl isocyanate and the like. be able to.

  Examples of epoxy compounds among the end-capping agents that can be used in the present invention include, for example, N-glycidylphthalimide, N-glycidyl-4-methylphthalimide, N-glycidyl-4,5-dimethylphthalimide, N-glycidyl- 3-methylphthalimide, N-glycidyl-3,6-dimethylphthalimide, N-glycidyl-4-ethoxyphthalimide, N-glycidyl-4-chlorophthalimide, N-glycidyl-4,5-dichlorophthalimide, N-glycidyl- 3,4,5,6-tetrabromophthalimide, N-glycidyl-4-n-butyl-5-bromophthalimide, N-glycidylsuccinimide, N-glycidylhexahydrophthalimide, N-glycidyl-1,2,3 6-tetrahydrophthalimide, N-glycidyl male N-glycidyl-α, β-dimethylsuccinimide, N-glycidyl-α-ethylsuccinimide, N-glycidyl-α-propylsuccinimide, N-glycidylbenzamide, N-glycidyl-p-methylbenzamide, N- Glycidylnaphthamide, N-glycidylsteramide, N-methyl-4,5-epoxycyclohexane-1,2-dicarboxylic imide, N-ethyl-4,5-epoxycyclohexane-1,2-dicarboxylic imide, N- Phenyl-4,5-epoxycyclohexane-1,2-dicarboxylic imide, N-naphthyl-4,5-epoxycyclohexane-1,2-dicarboxylic imide, N-tolyl-3-methyl-4,5-epoxycyclohexane -1,2-dicarboxylic acid imide, orthophenyl phenylglycol Sidyl ether, 2-methyloctyl glycidyl ether, phenyl glycidyl ether, 3- (2-xenyloxy) -1,2-epoxypropane, allyl glycidyl ether, butyl glycidyl ether, lauryl glycidyl ether, benzyl glycidyl ether, cyclohexyl glycidyl ether, α -Cresyl glycidyl ether, pt-butylphenyl glycidyl ether, glycidyl methacrylate ether, ethylene oxide, propylene oxide, styrene oxide, octylene oxide, hydroquinone diglycidyl ether, resorcin diglycidyl ether, 1,6-hexanediol di Glycidyl ether, hydrogenated bisphenol A-diglycidyl ether, and the like. Diester, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, phthalic acid dimethyl diglycidyl ester, phenylene diglycidyl ether, ethylene diglycidyl ether, trimethylene diglycidyl ether, tetramethylene diglycidyl ether, hexamethylene di Examples thereof include glycidyl ether. One or more compounds selected from these epoxy compounds may be arbitrarily selected to block the carboxyl terminal of the polylactic acid unit, but in terms of reactivity, ethylene oxide, propylene oxide, phenyl glycidyl ether, ortho Preferred are phenylphenyl glycidyl ether, pt-butylphenyl glycidyl ether, N-glycidyl phthalimide, hydroquinone diglycidyl ether, resorcin diglycidyl ether, 1,6-hexanediol diglycidyl ether, hydrogenated bisphenol A-diglycidyl ether, and the like. .

  Examples of oxazoline compounds among the end-capping agents that can be used in the present invention include, for example, 2-methoxy-2-oxazoline, 2-ethoxy-2-oxazoline, 2-propoxy-2-oxazoline, 2-butoxy-2 -Oxazoline, 2-pentyloxy-2-oxazoline, 2-hexyloxy-2-oxazoline, 2-heptyloxy-2-oxazoline, 2-octyloxy-2-oxazoline, 2-nonyloxy-2-oxazoline, 2-decyloxy -2-oxazoline, 2-cyclopentyloxy-2-oxazoline, 2-cyclohexyloxy-2-oxazoline, 2-allyloxy-2-oxazoline, 2-methallyloxy-2-oxazoline, 2-crotyloxy-2-oxazoline, 2 -Phenoxy-2-oxazo , 2-cresyl-2-oxazoline, 2-o-ethylphenoxy-2-oxazoline, 2-o-propylphenoxy-2-oxazoline, 2-o-phenylphenoxy-2-oxazoline, 2-m-ethylphenoxy- 2-oxazoline, 2-m-propylphenoxy-2-oxazoline, 2-p-phenylphenoxy-2-oxazoline, 2-methyl-2-oxazoline, 2-ethyl-2-oxazoline, 2-propyl-2-oxazoline, 2-butyl-2-oxazoline, 2-pentyl-2-oxazoline, 2-hexyl-2-oxazoline, 2-heptyl-2-oxazoline, 2-octyl-2-oxazoline, 2-nonyl-2-oxazoline, 2- Decyl-2-oxazoline, 2-cyclopentyl-2-oxazoline, 2-cycl Hexyl-2-oxazoline, 2-allyl-2-oxazoline, 2-methallyl-2-oxazoline, 2-crotyl-2-oxazoline, 2-phenyl-2-oxazoline, 2-o-ethylphenyl-2-oxazoline, 2 -O-propylphenyl-2-oxazoline, 2-o-phenylphenyl-2-oxazoline, 2-m-ethylphenyl-2-oxazoline, 2-m-propylphenyl-2-oxazoline, 2-p-phenylphenyl- 2-oxazoline and the like, and further, 2,2'-bis (2-oxazoline), 2,2'-bis (4-methyl-2-oxazoline), 2,2'-bis (4,4 ' -Dimethyl-2-oxazoline), 2,2'-bis (4-ethyl-2-oxazoline), 2,2'-bis (4,4'-diethyl-2) -Oxazoline), 2,2'-bis (4-propyl-2-oxazoline), 2,2'-bis (4-butyl-2-oxazoline), 2,2'-bis (4-hexyl-2-oxazoline) ), 2,2'-bis (4-phenyl-2-oxazoline), 2,2'-bis (4-cyclohexyl-2-oxazoline), 2,2'-bis (4-benzyl-2-oxazoline), 2,2'-p-phenylenebis (2-oxazoline), 2,2'-m-phenylenebis (2-oxazoline), 2,2'-o-phenylenebis (2-oxazoline), 2,2'- p-phenylenebis (4-methyl-2-oxazoline), 2,2'-p-phenylenebis (4,4'-dimethyl-2-oxazoline), 2,2'-m-phenylenebis (4-methyl- 2-oxazoline), , 2'-m-phenylenebis (4,4'-dimethyl-2-oxazoline), 2,2'-ethylenebis (2-oxazoline), 2,2'-tetramethylenebis (2-oxazoline), 2, 2'-hexamethylenebis (2-oxazoline), 2,2'-octamethylenebis (2-oxazoline), 2,2'-decamethylenebis (2-oxazoline), 2,2'-ethylenebis (4- Methyl-2-oxazoline), 2,2′-tetramethylenebis (4,4′-dimethyl-2-oxazoline), 2,2′-9,9′-diphenoxyethanebis (2-oxazoline), 2, Examples thereof include 2'-cyclohexylenebis (2-oxazoline) and 2,2'-diphenylenebis (2-oxazoline). Furthermore, a polyoxazoline compound containing the above-described compound as a monomer unit, such as a styrene-2-isopropenyl-2-oxazoline copolymer, can be mentioned. One or more compounds may be arbitrarily selected from these oxazoline compounds to block the carboxyl terminal of the polylactic acid unit.

  Examples of the oxazine compound among the end-capping agents that can be used in the present invention include, for example, 2-methoxy-5,6-dihydro-4H-1,3-oxazine, 2-ethoxy-5,6-dihydro-4H. -1,3-oxazine, 2-propoxy-5,6-dihydro-4H-1,3-oxazine, 2-butoxy-5,6-dihydro-4H-1,3-oxazine, 2-pentyloxy-5 6-dihydro-4H-1,3-oxazine, 2-hexyloxy-5,6-dihydro-4H-1,3-oxazine, 2-heptyloxy-5,6-dihydro-4H-1,3-oxazine, 2-octyloxy-5,6-dihydro-4H-1,3-oxazine, 2-nonyloxy-5,6-dihydro-4H-1,3-oxazine, 2-decyloxy-5,6-dihydro 4H-1,3-oxazine, 2-cyclopentyloxy-5,6-dihydro-4H-1,3-oxazine, 2-cyclohexyloxy-5,6-dihydro-4H-1,3-oxazine, 2-allyloxy- 5,6-dihydro-4H-1,3-oxazine, 2-methallyloxy-5,6-dihydro-4H-1,3-oxazine, 2-crotyloxy-5,6-dihydro-4H-1,3- Oxazine and the like, and 2,2'-bis (5,6-dihydro-4H-1,3-oxazine), 2,2'-methylenebis (5,6-dihydro-4H-1,3- Oxazine), 2,2'-ethylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2'-propylenebis (5,6-dihydro-4H-1,3-oxazine), 2 , 2 ' Butylene bis (5,6-dihydro-4H-1,3-oxazine), 2,2′-hexamethylene bis (5,6-dihydro-4H-1,3-oxazine), 2,2′-p-phenylene bis (5,6-dihydro-4H-1,3-oxazine), 2,2'-m-phenylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2'-naphthylenebis (5 6-dihydro-4H-1,3-oxazine), 2,2'-P, P'-diphenylenebis (5,6-dihydro-4H-1,3-oxazine) and the like. Furthermore, the polyoxazine compound etc. which contain an above-described compound as a monomer unit are mentioned. One or two or more compounds may be arbitrarily selected from these oxazine compounds to block the carboxyl terminal of the polylactic acid unit.

  Further, one or more compounds selected from the oxazoline compounds exemplified above and the above-mentioned oxazine compounds may be arbitrarily selected and used together to block the carboxyl end of polylactic acid. 2,2′-m-phenylenebis (2-oxazoline) and 2,2′-p-phenylenebis (2-oxazoline) are preferable from the viewpoints of affinity and affinity with aliphatic polyester.

  Examples of the aziridine compound among the end-capping agents that can be used in the present invention include, for example, an addition reaction product of a mono-, bis- or polyisocyanate compound and ethyleneimine.

  Moreover, 2 or more types of compounds can also be used together as a terminal blocker among compounds, such as the carbodiimide compound mentioned above as an end blocker which can be used for this invention, an epoxy compound, an oxazoline compound, an oxazine compound, and an aziridine compound.

In the resin composition of the present invention, the carboxyl end group may be appropriately blocked according to the use. As a specific degree of carboxyl group end blocking, the concentration of the carboxyl group end of the polylactic acid unit is 10 equivalents / 10. preferably from the viewpoint of hydrolysis resistance is improved is at ³ kg or less, still more preferably not more than 6 equivalents / 10 ³ kg.

  As a method for blocking the carboxyl group terminal of polylactic acid (component B) in the resin composition of the present invention, a terminal blocking agent such as a condensation reaction type or an addition reaction type may be reacted. As a method for blocking, a carboxyl group terminal is blocked by adding a suitable amount of a condensation reaction type terminal blocking agent such as aliphatic alcohol or amide compound into the polymerization system during polymer polymerization and dehydrating condensation reaction under reduced pressure. However, from the viewpoint of increasing the degree of polymerization of the polymer, it is preferable to add a condensation reaction type end-capping agent at the end of the polymerization reaction.

  As a method for blocking the carboxyl group terminal by addition reaction, it can be obtained by reacting an appropriate amount of a terminal blocking agent such as a carbodiimide compound, an epoxy compound, an oxazoline compound, an oxazine compound, or an aziridine compound in the molten state of polylactic acid. It is possible to add / react the end-capping agent after the completion of the polymerization reaction of polylactic acid unit (components B-1 to B-3) mainly composed of L-lactic acid units and When the lactic acid unit (components B-4 to B-6) is mixed in advance before mixing with the aromatic polycarbonate resin (component A), the method of adding them together, Before mixing the polylactic acid unit, if the method of mixing in each polylactic acid unit in advance is taken, the aromatic polycarbonate resin (component A) Particularly preferred for the solution and degradation can be suppressed.

  The content of the end-blocking agent (component E) is 0.01 to 5 parts by weight, preferably 0.05 to 4 parts by weight, more preferably 0.04 parts by weight per 100 parts by weight of the polylactic acid component (component B). 1 to 3 parts by weight.

<About other ingredients>
(I) Flame retardant A flame retardant can also be mix | blended with the resin composition of this invention. Flame retardants include brominated epoxy resins, brominated polystyrenes, brominated polycarbonates, brominated polyacrylates, halogenated flame retardants such as chlorinated polyethylene, phosphate ester flame retardants such as monophosphate compounds and phosphate oligomer compounds, Organophosphorous flame retardants other than phosphate ester flame retardants such as phosphonate oligomer compounds, phosphonitrile oligomer compounds, phosphonic acid amide compounds, organic sulfonate alkali (earth) metal salts, borate metal salt flame retardants, and tin Examples include organic metal salt flame retardants such as acid metal salt flame retardants, and silicone flame retardants. Separately, a flame retardant aid (for example, sodium antimonate, antimony trioxide, etc.), an anti-drip agent (polytetrafluoroethylene having fibril-forming ability, etc.), etc. may be blended and used together with the flame retardant.

  Among the above-mentioned flame retardants, compounds that do not contain chlorine and bromine atoms have reduced features that are undesirable when performing incineration and thermal recycling. It is more suitable as a flame retardant in the molded article of the present invention.

  Furthermore, the phosphate ester flame retardant is particularly preferable because a good hue can be obtained and an effect of improving molding processability is also exhibited. Specific examples of the phosphate ester flame retardant include one or more phosphate ester compounds represented by the following general formula (ii).

（但し上記式中のＸは、ハイドロキノン、レゾルシノール、ビス（４−ヒドロキシジフェニル）メタン、ビスフェノールＡ、ジヒドロキシジフェニル、ジヒドロキシナフタレン、ビス（４−ヒドロキシフェニル）スルホン、ビス（４−ヒドロキシフェニル）ケトン、ビス（４−ヒドロキシフェニル）サルファイドから誘導される基が挙げられ、ｎは０〜５の整数であり、またはｎ数の異なるリン酸エステルの混合物の場合は０〜５の平均値であり、Ｒ¹¹、Ｒ¹²、Ｒ¹³、およびＲ¹⁴はそれぞれ独立して１個以上のハロゲン原子を置換したもしくは置換していないフェノール、クレゾール、キシレノール、イソプロピルフェノール、ブチルフェノール、ｐ−クミルフェノールから誘導される基である。）

(However, X in the above formula is hydroquinone, resorcinol, bis (4-hydroxydiphenyl) methane, bisphenol A, dihydroxydiphenyl, dihydroxynaphthalene, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis A group derived from (4-hydroxyphenyl) sulfide, and n is an integer of 0 to 5, or an average value of 0 to 5 in the case of a mixture of phosphate esters having different numbers of n, R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ are each independently a group derived from phenol, cresol, xylenol, isopropylphenol, butylphenol, or p-cumylphenol substituted or unsubstituted with one or more halogen atoms. .)

  More preferable examples include groups in which X in the above formula is derived from hydroquinone, resorcinol, bisphenol A, and dihydroxydiphenyl, and n is an integer of 1 to 3, or a different number of phosphate esters. In the case of blends of R, R 11, R 12, R 13, and R 14 are each independently derived from phenol, cresol, or xylenol that is substituted or more preferably substituted with one or more halogen atoms. It is a group.

  Among such organophosphate flame retardants, triphenyl phosphate is preferable as a phosphate compound, and resorcinol bis (dixylenyl phosphate) and bisphenol A bis (diphenyl phosphate) are preferable as phosphate oligomers because of excellent hydrolysis resistance. Can be used. More preferable are resorcinol bis (dixylenyl phosphate) and bisphenol A bis (diphenyl phosphate) from the viewpoint of heat resistance. This is because they have good heat resistance and are free from adverse effects such as thermal deterioration and volatilization.

  In the resin composition of this invention, when mix | blending these flame retardants, the range of 0.05-50 weight part is preferable per 100 weight part of aromatic polycarbonate resin (A component). If the amount is less than 0.05 parts by weight, sufficient flame retardancy is not exhibited. If the amount exceeds 50 parts by weight, the strength and heat resistance of the molded product are impaired.

(Ii) Thermal Stabilizer In the resin composition of the present invention, it is preferable to contain a phosphorus stabilizer in order to obtain a better hue and stable fluidity. In particular, a pentaerythritol-type phosphite compound represented by the following general formula (iii) is preferably blended as a phosphorus stabilizer.

［式中Ｒ¹、Ｒ²はそれぞれ水素原子、炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基ないしアルキルアリール基、炭素数７〜３０のアラルキル基、炭素数４〜２０のシクロアルキル基、炭素数１５〜２５の２−（４−オキシフェニル）プロピル置換アリール基を示す。なお、シクロアルキル基およびアリール基は、アルキル基で置換されていてもよい。］

[Wherein R ¹ and R ² are each a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an alkylaryl group, an aralkyl group having 7 to 30 carbon atoms, and an alkyl group having 4 to 20 carbon atoms. A cycloalkyl group, a 2- (4-oxyphenyl) propyl-substituted aryl group having 15 to 25 carbon atoms is shown. In addition, the cycloalkyl group and the aryl group may be substituted with an alkyl group. ]

  More specifically, examples of the pentaerythritol type phosphite compound include distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, and bis (2,6 -Di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, Bis (nonylphenyl) pentaerythritol diphosphite, dicyclohexylpentaerythritol diphosphite, and the like are preferable. Among them, distearyl pentaerythritol diphosphite and bis (2,4-di-te) are preferable. Include t- butylphenyl) pentaerythritol diphosphite.

  Examples of other phosphorus stabilizers include various other phosphite compounds, phosphonite compounds, and phosphate compounds.

  Examples of the phosphite compound include triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl Monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, tris (diethylphenyl) phos Phyto, tris (di-iso-propylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite Ito, and tris (2,6-di -tert- butylphenyl) phosphite and the like.

  Still other phosphite compounds that react with dihydric phenols and have a cyclic structure can be used. For example, 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2,4-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-tert- Butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2′-methylenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite 2,2′-ethylidenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite.

  Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, Examples thereof include diisopropyl phosphate, and triphenyl phosphate and trimethyl phosphate are preferable.

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

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

  Said phosphorus stabilizer can be used individually or in combination of 2 or more types, It is preferable to mix | blend an effective amount of a pentaerythritol type | mold phosphite compound at least. The phosphorus stabilizer is preferably 0.001 to 1 part by weight, more preferably 0.01 to 0.5 part by weight, and still more preferably 0.01 to 0.00 part by weight per 100 parts by weight of the aromatic polycarbonate resin (component A). 3 parts by weight is blended.

(Iii) Elastic polymer In the resin composition of the present invention, an elastic polymer can be used as an impact modifier. Examples of the elastic polymer include a rubber component having a glass transition temperature of 10 ° C. or less, an aromatic And a graft copolymer obtained by copolymerizing one or more monomers selected from the group consisting of vinyl, vinyl cyanide, acrylic acid ester, methacrylic acid ester, and vinyl compounds copolymerizable therewith. . A more preferable elastic polymer is a core-shell type graft copolymer in which one or more shells of the above-mentioned monomer are graft-copolymerized on the core of the rubber component.

  Moreover, the rubber component and the block copolymer of the said monomer are also mentioned. Specific examples of such block copolymers include thermoplastic elastomers such as styrene / ethylenepropylene / styrene elastomers (hydrogenated styrene / isoprene / styrene elastomers) and hydrogenated styrene / butadiene / styrene elastomers. Furthermore, various elastic polymers known as other thermoplastic elastomers such as polyurethane elastomers, polyester elastomers, polyether amide elastomers and the like can also be used.

  A core-shell type graft copolymer is more suitable as an impact modifier. In the core-shell type graft copolymer, the core particle size is preferably 0.05 to 0.8 μm, more preferably 0.1 to 0.6 μm, and more preferably 0.1 to 0.5 μm in weight average particle size. Is more preferable. If it is in the range of 0.05 to 0.8 μm, better impact resistance is achieved. The elastic polymer preferably contains 40% or more of a rubber component, and more preferably contains 60% or more.

  Rubber components include butadiene rubber, butadiene-acrylic composite rubber, acrylic rubber, acrylic-silicone composite rubber, isobutylene-silicone composite rubber, isoprene rubber, styrene-butadiene rubber, chloroprene rubber, ethylene-propylene rubber, nitrile rubber, ethylene- Acrylic rubber, silicone rubber, epichlorohydrin rubber, fluororubber, and those in which hydrogen is added to these unsaturated bonds may include halogen atoms because of concerns about the generation of harmful substances during combustion. No rubber component is preferable in terms of environmental load.

  The glass transition temperature of the rubber component is preferably −10 ° C. or lower, more preferably −30 ° C. or lower. As the rubber component, butadiene rubber, butadiene-acrylic composite rubber, acrylic rubber, and acrylic-silicone composite rubber are particularly preferable. The composite rubber is a rubber obtained by copolymerizing two kinds of rubber components or a rubber polymerized so as to have an IPN structure entangled with each other so as not to be separated.

  Examples of the aromatic vinyl in the vinyl compound copolymerized with the rubber component include styrene, α-methylstyrene, p-methylstyrene, alkoxystyrene, halogenated styrene and the like, and styrene is particularly preferable. Examples of acrylic esters include methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, octyl acrylate, etc., and examples of methacrylic esters include methyl methacrylate, ethyl methacrylate, methacrylic acid. Examples thereof include butyl, cyclohexyl methacrylate, octyl methacrylate and the like, and methyl methacrylate is particularly preferable. Among these, it is particularly preferable to contain a methacrylic acid ester such as methyl methacrylate as an essential component. Since this is excellent in affinity with the aromatic polycarbonate resin, more elastic polymers are present in the resin, and the good impact resistance of the aromatic polycarbonate resin is more effectively exhibited. As a result, the impact resistance of the resin composition is improved. More specifically, the methacrylic acid ester is contained in 100% by weight of the graft component (in the case of 100% by weight of the shell in the case of the core-shell type polymer), preferably 10% by weight or more, more preferably 15% by weight or more. Is done.

  The elastic polymer containing a rubber component having a glass transition temperature of 10 ° C. or less may be produced by any polymerization method including bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. It can be a single-stage graft or a multi-stage graft. Moreover, the mixture with the copolymer of only the graft component byproduced in the case of manufacture may be sufficient. Furthermore, examples of the polymerization method include a general emulsion polymerization method, a soap-free polymerization method using an initiator such as potassium persulfate, a seed polymerization method, and a two-stage swelling polymerization method. In the suspension polymerization method, the aqueous phase and the monomer phase are individually maintained, both are accurately supplied to the continuous disperser, and the particle diameter is controlled by the rotation speed of the disperser, and the continuous production is performed. In the method, a method may be used in which the monomer phase is supplied by passing it through a fine orifice having a diameter of several to several tens of μm or a porous filter in an aqueous liquid having dispersibility to control the particle size. In the case of a core-shell type graft polymer, the reaction may be one stage or multistage for both the core and the shell.

  Such elastic polymers are commercially available and can be easily obtained. For example, as rubber components mainly composed of butadiene rubber, acrylic rubber or butadiene-acrylic composite rubber, Kane Ace B series (for example, B-56 etc.) of Kanegafuchi Chemical Industry Co., Ltd. and Metabrene of Mitsubishi Rayon Co., Ltd. C series (for example, C-223A), W series (for example, W-450A), paraloid EXL series (for example, EXL-2602) by Kureha Chemical Industry, HIA series (for example, HIA-15), BTA series (E.g., BTA-III), KCA series, Rohm and Haas Paraloid EXL series, KM series (e.g., KM-336P, KM-357P, etc.) and UCL modifier resin series (UMG) of Ube Saikon Co., Ltd.・ ABS's MG AXS Resin Series) and the like, and those mainly composed of acrylic-silicone composite rubber as the rubber component are those commercially available from Mitsubishi Rayon Co., Ltd. under the trade name Methbrene S-2001 or SRK-200. It is done.

  The composition ratio of the impact modifier is preferably 0.2 to 50 parts by weight, preferably 1 to 30 parts by weight, and more preferably 1.5 to 20 parts by weight per 100 parts by weight of the aromatic polycarbonate resin (component A). Such a composition range can give good impact resistance to the composition while suppressing a decrease in rigidity.

(Iv) Other additives In the resin composition of the present invention, other thermoplastic resins (for example, polyalkylene terephthalate resin, polyarylate resin, liquid crystalline polyester resin, polyamide resin are used within the range where the effects of the present invention are exhibited. , Polyimide resin, polyetherimide resin, polyurethane resin, silicone resin, polyphenylene ether resin, polyphenylene sulfide resin, polysulfone resin, polyolefin resin such as polyethylene and polypropylene, polystyrene resin, acrylonitrile / styrene copolymer (AS resin), acrylonitrile / Butadiene / styrene copolymer (ABS resin), polystyrene resin, high impact polystyrene resin, syndiotactic polystyrene resin, polymethacrylate resin, and phenoxy or epoxy resin Fats), antioxidants (eg hindered phenol compounds, sulfur antioxidants, etc.), ultraviolet absorbers (benzotriazoles, triazines, benzophenones, etc.), light stabilizers (HALS, etc.), Release agents (saturated fatty acid esters, unsaturated fatty acid esters, polyolefin waxes, fluorine compounds, paraffin wax, beeswax, etc.), flow modifiers (polycaprolactone, etc.), colorants (carbon black, titanium dioxide, various organics) Dyes, metallic pigments, etc.), light diffusing agents (acrylic crosslinked particles, silicone crosslinked particles, etc.), fluorescent brighteners, phosphorescent pigments, fluorescent dyes, antistatic agents, inorganic and organic antibacterial agents, photocatalytic antifouling agents (fine particles) Titanium oxide, fine zinc oxide, etc.), infrared absorbers, photochromic agents, ultraviolet absorbers, etc. . These various additives can be used in known blending amounts when blended with the aromatic polycarbonate resin.

<About the manufacturing method of a resin composition>
Arbitrary methods are employ | adopted in order to manufacture the resin composition of this invention. For example, each component and optionally other components can be premixed and then melt-kneaded and pelletized. Examples of the premixing means include a Nauter mixer, a V-type blender, a Henschel mixer, a mechanochemical apparatus, and an extrusion mixer. In the preliminary mixing, granulation can be performed by an extrusion granulator or a briquetting machine depending on the case. After the preliminary mixing, the mixture is melt-kneaded by a melt-kneader represented by a vent type twin-screw extruder and pelletized by a device such as a pelletizer. Other examples of the melt kneader include a Banbury mixer, a kneading roll, and a constant temperature stirring vessel, but a vent type twin screw extruder is preferred. In addition, each component and optionally other components can be independently supplied to a melt-kneader represented by a twin-screw extruder without being premixed.

  In addition, when the pulverized material of a molded product is mix | blended as polycarbonate resin (A component) of this invention, this pulverized material has a comparatively high characteristic. Therefore, in the supply of the extruder, it is preferable to mix with other components having a high bulk density, or to supply to the extruder together with the components having a high bulk density even when they are supplied independently. The deterioration of the resin caused by the aromatic polycarbonate resin reused by such a production method is further suppressed, and a resin composition part having a more suitable hue can be obtained. The liquid raw material is preferably supplied independently using a separate liquid injection device. Furthermore, when mix | blending an inorganic filler, they can also be supplied from the 1st supply port of an extruder screw base, However, The supply by the side feeder from the 2nd supply port in the middle of an extruder is more preferable.

In the resin composition of the present invention, in the melting peak derived from polylactic acid in the temperature rising process of differential scanning calorimeter (DSC) measurement, the ratio of the melting peak at 195 ° C. or higher is 50% or higher, preferably 80% or higher, Preferably it is 95% or more. The larger the ratio of the melting peak at 195 ° C. or higher, the higher the hydrolysis resistance of the molded product.

  The melting point is preferably in the range of 195 to 250 ° C, more preferably in the range of 200 to 220 ° C. The melting enthalpy is preferably 20 J / g or more, more preferably 30 J / g or more.

Specifically, in the melting peak derived from polylactic acid in the temperature rising process of differential scanning calorimetry (DSC) measurement, the ratio of the melting peak at 195 ° C. or higher is 50% or higher, and the melting point is in the range of 195 to 250 ° C. The melting enthalpy is preferably 20 J / g or more.

<Manufacture of molded products>
The resin composition of the present invention is usually obtained as pellets produced by the above-described method, and products by various molding methods such as injection molding and extrusion molding can be produced using this as a raw material.

  In the injection molding, not only a normal cold runner molding method but also a hot runner molding method is possible. In such injection molding, not only a normal molding method but also an injection compression molding, an injection press molding, a gas assist injection molding, a foam molding (including those by injection of a supercritical fluid), an insert molding, depending on the purpose as appropriate. A molded product can be obtained using an injection molding method such as in-mold coating molding, heat insulating mold molding, rapid heating / cooling mold molding, two-color molding, sandwich molding, and ultrahigh-speed injection molding. The advantages of these various molding methods are already widely known.

  In extrusion molding, products such as various profile extrusion molded articles, sheets, and films can be obtained. For forming sheets and films, an inflation method, a calendar method, a casting method, or the like can also be used. It is also possible to form a heat-shrinkable tube by applying a specific stretching operation.

  A hollow molded article can be obtained by subjecting the resin composition of the present invention to rotational molding or blow molding.

  The molded product formed by molding the resin composition of the present invention is suitable for, for example, an exterior material for OA equipment and home appliances. For example, a personal computer, a notebook computer, a game machine (home game machine, arcade game machine, pachinko machine, And slot machines), display devices (such as CRT, liquid crystal, plasma, projector, and organic EL), mice, and exterior materials such as printers, copiers, scanners, and fax machines (including these multifunction devices), keyboard keys And switch molded products such as various switches. Furthermore, the molded article of the present invention is useful for a wide variety of other applications, such as portable information terminals (so-called PDAs), cellular phones, portable books (dictionaries, etc.), portable televisions, recording media (CD, MD, DVD, etc.) Generation high-density disk, hard disk, etc.) drive, recording media (IC card, smart media, memory stick, etc.) reader, optical camera, digital camera, parabolic antenna, electric tool, VTR, iron, hair dryer, rice cooker, electronics Electric and electronic equipment such as a range, sound equipment, lighting equipment, refrigerator, air conditioner, air cleaner, negative ion generator, and typewriter can be listed. The molded product of the present invention can be applied to various parts such as exterior materials. Can be applied. It is also suitable for various miscellaneous goods such as various containers, covers, writing instrument bodies, and ornaments. Further examples include vehicle parts such as lamp sockets, lamp reflectors, lamp housings, instrument panels, center console panels, deflector parts, car navigation parts, car audio visual parts, and auto mobile computer parts.

  Furthermore, a molded product formed by molding the resin composition of the present invention can be given further functions by surface modification. Surface modification here means a new layer on the surface of resin molded products such as vapor deposition (physical vapor deposition, chemical vapor deposition, etc.), plating (electroplating, electroless plating, hot dipping, etc.), painting, coating, printing, etc. The method used for normal resin molded products can be applied.

  Hereinafter, the present invention will be described in detail by way of examples. However, the present invention is not limited to these.

Polylactic acid units were produced by the method shown in the production examples below. Moreover, each value in a manufacture example was calculated | required with the following method.
(1) Reduced viscosity: 0.12 g of polylactic acid unit was dissolved in 10 mL of tetrachloroethane / phenol (volume ratio 1/1), and the reduced viscosity (mL / g) at 35 ° C. was measured.
(2) Weight average molecular weight (Mw): The weight average molecular weight of the polylactic acid unit was determined by GPC (column temperature 40 ° C., chloroform) in comparison with a polystyrene standard sample.
(3) Crystallization point and melting point: The polylactic acid unit was measured using DSC in a nitrogen atmosphere at a heating rate of 20 ° C./min to determine the crystallization point (Tc) and the melting point (Tm).

<Production Example 1: Production of polylactic acid unit B-21 component>
After 48.75 parts by weight of L-lactide (Musashino Chemical Laboratory Co., Ltd.) and 1.25 parts by weight of D-lactide (made by Musashino Chemical Laboratory Co., Ltd.) were added to the polymerization tank, the inside of the system was purged with nitrogen, and then stearyl alcohol 0.05 parts by weight and 25 × 10 ⁻³ parts by weight of tin octylate as a catalyst were added, and polymerization was carried out at 190 ° C. for 2 hours to obtain a polylactic acid unit B-21 component. The resulting polylactic acid unit B-21 component had a reduced viscosity of 1.48 (mL / g) and a weight average molecular weight of 110,000. The melting point (Tm) was 158 ° C. The crystallization point (Tc) was 117 ° C.

<Production Example 2: Production of polylactic acid unit B-22 component>
After 48.75 parts by weight of L-lactide (Musashino Chemical Laboratory Co., Ltd.) and 1.25 parts by weight of D-lactide (made by Musashino Chemical Laboratory Co., Ltd.) were added to the polymerization tank, the inside of the system was purged with nitrogen, and then stearyl alcohol 0.1 part by weight and 25 × 10 ⁻³ parts by weight of tin octylate as a catalyst were added, and polymerization was performed at 190 ° C. for 2 hours to obtain a polylactic acid unit B-22 component. The resulting polylactic acid unit B-22 component had a reduced viscosity of 2.48 mL / g and a weight average molecular weight of 170,000. The melting point (Tm) was 158 ° C. The crystallization point (Tc) was 117 ° C.

<Production Example 3: Production of polylactic acid unit B-5 component>
After adding 1.25 parts by weight of L-lactide (manufactured by Musashino Chemical Laboratories Co., Ltd.) and 48.75 parts by weight of D-lactide (manufactured by Musashino Chemical Laboratories Co., Ltd.) to the polymerization tank and replacing the system with nitrogen, stearyl 0.1 parts by weight of alcohol and 25 × 10 ⁻³ parts by weight of tin octylate as a catalyst were added, and polymerization was carried out at 190 ° C. for 2 hours to obtain a polylactic acid unit B-5 component. The resulting polylactic acid unit B-5 component had a reduced viscosity of 2.26 (mL / g) and a weight average molecular weight of 190,000. The melting point (Tm) was 156 ° C. The crystallization point (Tc) was 117 ° C.

<Production Example 4: Production of polylactic acid 1>
100 parts by weight of the polylactic acid unit B-22 component obtained in Production Example 2 and 100 parts by weight of the polylactic acid unit B-5 component obtained in Production Example 3 were added to a bent type twin screw extruder [(stock) ) Nippon Steel Works TEX30XSST] was melt-extruded and pelletized at a cylinder temperature of 280 ° C., a screw rotation speed of 150 rpm, a discharge rate of 15 kg / h, and a vent vacuum of 3 kPa to obtain polylactic acid 1.

<Production Example 5: Production of polylactic acid 2>
100 parts by weight of the polylactic acid unit B-22 component obtained in Production Example 2, 100 parts by weight of the polylactic acid unit B-5 component obtained in Production Example 3, and a carbodiimide compound (Carbodilite HMV-8CA: manufactured by Nisshinbo Co., Ltd.) ) 1 part by weight is supplied to a vent type twin screw extruder [TEX30XSST, manufactured by Nippon Steel Works, Ltd.] having a diameter of 30 mmφ, a cylinder temperature of 280 ° C., a screw rotation speed of 150 rpm, a discharge rate of 15 kg / h, and a vent pressure reduction degree of 3 kPa To obtain polylactic acid 2.

The resin composition pellets of polycarbonate resin and polylactic acid were produced by the methods shown in the following examples and comparative examples. Moreover, each value in an Example was calculated | required with the following method.
(1) Melting peak ratio of 195 ° C. or higher: The resin composition pellets were measured using a DSC in a nitrogen atmosphere at a temperature rising rate of 20 ° C./min. It calculated by the following formula | equation from the melting peak area of 195 degreeC or more (high temperature) and the 140-180 degreeC (low temperature) melting peak area.
R _{195 or more} (%) = A _{195 or more} / (A _{195 or more} + A _{140 to 180} ) × 100
R _{195 or higher} : ratio of melting peak at 195 ° C. or higher
A _{195 or higher} : melting peak area of 195 ° C. or higher
A _140-180 : melting peak area of 140-180 ° C.

Moreover, the molded product was manufactured by the method shown to the following Example and a comparative example using the said resin composition pellet. Moreover, each value in an Example was calculated | required with the following method.
(1) Melting peak ratio of 195 ° C. or higher: Measured at a heating rate of 20 ° C./min under a nitrogen atmosphere using DSC, and the melting peak ratio (%) of 195 ° C. or higher is 195 ° C. ) And a melting peak area of 140 to 180 ° C. (low temperature).
R _{195 or more} (%) = A _{195 or more} / (A _{195 or more} + A _{140 to 180} ) × 100
R _{195 or higher} : ratio of melting peak at 195 ° C. or higher
A _{195 or higher} : melting peak area of 195 ° C. or higher
A _140-180 : melting peak area of 140-180 ° C. (2) bending strength: bending strength was measured in accordance with ISO178. Test piece shape: length 80 mm × width 10 mm × thickness 4 mm.
(3) Flexural modulus: The flexural modulus was measured according to ISO178. Test piece shape: length 80 mm × width 10 mm × thickness 4 mm.
(4) Heat resistance: The deflection temperature under load was measured according to ISO75-1 and 2. Load: 1.80 MPa.
(5) Flammability: Flame retardancy at a test piece thickness of 1.6 mm was evaluated by a method (UL94) defined by US Underwriters Laboratories (evaluated only for those containing a phosphate ester flame retardant).
(6) Hydrolysis resistance: The molecular weight of the aromatic polycarbonate after processing the molded article for 8 hours under the condition of 120 ° C. × 100% relative humidity with a pressure cooker tester in terms of the retention rate relative to the value before the treatment. evaluated.

The following were used as raw materials.
(A component)
A-1: Aromatic polycarbonate resin powder (manufactured by Teijin Chemicals Ltd .: Panlite L-1250WP, viscosity average molecular weight 23,900)
(C component)
C-1: Talc (manufactured by Sakai Kogyo Co., Ltd .: HiTalc Premium HTP ultra 5C)
(D component)
D-1: Glass fiber (manufactured by Nippon Electric Glass Co., Ltd .: ECS-03T-511, chopped strand having an average diameter of 13 μm and a cut length of 3 mm)
D-2: Talc (Made by Hayashi Kasei Co., Ltd .: HST-0.8)
(Other ingredients)
F-1: Phosphate ester flame retardant (manufactured by Daihachi Chemical Co., Ltd .: PX-200)
F-2: Polytetrafluoroethylene having a fibril-forming ability (manufactured by Daikin Industries, Ltd .: Polyflon MPA FA-500)
P-1: Distearyl pentaerythritol diphosphite (Asahi Denka Kogyo Co., Ltd .: ADK STAB PEP-8)

<Examples 8 to 12 and Comparative Examples 1 to 8 >
A vent type twin screw extruder having a diameter of 30 mmφ with an aromatic polycarbonate resin, polylactic acid, crystal nucleating agent, inorganic filler, phosphorus stabilizer, and phosphate ester flame retardant having the composition shown in Table 2 [Co., Ltd. Nippon Steel Works TEX30XSST] was melt-extruded and pelletized at a cylinder temperature of 260 ° C., a screw speed of 150 rpm, a discharge rate of 20 kg / h, and a vent vacuum of 3 kPa.

  The screw configuration is the first kneading zone (consisting of feed kneading disk x 2, feed rotor x 1, return rotor x 1 and return kneading disk x 1) before the side feeder position. A second-stage kneading zone (consisting of a feed rotor × 1 and a return rotor × 1) was provided after the feeder position.

In each of the examples and comparative examples, the production of such pellets was carried out as follows (components are described with the above symbols).
(I) Examples 8 to 9 and Comparative Examples 1 to 3 and 6 to 8
All the components were uniformly mixed using a tumbler to prepare a premix, and the mixture was fed from the first feed port of the extruder. In addition, PTFE was mixed uniformly in advance at a concentration of 2.5% by weight in A-1, and the mixture was supplied to a tumbler.
(Ii) Examples 10 to 12 and Comparative Examples 4 and 5
D-1 of the inorganic filler was supplied from the second supply port using a side feeder, and all the remaining components were premixed with a tumbler and supplied from the first supply port. In addition, PTFE was mixed uniformly in advance at a concentration of 2.5% by weight in A-1, and the mixture was supplied to a tumbler.

About the obtained resin composition pellet, the ratio (%) of the melting peak of 195 ° C. or higher was determined.
Subsequently, the resin composition pellets were dried with a hot air circulation dryer at 100 ° C. for 5 hours. After drying, a test for evaluating a bending elastic modulus, a deflection temperature under load, and a flammability by an injection molding machine (Toshiba Machine Co., Ltd .: IS-150EN) with a cylinder temperature of 240 ° C., a mold temperature of 80 ° C., and a molding cycle of 40 seconds. A piece was molded. Each characteristic was measured using these molded articles. The results are shown in Table 2.

  As is apparent from the results in Table 2, it can be seen that the molded article obtained from the composition comprising the aromatic polycarbonate resin and polylactic acid has a greatly improved hydrolysis resistance by using high molecular weight polylactic acid. Moreover, when using together the polylactic acid unit which mainly consists of L-lactic acid components, and the polylactic acid unit which mainly consists of D-lactic acid units, the hydrolysis-resistant improvement effect by forming a stereocomplex is also recognized. In this case, the polylactic acid component is prepared by mixing the polylactic acid unit component mainly composed of L-lactic acid units and the polylactic acid unit component mainly composed of D-lactic acid units before mixing with the aromatic polycarbonate resin. As a result, a molded product having a high stereo complex formation ratio is obtained, and as a result, the hydrolysis resistance is further improved. Further, it can be seen that the mechanical properties are improved by including the inorganic filler, the flame retardancy is achieved by including the flame retardant, and the hydrolysis resistance is further improved by including the end-blocking agent.

Claims (7)

(A) aromatic polycarbonate resin (component A) 100 parts by weight, and (B) stereocomplex polylactic acid (component B) 1 to 200 parts by weight,
Weight average molecular weight in terms of polystyrene in GPC measurement of polylactic acid units (B-2 component, B-3 component, B-5 component and B-6 component) which are raw materials of stereocomplex polylactic acid (B component) is 120,000 or more. And
In stereo complex polylactic acid (component B),
(I) Stereocomplex polylactic acid (component B) consists of a combination 1, 2 or 3,
Combination 1 comprises (B-2) a polylactic acid unit (component B-2) and (B-5) a polylactic acid unit (component B-5), and the weight ratio of the component B-2 to the component B-5 (B-2 component / B-5 component) is in the range of 10/90 to 90/10,
Combination 2 comprises (B-3) a polylactic acid unit (component B-3) and (B-5) a polylactic acid unit (component B-5), and the weight ratio of the component B-3 to the component B-5 (B-3 component / B-5 component) is in the range of 10/90 to 90/10,
Combination 3 comprises (B-6) polylactic acid unit (component B-6) and (B-2) polylactic acid unit (component B-2), and the weight ratio of component B-6 to component B-2 (B-6 component / B-2 component) is in the range of 10/90 to 90/10,
The polylactic acid unit (B-2) is composed of 90 to 99 mol% of L-lactic acid units and 1 to 10 mol% of D-lactic acid units and / or copolymer component units other than lactic acid (B- The polylactic acid unit (B-3) is composed of more than 99 mol% of L-lactic acid units and 100 mol% or less, and 0 to 1 mol% of D-lactic acid units and / or copolymer component units other than lactic acid. The polylactic acid unit (B-5) is composed of 90 to 99 mol% of D-lactic acid units and L-lactic acid units and / or copolymerization components other than lactic acid. It consists of a polylactic acid unit (B-5 component) composed of 1 to 10 mol% of the unit. The polylactic acid unit (B-6) exceeds 99 mol% of the D-lactic acid unit and 100 mol% or less, and the L-lactic acid unit. And / or 0 mol of copolymer component units other than lactic acid % Of polylactic acid units (component B-6) composed of at least 1 mol% and (ii) before mixing 1, 2, or 3 of the stereocomplex polylactic acid (component B) with the polycarbonate resin An aromatic polycarbonate resin composition obtained by heat treatment at 245 to 300 ° C. in advance.   The aromatic polycarbonate resin composition according to claim 1, comprising 0.01 to 5 parts by weight of (C) a crystal nucleating agent (C component) per 100 parts by weight of a polylactic acid component (B component). The aromatic polycarbonate resin composition according to claim 2 , wherein the crystal nucleating agent (component C) is talc. The aromatic polycarbonate according to any one of claims 1 to 3 , wherein (D) the inorganic filler (component D) comprises 0.3 to 200 parts by weight per 100 parts by weight of the aromatic polycarbonate resin (component A). Resin composition. The aromatic polycarbonate resin according to any one of claims 1 to 4 , wherein (E) the end-capping agent (E component) comprises 0.01 to 5 parts by weight per 100 parts by weight of the polylactic acid component (B component). Composition. A molded article obtained by injection molding the aromatic polycarbonate resin composition according to any one of claims 1 to 5 . (A) A method for producing an aromatic polycarbonate resin composition by mixing 100 parts by weight of an aromatic polycarbonate resin (component A) and (B) 1 to 200 parts by weight of the following stereocomplex polylactic acid (component B). ,
Weight average molecular weight in terms of polystyrene in GPC measurement of polylactic acid units (B-2 component, B-3 component, B-5 component and B-6 component) which are raw materials of stereocomplex polylactic acid (B component) is 120,000 or more. And
In stereo complex polylactic acid (component B),
(I) Stereocomplex polylactic acid (component B) consists of a combination 1, 2 or 3,
Combination 1 consists of (B-2) polylactic acid unit (component B-2) and (B-5) polylactic acid unit (component B-5), and the weight ratio of component B-2 to component B-5 (B-2 component / B-5 component) is in the range of 10/90 to 90/10,
Combination 2 comprises (B-3) a polylactic acid unit (component B-3) and (B-5) a polylactic acid unit (component B-5), and the weight ratio of the component B-3 to the component B-5 (B-3 component / B-5 component) is in the range of 10/90 to 90/10,
Combination 3 comprises (B-6) polylactic acid unit (component B-6) and (B-2) polylactic acid unit (component B-2), and the weight ratio of component B-6 to component B-2 (B-6 component / B-2 component) is in the range of 10/90 to 90/10,
The polylactic acid unit (B-2) is composed of 90 to 99 mol% of L-lactic acid units and 1 to 10 mol% of D-lactic acid units and / or copolymer component units other than lactic acid (B- The polylactic acid unit (B-3) is composed of more than 99 mol% of L-lactic acid units and 100 mol% or less, and 0 to 1 mol% of D-lactic acid units and / or copolymer component units other than lactic acid. The polylactic acid unit (B-5) is composed of 90 to 99 mol% of D-lactic acid units and L-lactic acid units and / or copolymerization components other than lactic acid. Consisting of a polylactic acid unit (B-5 component) composed of 1 to 10 mol% of units,
The polylactic acid unit (B-6) is composed of more than 99 mol% of D-lactic acid units and not more than 100 mol% and L-lactic acid units and / or copolymer component units other than lactic acid of 0 mol% or more and less than 1 mol%. (Ii) a combination of stereocomplex polylactic acid (component B) 1, 2 or 3 is pre-heated at 245 to 300 ° C. before mixing with polycarbonate resin. For producing a prepared aromatic polycarbonate resin composition.