JP2009179784A - Molded article composed of aromatic polycarbonate resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a molded article which is composed of an aromatic polycarbonate resin composition containing a polymer obtained from a biomass resource and is excellent in mechanical properties and hydrolysis resistance. <P>SOLUTION: The molded article is composed of the aromatic polycarbonate resin composition which contains 100 parts by weight of a resin component comprising (A) 95-5 wt.% aromatic polycarbonate resin (component A) and (B) 5-95 wt% polylactic acid resin (component B) and 0.001-10 parts by weight of at least one kind of compound selected from the group comprising (C) phosphoric ester metal salts (component C) and (D) triclinic inorganic nucleation agents (component D), and is characterized in that the content (X) of a stereo-complex crystal is ≥80% represented by formula (1). The formula (1) is as follows: X(%)=äΔHb/(ΔHa+ΔHb)}×100, (wherein, ΔHa represents melting enthalpy of a crystal melting point appearing in a temperature range lower than 190°C and Hb represents melting enthalpy of a crystal melting point appearing in the temperature range of ≥190°C and <250°C, in a temperature rising process of a differential scanning calorimeter (DSC)). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a molded article excellent in heat resistance, mechanical properties and hydrolysis resistance, comprising an aromatic polycarbonate resin composition containing a polymer obtained from biomass resources. More specifically, the present invention relates to a molded article excellent in heat resistance, mechanical properties and hydrolysis resistance, comprising an aromatic polycarbonate resin 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 a molded article excellent in heat resistance, mechanical properties and hydrolysis resistance, comprising an aromatic polycarbonate resin composition containing a polymer obtained from biomass resources.
As a result of intensive studies to achieve the above object, the present inventors have obtained a molded product obtained by blending a specific polylactic acid with an aromatic polycarbonate, which has excellent heat resistance, mechanical properties, and hydrolysis resistance. As a result, the present invention was completed.

That is, the present invention relates to (A) aromatic polycarbonate resin (component A) 95 to 5% by weight and (B) polylactic acid resin (component B) 5 to 95% by weight with respect to 100 parts by weight of resin component ( C) 0.001 to 10 parts by weight of at least one compound selected from the group consisting of a phosphoric acid ester metal salt (C component) and (D) a triclinic inorganic nucleating agent (D component), and It is a molded article made of an aromatic polycarbonate resin composition, wherein the stereocomplex crystal content (X) represented by the formula (1) is 80% or more.
X (%) = {ΔHb / (ΔHa + ΔHb)} × 100 (1)
[However, in the formula (1), ΔHa and ΔHb are the melting enthalpy (ΔHa) of the crystalline melting point appearing below 190 ° C. and 190 ° C. or more and 250, respectively, in the temperature rising process of the differential scanning calorimeter (DSC). It is the melting enthalpy (ΔHb) of the crystal melting point that appears below ° C. ]

  The molded article of the present invention comprises an aromatic polycarbonate resin, a polylactic acid unit component mainly composed of L-lactic acid units, a polylactic acid unit component composed of D-lactic acid units, a phosphate ester metal salt, and a triclinic inorganic nucleating agent. A molded article formed by molding a resin composition having a reduced environmental load comprising a mixture of at least one compound selected from the above, and has good heat resistance, mechanical properties and hydrolysis resistance, Its industrial effect is exceptional.

  Hereafter, each component in the resin composition which comprises the molded article of this invention, those compounding ratios, a preparation method, etc. are demonstrated concretely one by one.

<About component A>
Component A in the resin composition constituting the molded article of the present invention is an aromatic polycarbonate resin. 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 which is the component A in the resin composition constituting the molded article of the present invention is a polyester carbonate obtained by copolymerizing an aromatic or aliphatic (including alicyclic) bifunctional carboxylic acid, 2 It may be a copolymerized polycarbonate obtained by copolymerizing a functional alcohol (including an alicyclic group), and a polyester carbonate obtained by copolymerizing 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.

  There are various reaction modes such as interfacial polymerization, melt transesterification, solid phase transesterification of carbonate prepolymer, and ring-opening polymerization of cyclic carbonate compound, which are methods for producing the polycarbonate resin constituting the molded article of the present invention. This method is well known in the literature and patent publications.

  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 of polycarbonate resin in the resin composition which comprises the molded article 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 in 100% by weight of the A component aromatic polycarbonate resin, preferably 5% by weight or more, more preferably 10% by weight or more, and further preferably 15% by weight or more. 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>
B component in the resin composition which comprises the molded article of this invention is polylactic acid which has a L-lactic acid unit and a D-lactic acid unit as a basic structural component shown to following formula (3).

  The polylactic acid (B component) in the resin composition of the present invention is composed of the B-1 component which is a polylactic acid unit mainly composed of L-lactic acid units and the B-2 component which is a polylactic acid unit mainly composed of D-lactic acid units. Become.

  The B-1 component is a polylactic acid unit mainly composed of L-lactic acid units, and is composed of 90 to 100 mol% of L-lactic acid units and 0 to 10 mol% of copolymer components other than D-lactic acid units and / or lactic acid. Is done. The ratio of such B-1 component constitutional units is preferably 90 to 99 mol% of L-lactic acid units and 1 to 10 mol% of D-lactic acid units and / or copolymer components other than lactic acid, and L-lactic acid units 92 to 99. More preferably, it is 1% to 8% by mole of D-lactic acid units and / or copolymer components other than lactic acid.

  The B-2 component is a polylactic acid unit mainly composed of D-lactic acid units, and is composed of 90 to 100 mol% of D-lactic acid units and 0 to 10 mol% of L-lactic acid units and / or copolymerization components other than lactic acid. Is done. The proportion of such B-2 component constitutional units is preferably 90 to 99 mol% of D-lactic acid units and 1 to 10 mol% of copolymer components other than L-lactic acid units and / or lactic acid, and 92 to 99 D-lactic acid units. More preferably, it is 1 mol% of L-lactic acid units and / or copolymerization components other than lactic acid.

  In the polylactic acid (component B) in the resin composition constituting the molded article of the present invention, a polylactic acid unit (B-1 component) mainly composed of L-lactic acid units and a polylactic acid unit mainly composed of D-lactic acid units ( B-2 component) is a weight ratio (B-1 component / B-2 component) of 10/90 to 90/10. In order to form more stereo complexes, 25/75 to 75 / It is preferable that it is 25, More preferably, it is 40 / 60-60 / 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.

  Polylactic acid unit B-1 component in polylactic acid (B component), copolymer component unit other than lactic acid in B-2 component, dicarboxylic acid having two or more functional groups capable of forming ester bond, polyhydric alcohol , Units derived from hydroxycarboxylic acid, lactone, etc. and units derived from various polyesters, various polyethers, various polycarbonates, etc. composed of these various components can be used alone or in combination.

  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.

  The polylactic acid (component B) has a weight average molecular weight of 120,000 or more, preferably 120,000 to 500,000, more preferably 120,000 to 300,000. The weight average molecular weight is a weight average molecular weight value in terms of standard polystyrene as measured by gel permeation chromatography (GPC) using chloroform as an eluent.

<About the production method of polylactic acid (component B)>
Each of the polylactic acid units (B-1 and B-2 components) constituting the polylactic acid (component B) in the resin composition constituting the molded article of the present invention is manufactured by any known polylactic acid polymerization method. For example, it can be produced by ring-opening polymerization of lactide, dehydration condensation of lactic acid, and a method combining these with solid phase polymerization.

  When each polylactic acid unit (components B-1 and B-2) 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 in each polylactic acid unit (B-1, B-2 component) constituting polylactic acid (B component) is a dicarboxylic acid having two or more functional groups capable of forming an ester bond. 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 polylactic acid unit (components B-1 and B-2) constituting the polylactic acid (component B) may contain a catalyst involved in polymerization within a range that does not impair the thermal stability of the resin. 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-1 and B-2) 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.

<About component C>
The component C in the present invention is a phosphate metal salt represented by the following formula (1) or (2).

In the formula (1), R ₁ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms represented by R ₁ include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, iso-butyl group, and tert-butyl. Examples include groups.

In Formula (1), R ₂ and R ₃ each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. Examples of the alkyl group having 1 to 12 carbon atoms include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, iso-butyl group, tert-butyl group, amyl group, tert-amyl group, hexyl group, heptyl group, octyl group, iso-octyl group, tert-octyl group, 2-ethylhexyl group, nonyl group, iso-nonyl group, decyl group, iso-decyl group, tert-decyl group, An undecyl group, a dodecyl group, a tert-dodecyl group, etc. are mentioned.

In the formula (1), M ₁ represents an alkali metal atom such as Na, K or Li, an alkaline earth metal atom such as Mg or Ca, a zinc atom or an aluminum atom. p represents 1 or 2, q represents 0 when M ₁ is an alkali metal atom, alkaline earth metal atom or zinc atom, and 1 or 2 when M ₁ is an aluminum atom.

Preferable examples of the phosphoric acid ester metal salt represented by the formula (1) include those in which R ₁ is a hydrogen atom and R ₂ and R ₃ are both tert-butyl groups. More specifically, R ₁ is a hydrogen atom, R ₂ and R ₃ are both tert-butyl groups, M ₁ is a sodium atom, a compound represented by p = 1 and q = 0, and R ₁ is a hydrogen atom. , R ₂ and R ₃ are both tert-butyl groups, M ₁ is a zinc atom, a compound represented by p = 2 and q = 0, R ₁ is a hydrogen atom, and R ₂ and R ₃ are both tert-butyl. Preferred examples include compounds represented by the group, M ₁ is an aluminum atom, and p = 1, q = 2, or p = 2, q = 1. Among them, _{R 1} is a hydrogen _atom, R 2, _{R 3} are both tert- butyl group, an _{M 1} is a sodium atom, p = 1, phosphate 2,2'-methylenebis (4, represented by q = 0, 6-di-tert-butylphenyl) sodium is particularly preferred. These phosphoric acid ester metal salts can be synthesized by a known method. Commercially available products of these phosphate ester metal salts include ADEKA's trade names, ADK STAB NA-11, NA-21, and the like.

In the formula (2), R ₄ , R ₅ and R ₆ each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. Examples of the alkyl group having 1 to 12 carbon atoms include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, iso-butyl group, tert-butyl group, amyl group, tert-amyl group, hexyl group, heptyl group, octyl group, iso-octyl group, tert-octyl group, 2-ethylhexyl group, nonyl group, iso-nonyl group, decyl group, iso-decyl group, tert-decyl group, An undecyl group, a dodecyl group, a tert-dodecyl group, etc. are mentioned.

In the formula (2), M ₂ represents an alkali metal atom such as Na, K or Li, an alkaline earth metal atom such as Mg or Ca, a zinc atom or an aluminum atom. p represents 1 or 2, and q represents 0 when M ₂ is an alkali metal atom, alkaline earth metal atom or zinc atom, and represents 1 or 2 when M ₂ is an aluminum atom.

Among the phosphoric acid ester metal salts represented by the formula (2), for example, R ₄ and R ₆ are both hydrogen atoms, R ₅ is a tert-butyl group, R ₄ and R ₆ are both methyl groups, R ₅ is a tert-butyl group. More specifically, R ₄ and R ₆ are both hydrogen atoms, R ₅ is a tert-butyl group, M ₂ is a sodium atom, a compound represented by p = 1 and q = 0, R ₄ and R ₆ Is a methyl group, R ₅ is a tert-butyl group, M ₂ is a sodium atom, a compound represented by p = 1 and q = 0, R ₄ and R ₆ are both hydrogen atoms, and R ₅ is tert-butyl. A group, M ₂ is a zinc atom, a compound represented by p = 2 and q = 0, R ₄ and R ₆ are both hydrogen atoms, R ₅ is a tert-butyl group, M ₂ is an aluminum atom, p Preferred examples include compounds represented by = 2, q = 1 or p = 1, q = 2. Among them, R ₄ and R ₆ are both hydrogen atoms, R ₅ is a tert-butyl group, M ₂ is a sodium atom, and bis (4-tert-butylphenyl) phosphate represented by p = 1 and q = 0. Sodium is particularly preferred. These phosphoric acid ester metal salts can be synthesized by a known method. As a commercial item of these phosphate ester metal salts, ADEKA Corporation brand name, ADK STAB NA-10, etc. are mentioned.

  (C) The average particle diameter of the phosphoric acid ester metal salt (component C) is 0.01 μm or more and less than 10 μm, preferably 0.03 μm or more and less than 9 μm, more preferably 0.05 μm or more and less than 8 μm. When the average particle size is within this range, crystallization of stereocomplex crystals proceeds efficiently. As a measuring method of the average particle diameter, a static scattering method using an argon laser or a helium laser can be exemplified as the most practical measuring method.

  The content of (C) phosphate ester metal salt (component C) in the resin composition constituting the molded article of the present invention is (A) aromatic polycarbonate resin (component A) 95-5% by weight and (B) polylactic acid. It is 0.001 to 10 parts by weight, preferably 0.005 to 7 parts by weight, and more preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the resin component (component B) of 5 to 95% by weight. Part. When the content of the phosphoric acid ester metal salt is less than 0.001 part by weight, the stereocomplex crystal content does not increase. On the other hand, when the content exceeds 10 parts by weight, it re-aggregates and is effective as a crystal nucleating agent. Decreases.

<About D component>
The D component in the present invention is a triclinic inorganic nucleating agent. Such triclinic inorganic nucleating agents are effective as crystal nucleating agents for stereocomplex crystals because they have the same triclinic crystal lattice as stereocomplex crystals. Does not function as a crystal nucleating agent at all. As a result, it is possible to delay the growth of the homocrystal and promote the growth of the stereocomplex crystal during that time. Examples of the triclinic inorganic nucleating agent include calcium dihydrogen phosphate monohydrate, calcium metasilicate, sodium hydrogen sulfate, sodium perborate and the like. Among these, calcium metasilicate is preferable from the viewpoint of suppressing a decrease in the molecular weight of the resin composition.

  (D) The average particle size of the triclinic inorganic nucleating agent (component D) is 0.1 μm or more and less than 10 μm, preferably 0.3 μm or more and less than 10 μm, more preferably 0.5 μm or more and less than 10 μm. When the average particle size is within this range, crystallization of stereocomplex crystals proceeds efficiently. As a measuring method of the average particle diameter, a static scattering method using an argon laser or a helium laser can be exemplified as the most practical measuring method.

  The content of (D) triclinic inorganic nucleating agent (D component) in the resin composition constituting the molded article of the present invention is (A) aromatic polycarbonate resin (A component) 95-5 wt% and (B ) 0.001 to 10 parts by weight, preferably 0.005 to 7 parts by weight, more preferably 0.01 to 100 parts by weight of the resin component consisting of 5 to 95% by weight of polylactic acid resin (component B) ~ 5 parts by weight. When the content of the triclinic inorganic nucleating agent is less than 0.001 part by weight, the content of homocrystals increases. On the other hand, when the content exceeds 10 parts by weight, re-aggregation causes The effect is reduced.

  In addition, said C component and D component may be used together, and content of C component and D component is the total amount in that case, and (A) aromatic polycarbonate resin (A component) 95-5 weight% ( B) It is 0.001-10 weight part with respect to 100 weight part of resin components which consist of 5-95 weight% of polylactic acid resin (B component), Preferably it is 0.005-7 weight part, More preferably, it is 0.00. 01 to 5 parts by weight.

<About E component>
In the resin composition constituting the molded article of the present invention, when an inorganic filler (E component) is further blended, a molded article excellent in mechanical characteristics, dimensional characteristics, etc. can be obtained.
As inorganic fillers, various inorganic fillers generally 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, these inorganic fillers are non-petroleum resource materials as compared with petroleum resource materials such as carbon fiber, and therefore, raw materials with a lower environmental load are used. There is an effect that the significance of use is further enhanced. 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 diameter of mica that can be used in the present invention is a number average particle diameter calculated by a number average of a total of 1,000 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 the classifier, impactor type inertial force classifier (variable impactor, etc.), Coanda effect type inertial force classifier (elbow jet, etc.), centrifugal field classifier (multistage cyclone, microplex, dispersion separator) , Accucut, Turbo Classifier, Turboplex, Micron Separator, and Super Separator).

  Further, 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.

  The blending amount of these inorganic fillers is preferably 0.3 to 200 parts by weight, more preferably 1 to 100 parts by weight per 100 parts by weight in total of the aromatic polycarbonate resin (component A) and polylactic acid (component B). 5 to 70 parts by weight is more preferable, and 10 to 50 parts by weight is most preferable. 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. . Some of these inorganic fillers act as crystal nucleating agents. However, in order to sufficiently exert the effect as a crystal nucleating agent for the stereocomplex crystal in the present invention, the inorganic filler is contained in a polylactic acid resin. It is necessary to disperse sufficiently uniformly. In order to realize such a uniform dispersion state, it is preferable to melt and mix the polylactic acid resin and the inorganic filler in advance before mixing with the aromatic polycarbonate resin. In the method in which the aromatic polycarbonate resin, polylactic acid resin, and inorganic filler are simultaneously melt-mixed, the inorganic filler dispersion in the polylactic acid resin becomes non-uniform, and the effect as a nucleating agent can be sufficiently exerted. Can not.

  In addition, in the resin composition which comprises the molded article 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, and 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 0.01 to 2 parts by weight per 100 parts by weight of the resin component comprising 95 to 5% by weight of the aromatic polycarbonate resin (component A) of the present invention and 5 to 95% by weight of polylactic acid (component B). Is preferred, 0.05 to 1.5 parts by weight is more preferred, and 0.1 to 0.8 parts by weight is even more preferred.

<About F component>
In the resin composition constituting the molded article of the present invention, when a terminal blocking agent (F component) is further blended, the hydrolysis resistance of the resin composition and various molded articles obtained by processing the resin composition is increased. be able to.

  The F component end-blocking agent indicates a function of blocking by reacting with a part or all of the carboxyl group ends of polylactic acid (B component) in the resin composition constituting the molded article of the present invention. And condensation reaction type compounds such as aliphatic alcohols and 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, by adding, mixing, and reacting an addition reaction type end-capping agent, it is possible to obtain a sufficient carboxyl group end-capping effect while suppressing decomposition of the resin by a by-product, and practically sufficient resistance. A resin composition having hydrolyzability and a molded product made of the resin composition 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. Dilester, 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, an epoxy compound, an oxazoline compound, an oxazine compound, an aziridine compound, as a terminal blocker which can be used for this invention.

In the resin composition constituting the molded article of the present invention, the carboxyl end group may be appropriately blocked according to the use, but the specific carboxyl group end blocking level is the concentration of the carboxyl group end of the polylactic acid unit. preferably from the viewpoint of hydrolysis resistance improving it but less than 10 equivalents / 10 ³ kg, more preferably 6 or less equivalents / 10 ³ kg.

  As a method for blocking the carboxyl group terminal of polylactic acid (component B) in the resin composition constituting the molded article of the present invention, a condensation reaction type or addition reaction type terminal blocking agent may be reacted, and the condensation reaction As a method for blocking the carboxyl group terminal by the addition of a suitable amount of a condensation reaction type terminal blocking agent such as an aliphatic alcohol or an amide compound in the polymerization system at the time of polymer polymerization, a dehydration condensation reaction is performed under reduced pressure, etc. The terminal can be blocked, but from the viewpoint of increasing the degree of polymerization of the polymer, it is preferable to add a condensation reaction type terminal blocking 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 and react the end-capping agent after the polymerization reaction. Before mixing with the aromatic polycarbonate resin (component A), the resin composition constituting the molded article of the present invention comprises a polylactic acid unit (B-1 component) mainly composed of L-lactic acid units, and mainly a D-lactic acid unit. A coexisting composition of a polylactic acid unit (component B-2) comprising at least one compound selected from the group consisting of a phosphate ester metal salt (component C) and a triclinic inorganic nucleating agent (component D) Is prepared by heat treatment in advance, but if the method of adding the coexisting composition or adding it at the time of heat treatment is taken, decomposition and deterioration of the aromatic polycarbonate resin (component A) are suppressed, and high efficiency is achieved. This is particularly preferable because the hydrolysis resistance of the resin composition and a molded product made of the resin composition can be further enhanced by the end-capping reaction.

  The content of the end-blocking agent (component F) is 0.01 to 5 parts by weight, preferably 0.05 to 4 parts by weight, and more preferably 0.8 parts 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 which comprises the molded article 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 (4).

（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 organic phosphate ester 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 their 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 constituting the molded article of the present invention, when these flame retardants are blended, the aromatic polycarbonate resin (component A) is 95 to 5% by weight and the polylactic acid (component B) is 5 to 95% by weight. The range of 0.05 to 50 parts by weight is preferable per 100 parts by weight of the resin component. If it is less than 0.05 part by weight, sufficient flame retardancy will not be exhibited, and if it exceeds 50 parts by weight, the strength and heat resistance of the molded product will be impaired.

(Ii) Thermal stabilizer The resin composition constituting the molded article of the present invention preferably contains a phosphorus-based stabilizer in order to obtain a better hue and stable fluidity. In particular, a pentaerythritol-type phosphite compound represented by the following general formula (5) 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 0.001 to 1 part by weight per 100 parts by weight of a resin component comprising 95 to 5% by weight of an aromatic polycarbonate resin (component A) and 5 to 95% by weight of polylactic acid (component B), preferably 0.01 to 0.5 part by weight, more preferably 0.01 to 0.3 part by weight is blended.

(Iii) Elastic polymer In the resin composition constituting the molded article of the present invention, an elastic polymer can be used as an impact modifier. Examples of the elastic polymer include a glass transition temperature of 10 ° C or lower. Graft copolymer in which one or more monomers selected from aromatic vinyl, vinyl cyanide, acrylic ester, methacrylic ester, and vinyl compounds copolymerizable therewith are copolymerized with rubber component Can be mentioned. 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., 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 Ube modifier resin series (UMG)・ 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 0.2 to 50 parts by weight per 100 parts by weight of the resin component comprising 95 to 5% by weight of aromatic polycarbonate resin (component A) and 5 to 95% by weight of polylactic acid (component B). Is preferred, 1 to 30 parts by weight is more preferred, and 1.5 to 20 parts by weight is even more preferred. If it is this composition range, favorable impact resistance can be given to a composition, suppressing the fall of rigidity.

(Iv) Crystal nucleating agent In addition to the phosphoric acid ester metal salt (C component) and the triclinic inorganic nucleating agent (D component), the resin composition constituting the molded article of the present invention includes polylactic acid and aromatic polyester. A known compound that is generally used as a crystal nucleating agent for a crystalline resin such as a resin can also be used.

  Examples of the crystal nucleating agent include inorganic fine particles such as talc, silica, graphite, carbon powder, pyroferrite, gypsum, and neutral clay, metal oxides such as magnesium oxide, aluminum oxide, and titanium dioxide, sulfate, and phosphoric acid. Salt, phosphonate, oxalate, oxalate, stearate, benzoate, salicylate, tartrate, sulfonate, montan wax salt, montan wax ester salt, terephthalate, benzoate, carboxylic acid Examples include salt.

  Among these compounds used as the crystal nucleating agent, talc is particularly effective, and those having an average particle size of 0.5 to 30 μm can be used, but those having an average particle size of 0.5 to 20 μm are preferable. The thing of 1-10 micrometers is still more preferable. In order to obtain a composition or molded article having a high crystallinity, it is necessary to generate more crystal nuclei. In the case of talc having an average particle size exceeding 30 μm, a large amount of addition is required to form a large number of crystal nuclei, so the effectiveness as a crystal nucleating agent is lowered, and it is more effectively used as a reinforcing material. The On the contrary, talc having an average particle size of less than 1 μm has a strong cohesive force and therefore easily aggregates in polylactic acid, and the amount of crystal nuclei produced decreases on the contrary, so that it is less effective as a crystal nucleating agent.

  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. When the amount of the crystal nucleating agent is too small, the effect as a crystal nucleating agent is not expressed, and conversely, even if the amount is too much, the effectiveness as a crystal nucleating agent may decrease due to aggregation of the crystal nucleating agents. is there.

  Although there is no restriction | limiting in particular in the compounding method of the crystal nucleating agent used in this invention, The polylactic acid unit (B-1 component) which mainly consists of L-lactic acid units, and the polylactic acid unit (B-2 which mainly consists of D-lactic acid units) Component) and at least one compound selected from the group consisting of a phosphate ester metal salt (component C) and a triclinic inorganic nucleating agent (component D), or in the preparation of such a coexisting composition It is preferable to add at the time of heat treatment. A method of blending a crystal nucleating agent at the timing of mixing with an aromatic polycarbonate resin (component A) after preparation and heat treatment of a coexisting composition of component B-1, component B-2, component C and / or component D In the method of blending the B-1 component, the B-2 component, the C component and / or the D component, and the A component all at the same time, the dispersion of the crystal nucleating agent in the polylactic acid resin is not possible. It tends to be uniform, and its effectiveness as a crystal nucleating agent is not sufficiently exhibited.

(V) Other additives In the resin composition constituting the molded article of the present invention, other thermoplastic resins (for example, polyalkylene terephthalate resin, polyarylate resin, liquid crystallinity are included within the range where the effects of the present invention are exhibited. Polyester resin, polyamide resin, 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), antioxidants (eg, hindered phenol compounds, sulfur antioxidants, etc.), ultraviolet absorbers (benzotriazole, triazine, benzophenone, etc.), light stabilizers (HALS) 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 organic 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 Agents (fine titanium oxide, fine zinc oxide, etc.), infrared absorbers, photochromic agents, ultraviolet absorbers, etc. It may be blended. 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>
The resin composition constituting the molded article of the present invention may be produced by mixing all components at once, but before mixing with the aromatic polycarbonate resin (A component), polylactic acid (B component) And (C) a phosphoric acid ester metal salt (C component) and (D) a triclinic inorganic nucleating agent (D component). It is preferable because a stereo complex can be efficiently generated.

i) Preparation of coexisting composition Polylactic acid (B-1 component, B-2 component), phosphoric acid ester metal salt (C component) and triclinic inorganic prior to mixing with aromatic polycarbonate resin (A component) In the heat treatment of at least one compound selected from the group consisting of a nucleating agent (component D), as a method for allowing these components to coexist, polylactic acid units (B-1 component) mainly composed of L-lactic acid units, and mainly D -A method in which polylactic acid units (B-2 component) composed of lactic acid units are mixed as uniformly as possible is preferable because a stereocomplex can be efficiently generated when they are heat-treated. The coexisting composition can be prepared by any method as long as they are uniformly mixed when heat-treated. The method is carried out in the presence of a solvent, or the method is carried out in the absence of a solvent. Etc. are exemplified.

  Methods for preparing the coexisting composition in the presence of a solvent include a method of obtaining the coexisting composition by reprecipitation from a state dissolved in a solution, and a method of obtaining the coexisting composition by removing the solvent by heating. Preferably mentioned.

  In the case of obtaining such a coexisting composition by reprecipitation in the presence of a solvent, first, a polylactic acid unit (B-1 component) mainly composed of L-lactic acid units and a polylactic acid mainly composed of D-lactic acid units. A coexisting composition with the unit (component B-2) is prepared by reprecipitation. Here, the B-1 component and the B-2 component are preferably carried out by adjusting and mixing separately dissolved solutions in a solvent, or by dissolving and mixing both in a solvent together.

  Here, the weight ratio of the polylactic acid unit (B-1 component) mainly composed of L-lactic acid units to the polylactic acid unit (B-2 component) mainly composed of D-lactic acid units is 10/90 to 90/10. In order to efficiently produce a stereocomplex of polylactic acid (B-1 component, B-2 component) in the resin composition of the present invention, it is preferable to prepare such a range. The weight ratio of the B-1 component and the B-2 component is more preferably 25/75 to 75/25, and particularly preferably 40/60 to 60/40.

  The solvent is not particularly limited as long as polylactic acid (B-1 component, B-2 component) can be dissolved. For example, chloroform, methylene chloride, dichloroethane, tetrachloroethane, phenol, tetrahydrofuran, N- Preferred are methylpyrrolidone, N, N-dimethylformamide, butyrolactone, trioxane, hexafluoroisopropanol, etc., alone or in combination.

  Phosphoric acid ester metal salt (component C) and triclinic inorganic nucleating agent (component D) are insoluble in the above solvent or may remain in the solvent after reprecipitation even if dissolved in the solvent. The polylactic acid (B-1 component, B-2 component) mixture obtained by reprecipitation and at least one compound selected from the group consisting of C component and D component are separately mixed to form a coexisting composition. Need to be prepared.

  The method of obtaining these coexisting compositions by mixing such a polylactic acid mixture and at least one compound selected from the group consisting of the C component and the D component is not particularly limited as long as they are uniformly mixed. However, any method such as powder mixing or melt mixing can be used.

  Next, polylactic acid (B-1 component, B-2 component), phosphate metal salt (C component), and triclinic inorganic nucleating agent (D component) are obtained by removing the solvent from the presence of the solvent. In the case of preparing at the same time a coexisting composition of at least one compound selected from the group consisting of: B-1 component and B-2 component, and at least one selected from the group consisting of C component and D component Prepare and mix a dispersion in which each compound is dissolved or dispersed separately in a solvent, or prepare and mix a dispersion in which all components are dissolved or dispersed together in a solvent, and then heat. By evaporating the solvent.

  Here, the weight ratio of the polylactic acid unit (B-1 component) mainly composed of L-lactic acid units to the polylactic acid unit (B-2 component) mainly composed of D-lactic acid units is 10/90 to 90/10. In order to efficiently produce a stereocomplex of polylactic acid (B-1 component, B-2 component) in the resin composition of the present invention, it is preferable to prepare such a range. The weight ratio of the B-1 component and the B-2 component is more preferably 25/75 to 75/25, and particularly preferably 40/60 to 60/40.

The solvent dissolves at least one compound selected from the group consisting of polylactic acid (B-1 component, B-2 component), phosphate metal salt (C component) and triclinic inorganic nucleating agent (D component). For example, chloroform, methylene chloride, dichloroethane, tetrachloroethane, phenol, tetrahydrofuran, N-methylpyrrolidone, N, N-dimethylformamide, butyrolactone, trioxane, hexafluoroisopropanol These are preferably used alone or in combination of two or more.
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.

  A coexisting composition of at least one compound selected from the group consisting of polylactic acid (B-1 component, B-2 component), phosphate metal salt (C component) and triclinic inorganic nucleating agent (D component) The preparation can also be performed in the absence of a solvent. That is, at least one compound selected from the group consisting of the B-1 component and the B-2 component, and the C component and D component, which have been powdered or chipped in advance, is mixed in a predetermined amount, and then melted and mixed. A method or a method in which any one of the B-1 component and the B-2 component is melted and then the remaining components are added and mixed can be employed.

  Here, the size of the powder or chip is not particularly limited as long as the powder or chip of each polylactic acid unit (B-1 component, B-2 component) is uniformly mixed. The following is preferable, and the size is 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, mixing is performed. Is not preferable, and homocrystals are likely to precipitate.

  In addition, as a mixing device used to uniformly mix the above powder or chips, 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 In the case of mixing with an extruder or powder, a tumbler type powder mixer, a continuous powder mixer, various milling devices, or the like can be suitably used.

  Furthermore, when preparing such a coexisting composition, as an inorganic filler (E component), a terminal blocker (F component), and other additives, inorganic filler breakage inhibitor, lubricant, flame retardant, thermal stability Agent, elastic polymer (impact modifier), antioxidant, ultraviolet absorber, light stabilizer, mold release agent, flow modifier, colorant, light diffusing agent, fluorescent whitening agent, phosphorescent pigment, fluorescent dye, Various additives other than the aromatic polycarbonate resin (component A) such as an antistatic agent, an antibacterial agent, and a crystal nucleating agent may be allowed to coexist.

  In particular, the addition of an end-blocking agent (F component) at the stage of preparation of the coexisting composition means that the mixing of the end-blocking agent and polylactic acid (B component) becomes more uniform, so that the acidic terminal of polylactic acid Is more effective for improving the hydrolysis resistance of the final resin composition obtained. It is also possible to add a phosphorus-based heat stabilizer or a hindered phenol-based or sulfur-based antioxidant at the stage of preparing the coexisting composition. It is particularly preferable for improving the ratio.

ii) Heat treatment of coexisting composition From the group consisting of polylactic acid (B-1 component, B-2 component), phosphate metal salt (C component) and triclinic inorganic nucleating agent (D component) in the present invention The heat treatment of the coexisting composition of at least one selected compound means holding the composition in a temperature range of 240 to 300 ° C. for a certain period of time. The temperature of the heat treatment is preferably 250 to 300 ° C, more preferably 260 to 290 ° C. If it exceeds 300 ° C., it is difficult to suppress the decomposition reaction, which is not preferable, and if it is less than 240 ° C., uniform mixing by heat treatment does not proceed, and it is difficult to efficiently generate a stereocomplex. 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.

  As the apparatus and method used for the heat treatment, any apparatus and method that can be heated while adjusting the atmosphere can be used. For example, a batch type reactor, a continuous type reactor, a biaxial or uniaxial type can be used. It is also possible to adopt a method of processing while forming using an extruder or the like, or a press machine or a flow tube type extruder.

  Here, coexistence of at least one compound selected from the group consisting of polylactic acid (B-1 component, B-2 component), phosphate metal salt (C component) and triclinic inorganic nucleating agent (D component) When the composition is prepared by a method of melt mixing in the absence of a solvent, heat treatment of the coexisting composition can be achieved simultaneously with the preparation of the coexisting composition.

Furthermore, the heat treatment of the coexisting composition is performed by using an inorganic filler (E component), a terminal blocker (F component), and other additives as an inorganic filler breakage inhibitor, lubricant, flame retardant, thermal stabilizer, elasticity. Polymer (impact modifier), antioxidant, UV absorber, light stabilizer, mold release agent, flow modifier, colorant, light diffusing agent, fluorescent whitening agent, phosphorescent pigment, fluorescent dye, antistatic agent Various additives other than the aromatic polycarbonate resin (component A) such as an antibacterial agent and a crystal nucleating agent can also be added.
In particular, the end-capping agent (component F) is added at the stage of heat treatment in order to improve the hydrolysis resistance of the final resin composition because the capping reaction of the acidic end of polylactic acid proceeds efficiently during the heat treatment. It is preferable to keep it. Also, phosphorus-based heat stabilizers and hindered phenol-based and sulfur-based antioxidants are preferably added at the stage of heat treatment because they improve the heat stability during heat treatment.

iii) Preparation of resin composition The resin composition constituting the molded article of the present invention is produced by further mixing the heat-treated coexisting composition with an aromatic polycarbonate resin (component A) and other additive components. Is done.

  Other additive components include inorganic filler (E component), end-capping agent (F component), and other additives such as inorganic filler breakage inhibitor, lubricant, flame retardant, thermal stabilizer, elastic polymer (Impact modifier), antioxidant, UV absorber, light stabilizer, mold release agent, flow modifier, colorant, light diffusing agent, fluorescent whitening agent, phosphorescent pigment, fluorescent dye, antistatic agent, antibacterial Arbitrary additive components, such as an agent and a crystal nucleating agent, are mentioned.

  In order to produce the resin composition constituting the molded article of the present invention, an arbitrary method is adopted. For example, the heat-treated coexisting composition, the aromatic polycarbonate resin (component A), and optionally other components may 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 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 article is mix | blended as aromatic 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 due to the aromatic polycarbonate resin reused by such a production method is further suppressed, and a resin composition 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.

The resin composition constituting the molded article of the present invention is a stereo represented by the following formula (1) using the melting enthalpy derived from polylactic acid (component B) crystal in the temperature rising process of differential scanning calorimeter (DSC) measurement. The complex crystal content (X) is 80% or more.
X (%) = {ΔHb / (ΔHa + ΔHb)} × 100 (1)
[However, in the formula (1), ΔHa and ΔHb are the melting enthalpy (ΔHa) of the crystalline melting point appearing below 190 ° C. and 190 ° C. or more and 250, respectively, in the temperature rising process of the differential scanning calorimeter (DSC). It is the melting enthalpy (ΔHb) of the crystal melting point that appears below ° C. ]

The ΔHa and ΔHb were determined by measuring the resin composition using a differential scanning calorimeter (DSC) in a nitrogen atmosphere at a temperature rising rate of 20 ° C./min.
The higher the stereocomplex crystal content (X), the higher the hydrolysis resistance, and the various molded articles obtained by processing the composition also have higher hydrolysis resistance and heat resistance. The stereocomplex crystal content (X) is preferably 85% or more, more preferably 90% or more.

The melting point of the stereocomplex crystal is preferably in the range of 190 to 250 ° C, more preferably in the range of 200 to 230 ° C. The melting enthalpy is preferably 20 J / g or more, more preferably 30 J / g or more.
Specifically, the stereocomplex crystal content (X) is preferably 80% or more, the melting point is in the range of 190 to 250 ° C., and the melting enthalpy is preferably 20 J / g or more.

<Manufacture of molded products>
The molded article of the present invention can be produced in various products by molding, in particular, injection molding the pellets produced by the above-described method to obtain a molded article.
In such 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.

  The molded product of the present invention can also be used in the form of various profile extrusion molded products, sheets, films, etc. by extrusion molding. 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. The molded product of the present invention can also be obtained as a hollow molded product by rotational molding or blow molding.

The molded product according to the present invention has a stereocomplex crystal content (X) represented by the following formula (1) using a melting enthalpy derived from polylactic acid (component B) crystal in the temperature rising process of differential scanning calorimeter (DSC) measurement. ) Is 80% or more.
X (%) = {ΔHb / (ΔHa + ΔHb)} × 100 (1)
[However, in the formula (1), ΔHa and ΔHb are the melting enthalpy (ΔHa) of the crystalline melting point appearing below 190 ° C. and 190 ° C. or more and 250, respectively, in the temperature rising process of the differential scanning calorimeter (DSC). It is the melting enthalpy (ΔHb) of the crystal melting point that appears below ° C. ]

The ΔHa and ΔHb were determined by measuring the resin composition using a differential scanning calorimeter (DSC) in a nitrogen atmosphere at a temperature rising rate of 20 ° C./min.
The higher the stereocomplex crystal content (X), the higher the hydrolysis resistance, and the various molded articles obtained by processing the composition also have higher hydrolysis resistance and heat resistance. The stereocomplex crystal content (X) is preferably 85% or more, more preferably 90% or more.

  The molded article of the present invention is suitable, for example, as an exterior material for office automation equipment and home appliances. For example, personal computers, notebook computers, game machines (home game machines, commercial game machines, pachinko machines, slot machines, etc.), display devices, etc. (CRT, liquid crystal, plasma, projector, organic EL, etc.), mouse, and exterior materials such as printers, copiers, scanners and fax machines (including these multifunction devices), switch keys such as keyboard keys and various switches Is exemplified. 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.

  Further, the molded article of the present invention can be further imparted with other 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) 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.
(2) Crystallization point, 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-11 component>
After adding 97.5 parts by weight of L-lactide (Musashino Chemical Laboratories Co., Ltd.) and 2.5 parts by weight of D-lactide (Musashino Chemical Laboratories Co., Ltd.) to the polymerization tank and replacing the system with nitrogen, stearyl alcohol 0 0.1 part by weight and 0.05 part by weight of tin octylate as a catalyst were added, and polymerization was carried out at 190 ° C. for 2 hours. Thereafter, the remaining lactide was removed by reducing the pressure and chipped to obtain a polylactic acid unit B-11 component.
The resulting polylactic acid unit B-11 component had a weight average molecular weight (Mw) of 16.5 × 10 ⁴ , a crystallization point (Tc) of 117 ° C., and a melting point (Tm) of 158 ° C.

<Production Example 2: Production of polylactic acid unit B-21 component>
After adding 97.5 parts by weight of D-lactide (Musashino Chemical Laboratories Co., Ltd.) and 2.5 parts by weight of L-lactide (Musashino Chemical Laboratories Co., Ltd.) to the polymerization tank and replacing the system with nitrogen, stearyl alcohol 0 0.1 part by weight and 0.05 part by weight of tin octylate as a catalyst were added, and polymerization was carried out at 190 ° C. for 2 hours. Thereafter, the remaining lactide was removed by reducing the pressure, and chipped to obtain a polylactic acid unit B-21 component.
The resulting polylactic acid unit B-21 component had a weight average molecular weight (Mw) of 18.8 × 10 ⁴ , a crystallization point (Tc) of 117 ° C., and a melting point (Tm) of 156 ° C.

<Production Example 3: Production of polylactic acid unit B-12 component>
After adding 100 parts by weight of L-lactide (Musashino Chemical Laboratory Co., Ltd.) to the polymerization tank and replacing the system with nitrogen, 0.005 part by weight of octyltin as a catalyst was added, and polymerization was performed at 180 ° C. for 2 hours. Thereafter, the remaining lactide was removed by reducing the pressure and chipped to obtain a polylactic acid unit B-12 component.
The resulting polylactic acid unit B-12 component had a weight average molecular weight (Mw) of 14.3 × 10 ⁴ , a crystallization point (Tc) of 122 ° C., and a melting point (Tm) of 165 ° C.

<Production Example 4: Production of polylactic acid unit B-22 component>
After adding 100 parts by weight of D-lactide (Musashino Chemical Laboratory Co., Ltd.) to the polymerization tank and replacing the system with nitrogen, 0.005 part by weight of octyltin as a catalyst was added, and polymerization was performed at 180 ° C. for 2 hours. Thereafter, the remaining lactide was removed under reduced pressure, and chipped to obtain a polylactic acid unit B-22 component.
The resulting polylactic acid unit B-22 component had a weight average molecular weight (Mw) of 16.0 × 10 ⁴ , a crystallization point (Tc) of 126 ° C., and a melting point (Tm) of 169 ° C.

<Production Example 5: Production of polylactic acid 1>
50 parts by weight of the polylactic acid unit B-11 component obtained in Production Example 1, 50 parts by weight of the polylactic acid unit B-21 component obtained in Production Example 2, phosphoric acid-2,2′-methylenebis (4,6-di) -Tert-butylphenyl) sodium (Adeka Stub NA-11: manufactured by ADEKA Corporation) 0.3 parts by weight, calcium metasilicate (manufactured by Nacalai Tesque Co., Ltd.) 0.3 parts by weight, trimethyl phosphate (TMP: Daihachi Chemical) Kogyo Co., Ltd.) 0.02 parts by weight, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite (ADK STAB PEP-24G: manufactured by ADEKA) 0.04 parts by weight, and hinder 0.04 part by weight of a phenolic compound (Irganox 1076: manufactured by Ciba Specialty Chemicals) was added to a vent type twin-screw extruder having a diameter of 30 mmφ [Corporation Nippon Steel Works TEX30XSST] was melt-extruded and pelletized at a cylinder temperature of 250 ° C., a screw rotation speed of 150 rpm, a discharge rate of 5 kg / h, and a vent vacuum of 3 kPa to obtain polylactic acid 1.

<Production Example 6: Production of polylactic acid 2>
50 parts by weight of the polylactic acid unit B-12 component obtained in Production Example 3, 50 parts by weight of the polylactic acid unit B-22 component obtained in Production Example 4, phosphoric acid-2,2′-methylenebis (4,6-di) -Tert-butylphenyl) sodium (Adeka Stub NA-11: manufactured by ADEKA Corporation) 0.3 parts by weight, carbodiimide compound (Stabaxol P: manufactured by Rhein Chemie Co., Ltd.) 2.0 parts by weight, trimethyl phosphate (TMP: Daihachi) Chemical Industry Co., Ltd.) 0.02 parts by weight, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite (ADK STAB PEP-24G: ADEKA Co., Ltd.) 0.04 parts by weight, and 0.04 parts by weight of a hindered phenol compound (Irganox 1076: manufactured by Ciba Specialty Chemicals) Type twin screw extruder [TEX30XSST manufactured by Nippon Steel Works, Ltd.], melt extruded at a cylinder temperature of 250 ° C., a screw rotation speed of 250 rpm, a discharge rate of 9 kg / h, and a vent vacuum degree of 3 kPa to be pelletized, and polylactic acid 2 Got.

<Production Example 7: Production of polylactic acid 3>
50 parts by weight of the polylactic acid unit B-12 component obtained in Production Example 3, and 50 parts by weight of the polylactic acid unit B-22 component obtained in Production Example 4, phosphoric acid-2,2′-methylenebis (4,6- Di-tert-butylphenyl) sodium (Adeka Stub NA-11: manufactured by ADEKA Corporation) 0.3 parts by weight, calcium metasilicate (manufactured by Nacalai Tesque) 0.3 parts by weight, carbodiimide compound (carbodilite LA-1: Nisshinbo ( Co., Ltd.) 2.0 parts by weight, trimethyl phosphate (TMP: manufactured by Daihachi Chemical Industry Co., Ltd.) 0.02 parts by weight, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite (Adekastab) PEP-24G: 0.04 parts by weight (manufactured by ADEKA Corporation) and hindered phenolic compounds (Irganox 1076: Ciba Pesha) (Manufactured by Liti Chemicals Co., Ltd.) is supplied to a vent type twin screw extruder [TEX30XSST manufactured by Nippon Steel Works, Ltd.] with a diameter of 30 mmφ, cylinder temperature 250 ° C., screw rotation speed 250 rpm, discharge rate 9 kg / h, Then, it was melt-extruded at a reduced pressure of 3 kPa and pelletized to obtain polylactic acid 3.

<Production Example 8: Production of polylactic acid 4>
50 parts by weight of the polylactic acid unit B-12 component obtained in Production Example 3, and 50 parts by weight of the polylactic acid unit B-22 component obtained in Production Example 4, phosphoric acid-2,2′-methylenebis (4,6- Di-tert-butylphenyl) sodium (Adeka Stub NA-11: manufactured by ADEKA Corporation) 0.1 part by weight, calcium metasilicate (manufactured by Nacalai Tesque) 0.1 part by weight, carbodiimide compound (carbodilite LA-1: Nisshinbo ( Co., Ltd.) 2.0 parts by weight, talc (P-3: Nippon Talc Co., Ltd.) 1.0 part by weight, trimethyl phosphate (TMP: manufactured by Daihachi Chemical Industry Co., Ltd.) 0.02 part by weight, screw (2,4-di-tert-butylphenyl) pentaerythritol diphosphite (ADK STAB PEP-24G: manufactured by ADEKA Corporation) 0.04 parts by weight, and hindered pheno 0.04 parts by weight of a rubber-based compound (Irganox 1076: manufactured by Ciba Specialty Chemicals) was supplied to a vent type twin screw extruder [TEX30XSST manufactured by Nippon Steel Works, Ltd.] with a diameter of 30 mmφ, a cylinder temperature of 270 ° C., and a screw Polylactic acid 4 was obtained by being melt-extruded and pelletized at a rotational speed of 250 rpm, a discharge rate of 9 kg / h, and a vent vacuum of 3 kPa.

<Production Example 9: Production of polylactic acid 5>
50 parts by weight of the polylactic acid unit B-12 component obtained in Production Example 3, and 50 parts by weight of the polylactic acid unit B-22 component obtained in Production Example 4, phosphoric acid-2,2′-methylenebis (4,6- Di-tert-butylphenyl) sodium (ADK STAB NA-11: manufactured by ADEKA Corporation) 0.1 parts by weight, carbodiimide compound (Stabaxol P: manufactured by Rhein Chemie Co., Ltd.) 2.0 parts by weight, talc (P-3: Nippon Talc Co., Ltd.) 1.0 part by weight, trimethyl phosphate (TMP: manufactured by Daihachi Chemical Industry Co., Ltd.) 0.02 part by weight, bis (2,4-di-tert-butylphenyl) pentaerythritol diphos Fight (ADK STAB PEP-24G: manufactured by ADEKA Corporation) 0.04 parts by weight, and hindered phenolic compound (Irganox 1076: Ciba Pesha) (Manufactured by T Chemicals Co., Ltd.) is supplied to a bent type twin screw extruder [TEX30XSST manufactured by Nippon Steel Works, Ltd.] with a diameter of 30 mmφ, a cylinder temperature of 270 ° C., a screw rotation speed of 250 rpm, a discharge rate of 9 kg / h, Then, it was melt-extruded at a reduced pressure of 3 kPa and pelletized to obtain polylactic acid 5.

<Production Example 10: Production of polylactic acid 6>
50 parts by weight of the polylactic acid unit B-12 component obtained in Production Example 3, and 50 parts by weight of the polylactic acid unit B-22 component obtained in Production Example 4, a carbodiimide compound (Stabaxol P: manufactured by Rhein Chemie) 2 0.0 part by weight, talc (P-3: manufactured by Nippon Talc Co., Ltd.) 1.0 part by weight, trimethyl phosphate (TMP: manufactured by Daihachi Chemical Industry Co., Ltd.) 0.03 part by weight, bis (2,4- Di-tert-butylphenyl) pentaerythritol diphosphite (ADK STAB PEP-24G: manufactured by ADEKA Corporation) 0.06 parts by weight, and hindered phenolic compound (Irganox 1076: manufactured by Ciba Specialty Chemicals) 0.06 parts by weight Is supplied to a vent type twin screw extruder [TEX30XSST, manufactured by Nippon Steel Works, Ltd.] with a cylinder temperature of 27 mmφ. ° C., a screw rotation speed of 250 rpm, discharge rate 9 kg / h, and melt-extruded at a vent pressure reduction degree 3kPa pelletized to give polylactic acid 6.

<Production Example 11: Production of polylactic acid 7>
50 parts by weight of the polylactic acid unit B-12 component obtained in Production Example 3, and 50 parts by weight of the polylactic acid unit B-22 component obtained in Production Example 4, phosphoric acid-2,2′-methylenebis (4,6- Di-tert-butylphenyl) sodium (ADK STAB NA-11: manufactured by ADEKA Corporation) 24.0 parts by weight, carbodiimide compound (Stabaxol P: manufactured by Rhein Chemie Co.) 2.0 parts by weight, talc (P-3: Nippon Talc Co., Ltd.) 1.0 part by weight, trimethyl phosphate (TMP: manufactured by Daihachi Chemical Industry Co., Ltd.) 0.02 part by weight, bis (2,4-di-tert-butylphenyl) pentaerythritol diphos Fight (ADK STAB PEP-24G: manufactured by ADEKA Corporation) 0.04 parts by weight, and hindered phenolic compound (Irganox 1076: Ciba Pessi) (Manufactured by Liti Chemicals Co., Ltd.) is supplied to a vent type twin screw extruder [TEX30XSST manufactured by Nippon Steel Works, Ltd.] with a diameter of 30 mmφ, cylinder temperature 270 ° C., screw rotation speed 250 rpm, discharge rate 9 kg / h, And it was melt-extruded at a reduced pressure of 3 kPa and pelletized to obtain polylactic acid 7.

  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) Stereocomplex crystal content (X): Resin composition pellets were measured using a DSC in a nitrogen atmosphere at a heating rate of 20 ° C./min, and the melting enthalpy (ΔHa) of the crystal melting point appearing at less than 190 ° C. ) And the melting enthalpy (ΔHb) of the crystal melting point appearing at 190 ° C. or higher and lower than 250 ° C.
X (%) = {ΔHb / (ΔHa + ΔHb)} × 100
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.

(2) Stereocomplex crystal content (X): A crystal that appears at a temperature of less than 190 ° C. by measuring a test piece for measuring bending strength in accordance with ISO 178 using a DSC in a nitrogen atmosphere at a heating rate of 20 ° C./min. From the melting enthalpy (ΔHa) of the melting point and the melting enthalpy (ΔHb) of the crystalline melting point appearing at 190 ° C. or higher and lower than 250 ° C., the calculation was performed by the following formula.
X (%) = {ΔHb / (ΔHa + ΔHb)} × 100

(3) Flexural modulus: The flexural strength 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 under the conditions of loads of 0.45 MPa and 1.80 MPa in accordance with ISO75-1 and 2.

(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 flame retardant).

(6) Hydrolysis resistance: Retention rate of the molecular weight of the aromatic polycarbonate after the bending test piece was treated with a pressure cooker tester at 120 ° C. × 100% relative humidity for 8 hours with respect to the value before the treatment. It was evaluated with.

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: 2,2′-methylenebis (4,6-di-tert-butylphenyl) phosphate phosphate (manufactured by ADEKA: ADK STAB NA-11)
(D component)
D-1: Calcium metasilicate (manufactured by Nacalai Tesque)
(E component)
E-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)
E-2: Talc (Made by Hayashi Kasei Co., Ltd .: HST-0.8)
(F component)
F-1: Carbodiimide compound (Nisshinbo Co., Ltd .: Carbodilite LA-1)
F-2: Carbodiimide compound (Rhein Chemie Co., Ltd .: Stabaxol P)
(Other ingredients)
(Other crystal nucleating agents)
G-1: Talc (Nippon Talc Co., Ltd. product: P-3, average particle diameter of 3 μm)
(Stabilizer)
H-1: Trimethyl phosphate (manufactured by Daihachi Chemical Industry Co., Ltd .: TMP)
H-2: Bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite (manufactured by ADEKA: ADK STAB PEP-24G)
H-3: Hindered phenol-based compound (manufactured by Ciba Specialty Chemicals: Irganox 1076)
(Flame retardants)
I-1: Phosphate ester flame retardant (manufactured by Daihachi Chemical Industry Co., Ltd .: PX-200)
I-2: Polytetrafluoroethylene having a fibril forming ability (manufactured by Daikin Industries, Ltd .: Polyflon MPA FA-500)
I-3: Brominated flame retardant (manufactured by Teijin Chemicals Ltd .: Fireguard 7000)
I-4: Antimony trioxide (Nippon Seiko Co., Ltd .: PATOX-M)
In each of the examples and comparative examples, the injection molding pellets were manufactured as follows.

<Examples 1-3>
After the aromatic polycarbonate resin, polylactic acid, phosphoric acid ester metal salt, triclinic inorganic nucleating agent, end-blocking agent, and stabilizer were uniformly premixed with a tumbler in the composition shown in Table 1, This preliminary mixture is supplied from the first supply port of a vent type twin screw extruder [TEX30XSST manufactured by Nippon Steel Works, Ltd.] having a diameter of 30 mmφ, cylinder temperature 250 ° C., screw rotation speed 150 rpm, discharge rate 20 kg / h, and vent. It was melt extruded at a reduced pressure of 3 kPa and pelletized.

<Examples 4 to 14>
Polylactic acid 1 to 5 produced in Production Examples 5 to 9, aromatic polycarbonate resin, terminal blocking agent, C component, crystal nucleating agent other than D component, and stabilizer, all components in composition shown in Table 1, tumbler Then, the preliminary mixture is supplied from the first supply port of a vent type twin screw extruder [TEX30XSST manufactured by Nippon Steel Works, Ltd.] having a diameter of 30 mmφ, the cylinder temperature is 250 ° C., and the screw rotation speed is 150 rpm. The mixture was melt-extruded and pelletized at a discharge rate of 20 kg / h and a vent vacuum of 3 kPa. Here, the numbers in parentheses in Table 1 are parts by weight of each component already contained in the polylactic acids 1 to 5 produced in Production Examples 5 to 9, and the numbers outside the parentheses are the resin composition of each component. It represents parts by weight in the product.

<Comparative Examples 1 and 3>
Aromatic polycarbonate resin, polylactic acid, end-capping agent, C component, crystal nucleating agent other than D component, and stabilizer are preliminarily mixed in a tumbler with the composition shown in Table 1, and then the spare The mixture is supplied from the first supply port of a vent type twin screw extruder [TEX30XSST manufactured by Nippon Steel Works, Ltd.] having a diameter of 30 mmφ, cylinder temperature 250 ° C., screw rotation speed 150 rpm, discharge rate 20 kg / h, and vent pressure reduction degree. It was melt extruded at 3 kPa and pelletized.

<Comparative Examples 2 and 4>
Polylactic acid 6, polylactic acid 7, aromatic polycarbonate resin and stabilizers prepared in Production Examples 10 and 11 were uniformly premixed with a tumbler with the composition shown in Table 1, and then the premixed mixture was 30 mm in diameter. Supplied from the first supply port of a vent type twin screw extruder [TEX30XSST manufactured by Nippon Steel Works, Ltd.], and melt extruded at a cylinder temperature of 250 ° C., a screw rotation speed of 150 rpm, a discharge rate of 20 kg / h, and a vent pressure reduction degree of 3 kPa. And pelletized. Here, the numbers in parentheses in Table 1 are the parts by weight of each component already contained in polylactic acid 6 and polylactic acid 7 produced in Production Examples 10 and 11, and the numbers outside the parentheses are the numbers of each component. It represents parts by weight in the resin composition.

<Example 15-28>
Polylactic acid 2-5, aromatic polycarbonate resin, inorganic filler, stabilizer, and flame retardant produced in Production Examples 6 to 9 having the composition shown in Table 1 and a vent type twin screw extruder having a diameter of 30 mmφ [( Nippon Steel Works TEX30XSST] was melt-extruded and pelletized at a cylinder temperature of 250 ° C., a screw rotation speed of 150 rpm, a discharge rate of 20 kg / h, and a vent vacuum of 3 kPa. Here, the numbers in parentheses in Table 1 are the parts by weight of each component already contained in the polylactic acids 2 to 5 produced in Production Examples 6 to 9, and the numbers outside the parentheses are the resin composition of each component. It represents parts by weight in the product. In addition, supply of the composition for extrusion to the extruder is performed by supplying only the E-1 component of the inorganic filler from the second supply port using a side feeder, and the remaining components are all premixed with a tumbler. It supplied from the supply port. In addition, the flame retardant I-2 component (polytetrafluoroethylene having fibril-forming ability) is uniformly mixed in advance at a concentration of 2.5% by weight in the aromatic polycarbonate resin A-1, and the mixture is supplied to the tumbler. did.

<Comparative Examples 5-7>
Polylactic acid, aromatic polycarbonate resin, inorganic filler, end-capping agent, C component, crystal nucleating agent other than D component, and stabilizer having the composition shown in Table 1 and a vent type twin screw extruder having a diameter of 30 mmφ [ Nippon Steel Works TEX30XSST] was melt-extruded and pelletized at a cylinder temperature of 250 ° C., a screw rotation speed of 150 rpm, a discharge rate of 20 kg / h, and a vent vacuum of 3 kPa. As for the supply of the composition for extrusion to the extruder, the E-1 component of the inorganic filler is supplied from the second supply port using a side feeder, and the remaining components are all premixed with a tumbler in the first supply port. Sourced from.

In the production examples 5 to 11 and all the examples and comparative examples, the screw configuration of the twin screw extruder is the first stage kneading zone (feed kneading disk × 2, feed kneading disk before the side feeder position). Rotor x1, return rotor x1 and return kneading disk x1) are composed of the second stage kneading zone (feed rotor x1 and return rotor x1) after the side feeder position Was provided).
About the obtained resin composition pellet, stereocomplex crystal content X (%) was calculated | required.

  Subsequently, the obtained pellets were dried with a hot air circulation dryer at 100 ° C. for 5 hours. After drying, with an injection molding machine (Toshiba Machine Co., Ltd .: IS-150EN), the cylinder temperature is 240 ° C, the mold temperature is 120 ° C, and the stereocomplex crystal content, flexural modulus, deflection temperature under load, and combustion in 120 seconds molding cycle. Specimens for evaluation of resistance and hydrolysis resistance were molded. In Comparative Example 1 and Comparative Example 5, the molded product was insufficiently solidified at a mold temperature of 120 ° C. and could not be molded. Therefore, the test was performed at a mold temperature of 40 ° C. and a molding cycle of 60 seconds. A piece was molded. Tables 1 and 2 show the results of measuring the characteristics using these molded products.

  As is apparent from the results of Tables 1 and 2, a composition obtained from an aromatic polycarbonate resin and a composition comprising a polylactic acid component mainly composed of L-lactic acid units and a polylactic acid component mainly composed of D-lactic acid units is It can be seen that the inclusion of a phosphoric acid ester metal salt and / or a triclinic inorganic nucleating agent makes it easier for the polylactic acid component to form a stereocomplex crystal. In addition, a composition containing such a phosphoric ester metal salt or a triclinic inorganic nucleating agent can give a molded product having a high stereocomplex crystal content, exhibiting high heat resistance and excellent hydrolysis resistance. I understand. Also, a composition produced by a production method in which a polylactic acid component mainly composed of L-lactic acid units and a polylactic acid component mainly composed of D-lactic acid units is mixed in advance before mixing with an aromatic polycarbonate resin is used. By doing this, it is understood that a molded product having a higher stereo complex crystal content is obtained, and as a result, the heat resistance and hydrolysis resistance of the molded product are further increased. In addition, it can be seen that the inclusion of the inorganic filler enables the high-melting-point stereocomplex crystals to be connected to each other, and further improves the heat resistance as well as the mechanical properties. Moreover, it turns out that the flame retardance by containing a flame retardant and the further improvement of the hydrolysis resistance by containing a terminal blocker are also acquired.

Claims (13)

(C) Phosphoric acid ester metal salt with respect to 100 parts by weight of resin component consisting of 95 to 5% by weight of (A) aromatic polycarbonate resin (A component) and (B) 5 to 95% by weight of polylactic acid resin (B component) 0.001 to 10 parts by weight of at least one compound selected from the group consisting of (C component) and (D) triclinic inorganic nucleating agent (D component), and represented by the following formula (1) A molded article comprising an aromatic polycarbonate resin composition, wherein the stereocomplex crystal content (X) is 80% or more.
X (%) = {ΔHb / (ΔHa + ΔHb)} × 100 (1)
[However, in the formula (1), ΔHa and ΔHb are the melting enthalpy (ΔHa) of the crystalline melting point appearing below 190 ° C. and 190 ° C. or more and 250, respectively, in the temperature rising process of the differential scanning calorimeter (DSC). It is the melting enthalpy (ΔHb) of the crystal melting point that appears below ° C. ]   The polylactic acid resin (component B) is (B-1) a polylactic acid resin (component B-1) mainly composed of L-lactic acid, and (B-2) a polylactic acid resin mainly composed of D-lactic acid ( The molded article according to claim 1, wherein the weight ratio of the B-1 component to the B-2 component (B-1 component / B-2 component) is 10/90 to 90/10.   The molded article according to claim 1 or 2, wherein the polylactic acid resin (component B) has a weight average molecular weight of 120,000 or more. The molded article according to any one of claims 1 to 3, wherein the phosphoric acid ester metal salt (component C) is a compound represented by formula (1) or formula (2).

Wherein R ₁ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ₂ and R ₃ each independently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and M ₁ represents an alkali metal atom. Represents an alkaline earth metal atom, a zinc atom or an aluminum atom, p represents 1 or 2, q represents 0 when M ₁ is an alkali metal atom, an alkaline earth metal atom or a zinc atom; Time represents 1 or 2.)

(Wherein R ₄ , R ₅ and R ₆ each independently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and M ₂ represents an alkali metal atom, an alkaline earth metal atom, a zinc atom or an aluminum atom. P represents 1 or 2, and q represents 0 when M ₂ is an alkali metal atom, alkaline earth metal atom or zinc atom, and 1 or 2 when M ₂ is an aluminum atom.)   The molded article according to any one of claims 1 to 4, wherein the phosphate ester metal salt (component C) is sodium 2,2'-methylenebis (4,6-di-tert-butylphenyl) phosphate.   The molded article according to any one of claims 1 to 5, wherein an average particle diameter of the phosphoric acid ester metal salt (component C) is 0.01 µm or more and less than 10 µm.   The molded article according to any one of claims 1 to 6, wherein the triclinic inorganic nucleating agent (component D) is calcium metasilicate.   The molded article according to any one of claims 1 to 7, wherein the triclinic inorganic nucleating agent has an average particle size of 0.1 µm or more and less than 10 µm.   (E) The inorganic filler (E component) comprises 0.3 to 200 parts by weight per 100 parts by weight in total of the aromatic polycarbonate resin (A component) and the polylactic acid resin (B component). The molded article in any one of -8.   The molded article according to any one of claims 1 to 9, wherein (F) the terminal blocking agent (F component) comprises 0.01 to 5 parts by weight per 100 parts by weight of the polylactic acid resin (B component). Before mixing with the aromatic polycarbonate resin (component A), (B-1) a polylactic acid resin (B-1 component) mainly composed of L-lactic acid, (B-2) mainly composed of D-lactic acid By heat-treating in advance at least one compound selected from the group consisting of polylactic acid resin (component B-2), (C) phosphate ester metal salt (component C) and (D) triclinic inorganic nucleating agent A polycarbonate resin composition produced by a production method comprising mixing, wherein the aromatic polycarbonate resin composition comprises (A) an aromatic polycarbonate resin (component A) 95 to 5% by weight and (B) polylactic acid 100 parts by weight of resin component (component B) of 5 to 95% by weight is composed of (C) phosphoric acid ester metal salt (component C) and (D) triclinic inorganic nucleating agent (component D). 0.001 to 10 parts by weight of at least one compound selected from the group is contained, and the stereocomplex crystal content (X) represented by the following formula (1) is 80% or more. The molded article according to any one of claims 1 to 10, which is an aromatic polycarbonate resin composition.
X (%) = {ΔHb / (ΔHa + ΔHb)} × 100 (1)
[However, in the formula (1), ΔHa and ΔHb are the melting enthalpy (ΔHa) of the crystalline melting point appearing below 190 ° C. and 190 ° C. or more and 250, respectively, in the temperature rising process of the differential scanning calorimeter (DSC). It is the melting enthalpy (ΔHb) of the crystal melting point that appears below ° C. ] The molded article according to any one of claims 1 to 11, wherein the stereocomplex crystal content (X) represented by the following formula (1) is 80% or more.
X (%) = {ΔHb / (ΔHa + ΔHb)} × 100 (1)
[However, in the formula (1), ΔHa and ΔHb are the melting enthalpy (ΔHa) of the crystalline melting point appearing below 190 ° C. and 190 ° C. or more and 250, respectively, in the temperature rising process of the differential scanning calorimeter (DSC). It is the melting enthalpy (ΔHb) of the crystal melting point that appears below ° C. ]   The molded article according to any one of claims 1 to 12, wherein the molded article is a molded article obtained by injection molding.