JP6193724B2 - Polylactic acid resin composition and molded article - Google Patents

Description

  The present invention provides a resin composition and a molded article that contain polylactic acid, an aromatic polycarbonate, and a fibrous filler, have high rigidity and high strength, and have reduced anisotropy in molding shrinkage. Regarding technology.

  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. In particular, polylactic acid has relatively high heat resistance and mechanical properties among biomass plastics, so its use is expanding to tableware, packaging materials, sundries, etc. It has become.

  On the other hand, high rigidity and strength can be obtained by reinforcing thermoplastic resins such as polylactic acid with fibrous fillers such as glass fibers and carbon fibers. In light of various uses such as leisure, conventional metals are being replaced by lighter resins.

  Patent Document 1 discloses a composition containing carbon fiber relative to polylactic acid. Since polylactic acid is a crystalline resin, when a fibrous filler is added, the heat resistance is increased to near the melting point due to its reinforcing effect, and since the resin viscosity at the time of melting is low, the fibrous filler is less bent, It is characterized by high mechanical properties such as rigidity and strength. On the other hand, since the shrinkage due to crystallization is large, for example, in the case of injection molding, the direction parallel to the resin flow and the resin are influenced by the influence of the fibrous filler oriented along the resin flow direction due to the strong shear at the time of injection. The difference (anisotropy) in molding shrinkage in the direction perpendicular to the flow becomes large. For this reason, since the warpage of the molded product is induced and it is difficult to obtain dimensional accuracy, it is difficult to apply in applications where dimensional accuracy is required.

  Patent Documents 2 and 3 disclose resin compositions containing an inorganic filler such as glass fiber with respect to polylactic acid and aromatic polycarbonate. However, there is no indication of the molecular weight of polylactic acid, the molecular weight of aromatic polycarbonate, and the melt viscosity ratio of polylactic acid and aromatic polycarbonate, which are effective for reducing the mold shrinkage while maintaining mechanical properties such as rigidity and strength. It has not been.

JP 2006-137799 A JP 2008-156616 A JP 2008-255214 A

  An object of the present invention is to suppress anisotropy of molding shrinkage while maintaining excellent mechanical properties such as high rigidity and high strength in a polylactic acid resin composition reinforced with a fibrous filler.

  As a result of intensive research aimed at achieving the above object, the present inventors have included polylactic acid having a specific molecular weight range, aromatic polycarbonate having a specific molecular weight range, and a fibrous filler in order to solve the above problems. When the ratio between the melt viscosity of polylactic acid and the melt viscosity of aromatic polycarbonate is within a specific range, surprisingly, the anisotropy of molding shrinkage is remarkable while maintaining the high rigidity and high strength of polylactic acid. It has been found that the above problems can be solved.

That is, (A) 95 to 50% by weight of polylactic acid (component A) having a weight average molecular weight of 100,000 to 200,000 and (B) aromatic polycarbonate (component B) 5 having a viscosity average molecular weight of 10,000 to 19,000 100% by weight of a resin component consisting of ˜50% by weight and having a ratio of the melt viscosity of the A component to the melt viscosity of the B component measured by a high shear measuring machine represented by the following formula (1) is 0.1 or more A resin composition containing 10 to 110 parts by weight of (C) fibrous filler (C component) is provided with respect to parts.
Ratio of melt viscosity of component A to melt viscosity of component B = ηA / ηB (1)
[However, in the formula (1), ηA and ηB represent the melt viscosity of the A component and the melt viscosity of the B component, respectively, measured at 250 ° C. and 250 sec ⁻¹ using a high shear measuring machine. ]
Furthermore, 0.01-10 weight part of (D) carbodiimide compound (D component) can be included with respect to a total of 100 weight part of A component and B component.

  Since the present invention is a composition and a molded article having high rigidity and high strength, and anisotropy of molding shrinkage rate is suppressed, rigidity and strength are required, and a large size that easily induces warping due to fiber orientation. It is suitable for injection molded products and thin injection molded products that require strict dimensional accuracy. For example, it can be applied to injection molding products such as exterior materials for OA equipment, optical boxes, notebook computer housings, smartphones, tablet terminals, and camera barrels. Furthermore, the molded article of the present invention is useful for a wide variety of other applications, and is also suitable for sports and leisure applications such as reel exterior materials and bicycle frames. Furthermore, vehicle parts such as a steering wheel, a core material of a doorknob, and a wheel material of a tire can be cited.

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

<About component A>
As the polylactic acid used as the component A in the present invention, any of poly L-lactic acid mainly composed of L-lactic acid units, poly D-lactic acid mainly composed of D-lactic acid units, or a mixture thereof may be used.
The poly L-lactic acid (A-1 component) and poly D-lactic acid (A-2 component) of the present invention are substantially composed of an L-lactic acid unit or a D-lactic acid unit represented by the formula (1).

  The optical purity of poly L-lactic acid or poly D-lactic acid used in the present invention is preferably 90 to 100 mol%. If the optical purity is lower than this, the crystallinity and melting point of polylactic acid are lowered, and it is difficult to obtain high heat resistance. Therefore, the melting point of poly L-lactic acid or poly D-lactic acid is preferably 160 ° C. or higher, more preferably 170 ° C. or higher, and most preferably 175 ° C. or higher. In this respect, the optical purity of lactic acid and lactide of the polymer raw material is preferably 96 to 100 mol%, more preferably 97.5 to 100 mol%, still more preferably 98.5 to 100 mol%, and particularly preferably 99 to 100 mol%. A range of 100 mol% is selected.

  Examples of the copolymer unit include D-lactic acid units for poly L-lactic acid, L-lactic acid units for poly D-lactic acid, and units other than lactic acid units. The copolymerization ratio of copolymer units other than lactic acid units is preferably 10 mol% or less, more preferably 5 mol% or less, still more preferably 2 mol% or less, and most preferably 1 mol% or less.

  As copolymerized units, units derived from dicarboxylic acids, polyhydric alcohols, hydroxycarboxylic acids, lactones and the like having functional groups capable of forming two or more ester bonds, various polyesters composed of these various constituents, various polyethers, Examples are derived from various polycarbonates and the like.

  Examples of the dicarboxylic acid include succinic acid, adipic acid, azelaic acid, sebacic acid, terephthalic acid, and isophthalic acid. Polyhydric alcohols include ethylene glycol, 1,3-propanediol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, glycerin, sorbitan, neopentyl glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polytrimethylene Examples thereof include aliphatic polyhydric alcohols such as glycol and polypropylene glycol, and aromatic polyhydric alcohols obtained by adding ethylene oxide to bisphenol. Examples of the hydroxycarboxylic acid include glycolic acid and hydroxybutyric acid. Examples of the lactone include glycolide, ε-caprolactone, β-propiolactone, δ-butyrolactone, β- or γ-butyrolactone, pivalolactone, and δ-valerolactone.

Poly L-lactic acid and poly D-lactic acid can be produced by a conventionally known method, such as a melt ring-opening polymerization method of L-lactide or D-lactide, a solid-phase polymerization method of low molecular weight polylactic acid, Examples thereof include a direct polymerization method in which lactic acid is subjected to dehydration condensation. The polymerization reaction can be carried out in a conventionally known reaction apparatus. For example, a vertical reactor or a horizontal reactor equipped with a high-viscosity stirring blade such as a helical ribbon blade can be used alone or in parallel. Moreover, any of a batch type, a continuous type, a semibatch type may be sufficient, and these may be combined. In the solid-state polymerization method, it is preferable to crystallize the prepolymer in advance from the viewpoint of preventing fusion of pellets and production efficiency, and the container itself rotates like a fixed vertical or horizontal reaction vessel, or a tumbler or kiln. In a reaction vessel (such as a rotary kiln), the polymerization is carried out at a constant temperature in the temperature range from the glass transition temperature of the prepolymer to less than the melting point, or gradually with the progress of the polymerization. For the purpose of efficiently removing generated water, a method of reducing the pressure inside the reaction vessels or circulating a heated inert gas stream is also preferably used. For melt ring-opening polymerization of lactide, it is preferable to apply a metal-containing catalyst from the viewpoint of production efficiency and polymer quality. From the viewpoint of catalytic activity and side reaction, a catalyst containing tin, preferably a II-valent catalyst, is preferable. Tin compounds, specifically diethoxytin, dinonyloxytin, tin myristate, tin octylate, tin stearate and the like, among others, tin octylate is exemplified as a particularly preferable agent whose safety has been confirmed by FDA. The amount of the catalyst used is preferably 0.1 × 10 ⁻⁴ to 50 × 10 ⁻⁴ mol per kg of lactide, and further considering the reactivity, color tone and stability of the resulting polylactide, 1 × 10 ⁻⁴ to 30 × 10 ⁻⁴ mol is more preferable, and 2 × 10 ⁻⁴ to 15 × 10 ⁻⁴ mol is particularly preferable. Alcohol may be used as a polymerization initiator. Such alcohol is preferably non-volatile without inhibiting the polymerization of polylactic acid. For example, decanol, dodecanol, tetradecanol, hexadecanol, octadecanol and the like can be suitably used. The metal-containing catalyst used at the time of polymerization is preferably deactivated with a conventionally known deactivator prior to use. The deactivator is not particularly limited as long as it is a deactivator generally used as a deactivator for a polymerization catalyst of a polyester resin, but a phosphono fatty acid ester represented by the following general formula (2) is preferable.

In the formula, R _{11 to} R ₁₃ are each independently an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms. Examples of the alkenyl group include an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. Examples of the aryl group include a phenyl group and a naphthalenyl group. R _{11 to} R ₁₃ may be the same or different from each other. N ³¹ is an integer of 1 to 3. As the compound represented by the formula (2), ethyl diethylphosphonoacetate, ethyl di-n-propylphosphonoacetate, ethyl di-n-butylphosphonoacetate, ethyl di-n-hexylphosphonoacetate, di-n-octyl Ethyl phosphonoacetate, ethyl di-n-decylphosphonoacetate, ethyl di-n-dodecylphosphonoacetate, ethyl di-n-octadecylphosphonoacetate, ethyl diphenylphosphonoacetate, decyl diethylphosphonoacetate, dodecyl diethylphosphonoacetate , Octadecyl diethylphosphonoacetate, ethyl diethylphosphonopropionate, ethyl di-n-propylphosphonopropionate, ethyl di-n-butylphosphonopropionate, ethyl di-n-hexylphosphonopropionate, di-n -Ethyl octylphosphonopropionate, di-n-decylphosphono Ethyl lopionate, ethyl di-n-dodecylphosphonopropionate, ethyl di-n-octadecylphosphonopropionate, ethyl diphenylphosphonopropionate, decyl diethylphosphonopropionate, dodecyl diethylphosphonopropionate, diethylphosphono Octadecyl propionate, ethyl diethylphosphonobutyrate, ethyl di-n-propylphosphonobutyrate, ethyl di-n-butylphosphonobutyrate, ethyl di-n-hexylphosphonobutyrate, ethyl di-n-octylphosphonobutyrate, di- Ethyl n-decylphosphonobutyrate, ethyl di-n-dodecylphosphonobutyrate, ethyl di-n-octadecylphosphonobutyrate, ethyl diphenylphosphonobutyrate, decyl diethylphosphonobutyrate, dodecyl diethylphosphonobutyrate, octadecyl diethylphosphonobutyrate And the like. In view of efficacy and ease of handling, ethyl diethylphosphonoacetate, ethyl di-n-propylphosphonoacetate, ethyl di-n-butylphosphonoacetate, ethyl di-n-hexylphosphonoacetate, decyl diethylphosphonoacetate, Diethylphosphonoacetic acid octadecyl is preferred. In the formula (2), when the carbon number of R _{11 to} R ₁₃ is 20 or less, the melting point thereof is lower than the production temperature of polylactic acid or the composition, so that the mixture is sufficiently melt-mixed, and the metal polymerization catalyst is efficiently used. Can be supplemented. The phosphono fatty acid ester has an aliphatic hydrocarbon group between the phosphonic acid diester moiety and the carboxylic acid ester moiety. If n ³¹ is an integer of 1 to 3, it is possible to effectively supplement the metal polymerization catalyst of polylactic acid.

  The content of the phosphono fatty acid ester is preferably 0.001 to 0.5 parts by weight, more preferably 0.02 to 0.2 parts by weight with respect to 100 parts by weight of polylactic acid. If the content of the phosphono fatty acid ester is too small, the deactivation efficiency of the remaining metal polymerization catalyst is extremely poor, and a sufficient effect cannot be obtained. On the other hand, when the amount is too large, contamination of the mold used at the time of molding processing becomes significant. The polymerization deactivator is preferably added at the end of the polymerization, but can be optionally added in each process of extrusion and molding as necessary.

  When a mixture of poly L-lactic acid (A-1 component) and poly D-lactic acid (A-2 component) is used, the weight ratio (A-1 component / A-2 component) is 10:90 to 90:10. It is preferable to contain in the range. Furthermore, a phosphoric acid ester metal salt represented by the formula (3) and / or (4) is added to a poly L-lactic acid (A-1 component) and poly D-lactic acid (A-2 component) mixture. -By including in a range of preferably 0.01 to 2.0 parts by weight per 100 parts by weight of the total of lactic acid (component A-1) and poly D-lactic acid (component A-2), a highly stereocomplex crystal can be obtained. Since the formed polylactic acid can be obtained, it is preferable. If the phosphate metal salt is less than 0.01 parts by weight, there may be no effect on the formation of stereocomplex crystals and improvement in crystallinity. Decomposition of lactic acid component and generation of foreign matter may be caused. From this viewpoint, the application amount of the phosphate ester metal salt is more preferably selected in the range of 0.02 to 1.0 part by weight, and more preferably 0.03 to 1.0 part by weight.

(Wherein _{R 14} is a hydrogen atom or an alkyl group having 1 to 4 carbon _atoms, the R _15, R _{16, R 17} each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms,,, _{M 1} Represents an alkali metal atom, alkaline earth metal atom, zinc atom or aluminum atom, p ³² is 1 or 2, q ³² is 0 when M ₁ is an alkali metal atom, alkaline earth metal atom or zinc atom. In the case of an aluminum atom, 1 or 2 is represented.)

(Wherein _{R 18, R 19} each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms,, _{M 2} represents an alkali metal atom, an alkaline earth metal atom, zinc atom or aluminum ^{atom, p 33} Represents 1 or 2, and q ³³ 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 polylactic acid thus produced becomes a stereocomplex polylactic acid in which a stereocomplex crystal is highly formed, and is expressed by the following formula (2) using the melting enthalpy derived from the polylactic acid crystal in the temperature rising process of the differential scanning calorimeter (DSC) measurement. It is preferable that the stereocomplex crystallinity represented by
Stereocomplex crystallinity = [ΔHms / (ΔHms + ΔHmh)] × 100 (2)
[In the formula (2), ΔHmh and ΔHms are the melting enthalpy (ΔHmh) of the melting point of the crystal that appears below 190 ° C. in the temperature rising process of the differential scanning calorimeter (DSC), respectively, and 190 ° C. or more and 250 It is the melting enthalpy (ΔHms) of the crystalline melting point that appears below ° C. ]

The ΔHmh and ΔHms were determined by measuring the resin composition using a differential scanning calorimeter (DSC) in a nitrogen atmosphere at a heating rate of 20 ° C./min.
The higher the stereocomplex crystallinity, the higher the moldability and heat resistance, and the stereocomplex crystallinity is more preferably 85% or more, and even more preferably 90% or more. If the stereocomplex crystallinity is lower than 80%, the characteristics of homopolylactic acid crystals derived from poly-L-lactic acid or poly-D-lactic acid appear, resulting in insufficient heat resistance.

The melting point of stereocomplex polylactic acid is preferably 200 ° C. or higher, more preferably 205 ° C. or higher, and still more preferably 210 ° C. or higher. If the melting point of stereocomplex polylactic acid is lower than 200 ° C., the heat resistance is insufficient due to its crystallinity and low melting point.
The melting enthalpy is preferably 20 J / g or more, more preferably 30 J / g or more. When the melting enthalpy is lower than 20 J / g, the crystallinity is low and the heat resistance is insufficient.
Specifically, it is preferable that the stereocomplex crystallinity is 80% or more, the melting point is 200 ° C. or more, and the melting enthalpy is 20 J / g or more.

  The polylactic acid used in the present invention has a weight average molecular weight of 100,000 to 200,000, preferably 120,000 to 190,000, and more preferably 130,000 to 180,000. When the weight average molecular weight is less than 100,000, the polylactic acid is rapidly embrittled, so that strength cannot be obtained even if the fiber is reinforced. On the other hand, if the weight average molecular weight exceeds 200,000, the melt viscosity is too high, so that the fibers of the fibrous filler break, and sufficient rigidity and strength cannot be obtained.

<About B component>
The aromatic polycarbonate (component B) used in the present invention is obtained by reacting a dihydric phenol and a carbonate precursor. Examples of the reaction method include an interfacial polymerization method, a melt transesterification method, a solid phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound.

  Representative examples of the dihydric phenol used here include hydroquinone, resorcinol, 4,4′-biphenol, 1,1-bis (4-hydroxyphenyl) ethane, and 2,2-bis (4-hydroxyphenyl). ) Propane (commonly called 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-phenylenediisopropyl Pyridene) diphenol, 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, bis (4-hydroxy-3-methylphenyl) sulfide, 9,9-bis (4-hydroxyphenyl) Examples include fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene. A preferred dihydric phenol is bis (4-hydroxyphenyl) alkane, and bisphenol A is particularly preferred from the viewpoint of excellent toughness and deformation characteristics, and is widely used.

  In the present invention, besides the bisphenol A-based polycarbonate, which is a general-purpose polycarbonate, a special polycarbonate produced using other dihydric phenols can be used as the B 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 B constituting the resin composition is the following (1) to (3) copolymer polycarbonate. is there.
(1) In 100 mol% of the dihydric phenol component constituting the polycarbonate, the BPM component is 20 to 80 mol% (more preferably 40 to 75 mol%, more preferably 45 to 65 mol%), and A copolymeric polycarbonate in which the BCF component is 20 to 80 mol% (more preferably 25 to 60 mol%, more preferably 35 to 55 mol%).
(2) In 100 mol% of the dihydric phenol component constituting the polycarbonate, the BPA component is 10 to 95 mol% (more preferably 50 to 90 mol%, more preferably 60 to 85 mol%), and A copolymeric polycarbonate in which the BCF component is 5 to 90 mol% (more preferably 10 to 50 mol%, more preferably 15 to 40 mol%).
(3) In 100 mol% of the dihydric phenol component constituting the polycarbonate, the BPM component is 20 to 80 mol% (more preferably 40 to 75 mol%, more preferably 45 to 65 mol%), and Copolymer polycarbonate in which the Bis-TMC component 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 method 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, etc. 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%, preferably 0.06 to 0.13% and Tg of 120 to 180 ° C, or (ii) Tg of 160 to 250 ° C, Polycarbonate which is preferably 170 to 230 ° C. and has a water absorption of 0.10 to 0.30%, preferably 0.13 to 0.30%, more preferably 0.14 to 0.27%.

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.
As the carbonate precursor, carbonyl halide, carbonic acid diester, haloformate or the like is used, and specific examples include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, and the like.

  In producing polycarbonate by the interfacial polymerization method using the above dihydric phenol and carbonate precursor, a catalyst, a terminal terminator, an antioxidant to prevent the dihydric phenol from oxidizing, etc. are used as necessary. May be. The polycarbonate of the present invention is a branched polycarbonate obtained by copolymerization of a trifunctional or higher polyfunctional aromatic compound, a polyester carbonate obtained by copolymerization of an aromatic or aliphatic (including alicyclic) difunctional carboxylic acid, a bifunctional Copolymer polycarbonate obtained by copolymerizing a functional alcohol (including alicyclic), and polyester carbonate obtained by copolymerizing such a bifunctional carboxylic acid and a bifunctional alcohol together. Moreover, the mixture which mixed 2 or more types of the obtained polycarbonate may be sufficient.

  The branched polycarbonate increases the melt tension of the resin composition of the present invention, and can improve the molding processability in extrusion molding, foam molding and blow molding based on such properties. As a result, a molded product by these molding methods, which is superior in dimensional accuracy, is obtained.

  Examples of the trifunctional or higher polyfunctional aromatic compound used in the branched polycarbonate include 4,6-dimethyl-2,4,6-tris (4-hydroxydiphenyl) heptene-2, 2,4,6-trimethyl. -2,4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1, 1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, and 4- {4- [1,1-bis Preferred examples include trisphenol such as (4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol. Other polyfunctional aromatic compounds include phloroglucin, phloroglucid, tetra (4-hydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene. And trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, and acid chlorides thereof. Of these, 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are preferable, and 1,1,1-tris (4- Hydroxyphenyl) ethane is preferred.

  The structural unit derived from the polyfunctional aromatic compound in the branched polycarbonate is preferably a total of 100 mol% of the structural unit derived from the dihydric phenol and the structural unit derived from the polyfunctional aromatic compound. It is 0.03-1 mol%, More preferably, it is 0.07-0.7 mol%, Most preferably, it is 0.1-0.4 mol%.

Further, such a branched structural unit is not only derived from a polyfunctional aromatic compound but also derived without using a polyfunctional aromatic compound, such as a side reaction during a melt transesterification reaction. Also good. The ratio of such a branched structure can be calculated by ¹ H-NMR measurement.

  In addition, the aromatic polycarbonate serving as the component B in the resin composition of the present invention is a polyester carbonate obtained by copolymerizing an aromatic or aliphatic (including alicyclic) bifunctional carboxylic acid, or a bifunctional alcohol (alicyclic). And a polyester carbonate obtained by copolymerizing such a difunctional carboxylic acid and a difunctional alcohol together. Moreover, the mixture which blended 2 or more types of the obtained polycarbonate may be used.

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

Further, a polycarbonate-polyorganosiloxane copolymer obtained by copolymerizing polyorganosiloxane units can also be used.
The aromatic polycarbonate used as component B is a mixture of two or more of the above-mentioned polycarbonates having different dihydric phenols, polycarbonates containing branched components, polyester carbonates, polycarbonate-polyorganosiloxane copolymers and the like. 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.

Reaction forms such as interfacial polymerization, melt transesterification, solid phase transesterification of carbonate prepolymer, and ring-opening polymerization of cyclic carbonate compounds, which are methods for producing the polycarbonate of the present invention, are various documents and patent publications. This is a well-known method.
The viscosity average molecular weight of the aromatic polycarbonate of the present invention is 10,000 to 19,000, preferably 12,000 to 18,000, more preferably 14,000 to 17,000, and 15,500. ˜17,000 is most preferred. In the case of an aromatic polycarbonate having a viscosity average molecular weight of less than 10,000, the resin is severely brittle and sufficient strength cannot be obtained even if the fiber is reinforced. On the other hand, in the case of an aromatic polycarbonate having a viscosity average molecular weight exceeding 19,000, the fibers of the fibrous filler are easily broken, so that sufficient rigidity and strength cannot be obtained.

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 polycarbonate is dissolved in 100 ml of methylene chloride at 20 ° C. with a specific viscosity (η _SP ) calculated by the following formula (3). Seeking
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀ (3)
[T ₀ is methylene chloride falling seconds, t is sample solution falling seconds]
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) (4)
[Η] = 1.23 × 10 ⁻⁴ M ^0.83 (5)
c = 0.7

  The calculation of the viscosity average molecular weight in the resin composition of the present invention is performed as follows. That is, the composition is mixed with 20 to 30 times its weight of methylene chloride to dissolve the soluble component in the composition. Such soluble matter is collected by Celite filtration. Thereafter, the solvent in the obtained solution is removed. The solid after removal of the solvent is sufficiently dried to obtain a solid component that dissolves in methylene chloride. A specific viscosity at 20 ° C. is determined from a solution obtained by dissolving 0.7 g of the solid in 100 ml of methylene chloride in the same manner as described above, and the viscosity average molecular weight M is calculated from the specific viscosity in the same manner as described above.

  The aromatic polycarbonate which is B component of this invention can also use what was recycled. In that case, the proportion of components having a small environmental load is increased together with the component A of the non-petroleum resource material, which is a more preferable material in terms of the environmental load reduction effect. The recycled aromatic polycarbonate 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, from a used product. Representative examples include resin molded products that are separated and collected, resin molded products that are separated and collected from those that occurred as defective products during product manufacturing, and resin molded products that include unnecessary parts such as spools and runners that occur during molding. The 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. On the other hand, the so-called virgin aromatic polycarbonate is usually a resin produced in-house as well as a resin obtained from the market, and its form is usually granulated in the form of powder, pellets, chips or spheres. used. The recycled aromatic polycarbonate 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 or more. What to do 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 molded product in which a hard coat film is laminated on the surface of a transparent polycarbonate molded product is exemplified as a preferred embodiment. 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 can use both the pulverized resin molded product and the 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 molded product, it is more efficient to blend the pulverized product as it is because it is possible to achieve a good hue, and environmental impact is reduced. Contributes to reduction. The pulverized product can be produced by pulverizing a resin molded product using a known pulverizer.
The recycled aromatic polycarbonate can be contained in 100% by weight of the B component aromatic polycarbonate, 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.

  The ratio of polylactic acid (component A) to aromatic polycarbonate (component B) is 50 to 95% by weight of polylactic acid (component A) and 50 to 5% by weight of aromatic polycarbonate (component B). ) 60 to 90% by weight, aromatic polycarbonate (component B) 40 to 10% by weight is preferable, polylactic acid (component A) 65 to 85% by weight, and aromatic polycarbonate (component B) 35 to 15% by weight is more preferable. When the ratio of the aromatic polycarbonate exceeds 50% by weight, the adhesiveness between the fibrous filler and the resin component is significantly reduced, and sufficient strength cannot be obtained. When the aromatic polycarbonate is less than 5% by weight, the effect of suppressing the anisotropy of the molding shrinkage ratio is reduced, and the warpage of the molded product is increased.

The ratio of the melt viscosity of polylactic acid (component A) to the melt viscosity of aromatic polycarbonate (component B) is 0.1 or more, preferably 0.2 or more, more preferably 0.25 or more, 0.3 or more is more preferable. When the melt viscosity ratio is smaller than 0.1, the anisotropy of the mold shrinkage rate increases. There is no particular upper limit on the ratio of melt viscosity, but it is substantially determined by the ratio of the melt viscosity of component A having a weight average molecular weight of 200,000 as the upper limit of component A and component B having a viscosity average molecular weight of 10,000 as the lower limit of component B. , About 5. Here, the ratio of the melt viscosity is a value obtained using the following formula (1).
Ratio of melt viscosity of component A to melt viscosity of component B = ηA / ηB (1)
[However, in the formula (1), ηA and ηB represent the melt viscosity of the A component and the melt viscosity of the B component, respectively, measured at 250 ° C. and 250 sec ⁻¹ using a high shear measuring machine. ]

Measurement conditions of a high shear measuring machine, 250 ° C. is a melt kneading temperature of the resin composition, 250 sec ⁻¹ is a measurement assuming a maximum shear rate when the resin composition is melt kneaded in an extruder equipped with a twin screw. It is a condition. The maximum shear rate can be calculated from the following formula (6).
G _max = π · D · n / 60h (6)
[However, G _max is the maximum shear rate, π is the circumference, D is the screw diameter of the twin screw extruder, n is the screw rotation speed of the twin screw extruder, and h is the clearance between the screw and the cylinder. ]

  The reason why the anisotropy of the molding shrinkage rate is suppressed when the ratio of the melt viscosity of the A component to the melt viscosity of the B component is 0.1 or more is not clear, but the melt viscosity of the A component and the B component When the melt viscosity ratio is close, a relatively fine sea-island structure dispersion state is obtained, and strong shearing is applied by injection molding or the like, so that an island component (B component) having a small molding shrinkage is contained in the matrix. This is considered to be because the anisotropy of the molding shrinkage is efficiently suppressed by being stretched into a plate shape.

<About component C>
The composition of the present invention contains a fibrous filler (component C). By containing the fibrous filler, a composition having excellent mechanical properties, heat resistance, and moldability can be obtained. As the fibrous filler used in the present invention, those used for reinforcing ordinary thermoplastic resins can be used.
Specifically, for example, glass fiber, asbestos fiber, carbon fiber, graphite fiber, metal fiber, potassium titanate whisker, aluminum borate whisker, magnesium whisker, silicon whisker, wollastonite, slag fiber, gypsum fiber, silica Examples thereof include fibrous inorganic fillers such as fibers, alumina fibers, zirconia fibers, boron nitride fibers, silicon nitride fibers, and boron fibers.

  Among these fibrous fillers, carbon fibers (C-1 component) and glass fibers (C-2 component) are particularly preferable in terms of rigidity and strength, and carbon fibers (C-1 component) are more preferable. Content of C component is 10-110 weight part with respect to 100 weight part of resin components which consist of polylactic acid (A component) and aromatic polycarbonate (B component), 20-100 weight part is preferable, 30- 100 parts by weight is more preferable. When the C component is less than 10 parts by weight, the reinforcing effect is small and sufficient rigidity and strength cannot be obtained. On the other hand, if the amount of component C is more than 110 parts by weight, a resin clogging occurs at the die port of the extruder, causing serious problems in the process such as inability to extrude.

(C-1 component)
Examples of the carbon fiber (C-1 component) of the present invention include carbon fibers such as metal-coated carbon fibers, carbon milled fibers, and vapor-grown carbon fibers, and carbon nanotubes. The carbon nanotubes preferably have a fiber diameter of 0.003 to 0.1 μm. Further, they may be any of a single layer, a double layer, and a multilayer, and a multilayer (so-called MWCNT) is preferable. Among these, carbon fibers, particularly metal-coated carbon fibers, are preferred in that they are excellent in mechanical strength and can impart good electrical conductivity. Good electrical conductivity has become one of important characteristics required for resin materials in recent digital precision equipment (represented by, for example, a digital still camera).

  As the carbon fiber, any of cellulose, polyacrylonitrile, pitch and the like can be used. Also obtained by a method in which a raw material composition composed of a polymer and a solvent with aromatic methylene bonds of aromatic sulfonic acids or their salts and a solvent is spun or molded and then carbonized without passing through an infusibilization step represented by a method such as carbonization. It is also possible to use those that have been used. Furthermore, any of general-purpose type, medium elastic modulus type, and high elastic modulus type can be used. Among these, polyacrylonitrile-based high elastic modulus type is particularly preferable.

  Moreover, although the average fiber diameter of carbon fiber is not specifically limited, 3-15 micrometers is preferable, More preferably, it is 4-13 micrometers. A carbon fiber having an average fiber diameter in such a range can exhibit good mechanical strength and fatigue characteristics without impairing the appearance of the molded product. Moreover, 60-500 micrometers is preferable as a number average fiber length in a resin composition, as for the preferable fiber length of a carbon fiber, More preferably, it is 80-400 micrometers, Most preferably, it is a thing of 100-300 micrometers. In addition, the number average fiber length is a value calculated by an image analysis device from an optical microscope observation from a residue of carbon fiber collected by processing such as high-temperature ashing of a molded product, dissolution with a solvent, and decomposition with a chemical. It is. Further, when calculating such a value, a value having a length equal to or less than the fiber diameter is a value obtained by a method not counting.

  Further, the surface of the carbon fiber is preferably oxidized for the purpose of improving the adhesion with the matrix resin and improving the mechanical strength. Although the oxidation treatment method is not particularly limited, for example, (1) a method in which a fibrous carbon filler is treated with an acid or alkali or a salt thereof, or an oxidizing gas, (2) a fiber that can be converted into a fibrous carbon filler, or A method of firing the fibrous carbon filler at a temperature of 700 ° C. or higher in the presence of an inert gas containing an oxygen-containing compound; and (3) after the fibrous carbon filler is oxidized and then in the presence of the inert gas. The method of heat-treating with is suitably exemplified.

The metal-coated carbon fiber is obtained by coating the surface of the carbon fiber with a metal layer. Examples of the metal include silver, copper, nickel, and aluminum, and nickel is preferable from the viewpoint of the corrosion resistance of the metal layer. A plating method is suitably used as the metal coating method. In addition, in the case of such metal-coated carbon fiber, as the original carbon fiber, those mentioned as the above carbon fiber can be used. The thickness of the metal coating layer is preferably 0.1 to 1 μm, more preferably 0.15 to 0.5 μm. More preferably, it is 0.2-0.35 micrometer.
Such carbon fibers and metal-coated carbon fibers are preferably subjected to a bundling treatment with an olefin resin, a styrene resin, an acrylic resin, a polyester resin, an epoxy resin, a urethane resin, or the like. In particular, a fibrous carbon filler treated with a urethane resin or an epoxy resin is suitable in the present invention because of its excellent mechanical strength.

(C-2 component)
The glass fiber used as the C-2 component of the present invention may have a round cross section or a flat cross section. The average fiber diameter is not particularly limited, but in the case of a round cross section, the fiber diameter is preferably 2 to 30 μm, more preferably 3 to 25 μm, and even more preferably 5 to 20 μm. When the fiber diameter is 2 μm or less, the converging property of the glass fiber is deteriorated, and the handling during melt kneading using an extruder may be lowered. On the other hand, when the fiber diameter is 30 μm or more, the fiber diameter is too large and the reinforcing effect may be reduced. In the case of a flat cross section, the average value of the major axis of the fiber cross section is 10 to 50 μm, preferably 15 to 40 μm, more preferably 20 to 35 μm, and the average value of the ratio of major axis to minor axis (major axis / minor axis) (flat ratio). Is a glass fiber of 1.5 to 10, preferably 2 to 8, and more preferably 2.5 to 6. When flat glass fibers having a flatness in this range are used, the strength, particularly anisotropy, is greatly improved as compared with the case of using non-flat cross-section glass fibers of less than 1.5. In addition to the flat shape, the flat cross-sectional shape includes an elliptical shape, an eyebrow shape, a trefoil shape, or a similar non-circular cross-sectional shape. Of these, a flat shape is preferable from the viewpoint of improving mechanical strength and low anisotropy.

  The fiber length of the glass fiber is preferably 60 to 700 μm, more preferably 100 to 500 μm, particularly preferably 150 to 400 μm as the number average fiber length in the resin composition. In addition, the number average fiber length is a value calculated by an image analyzer from an optical microscope observation or the like from a residue of glass fibers collected by processing such as high-temperature ashing of a molded product, dissolution with a solvent, and decomposition with a chemical. It is. Further, when calculating such a value, a value having a length equal to or less than the fiber diameter is a value obtained by a method not counting.

Various glass compositions represented by S glass, C glass, T glass, E glass, etc. are applied to the glass composition of said glass fiber, and it is not specifically limited. Such glass fibers may contain components such as TiO ₂ , SO ₃ , and P ₂ O ₅ as necessary. Among these, E glass (non-alkali glass) is more preferable. Such a glass fiber is preferably subjected to a surface treatment with a known surface treatment agent such as a silane coupling agent, a titanate coupling agent, or an aluminate coupling agent from the viewpoint of improving mechanical strength. In addition, those that have been subjected to bundling treatment with olefin resin, styrene resin, acrylic resin, polyester resin, epoxy resin, urethane resin, etc. are preferable. From the viewpoint of mechanical strength, epoxy resin and urethane resin are preferred. Particularly preferred. The amount of the sizing agent attached to the glass fiber subjected to the sizing treatment is preferably 0.1 to 3% by weight, more preferably 0.2 to 2% by weight in 100% by weight of the glass fiber.

<About D component>
As the D component carbodiimide compound, either a cyclic carbodiimide compound having a cyclic structure or a linear carbodiimide having no cyclic structure can be used.

<Cyclic carbodiimide compound>
The cyclic structure of the cyclic carbodiimide used in the present invention has one carbodiimide group (—N═C═N—), and the first nitrogen and the second nitrogen are bonded by a bonding group. One cyclic structure has only one carbodiimide group. The number of atoms in the cyclic structure is preferably 8 to 50, more preferably 10 to 30, further preferably 10 to 20, and most preferably 10 to 15.

  Here, the number of atoms in the ring structure means the number of atoms that directly constitute the ring structure, and is, for example, 8 for an 8-membered ring and 50 for a 50-membered ring. This is because if the number of atoms in the cyclic structure is smaller than 8, the stability of the cyclic carbodiimide compound is lowered, and it may be difficult to store and use. From the standpoint of reactivity, there is no particular limitation on the upper limit of the number of ring members, but cyclic carbodiimide compounds having more than 50 atoms are difficult to synthesize, and the cost may increase significantly. From this viewpoint, the number of atoms in the cyclic structure is preferably 10-30, more preferably 10-20, and most preferably 10-15.

The cyclic structure is a structure represented by the following formula (5).

In the formula, Q is a divalent to tetravalent linking group represented by the following formula (5-1), (5-2), or (5-3).

In the formula, Ar ¹ and Ar ² are each independently a 2- to 4-valent aromatic group having 5 to 15 carbon atoms which may contain a hetero atom and a substituent.
As an aromatic group, each of which contains a hetero atom and may have a heterocyclic structure, an arylene group having 5 to 15 carbon atoms, an arenetriyl group having 5 to 15 carbon atoms, an arenetetra having 5 to 15 carbon atoms Yl group. Examples of the arylene group (divalent) include a phenylene group and a naphthalenediyl group. Examples of the arenetriyl group (trivalent) include a benzenetriyl group and a naphthalenetriyl group. Examples of the arenetetrayl group (tetravalent) include a benzenetetrayl group and a naphthalenetetrayl group. These aromatic groups may be substituted. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.

R ¹ and R ² each independently contain a heteroatom and a substituent, each having 2 to 4 valent aliphatic groups having 1 to 20 carbon atoms and 2 to 4 valent fatty acids having 3 to 20 carbon atoms A cyclic group, and a combination thereof, or a combination of the aliphatic group, the alicyclic group, and a divalent to tetravalent aromatic group having 5 to 15 carbon atoms.

  Examples of the aliphatic group include an alkylene group having 1 to 20 carbon atoms, an alkanetriyl group having 1 to 20 carbon atoms, and an alkanetetrayl group having 1 to 20 carbon atoms. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, a dodecylene group, and a hexadecylene group. As the alkanetriyl group, methanetriyl group, ethanetriyl group, propanetriyl group, butanetriyl group, pentanetriyl group, hexanetriyl group, heptanetriyl group, octanetriyl group, nonanetriyl group, decantriyl group, dodecantriyl group, Examples include a hexadecantriyl group. As alkanetetrayl group, methanetetrayl group, ethanetetrayl group, propanetetrayl group, butanetetrayl group, pentanetetrayl group, hexanetetrayl group, heptanetetrayl group, octanetetrayl group, nonanetetrayl group Decanetetrayl group, dodecanetetrayl group, hexadecanetetrayl group and the like. These aliphatic groups may be substituted. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.

  Examples of the alicyclic group include a cycloalkylene group having 3 to 20 carbon atoms, a cycloalkanetriyl group having 3 to 20 carbon atoms, and a cycloalkanetetrayl group having 3 to 20 carbon atoms. Examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, a cyclononylene group, a cyclodecylene group, a cyclododecylene group, and a cyclohexadecylene group. As cycloalkanetriyl group, cyclopropanetriyl group, cyclobutanetriyl group, cyclopentanetriyl group, cyclohexanetriyl group, cycloheptanetriyl group, cyclooctanetriyl group, cyclononanetriyl group, cyclodecanetriyl group Group, cyclododecane triyl group, cyclohexadecane triyl group and the like. As cycloalkanetetrayl group, cyclopropanetetrayl group, cyclobutanetetrayl group, cyclopentanetetrayl group, cyclohexanetetrayl group, cycloheptanetetrayl group, cyclooctanetetrayl group, cyclononanetetrayl group, cyclodecanetetrayl group Yl group, cyclododecanetetrayl group, cyclohexadecanetetrayl group and the like. These alicyclic groups may be substituted. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.

  As an aromatic group, each of which contains a hetero atom and may have a heterocyclic structure, an arylene group having 5 to 15 carbon atoms, an arenetriyl group having 5 to 15 carbon atoms, an arenetetra having 5 to 15 carbon atoms Yl group. Examples of the arylene group include a phenylene group and a naphthalenediyl group. Examples of the arenetriyl group (trivalent) include a benzenetriyl group and a naphthalenetriyl group. Examples of the arenetetrayl group (tetravalent) include a benzenetetrayl group and a naphthalenetetrayl group. These aromatic groups may be substituted. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.

X ¹ and X ² each independently contain a heteroatom and a substituent, each having a 2 to 4 valent aliphatic group having 1 to 20 carbon atoms and a 2 to 4 valent fatty acid having 3 to 20 carbon atoms It is a cyclic group, a divalent to tetravalent aromatic group having 5 to 15 carbon atoms, or a combination thereof.

  Examples of the aliphatic group include an alkylene group having 1 to 20 carbon atoms, an alkanetriyl group having 1 to 20 carbon atoms, and an alkanetetrayl group having 1 to 20 carbon atoms. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, a dodecylene group, and a hexadecylene group. As the alkanetriyl group, methanetriyl group, ethanetriyl group, propanetriyl group, butanetriyl group, pentanetriyl group, hexanetriyl group, heptanetriyl group, octanetriyl group, nonanetriyl group, decantriyl group, dodecantriyl group, Examples include a hexadecantriyl group. As alkanetetrayl group, methanetetrayl group, ethanetetrayl group, propanetetrayl group, butanetetrayl group, pentanetetrayl group, hexanetetrayl group, heptanetetrayl group, octanetetrayl group, nonanetetrayl group Decanetetrayl group, dodecanetetrayl group, hexadecanetetrayl group and the like. These aliphatic groups may be substituted. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.

  Examples of the alicyclic group include a cycloalkylene group having 3 to 20 carbon atoms, a cycloalkanetriyl group having 3 to 20 carbon atoms, and a cycloalkanetetrayl group having 3 to 20 carbon atoms. Examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, a cyclononylene group, a cyclodecylene group, a cyclododecylene group, and a cyclohexadecylene group. As the alkanetriyl group, cyclopropanetriyl group, cyclobutanetriyl group, cyclopentanetriyl group, cyclohexanetriyl group, cycloheptanetriyl group, cyclooctanetriyl group, cyclononanetriyl group, cyclodecanetriyl group , Cyclododecanetriyl group, cyclohexadecanetriyl group and the like. As the alkanetetrayl group, cyclopropanetetrayl group, cyclobutanetetrayl group, cyclopentanetetrayl group, cyclohexanetetrayl group, cycloheptanetetrayl group, cyclooctanetetrayl group, cyclononanetetrayl group, cyclodecanetetrayl group Group, cyclododecanetetrayl group, cyclohexadecanetetrayl group and the like. These alicyclic groups may be substituted. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.

  As an aromatic group, each of which contains a hetero atom and may have a heterocyclic structure, an arylene group having 5 to 15 carbon atoms, an arenetriyl group having 5 to 15 carbon atoms, an arenetetra having 5 to 15 carbon atoms Yl group. Examples of the arylene group include a phenylene group and a naphthalenediyl group. Examples of the arenetriyl group (trivalent) include a benzenetriyl group and a naphthalenetriyl group. Examples of the arenetetrayl group (tetravalent) include a benzenetetrayl group and a naphthalenetetrayl group. These aromatic groups may be substituted. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.

In formulas (5-1) and (5-2), s and k are integers of 0 to 10, preferably 0 to 3, more preferably 0 to 1. When s and k exceed 10, the cyclic carbodiimide compound is difficult to synthesize, and the cost may increase significantly. From this viewpoint, the integer is preferably selected in the range of 0 to 3. When s or k is 2 or more, X ¹ or X ² as a repeating unit may be different from other X ¹ or X ² .
X ³ is a divalent to tetravalent C 1-20 aliphatic group, a divalent to tetravalent C 3-20 alicyclic group, each of which may contain a heteroatom and a substituent, A tetravalent aromatic group having 5 to 15 carbon atoms, or a combination thereof.

  Examples of the aliphatic group include an alkylene group having 1 to 20 carbon atoms, an alkanetriyl group having 1 to 20 carbon atoms, and an alkanetetrayl group having 1 to 20 carbon atoms. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, a dodecylene group, and a hexadecylene group. As the alkanetriyl group, methanetriyl group, ethanetriyl group, propanetriyl group, butanetriyl group, pentanetriyl group, hexanetriyl group, heptanetriyl group, octanetriyl group, nonanetriyl group, decantriyl group, dodecantriyl group, Examples include a hexadecantriyl group. As alkanetetrayl group, methanetetrayl group, ethanetetrayl group, propanetetrayl group, butanetetrayl group, pentanetetrayl group, hexanetetrayl group, heptanetetrayl group, octanetetrayl group, nonanetetrayl group Decanetetrayl group, dodecanetetrayl group, hexadecanetetrayl group and the like. These aliphatic groups may contain a substituent, such as an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, or an ester group. , Ether group, aldehyde group and the like.

  Examples of the alicyclic group include a cycloalkylene group having 3 to 20 carbon atoms, a cycloalkanetriyl group having 3 to 20 carbon atoms, and a cycloalkanetetrayl group having 3 to 20 carbon atoms. Examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, a cyclononylene group, a cyclodecylene group, a cyclododecylene group, and a cyclohexadecylene group. As the alkanetriyl group, cyclopropanetriyl group, cyclobutanetriyl group, cyclopentanetriyl group, cyclohexanetriyl group, cycloheptanetriyl group, cyclooctanetriyl group, cyclononanetriyl group, cyclodecanetriyl group , Cyclododecanetriyl group, cyclohexadecanetriyl group and the like. As the alkanetetrayl group, cyclopropanetetrayl group, cyclobutanetetrayl group, cyclopentanetetrayl group, cyclohexanetetrayl group, cycloheptanetetrayl group, cyclooctanetetrayl group, cyclononanetetrayl group, cyclodecanetetrayl group Group, cyclododecanetetrayl group, cyclohexadecanetetrayl group and the like. These alicyclic groups may contain a substituent, such as an alkyl group having 1 to 20 carbon atoms, an arylene group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, and an ester. Group, ether group, aldehyde group and the like.

  As an aromatic group, each of which contains a hetero atom and may have a heterocyclic structure, an arylene group having 5 to 15 carbon atoms, an arenetriyl group having 5 to 15 carbon atoms, an arenetetra having 5 to 15 carbon atoms Yl group. Examples of the arylene group include a phenylene group and a naphthalenediyl group. Examples of the arenetriyl group (trivalent) include a benzenetriyl group and a naphthalenetriyl group. Examples of the arenetetrayl group (tetravalent) include a benzenetetrayl group and a naphthalenetetrayl group. These aromatic groups may be substituted. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.

Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ² and X ³ may contain a hetero atom, and when Q is a divalent linking group, Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ² and X ³ are all divalent groups. When Q is a trivalent linking group, one of Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ² and X ³ is a trivalent group. When Q is a tetravalent linking group, one of Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ² and X ³ is a tetravalent group or two are trivalent It is a group.

Examples of the cyclic carbodiimide used in the present invention include compounds represented by the following formulas (5), (7) and (8).
<Cyclic carbodiimide (2)>

In the formula, Q is a divalent linking group represented by the following formula (6-1), (6-2) or (6-3).

In the formula, Ar _a (a is a subscript, the same applies hereinafter) ¹ and Ar _a ² are each independently a divalent aromatic group having 5 to 15 carbon atoms. R _a ¹ and R _a ² are each independently a divalent aliphatic group having 1 to 20 carbon atoms, a divalent alicyclic group having 3 to 20 carbon atoms, and a combination thereof, or these aliphatic groups, It is a combination of an alicyclic group and a divalent aromatic group having 5 to 15 carbon atoms. s _a is an integer of 0. k _a is an integer of 0 to 10. X _a ¹ and X _a ² are each independently a divalent aliphatic group having 1 to 20 carbon atoms, a divalent carbon group having 3 to 20 alicyclic groups, or a divalent aromatic group having 5 to 15 carbon atoms. A group, or a combination thereof. X _a ³ is preferably a divalent aliphatic group having 1 to 20 carbon atoms, a divalent alicyclic group having 3 to 20 carbon atoms, a divalent aromatic group having 5 to 15 carbon atoms, or a combination thereof, is there. However, Ar _a ¹ , Ar _a ² , R _a ¹ , R _a ² , X _a ¹ , X _a ² and X _a ³ may contain a hetero atom. Examples of the cyclic carbodiimide compound (2) include the following compounds.

<Cyclic carbodiimide (3)>

In the formula, Q _b (b is a subscript, the same applies hereinafter) is a trivalent linking group represented by the following formula (7-1), (7-2) or (7-3), and Y is cyclic. A carrier carrying the structure.

_{^{Wherein, Ar b 1, Ar b 2}} , R b 1, R b 2, X b 1, X b 2, X b 3, s b and _{k b} are each formula (5-1) to (5-3 ) Are the same as Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ² , X ³ , s and k. However, one of these is a trivalent group.
Y is a single bond, a double bond, an atom, an atomic group or a polymer. Y is a bonding portion, and a plurality of cyclic structures are bonded via Y to form a structure represented by the formula (7). Examples of the cyclic carbodiimide compound (7) include the following compounds.

<Cyclic carbodiimide (4)>

In the formula, Q _c (c is a subscript, the same applies hereinafter) is a tetravalent linking group represented by the following formula (8-1), (8-2) or (8-3), and Z ¹ and Z ² is a carrier supporting a cyclic structure. Z ¹ and Z ² may be bonded to each other to form a cyclic structure.

Ar _c ¹ , Ar _c ² , R _c ¹ , R _c ² , X _c ¹ , X _c ² , X _c ³ , s _c and k _c are respectively represented by the formulas (5-1) to (5-3): The same as Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ² , X ³ , s and k. Provided that Ar _c ¹ , Ar _c ² , R _c ¹ , R _c ² , X _c ¹ , X _c ² and X _c ³ are one of which is a tetravalent group or two of which are trivalent It is a group.
Z ¹ and Z ² are each independently a single bond, a double bond, an atom, an atomic group or a polymer. Z ¹ and Z ² are bonding parts, and a plurality of cyclic structures are bonded via Z ¹ and Z ² to form a structure represented by the formula (8). Examples of the cyclic carbodiimide compound (8) include the following compounds.

<Method for producing cyclic carbodiimide compound>
The cyclic carbodiimide compound can be produced by a conventionally known method. For example, a method for producing an amine body via an isocyanate body, a method for producing an amine body via an isothiocyanate body, a method for producing an amine body via a triphenylphosphine body, a urea body from an amine body The method of manufacturing via a thiourea body, the method of manufacturing via a thiourea body, the method of manufacturing from a carboxylic acid body via an isocyanate body, the method of manufacturing a lactam body, etc. are mentioned.
In addition, the cyclic carbodiimide compound of the present invention can be produced by combining and modifying the methods described in the following documents, and an appropriate method can be adopted depending on the compound to be produced.

Tetrahedron Letters, Vol. 34, no. 32, 515-5158, 1993.
Medium- and Large-Membered Rings from Bis (iminophosphoranes): An Efficient Preparation of Cyclic Carbidiimides, Pedro Molina et al.
Journal of Organic Chemistry, Vol. 61, no. 13, 4289-4299, 1996.
New Models for the Study of the Racemization Mechanism of Carbodiimides. Synthesis and Structure (X-ray Crystallography and 1H NMR) of Cyclic Carbodiimides, Pedro Molina et al.
Journal of Organic Chemistry, Vol. 43, No8, 1944-1946, 1978.
Macrocyclic Ureas As Masked Isocynates, Henri Ulrich et al.
Journal of Organic Chemistry, Vol. 48, no. 10, 1694-1700, 1983.
Synthesis and Reactions of Cyclic Carbodiimides,
R. Richter et al.
Journal of Organic Chemistry, Vol. 59, no. 24, 7306-7315, 1994.
A New and Efficient Preparation of Cyclic Carbodiamids from Bis (iminophosphoranea) and the System Boc ₂ O / DMAP, Pedro Molina et al.

Depending on the compound to be produced, an appropriate production method may be employed. For example, (1) nitrophenol represented by the following formula (a-1), nitrophenol represented by the following formula (a-2), and A step of reacting a compound represented by the following formula (b) to obtain a nitro compound represented by the following formula (c);

(2) A step of reducing the obtained nitro body to obtain an amine body represented by the following formula (d);

(3) a step of reacting the obtained amine body with triphenylphosphine dibromide to obtain a triphenylphosphine body represented by the following formula (e); and

(4) What was manufactured by the process of carrying out the direct decarboxylation after isocyanate-izing the obtained triphenylphosphine body in a reaction system can be used suitably as a cyclic carbodiimide compound used for this invention. (In the above formula, Ar ¹ and Ar ² are each independently an aromatic group optionally substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group. E ¹ and E ² are each independently a halogen atom. A group selected from the group consisting of an atom, a toluenesulfonyloxy group, a methanesulfonyloxy group, a benzenesulfonyloxy group, and a p-bromobenzenesulfonyloxy group, Ar ^a3 is a phenyl group, and X is a group represented by the following formula (i -1) to (i-3).

（式中、ｎ^ｉ−１は１〜６の整数である。）

(Where n ^i-1 is an integer of ¹ to 6)

（式中、ｍ^ｉ−２およびｎ^ｉ−２は各々独立に０〜３の整数である。）

(In the formula, ^mi-2 and ^ni-2 are each independently an integer of 0-3.)

（式中、Ｒ^ｉ−３およびＲ’^ｉ−３は各々独立に、炭素数１〜６のアルキル基、フェニル基を表す。）

(In the formula, R ^i-3 and R ′ ^i-3 each independently represent an alkyl group having 1 to 6 carbon atoms or a phenyl group.)

  As the linear carbodiimide (including polycarbodiimide compound) used in the present invention, those synthesized by a generally well-known method can be used. For example, an organophosphorus compound or an organometallic compound is used as a catalyst. Examples thereof include those 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.

  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.

As a specific degree of carboxyl group terminal blocking, the concentration of the carboxyl group terminal of polylactic acid is preferably 10 equivalents / 10 ³ kg or less from the viewpoint of improving hydrolysis resistance, and is 6 equivalents / 10 ³ kg or less. More preferably.
The content of component D is preferably 0.01 to 10 parts by weight, more preferably 0.01 to 5 parts by weight, and still more preferably 0 to 100 parts by weight of the total of component A and component B. 0.1 to 3 parts by weight. If the content is less than 0.01 parts by weight, the amount of the end-capping agent added to the carboxyl terminal is too small, and sufficient hydrolysis resistance may not be obtained. Fluidity may be significantly reduced.

<About other ingredients>
<Antioxidant>
In the resin composition of the present invention, at least one antioxidant selected from the group consisting of hindered phenol compounds, phosphite compounds, phosphonite compounds, and thioether compounds is used as an antioxidant. Can do. By blending an antioxidant, not only is the hue and fluidity at the time of molding stabilized, it is also effective in improving hydrolysis resistance.

  Examples of the hindered phenol compound include α-tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, n-octadecyl-β- (4′-hydroxy-3 ′, 5′-di-tert-butylfel) propionate. 2-tert-butyl-6- (3′-tert-butyl-5′-methyl-2′-hydroxybenzyl) -4-methylphenyl acrylate, 2,6-di-tert-butyl-4- (N, N-dimethylaminomethyl) phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-methylenebi (2,6-di-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-cyclohexylphenol), 2,2′-dimethylene-bis (6-α-methyl-benzyl-p-cresol) ) 2,2′-ethylidene-bis (4,6-di-tert-butylphenol), 2,2′-butylidene-bis (4-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3- Methyl-6-tert-butylphenol), triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1,6-hexanediol bis [3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionate], bis [2-tert-butyl-4-methyl 6- ( -Tert-butyl-5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1 , 1, -dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, 4,4′-thiobis (6-tert-butyl-m-cresol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2,2′-thiobis (4-methyl-6-tert-butylphenol), bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4 , 4′-di-thiobis (2,6-di-tert-butylphenol), 4,4′-tri-thiobis (2,6-di-tert-butylphenol) ), 2,2-thiodiethylenebis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis (n-octylthio) -6- (4-hydroxy -3 ′, 5′-di-tert-butylanilino) -1,3,5-triazine, N, N′-hexamethylenebis- (3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N, N′-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butyl Phenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl) 4-hydroxyphenyl) isocyanurate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6- Dimethylbenzyl) isocyanurate, 1,3,5-tris 2 [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate, and tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4-hydroxyphenyl) propionate] methane and the like. Among the above compounds, tetrakis [methylene-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] methane, octadecyl-3- (3,5-di-tert-butyl-) is used in the present invention. 4-hydroxyphenyl) propionate and 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4 , 8,10-Tetraoxaspiro [5,5] undecane is preferably used. Particularly preferred is octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate. All of these are readily available. The said hindered phenol type compound can be used individually or in combination of 2 or more types.

  Phosphite compounds include triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl mono Phenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, tris (diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di-n-butylphenyl) ) Phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, distearyl pentae Thritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis ( 2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, bis {2,4-bis (1-methyl-1-phenylethyl) phenyl} pentaerythritol diphosphite, phenylbisphenol A penta Examples include erythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, and dicyclohexylpentaerythritol diphosphite. Furthermore, as other phosphite compounds, those 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 (4,6-di-tert-butylphenyl) octyl phosphite, and the like. Suitable phosphite compounds are distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methyl). Phenyl) pentaerythritol diphosphite, and bis {2,4-bis (1-methyl-1-phenylethyl) phenyl} pentaerythritol diphosphite. All of these are readily available. The above phosphite compounds can be used alone or in combination of two or more.

  Also, for example, 2,4,8,10-tetra-t-butyl-6- [3- (3-methyl-4-hydroxy-5-t-butylphenyl) propoxy] dibenzo [d, f] [1,3 , 2] dioxaphosphine [commercially available as “Sumilyzer GP” (manufactured by Sumitomo Chemical Co., Ltd.). 2,10-dimethyl-4,8-di-t-butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propoxy] -12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,4,8,10-tetra-t-butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propoxy] dibenzo [D, f] [1,3,2] dioxaphosphine, 2,4,8,10-tetra-t-pentyl-6- [3- (3,5-di-t-butyl-4- Hydroxyphenyl) propoxy] -12-methyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,10-dimethyl-4,8-di-t-butyl-6- [3 -(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -12H Dibenzo [d, g] [1,3,2] dioxaphosphocine, 2,4,8,10-tetra-t-pentyl-6- [3- (3,5-di-t-butyl-4- Hydroxyphenyl) propionyloxy] -12-methyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,4,8,10-tetra-t-butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -dibenzo [d, f] [1,3,2] dioxaphosphine, 2,10-dimethyl-4,8-di -T-butyl-6- (3,5-di-t-butyl-4-hydroxybenzoyloxy) -12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,4,8 , 10-Tetra-t-butyl-6- (3,5-di-t-butyl-4- Roxybenzoyloxy) -12-methyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,10-dimethyl-4,8-di-t-butyl-6- [3- (3-Methyl-4-hydroxy-5-t-butylphenyl) propoxy] -12H-dibenzo [d, g] [1,3,2] dioxaphosphocine, 2,4,8,10-tetra-t -Butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propoxy] -12H-dibenzo [d, g] [1,3,2] dioxaphosphocine, 2,10 -Diethyl-4,8-di-t-butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propoxy] -12H-dibenzo [d, g] [1,3 2] Dioxaphosphocin, 2,4,8,10-tetra-t-butyl Ru-6- [2,2-dimethyl-3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -dibenzo [d, f] [1,3,2] dioxaphosphine And so on. All of these are readily available. The above phosphite compounds can be used alone or in combination of two or more.

  Examples of the phosphonite compound include tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenyl. Range phosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4'-biphenylene diphospho Knight, 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- -Tert-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-n-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) Examples include -4-phenyl-phenyl phosphonite, bis (2,6-di-tert-butylphenyl) -3-phenyl-phenyl phosphonite. Tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite, bis (di-tert-butylphenyl) -phenyl-phenylphosphonite are preferred, and tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite Knight and bis (2,4-di-tert-butylphenyl) -phenyl-phenylphosphonite are more preferred. 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. The phosphonite compound is preferably tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite, and stabilizers based on the phosphonite are Sandostab P-EPQ (trademark, manufactured by Clariant) and Irgafos. P-EPQ (trademark, manufactured by CIBA SPECIALTY CHEMICALS) is commercially available and any of them can be used. The said phosphonite type compound can be used individually or in combination of 2 or more types.

  Specific examples of thioether compounds include dilauryl thiodipropionate, ditridecyl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, pentaerythritol-tetrakis (3-lauryl thiopropionate), Pentaerythritol-tetrakis (3-dodecylthiopropionate), pentaerythritol-tetrakis (3-octadecylthiopropionate), pentaerythritol tetrakis (3-myristylthiopropionate), pentaerythritol-tetrakis (3-stearylthio) Propionate) and the like. The said thioether type compound can be used individually or in combination of 2 or more types.

  The content of the antioxidant is preferably from 0.01 to 2 parts by weight, more preferably from 0.03 to 1 part by weight, and even more preferably from 0.05 to 1 part by weight based on 100 parts by weight of the total of the component A and the component B. 0.5 parts by weight. When the content of the antioxidant is less than 0.01 parts by weight, the antioxidant effect is insufficient, and not only the hue and fluidity at the time of molding become unstable, but also the hydrolysis resistance may deteriorate. . In addition, when the content is more than 2 parts by weight, the reaction component derived from the antioxidant may be deteriorated and the hydrolysis resistance may be deteriorated.

  Further, it is preferable to use a combination of one or more of the hindered phenol compounds and phosphite compounds, phosphonite compounds, and thioether compounds. By using a combination of one or more of hindered phenol compounds and phosphite compounds, phosphonite compounds, and thioether compounds, a synergistic effect as a stabilizer is exhibited, and hue and flow during molding are further improved. It is effective in stabilizing the properties and improving the hydrolysis resistance.

<About plasticizer>
In the present invention, a plasticizer represented by the following general formula (9) can be used.

(In the formula, R ₃ represents a linear or branched alkyl group having 8 to 22 carbon atoms, R ₄ represents an alkyl group having 1 to 3 carbon atoms, n is in the range of 5 to 20, and AO is ethylene. It represents at least one selected from glycol, propylene glycol and butylene glycol, and may be single or copolymerized.)

R ₃ represents a linear or branched alkyl group having 8 to 22 carbon atoms, preferably 10 to 22 carbon atoms, and more preferably 12 to 20 carbon atoms. If the number of carbon atoms in R ₃ is less than 8, the plasticizer is likely to gasify, and an appearance defect that leaves a gas transfer mark on the molded product is likely to occur. When the carbon number of R ₃ is larger than 22, the familiarity with the resin is deteriorated, and the plasticizer tends to bleed out on the surface of the molded product. n is in the range of 5-20, preferably 5-15, more preferably 5-12. When n is less than 5, the plasticizer is easily gasified, and appearance defects in which gas transfer marks remain on the surface of the molded product are likely to occur. If n is larger than 20, the plasticizing effect is lowered, so that sufficient moldability cannot be obtained.

AO is ethylene glycol, propylene glycol, or butylene glycol. If AO has fewer carbon atoms than ethylene glycol, the plasticizer tends to gasify, leaving gas transfer marks on the surface of the molded product. If AO has more carbon atoms than butylene glycol, it will not fit well with the resin. As a result, not only the bleeding is likely to occur but also the plasticizing effect is lowered, so that sufficient moldability cannot be obtained. Ethylene glycol, propylene glycol, and butylene glycol may be copolymerized alone or in combination, and are preferably copolymerized from the viewpoints of gas generation, compatibility with the resin, and plasticizing effect.
R ₄ is an alkyl group having 1 to 3 carbon atoms, and if R ₄ has more than 3 carbon atoms, the compatibility with the resin is deteriorated and bleed out is not preferable.

If the acid value of the plasticizer is high, the hydrolysis resistance of polylactic acid is greatly reduced. Therefore, the total acid value of the plasticizer used in the present invention is preferably 3 mmgKOH / g or less, and more preferably 1.5 mmgKOH / g or less. The acid value can be measured by neutralization titration in which a titration solution in which potassium hydroxide is dissolved in ethanol is dropped into a solution in which a plasticizer is dissolved in ethanol.
If the plasticizer contains a large amount of moisture, polylactic acid is hydrolyzed at the time of extrusion, which is not preferable because it causes a decrease in physical properties and a decrease in hydrolysis resistance. The amount of water contained in the plasticizer is preferably 1% or less, more preferably 0.5% or less, and even more preferably 0.1% or less.

As such a plasticizer, Leo Fat OC-0503M manufactured by Lion Corporation can be obtained as a commercial product.
The content of the plasticizer is preferably 0.5 to 10 parts by weight, more preferably 1 to 8 parts by weight, and still more preferably 2 to 7 parts by weight with respect to 100 parts by weight of the total of the A component and the B component. If the content of the plasticizer is less than 0.5 parts by weight, the effect as a plasticizer is insufficient, and the effect of reducing the mold temperature cannot be sufficiently obtained. If the content is more than 10 parts by weight, the plasticizer component is molded. Since it bleeds out to the surface of the product, there is a problem of causing defects such as mold contamination.

<Release agent>
A release agent can be used in the composition of the present invention. Specific examples of release agents include fatty acids, fatty acid metal salts, oxy fatty acids, paraffins, low molecular weight polyolefins, fatty acid amides, alkylene bis fatty acid amides, aliphatic ketones, fatty acid partial saponified esters, fatty acid lower alcohol esters, fatty acid polyvalents. Examples include alcohol esters, fatty acid polyglycol esters, and modified silicones. By blending these, a polylactic acid molded product excellent in mechanical properties, moldability, and heat resistance can be obtained.

  Fatty acids having 6 to 40 carbon atoms are preferred. Specifically, oleic acid, stearic acid, lauric acid, hydroxystearic acid, behenic acid, arachidonic acid, linoleic acid, linolenic acid, ricinoleic acid, palmitic acid, montan Examples thereof include acids and mixtures thereof. The fatty acid metal salt is preferably an alkali (earth) metal salt of a fatty acid having 6 to 40 carbon atoms, and specific examples include calcium stearate, sodium montanate, calcium montanate, and the like.

  Examples of the oxy fatty acid include 1,2-oxysteric acid. Paraffin having 18 or more carbon atoms is preferable, and examples thereof include liquid paraffin, natural paraffin, microcrystalline wax, petrolactam and the like.

  As the low molecular weight polyolefin, for example, those having a molecular weight of 5000 or less are preferable, and specific examples include polyethylene wax, maleic acid-modified polyethylene wax, oxidized type polyethylene wax, chlorinated polyethylene wax, and polypropylene wax. Fatty acid amides having 6 or more carbon atoms are preferred, and specific examples include oleic acid amide, erucic acid amide, and behenic acid amide.

  The alkylene bis fatty acid amide is preferably one having 6 or more carbon atoms, and specifically includes methylene bis stearic acid amide, ethylene bis stearic acid amide, N, N-bis (2-hydroxyethyl) stearic acid amide and the like. As the aliphatic ketone, those having 6 or more carbon atoms are preferable, and examples thereof include higher aliphatic ketones.

  Examples of the fatty acid partial saponified ester include a montanic acid partial saponified ester. Examples of the fatty acid lower alcohol ester include stearic acid ester, oleic acid ester, linoleic acid ester, linolenic acid ester, adipic acid ester, behenic acid ester, arachidonic acid ester, montanic acid ester, isostearic acid ester and the like.

  Examples of fatty acid polyhydric alcohol esters include glycerol tristearate, glycerol distearate, glycerol monostearate, pentaerythritol tetrastearate, pentaerythritol tristearate, pentaerythritol dimyristate, pentaerythritol Examples include tall monostearate, pentaerythritol adipate stearate, sorbitan monobehenate and the like. Examples of fatty acid polyglycol esters include polyethylene glycol fatty acid esters, polytrimethylene glycol fatty acid esters, and polypropylene glycol fatty acid esters.

Examples of the modified silicone include polyether-modified silicone, higher fatty acid alkoxy-modified silicone, higher fatty acid-containing silicone, higher fatty acid ester-modified silicone, methacryl-modified silicone, and fluorine-modified silicone.
Of these, fatty acid, fatty acid metal salt, oxy fatty acid, fatty acid ester, fatty acid partial saponified ester, paraffin, low molecular weight polyolefin, fatty acid amide, and alkylene bis fatty acid amide are preferred, and fatty acid partial saponified ester and alkylene bis fatty acid amide are more preferred. Of these, montanic acid ester, montanic acid partially saponified ester, polyethylene wax, acid value polyethylene wax, sorbitan fatty acid ester, erucic acid amide, and ethylene bisstearic acid amide are preferable, and particularly, montanic acid partially saponified ester and ethylene bisstearic acid amide are preferable. .

  A mold release agent may be used by 1 type and may be used in combination of 2 or more type. The content of the release agent is preferably 0.01 to 3 parts by weight, more preferably 0.03 to 2 parts by weight with respect to 100 parts by weight of the total of the A component and the B component.

<Crystallization accelerator>
The composition of the present invention can use a crystallization accelerator. By including the crystallization accelerator, the moldability and crystallinity of polylactic acid are further improved, and a highly crystallized product can be obtained in normal injection molding, and a molded product having excellent heat resistance and moist heat resistance can be obtained. In addition, the manufacturing time for manufacturing the molded product can be greatly shortened, and the economic effect is great.

As the crystallization accelerator, either an inorganic crystallization nucleating agent or an organic crystallization nucleating agent can be used.
As inorganic crystallization nucleating agents, talc, silica, zeolite, graphite, carbon black, zinc oxide, magnesium oxide, titanium oxide, calcium carbonate, calcium sulfate, barium sulfate, calcium sulfide, boron nitride, neodymium oxide, aluminum oxide, Examples thereof include phenylphosphonate metal salts. These inorganic crystallization nucleating agents are treated with various dispersing aids in order to enhance the dispersibility in the composition and the effect thereof, and are in a highly dispersed state with a primary particle size of about 0.01 to 0.5 μm. Are preferred.

  Organic crystallization nucleating agents include calcium benzoate, sodium benzoate, lithium benzoate, potassium benzoate, magnesium benzoate, barium benzoate, calcium oxalate, disodium terephthalate, dilithium terephthalate, dipotassium terephthalate, Sodium laurate, potassium laurate, sodium myristate, potassium myristate, calcium myristate, barium myristate, sodium octacolate, calcium octacolate, sodium stearate, potassium stearate, lithium stearate, calcium stearate, magnesium stearate , Barium stearate, sodium montanate, calcium montanate, sodium toluate, sodium salicylate, potassium salicylate, salicy Organic carboxylic acid metal salts such as zinc acid, aluminum dibenzoate, β-naphthoic acid sodium, β-naphthoic acid potassium, sodium cyclohexanecarboxylic acid and the like, and organic sulfonic acid metal salts such as sodium p-toluenesulfonate and sodium sulfoisophthalate. Can be mentioned.

Also, low density polyethylene, high density polyethylene, polyisopropylene, polybutene, poly-4-methylpentene, poly-3-methylbutene-1, polyvinylcycloalkane, polyvinyltrialkylsilane, ethylene-acrylic acid copolymer sodium salt, styrene -Sodium salt of maleic anhydride copolymer (so-called ionomer), benzylidene sorbitol and its derivatives such as dibenzylidene sorbitol.
Of these, talc and phenylphosphonate are preferably used. Only one crystallization nucleating agent may be used in the present invention, or two or more crystallization nucleating agents may be used in combination.
The content of the crystallization accelerator is preferably 0.01 to 30 parts by weight, more preferably 0.05 to 20 parts by weight with respect to 100 parts by weight of the total of the A component and the B component.

<Organic filler>
The composition of the present invention can use an organic filler. By containing the organic filler, a composition excellent in mechanical properties, heat resistance and moldability can be obtained.
Organic fillers such as rice husks, wood chips, okara, waste paper ground materials, clothing ground materials, cotton fibers, hemp fibers, bamboo fibers, wood fibers, kenaf fibers, jute fibers, banana fibers, coconut fibers Plant fibers such as pulp or cellulose fibers processed from these plant fibers and fibrous fibers such as animal fibers such as silk, wool, angora, cashmere and camel, synthetic fibers such as polyester fibers, nylon fibers and acrylic fibers , Paper powder, wood powder, cellulose powder, rice husk powder, fruit husk powder, chitin powder, chitosan powder, protein, starch and the like. From the viewpoint of moldability, powdery materials such as paper powder, wood powder, bamboo powder, cellulose powder, kenaf powder, rice husk powder, fruit husk powder, chitin powder, chitosan powder, protein powder, and starch are preferred. Powder, bamboo powder, cellulose powder and kenaf powder are preferred. Paper powder and wood powder are more preferable. Paper dust is particularly preferable. Here, since the organic filler is not easily oriented in the flow direction in the resin, it is difficult to cause anisotropy of the molding shrinkage rate. For this reason, in this invention, the fibrous filler of C component and an organic filler differ.

These organic fillers may be those directly collected from natural products, but may also be those obtained by recycling waste materials such as waste paper, waste wood and old clothes. The wood is preferably a softwood material such as pine, cedar, oak or fir, or a hardwood material such as beech, shii or eucalyptus.
Paper powder is an adhesive from the viewpoint of moldability, especially emulsion-based adhesives such as vinyl acetate resin-based emulsions and acrylic resin-based emulsions when processing paper, polyvinyl alcohol-based adhesives, polyamide-based adhesives, etc. Preferred examples include those containing a hot melt adhesive.

  In the present invention, the content of the organic filler is preferably 1 to 300 parts by weight, more preferably 5 to 200 parts by weight, based on the total 100 parts by weight of the component A and the component B, from the viewpoints of moldability and heat resistance. More preferably, it is 10 to 150 parts by weight, particularly preferably 15 to 100 parts by weight.

<Others>
In the present invention, a thermosetting resin such as a phenol resin, a melamine resin, a thermosetting polyester resin, a silicone resin, and an epoxy resin, a polyester resin, a polyarylate resin, and a liquid crystalline polyester are used without departing from the spirit of the present invention. A thermoplastic resin such as a resin, a polyamide resin, a polyimide resin, a polyetherimide resin, a polyphenylene ether resin, a polyphenylene sulfide resin, or a polysulfone resin may be included. Colorants containing organic and inorganic dyes and pigments, for example, oxides such as titanium dioxide, hydroxides such as alumina white, sulfides such as zinc sulfide, ferrocyanides such as bitumen, and chromium such as zinc chromate Contains acid salts, sulfates such as barium sulfate, carbonates such as calcium carbonate, silicates such as ultramarine, phosphates such as manganese violet, carbon such as carbon black, metal colorants such as bronze powder and aluminum powder, etc. You may let them. Also, nitroso type such as naphthol green B, nitro type such as naphthol yellow S, azo type such as naphthol red, chromophthal yellow, phthalocyanine type such as phthalocyanine blue and fast sky blue, and condensed polycyclic colorants such as indanthrone blue In addition, additives such as slidability improvers such as graphite and fluorine resin may be added. These additives can be used alone or in combination of two or more.

<About the manufacturing method of a resin composition>
i) Preparation of Coexisting Composition In the present invention, when poly L-lactic acid (A-1 component) and poly D-lactic acid (A-2 component) are mixed as polylactic acid (A component), other additive components Before melting and mixing with the phosphoric acid ester metal salt represented by formula (3) or formula (4), poly L-lactic acid (A-1 component) and poly D-lactic acid (A-2 component) It is preferable to keep it. As a method of coexistence, a method of mixing poly L-lactic acid (A-1 component) and poly D-lactic acid (A-2 component) as uniformly as possible is effective in stereocomplex crystals when they are heat-treated. This is preferable because it can be generated. 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.

  When obtaining such a coexisting composition by reprecipitation in the presence of a solvent, first, a coexisting composition of poly L-lactic acid (A-1 component) and poly D-lactic acid (A-2 component) Is prepared by reprecipitation. Here, the A-1 component and the A-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 (A-1 component / A-2 component) between poly L-lactic acid (A-1 component) and poly D-lactic acid (A-2 component) is 10/90 to 90/10. It is preferable to prepare so that it may become a range in order to produce | generate the stereocomplex crystal | crystallization of polylactic acid (A-1 component, A-2 component) efficiently in the resin composition of this invention. The weight ratio of the A-1 component to the A-2 component is more preferably 25/75 to 75/25, particularly preferably 40/60 to 60/40. The solvent is not particularly limited as long as polylactic acid (A-1 component, A-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.

  The phosphate ester metal salt represented by the formula (3) or the formula (4) is insoluble in the above solvent or may remain in the solvent after reprecipitation even when dissolved in the solvent. The polylactic acid (A-1 component, A-2 component) mixture obtained by the above and the phosphate ester metal salt represented by the formula (3) or formula (4) must be mixed separately to prepare a coexisting composition There is. The method of obtaining the coexisting composition of polylactic acid (A-1 component, A-2 component) mixture and the phosphoric acid ester metal salt represented by Formula (3) or Formula (4) is as long as they are uniformly mixed. It is not particularly limited, and any method such as powder mixing or melt mixing can be used.

  Next, by the method of removing the solvent from the presence of the solvent, polylactic acid (A-1 component, A-2 component) and the coexisting composition of the phosphate ester metal salt represented by formula (3) or formula (4) When the product is prepared at once, the A-1 component and the A-2 component, and the phosphoric acid ester metal salt represented by the formula (3) or the formula (4) are separately dissolved or dispersed in a solvent. This can be done by preparing and mixing the dispersion or by preparing and mixing a dispersion in which all components are dissolved or dispersed together in a solvent and then evaporating the solvent by heating. The solvent is not particularly limited as long as it dissolves polylactic acid (A-1 component, A-2 component) and the phosphate ester metal salt represented by formula (3) or formula (4). However, for example, chloroform, methylene chloride, dichloroethane, tetrachloroethane, phenol, tetrahydrofuran, N-methylpyrrolidone, N, N-dimethylformamide, butyrolactone, trioxane, hexafluoroisopropanol, or a mixture of two or more of them is preferable. 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.

  Preparation of the coexisting composition of polylactic acid (A-1 component, A-2 component) and the phosphoric acid ester metal salt represented by formula (3) or formula (4) can also be performed in the absence of a solvent. . That is, the A-1 component and the A-2 component, which have been pulverized or pelletized, and the phosphoric acid ester metal salt represented by the formula (3) or the formula (4) are mixed in a predetermined amount and then melted and mixed. Or a method in which any one of the A-1 component and the A-2 component is melted and then the remaining components are added and mixed. Here, the size of the powder or pellet is not particularly limited as long as the powder or pellet of each polylactic acid unit (component A-1, component A-2) is uniformly mixed, but 3 mm 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 pellets are simply melted after being uniformly mixed, if the diameter of the powder or pellets exceeds 3 mm, the mixture is mixed. Is not preferable, and homopolylactic acid crystals are likely to precipitate. In addition, as a mixing device used to uniformly mix the powder or pellets, 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, an aromatic polycarbonate (component B), a fibrous filler (component C), a carbodiimide compound (component D), and other additives, antioxidants, plasticizers, Release agents, crystallization accelerators, lubricants, UV absorbers, light stabilizers, flow modifiers, colorants, light diffusing agents, fluorescent whitening agents, phosphorescent pigments, fluorescent dyes, antistatic agents, antibacterial agents, etc. Additives can be allowed to coexist.
In particular, the addition of a carbodiimide compound (component D) at the stage of preparation of the coexisting composition means that the mixing of the carbodiimide compound and polylactic acid (component A) becomes more uniform, so that the acidic end of polylactic acid is more In order to block efficiently, it is preferable when improving the hydrolysis resistance of the obtained final resin composition. In addition, it is possible to add an antioxidant such as a hindered phenol compound, a phosphite compound, a phosphonite compound, or a thioether compound at the stage of preparing the coexisting composition, It is particularly preferable for improving the thermal stability.

ii) Heat treatment of coexisting composition In the present invention, when poly L-lactic acid (A-1 component) and poly D-lactic acid (A-2 component) are mixed as polylactic acid (A component), other additive components It is preferable to heat-treat the coexisting composition of polylactic acid (A-1 component, A-2 component) and the phosphoric acid ester metal salt represented by formula (3) or formula (4) before being melt-mixed. Such heat treatment refers to 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 stereocomplex crystals are not easily generated efficiently. 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, the preparation of the coexisting composition of polylactic acid (A-1 component, A-2 component) and the phosphoric acid ester metal salt represented by formula (3) or formula (4) was conducted in the absence of a solvent. In the case of carrying out by the melt mixing method, heat treatment of the coexisting composition can be achieved simultaneously with the preparation of the coexisting composition.

iii) Preparation of resin composition The resin composition of the present invention comprises polylactic acid (component A) (including the heat-treated coexisting composition), aromatic polycarbonate (component B), fibrous filler (component C), It is produced by mixing a carbodiimide compound (D component) and other additive components. (However, the components contained in the coexisting composition are excluded.)
Other additives include antioxidants, plasticizers, mold release agents, crystallization accelerators, lubricants, UV absorbers, light stabilizers, flow modifiers, colorants, light diffusing agents, fluorescent whitening agents, and phosphorescents. Arbitrary additives, such as a pigment, a fluorescent dye, an antistatic agent, and an antimicrobial agent, are mentioned.

  In order to produce the resin composition of the present invention, any method is adopted. For example, polylactic acid (component A) and other components can be premixed, and then melt-kneaded and pelletized. Examples of the premixing means include a Nauter mixer, a V-type blender, a Henschel mixer, a mechanochemical apparatus, and an extrusion mixer. In the preliminary mixing, granulation can be performed by an extrusion granulator or a briquetting machine depending on the case. After the preliminary mixing, the mixture is melt-kneaded by a melt-kneader represented by a vent type twin-screw extruder and pelletized by a device such as a pelletizer. Other examples of the melt kneader include a Banbury mixer, a kneading roll, and a constant temperature stirring vessel, but a vent type twin screw extruder is preferred. In addition, each component can be independently supplied to a melt-kneader represented by a twin-screw extruder without being premixed.

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

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

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

1. Production of polylactic acid Polylactic acid was 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) Polymer weight average molecular weight (Mw)
It was measured by gel permeation chromatography (GPC) and converted to standard polystyrene. The GPC measurement instrument used a differential refractometer Shimadzu RID-6A as a detector and Toso-TSKgel G3000HXL as a column. The measurement was performed by injecting 10 μl of a sample having a concentration of 1 mg / ml (chloroform containing 1% hexafluoroisopropanol) at a temperature of 40 ° C. and a flow rate of 1.0 ml / min using chloroform as an eluent.

(2) Carboxyl group concentration The sample was dissolved in purified o-cresol under a nitrogen stream, and then titrated with 0.05 N potassium hydroxide in ethanol using bromocresol blue as an indicator.

(3) Stereocomplex crystallinity Degree of stereocomplex crystal from the following formula (1), using melting enthalpy derived from polylactic acid (component A) crystal in DSC (TA-2920 manufactured by TA Instruments Inc.) The degree of conversion parameter was evaluated.
Stereo complex crystallinity = [ΔHms / (ΔHms + ΔHmh)] × 100 (1)
[In the formula (1), ΔHmh and ΔHms are the melting enthalpy (ΔHmh) of the melting point of the crystal, which appears below 190 ° C. in the temperature rising process of the differential scanning calorimeter (DSC), respectively, and 190 ° C. or more and 250 It is the melting enthalpy (ΔHms) of the crystalline melting point that appears below ° C. ]
The ΔHmh and ΔHms were determined by measuring the resin composition using a differential scanning calorimeter (DSC) in a nitrogen atmosphere at a heating rate of 20 ° C./min.

(4) Melt viscosity It measured using the high shear measuring device (Rheograph 2002 by God felt company). The measurement was performed under the conditions of a die length of 20 mm, a die diameter of 1 mm, a piston diameter of 12 mm, and a measurement temperature of 250 ° C. After filling the resin in the cylinder and holding it for 3 minutes, it was measured under conditions of shear rate 100, 200, 300, 500, 1000, 2000, 3000 sec ⁻¹ , and the melt viscosity at each shear rate was measured. . Next, the melt viscosity under a shear rate of 250 sec ⁻¹ was estimated from the melt viscosity plot against the shear rate, and the melt viscosity was determined.

In the examples and comparative examples of the present invention, the following materials were used.
[A-1 component: poly L-lactic acid (PLLA)]
[Production Example 1-1]
To 100 parts by weight of L-lactide (manufactured by Musashino Chemical Laboratory, Inc., optical purity 100%), 0.005 part by weight of octylate and 0.3 part by weight of decanol were added, and a stirring blade was attached in a nitrogen atmosphere. In the reactor, the reaction was carried out at 180 ° C. for 2 hours, and 1.2 times equivalent of phosphoric acid was added to tin octylate, then the remaining lactide was removed at 13.3 Pa, pelletized, and poly-L-lactic acid (A -1) was obtained.
The resulting poly L-lactic acid had a weight average molecular weight of 181,000, a melting enthalpy (ΔHmh) of 49 J / g, a melting point (Tmh) of 175 ° C., a glass transition point (Tg) of 59 ° C., and a carboxyl group content of 10 0.9 eq / ton and melt viscosity of 411 Pa · s.

[A′-1 component: production of poly L-lactic acid (PLLA)]
[Production Example 1-2]
To 100 parts by weight of L-lactide (manufactured by Musashino Chemical Laboratory, Inc., optical purity 100%), 0.005 part by weight of octylate and 0.2 part by weight of decanol were added, and a stirring blade was attached in a nitrogen atmosphere. In the reactor, the reaction was carried out at 180 ° C. for 2 hours, and 1.2 times equivalent of phosphoric acid was added to tin octylate, then the remaining lactide was removed at 13.3 Pa, pelletized, and poly-L-lactic acid (A '-1) was obtained.
The resulting poly L-lactic acid had a weight average molecular weight of 212,000, a melting enthalpy (ΔHmh) of 43 J / g, a melting point (Tmh) of 172 ° C., a glass transition point (Tg) of 60 ° C., and a carboxyl group content of 8 It was 0.7 eq / ton and melt viscosity was 613 Pa · s.

[Component A-2: Production of poly-D-lactic acid (PDLA)]
[Production Example 1-3]
Poly D-lactic acid was prepared in the same manner as in Production Example 1-1 except that D-lactide (manufactured by Musashino Chemical Laboratory, Inc., optical purity 100%) was used instead of L-lactide in Production Example 1-1. (A-2) was obtained. The resulting poly-D-lactic acid had a weight average molecular weight of 184,000, a melting enthalpy (ΔHmh) of 48 J / g, a melting point (Tmh) of 175 ° C., a glass transition point (Tg) of 59 ° C., and a carboxyl group content of 10 It was 9 eq / ton and melt viscosity was 424 Pa · s.

[A-3-1: Production of stereocomplex polylactic acid (scPLA)]
[Production Example 1-4]
100 parts by weight of a polylactic acid meter comprising 50 parts by weight of PLLA and PDLA obtained in Production Examples 1-1 and 1-3, and phosphoric acid-2,2′-methylenebis (4,6-di-tert-butylphenyl) Sodium (ADK STAB NA-11: manufactured by ADEKA Co., Ltd.) 0.1 parts by weight was mixed with a blender, dried at 110 ° C. for 5 hours, and vented twin screw extruder with a diameter of 30 mmφ [TEX30XSST manufactured by Nippon Steel Works, Ltd. The mixture was melt-extruded and pelletized at a cylinder temperature of 280 ° C., a screw rotational speed of 200 rpm, a discharge rate of 9 kg / h, and a vent vacuum of 3 kPa to obtain stereocomplex polylactic acid (A-3-1). The resulting stereocomplex polylactic acid had a weight average molecular weight of 1470,000, a melting enthalpy (ΔHms) of 56 J / g, a melting point (Tms) of 220 ° C., a glass transition point (Tg) of 60 ° C., and a carboxyl group content of 14 0.1 eq / ton, melt viscosity 248 Pa · s, and the stereocomplex crystallinity calculated using the formula (1) was 100%.

[A-3-2: Production of stereocomplex polylactic acid (scPLA)]
[Production Example 1-5]
100 parts by weight of a polylactic acid meter comprising 50 parts by weight of PLLA and PDLA obtained in Production Examples 1-1 and 1-2, and phosphoric acid-2,2′-methylenebis (4,6-di-tert-butylphenyl) Sodium (ADK STAB NA-11: manufactured by ADEKA Co., Ltd.) 0.1 parts by weight was mixed with a blender, dried at 110 ° C. for 5 hours, and vented twin screw extruder with a diameter of 30 mmφ [TEX30XSST manufactured by Nippon Steel Works, Ltd. The mixture was melt-extruded and pelletized at a cylinder temperature of 280 ° C., a screw rotation speed of 400 rpm, a discharge rate of 8 kg / h, and a vent vacuum of 3 kPa to obtain stereocomplex polylactic acid (A-3-2). The resulting stereocomplex polylactic acid had a weight average molecular weight of 105,000, a melting enthalpy (ΔHms) of 59 J / g, a melting point (Tms) of 217 ° C., a glass transition point (Tg) of 60 ° C., and a carboxyl group content of 23 eq. / Ton, melt viscosity 73 Pa · s, the stereocomplex crystallinity calculated using the formula (1) was 100%.

[A′-3: Production of stereocomplex polylactic acid (scPLA)]
[Production Example 1-6]
100 parts by weight of a polylactic acid meter comprising 50 parts by weight of PLLA and PDLA obtained in Production Examples 1-1 and 1-2, and phosphoric acid-2,2′-methylenebis (4,6-di-tert-butylphenyl) Sodium (ADK STAB NA-11: manufactured by ADEKA Co., Ltd.) 0.1 parts by weight was mixed with a blender, dried at 110 ° C. for 5 hours, and vented twin screw extruder with a diameter of 30 mmφ [TEX30XSST manufactured by Nippon Steel Works, Ltd. The mixture was melt-extruded and pelletized at a cylinder temperature of 300 ° C., a screw rotation speed of 400 rpm, a discharge rate of 8 kg / h, and a vent vacuum of 3 kPa to obtain stereocomplex polylactic acid (A′-3). The resulting stereocomplex polylactic acid had a weight average molecular weight of 92,000, a melting enthalpy (ΔHms) of 59 J / g, a melting point (Tms) of 214 ° C., a glass transition point (Tg) of 61 ° C., and a carboxyl group content of 29 eq. / Ton, melt viscosity 36 Pa · s, the stereocomplex crystallinity calculated using the formula (1) was 100%.

  The results are summarized in Table 1. In Table 1, ΔHms is the melting enthalpy of the crystalline melting point appearing at 190 ° C. or higher and lower than 250 ° C., and ΔHmh is the melting enthalpy of the crystalline melting point appearing below 190 ° C. Tms is a crystalline melting point appearing at 190 ° C. or more and less than 250 ° C., and Tmh is a crystalline melting point appearing at less than 190 ° C.

2. Production of cyclic carbodiimide Cyclic carbodiimide was produced by the method shown in the following production examples. Moreover, each value in a manufacture example was calculated | required with the following method.

(1) Identification of cyclic carbodiimide structure by NMR Identification of the synthesized cyclic carbodiimide compound by NMR was confirmed by ¹ H-NMR and ¹³ C-NMR using JNR-EX270 manufactured by JEOL Ltd. In addition, deuterated chloroform was used as a solvent.

(2) Identification of carbodiimide skeleton of cyclic carbodiimide by IR Identification of the carbodiimide skeleton of the synthesized cyclic carbodiimide compound uses Magna-750 manufactured by Nicorey Co., Ltd., and 2100-2200 cm ⁻¹ characteristic of carbodiimide by FT-IR. This was done by confirming the absorption peak of.

In the examples of the present invention, the following materials were used.
[D-1 component: Production of cyclic carbodiimide (CC1)]
[Production Example 2]
Reaction in which 200 ml of o-nitrophenol (0.11 mol), 1,2-dibromoethane (0.05 mol), potassium carbonate (0.33 mol), and N, N-dimethylformamide (DMF) were installed with a stirrer and a heating device The apparatus was charged in an N ₂ atmosphere and reacted at 130 ° C. for 12 hours. After that, DMF was removed under reduced pressure, and the resulting solid was dissolved in 200 ml of dichloromethane and separated three times with 100 ml of water. The organic layer was dehydrated with 5 g of sodium sulfate, and dichloromethane was removed under reduced pressure to obtain an intermediate product A (nitro form).

  Next, intermediate product A (0.1 mol), 5% palladium carbon (Pd / C) (1 g), and 200 ml of ethanol / dichloromethane (70/30) were charged into a reactor equipped with a stirrer, and 5 hydrogen substitution was performed. The reaction is performed in a state where hydrogen is constantly supplied at 25 ° C., and the reaction is terminated when there is no decrease in hydrogen. When Pd / C was recovered and the mixed solvent was removed, an intermediate product B (amine body) was obtained.

Next, in a reactor equipped with a stirrer, a heating device, and a dropping funnel, triphenylphosphine dibromide (0.11 mol) and 150 ml of 1,2-dichloroethane are charged and stirred in an N ₂ atmosphere. A solution prepared by dissolving intermediate product B (0.05 mol) and triethylamine (0.25 mol) in 50 ml of 1,2-dichloroethane is gradually added dropwise thereto at 25 ° C. After completion of dropping, the reaction is carried out at 70 ° C. for 5 hours. Thereafter, the reaction solution was filtered, and the filtrate was separated 5 times with 100 ml of water. The organic layer was dehydrated with 5 g of sodium sulfate, and 1,2-dichloroethane was removed under reduced pressure to obtain an intermediate product C (triphenylphosphine compound).

Next, in a reactor equipped with a stirrer and a dropping funnel, di-tert-butyl dicarbonate (0.11 mol), N, N-dimethyl-4-aminopyridine (0.055 mol), dichloromethane under N ₂ atmosphere. 150 ml was charged and stirred. Thereto, 100 ml of dichloromethane in which the intermediate product C (0.05 mol) was dissolved was slowly added dropwise at 25 ° C. After dropping, react for 12 hours. Then, CC1 was obtained by refine | purifying the solid substance obtained by removing dichloromethane. As a result of confirming the structure of CC1 by NMR and IR, it was a structure represented by the following formula.

As other raw materials, the following were used.
<B component>
B-1: Panlite CM-1000 manufactured by Teijin Ltd. [Linear aromatic polycarbonate powder synthesized by interfacial polycondensation from bisphenol A and p-tert-butylphenol as a terminator and phosgene] Viscosity average molecular weight 16, 000 melt viscosity 805 Pa · s]
B-2: Aromatic polycarbonate manufactured by Teijin Limited [Linear aromatic polycarbonate powder synthesized from bisphenol A and p-tert-butylphenol as a terminal terminator and phosgene by the interfacial polycondensation method] Viscosity average molecular weight 12,300 Melting Viscosity 288 Pa · s]
B-3: Aromatic polycarbonate manufactured by Teijin Limited [Linear aromatic polycarbonate powder synthesized from bisphenol A and p-tert-butylphenol as a terminator and phosgene by the interfacial polycondensation method] Viscosity average molecular weight 17,500 Melting Viscosity 1394 Pa · s]
B′-1: Aromatic polycarbonate manufactured by Teijin Limited [Linear aromatic polycarbonate powder synthesized from bisphenol A and p-tert-butylphenol as a terminator and phosgene by an interfacial polycondensation method] Viscosity average molecular weight 9,100 Melt viscosity 77 Pa · s]
B′-2: Panlite L-1225WX manufactured by Teijin Limited [Linear aromatic polycarbonate powder synthesized by interfacial polycondensation from bisphenol A and p-tert-butylphenol as a terminal terminator and phosgene] Viscosity average molecular weight 19 700 melt viscosity 2077 Pa · s]
<C component>
C-1: HO C422 6MM manufactured by Toho Tenax Co., Ltd. [carbon fiber chopped strand having an average diameter of 7 μm and a cut length of 6 mm]
C-2: 3PE-937S manufactured by Nittobo Co., Ltd. [glass fiber chopped strand having an average diameter of 13 μm and a cut length of 3 mm]

3. Production and Evaluation of Polylactic Acid Pellets Resin composition pellets of polylactic acid (component A) and additives 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) Deflection temperature under load Using an injection molding machine (manufactured by Toshiba Machine Co., Ltd .: IS-150EN), the cylinder temperature is 230 ° C., the mold temperature is 120 ° C., and the molding cycle is 70 seconds, and 80 mm × 10 mm. A test piece conforming to ISO standards of 4 mm was molded and allowed to stand for 24 hours in an environment of a temperature of 23 ° C. and a relative humidity of 50%, and then measured at a load of 0.45 MPa according to ISO 75-1 and 2. .

(2) Flexural modulus, flexural strength The composition was injected using an injection molding machine (Toshiba Machine Co., Ltd .: IS-150EN) at a cylinder temperature of 230 ° C, a mold temperature of 120 ° C, and a molding cycle of 70 seconds. A test piece conforming to the ISO standard of 80 mm × 10 mm × 4 mm was molded, allowed to stand in an environment of a temperature of 23 ° C. and a relative humidity of 50% for 24 hours, and then measured according to ISO 78.

(3) Mold Shrinkage The composition was 80 mm × 10 mm at a cylinder temperature of 230 ° C., a mold temperature of 120 ° C., and a molding cycle of 70 seconds using an injection molding machine (Toshiba Machine Co., Ltd .: IS-150EN). A test piece conforming to the ISO standard of 4 mm was molded and left for 24 hours in an environment of a temperature of 23 ° C. and a relative humidity of 50%. Using a three-dimensional measuring machine (FJ604 manufactured by Mitutoyo Corporation), the dimensions of any three points in the longitudinal direction (parallel direction) of the test piece were measured, and the average value was taken as the dimension in the parallel direction. The dimensions in the transverse direction (vertical direction) were determined in the same manner as in the parallel direction. Subsequently, the mold used for molding was measured in the same manner as the test piece, and the mold shrinkage ratio [100 × (dimension dimension−test piece dimension) / (mold dimension)] in the parallel direction. , For each vertical direction.

(4) Hydrolysis resistance Using an injection molding machine (Toshiba Machine Co., Ltd .: IS-150EN), the resin composition was subjected to ISO 527 at a cylinder temperature of 230 ° C, a mold temperature of 120 ° C, and a molding cycle of 70 seconds. A molded piece of 1A type described in -2. Next, this molded piece was subjected to wet heat treatment for 300 hours under the condition of 80 ° C. × 95% RH. In accordance with ISO527-1 and ISO527-2, a tensile test was performed, and the retention rate [(maximum tensile stress after wet heat treatment / before wet heat treatment) was determined from the maximum tensile stress before wet heat treatment and the maximum tensile stress after wet heat treatment. Maximum tensile stress) × 100] was calculated.

<Example 1>
Using polylactic acid A-1 produced in Production Example 1-1 as polylactic acid, the components except for component C in the composition of Table 2 are uniformly premixed by dry blending, and then this premixed mixture is supplied first. C component was supplied from the second supply port, melt extruded and pelletized. Here, the first supply port is a base supply port, and the second supply port is a supply port provided with a side screw. The melt extrusion was carried out using a vent type twin screw extruder [TEX30XSST manufactured by Nippon Steel Works, Ltd.] with a diameter of 30 mmφ equipped with a side screw. The extrusion temperature is C1 / C2 to C11 / D = 10 ° C./250° C./240° C., the main screw rotation speed is 150 rpm, the side screw rotation speed is 100 rpm, the discharge amount is 20 kg / h, and the vent pressure reduction degree is 3 kPa. It was.
The obtained pellets were dried with a hot air circulation dryer at 100 ° C. for 5 hours, molded with an injection molding machine (Toshiba Machine Co., Ltd .: IS-150EN), and evaluated. The results are shown in Table 2.

<Examples 2, 9, 11 and Comparative Example 3>
Except having used polylactic acid A-2 manufactured by manufacture example 1-2 as polylactic acid, it pelletized by the method similar to Example 1, and implemented the evaluation. The results are shown in Table 2 and Table 3.

<Examples 3-8, 12-14, Comparative Examples 1-2, Comparative Examples 8-9>
Except having used polylactic acid A-3-1 manufactured by manufacture example 1-4 as polylactic acid, it pelletized by the method similar to Example 1, and the evaluation was implemented. The results are shown in Tables 2-4.

<Example 10, Comparative Examples 4 and 7>
Except having used polylactic acid A-3-2 manufactured by manufacture example 1-5 as polylactic acid, it pelletized by the method similar to Example 1, and the evaluation was implemented. The results are shown in Table 2 and Table 3.

<Comparative Example 5>
Except having used polylactic acid A'-1 manufactured by manufacture example 1-3 as polylactic acid, it pelletized by the method similar to Example 1, and the evaluation was implemented. The results are shown in Table 3.

<Comparative Example 6>
Except that polylactic acid A′-3 produced in Production Example 1-6 was used as the polylactic acid, it was pelletized by the same method as in Example 1 and evaluated. The results are shown in Table 3.

<Examples 1 to 12>
A polylactic acid having a weight average molecular weight of 100,000 to 200,000 and an aromatic polycarbonate having a viscosity average molecular weight of 10,000 to 19,000 are used, and the melt viscosity ratio of the polylactic acid and the aromatic polycarbonate is 0.1 or more. Therefore, it was an excellent material having excellent mechanical properties such as bending elastic modulus and bending strength, and a small difference between the molding shrinkage in the parallel direction and the molding shrinkage in the vertical direction.

<Examples 13 and 14>
A polylactic acid having a weight average molecular weight of 100,000 to 200,000 and an aromatic polycarbonate having a viscosity average molecular weight of 10,000 to 19,000 are used, and the melt viscosity ratio of the polylactic acid and the aromatic polycarbonate is 0.1 or more. Therefore, the mechanical properties of bending elastic modulus and bending strength were excellent, and the difference between the molding shrinkage rate in the parallel direction and the molding shrinkage rate in the vertical direction was small, and the hydrolysis resistance was also very good.

<Comparative Example 1>
Since the resin component was only polylactic acid, the difference between the molding shrinkage in the parallel direction and the molding shrinkage in the vertical direction was large.

<Comparative example 2>
Since the ratio of the aromatic polycarbonate was large, compared with Example 7, the adhesion of the CF was lowered and the CF was bent, and the mechanical properties of the bending elastic modulus and bending strength were low.

<Comparative Example 3>
Since the viscosity average molecular weight of the aromatic polycarbonate was larger than 19,000, the CF was bent and the mechanical properties of bending elastic modulus and bending strength were lower than those of Example 7.

<Comparative Example 4>
Since the viscosity average molecular weight of the aromatic polycarbonate was less than 10,000, the mechanical properties of the bending strength were low compared to Example 7.

<Comparative Example 5>
Since the polylactic acid had a weight average molecular weight larger than 200,000, it caused the CF to fold, resulting in lower mechanical properties of flexural modulus and flexural strength than Example 7.

<Comparative Example 6>
Since the weight average molecular weight of polylactic acid was less than 100,000, the mechanical properties of bending strength were low.

<Comparative Example 7>
Polylactic acid having a weight average molecular weight of 100,000 to 200,000 and an aromatic polycarbonate having a viscosity average molecular weight of 10,000 to 19,000 were used, but the melt viscosity ratio of polylactic acid and aromatic polycarbonate was less than 0.1. Therefore, the difference between the molding shrinkage in the parallel direction and the molding shrinkage in the vertical direction was large.

<Comparative Example 8>
Since the fibrous filler was less than 10 parts by weight, the mechanical properties of bending elastic modulus and bending strength were low.

<Comparative Example 9>
Since the fibrous filler was larger than 110 parts by weight, the resin was clogged at the die portion of the extruder, and extrusion was not possible.

Claims (7)

(A) Polylactic acid having a weight average molecular weight of 100,000 to 200,000 (component A) 95 to 60 % by weight and (B) Aromatic polycarbonate having a viscosity average molecular weight of 10,000 to 19,000 (component B) 5 to 40 100 parts by weight of a resin component having a ratio of the melt viscosity of the component A to the melt viscosity of the component B measured by a high shear measuring machine represented by the following formula (1) is 0.1% or more. On the other hand, (C) A resin composition containing 10 to 110 parts by weight of a fibrous filler (component C).
Ratio of melt viscosity of component A to melt viscosity of component B = ηA / ηB (1)
[However, in the formula (1), ηA and ηB represent the melt viscosity of the A component and the melt viscosity of the B component, respectively, measured at 250 ° C. and 250 sec ⁻¹ using a high shear measuring machine. ]   The resin composition according to claim 1, wherein the C component is at least one fibrous filler selected from the group consisting of carbon fiber (C-1 component) and glass fiber (C-2 component).   A component contains (A-1) poly L-lactic acid (A-1 component) mainly composed of L-lactic acid units and (A-2) poly D-lactic acid (A-2 component) mainly composed of D-lactic acid units. The weight ratio of the A-1 component and the A-2 component is in the range of 10:90 to 90:10, and the poly L-lactic acid (A-1 component) contains 90 mol% or more of L-lactic acid units. The poly D-lactic acid (component A-2) is a resin composition according to claim 1 or 2, which contains 90 mol% or more of D-lactic acid units. The A component has a stereocomplex crystallinity represented by the following formula (2) using a melting enthalpy in a temperature rising process of differential scanning calorimetry (DSC) measurement, and the degree of stereocomplexity is 80% or more. 2. The resin composition according to item 1.
Stereo complex crystallinity = [ΔHms / (ΔHms + ΔHmh)] × 100 (2)
[In the formula (2), ΔHmh and ΔHms are the melting enthalpy (ΔHmh) of the melting point of the crystal that appears below 190 ° C. in the temperature rising process of the differential scanning calorimeter (DSC), respectively, and 190 ° C. or more and 250 It is the melting enthalpy (ΔHms) of the crystalline melting point that appears below ° C. ]   The resin composition of any one of Claims 1-4 which contains 0.01-10 weight part of (D) carbodiimide compound (D component) with respect to a total of 100 weight part of A component and B component.   The molded article which consists of a composition of any one of Claims 1-5.   An injection-molded article comprising the composition according to any one of claims 1 to 5.