JP5378904B2 - Flame retardant polylactic acid resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an excellent industrial material that is environmentally friendly and has high flame retardance and high hydrolysis resistance. <P>SOLUTION: A polylactic acid resin composition comprises: 100 pts.wt. resin component comprising (A) 5-95 wt.% polylactic acid resin (component A) and (B) 95-5 wt.% thermoplastic resin (component B) other than component A; (C) 5-100 pts.wt. at least one flame retardant (component C) selected from the group consisting of a phosphorus flame retardant, a nitrogen flame retardant, a metal oxide and a metal hydroxide; and (D) 0-30 pts.wt. flame retardant aid (component D). The polylactic acid resin composition is obtained by: melt-kneading a mixture of &ge;20 wt.% thermoplastic resin (component B) other than component A, &le;70 wt.% a portion or all of flame retardant (component C) and 0-30 wt.% flame retardant aid (component D) so as to prepare a thermoplastic resin composition; and melt-kneading the thermoplastic resin composition, the polylactic acid resin (component A) and the flame retardant (component C) not used for preparing the thermoplastic resin composition at a temperature equal to or higher than the melting points of the polylactic acid resin (component A) and the thermoplastic resin (component B) other than component A. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  The present invention has flame retardancy that can be prepared by blending a non-halogen flame retardant with a specific blending technique into a polylactic acid resin that is a polymer obtained from biomass resources and a thermoplastic resin other than polylactic acid. The present invention relates to a flame retardant polylactic acid resin composition having hydrolysis resistance.

  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 resin has relatively high heat resistance and mechanical properties among biomass plastics, so its application is expanding to tableware, packaging materials, general merchandise, etc. It has become like this. However, polylactic acid has not been fully developed into industrial materials that require durability due to its lack of flame retardancy and hydrolysis resistance.

  Patent Document 1 discloses a flame-retarding technique in which a halogen-based flame retardant is added to an alloy of polylactic acid and polybutylene terephthalate, but the halogen-based flame retardant may generate a toxic gas during combustion. There is. Patent Document 2 shows that by adding a metal hydroxide subjected to surface treatment to a lactic acid-based resin, thermal decomposition during molding can be suppressed and high flame retardancy can be obtained. However, in order to actually develop as an industrial material, hydrolysis resistance is still insufficient, and further improvement is necessary. Patent Document 3 discloses a technique for adding an aromatic condensed phosphate ester compound to a polylactic acid resin, but when a phosphorus-based flame retardant such as a condensed phosphate ester is added to the polylactic acid resin. However, the hydrolysis resistance is often deteriorated, and the hydrolysis resistance is still insufficient for practical development as an industrial material. Patent Document 4 discloses a technique for improving flame retardancy and moldability by blending flame retardant fine particles composed of a metal salt flame retardant and a thermoplastic resin into a thermoplastic polyester resin such as polylactic acid. However, not only the effect on hydrolysis resistance is not shown, but also when such flame-retardant fine particles are used, there is a problem of causing a granular appearance defect in the molded product.

JP 2008-50580 A JP 2008-308693 A JP 2005-89546 A JP 2008-303289 A

  In the present invention, in order to solve the above-mentioned problems, a non-halogen flame retardant having a low environmental load is blended with a resin component composed of a polylactic acid resin and a thermoplastic resin other than polylactic acid, and the environmental load is low and high. It aims at providing the outstanding industrial material which has a flame retardance and hydrolysis resistance. As a result of diligent research to achieve the above object, the present inventors blended a non-halogen flame retardant with a specific blending technique with respect to a resin component composed of a polylactic acid resin and a thermoplastic resin other than polylactic acid, The inventors have found that an industrial material having excellent flame retardancy and hydrolysis resistance can be obtained, thereby completing the present invention.

  That is, the present invention relates to 100 parts by weight of a resin component comprising (A) a polylactic acid resin (component A) 5 to 95% by weight and (B) a thermoplastic resin (component B) other than A component 95 to 5% by weight. (C) 5 to 100 parts by weight of at least one flame retardant (component C) selected from the group consisting of phosphorus-based flame retardants, nitrogen-based flame retardants, metal oxides, and metal hydroxides, and (D) flame retardants A polylactic acid resin composition containing 0 to 30 parts by weight of an auxiliary agent (D component), wherein a thermoplastic resin (B component) other than the A component is 20% by weight or more, and part or all of the flame retardant (C component) 70 After preparing a thermoplastic resin composition by melt-kneading a mixture of 0 wt% or less and flame retardant aid (D component) 0-30 wt%, the thermoplastic resin composition, polylactic acid resin (A component), and Flame retardant (C which was not used for preparation of said thermoplastic resin composition Minute), a polylactic acid resin composition characterized by being obtained by melt-kneading at least the melting point of the polylactic acid resin (A component) and component A other than the thermoplastic resin (B component). Furthermore, it is preferable that the terminal blocking agent (component E) is contained in an amount of 0.01 to 5 parts by weight with respect to a total of 100 parts by weight of the polylactic acid resin (component A) and the thermoplastic resin other than the component A (component B). The inorganic filler (F component) is preferably contained in an amount of 0.05 to 150 parts by weight with respect to a total of 100 parts by weight of the polylactic acid resin (A component) and the thermoplastic resin (B component) other than the A component.

  The present invention is obtained by blending a non-halogen flame retardant having a low environmental burden with a specific blending technique with respect to a resin component composed of a polylactic acid resin and a thermoplastic resin other than polylactic acid, and has a low environmental burden. Providing excellent industrial materials that combine high flame resistance and hydrolysis resistance.

  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 resin (component A) used 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 resin (component A-1) and the poly-D lactic acid resin (component A-2) of the present invention substantially consist of an L-lactic acid unit or a D-lactic acid unit represented by the formula (I). .

  The optical purity of the poly-L lactic acid resin or poly-D lactic acid resin 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. For this reason, the melting point of the poly-L lactic acid resin or the poly-D lactic acid resin 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 a D-lactic acid unit in the case of a poly-L lactic acid resin, an L-lactic acid unit in the case of a poly-D lactic acid resin, and units other than the lactic acid unit. 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. Examples of the polyhydric alcohol include aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, glycerin, sorbitan, neopentyl glycol, diethylene glycol, triethylene glycol, polyethylene glycol, and polypropylene glycol. Or aromatic polyhydric alcohol etc., such as what added ethylene oxide to bisphenol, etc. are mentioned. Examples of the hydroxycarboxylic acid include glycolic acid and hydroxybutyric acid. Examples of the lactone include glycolide, ε-caprolactone, β-propiolactone, δ-butyrolactone, β- or γ-butyrolactone, pivalolactone, and δ-valerolactone.

  The weight average molecular weights of the poly L-lactic acid resin and the poly D-lactic acid resin are preferably 80,000 to 300,000, more preferably 100,000 to 250,000, in order to achieve both the mechanical properties and moldability of the composition of the present invention. Preferably, a range of 120,000 to 230,000 is selected.

Poly L-lactic acid resin and poly D-lactic acid resin can be produced by a conventionally known method, for example, melt ring-opening polymerization method of L-lactide or D-lactide, solid-phase polymerization method of low molecular weight polylactic acid Furthermore, a direct polymerization method in which lactic acid is dehydrated and condensed can be exemplified. 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 1 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. Such a 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 (II) 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 is an integer of 1 to 3. As a compound represented by the formula (II), 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-decylphospho Ethyl propionate, 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 (II), 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 it is sufficiently melted and 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 is an integer of 1-3, the metal polymerization catalyst in polylactic acid can be supplemented efficiently.

  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 resin (component A-1) and poly D-lactic acid resin (component A-2) is used, the weight ratio (component A-1 / component A-2) is 10:90 to 90: It is preferable to contain in 10 range. Furthermore, a phosphate ester metal salt represented by the formula (III) and / or (IV) is added to a mixture of the poly L-lactic acid resin (A-1 component) and the poly D-lactic acid resin (A-2 component). By including in the range of preferably 0.01 to 2.0 parts by weight per 100 parts by weight in total of the poly L-lactic acid resin (component A-1) and the poly D-lactic acid resin (component A-2), A stereocomplexed polylactic acid resin can be obtained, which is preferable. If the phosphate metal salt is less than 0.01 parts by weight, there may be no effect on the formation of the stereocomplex and the improvement of crystallinity. Decomposition of components and generation of foreign matter may occur. 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.

（式中Ｒ_１４は水素原子、または炭素原子数１〜４のアルキル基を、Ｒ_１５、Ｒ_１６、Ｒ_１７はそれぞれ独立に水素原子、または炭素原子数１〜１２のアルキル基を、Ｍ_１はアルカリ金属原子、アルカリ土類金属原子、亜鉛原子またはアルミニウム原子を表し、ｐは１または２を、ｑはＭ_１がアルカリ金属原子、アルカリ土類金属原子または亜鉛原子のときは０を、アルミニウム原子のときは１または２を表す。）

(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 is 1 or 2, q is 0 when M ₁ is an alkali metal atom, alkaline earth metal atom or zinc atom, aluminum When it is an atom, it represents 1 or 2.)

（式中Ｒ_１８、Ｒ_１９はそれぞれ独立に水素原子、または炭素原子数１〜１２のアルキル基を、Ｍ_２はアルカリ金属原子、アルカリ土類金属原子、亜鉛原子またはアルミニウム原子を表し、ｐは１または２を、ｑはＭ_２がアルカリ金属原子、アルカリ土類金属原子または亜鉛原子のときは０を、アルミニウム原子のときは１または２を表す。）

(Wherein R ₁₈ and R ₁₉ each independently represents 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, a zinc atom or an aluminum atom, and p represents 1 or 2, q represents 0 when M ₂ is an alkali metal atom, an alkaline earth metal atom or a zinc atom, and 1 or 2 when M ₂ is an aluminum atom.

The polylactic acid produced in this way becomes a highly stereocomplexed stereocomplex polylactic acid, which is described below using the melting enthalpy derived from the polylactic acid resin (component A) crystal in the temperature rising process of differential scanning calorimetry (DSC) measurement. It is preferable that the degree of stereoification represented by Formula (1) is 80% or more.
Stereoization degree = 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.

  The higher the degree of stereoification, the higher the moldability and heat resistance. The degree of stereoization is more preferably 85% or more, and still more preferably 90% or more. If the degree of stereogenicity is lower than 80%, the characteristics of homocrystals derived from poly-L lactic acid resin or poly-D lactic acid resin will appear, resulting in insufficient heat resistance.

  The melting point of the stereocomplex crystal is preferably 200 ° C. or higher, more preferably 205 ° C. or higher, and further preferably 210 ° C. or higher. If the melting point of stereocomplex polylactic acid is lower than 195 ° 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 degree of stereoification is 80% or more, the melting point is 200 ° C. or more, and the melting enthalpy is 20 J / g or more.

<About B component>
The thermoplastic resin other than the polylactic acid of the present invention is not particularly limited as long as it is a thermoplastic resin. The thermoplastic resins that can be used in the present invention include aromatic polyester resins, aliphatic polyester resins, polycarbonate resins, polyarylate resins, polyamide resins, acrylic resins, polyimide resins, polyetherimide resins, polyurethane resins, silicone resins, polyphenylene sulfide. Resin, polysulfone resin, polyolefin resin such as polyethylene and polypropylene, polystyrene resin, acrylonitrile / styrene copolymer (AS resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), high impact polystyrene resin, syndiotactic polystyrene resin , Polymethacrylate resins, and phenoxy or epoxy resins.

Aromatic polyester resins are preferred from the viewpoints of resistance to flame retardants, heat resistance, and compatibility with polylactic acid resin (component A).
The aromatic polyester resin is preferably an aromatic polyester resin in which 70 mol% or more of 100 mol% of the dicarboxylic acid component among the dicarboxylic acid component and the diol component forming the polyester is an aromatic dicarboxylic acid, more preferably 90 mol. % Or more, and most preferably 99 mol% or more is an aromatic polyester resin which is an aromatic dicarboxylic acid.

  Examples of this dicarboxylic acid include terephthalic acid, isophthalic acid, adipic acid, 2-chloroterephthalic acid, 2,5-dichloroterephthalic acid, 2-methylterephthalic acid, 4,4-stilbene dicarboxylic acid, 4,4-biphenyldicarboxylic acid Acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, bisbenzoic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4-diphenyl ether dicarboxylic acid, 4,4- Examples thereof include diphenoxyethanedicarboxylic acid, 5-Na sulfoisophthalic acid, and ethylene-bis-p-benzoic acid. These dicarboxylic acids can be used alone or in admixture of two or more.

  In addition to the above aromatic dicarboxylic acid, the aromatic polyester resin of the present invention can be copolymerized with an aliphatic dicarboxylic acid component of less than 30 mol%. Specific examples thereof include adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and the like.

  Examples of the diol component of the present invention include ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, trans- or cis-2,2, 4,4-tetramethyl-1,3-cyclobutanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,3 -Cyclohexanedimethanol, decamethylene glycol, cyclohexanediol, p-xylenediol, bisphenol A, tetrabromobisphenol A, tetrabromobisphenol A-bis (2-hydroxyethyl ether) and the like. These can be used alone or in admixture of two or more. In addition, it is preferable that the dihydric phenol in a diol component is 30 mol% or less.

  Specific aromatic polyester resins include polyethylene terephthalate (PET), polypropylene terephthalate, polybutylene terephthalate (PBT), polyhexylene terephthalate, polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polyethylene-1, In addition to 2-bis (phenoxy) ethane-4,4′-dicarboxylate, copolymer polyester resins such as polyethylene isophthalate / terephthalate copolymer, polybutylene terephthalate / isophthalate copolymer, and the like can be given.

  In addition, the terminal group structure of the aromatic polyester resin used in the present invention is not particularly limited, and it may be a case where the ratio of one of the hydroxyl groups and the carboxyl group in the terminal group is large, except when the ratio is almost the same. May be. Moreover, those terminal groups may be sealed by reacting a compound having reactivity with such terminal groups.

  About the manufacturing method of the aromatic polyester resin used for this invention, a dicarboxylic acid component and the said diol component are superposed | polymerized in the presence of the polycondensation catalyst containing titanium, germanium, antimony, etc. according to a conventional method. The by-product water or lower alcohol is discharged out of the system. For example, germanium-based polymerization catalysts include germanium oxides, hydroxides, halides, alcoholates, phenolates, and the like. More specifically, germanium oxide, germanium hydroxide, germanium tetrachloride, tetramethoxygermanium, etc. Can be illustrated. Further, in the present invention, compounds such as manganese, zinc, calcium, magnesium, etc., which are used in a transesterification reaction that is a prior stage of a conventionally known polycondensation, can be used in combination, and phosphoric acid or phosphorous after completion of the transesterification reaction. Such a catalyst can be deactivated and polycondensed with an acid compound or the like. Furthermore, the production method of the aromatic polyester resin can be either batch type or continuous polymerization type.

  Further, among the aromatic polyester resins, polybutylene terephthalate and polyethylene terephthalate are preferable, and polybutylene terephthalate is particularly preferable. The polybutylene terephthalate of the present invention is a polymer obtained by polycondensation reaction from terephthalic acid or a derivative thereof and 1,4-butanediol or a derivative thereof, but as described above, other dicarboxylic acid components and other alkylenes. Includes copolymerized glycol components.

  The end group structure of polybutylene terephthalate is not particularly limited, as described above, but more preferably it has less terminal carboxyl groups than terminal hydroxyl groups. Moreover, although the said various methods can be taken also about a manufacturing method, the thing of a continuous polymerization type is preferable. This is because the quality stability is high and the cost is advantageous. Further, an organic titanium compound is preferably used as the polymerization catalyst. This is because the influence on the transesterification reaction tends to be small.

  Preferred examples of such organic titanium compounds include titanium tetrabutoxide, titanium isopropoxide, titanium oxalate, titanium acetate, titanium benzoate, titanium trimellitic acid, a reaction product of tetrabutyl titanate and trimellitic anhydride, and the like. be able to. The amount of the organic titanium compound used is preferably such that the titanium atom is 3 to 12 mg atomic% with respect to the acid component constituting the polybutylene terephthalate.

  The molecular weight of the thermoplastic resin of the present invention is not particularly limited, but the intrinsic viscosity measured at 35 ° C. using o-chlorophenol as a solvent is preferably 0.5 to 1.5, particularly preferably 0.6 to 1.2.

  The ratio of the polylactic acid resin (component A) to the thermoplastic resin (component B) is 5 to 95% by weight of the polylactic acid resin (component A) and 95 to 5% by weight of the thermoplastic resin (component B). (A component) 25-95 weight%, thermoplastic resin (B component) 75-5 weight% is preferable, polylactic acid resin (A component) 50-95 weight%, thermoplastic resin (B component) 50-5 weight% Is more preferable. When the ratio of the thermoplastic resin is 95% by weight or more, the environmental load reducing effect is reduced. For this reason, it is preferable that there is little thermoplastic resin.

<About component C>
The flame retardant used in the present invention is at least one flame retardant which does not contain a halogen atom and is selected from the group consisting of a phosphorus flame retardant, a nitrogen flame retardant, a metal oxide, and a metal hydroxide.

  Examples of the phosphorus flame retardant include phosphate ester flame retardants such as phosphate ester compounds and phosphaphenanthrene compounds, phosphonate oligomer compounds, phosphonitrile oligomer compounds, organic phosphinic acid metal salts, and phosphate metal salts. In particular, organic phosphinic acid metal salts and phosphoric acid metal salts, which have a high phosphorus content and are easy to obtain high flame retardancy, are preferred.

Examples of the organic phosphinic acid metal salt include one or more of the following general formulas (V) and (VI).

In the formula, each of R ₂₁ , R ₂₂ , R ₂₃ , and R ₂₄ is independently a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, or an aryl having 6 to 20 carbon atoms. Group, or an aralkyl group having 7 to 20 carbon atoms. R ₂₅ is a linear or branched alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 6 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, an alkylene arylene group having 7 to 20 carbon atoms, or 7 carbon atoms. ˜20 cycloalkylenearylene groups. M ¹ and M ² are Mg, Ca, Al, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K, or a protonated nitrogen base. X is 1 or 2, m is 2 or 3, and n is 1 or 3.

R ₂₁ , R ₂₂ , and R ₂₄ appropriately maintain the phosphorus content in the component B, preferably exhibit flame retardancy, and at the same time, preferably exhibit the crystallinity of the composition. A linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms is preferably selected. Of these, a linear or branched alkyl group having an average carbon number in the range of 1 to 10 and an aryl group having 6 to 20 carbon atoms are preferably selected.
Specifically, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an n-pentyl group, or a phenyl group is preferably exemplified.

R ₂₃ is properly retain a phosphorus content in component B, at the same time desirably developing a flame retardant, for desirably developing a crystalline composition, straight chain carbon atoms in the range of 1 to 10 Alternatively, a branched alkylene group, a cycloalkylene group having 6 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, an alkylene arylene group having 7 to 20 carbon atoms, and a cycloalkylene arylene group having 7 to 20 carbon atoms are preferably selected. .

  Specifically, for example, methylene group, ethylene group, methylethane-1,3-diyl group, propane-1,3-diyl group, 2,2-dimethylpropane-1,3-diyl group, butane-1,4-diyl Group, octane-1,8-diyl group, phenylene group, naphthylene group, ethylphenylene group, tert-butylphenylene group, methylnaphthylene group, ethylnaphthylene group, phenylenemethylene group, phenyleneethylene group, phenylenepropylene group, phenylenebutylene group Etc. are exemplified.

M ¹ and M ² are at least one selected from Mg, Ca, Al, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K and protonated nitrogen base, and protonated nitrogen Examples of the base include an amide group, an ammonium group, an alkylammonium group, or a group derived from melamine.

In order to improve the flame retardancy, crystallinity, moldability, etc. of the composition of the present invention, M ¹ and M ² are derived from Mg, Ca, Al, Zn and groups derived from amide, ammonium, alkylammonium or melamine. It is a kind selected from the group. Among these, Al is most preferably selected.
When the phosphinic acid salts represented by the formulas (V) and (VI) are used in combination, the weight ratio of (V) / (VI) is preferably selected from the range of 10/90 to 30/70.

  Examples of the metal phosphate include aluminum, aluminum phosphite represented by the following general formula (VII), primary aluminum phosphate represented by the following general formula (VIII), and the following general formula (IX). The represented tertiary aluminum phosphate is preferred.

  Of the flame retardants represented by the general formulas (VII) to (IX), the flame retardants represented by the general formulas (VII) and (VIII) are included in terms of the thermal stability and flame retardancy of the polylactic acid resin composition. Preferably, aluminum phosphite represented by the general formula (VII) is particularly preferable from the viewpoint of heat stability and flame retardancy, and foamable aluminum phosphite is most preferable from the viewpoint of flame retardancy.

The foamable aluminum phosphite salt is obtained by reacting phosphoric acid or a phosphorous acid component, an aluminum compound, and, if necessary, a base component. Instead of the aluminum compound and the base component, a basic aluminum compound (such as aluminum hydroxide) may be used. Such foamable aluminum phosphite can be obtained from Taihei Chemical Industry Co., Ltd. under the trade name “APA series (APA-100, etc.)”, for example.
The foamable aluminum phosphite can be foamed usually at a temperature of 380 ° C. to 480 ° C., preferably 10 to 70 times, more preferably 20 to 50 times, and even more preferably about 30 to 40 times.

The aluminum content in aluminum phosphite, which is the most preferred metal phosphate, is preferably about 5 to 25% by weight, more preferably about 8 to 20% by weight. Moreover, phosphorus content becomes like this. Preferably it is 15 to 35 weight%, More preferably, it is 16 to 35 weight%, More preferably, it is about 17 to 33 weight%. The pH of the aqueous dispersion containing aluminum phosphite at a concentration of 5% by weight is preferably 3.5 to 8.5, more preferably 4 to 8, and still more preferably about 4.5 to 7.5. Aluminum phosphite can usually be used in the form of granules. The average particle size of the particulate aluminum phosphite is preferably about 0.01 to 100 μm, more preferably about 0.1 to 50 μm. The oil absorption amount of aluminum phosphite is preferably about 15 to 50 mL / 100 g, more preferably about 20 to 40 mL / 100 g, and still more preferably about 25 to 30 mL / 100 g. The BET specific surface area of aluminum phosphite is preferably about 0.3 to ² m ² / g, more preferably about 0.5 to 1.5 m ² / g, and still more preferably about 0.8 to 1.2 m ² / g. is there. Such a metal salt is excellent in safety, has a low environmental impact and is economically advantageous, and when added to a polylactic acid resin composition, it has excellent thermal stability, heat resistance, and moldability. Material.

  In order to improve moisture resistance, the organic phosphinic acid metal salt and phosphoric acid metal salt flame retardant used in the present invention may be used after coating the surface, or may be coated with a thermosetting resin or the like. Examples of the thermosetting resin include a phenol resin, a melamine resin, a urea resin, an alkyd resin, an unsaturated polyester resin, an epoxy resin, a silicone resin, and the like. Also good.

  The organic phosphinic acid metal salt and phosphoric acid metal salt flame retardant used in the present invention may be used after being surface-treated with a surface treating agent or the like in order to improve the adhesion to the base resin. As such a surface treatment agent, a functional compound (for example, an epoxy compound, a silane compound, a titanate compound, etc.) can be used.

Specific examples of the phosphate ester flame retardant used in the present invention include one or more phosphate ester compounds represented by the following general formula (X).

However, X in the above formula is hydroquinone, resorcinol, bis (4-hydroxydiphenyl) methane, bisphenol A, dihydroxydiphenyl, dihydroxynaphthalene, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis ( And groups derived from 4-hydroxyphenyl) sulfide. n is an integer of 0 to 5, or an average value of 0 to 5 in the case of a mixture of phosphate esters having different n numbers. R ₂₆ , R ₂₇ , R ₂₈ , and R ₂₉ are each independently derived from phenol, cresol, xylenol, isopropylphenol, butylphenol, p-cumylphenol substituted or unsubstituted with one or more halogen atoms. It is a group.

More preferably, X in the formula is a group derived from hydroquinone, resorcinol, bisphenol A, and dihydroxydiphenyl, n is an integer of 1 to 3, or a blend of n different phosphate esters. In the case of R ₂₆ , R ₂₇ , R ₂₈ , and R ₂₉ each independently from phenol, cresol, xylenol that is substituted or more preferably substituted with one or more halogen atoms. Those that are groups to be derived are mentioned.

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

  Examples of the nitrogen-based flame retardant used in the present invention include at least one selected from the group consisting of flame retardants represented by the formula (XI) or (XII).

［式中、Ｒ_３１〜Ｒ_３６は、各々独立に水素原子、炭素数１〜８のアルキル基、炭素数５〜１６のシクロアルキル基、（これらは置換されていないか、水酸基または炭素数１〜４のヒドロキシアルキル基によって置換されている。）、炭素数２〜８のアルケニル基、炭素数１〜８のアルコキシ基、アシル基、アシルオキシ基、炭素数６〜１２のアリール基、−Ｏ−ＲＡ、−Ｎ（ＲＡ）（ＲＢ）で表される基である。なお、ＲＡ及びＲＢ は、水素原子、炭素数１〜８のアルキル基、炭素数５〜１６のシクロアルキル基（ これらは置換されていないか、ヒドロキシル基または炭素数１〜４のヒドロキシアルキル官能基によって置換されている。）、炭素数２〜８のアルケニル基、炭素数１〜８のアルコキシ基、アシル基またはアシルオキシ基、炭素数６〜１２のアリール基である。但し、Ｒ_３１からＲ_３６ の全てが同時に水素原子であることはなく、かつ式（ＸＩ）、（ＸＩＩ）においてＲ_３１からＲ_３６ の全てが同時に−ＮＨ_２であることはない。Ｘは、メラミンまたはトリアジン化合物（ＸＩ）、（ＸＩＩ）と付加物を形成することができる酸であり、ｓ、ｔは各々独立に１または２である。］

[Wherein R _{31 to} R ₃₆ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 16 carbon atoms, (these are not substituted, hydroxyl groups or carbon atoms 1 Substituted with a hydroxyalkyl group having 4 to 4 carbon atoms), an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an acyl group, an acyloxy group, an aryl group having 6 to 12 carbon atoms, -O- It is a group represented by RA, -N (RA) (RB). In addition, RA and RB are a hydrogen atom, a C1-C8 alkyl group, a C5-C16 cycloalkyl group (These are not substituted, a hydroxyl group, or a C1-C4 hydroxyalkyl functional group. A alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an acyl group or an acyloxy group, and an aryl group having 6 to 12 carbon atoms. However, all of R ₃₁ to R ₃₆ are not simultaneously hydrogen atoms, and all of R ₃₁ to R ₃₆ are not simultaneously —NH ₂ in formulas (XI) and (XII). X is an acid capable of forming an adduct with melamine or triazine compounds (XI) and (XII), and s and t are each independently 1 or 2. ]

  Preferred examples of (XI) and (XII) include dimelamine pyrophosphate, melamine polyphosphate, melem polyphosphate, melam polyphosphate, and melon polyphosphate.

  Metal oxides and metal hydroxide flame retardants that can be used in this patent are magnesium hydroxide, aluminum hydroxide, calcium hydroxide, zinc hydroxide, potassium hydroxide, silicon hydroxide, titanium hydroxide, iron hydroxide, Copper hydroxide, sodium hydroxide, nickel hydroxide, boron hydroxide, manganese hydroxide, lithium hydroxide, magnesium oxide, aluminum oxide, calcium oxide, zinc oxide, potassium oxide, silicon oxide, titanium oxide, iron oxide, copper oxide , Sodium oxide, nickel oxide, boron oxide, manganese oxide, lithium oxide and the like. In particular, magnesium hydroxide, aluminum hydroxide, and calcium hydroxide are desirable because of their high flame retardancy due to their high hydroxyl group concentration per molecular weight, low toxicity, and low cost.

  In order to improve moisture resistance, the metal oxide and metal hydroxide flame retardant used in the present invention may be coated on the surface or may be coated with a thermosetting resin or the like. Examples of the thermosetting resin include a phenol resin, a melamine resin, a urea resin, an alkyd resin, an unsaturated polyester resin, an epoxy resin, a silicone resin, and the like. Also good.

  The metal oxide and metal hydroxide flame retardant used in the present invention may be used after being surface-treated with a surface treatment agent or the like in order to improve adhesion with the base resin. As such a surface treatment agent, a functional compound (for example, an epoxy compound, a silane compound, a titanate compound, etc.) can be used.

  The phosphorus flame retardant, nitrogen flame retardant, metal oxide, and metal hydroxide used in the present invention may be used alone or in combination of two or more. Content of a flame retardant (C component) is 5-100 weight part with respect to a total of 100 weight part of polylactic acid resin (A component) and thermoplastic resins (B component) other than A component, Preferably it is 10 It is -90 weight part, More preferably, it is 10-80 weight part. When the content of the flame retardant (C component) is less than 5 parts by weight, the flame retardant effect is insufficient, and when it is more than 100 parts by weight, fluidity, physical properties, and hydrolysis resistance are deteriorated.

<About D component>
As the flame retardant aid (D component) used in the present invention, an aromatic resin is preferably used. For example, a polyphenylene ether resin, a phenol resin, an aromatic epoxy resin, a phenoxy resin, a polyphenylene sulfide resin, a polycarbonate resin, Examples include arylate resins, aromatic polyamide resins, aromatic polyester resins, and aromatic polyester amide resins. Particularly, polyphenylene ether resins, phenol resins, aromatic epoxy resins, phenoxy, which have high carbonization promotion efficiency during combustion. Resins are preferred. In addition, when using an aromatic resin as a flame retardant adjuvant, resin different from thermoplastic resins (B component) other than A component can be used. For example, when the thermoplastic resin (component B) other than the component A is a polyester resin (aromatic saturated polyester resin), as the aromatic resin, a non-polyester aromatic resin (for example, polyphenylene ether resin, phenol resin) Aromatic epoxy resins, phenoxy resins, polyphenylene sulfide resins, polycarbonate resins, polyarylate resins, aromatic polyamide resins, aromatic polyesteramide resins, and the like. The polyphenylene ether resin of the present invention is a phenol polymer or copolymer having a phenylene ether structure.

  Specific examples of the polyphenylene ether resin include poly (oxy-1,4-phenylene), poly (oxy-2,6-dimethylphenylene-1,4-diyl), and poly (oxy-2-methyl-6-ethylphenylene). -1,4-diyl), poly (oxy-2,6-diethylphenylene-1,4-diyl), poly (oxy-2-ethyl-6-n-propylphenylene-1,4-diyl), poly ( Oxy-2,6-di (n-propyl) phenylene-1,4-diyl), poly (oxy-2-methyl-6-n-butylphenylene-1,4-diyl), poly (oxy-2-ethyl) -6-isopropylphenylene-1,4-diyl), poly (oxy-2-methyl-6-hydroxyethylphenylene-1,4-diyl), poly (oxy-2-methyl-6-chloroe) Rufeniren-1,4-diyl), and the like. Of these, poly (oxy-2,6-dimethylphenylene-1,4-diyl) is particularly preferred.

  Examples of the copolymer having a phenylene ether structure include a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, a copolymer of 2,6-dimethylphenol and o-cresol, or 2, Examples include a copolymer of 6-dimethylphenol, 2,3,6-trimethylphenol and o-cresol. The production method of the polyphenylene ether polymer is not particularly limited, and can be produced by oxidative coupling polymerization according to, for example, the method described in US Pat. No. 4,788,277.

  The molecular weight of the polyphenylene ether resin is, for example, preferably as a molecular weight parameter (0.5 g / dl chloroform solution, 30 ° C.), with a reduced viscosity of 0.20 to 0.70 dl / g, preferably 0.30 to 0.55 dl. The range of / g is more preferable.

  In addition, the polyphenylene ether resin of the present invention may contain various phenylene ether units as partial structures as long as not departing from the gist of the present invention. As such a structure, for example, oxy-2- (N, N-dialkylaminomethyl) -6-methylphenylene-1 described in Japanese Patent Application No. 63-12698, Japanese Patent Application Laid-Open No. 63-301222, and the like. , 4-diyl unit, oxy-2- (N-alkyl-N-phenylaminomethyl) -6-methylphenylene-1,4-diyl unit, and the like. Also included are those in which a small amount of diphenoquinone or the like is bonded to the main chain of the polyphenylene ether resin.

  The polyphenylene ether resin of the present invention can also include a polyphenylene ether resin modified with an ethylenically unsaturated compound such as an α, β-unsaturated carboxylic acid or its anhydride. When such a modified polyphenylene ether resin is used, it is possible to provide a molded article having excellent mixing properties with a vinyl compound polymer and free from phase peeling. Examples of α, β-unsaturated carboxylic acids or anhydrides thereof include maleic anhydride, phthalic acid, itaconic anhydride, and glutaconic anhydride described in JP-B-49-2343 and JP-B-3-52486. Citraconic anhydride, aconitic anhydride, hymic anhydride, 5-norbornene-2-methyl-2-carboxylic acid, or maleic acid, fumaric acid, etc., but are not limited thereto, maleic anhydride Is particularly preferred.

  The polyphenylene ether resin can be modified with the ethylenically unsaturated compound by heating to a temperature equal to or higher than the glass transition temperature of the polyphenylene ether resin in the presence or absence of an organic peroxide. In the present invention, a polyphenylene ether resin previously modified with the ethylenically unsaturated compound may be used. Moreover, it can also be made to react with a polyphenylene ether polymer by adding the said ethylenically unsaturated compound simultaneously when manufacturing this invention composition.

  The phenol resin used in the present invention is arbitrary as long as it is a polymer having a plurality of phenolic hydroxyl groups, and examples thereof include novolak type, resol type and thermal reaction type resins, and resins obtained by modifying these. These may be an uncured resin, a semi-cured resin, or a cured resin to which no curing agent is added. Among these, a phenol novolak resin that is non-reactive with no addition of a curing agent is preferred in terms of flame retardancy, impact resistance, and economy. Further, the shape is not particularly limited, and any of pulverized product, granular shape, flake shape, powder shape, needle shape, liquid state, and the like can be used. The said phenol resin can be used as a 1 type, or 2 or more types of mixture as needed. The phenol resin is not particularly limited, and commercially available products can be used. For example, in the case of a novolak-type phenol resin, the reaction vessel is charged with a molar ratio of phenols to aldehydes of 1: 0.7 to 1: 0.9, and oxalic acid, hydrochloric acid, sulfuric acid, toluenesulfonic acid, etc. After adding the catalyst, heating and refluxing reaction are performed. In order to remove the generated water, it is obtained by vacuum dehydration or standing dehydration, and further removing remaining water and unreacted phenols. By using a plurality of raw material components for these resins, a co-condensed phenol resin can be obtained, and this can also be used in the same manner. In the case of a resol-type phenol resin, a reaction vessel is prepared so that the molar ratio of phenols to aldehydes is 1: 1 to 1: 2, and further a catalyst such as sodium hydroxide, aqueous ammonia, and other basic substances. After adding, it can obtain by performing operation similar to a novolak-type phenol resin. Here, phenols are phenol, o-cresol, m-cresol, p-cresol, thymol, p-tert-butylphenol, tert-butylcatechol, catechol, isoeugenol, o-methoxyphenol, 4,4′-dihydroxy. Examples include phenylpropane, isoamyl salicylate, benzyl salicylate, methyl salicylate, and 2,6-di-tert-butyl-p-cresol. These phenols can be used as one or a mixture of two or more as required. On the other hand, aldehydes include formaldehyde, paraformaldehyde, polyoxymethylene, trioxane and the like. These aldehydes can also be used as one or a mixture of two or more as required. The molecular weight of the phenolic resin is not particularly limited, but preferably has a number average molecular weight of 200 to 2,000, more preferably 400 to 1,500 in the range of mechanical properties, molding processability, and economic efficiency. Excellent and preferable.

  The aromatic epoxy resin and phenoxy resin used in the present invention are an epoxy resin and a phenoxy resin synthesized from an aromatic polyol and epihalogenohydrin. Among these, an epoxy resin and a phenoxy resin formed by condensation reaction of bisphenol A and epichlorohydrin are particularly preferable, and the average molecular weight is preferably 10,000 to 50,000, more preferably 10,000 to 40,000. Can be used. Specific examples of aromatic epoxy resins include the Etototo YD series manufactured by Toto Kasei Co., Ltd., and specific examples of phenoxy resins include the Toto Kasei Co., Ltd. phenototo, which are readily available on the market. it can.

  The flame retardant aids used in the present invention may be used alone or in combination of two or more. The content of the flame retardant aid (component D) is 0 to 30 parts by weight, preferably 100 parts by weight in total of the polylactic acid resin (component A) and the thermoplastic resin (component B) other than the component A, preferably Is 2 to 25 parts by weight, more preferably 5 to 20 parts by weight. When the content of the flame retardant (component D) is more than 30 parts by weight, the physical properties are deteriorated, which is not preferable.

<About E component>
The polylactic acid resin of the present invention may contain a terminal blocking agent (E component). The end-capping agent has a function of blocking by reacting with some or all of the carboxyl group ends of the polylactic acid resin (component A). For example, a condensation reaction type compound such as an aliphatic alcohol or an amide compound, , Carbodiimide compounds, epoxy compounds, oxazoline compounds, oxazine compounds, and aziridine compounds, and the like. If the latter addition reaction type compound is used, there is no need to discharge an extra by-product out of the reaction system as in the case of end-capping by dehydration condensation reaction of alcohol and carboxyl group. Therefore, by adding, mixing, and reacting an addition reaction type end-capping agent, it is possible to obtain a sufficient carboxyl group end-capping effect while suppressing decomposition of the resin by a by-product, and practically sufficient resistance. A resin composition having hydrolyzability and a molded product made of the resin composition can be obtained.

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

  Examples of the monocarbodiimide compound contained in the carbodiimide compound include dicyclohexylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, t-butylisopropylcarbodiimide, diphenylcarbodiimide, di-t-butylcarbodiimide, di-β-naphthylcarbodiimide and the like. Of these, dicyclohexylcarbodiimide or diisopropylcarbodiimide is preferred from the viewpoint of easy industrial availability. In addition, as the polycarbodiimide compound contained in the carbodiimide compound, those produced by various methods can be used. Basically, conventional polycarbodiimide production methods (US Pat. No. 2,941,956, No. 47-33279, J.0rg.Chem.28, 2069-2075 (1963), Chemical Review 981, Vol.81 No.4, p619-621) can be used.

  Examples of the organic diisocyanate that is a synthetic raw material in the production of the polycarbodiimide compound include aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, and mixtures thereof. Specifically, 1,5-naphthalene diisocyanate. 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2, , 4-tolylene diisocyanate and 2,6-tolylene diisocyanate, hexamethylene diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophor Diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, methylcyclohexane diisocyanate, tetramethylxylylene diisocyanate, 2,6-diisopropylphenyl isocyanate, 1,3,5-triisopropylbenzene-2,4-diisocyanate, etc. be able to. Moreover, in the case of the said polycarbodiimide compound, it can also control to a suitable polymerization degree using the compound which reacts with the terminal isocyanate of polycarbodiimide compound, such as monoisocyanate. Examples of the monoisocyanate for sealing the end of such a polycarbodiimide compound and controlling the degree of polymerization thereof include phenyl isocyanate, tolyl isocyanate, dimethylphenyl isocyanate, cyclohexyl isocyanate, butyl isocyanate, naphthyl isocyanate and the like. be able to.

  Examples of epoxy compounds among the end-capping agents that can be used in the present invention include, for example, N-glycidylphthalimide, N-glycidyl-4-methylphthalimide, N-glycidyl-4,5-dimethylphthalimide, N-glycidyl- 3-methylphthalimide, N-glycidyl-3,6-dimethylphthalimide, N-glycidyl-4-ethoxyphthalimide, N-glycidyl-4-chlorophthalimide, N-glycidyl-4,5-dichlorophthalimide, N-glycidyl- 3,4,5,6-tetrabromophthalimide, N-glycidyl-4-n-butyl-5-bromophthalimide, N-glycidylsuccinimide, N-glycidylhexahydrophthalimide, N-glycidyl-1,2,3 6-tetrahydrophthalimide, N-glycidyl male N-glycidyl-α, β-dimethylsuccinimide, N-glycidyl-α-ethylsuccinimide, N-glycidyl-α-propylsuccinimide, N-glycidylbenzamide, N-glycidyl-p-methylbenzamide, N- Glycidylnaphthamide, N-glycidylsteramide, N-methyl-4,5-epoxycyclohexane-1,2-dicarboxylic imide, N-ethyl-4,5-epoxycyclohexane-1,2-dicarboxylic imide, N- Phenyl-4,5-epoxycyclohexane-1,2-dicarboxylic imide, N-naphthyl-4,5-epoxycyclohexane-1,2-dicarboxylic imide, N-tolyl-3-methyl-4,5-epoxycyclohexane -1,2-dicarboxylic acid imide, orthophenyl phenylglycol Sidyl ether, 2-methyloctyl glycidyl ether, phenyl glycidyl ether, 3- (2-xenyloxy) -1,2-epoxypropane, allyl glycidyl ether, butyl glycidyl ether, lauryl glycidyl ether, benzyl glycidyl ether, cyclohexyl glycidyl ether, α -Cresyl glycidyl ether, pt-butylphenyl glycidyl ether, glycidyl methacrylate ether, ethylene oxide, propylene oxide, styrene oxide, octylene oxide, hydroquinone diglycidyl ether, resorcin diglycidyl ether, 1,6-hexanediol di Glycidyl ether, hydrogenated bisphenol A-diglycidyl ether, terephthalic acid diglycidyl ester, tetra Lophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, phthalic acid dimethyl diglycidyl ester, phenylene diglycidyl ether, ethylene diglycidyl ether, trimethylene diglycidyl ether, tetramethylene diglycidyl ether, hexamethylene diglycidyl ether, 3 , 4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene diepoxide and the like. Furthermore, in the present invention, a polymer containing an epoxy group can be used, and an acrylic polymer is preferably used because of compatibility with a polylactic acid resin. As such a polymer, for example, a polymer of (meth) acrylic acid ester monomers containing an epoxy group, a (meth) acrylic acid ester monomer containing an epoxy group and a (meth) acrylic acid ester monomer Copolymer of acrylate monomers having an epoxy group, copolymer of acrylate monomer and acrylate monomer having an epoxy group, (meth) having an epoxy group Examples thereof include a copolymer of an acrylate monomer and an acrylate monomer, and a copolymer of an acrylate monomer having an epoxy group and a (meth) acrylate monomer. In addition, as an acrylic-styrene copolymer having an epoxy group, a copolymer of a styrene monomer and a (meth) acrylic acid ester monomer having an epoxy group, an acrylic acid having a styrene monomer and an epoxy group Examples include a copolymer of ester monomers. One or more compounds selected from these epoxy compounds may be arbitrarily selected to block the carboxyl terminal of the polylactic acid unit, but in terms of reactivity, ethylene oxide, propylene oxide, phenyl glycidyl ether, ortho Preferred are phenylphenyl glycidyl ether, pt-butylphenyl glycidyl ether, N-glycidyl phthalimide, hydroquinone diglycidyl ether, resorcin diglycidyl ether, 1,6-hexanediol diglycidyl ether, hydrogenated bisphenol A-diglycidyl ether, and the like. .

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

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

  Furthermore, one or more compounds may be arbitrarily selected from the oxazoline compounds already exemplified and the above-mentioned oxazine compounds and used together to block the carboxyl terminal of the polylactic acid resin. 2,2'-m-phenylenebis (2-oxazoline) and 2,2'-p-phenylenebis (2-oxazoline) are preferable from the viewpoint of reactivity and affinity with polylactic acid resin.

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

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

As a specific degree of carboxyl group terminal blocking, the concentration of the carboxyl group terminal of the polylactic acid resin is preferably 10 equivalents / 10 ³ kg or less from the viewpoint of improving hydrolysis resistance, and 6 equivalents / 10 ³ kg or less. More preferably it is.

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

  As a method of blocking the carboxyl group terminal by an addition reaction, it can be obtained by reacting an appropriate amount of a terminal blocking agent such as a carbodiimide compound, an epoxy compound, an oxazoline compound, an oxazine compound, an aziridine compound in a molten state of a polylactic acid resin, It is possible to add and react with a terminal blocking agent after completion of the polymerization reaction of the polymer.

  The content of the terminal blocking agent is preferably 0.01 to 5 parts by weight, more preferably 0, per 100 parts by weight in total of the polylactic acid resin (component A) and the thermoplastic resin other than the component A (component B). 0.1-5 parts by weight, more preferably 0.2-3 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 cannot be obtained. It drops significantly.

<About F component>
The polylactic acid resin composition of the present invention may contain an inorganic filler. By blending the inorganic filler (F component), it becomes possible to obtain a molded product having excellent mechanical characteristics, dimensional characteristics, and the like.

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

  The average particle diameter of mica that can be used in the present invention is a number average particle diameter calculated by a number average of a total of 1,000 particles observed with a scanning electron microscope and extracted those having a size of 1 μm or more. The number average particle diameter is preferably 10 to 500 μm, more preferably 30 to 400 μm, still more preferably 30 to 200 μm, and most preferably 35 to 80 μm. When the number average particle diameter is less than 10 μm, the impact strength may be lowered. On the other hand, if it exceeds 500 μm, the impact strength is improved, but the appearance tends to deteriorate.

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

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

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

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

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

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

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

  The glass fiber that can be used in the present invention can be selected from, for example, a long fiber type (roving), a short fiber chopped strand, a milled fiber, and the like. In the milled fiber, the number average aspect ratio is preferably 5 or more.

  Fibrous inorganic reinforcing materials include sizing agents (eg, polyvinyl acetate, urethane, acrylic, epoxy, polyester sizing agents, etc.), coupling agents (eg, silane compounds, boron compounds, alkylalkoxysilanes, polyorganohydrogensiloxanes, etc.) Titanium compound etc.) and other surface treatment agents may be used. Examples of such other surface treatment agents include higher fatty acid esters, acid compounds (for example, phosphorous acid, phosphoric acid, carboxylic acid, and carboxylic acid anhydride), and waxes. Furthermore, it may be granulated with a sizing agent such as various resins, higher fatty acid esters, and waxes.

  The content of these inorganic fillers is preferably 0.05 to 150 parts by weight per 100 parts by weight in total of the polylactic acid resin (A component) and the thermoplastic resin other than the A component (B component), and 0.5 to 120 parts by weight. Part by weight is more preferable, and 1 to 100 parts by weight is still more preferable. When the blending amount is smaller than 0.05 parts by weight, the reinforcing effect is not sufficient, and when it exceeds 150 parts by weight, the appearance of the molded product is deteriorated or the strand breaks during extrudability. Some of these inorganic fillers act as crystal nucleating agents, but in order to fully exhibit the effect of polylactic acid resin (component A) as a crystal nucleating agent, the inorganic filler is made of polylactic acid resin. It is necessary to disperse it sufficiently uniformly. In order to realize such a uniform dispersion state, it is preferable to melt and mix the polylactic acid resin and the inorganic filler in advance, and then add various additives.

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

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

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

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

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

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

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

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

The composition ratio of the impact modifier is preferably 0.2 to 50 parts by weight, preferably 1 to 30 parts by weight per 100 parts by weight in total of the polylactic acid resin (component A) and the thermoplastic resin other than the component A (component B). Is more preferable, and 3 to 25 parts by weight is still more preferable. If it is this composition range, favorable impact resistance can be given to a composition, suppressing the fall of rigidity.
In addition to these elastic polymers, it is preferable to use a polymer compound obtained by grafting or copolymerizing a glycidyl compound or an acid anhydride.

  Examples of the glycidyl compound include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl esters of unsaturated organic acids such as glycidyl itaconic acid, glycidyl ethers such as allyl glycidyl ether, and derivatives thereof. Among them, glycidyl acrylate and glycidyl methacrylate can be preferably used, and these can be used alone or in combination of two or more. Preferred examples of the acid anhydride include maleic anhydride.

  The amount used when grafting or copolymerizing the glycidyl compound or acid anhydride to the polymer compound is not particularly limited, but may be 0.05% by weight or more and 20% by weight or less based on the polymer compound. Preferably, it is 0.1 to 5% by weight.

  The polymer compound obtained by grafting or copolymerizing a glycidyl compound or acid anhydride is not limited, but the glycidyl compound or acid anhydride is grafted or copolymerized on acrylonitrile / styrene, ethylene copolymer, polyamide resin, or the like. It is a polymer compound contained by polymerization, and is used as one or two or more selected from among them. Examples of the above ethylene copolymers include ethylene as a monomer, and copolymerizable monomers include propylene, butene-1, vinyl acetate, isoprene, butadiene, monocarboxylic acids such as acrylic acid and methacrylic acid, or the like. Copolymers prepared from dicarboxylic acids such as maleic acid, maleic acid, fumaric acid or itaconic acid, and polymer compounds grafted with methyl methacrylate are also preferably used. Acrylonitrile / styrene / glycidyl methacrylate, ethylene / Propylene-g-maleic anhydride, ethylene / glycidyl methacrylate, ethylene ethyl acrylate-g-maleic anhydride, ethylene / butene 1-g-maleic anhydride, ethylene / ethyl acrylate / maleic anhydride-g Specific examples include methyl methacrylate, ethylene / glycidyl methacrylate-g-methyl methacrylate, etc. ("-/-" represents copolymerization, "-g-" represents graft, and so on). .

  By using such a polymer compound grafted or copolymerized with a glycidyl compound or an acid anhydride together with the elastic polymer, dispersion of the elastic polymer in the polylactic acid resin is increased, and a higher impact modification effect can be obtained.

  The content of the polymer compound grafted or copolymerized with the glycidyl compound or acid anhydride is 0.2 per 100 parts by weight of the total of the polylactic acid resin (component A) and the thermoplastic resin other than component A (component B). -30 parts by weight is preferred, 1-20 parts by weight is more preferred, and 3-15 parts by weight is even more preferred. Within such a composition range, good impact resistance can be imparted to the composition.

(Ii) Heat stabilizer A hindered phenol stabilizer and a phosphorus stabilizer can be used as the heat stabilizer in the resin composition of the present invention. By blending a heat stabilizer, not only the hue and fluidity during molding are stabilized, but also effective in improving hydrolysis resistance.

  Examples of the hindered phenol-based stabilizer include α-tocopherol, butylhydroxytoluene, sinapir 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. All of these are readily available. The said hindered phenol type stabilizer can be used individually or in combination of 2 or more types.

  The content of the hindered phenol stabilizer is preferably 0.001 to 0.5 parts by weight per 100 parts by weight in total of the polylactic acid resin (component A) and the thermoplastic resin other than the component A (component B). More preferably, it is 0.01-0.5 weight part, More preferably, it is 0.01-0.3 weight part.

In particular, it is preferable to blend a pentaerythritol phosphite compound as the phosphorus stabilizer.
Specific examples of the pentaerythritol phosphite compound include distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, and bis (2,6- Di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, bis (Nonylphenyl) pentaerythritol diphosphite, dicyclohexylpentaerythritol diphosphite, and the like. Among them, distearyl pentaerythritol diphosphite and bis (2,4-di-tert) are preferable. A butyl phenyl) pentaerythritol diphosphite.
Examples of other phosphorus stabilizers include various other phosphite compounds, phosphonite compounds, and phosphate compounds.

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

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

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

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

Examples of the phosphonate compound include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate.
Said phosphorus stabilizer can be used individually or in combination of 2 or more types. The content of the phosphorus stabilizer is preferably 0.005 to 0.5 parts by weight, more preferably 100 parts by weight in total of the polylactic acid resin (component A) and the thermoplastic resin (component B) other than the component A. 0.01 to 0.5 part by weight, more preferably 0.01 to 0.3 part by weight.

  In addition, it is preferable to use a combination of the hindered phenol stabilizer and the phosphorus stabilizer. By using a combination of a hindered phenol stabilizer and a phosphorus stabilizer, a synergistic effect as a stabilizer is demonstrated, and it is more effective in stabilizing hue and fluidity during molding and improving hydrolysis resistance. There is.

(Iii) Other additives In the resin composition of the present invention, an ultraviolet absorber (benzotriazole-based, triazine-based, benzophenone-based, etc.), light stabilizer (HALS, etc.), as long as the effects of the present invention are exhibited. Release agents (saturated fatty acid esters, unsaturated fatty acid esters, polyolefin waxes, fluorine compounds, paraffin wax, beeswax, etc.), flow modifiers (polycaprolactone, etc.), colorants (carbon black, titanium dioxide, various organics) Dyes, metallic pigments, etc.), light diffusing agents (acrylic crosslinked particles, silicone crosslinked particles, etc.), fluorescent brighteners, phosphorescent pigments, fluorescent dyes, antistatic agents, inorganic and organic antibacterial agents, photocatalytic antifouling agents (fine particles) (Titanium oxide, fine particle zinc oxide, etc.), infrared absorber, photochromic agent, ultraviolet absorber and the like may be blended. These various additives can be used in known amounts.

<About the manufacturing method of a resin composition>
i) Preparation of Coexisting Composition In the present invention, when a mixture of poly-L lactic acid resin (A-1 component) and poly-D lactic acid resin (A-2 component) is used as the polylactic acid resin (A component), other Before melt-mixing with the additive component of the phosphoric acid ester metal salt represented by formula (III) and / or formula (IV), poly-L lactic acid resin (A-1 component) and poly-D lactic acid resin (A -2 component) is preferably allowed to coexist in advance. As a method of coexistence, a method of mixing a polylactic acid resin mainly composed of L-lactic acid units (component A-1) and a polylactic acid resin mainly composed of D-lactic acid units (component A-2) as much as possible, A stereocomplex can be efficiently generated when these are heat-treated, which is preferable. The coexisting composition can be prepared by any method as long as they are uniformly mixed when heat-treated. The method is carried out in the presence of a solvent, or the method is carried out in the absence of a solvent. Etc. are exemplified.
Methods for preparing the coexisting composition in the presence of a solvent include a method of obtaining the coexisting composition by reprecipitation from a state dissolved in a solution, and a method of obtaining the coexisting composition by removing the solvent by heating. Preferably mentioned.

  In the case of obtaining such a coexisting composition by reprecipitation in the presence of a solvent, first, a polylactic acid resin (component A-1) mainly composed of L-lactic acid units and a polylactic acid mainly composed of D-lactic acid units. A coexisting composition with resin (component A-2) is prepared by reprecipitation. Here, the A-1 component and the A-2 component are preferably prepared by separately preparing and mixing solutions dissolved in a solvent, or by dissolving and mixing both in a solvent together. Here, the weight ratio (A-1 component / A-2) of the polylactic acid resin (A-1 component) mainly composed of L-lactic acid units and the polylactic acid resin (A-2 component) mainly composed of D-lactic acid units. It is possible to prepare the stereocomplex of the polylactic acid resin (A-1 component, A-2 component) efficiently in the resin composition of the present invention by preparing the component so as to be in the range of 10/90 to 90/10. It is preferable when it is made to produce. 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. Although a solvent will not be specifically limited if polylactic acid resin (A-1 component, A-2 component) melt | dissolves, For example, chloroform, a methylene chloride, a dichloroethane, tetrachloroethane, a phenol, tetrahydrofuran, N -Methylpyrrolidone, N, N-dimethylformamide, butyrolactone, trioxane, hexafluoroisopropanol or the like, or a mixture of two or more of them is preferred.

  The phosphoric acid ester metal salt represented by the formula (III) and / or the formula (IV) is insoluble in the solvent, or may remain in the solvent after reprecipitation even when dissolved in the solvent. The polylactic acid resin (A-1 component, A-2 component) mixture obtained by reprecipitation and the phosphate ester metal salt represented by the formula (III) and / or the formula (IV) are mixed separately and coexisting composition Need to be prepared. The method of obtaining the coexisting composition of the polylactic acid resin (A-1 component, A-2 component) mixture and the phosphate ester metal salt represented by the formula (III) and / or the formula (IV) is uniformly mixed. Any method such as mixing with powder or melt mixing can be used.

  Next, by a method of removing the solvent from the presence of the solvent, a polylactic acid resin (A-1 component, A-2 component) and a phosphate ester metal salt represented by formula (III) and / or formula (IV) When the coexisting composition is prepared at once, the A-1 component and the A-2 component, and the phosphoric acid ester metal salt represented by the formula (III) and / or the formula (IV) are each separately used in a solvent. Prepare and mix dissolved or dispersed dispersions, or prepare and mix dispersions in which all ingredients are dissolved or dispersed together in a solvent, and then evaporate the solvent by heating Can do. A solvent will be specifically limited if polylactic acid resin (A-1 component, A-2 component) and the phosphate ester metal salt represented by Formula (III) and / or Formula (IV) are melt | dissolved. For example, chloroform, methylene chloride, dichloroethane, tetrachloroethane, phenol, tetrahydrofuran, N-methylpyrrolidone, N, N-dimethylformamide, butyrolactone, trioxane, hexafluoroisopropanol, or a mixture of two or more Is preferred. 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 resin (A-1 component, A-2 component) and the phosphoric acid ester metal salt represented by the formula (III) and / or the formula (IV) is also performed in the absence of a solvent. be able to. That is, the A-1 component and the A-2 component, which are powdered or chipped in advance, and the phosphate metal salt represented by the formula (III) and / or the formula (IV) are mixed and melted after mixing a predetermined amount. A method of mixing, a method of mixing any one of the A-1 component and the A-2 component and then mixing the remaining components after melting can be employed. Here, the size of the powder or chip is not particularly limited as long as the powder or chip of each polylactic acid resin (A-1 component, A-2 component) 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 chip is simply melted after being uniformly mixed, if the diameter of the powder or chip becomes 3 mm or more, mixing is performed. Is not preferable, and homocrystals are likely to precipitate. In addition, as a mixing device used to uniformly mix the above powder or chips, in the case of mixing by melting, in addition to a reactor with a batch type stirring blade, a continuous reactor, a biaxial or uniaxial In the case of mixing with an extruder or powder, a tumbler type powder mixer, a continuous powder mixer, various milling devices, or the like can be suitably used.

  Further, when preparing such a coexisting composition, as a flame retardant (C component), a flame retardant aid (D component) end-capping agent (E component), an inorganic filler (F component), and other additives , Inorganic filler breakage inhibitor, lubricant, elastic polymer (impact modifier), ultraviolet absorber, light stabilizer, mold release agent, flow modifier, colorant, light diffusing agent, fluorescent whitening agent, phosphorescent pigment Various additives such as fluorescent dyes, antistatic agents, antibacterial agents, and crystal nucleating agents may be allowed to coexist.

  In particular, the addition of the end-blocking agent (E component) at the stage of preparation of the coexisting composition means that the mixing of the end-blocking agent and the polylactic acid resin (A component) becomes more uniform, so that the acidity of polylactic acid is increased. Since the terminal is blocked more efficiently, it is preferable for improving the hydrolysis resistance of the obtained final resin composition. In addition, it is particularly preferable to add a hindered phenol-based or phosphorus-based heat stabilizer at the stage of preparing the coexisting composition in order to improve the thermal stability of the coexisting composition in the subsequent heat treatment stage.

ii) Heat treatment of coexisting composition In the present invention, when a mixture of poly-L lactic acid resin (A-1 component) and poly-D lactic acid resin (A-2 component) is used as polylactic acid resin (A component), other Before the melt-mixing with the additive component, the polylactic acid resin (component A-1, component A-2) and the phosphate metal salt represented by the formula (III) and / or the formula (IV) are mixed. Heat treatment is preferred. 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 it is difficult to efficiently generate a stereocomplex. The heat treatment time is not particularly limited, but is 0.2 to 60 minutes, preferably 1 to 20 minutes. As an atmosphere during the heat treatment, either an inert atmosphere at normal pressure or a reduced pressure can be applied. As the apparatus and method used for the heat treatment, any apparatus and method that can be heated while adjusting the atmosphere can be used. For example, a batch type reactor, a continuous type reactor, a biaxial or uniaxial type can be used. It is also possible to adopt a method of processing while forming using an extruder or the like, or a press machine or a flow tube type extruder. Here, the preparation of the coexisting composition of the polylactic acid resin (component A-1 and component A-2) and the phosphoric acid ester metal salt represented by the formula (III) and / or the formula (IV) is carried out in the absence of a solvent. In the case of carrying out by the melt mixing method below, 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 specifies a thermoplastic resin (component B) other than component A, part or all of a flame retardant (component C), and a flame retardant aid (component D). After the thermoplastic resin composition was prepared by melt-kneading in advance at a ratio of 5%, the thermoplastic resin composition, the polylactic acid resin (component A), and a flame retardant (C that was not used in the preparation of the thermoplastic resin composition) Component), optionally end-capping agent (E component), inorganic filler (F component) and other components in specific proportions, above the melting point of thermoplastic resin (B component) other than polylactic acid resin (A component) and A component It is manufactured by melt-kneading. (However, the components contained in the coexisting composition are excluded.) By taking such a production method, a polylactic acid resin composition excellent in flame retardancy and hydrolysis resistance can be obtained. Other additive components include inorganic filler breakage inhibitors, lubricants, elastic polymers (impact modifiers), antioxidants, UV absorbers, light stabilizers, mold release agents, flow modifiers, colorants, light Arbitrary additive components, such as a diffusing agent, a fluorescent brightening agent, a phosphorescent pigment, a fluorescent dye, an antistatic agent, an antibacterial agent and a crystal nucleating agent, can be mentioned.

  As the method for producing the resin composition of the present invention, any method is employed within the scope of the production method described in the present invention. For example, a thermoplastic resin (B component) other than the A component, a part or all of the flame retardant (C component), and a flame retardant aid (D component) are premixed at a specific ratio, and melt-kneaded to form a pellet. Thus, a thermoplastic resin composition is prepared. Furthermore, the thermoplastic resin composition, polylactic acid resin (component A), flame retardant (C component) that was not used in the preparation of the thermoplastic resin composition, optionally end-capping agent (E component), inorganic filler (F component) and other components are premixed at a specific ratio, then melt-kneaded above the melting point of the polylactic acid resin (component A) and the thermoplastic resin (component B) other than component A and pelletized. The 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.

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

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

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

  Furthermore, 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. Manufacture of polylactic acid resin Polylactic acid resin was manufactured by the method shown in the following manufacture example. Moreover, each value in a manufacture example was calculated | required with the following method.
(1) Weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer
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) Degree of stereocomplex formation Using the melting enthalpy derived from polylactic acid resin (component A) crystal in the temperature rising process of DSC (TA-2920 manufactured by TA Instruments), stereocomplex formation from the following formula (1) The degree parameter was evaluated.
Stereoization degree = 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.

In the examples and comparative examples of the present invention, the following materials were used.
[A-1 component: poly L-lactic acid resin (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 tin octylate was added, and the reactor was stirred at 180 ° C. in a nitrogen atmosphere with a stirring blade. Then, 1.2 times equivalent of phosphoric acid was added to tin octylate, and then the remaining lactide was removed at 13.3 Pa to obtain chips, thereby obtaining a poly L-lactic acid resin.
The resulting poly L-lactic acid resin has a weight average molecular weight of 152,000, a melting enthalpy (ΔHmh) of 49 J / g, a melting point (Tmh) of 175 ° C., a glass transition point (Tg) of 55 ° C., and a carboxyl group content of 14 eq / ton.

[Component A-2: Production of poly-D-lactic acid resin (PDLA)]
[Production Example 1-2]
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 resin was obtained. The resulting poly-D-lactic acid resin has a weight average molecular weight of 151,000, a melting enthalpy (ΔHmh) of 48 J / g, a melting point (Tmh) of 175 ° C., a glass transition point (Tg) of 55 ° C., and a carboxyl group content of 15 eq / ton.

[Component A-3: Production of stereocomplex polylactic acid resin (scPLA)]
[Production Example 2]
100 parts by weight of polylactic acid resin composed of 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 [manufactured by Nippon Steel Works, Ltd. TEX30XSST] was melt-extruded and pelletized at a cylinder temperature of 250 ° C., a screw rotation speed of 250 rpm, a discharge rate of 9 kg / h, and a vent vacuum of 3 kPa to obtain a polylactic acid resin 1. The resulting stereocomplex polylactic acid resin had a weight average molecular weight of 130,000, a melting enthalpy (ΔHms) of 56 J / g, a melting point (Tms) of 220 ° C., a glass transition point (Tg) of 58 ° C., and a carboxyl group content of 17 eq / Ton, the degree of stereogenicity calculated using equation (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. Further, Tms is a crystal melting point appearing at 190 ° C. or more and less than 250 ° C., and Tmh is a crystal melting point appearing at less than 190 ° C.

2. Production and Evaluation of Polylactic Acid Resin Pellets Resin composition pellets of polylactic acid resin (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) Hydrolysis resistance Using a polylactic acid resin composition with an injection molding machine (Toshiba Machine Co., Ltd .: IS-150EN) at a cylinder temperature of 230 ° C and a mold temperature of 120 ° C, a thickness of 4 mm A molded piece for ISO measurement was prepared. Next, this molded piece was subjected to wet heat treatment for 100 h under the conditions 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.
(2) Heat resistance Based on ISO75-1 and 2, the deflection temperature under load was measured under the condition of a load of 0.45 MPa.
(3) Flame retardance Flame retardancy at a test piece thickness of 1.5 mm was evaluated by a method (UL94) defined by US Underwriters Laboratory.

As the A component, A-1 to A-3 described above were used. As other raw materials, the following were used.
<B component>
B-1: Polyplastics Co., Ltd. Juranex 2000 [Polybutylene terephthalate]
B-2: TR-4550BH manufactured by Teijin Limited [Polyethylene terephthalate]
B-3: Nippon A & L Co., Ltd. Santac UT-61 [acrylonitrile-butadiene-styrene copolymer]
<C component>
C-1: ExolitOP1240 [Aluminum diethylphosphinate] manufactured by Clariant Japan Co., Ltd.
C-2: Taihei Chemical Industry Co., Ltd. APA-100 [Aluminum phosphite]
C-3: MELAPUR200 [melamine polyphosphate] manufactured by Ciba Specialty Chemicals Co., Ltd.
C-4: Nissan Chemical Industries, Ltd. MC-4000 [melamine cyanurate]
C-5: Pyrolyzer HG [Aluminum hydroxide] manufactured by Ishizuka Glass Industry Co., Ltd.
<D component>
D-1: SA-120 [polyphenylene ether oligomer] manufactured by SABIC Innovative Plastics Japan
D-2: Sumitomo Bakelite Co., Ltd. Sumilite Resin PR-53647 [Phenolic Resin]
<E component>
E-1: Carbodilite LA-1 manufactured by Nisshinbo Co., Ltd. [aliphatic carbodiimide]
E-2: ASF-4368CS manufactured by BASF Japan Ltd. [Epoxy group-containing acrylic-styrene copolymer]
<F component>
F-1: 3PE-937S manufactured by Nittobo Co., Ltd. (chopped strand having an average diameter of 13 μm and a cut length of 3 mm)

<Reference Examples 1-12>
After the ingredients shown in Table 2 were uniformly premixed by dry blending, the premixture was supplied from the first supply port, melt extruded and pelletized. Here, the first supply port is a base supply port. 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-C5 / C6 / C7-C11 / D = 10 ° C./260° C./260° C./260° C./260° C., the main screw rotation speed is 200 rpm, the side screw rotation speed is 100 rpm, The discharge amount was 10 kg / h, and the vent pressure reduction was 3 kPa.

  In addition, since the resin composition 12 has a low content of the B component serving as the resin component and too much flame retardant (C component), the resin clogging occurs at the extruder die port, and melt extrusion cannot be performed. It was.

<Example 1>
Using the polylactic acid resin A-1 component produced in Production Example 1-1 as a polylactic acid resin, the A component and the E component of the composition in Table 3 were uniformly premixed by dry blending, and then the premixed mixture was mixed. It supplied from the 1st supply port, the thermoplastic resin composition 1 and F component were supplied from the 2nd supply port, it melt-extruded and pelletized, and the polylactic acid tree composition was obtained. In Table 3, numerical values in parentheses indicate parts by weight derived from the used thermoplastic resin composition among the B component, C component, and D component in the polylactic acid resin composition. 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 C5 / C6 / C7 to C11 / D = 10 ° C./260° C./260° C./260° C./260° C., the main screw rotation speed is 150 rpm, the side screw rotation speed is 50 rpm, The discharge rate was 20 kg / h, and the vent pressure reduction was 3 kPa. 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 3.

<Comparative Example 1>
Using the polylactic acid resin A-1 component produced in Production Example 1-1 as the polylactic acid resin, the A component, the B component, and the E component in the composition of Table 4 are uniformly premixed by dry blending, and then applied. Except that the preliminary mixture was supplied from the first supply port and the C component, the D component, and the F component were supplied from the second supply port, they were pelletized by the same method as in Example 1 and evaluated. The results are shown in Table 4.

<Examples 2 to 19>
The polylactic acid resin composition having the composition described in Tables 3 to 8 was pelletized by the same method as in Example 1 and evaluated. The results are shown in Tables 3-8. In addition, the parentheses in Tables 3 to 8 indicate parts by weight derived from the used thermoplastic resin composition among the B component, C component, and D component in the polylactic acid resin composition.

<Comparative Examples 2-20>
The polylactic acid resin composition described in Tables 3 to 8 was pelletized by the same method as in Comparative Example 1 and evaluated. The results are shown in Tables 3-8.

<Examples 1 to 19 and Comparative Examples 1 to 11 and 14 to 20>
Examples 1-19 using a thermoplastic resin composition are excellent in hydrolysis resistance compared with Comparative Examples 1-11, 14-20 which do not use a thermoplastic resin composition.

<Comparative Examples 12-13>
Since the amount of component C added was too small, a sufficient flame retardant effect could not be obtained.

Claims (11)

(C) Phosphorus based on 100 parts by weight of a resin component composed of 5 to 95% by weight of a polylactic acid resin (component A) and (B) 95 to 5% by weight of a thermoplastic resin (component B) other than the component A 5 to 100 parts by weight of at least one flame retardant (component C) selected from the group consisting of a flame retardant, a nitrogen-based flame retardant, a metal oxide, and a metal hydroxide, and (D) a flame retardant aid (component D) ) a polylactic acid resin composition comprising 0 to 30 parts by weight, the thermoplastic resin (B component other than component a) 20 wt% or more, less total parts 70 wt% of the flame retardant component (C), and flame retardant After preparing a thermoplastic resin composition by melting and kneading a mixture of 0 to 30% by weight of auxiliary agent (D component), the thermoplastic resin composition and polylactic acid resin (A component ) are mixed with polylactic acid resin (A Component) and melt blending above the melting point of the thermoplastic resin (component B) other than component A Polylactic acid resin composition, characterized in that obtained by.   The flame retardant aid (component D) is at least one flame retardant aid selected from the group consisting of polyphenylene ether resins, phenol resins, aromatic epoxy resins, and phenoxy resins. Polylactic acid resin composition.   The terminal blocking agent (component E) is contained in an amount of 0.01 to 5 parts by weight with respect to a total of 100 parts by weight of the polylactic acid resin (component A) and the thermoplastic resin (component B) other than the component A. The polylactic acid resin composition according to claim 1 or 2.   The inorganic filler (F component) is contained in an amount of 0.05 to 150 parts by weight with respect to a total of 100 parts by weight of the polylactic acid resin (A component) and the thermoplastic resin (B component) other than the A component. The polylactic acid resin composition as described in any one of Claims 1-3. 4. The polylactic acid resin composition according to claim 3, wherein the terminal blocking agent (component E) is at least one terminal blocking agent selected from the group consisting of a carbodiimide compound and an epoxy compound.   Thermoplastic resin (B component) other than A component is aromatic polyester, The polylactic acid resin composition as described in any one of Claims 1-5 characterized by the above-mentioned.   The polylactic acid resin composition according to claim 6, wherein the thermoplastic resin (component B) other than the component A is at least one thermoplastic resin selected from the group consisting of polybutylene terephthalate and polyethylene terephthalate. The phosphorus-based flame retardant is at least one flame retardant selected from the group consisting of flame retardants represented by the following formulas (V) and (VI). Polylactic acid resin composition.

[Wherein R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ are each independently a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, or a carbon number having 6 to 20 carbon atoms. An aryl group or an aralkyl group having 7 to 20 carbon atoms. R ₂₅ is a linear or branched alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 6 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, an alkylene arylene group having 7 to 20 carbon atoms, or 7 carbon atoms. ˜20 cycloalkylenearylene groups. M ¹ and M ² are Mg, Ca, Al, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K, or a protonated nitrogen base. X is 1 or 2, m is 2 or 3, and n is 1 or 3. ]   The nitrogen-based flame retardant is at least one flame retardant selected from the group consisting of dimelamine pyrophosphate, melamine polyphosphate, melem polyphosphate, melam polyphosphate, and melon polyphosphate. The polylactic acid resin composition as described.   The polylactic acid resin composition according to any one of claims 1 to 7, wherein the metal hydroxide is at least one flame retardant selected from the group consisting of aluminum hydroxide, magnesium hydroxide, and calcium hydroxide.   The molded article which consists of a polylactic acid resin composition of any one of Claims 1-10.