JP2011256277A - Polylactic acid composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition which prevents release of a compound having an isocyanate group, ensures a good work environment, and is excellent in hydrolysis resistance and in heat resistance, impact resistance and ductility as well, by blending a resin component comprising polylactic acid having a low environmental burden and a polyolefin resin with a cyclic carbodiimide compound having a carbodiimide group in the cyclic structure and an antioxidant.SOLUTION: The composition comprises: 100 pts.wt. of a resin component (A) comprising 5-95 wt.% of polylactic acid (A-α) and 95-5 wt.% of a polyolefin (A-β); 0.001-10 pts.wt. of a compound (B) having one carbodiimide group, wherein the first and second nitrogen atoms are bonded to each other via a bonding group to form a cyclic structure represented by formula (1), the cyclic structure consisting of 8-50 atoms; and 0.001-2 pts.wt. of at least one of antioxidant (C) selected from the group consisting of a phosphite compound, a phosphonite compound, a hindered phenol compound and a thioether compound.

Description

  The present invention blends a cyclic carbodiimide compound and an antioxidant with a resin component composed of polylactic acid and a polyolefin resin, so that it is excellent in working environment and excellent in hydrolysis resistance, heat resistance, and impact resistance. Relates to the composition.

  In recent years, due to concerns about the depletion of petroleum resources and the problem of increased carbon dioxide in the air that causes global warming, biomass resources that do not depend on petroleum as a raw material and that do not increase carbon dioxide even when burned are formed. In the polymer field, biomass plastics produced from biomass resources are actively developed. In particular, polylactic acid has relatively high heat resistance and mechanical properties among biomass plastics, so its use is expanding to tableware, packaging materials, sundries, etc. It has become.

  However, due to its low hydrolysis resistance, polylactic acid has not been developed to industrial materials such as electric / electronic parts, automobile parts, etc. in which PC, PBT, PET and the like typified by engineering plastics are used.

  In Patent Document 1, an end-blocking agent is added to polylactic acid, and at least a part of the carboxyl group ends of polylactic acid is blocked to suppress a decrease in strength due to hot water treatment. , Its level of hydrolysis resistance is insufficient.

  Patent Documents 2 and 3 show a technology for improving hydrolysis resistance by adding a stabilizer such as a carbodiimide compound and an antioxidant to polylactic acid. The carbodiimide that is present is not a cyclic carbodiimide. For this reason, with the reaction in which the carbodiimide compound is bonded to the terminal of the polyester, the compound having an isocyanate group is liberated, a unique odor of the isocyanate compound is generated, and the working environment is deteriorated.

  Patent Document 4 discloses a technique in which a carbodiimide compound is blended with a resin component composed of polylactic acid and a polyolefin resin. However, the carbodiimide shown here is not a cyclic carbodiimide. For this reason, with the reaction in which the carbodiimide compound is bonded to the terminal of the polyester, the compound having an isocyanate group is liberated, a unique odor of the isocyanate compound is generated, and the working environment is deteriorated. Further, when a non-cyclic carbodiimide is added to a resin component composed of polylactic acid and polyolefin, there is a problem that impact resistance, ductility, and the like are lowered.

JP 2002-30208 A JP 2008-50584 A Japanese Patent No. 40855943 JP 2008-156616 A

  By blending a cyclic carbodiimide compound having a carbodiimide group in the cyclic structure and an antioxidant to a resin component consisting of polylactic acid and polyolefin resin with low environmental impact, the release of the compound having an isocyanate group is prevented, and the working environment The present invention was completed by finding out that it was excellent not only in hydrolysis resistance but also in heat resistance, impact resistance and ductility.

  That is, 100 parts by weight of a resin component (component A) consisting of 5 to 95% by weight of polylactic acid (A-α component) and 95 to 5% by weight of polyolefin (A-β component), 0.001 to 10 parts by weight of carbodiimide group And a compound (component B) having a cyclic structure in which the number of atoms forming the cyclic structure is 8 to 50, 0.001 A composition containing 2 parts by weight of at least one antioxidant (component C) selected from the group consisting of phosphite compounds, phosphonite compounds, hindered phenol compounds and thioether compounds. Further, it contains 0.001 to 10 parts by weight of at least one terminal blocking agent (component D) selected from the group consisting of an epoxy compound, an oxazoline compound and an oxazine compound with respect to 100 parts by weight of the resin component (component A). Preferably, it contains 0.01 to 0.3 parts by weight of hydrotalcite (E component) with respect to 100 parts by weight of the resin component (A component).

  The present invention prevents the liberation of a compound having an isocyanate group by adding a cyclic carbodiimide compound having a carbodiimide group in a cyclic structure and an antioxidant to a resin component consisting of polylactic acid and polyolefin having a low environmental load. It provides a resin material with a good working environment, excellent hydrolysis resistance, heat resistance, impact resistance, ductility, and low environmental impact.

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>
<About A-α component>
The polylactic acid used as the A-α component of the present invention may be 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.

  The poly-L lactic acid (A-α-1 component) and poly-D lactic acid (A-α-2 component) of the present invention are substantially composed of an L-lactic acid unit or a D-lactic acid unit represented by the formula (1). Become.

  The optical purity of poly-L lactic acid or poly-D lactic acid used in the present invention is preferably 90 to 100 mol%. If the optical purity is lower than this, the crystallinity and melting point of polylactic acid are lowered, and it is difficult to obtain high heat resistance. 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 copolymerized unit include D-lactic acid units for poly-L lactic acid, L-lactic acid units for poly-D lactic acid, and units other than lactic acid units. The copolymerization ratio of copolymer units other than lactic acid units is preferably 10 mol% or less, more preferably 5 mol% or less, still more preferably 2 mol% or less, and most preferably 1 mol% or less.

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

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

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

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

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

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

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

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

(Wherein _{R 18, R 19} each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms,, _{M 2} represents an alkali metal atom, an alkaline earth metal atom, zinc atom or aluminum ^{atom, p 33} Represents 1 or 2, and q ³³ represents 0 when M ₂ is an alkali metal atom, alkaline earth metal atom or zinc atom, and 1 or 2 when M ₂ is an aluminum atom.

The polylactic acid thus produced becomes a stereocomplex polylactic acid in which a stereocomplex crystal is highly formed, and the melting enthalpy derived from the polylactic acid (A-α component) crystal in the temperature rising process of the differential scanning calorimeter (DSC) measurement. The stereocomplex crystallinity represented by the following formula (1) is preferably 80% or more.
Stereo complex crystallinity = ΔHms / (ΔHms + ΔHmh) × 100 (1)
[In the formula (1), ΔHmh and ΔHms are the melting enthalpy (ΔHmh) of the melting point of the crystal, which appears below 190 ° C. in the temperature rising process of the differential scanning calorimeter (DSC), respectively, and 190 ° C. or more and 250 It is the melting enthalpy (ΔHms) of the crystalline melting point that appears below ° C. ]

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

  The melting point of stereocomplex polylactic acid is preferably 200 ° C. or higher, more preferably 205 ° C. or higher, and still more preferably 210 ° C. or higher. If the melting point of stereocomplex polylactic acid is lower than 200 ° C., the heat resistance is insufficient due to its crystallinity and low melting point.

The melting enthalpy is preferably 20 J / g or more, more preferably 30 J / g or more. When the melting enthalpy is lower than 20 J / g, the crystallinity is low and the heat resistance is insufficient.
Specifically, it is preferable that the stereocomplex crystallinity is 80% or more, the melting point is 200 ° C. or more, and the melting enthalpy is 20 J / g or more.

<About A-β component>
The polyolefin resin (A-β component) is a homopolymer or copolymer of olefins such as ethylene, propylene and butene, or a copolymer of monomer components copolymerizable with these olefins. Specifically, it is at least one selected from the group consisting of polyethylene and polypropylene. Polypropylene is particularly preferable from the viewpoint of crystallinity of the composition. Polypropylene here means a polyolefin containing at least 1 mol% of propylene units as constituent units. The polypropylene contains at least 1 mol%, preferably 10 mol% or more, particularly preferably 75 mol% or more of propylene units as constituent units. Other constituents include ethylene or an α-olefin having 4 to 20 carbon atoms, specifically 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1 -Tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl -1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, and the like, and these are used alone. But you may combine 2 or more types.

The polyolefin resin of the present invention have a melt volume flow rate (MVR, ISO1133,240 ℃, 2.16kg) as the value of, but can be used for 1~80cm ^3/10 min, 2~70cm ^3/10 min If it is used, it is more preferable because it becomes a resin composition having an excellent appearance of a molded product, and a resin composition of ^{3 to} 60 cm 3/10 minutes is particularly preferable.

  The ratio of polylactic acid (A-α component) to polyolefin resin (A-β component) is 5 to 95% by weight of polylactic acid (A-α component) and 95 to 5% by weight of polyolefin resin (A-β component). , Polylactic acid (A-α component) 25 to 95% by weight, polyolefin resin (A-β component) 75 to 5% by weight, polylactic acid (A-α component) 50 to 95% by weight, polyolefin resin (A- (beta component) 50-5 weight% is still more preferable. When the proportion of the polyolefin resin is 95% by weight or more, the effect of reducing the environmental load is small, and when the proportion of the polyolefin resin is 5% by weight or less, the impact resistance and ductility cannot be improved.

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

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

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

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

In the formula, Ar ¹ and Ar ² are each independently a 2- to 4-valent aromatic group having 5 to 15 carbon atoms which may contain a hetero atom and a substituent.

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

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

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

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

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

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

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

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

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

In formulas (5-1) and (5-2), s and k are integers of 0 to 10, preferably 0 to 3, more preferably 0 to 1. This is because if s and k exceed 10, the cyclic carbodiimide compound is difficult to synthesize, and the cost may increase significantly. From this viewpoint, the integer is preferably selected in the range of 0 to 3. When s or k is 2 or more, X ¹ or X ² as a repeating unit may be different from other X ¹ or X ² .

X ³ is a divalent to tetravalent C 1-20 aliphatic group, a divalent to tetravalent C 3-20 alicyclic group, each of which may contain a heteroatom and a substituent, A tetravalent aromatic group having 5 to 15 carbon atoms, or a combination thereof.

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

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

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

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

  Examples of the cyclic carbodiimide used in the present invention include compounds represented by the above formulas (5), (7) and (8).

<Cyclic carbodiimide (2)>

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

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

<Cyclic carbodiimide (3)>

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

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

<Cyclic carbodiimide (4)>

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

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

  Content of this cyclic carbodiimide compound is 0.001-10 weight part with respect to 100 weight part of resin components (A component), Preferably, it is 0.01-7 weight part, More preferably, it is 0.1 weight. Parts to 5 parts by weight. When the content of the cyclic carbodiimide compound is less than 0.001 part by weight, since the number of carbodiimide groups of the cyclic carbodiimide is too small with respect to the terminal amount of the polylactic acid (component A), sufficient hydrolysis resistance improvement effect Cannot be obtained. Moreover, when there are more addition amounts of a cyclic carbodiimide compound than 10 weight part, a hydrolysis resistance will be deteriorated on the contrary.

<Method for producing cyclic carbodiimide compound>
The cyclic carbodiimide compound can be produced by a conventionally known method. For example, a method for producing an amine body via an isocyanate body, a method for producing an amine body via an isothiocyanate body, a method for producing an amine body via a triphenylphosphine body, a urea body from an amine body The method of manufacturing via a thiourea body, the method of manufacturing via a thiourea body, the method of manufacturing from a carboxylic acid body via an isocyanate body, the method of manufacturing a lactam body, etc. are mentioned.

  In addition, the cyclic carbodiimide compound of the present invention can be produced by combining and modifying the methods described in the following documents, and an appropriate method can be adopted depending on the compound to be produced.

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

（２）得られたニトロ体を還元して下記式（ｄ）で表わされるアミン体を得る工程、

（３）得られたアミン体とトリフェニルホスフィンジブロミドを反応させ下記式（ｅ）で表されるトリフェニルホスフィン体を得る工程、および

（４）得られたトリフェニルホスフィン体を反応系中でイソシアネート化した後、直接脱炭酸させる工程により製造したものは、本願発明に用いる環状カルボジイミド化合物として好適に用いることができる。（上記式中、Ａｒ^１およびＡｒ^２は各々独立に、炭素数１〜６のアルキル基またはフェニル基で置換されていてもよい芳香族基である。Ｅ^１およびＥ^２は各々独立に、ハロゲン原子、トルエンスルホニルオキシ基およびメタンスルホニルオキシ基、ベンゼンスルホニルオキシ基、ｐ−ブロモベンゼンスルホニルオキシ基からなる群から選ばれる基である。Ａｒ^ａは、フェニル基である。Ｘは、下記式（ｉ−１）から（ｉ−３）の結合基である。） Depending on the compound to be produced, an appropriate production method may be employed. For example, (1) nitrophenol represented by the following formula (a-1), nitrophenol represented by the following formula (a-2), and A step of reacting a compound represented by the following formula (b) to obtain a nitro compound represented by the following formula (c);

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

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

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

（式中、ｎ^ｉ−１は１〜６の整数である。）

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

（式中、ｍ^ｉ−２およびｎ^ｉ−２は各々独立に０〜３の整数である。）

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

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

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

<About component C>
The resin composition of the present invention contains at least one antioxidant selected from the group consisting of hindered phenol compounds, phosphite compounds, phosphonite compounds, and thioether compounds as an antioxidant (C component). use. By blending an antioxidant (component C), not only the hue and fluidity during molding are stabilized, but also effective in improving hydrolysis resistance and long-term heat resistance.

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

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

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

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

  Content of antioxidant is 0.001-2 weight part with respect to 100 weight part of resin components (A component), Preferably it is 0.005-1 weight part, More preferably, it is 0.01-0.5. Parts by weight. When the blending amount is less than 0.001 part by weight, the antioxidant effect is insufficient, and not only the hue and fluidity during the molding process become unstable, but also the hydrolysis resistance deteriorates. On the other hand, when the blending amount is more than 2 parts by weight, the reaction component derived from the antioxidant and the like deteriorates the hydrolysis resistance.

  Further, it is preferable to use the hindered phenol compound in combination with at least one of a phosphite compound, a phosphonite compound, and a thioether compound. By using a combination of a hindered phenol compound and one or more of a phosphite compound, a phosphonite compound, or a thioether compound, a synergistic effect as a stabilizer is exhibited, and the hue during molding is further improved. , Effective in stabilizing fluidity and improving hydrolysis resistance.

<About D component>
The end-blocking agent of component D shows a function of blocking by reacting with part or all of the carboxyl group ends of the resin component (component A). For example, condensation reaction type such as aliphatic alcohol and amide compound Examples thereof include compounds and addition reaction type compounds such as epoxy compounds, oxazoline compounds, oxazine compounds, and aziridine compounds. Here, the cyclic carbodiimide of the B component is not included in the terminal blocking agent (D component). 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.

  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, p-tert-butylphenyl glycidyl ether, glycidyl methacrylate, 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, Lahydrophthalic 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 can be preferably used because of compatibility with polylactic acid. 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, p-tert-butylphenyl glycidyl ether, N-glycidyl phthalimide, hydroquinone diglycidyl ether, resorcin diglycidyl ether, 1,6-hexanediol diglycidyl ether, hydrogenated bisphenol A-diglycidyl ether, and the like. .

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

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

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

  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 an epoxy compound mentioned above as an endblocker which can be used for this invention, 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 resin component is preferably 10 equivalents / 10 ³ kg or less from the viewpoint of improving hydrolysis resistance, and is 6 equivalents / 10 ³ kg or less. More preferably.

  As a method for blocking the carboxyl group terminal of the resin component (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, a polymer is used. At the time of polymerization, the end of the carboxyl group can be blocked by adding a suitable amount of a condensation reaction type end-capping agent such as aliphatic alcohol or amide compound into the polymerization system and performing dehydration 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 for 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 an epoxy compound, an oxazoline compound, an oxazine compound, or an aziridine compound in a molten state of polylactic acid. After completion, it is possible to add and react with a terminal blocking agent.

  The content of the terminal blocking agent (component D) can be contained in an amount of 0.001 to 10 parts by weight per 100 parts by weight of the resin component (component A). Preferably, it is 0.01-5 weight part, More preferably, it is 0.1-3 weight part. If the content is less than 0.001 part by weight, the amount of the end-capping agent added to the carboxyl terminal is too small, and sufficient hydrolysis resistance cannot be obtained. If the content exceeds 10 parts by weight, gelation occurs and the fluidity is increased. It drops significantly.

<E component>
In this invention, a hydrotalcite (E component) can be included. The hydrotalcite (E component) used in the present invention is preferably a synthetic hydrotalcite represented by the following general formula (9).

(Expressed M ²⁺ is magnesium ions in the formula, the divalent metal ions such as zinc ion, N ³⁺ is aluminum ions, trivalent metal ions such as chromium ions, A ^n-is an n-valent interlayer anion, x Is 0 <x ≦ 0.33, m is 0 ≦ m <2, and n is an integer of 1 ≦ n ≦ 5.)

[M ²⁺ _1-X N ³⁺ _x (OH) ₂ ] in the formula (9) is a hydroxide sheet, which is formed by the fact that octahedrons formed by surrounding six OHs with metal ions share each other. . The hydroxide sheets overlap to form a layered structure. [A ⁿ⁻ _{x / n} · mH ₂ O] in the formula (9) represents an n-valent anion and water of crystallization entering between the hydroxide sheets.

M ²⁺ is not particularly limited as long as it is a divalent metal ion, but generally magnesium ion is preferably used. Further, N ³⁺ is not particularly limited as long as it is a trivalent metal ion, typically aluminum ions are preferably used are in, A ^n-is are preferably used carbonate ions.

  The mechanism by which hydrotalcite improves the hydrolysis resistance of polylactic acid is not clear, but it is thought to be because it adsorbs acids that catalyze the hydrolysis reaction of polylactic acid, such as lactic acid generated by thermal decomposition and hydrolysis. .

The hydrotalcite used in the present invention is preferably dehydrated by firing. The temperature for the baking treatment can be arbitrarily selected according to the chemical structure of the hydrotalcite. For ^{example, M 2+} is magnesium ^{ion, N 3+} is aluminum ^{ion, A n-carbonate} ions, magnesium ions: aluminum ion = 2: 1 (x = 0.33 ) if it was, dehydration temperature of crystal water is Since it is 210 ° C., it can be dehydrated by baking at this temperature or higher. As x becomes smaller than 0.33, the dehydration temperature of crystal water decreases. By using hydrotalcite that has been subjected to dehydration treatment, it is possible to prevent the resin from being decomposed in a process such as extrusion or molding, and thus a resin composition having more excellent hydrolysis resistance can be obtained. Therefore, the range of m in Formula (9) is preferably 0 ≦ m <0.5, and most preferably 0 ≦ m <0.1.

  Moreover, it is preferable that the hydrotalcite used by this invention is surface-treated. Examples of the surface treatment agent include silane coupling agents, titanate coupling agents, silicone compounds, fatty acids, fatty acid salts, synthetic resins, and particularly, fatty acids and fatty acid salts that are familiar with polylactic acid are preferably used. Surface treatment of hydrotalcite not only prevents the degradation of polylactic acid in processes such as extrusion and molding, but also increases the dispersion of hydrotalcite in polylactic acid, effectively adsorbing acid Thus, a resin composition having more excellent hydrolysis resistance can be obtained.

  The fatty acid used for the surface treatment is not particularly limited as long as it is a fatty acid, but a higher fatty acid having a relatively high boiling point and having 12 or more carbon atoms is preferable. Specific examples include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, and the like. The fatty acid salt used for the surface treatment is not particularly limited as long as it is a fatty acid salt, but a higher fatty acid salt having a relatively high boiling point and having 12 or more carbon atoms is preferable. Specific examples include laurate, myristate, palmitate, stearate, oleate, linoleate, and linolenate. As the salt used in the higher fatty acid salt, inorganic compounds such as sodium, potassium and zinc are preferable.

  The present invention may use any of hydrotalcite that has been either dehydrated or untreated, hydrotalcite that has been subjected to dehydration or surface treatment, or hydrotalcite that has been subjected to both dehydration or surface treatment. Preferably, hydrotalcite subjected to either dehydration treatment or surface treatment, more preferably hydrotalcite subjected to both dehydration treatment or surface treatment, can be used.

  DHT-6 (manufactured by Kyowa Chemical Industry Co., Ltd.) is a hydrotalcite that has not been subjected to dehydration or surface treatment, and DHT-4C (Kyowa Chemical Industry Co., Ltd.) is a hydrotalcite that has only been dehydrated. ), As hydrotalcite that is only surface-treated, DHT-4A (manufactured by Kyowa Chemical Industry Co., Ltd.), as hydrotalcite that is both dehydrated and surface-treated, DHT-4A-2 (Manufactured by Kyowa Chemical Industry Co., Ltd.) can be obtained as commercial products.

  The amount of hydrotalcite added may be 0.01 to 0.3 parts by weight with respect to 100 parts by weight of the resin component (component A). Preferably, it is 0.03-0.2 weight part, More preferably, it is 0.05-0.2 weight part. If the amount of hydrotalcite added is 0.01 parts by weight or less, the effect of improving hydrolysis resistance cannot be obtained, and if the amount of hydrotalcite added is 0.3 parts by weight or more, it causes thermal decomposition of polylactic acid. In turn, the hydrolysis resistance deteriorates.

<About F component>
The composition of the present invention may contain an impact modifier (F component). By blending an impact modifier (F component), not only impact resistance but also hydrolysis resistance is effective. As an impact modifier (F component), (F-α) has at least one rubber layer therein, and the component is an acrylic component, a silicon component, a styrene component, a nitrile component, a conjugate. One or more selected from the group consisting of diene-based components, urethane-based components, and ethylene-propylene-based components, and an impact modifier (F-α component) in which components other than the rubber layer are vinyl monomers and / or (F-β) An impact modifier (F-β component) containing substantially no rubber component is preferably used. These two types may be used alone or in combination, and it goes without saying that one or more compounds may be used in each type. It is preferable to use it properly according to the purpose.

(F-α component)
It has at least one rubber layer inside, and its components are made of the group consisting of acrylic component, silicon component, styrene component, nitrile component, conjugated diene component, urethane component, and ethylene propylene component. As an impact modifier (F-α component) which is one or more selected and the components other than the rubber layer are vinyl monomers, a vinyl unit containing a rubber component and containing less than 40% by weight At least one resin selected from the group consisting of a resin containing resin (F-α-1 component) and a vinyl unit-containing resin (F-α-2 component) having a rubber component content of 40% by weight or more is preferable.

(F-α-1 component)
A vinyl unit-containing resin (F-α-1 component) containing a rubber component and containing less than 40% by weight is a polymer of at least one vinyl monomer and less than 40% by weight of a rubber component. This is a resin obtained.

  Examples of the vinyl monomer include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, vinylxylene, ethylstyrene, dimethylstyrene, p-tert-butylstyrene, vinylnaphthalene, methoxystyrene, and monobromostyrene. Styrene compounds such as styrene derivatives such as dibromostyrene, fluorostyrene and tribromostyrene, vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, aryl acrylates such as phenyl acrylate and benzyl acrylate, methyl acrylate and ethyl acrylate , Propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, cyclohexyl acrylate Acrylic acid alkyl esters such as dodecyl acrylate, methacrylic acid aryl esters such as phenyl methacrylate and benzyl methacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, cyclohexyl methacrylate, Methacrylic acid alkyl esters such as dodecyl methacrylate, epoxy group-containing methacrylic acid esters such as glycidyl methacrylate, maleimide monomers such as maleimide, N-methylmaleimide, N-phenylmaleimide, acrylic acid, methacrylic acid, maleic acid, maleic anhydride Α, β-unsaturated carboxylic acids such as acid, phthalic acid, itaconic acid and the like Anhydride, and the like. Furthermore, these can be used alone or in combination of two or more.

  Examples of the rubber component copolymerizable with the vinyl monomer include polybutadiene, polyisoprene, styrene / butadiene random copolymer and block copolymer, acrylonitrile / butadiene copolymer, alkyl acrylate ester and / or methacrylic acid. Alkyl ester and butadiene copolymers, diene copolymers such as butadiene / isoprene copolymers, ethylene / propylene random copolymers and block copolymers, ethylene / butene random copolymers and block copolymers, etc. Ethylene / α-olefin copolymer, ethylene / methacrylate copolymer, ethylene / butyl acrylate copolymer, etc., ethylene / unsaturated carboxylic acid ester copolymer, ethylene / vinyl acetate copolymer, etc. Co-weight of ethylene and aliphatic vinyl , Ethylene, propylene and non-conjugated diene terpolymers such as ethylene / propylene / hexadiene copolymer, acrylic rubber such as polybutyl acrylate, and polyorganosiloxane rubber component and polyalkyl (meth) acrylate rubber component are separated Examples thereof include a composite rubber (hereinafter referred to as IPN type rubber) having a structure entangled with each other so as not to be able to do so.

  As the vinyl unit component-containing resin (F-α-1 component) containing such a rubber component and having a content of less than 40% by weight, for example, styrene / butadiene / styrene copolymer (SBS resin), hydrogenated styrene / Butadiene / styrene copolymer (hydrogenated SBS resin), hydrogenated styrene / isoprene / styrene copolymer (hydrogenated SIS resin), high impact polystyrene (HIPS resin), acrylonitrile / styrene copolymer (AS resin), acrylonitrile・ Butadiene / styrene copolymer (ABS resin), methyl methacrylate / butadiene / styrene copolymer (MBS resin), methyl methacrylate / acrylonitrile / butadiene / styrene copolymer (MABS resin), acrylonitrile / styrene / acrylic rubber copolymer Combined (ASA resin), acrylonitrile, Tylene propylene rubber / styrene copolymer (AES resin), styrene / methyl methacrylate copolymer (MS resin), methyl methacrylate / acrylonitrile / styrene copolymer (MAS resin), styrene / maleic anhydride copolymer (SMA) Resin) and resins such as styrene / IPN type rubber copolymer, or a mixture thereof. Such a styrenic thermoplastic resin may have a high stereoregularity such as syndiotactic polystyrene by using a catalyst such as a metallocene catalyst during the production thereof. Further, in some cases, polymers and copolymers having a narrow molecular weight distribution, block copolymers, polymers with high stereoregularity, and copolymers obtained by anionic living polymerization, radical living polymerization, or the like are used. It is also possible. These may be used alone or in combination of two or more.

  Among these, high impact polystyrene (HIPS resin), acrylonitrile / styrene copolymer (AS resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), acrylonitrile / styrene / acrylic rubber copolymer (ASA resin), acrylonitrile. -Ethylene propylene rubber-Styrene copolymer (AES resin) methyl methacrylate-Butadiene-Styrene copolymer (MBS resin) It is preferable to use 1 type or 2 types or more mixed, Of these, ABS resin, ASA resin, and AES resin are most preferable.

  The ABS resin used in the present invention is a thermoplastic graft copolymer (ABS copolymer) obtained by graft polymerization of a vinyl cyanide compound and an aromatic vinyl compound to a diene rubber component, a vinyl cyanide compound and an aromatic vinyl compound. It is a mixture of the copolymer (AS copolymer). The copolymer of the vinyl cyanide compound and the aromatic vinyl compound is used for the production of a resin comprising a thermoplastic graft copolymer obtained by graft copolymerizing a vinyl cyanide compound and an aromatic vinyl compound with a diene rubber component. It may be a copolymer produced as a by-product, or a copolymer obtained by separately copolymerizing an aromatic vinyl compound and a vinyl cyanide compound. The molecular weight of the copolymer comprising the vinyl cyanide compound and the aromatic vinyl compound is preferably 0.2 to 1.0, more preferably 0.25 to 0.5 in terms of reduced viscosity. The ratio of the AS copolymer can be collected by a technique such as dissolving the ABS resin in a good solvent for the AS copolymer such as acetone and centrifuging the soluble component. On the other hand, the insoluble matter (gel) becomes a net ABS copolymer.

  Further, the weight ratio (graft ratio) of the grafted vinyl cyanide compound and aromatic vinyl compound to the diene rubber component is preferably 20 to 200% by weight, more preferably 20 to 70% by weight.

  As the diene rubber component forming the ABS resin, for example, a rubber having a glass transition point of 10 ° C. or lower such as polybutadiene, polyisoprene, and styrene-butadiene copolymer is used, and the ratio is 5% in 100% by weight of the ABS resin component. It is preferable that it is -39.9 weight%, More preferably, it is 10-35 weight%, More preferably, it is 10-25 weight%.

  Examples of the vinyl cyanide compound grafted onto the diene rubber component include those described above, and acrylonitrile is particularly preferably used. As the aromatic vinyl compound grafted onto the diene rubber component, those described above can be used in the same manner, but styrene and α-methylstyrene are particularly preferably used. The proportion of the component grafted to the diene rubber component is preferably 60.1 to 95% by weight, more preferably 65 to 90% by weight, and further preferably 75 to 90% by weight in 100% by weight of the ABS resin component. . Further, the vinyl cyanide compound is 5 to 50% by weight and more preferably 10 to 30% by weight and the aromatic vinyl compound is 95 to 50% with respect to 100% by weight of the total amount of the vinyl cyanide compound and the aromatic vinyl compound. It is preferred to be 90% by weight and more preferably 90-70% by weight. Further, methyl (meth) acrylate, ethyl acrylate, maleic anhydride, N-substituted maleimide and the like can be mixed and used for some of the components grafted to the diene rubber component, and the content ratio thereof is in the ABS resin component. What is 15 weight% or less is preferable. Furthermore, conventionally well-known various things can be used for the initiator, chain transfer agent, emulsifier, etc. which are used by reaction as needed.

  In the ABS resin, the rubber particle diameter is preferably from 0.1 to 5.0 μm, more preferably from 0.3 to 3.0 μm, still more preferably from 0.4 to 1.5 μm, particularly preferably from 0.4 to 0.00. 9 μm. The rubber particle diameter distribution can be either a single distribution or a rubber having a plurality of peaks of two or more, and the rubber particles form a single phase in the morphology. Alternatively, it may have a salami structure by containing an occluded phase around the rubber particles.

  This ABS resin may be produced by any of bulk polymerization, suspension polymerization, and emulsion polymerization, and the copolymerization method may be one-stage copolymerization or multistage copolymerization. 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 maintained separately, and both are accurately supplied to the continuous disperser, and the particle diameter is controlled by the rotational 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.

  The ASA resin used in the present invention is a thermoplastic graft copolymer obtained by graft polymerization of a vinyl cyanide compound and an aromatic vinyl compound to an acrylic rubber component, or the thermoplastic graft copolymer, a vinyl cyanide compound and an aromatic resin. A mixture with a copolymer of a group vinyl compound. The acrylic rubber referred to in the present invention contains an alkyl acrylate unit having 2 to 10 carbon atoms, and further contains styrene, methyl methacrylate, butadiene as other copolymerizable components as necessary. Also good. Preferred examples of the alkyl acrylate having 2 to 10 carbon atoms include 2-ethylhexyl acrylate and n-butyl acrylate. The alkyl acrylate is preferably contained in an amount of 50% by weight or more in 100% by weight of the acrylate rubber. Further, the acrylate rubber is at least partially crosslinked, and examples of the crosslinking agent include ethylene glycol diacrylate, butylene glycol diacrylate, ethylene glycol dimethacrylate, allyl methacrylate, polypropylene glycol diacrylate, and the like. The crosslinking agent is preferably used in an amount of 0.01 to 3% by weight based on the acrylate rubber. The proportion of the acrylic rubber component is preferably 5 to 39.9% by weight, more preferably 10 to 35% by weight, and still more preferably 10 to 25% by weight in 100% by weight of the ASA resin.

  The proportion of the vinyl cyanide compound and the aromatic vinyl compound is preferably 5 to 50% by weight of the vinyl cyanide compound and 95 to 50% by weight of the aromatic vinyl compound with respect to the total amount of 100% by weight. More preferably, the vinyl compound is 15 to 35% by weight and the aromatic vinyl compound is 85 to 65% by weight. As the production method, the same one as the above ABS resin can be used.

  The AES resin used in the present invention is a thermoplastic graft copolymer obtained by graft polymerization of a vinyl cyanide compound and an aromatic vinyl compound to an ethylene-propylene rubber component or an ethylene-propylene-diene rubber component, or the thermoplastic graft copolymer. And a mixture of a vinyl cyanide compound and a copolymer of an aromatic vinyl compound. As the production method, the same one as the above ABS resin can be used.

(F-α-2 component)
The vinyl unit-containing resin having a rubber component content of 40% by weight or more is a resin obtained by polymerizing at least one vinyl monomer and 40% by weight or more of a 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.

  The rubber component here is butadiene rubber, butadiene-acrylic composite rubber, acrylic rubber, acrylic-silicon composite rubber, isobutylene-silicon composite rubber, isoprene rubber, styrene-butadiene rubber, chloroprene rubber, ethylene-propylene rubber, nitrile rubber. , Ethylene-acrylic rubber, silicon rubber, epichlorohydrin rubber, fluororubber, and those obtained by adding hydrogen to the unsaturated bond portion.

  Among them, an impact modifier containing a rubber component having a glass transition temperature of 10 ° C. or lower, more preferably −10 ° C. or lower, and further preferably −30 ° C. or lower is preferable. Particularly, butadiene rubber, butadiene-acrylic composite rubber, acrylic rubber, An impact modifier using acrylic-silicon composite rubber is preferred. 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 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.

  The vinyl unit-containing resin having a rubber component content of 40% by weight or more may be produced by any polymerization method such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization, and the copolymerization method is a one-stage graft. It can be 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.

  Such resins are commercially available and can be easily obtained. For example, rubber components mainly composed of butadiene rubber, acrylic rubber or butadiene-acrylic composite rubber include Kane Ace B series from Kaneka Chemical Industry Co., Ltd., Metabrene C series from Mitsubishi Rayon Co., Ltd., Kureha Chemical Industry Co., Ltd. ( The EXL series, HIA series, BTA series, KCA series, and UCL modifier resin series from Ube Saikon Co., Ltd. are listed. Mitsubishi Rayon Co., Ltd. is mainly composed of acrylic-silicon composite rubber as a rubber component. Further, those commercially available under the trade name of Metabrene S-2001 or SRK-200 can be mentioned.

  The combined use of a vinyl unit component-containing resin containing such a rubber component, the content of which is less than 40% by weight, and a vinyl unit component-containing resin having a rubber component content of 40% by weight or more further improves the impact resistance. As a preferred embodiment, the vinyl unit component-containing resin having a rubber component content of 40% by weight or more is 0.5 to 50% by weight with respect to 100% by weight of the vinyl unit component-containing resin having a rubber component of less than 40% by weight. The aspect containing part is mentioned.

(F-β component)
As the impact modifier (F-β component) containing substantially no rubber component of the present invention, at least one resin selected from the group consisting of copolymerized polyester and copolymerized polyethylene is preferred.

  Examples of the copolyester include a copolyester containing a polylactic acid component and a copolyester having a star structure containing a polybutylene adipate terephthalate component. Specifically, for example, Plumate PD-150, PD-350 and the like sold under the trade name of Puramate from Dainippon Ink and Chemicals, Inc. are exemplified. Moreover, Ecoflex SBX7025 sold by BASF Japan Co., Ltd. under the trade name of Ecoflex is exemplified.

  Examples of the copolymer polyethylene include ethylene marketed by Sumitomo Chemical Co., Ltd. under the trade name Bondfast, Bondfast E composed of glycidyl methacrylate, 7M containing methyl acrylate units, and BioMaxStrong100 manufactured by DuPont. The

  The polyester elastomer is an elastomer in which a polybutylene terephthalate skeleton is a main skeleton and a polyalkylene glycol is copolymerized. Examples thereof include TR-EL-1 manufactured by Teijin Limited.

The polyamide elastomer is an elastomer having a polyamide oligomer as a hard segment and polyester or polyether ester as a soft segment, and examples thereof include TPAE31, TPAE32, and TPAE38 manufactured by Fuji Kasei Kogyo Co., Ltd.
The content of the impact modifier (F component) can be 2 to 100 parts by weight with respect to 100 parts by weight of the resin component (A component). More preferably, it is 3-90 weight part, More preferably, it is 5-80 weight part. If the content is less than 2 parts by weight, the amount of impact modifier added is too small, and sufficient impact resistance and hydrolysis resistance cannot be obtained. If the content exceeds 100 parts by weight, not only the heat resistance deteriorates, Many impact modifiers are derived from petroleum, which is not preferable from the viewpoint of environmental load.

<About G component>
The composition of the present invention comprises a phosphorus flame retardant (G-1 component), a nitrogen flame retardant (G-2 component), a metal hydroxide flame retardant (G-3 component), a metal oxide flame retardant (G -4 component) and at least one flame retardant (C component) selected from the group consisting of a brominated flame retardant (G-5 component). These flame retardants (component G) may be used alone or in combination of two or more, and one or more compounds may be used in each type. It is preferable to use it properly according to the purpose.

(Phosphorus flame retardant: G-1 component)
Phosphorus flame retardants (G-1 component) include (1) phosphate ester flame retardants, (2) phosphonitrile flame retardants, (3) phosphonate flame retardants, and (4) phosphinic acid metal salt flame retardants. (5) Metal phosphate-based flame retardants.

(1) Phosphate ester flame retardant Examples of the phosphate ester flame retardant usable in the present invention include phosphate ester compounds and phosphaphenanthrene compounds. Specific examples of phosphate ester flame retardants include one or more phosphate ester compounds represented by the following formula (10).

In the formula, X ³⁴ represents hydroquinone, resorcinol, bis (4-hydroxydiphenyl) methane, bisphenol A, dihydroxydiphenyl, dihydroxynaphthalene, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4- Hydroxyphenyl) is a group derived from sulfide. n ³⁴ is an integer of 0 to 5, or when n number of different mixtures of phosphoric acid ester is an average value of 0 to 5. R ₂₁ , R ₂₂₂ , R ₂₃ and R ₂₄ 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 ³⁴ in the formula is a group derived from hydroquinone, resorcinol, bisphenol A, and dihydroxydiphenyl, n ³⁴ is an integer of 1 to 3, or n different phosphates of an average value in the case of _{blends, R 21, R 22, R} 23, and R ₂₄ are not independently preferably substituted from or with substitution of one or more halogen atoms phenol, cresol, Examples thereof are groups derived from xylenol.

  Among such phosphate ester flame retardants, triphenyl phosphate is preferred as a phosphate compound, and resorcinol bis (dixylenyl phosphate) and bisphenol A bis (diphenyl phosphate) are preferred as phosphate oligomers because of their excellent hydrolysis resistance. it can. 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.

(2) Phosphononitrile-based flame retardant The phosphonitrile-based flame retardant used in the present invention is a phosphonitrile linear polymer, a phosphonitrile cyclic polymer, or the like, and an oligomer or polymer having a repeating unit represented by the following formula (11) The number average degree of polymerization is preferably 3 or more. Although it may be either linear or cyclic, a cyclic trimer is particularly preferably used. Further, it may be a mixture in which a linear product and a cyclic product are mixed at an arbitrary ratio.

In the formula, A and B each independently represent an O, N, or S atom. R ₂₅ and R ₂₆ are each independently an aryl group having 6 to 15 carbon atoms, an alkyl group having 6 to 15 carbon atoms, an aralkyl group having 6 to 15 carbon atoms, or a cycloalkyl group having 6 to 15 carbon atoms. A ring structure in which R ₂₅ and R ₂₆ are linked may be used. x ³⁵ and y ³⁵ are 0 or 1. n ³⁵ denotes the number average polymerization degree, represent 3 or more than 3 values.

  Such phosphonitrile linear polymer and phosphonitrile cyclic polymer are poly (dichlorophosphazene) obtained by ring-opening polymerization of hexachlorocyclotriphosphazene, octachlorocyclotetraphosphazene, or these cyclic oligomers, and alcohol, phenol, amine, thiol, It can be synthesized by reacting with a nucleophilic reagent such as a Grignard reagent by a known method.

(3) Phosphonate flame retardant The phosphonate flame retardant is preferably represented by the following general formula (12).

In the formula, each of R ₂₇ and R ₂₈ independently represents a branched or unbranched alkylene group having 1 to 24 carbon atoms, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, or a substituted or non-substituted group having 6 to 30 carbon atoms. A substituted aralkylene group or a substituted or unsubstituted alkarylene group having 6 to 30 carbon atoms.

R ₂₉ is a hydrogen atom, a branched or unbranched alkyl group having 1 to 24 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 30 carbon atoms, Or it is a C6-C30 substituted or unsubstituted alkaryl group. x ³⁶ and ^{y 36} is the number of independently 1 to 50.

(4) Phosphinic acid metal salt-based flame retardant Examples of the organic phosphinic acid metal salt include one or more of the following general formulas (13) and (14).

In the formula, each of R ₃₁ , R ₃₂ , R ₃₃ , and R ₃₄ 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 ₃₅ 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 ₃ and M ₄ are Mg, Ca, Al, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K, or a protonated nitrogen base. X ³⁸ is 1 or 2, m ³⁷ and m ³⁸ are 2 or 3, and n ³⁸ is 1 or 3.

R ₃₁ , R ₃₂ , R ₃₃ , and R ₃₄ appropriately retain the phosphorus content in the flame retardant and suitably exhibit the flame retardancy, while at the same time suitably expressing the crystallinity of the composition. A linear or branched alkyl group having -20, a cycloalkyl group having 6-20 carbon atoms, an aryl group having 6-20 carbon atoms, or an aralkyl group having 7-20 carbon atoms is preferably selected. Of these, a linear or branched alkyl group having 1 to 20 carbon atoms 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.

Since R ₃₅ appropriately maintains the phosphorus content in the flame retardant and suitably expresses the flame retardancy, it also suitably expresses the crystallinity of the composition. Therefore, R ₃₅ is a straight chain having 1 to 10 carbon atoms. 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 ₃ and M ₄ 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 ₃ and M ₄ are derived from Mg, Ca, Al, Zn and groups derived from amide, ammonium, alkylammonium or melamine. It is preferable that it is 1 type selected from the group which consists of. Among these, Al is most preferably selected.
When the phosphinic acid salts represented by the formulas (13) and (14) are used in combination, the weight ratio of (13) / (14) is preferably selected from the range of 10/90 to 30/70.

  In order to improve moisture resistance, the phosphinic acid metal salt flame retardant used in the present invention may be used after the surface is coated 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 phosphinic 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 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.

(5) Phosphoric acid metal salt-based flame retardant As the phosphoric acid metal salt, aluminum containing aluminum phosphite represented by the following general formula (15) and primary phosphorus represented by the following general formula (16) Aluminum acid phosphate and tertiary aluminum phosphate represented by the following general formula (17) are preferred.

  Of the flame retardants represented by the general formulas (15) to (17), the flame retardants represented by the general formulas (15) and (16) are preferable from the viewpoint of the thermal stability and flame retardancy of the polylactic acid composition. The aluminum phosphite represented by the general formula (15) is particularly preferable from the viewpoint of thermal stability and flame retardancy, and the 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 composition, it has excellent thermal stability, heat resistance, and moldability. Become a material.

  In order to improve moisture resistance, the metal phosphate 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 metal phosphate-based 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.

(Nitrogen flame retardant: G-2 component)
The nitrogen-based flame retardant used in the present invention is preferably at least one selected from the group consisting of melamine compounds, reaction products of melamine compounds and polyphosphoric acid, and reaction products of melamine condensates and polyphosphoric acid. Particularly preferred is at least one selected from the group consisting of flame retardants used and represented by formula (18) or (19).

[Wherein R _{41 to} R ₄₆ 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 _{41 to} R ₄₆ are not simultaneously hydrogen atoms, and in the formulas (18) and (19), all of R _{41 to} R ₄₆ are not simultaneously —NH ₂ . X ⁴³ is an acid capable of forming an adduct with a melamine or triazine compound, and s ⁴³ and t ⁴³ are each independently 1 or 2. ]

  Preferred examples of (18) and (19) include dimelamine pyrophosphate, melamine polyphosphate, melem polyphosphate, melam polyphosphate, melon polyphosphate, and the like.

  In the present invention, the flame retardancy of the composition of the present invention is improved by additionally using at least one compound represented by the following formulas (20) to (23) in addition to the nitrogen-based flame retardant having a triazine skeleton. Can be made.

In the formula, R _{47 to} R ₄₉ , R _{51 to} R ₅₉ , and R _{61 to} R ₆₄ are each preferably independently exemplified by the functional groups described as R _{41 to} R ₄₆ . For example, tris (hydroxyethyl) isocyanurate, allanin, glycoluril, urea. Cyanurate and the like are preferably exemplified. Such an agent is applied in the range of 10 to 50% by weight based on the nitrogen-based flame retardant containing a triazine skeleton.

(Metal hydroxide flame retardant: G-3 component)
Metal hydroxide flame retardants that can be used in this patent include 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 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.

The metal hydroxide flame retardant used in the present invention preferably has a high purity for improving the thermal stability of the composition, and particularly preferably has a purity of 99.5% or more. The purity of the metal hydroxide flame retardant can be measured by a known method. For example, the content of impurities contained in the metal hydroxide flame retardant is measured by a known method, and the purity of the metal hydroxide flame retardant is obtained by subtracting the impurity content from the total amount. be able to. For example, in the case of aluminum hydroxide, examples of impurities include Fe ₂ O ₃ , SiO ₂ , T—Na ₂ O, S—Na ₂ O and the like. The content of Fe ₂ O ₃ is determined by O-phenanthroline spectrophotometry (JISH 1901) after melting in sodium carbonate-boric acid solution. The content of SiO ₂ is determined by the molybdenum blue absorptiometry (JISH 1901) after melting in sodium carbonate-boric acid solution. The content of T-Na ₂ O is obtained by flame photometry after melting in sulfuric acid, and S-Na ₂ O is obtained by flame photometry after extraction with hot water. The purity of the hydroxide can be obtained by reducing the content determined as described above from the weight of aluminum hydroxide. Of course, it is needless to say that different types of metal hydroxide flame retardants can be used in combination.

  The shape of the metal hydroxide flame retardant used in the present invention is not particularly limited, but is preferably granular. As for the particle diameter, it is preferable that the average particle diameter calculated | required by the laser diffraction method is about 100 micrometers or less. In this case, the particle size distribution does not matter. From the viewpoint of injection moldability in the molding process and dispersibility at the time of kneading, the average particle diameter is preferably in the above range, and more preferably in the above range. Of course, a plurality of metal hydroxide flame retardants having different average particle diameters can be used in combination in order to increase the filling rate of the composition.

Furthermore, it is preferable to use particles having a BET specific surface area of about 5.0 m ² / g or less determined by a nitrogen gas adsorption method. Of course, in order to increase the filling rate of the composition, a plurality of types of metal hydroxide flame retardants having different BET specific surface areas can be used in combination. From the viewpoint of moldability, the BET specific surface area is preferably in the above range, and a smaller one is more preferable in the above range.

  In order to improve moisture resistance, the metal hydroxide 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 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.

(G-4 component: metal oxide flame retardant)
Metal oxide flame retardants that can be used in this patent include magnesium oxide, aluminum oxide, calcium oxide, zinc oxide, potassium oxide, silicon oxide, titanium oxide, iron oxide, copper oxide, sodium oxide, nickel oxide, boron oxide, Examples thereof include manganese oxide, lithium oxide, and antimony oxide.

  The shape of the metal oxide flame retardant used in the present invention is not particularly limited, but is preferably granular. As for the particle diameter, it is preferable that the average particle diameter calculated | required by the laser diffraction method is about 100 micrometers or less. In this case, the particle size distribution does not matter. From the viewpoint of injection moldability in the molding process and dispersibility at the time of kneading, the average particle diameter is preferably in the above range, and more preferably in the above range. Of course, a plurality of metal oxide flame retardants having different average particle diameters can be used in combination in order to increase the filling rate of the composition.

Furthermore, it is preferable to use particles having a BET specific surface area of about 5.0 m ² / g or less determined by a nitrogen gas adsorption method. Of course, in order to increase the filling rate into the composition, a plurality of kinds of metal oxide flame retardants having different BET specific surface areas can be used in combination. From the viewpoint of moldability, the BET specific surface area is preferably in the above range, and a smaller one is more preferable in the above range.

  In order to improve moisture resistance, the metal oxide 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 metal oxide 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.

  Such metal oxide-based flame retardants can be used alone, but are preferably used in combination with phosphorus-based flame retardants, nitrogen-based flame retardants, and bromine-based flame retardants because particularly high flame retardant effects can be obtained. .

(Brominated flame retardant: G-5 component)
As the brominated flame retardant used in the present invention, for example, a brominated bisphenol A type polycarbonate flame retardant having a bromine content of 20% by weight or more, a brominated bisphenol A type epoxy resin and / or a part or all of its terminal glycidyl groups are blocked. Modified products, brominated diphenyl ether flame retardants, brominated imide flame retardants, brominated polystyrene flame retardants and the like.

  Specific examples include decabromodiphenyl oxide, octabromodiphenyl oxide, tetrabromodiphenyl oxide, tetrabromophthalic anhydride, hexabromocyclododecane, bis (2,4,6-tribromophenoxy) ethane, ethylene bistetrabromophthalimide, Hexabromobenzene, 1,1-sulfonyl [3,5-dibromo-4- (2,3-dibromopropoxy)] benzene, polydibromophenylene oxide, tetrabromobisphenol S, tris (2,3-dibromopropyl-1) Isocyanurate, tribromophenol, tribromophenyl allyl ether, tribromoneopentyl alcohol, brominated polystyrene, brominated polyethylene, tetrabromobisphenol A, tetrabromobisphenol Abromide A derivatives, tetrabromobisphenol A-epoxy oligomer or polymer, tetrabromobisphenol A-carbonate oligomer or polymer, brominated epoxy resins such as brominated phenol novolac epoxy, tetrabromobisphenol A-bis (2-hydroxydiethyl ether) , Tetrabromobisphenol A-bis (2,3-dibromopropyl ether), tetrabromobisphenol A-bis (allyl ether), tetrabromocyclooctane, ethylenebispentabromodiphenyl, tris (tribromoneopentyl) phosphate, poly ( Pentabromobenzyl polyacrylate), octabromotrimethylphenylindane, dibromoneopentyl glycol, pentabromobenzyl polyacrylate Over DOO, dibromo cresyl glycidyl ether, N, N'ethylene - bis - such as tetrabromo phthalic imide. Of these, tetrabromobisphenol A-epoxy oligomer, tetrabromobisphenol A-carbonate oligomer, and brominated epoxy resin are preferable.

  Phosphorus flame retardant (G-1 component), nitrogen flame retardant (G-2 component), metal hydroxide flame retardant (G-3 component), metal oxide flame retardant (G-4 component) and bromine The content of one or more flame retardants (G component) selected from a series flame retardant (G-5 component) is 1 to 100 parts by weight, more preferably 3 parts per 100 parts by weight of the resin component (A component). It is -90 weight part, More preferably, it is 5-80 weight part. If the content is less than 1 part by weight, the amount of flame retardant added is too small and flame retardancy cannot be obtained. If the content exceeds 100 parts by weight, the heat resistance deteriorates and the releasability decreases, which is not preferable.

<About H component>
The composition of the present invention may contain an inorganic filler (H component). A composition excellent in mechanical properties, heat resistance and moldability can be obtained by the inorganic filler. As the inorganic filler used in the present invention, a fibrous, plate-like, or powder-like material used for reinforcing ordinary thermoplastic resins can be used.

  Specifically, for example, carbon nanotube, glass fiber, asbestos fiber, carbon fiber, graphite fiber, metal fiber, potassium titanate whisker, aluminum borate whisker, magnesium whisker, silicon whisker, wollastonite, imogolite, sepiolite, Asbestos, slag fiber, zonolite, gypsum fiber, silica fiber, silica. Fibrous inorganic fillers such as alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber and boron fiber, layered silicate, layered silicate exchanged with organic onium ions, glass flake, non-swellable mica, graphite, metal Foil, ceramic beads, talc, clay, mica, sericite, zeolite, bentonite, dolomite, kaolin, powdered silicic acid, feldspar powder, potassium titanate, shirasu balloon, calcium carbonate, magnesium carbonate, barium sulfate, calcium oxide, aluminum oxide, Examples thereof include plate-like and particulate inorganic fillers such as carbon nanoparticles such as titanium oxide, aluminum silicate, silicon oxide, gypsum, novaculite, dawsonite, and white clay fullerene.

  Specific examples of layered silicates include smectite clay minerals such as montmorillonite, beidellite, nontronite, saponite, hectorite, and soconite, various clay minerals such as vermiculite, halosite, kanemite, and kenyanite, Li-type fluorine teniolite, Na And swellable mica such as Li-type fluorine teniolite, Li-type tetrasilicon fluorine mica and Na-type tetrasilicon fluorine mica. These may be natural or synthetic. Among these, smectite clay minerals such as montmorillonite and hectorite, and swellable synthetic mica such as Li type fluorine teniolite and Na type tetrasilicon fluorine mica are preferable.

  Among these inorganic fillers, fibrous or plate-like inorganic fillers are preferable, and glass fiber, wollastonite, aluminum borate whisker, potassium titanate whisker, mica, and kaolin, a cation-exchanged layered silicate. Is preferred. The aspect ratio of the fibrous filler is preferably 5 or more, more preferably 10 or more, and further preferably 20 or more.

  Such a filler may be coated or converged with a thermoplastic resin such as an ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin, or may be treated with a coupling agent such as aminosilane or epoxysilane. May be.

  The content of the inorganic filler (H component) is preferably 0.05 to 150 parts by weight, more preferably 0.5 to 100 parts by weight, still more preferably 1 to 100 parts by weight of the resin component (component A). 70 parts by weight, particularly preferably 1 to 50 parts by weight, most preferably 1 to 30 parts by weight. 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.

<About I component>
The composition of the present invention may contain a flame retardant aid (component I). As the flame retardant aid (component I) used in the present invention, an aromatic resin and / or a fluorinated polymer having a fibril-forming ability are preferably used.

  Examples of aromatic resins include polyphenylene ether resins, phenol resins, aromatic epoxy resins, phenoxy resins, polyphenylene sulfide resins, polyarylate resins, aromatic polyamide resins, and aromatic polyester amide resins. In particular, polyphenylene ether resin, phenol resin, aromatic epoxy resin, and phenoxy resin, which have high carbonization promotion efficiency during combustion, are preferable. 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 no 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. 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 content of the aromatic resin is preferably 0.1 to 30 parts by weight, more preferably 0.5 to 25 parts by weight, and further preferably 1 to 20 parts by weight per 100 parts by weight of the resin component (component A). .

  Examples of the fluorinated polymer having fibril-forming ability used in the present invention include polytetrafluoroethylene, a tetrafluoroethylene copolymer (for example, tetrafluoroethylene / hexafluoropropylene copolymer, etc.), US Pat. No. 4,379,910 And a polycarbonate resin produced from a fluorinated diphenol, preferably polytetrafluoroethylene (hereinafter sometimes referred to as PTFE).

Polytetrafluoroethylene (fibrillated PTFE) having fibril-forming ability has a very high molecular weight, and exhibits a tendency to bind PTFE to each other by an external action such as shearing force to form a fiber. The number average molecular weight is preferably in the range of 1.5 million to tens of millions. The lower limit is more preferably 3 million. The number average molecular weight is calculated based on the melt viscosity of polytetrafluoroethylene at 380 ° C. as disclosed in JP-A-6-145520. That is, the fibrillated PTFE has a melt viscosity at 380 ° C. measured by the method described in the above publication of preferably 10 ⁷ to 10 ¹³ poise, and more preferably 10 ⁸ to 10 ¹² poise.

  Such PTFE can be used in solid form or in the form of an aqueous dispersion. In addition, PTFE having such fibril-forming ability can improve the dispersibility in the resin, and it is also possible to use a PTFE mixture in a mixed form with other resins in order to obtain better flame retardancy and mechanical properties. is there. Further, as disclosed in JP-A-6-145520, those having a structure having such a fibrillated PTFE as a core and a low molecular weight polytetrafluoroethylene as a shell are also preferably used.

  Examples of commercially available fibrillated PTFE include Teflon (registered trademark) 6J from Mitsui DuPont Fluorochemical Co., Ltd., Polyflon MPA FA500, F-201L from Daikin Chemical Industries, Ltd., and the like. Commercially available aqueous dispersions of fibrillated PTFE include: Fluon AD-1, AD-936 manufactured by Asahi IC Fluoropolymers, Fluon D-1, D-2 manufactured by Daikin Industries, Ltd., Mitsui A representative example is Teflon (registered trademark) 30J manufactured by DuPont Fluorochemical Co., Ltd.

  As a mixed form of fibrillated PTFE, (1) a method in which an aqueous dispersion of fibrillated PTFE and an aqueous dispersion or solution of an organic polymer are mixed and co-precipitated to obtain a co-agglomerated mixture (JP-A-60-258263). (2) A method of mixing an aqueous dispersion of fibrillated PTFE and dried organic polymer particles (Japanese Patent Laid-Open No. 4-272957). Described method), (3) A method in which an aqueous dispersion of fibrillated PTFE and an organic polymer particle solution are uniformly mixed, and the respective media are simultaneously removed from the mixture (Japanese Patent Laid-Open Nos. 06-220210, (Method described in Japanese Patent Application Laid-Open No. 08-188653), (4) A method of polymerizing monomers forming an organic polymer in an aqueous dispersion of fibrillated PTFE (Method described in JP-A-9-95583), and (5) an aqueous dispersion of PTFE and an organic polymer dispersion are uniformly mixed, and then a vinyl monomer is further polymerized in the mixed dispersion. Thereafter, those obtained by a method for obtaining a mixture (a method described in JP-A-11-29679, etc.) can be used. Commercial products of these mixed forms of fibrillated PTFE include “Metablene A3800” (trade name) manufactured by Mitsubishi Rayon Co., Ltd., “BLENDEX B449” (trade name) manufactured by GE Specialty Chemicals, and “Products manufactured by Pacific Interchem Corporation” “POLY TS AD001” (product name) is exemplified. The proportion of fibrillated PTFE in the mixed form is preferably 10 to 80% by weight, more preferably 15 to 75% by weight, in 100% by weight of the mixture. When the ratio of fibrillated PTFE is in such a range, good dispersibility of fibrillated PTFE can be achieved.

The content of the fluoropolymer having fibril-forming ability is preferably 0.01 to 3 parts by weight, more preferably 0.01 to 2 parts by weight, and still more preferably based on 100 parts by weight of the resin component (component A). 0.05 to 1.5 parts by weight.
In addition, according to use and the objective, you may use combining the said aromatic resin and the fluorine-containing polymer which has fibril formation ability.

<About other ingredients>
<Light stabilizer>
The composition of the present invention may contain a light stabilizer. Specific examples of the light stabilizer include benzophenone compounds, benzotriazole compounds, aromatic benzoate compounds, oxalic acid anilide compounds, cyanoacrylate compounds, hindered amine compounds, and the like.

  Examples of the benzophenone compounds include benzophenone, 2,4-dihydroxybenzophenone, 2,2′-dihydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2 ′. -Dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sulfobenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, 5-chloro-2-hydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-methoxy -2 - carboxy benzophenone, 2-hydroxy-4- (2-hydroxy-3-methyl - acryloxy-isopropoxyphenyl) benzophenone.

  Examples of the benzotriazole compound include 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- (3,5- Di-tert-amyl-2-hydroxyphenyl) benzotriazole, 2- (3 ′, 5′-di-tert-butyl-4′-methyl-2′-hydroxyphenyl) benzotriazole, 2- (3,5- Di-tert-amyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (5-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis (Α, α-Dimethylbenzyl) phenyl] benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis (α, α Dimethylbenzyl) phenyl] -2H- benzotriazole, 2- (4'-octoxy-2'-hydroxyphenyl) benzotriazole.

  Examples of the aromatic benzoate compounds include alkylphenyl salicylates such as p-tert-butylphenyl salicylate and p-octylphenyl salicylate.

  Examples of oxalic acid anilide compounds include 2-ethoxy-2′-ethyloxalic acid bisanilide, 2-ethoxy-5-tert-butyl-2′-ethyloxalic acid bisanilide, and 2-ethoxy-3′-. Examples include dodecyl oxalic acid bisanilide.

  Examples of the cyanoacrylate compound include ethyl-2-cyano-3,3'-diphenyl acrylate, 2-ethylhexyl-cyano-3,3'-diphenyl acrylate, and the like.

  Examples of hindered amine compounds include 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-2,2,6, 6-tetramethylpiperidine, 4- (phenylacetoxy) -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-methoxy-2,2, 6,6-tetramethylpiperidine, 4-octadecyloxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6,6-tetramethylpiperidine, 4-benzyloxy-2,2 , 6,6-tetramethylpiperidine, 4-phenoxy-2,2,6,6-tetramethylpiperidine, 4- (ethylcarba Yloxy) -2,2,6,6-tetramethylpiperidine, 4- (cyclohexylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (phenylcarbamoyloxy) -2,2,6,6 -Tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl) carbonate, bis (2,2,6,6-tetramethyl-4-piperidyl) oxalate, bis (2,2,6 , 6-tetramethyl-4-piperidyl) malonate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethylpi-4-peridyl) adipate, bis (2,2,6,6-tetramethylpi-4-peridyl) terephthalate, 1,2-bis (2,2,6,6-tetramethylpi-4-peridylo) Cis) -ethane, α, α′-bis (2,2,6,6-tetramethyl-4-piperidyloxy) -p-xylene, bis (2,2,6,6-tetramethyl-4-piperidyl) -Tolylene-2,4-dicarbamate, bis (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylene-1,6-dicarbamate, tris (2,2,6,6-tetramethyl -4-piperidyl) -benzene-1,3,5-tricarboxylate, tris (2,2,6,6-tetramethyl-4-piperidyl) -benzene-1,3,4-tricarboxylate, 1- “2- {3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy} -2,2,6,6-tetramethylpiperidine, 1,2,3,4-butanetetracarboxylic acid And 1,2,2, , 6-Pentamethyl-4-piperidinol and β, β, β ′, β′-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] dimethanol And the like.

  The content of the light stabilizer is preferably 0.01 to 3 parts by weight, more preferably 0.03 to 2 parts by weight, per 100 parts by weight of the resin component (component A).

<Crystal Accelerator>
The composition of the present invention may contain a crystallization accelerator. By containing the crystallization accelerator, a molded product having excellent mechanical properties, heat resistance, and moldability can be obtained.
That is, by applying a crystallization accelerator, the moldability and crystallinity of the resin component (component A) composed of polylactic acid and polyolefin are improved, and it is sufficiently crystallized even in normal injection molding to be excellent in heat resistance and moist heat resistance. A molded product can be obtained. In addition, the manufacturing time for manufacturing the molded product can be greatly shortened, and the economic effect is great.

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

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

  Also, organic carboxylic acid amides such as stearic acid amide, ethylenebislauric acid amide, palmitic acid amide, hydroxystearic acid amide, erucic acid amide, trimesic acid tris (tert-butylamide), low density polyethylene, high density polyethylene, polyiso Propylene, polybutene, poly-4-methylpentene, poly-3-methylbutene-1, polyvinylcycloalkane, polyvinyltrialkylsilane, high melting point polylactic acid, sodium salt of ethylene-acrylic acid copolymer, sodium of styrene-maleic anhydride copolymer Examples thereof include salts (so-called ionomers), benzylidene sorbitol and derivatives thereof such as dibenzylidene sorbitol.

Among these, at least one selected from talc and organic carboxylic acid metal salts is preferably used. Only one type of crystallization nucleating agent may be used in the present invention, or two or more types may be used in combination.
The content of the crystallization accelerator is preferably 0.01 to 30 parts by weight, more preferably 0.05 to 20 parts by weight per 100 parts by weight of the resin component (component A).

<Organic filler>
The composition of the present invention can contain an organic filler. By containing the organic filler, a composition excellent in mechanical properties, heat resistance and moldability can be obtained.
Organic fillers such as rice husks, wood chips, okara, waste paper ground materials, clothing ground materials, cotton fibers, hemp fibers, bamboo fibers, wood fibers, kenaf fibers, jute fibers, banana fibers, coconut fibers Plant fibers such as pulp or cellulose fibers processed from these plant fibers and fibrous fibers such as animal fibers such as silk, wool, angora, cashmere and camel, synthetic fibers such as polyester fibers, nylon fibers and acrylic fibers , Paper powder, wood powder, cellulose powder, rice husk powder, fruit husk powder, chitin powder, chitosan powder, protein, starch and the like. From the viewpoint of moldability, powdery materials such as paper powder, wood powder, bamboo powder, cellulose powder, kenaf powder, rice husk powder, fruit husk powder, chitin powder, chitosan powder, protein powder, and starch are preferred. Powder, bamboo powder, cellulose powder and kenaf powder are preferred. Paper powder and wood powder are more preferable. Paper dust is particularly preferable.

  These organic fillers may be those directly collected from natural products, but may also be those obtained by recycling waste materials such as waste paper, waste wood and old clothes. The wood is preferably a softwood material such as pine, cedar, oak or fir, or a hardwood material such as beech, shii or eucalyptus.

  Paper powder is an adhesive from the viewpoint of moldability, especially emulsion-based adhesives such as vinyl acetate resin-based emulsions and acrylic resin-based emulsions when processing paper, polyvinyl alcohol-based adhesives, polyamide-based adhesives, etc. Preferred examples include those containing a hot melt adhesive.

  In the present invention, the content of the organic filler is preferably 1 to 300 parts by weight, more preferably 5 to 200 parts by weight, and still more preferably 100 parts by weight of the resin component (component A) from the viewpoint of moldability and heat resistance Is 10 to 150 parts by weight, particularly preferably 15 to 100 parts by weight.

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

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

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

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

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

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

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

  Examples of the modified silicone include polyether-modified silicone, higher fatty acid alkoxy-modified silicone, higher fatty acid-containing silicone, higher fatty acid ester-modified silicone, methacryl-modified silicone, and fluorine-modified silicone.

  Of these, fatty acid, fatty acid metal salt, oxy fatty acid, fatty acid ester, fatty acid partial saponified ester, paraffin, low molecular weight polyolefin, fatty acid amide, and alkylene bis fatty acid amide are preferred, and fatty acid partial saponified ester and alkylene bis fatty acid amide are more preferred. Of these, montanic acid ester, montanic acid partially saponified ester, polyethylene wax, acid value polyethylene wax, sorbitan fatty acid ester, erucic acid amide, and ethylene bisstearic acid amide are preferable, and particularly, montanic acid partially saponified ester and ethylene bisstearic acid amide are preferable. .

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

<Antistatic agent>
The composition of the present invention may contain an antistatic agent. Examples of the antistatic agent include quaternary ammonium salt compounds such as (β-lauramidopropionyl) trimethylammonium sulfate and sodium dodecylbenzenesulfonate, sulfonate compounds, and alkyl phosphate compounds.
One type of antistatic agent may be used, or two or more types may be used in combination. The content of the antistatic agent is preferably 0.05 to 5 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the resin component (component A).

<Plasticizer>
The composition of the present invention may contain a plasticizer. Examples of the plasticizer include polyester plasticizers, glycerin plasticizers, polycarboxylic acid ester plasticizers, phosphate ester plasticizers, polyalkylene glycol plasticizers, and epoxy plasticizers.

  As a polyester plasticizer, acid components such as adipic acid, sebacic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid and ethylene glycol, 1,3-propanediol, propylene glycol, 1,3-butanediol, Examples thereof include polyesters composed of diol components such as 1,4-butanediol, 1,6-hexanediol and diethylene glycol, and polyesters composed of hydroxycarboxylic acid such as polycaprolactone. These polyesters may be end-capped with a monofunctional carboxylic acid or a monofunctional alcohol.

  Examples of the glycerol plasticizer include glycerol monostearate, glycerol distearate, glycerol monoacetomonolaurate, glycerol monoacetomonostearate, glycerol diacetomonooleate, and glycerol monoacetomonomontanate.

  Polyvalent carboxylic acid plasticizers include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, trimellitic acid tributyl, trimellitic acid trioctyl, Trimellitic acid esters such as trihexyl meritate, isodecyl adipate, adipic acid esters such as adipate-n-decyl-n-octyl, citrate esters such as tributyl acetylcitrate, and bis (2-ethylhexyl) azelate Examples include sebacic acid esters such as azelaic acid ester, dibutyl sebacate, and bis (2-ethylhexyl) sebacate.

  Examples of the phosphate ester plasticizer include tributyl phosphate, tris phosphate (2-ethylhexyl), trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, diphenyl-2-ethylhexyl phosphate, and the like.

  As polyalkylene glycol plasticizers, polyethylene glycol, polytrimethylene glycol, polypropylene glycol, polytetramethylene glycol, poly (ethylene oxide.propylene oxide) block and / or random copolymer, ethylene oxide addition polymer of bisphenols, bisphenols Examples thereof include polyalkylene glycols such as tetrahydrofuran addition polymers, or end-capping compounds such as terminal epoxy-modified compounds, terminal ester-modified compounds, and terminal ether-modified compounds.

  Examples of the epoxy plasticizer include an epoxy triglyceride composed of alkyl epoxy stearate and soybean oil, and an epoxy resin using bisphenol A and epichlorohydrin as raw materials.

  Specific examples of other plasticizers include benzoic acid esters of aliphatic polyols such as neopentyl glycol dibenzoate, diethylene glycol dibenzoate, triethylene glycol-bis (2-ethylbutyrate), and fatty acids such as stearamide. Examples thereof include fatty acid esters such as amide and butyl oleate, oxyacid esters such as methyl acetylricinoleate and butyl acetylricinoleate, pentaerythritol, various sorbitols, polyacrylic acid esters, silicone oils, and paraffins.

  As the plasticizer, at least one selected from polyester-type plasticizers and polyalkylene-type plasticizers can be preferably used, and only one type may be used, or two or more types may be used in combination.

  The content of the plasticizer is preferably 0.01 to 30 parts by weight, more preferably 0.05 to 20 parts by weight, still more preferably 0.1 to 10 parts by weight per 100 parts by weight of the resin component (component A). is there. In the present invention, each of the crystallization nucleating agent and the plasticizer may be used alone, or more preferably used in combination.

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

<About the manufacturing method of a resin composition>
i) Preparation of Coexisting Composition In the present invention, poly-L lactic acid resin (A-α-1 component) and poly-D lactic acid resin (A-α-2 component) as polylactic acid (A-α component) Is used, prior to melt mixing with other additive components, the phosphoric acid ester metal salt represented by formula (3) and / or formula (4), poly-L lactic acid resin (A-α-1 component) and It is preferable that a poly-D lactic acid resin (A-α-2 component) coexists in advance. As a method of coexistence, a method in which poly-L lactic acid resin (A-α-1 component) and poly-D lactic acid resin (A-α-2 component) are mixed as uniformly as possible is when they are heat-treated. This is preferable because a stereocomplex crystal can be efficiently generated. The coexisting composition can be prepared by any method as long as they are uniformly mixed when heat-treated. The method is carried out in the presence of a solvent, or the method is carried out in the absence of a solvent. Etc. are exemplified.

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

  In the case of obtaining such a coexisting composition by reprecipitation in the presence of a solvent, first, a poly-L lactic acid resin (A-α-1 component) and a poly-D lactic acid resin (A-α-2 component) are used. A coexisting composition with) is prepared by reprecipitation. Here, the A-α-1 component and the A-α-2 component are preferably prepared by separately preparing a solution dissolved in a solvent and mixing them, or by dissolving both in a solvent together. . Here, the weight ratio of the poly-L lactic acid resin (A-α-1 component) to the poly-D lactic acid resin (A-α-2 component) (A-α-1 component / A-α-2 component). Can be prepared so as to be in the range of 10/90 to 90/10, and stereocomplex crystals of polylactic acid (A-α-1 component, A-α-2 component) in the resin composition of the present invention. It is preferable for efficient production. The weight ratio of the A-α-1 component to the A-α-2 component is more preferably 25/75 to 75/25, and particularly preferably 40/60 to 60/40. The solvent is not particularly limited as long as polylactic acid (A-α-1 component, A-α-2 component) can be dissolved. For example, chloroform, methylene chloride, dichloroethane, tetrachloroethane, phenol, Preferred are tetrahydrofuran, N-methylpyrrolidone, N, N-dimethylformamide, butyrolactone, trioxane, hexafluoroisopropanol, or a mixture of two or more.

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

  Next, polylactic acid (A-α-1 component, A-α-2 component) and a phosphate ester metal represented by formula (3) or formula (4) are removed by a method of removing the solvent from the presence of the solvent. When the salt coexisting composition is prepared at a time, the A-α-1 component and the A-α-2 component, and the phosphate metal salt represented by the formula (3) or the formula (4) are separately prepared. Prepare and mix a dispersion dissolved or dispersed in a solvent, or prepare and mix a dispersion in which all components are dissolved or dispersed together in a solvent, and then evaporate the solvent by heating. Can be done by. The solvent is not particularly limited as long as it dissolves polylactic acid (A-α-1 component, A-α-2 component) and the phosphate metal salt represented by formula (3) or formula (4). Although not intended, for example, chloroform, methylene chloride, dichloroethane, tetrachloroethane, phenol, tetrahydrofuran, N-methylpyrrolidone, N, N-dimethylformamide, butyrolactone, trioxane, hexafluoroisopropanol, etc., alone or in combination Those are 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 (A-α-1 component, A-α-2 component) and the phosphoric acid ester metal salt represented by formula (3) or formula (4) is possible even in the absence of a solvent. It can be carried out. That is, after mixing a predetermined amount of A-α-1 component and A-α-2 component, which have been powdered or chipped in advance, and a phosphoric acid ester metal salt represented by formula (3) or formula (4) A method of melting and mixing, or a method of melting any one of the A-α-1 component and the A-α-2 component and then adding and mixing the remaining components can be employed. Here, the size of the powder or chip is not particularly limited as long as the powder or chip of each polylactic acid unit (A-α-1 component, A-α-2 component) is uniformly mixed. However, it is preferably 3 mm or less, and more preferably 1 to 0.25 mm. When melting and mixing, a stereocomplex crystal is formed regardless of the size. However, when the powder or chip is simply melted after being uniformly mixed, if the diameter of the powder or chip becomes 3 mm or more, mixing is performed. Is not preferable, and homopolylactic acid crystals are likely to precipitate. In addition, as a mixing device used to uniformly mix the above powder or chips, in the case of mixing by melting, in addition to a reactor with a batch type stirring blade, a continuous reactor, a biaxial or uniaxial In the case of mixing with an extruder or powder, a tumbler type powder mixer, a continuous powder mixer, various milling devices, or the like can be suitably used.

  Furthermore, when preparing such a coexisting composition, polyolefin resin (A-β component), cyclic carbodiimide (B component), antioxidant (C component), terminal blocker (D component), hydrotalcite (E component) ), Impact modifier (F component), flame retardant (G component), inorganic filler (H component), flame retardant aid (I component) and other additives, inorganic filler breakage inhibitor, lubricant UV absorbers, light stabilizers, release agents, flow modifiers, colorants, light diffusing agents, fluorescent whitening agents, phosphorescent pigments, fluorescent dyes, antistatic agents, antibacterial agents, crystal nucleating agents, plasticizers, etc. Various additives can be allowed to coexist.

  In particular, adding a cyclic carbodiimide (B component) or a terminal blocking agent (D component) at the stage of preparing the coexisting composition means that the mixing of the terminal blocking agent and polylactic acid (A-α component) is more uniform. Thus, the acidic terminal of polylactic acid is more efficiently blocked, which is preferable in improving the hydrolysis resistance of the obtained final resin composition.

ii) Heat treatment of coexisting composition In the present invention, as polylactic acid (A-α component), a mixture of poly-L lactic acid resin (A-α-1 component) and poly-D lactic acid resin (A-α-2 component) In the case of using a polyphosphate (A-α-1 component, A-α-2 component) and a phosphate ester metal represented by formula (3) or formula (4) before being melt-mixed with other additive components It is preferable to heat-treat the salt coexisting composition. Such heat treatment refers to holding the composition in a temperature range of 240 to 300 ° C. for a certain period of time. The temperature of the heat treatment is preferably 250 to 300 ° C, more preferably 260 to 290 ° C. If it exceeds 300 ° C., it is difficult to suppress the decomposition reaction, which is not preferable, and if it is less than 240 ° C., uniform mixing by heat treatment does not proceed, and stereocomplex crystals are not easily generated efficiently. The heat treatment time is not particularly limited, but is 0.2 to 60 minutes, preferably 1 to 20 minutes. As an atmosphere during the heat treatment, either an inert atmosphere at normal pressure or a reduced pressure can be applied. As the apparatus and method used for the heat treatment, any apparatus and method that can be heated while adjusting the atmosphere can be used. For example, a batch type reactor, a continuous type reactor, a biaxial or uniaxial type can be used. It is also possible to adopt a method of processing while forming using an extruder or the like, or a press machine or a flow tube type extruder. Here, the preparation of the coexisting composition of polylactic acid (A-α-1 component, A-α-2 component) and the phosphoric acid ester metal salt represented by formula (3) or formula (4) was carried out using a non-solvent. In the case of carrying out by the method of melt mixing in the presence, heat treatment of the coexisting composition can be achieved simultaneously with the preparation of the coexisting composition.

iii) Preparation of resin composition The resin composition of the present invention comprises polylactic acid (A-α component) (including the heat-treated coexisting composition), polyolefin resin (A-β component), and cyclic carbodiimide (B component). , Antioxidants (component C), and end-capping agents (component D), hydrotalcite (component E), impact modifiers (component F), flame retardant (component G), and inorganic fillers as necessary. (H component), flame retardant aid (I component) and other additive components are mixed. (However, the components contained in the coexisting composition are excluded.)
Other additive components include inorganic filler breakage inhibitors, lubricants, UV absorbers, light stabilizers, mold release agents, flow modifiers, colorants, light diffusing agents, fluorescent whitening agents, phosphorescent pigments, fluorescent dyes And optional additive components such as antistatic agents, antibacterial agents, crystal nucleating agents, and plasticizers.

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

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

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 (scPLA)]
[Production Example 1-3]
100 parts by weight of a polylactic acid meter comprising 50 parts by weight of PLLA and PDLA obtained in Production Examples 1-1 and 1-2, and phosphoric acid-2,2′-methylenebis (4,6-di-tert-butylphenyl) Sodium (ADK STAB NA-11: manufactured by ADEKA Co., Ltd.) 0.1 parts by weight was mixed with a blender, dried at 110 ° C. for 5 hours, and vented twin screw extruder with a diameter of 30 mmφ [TEX30XSST manufactured by Nippon Steel Works, Ltd. The mixture was melt-extruded and pelletized at a cylinder temperature of 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 polylactic acid 1. The resulting stereocomplex polylactic acid has 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 stereocomplex crystallinity calculated using the formula (1) was 100%.

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

2. Production of cyclic carbodiimide Cyclic carbodiimide was produced by the method shown in the following production examples. Moreover, each value in a manufacture example was calculated | required with the following method.
(1) Identification of cyclic carbodiimide structure by NMR Identification of the synthesized cyclic carbodiimide compound by NMR was confirmed by ¹ H-NMR and ¹³ C-NMR using JNR-EX270 manufactured by JEOL Ltd. In addition, deuterated chloroform was used as a solvent.
(2) Identification of carbodiimide skeleton of the cyclic carbodiimide compound identified synthesis by IR carbodiimide skeleton of the cyclic carbodiimide uses Nicolet Co. Magna-750, characteristic 2100～2200Cm ^-1 in FT-IR Accordingly carbodiimide This was done by confirming the absorption peak of.

In the examples of the present invention, the following materials were used.
[Component B-1: Production of cyclic carbodiimide]
[Production Example 2]
o- nitrophenol (0.11 mol) and pentaerythrityl tetra bromide (0.025 mol), potassium carbonate (0.33mol), _N, N ₂ N- dimethylformamide 200ml in reactor installed with a stirrer and a heating device After charging in an atmosphere and reacting at 130 ° C. for 12 hours, DMF was removed under reduced pressure, and the resulting solid was dissolved in 200 ml of dichloromethane and separated three times with 100 ml of water. The organic layer was dehydrated with 5 g of sodium sulfate, and dichloromethane was removed under reduced pressure to obtain an intermediate product D (nitro form).

  Next, intermediate product D (0.1 mol), 5% palladium carbon (Pd / C) (2 g), and 400 ml of ethanol / dichloromethane (70/30) were charged into a reactor equipped with a stirrer, and 5 hydrogen substitution was performed. The reaction was performed in a state where hydrogen was constantly supplied at 25 ° C., and the reaction was terminated when there was no decrease in hydrogen. When Pd / C was recovered and the mixed solvent was removed, an intermediate product E (amine body) was obtained.

Next, triphenylphosphine dibromide (0.11 mol) and 150 ml of 1,2-dichloroethane were charged and stirred in a reactor equipped with a stirrer, a heating device, and a dropping funnel in an N ₂ atmosphere. A solution prepared by dissolving the intermediate product E (0.025 mol) and triethylamine (0.25 mol) in 50 ml of 1,2-dichloroethane was gradually added dropwise thereto at 25 ° C. After completion of dropping, the reaction is carried out at 70 ° C. for 5 hours. Thereafter, the reaction solution was filtered, and the filtrate was separated 5 times with 100 ml of water. The organic layer was dehydrated with 5 g of sodium sulfate, and 1,2-dichloroethane was removed under reduced pressure to obtain an intermediate product F (triphenylphosphine compound).

Next, in a reactor equipped with a stirrer and a dropping funnel, di-tert-butyl dicarbonate (0.11 mol), N, N-dimethyl-4-aminopyridine (0.055 mol), dichloromethane under N ₂ atmosphere. 150 ml is charged and stirred. Thereto, 100 ml of dichloromethane in which the intermediate product F (0.025 mol) was dissolved was slowly added dropwise at 25 ° C. After dropping, react for 12 hours. Then, the B-1 component was obtained by refine | purifying the solid substance obtained by removing dichloromethane. The structure of the B-1 component was confirmed by NMR and IR.

3. Production and Evaluation of Polylactic Acid Pellets Resin composition pellets of polylactic acid (component A) and additives were produced by the methods shown in the following examples and comparative examples. Moreover, each value in an Example was calculated | required with the following method.
(1) Good or bad working environment Sensory evaluation of whether or not the operator felt an irritating odor derived from isocyanate gas during extrusion / molding work. did.
(2) Qualitative / Quantitative Determination of Isocyanate Gas by GC / MS The resin composition pellets were heated at 230 ° C. for 5 minutes and qualitatively / quantified by pyrolysis GC / MS analysis. In addition, fixed_quantity | quantitative_assay was performed using the analytical curve created with isocyanate. GC / MS used was GC / MS Jms Q1000GC K9 manufactured by JEOL Ltd.
(3) Deflection temperature under load Using an injection molding machine (manufactured by Toshiba Machine Co., Ltd .: IS-150EN), the cylinder temperature is 230 ° C., the mold temperature is 120 ° C., the molding cycle is 70 seconds, and the thickness is 4 mm. A test piece conforming to the ISO standard was molded and allowed to stand for 24 hours in an environment of a temperature of 23 ° C. and a relative humidity of 50%, and then measured according to ISO 75-1 and 2 at a load of 0.45 MPa.
(4) Tensile fracture strain Using a polylactic acid resin composition with an injection molding machine (Toshiba Machine Co., Ltd .: IS-150EN) at a cylinder temperature of 230 ° C., a mold temperature of 120 ° C., and a molding cycle of 70 seconds. Then, a molded piece for ISO measurement having a thickness of 4 mm was prepared. Based on ISO527-1 and ISO527-2, a tensile test was performed at a tensile speed of 5 mm / min, and the amount of strain when the test piece broke was measured.
(5) Impact value with notch Using composition of injection molding machine (Toshiba Machine Co., Ltd .: IS-150EN), cylinder temperature 230 ° C, mold temperature 120 ° C, molding cycle 70 seconds, thickness 4mm A test piece conforming to the ISO standard was molded and allowed to stand for 24 hours in an environment of a temperature of 23 ° C. and a relative humidity of 50%, and then an impact value with a notch was measured according to the ISO standard.
(6) Hydrolysis resistance Using a polylactic acid resin composition with an injection molding machine (Toshiba Machine Co., Ltd .: IS-150EN), the cylinder temperature was 230 ° C, the mold temperature was 120 ° C, and the molding cycle was 70 seconds. Thus, a molded piece for ISO measurement having a thickness of 4 mm was prepared. Next, this molded piece was subjected to a wet heat treatment at 80 ° C. × 95% RH for 200 hours. 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.
As other raw materials, the following were used.
(7) 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-α component, A-α-1 to A-α-3 described above were used. As other raw materials, the following were used.

<A-β component>
A-beta: Mitsui Chemicals Co., Ltd. NOVATEC FA3DA, MVR [240 ℃, 2.16kg ] = 12cm 3/10 minutes [Polypropylene Resin]

<B 'component>
B′-1: Carbodilite LA-1 manufactured by Nisshinbo Co., Ltd. [Aliphatic polycarbodiimide]
B′-2: stabaxol-P [aromatic polycarbodiimide] manufactured by Rhein Chemie Japan

<C component>
C-1: Irganox 1076 [n-octadecyl-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] manufactured by Ciba Specialty Chemicals Co., Ltd.
C-2: Pade-24G manufactured by ADEKA Corporation [Bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite]
C-3: Sandstub P-EPQ [tetrakis (2,4-di-tert-butylphenyl) [1,1-biphenyl] -4,4′-diylbisphosphonite] manufactured by Clariant Japan Co., Ltd.
C-4: Adeka Co., Ltd. Adekastab AO-412S [3-laurylthiopropionate]

<D component>
D-1: ASF-4368CS manufactured by BASF Japan Ltd. [Epoxy group-containing acrylic-styrene copolymer]
D-2: BOX-210 [2,2- (1,3-phenylene) bis-2-oxazoline] manufactured by Takemoto Oil & Fat Co., Ltd.

<E component>
E-1: DHT-4A-2 [calcined hydrotalcite] manufactured by Kyowa Chemical Industry Co., Ltd.

<F component>
F-1: Mitsubishi Rayon Co., Ltd. Metablen S-2001 [Silicon Core Shell Rubber]
F-2: Rohm and Haas Co., Ltd. Paraloid BPM500 [Acrylic core shell rubber]
F-3: Nippon A & L Co., Ltd. AT-05 [Acrylonitrile-butadiene-styrene copolymer]
F-4: Bondfast 7M manufactured by Sumitomo Chemical Co., Ltd. [Polyethine-glycidyl methacrylate copolymer]
F-5: TPAE-32 [polyether ester amide elastomer] manufactured by Fuji Chemical Industry Co., Ltd.

<G component>
G-1-1: PX-200 manufactured by Daihachi Chemical Industry Co., Ltd. [resorcinol bis (G 2,6-xylyl phosphate)]
G-1-2: Clariant Japan Co., Ltd. Exolit OP1240 [Aluminum diethylphosphinate]
G-1-3: Taihei Chemical Industry Co., Ltd. APA-100 [Aluminum phosphite]
G-2-1: MELAPUR200 [melamine polyphosphate] manufactured by Ciba Specialty Chemicals Co., Ltd.
G-2-2: MC610 manufactured by Nissan Chemical Co., Ltd. [melamine isocyanurate]
G-3: EP-1 [magnesium hydroxide] manufactured by Kamishima Chemical Co., Ltd.
G-4: PATOX-K [antimony trioxide] manufactured by Nippon Seiko Co., Ltd.
G-5: EP-100 manufactured by Dainippon Ink and Chemicals, Inc. [brominated epoxy resin]

<H component>
H-1: 3PE-937S manufactured by Nittobo Co., Ltd. (chopped strand having an average diameter of 13 μm and a cut length of 3 mm)

<I component>
I-1: SA-120 [polyphenylene ether oligomer] manufactured by SABIC Innovative Plastics Japan
I-2: FA-500C [Tetrafluoroethylene] manufactured by Daikin Industries, Ltd.

<Example 1>
Using the polylactic acid A-α-1 component produced in Production Example 1-1 as polylactic acid, the composition shown in Table 2 was uniformly premixed by dry blending, and then this premixed mixture 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./240° C./230° C./220° C./220° 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 2.

<Example 2>
Except that the polylactic acid A-α-2 component produced in Production Example 1-2 was used as the polylactic acid, it was pelletized by the same method as in Example 1 and evaluated. The results are shown in Table 2.

<Examples 3-34, Comparative Examples 1-7>
Except that the polylactic acid A-α-3 component produced in Production Example 1-3 was used as the polylactic acid, it was pelletized by the same method as in Example 1 and evaluated. In addition, in the composition using I-1, after pre-mixing uniformly the composition except I-1 by dry blend, this pre-mixture is supplied from a 1st supply port, and I-1 component is supplied 2nd. It was supplied from the mouth. Here, the second supply port is a supply port provided in the side screw. The results are shown in Tables 2-5. In addition, the hydrolysis resistance breakdown in the table indicates that the molded product did not retain its original shape after the wet heat treatment, and the tensile test could not be performed.

<Examples 1-15>
Examples 1 to 15 were materials having a good working environment, no generation of isocyanate gas, excellent load deflection temperature, tensile breaking strain, impact value with notch, and hydrolysis resistance.

<Examples 16 and 17>
In Examples 16 and 17 in which D component was further added, hydrolysis resistance was further improved.

<Example 18>
Further, Example 18 to which the E-1 component was added was a material that was further improved in hydrolysis resistance and was excellent in load deflection temperature, notched impact value, and tensile breaking strain.

<Examples 19 to 24>
In Examples 19 to 24, the impact value with notch and the tensile fracture strain were improved by including the F component, the working environment was good, there was no generation of isocyanate gas, and the deflection temperature under load and hydrolysis resistance were also good. It was an excellent material.

<Examples 25-34>
In Examples 25 to 34, the work environment was good, the generation of isocyanate gas was not caused, and the deflection temperature under load, the impact value with notch, the tensile breaking strain, and the hydrolysis resistance were also excellent while imparting flame retardancy. It was a material.

<Comparative Example 1>
Since Comparative Example 1 did not contain the A-β component, the results were inferior in notched impact value, tensile fracture strain, and hydrolysis resistance.

<Comparative example 2>
Since Comparative Example 2 did not contain the B-1 component, the hydrolysis resistance was greatly inferior and the tensile fracture strain was also inferior.

<Comparative Example 3>
In Comparative Example 3, since the B-1 component was too much, not only the hydrolysis resistance was deteriorated, but also the notched impact value and the tensile fracture strain were inferior.

<Comparative Examples 4 and 5>
Since Comparative Examples 4 and 5 contained a carbodiimide B ′ component that was not cyclic, the working environment was deteriorated by an irritating odor, and isocyanate gas was detected from GC / MS measurement. In addition, when non-cyclic carbodiimide was added, the impact value with notch, tensile fracture strain, and hydrolysis resistance were inferior compared with the case where cyclic carbodiimide was added.

<Comparative Examples 6 and 7>
The comparative example 6 which does not contain C component resulted in inferior hydrolysis resistance. Moreover, since the comparative example 7 added too much C component, it resulted in the deterioration of hydrolysis resistance on the contrary.

Claims (14)

100 parts by weight of a resin component (component A) comprising 5 to 95% by weight of polylactic acid (A-α component) and 95 to 5% by weight of a polyolefin resin (A-β component), and 0.001 to 10 parts by weight of carbodiimide groups. A compound having a cyclic structure represented by the following formula (1) in which one is present and the first nitrogen and the second nitrogen are bonded by a bonding group, and the number of atoms forming the cyclic structure is 8 to 50 ( B component), a composition containing 0.001 to 2 parts by weight of at least one antioxidant (C component) selected from the group consisting of phosphite compounds, phosphonite compounds, hindered phenol compounds and thioether compounds. object.

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

(In the formula, Ar ¹ and Ar ² are each independently an aromatic group having 2 to 4 carbon atoms and 5 to 15 carbon atoms. R ¹ and R ² are each independently 1 to 2 carbon atoms having 1 to 4 carbon atoms. 20 aliphatic groups, 2 to 4 valent alicyclic groups having 3 to 20 carbon atoms, and combinations thereof, or these aliphatic groups, alicyclic groups and 2 to 4 valent fragrances having 5 to 15 carbon atoms S is an integer of 0 to 10. k is an integer of 0 to 10. X ¹ and X ² are each independently a divalent to tetravalent C 1-20 aliphatic. A group, a divalent to tetravalent alicyclic group having 3 to 20 carbon atoms, a divalent to tetravalent aromatic group having 5 to 15 carbon atoms, or a combination thereof, and X ³ is a divalent to tetravalent carbon. These are an aliphatic group having 1 to 20 carbon atoms, an alicyclic group having 2 to 4 carbon atoms and 3 to 20 carbon atoms, an aromatic group having 2 to 4 carbon atoms and 5 to 15 carbon atoms, or a combination thereof. However, Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ² and X ³ may contain a hetero atom, and when Q is a divalent linking group, Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ² and X ³ are all divalent groups, and when Q is a trivalent linking group, Ar ¹ , Ar ² , R ¹ , R ² , One of X ¹ , X ² and X ³ is a trivalent group, and when Q is a tetravalent linking group, Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ² and One of X ³ is a tetravalent group, or two are trivalent groups.) The composition according to claim 1, wherein Q in the formula (1) is a divalent linking group represented by the following formula (2-1), (2-2), or (2-3).

(Wherein, _Ar a (a cuff, hereinafter the ^same) to ¹ and _Ar ^{a 2} are each independently a divalent aromatic group having 5 to 15 carbon atoms _.R ^{a 1} and _R ^{a 2} are each independently A divalent aliphatic group having 1 to 20 carbon atoms, a divalent alicyclic group having 3 to 20 carbon atoms, and a combination thereof, or these aliphatic groups, alicyclic groups and divalent carbon numbers. a combination of aromatic groups 5 to 15 .s _a is .k _a is each independently _.X ^{a 1} and _X ^{a 2} is an integer of 0 is an integer of 0, divalent carbon An aliphatic group having 1 to 20 carbon atoms, an alicyclic group having 3 to 20 carbon atoms, a divalent aromatic group having 5 to 15 carbon atoms, or a combination thereof, and X _a ³ is divalent. An aliphatic group having 1 to 20 carbon atoms, a divalent alicyclic group having 3 to 20 carbon atoms, a divalent aromatic group having 5 to 15 carbon atoms, or a combination thereof. Provided that Ar _a ¹ , Ar _a ² , R _a ¹ , R _a ² , X _a ¹ , X _a ² and X _a ³ may contain a hetero atom.) The composition according to claim 1, wherein the component B which is a compound containing a cyclic structure is a compound represented by the following formula (3).

(Wherein Q _b (b is a subscript, the same applies hereinafter) is a trivalent linking group represented by the following formula (3-1), (3-2) or (3-3), and Y is cyclic. A carrier carrying a structure, which is a single bond, double bond, atom, atomic group or polymer.)

(In the formula, Ar _b ¹ , Ar _b ² , R _b ¹ , R _b ² , X _b ¹ , X _b ² , X _b ³ , s _b and k _b are respectively represented by the formulas (1-1) to (1- 3) Ar ¹ , Ar ² , R ¹ , R ² , X ¹ , X ² , X ³ , s _b and k _b are the same, provided that one of them is a trivalent group.) The composition according to claim 1, wherein the component B which is a compound containing a cyclic structure is represented by the following formula (4).

(Wherein Q _c (c is a subscript, the same applies hereinafter) is a tetravalent linking group represented by the following formula (4-1), (4-2) or (4-3), and Z ¹ and Z ² is a carrier carrying a cyclic structure, and each independently represents a single bond, a double bond, an atom, an atomic group or a polymer.)

_{^{(Wherein, Ar c 1, Ar c 2}} , R c 1, R c 2, X c 1, X c 2, X c 3, s c and k _c are each formula (1-1) to (1- 3) ^is the same as ^{Ar 1, Ar 2, R 1} , R 2, X 1, X 2, X 3, s c and k _c. However, if one of these is a tetravalent group And two are trivalent groups.)   Claims containing 0.001 to 10 parts by weight of at least one terminal blocker (D component) selected from the group consisting of (D) an epoxy compound, an oxazoline compound and an oxazine compound with respect to 100 parts by weight of the resin component (component A). Item 5. The composition according to any one of Items 1 to 4.   The composition of any one of Claims 1-5 containing 0.01-0.3 weight part of (E) hydrotalcite (E component) with respect to 100 weight part of resin components (A component).   The composition as described in any one of Claims 1-6 containing 2-100 weight part of (F) impact modifiers (F component) with respect to 100 weight part of resin components (A component).   (G) Phosphorus flame retardant (G-1 component), nitrogen flame retardant (G-2 component), metal hydroxide flame retardant (G-3 component) per 100 parts by weight of resin component (A component) ), A metal oxide flame retardant (G-4 component), and 1 to 100 parts by weight of at least one flame retardant (G component) selected from the group consisting of a bromine-based flame retardant (G-5 component). The composition according to any one of 1 to 7.   Polylactic acid (A-α component) consists of poly-L lactic acid (A-α-1 component) mainly composed of L-lactic acid units and poly-D lactic acid (A-α-2 component) mainly composed of D-lactic acid units. The composition according to any one of claims 1 to 8, wherein the composition is contained and the weight ratio of the A-α-1 component and the A-α-2 component is in the range of 10:90 to 90:10.   The poly-L lactic acid (A-α-1 component) contains 90 mol% or more of L-lactic acid units, and the poly-D lactic acid (A-α-2 component) contains 90 mol% or more of D-lactic acid units. Item 10. The composition according to Item 9. The polylactic acid (A-α component) has a stereocomplex crystallinity represented by the following formula (5) of 80% or more using melting enthalpy in a temperature rising process of differential scanning calorimetry (DSC) measurement. The composition according to 9 or 10.
Stereo complex crystallinity = ΔHms / (ΔHms + ΔHmh) × 100 (5)
[In the formula (5), ΔHmh and ΔHms are the melting enthalpy (ΔHmh) of the melting point of the crystal that appears below 190 ° C. in the temperature rising process of the differential scanning calorimeter (DSC), respectively, and 190 ° C. or more and 250 It is the melting enthalpy (ΔHms) of the crystalline melting point that appears below ° C. ]   The molded article which consists of a composition as described in any one of Claims 1-11.   The molded article according to claim 12, which is molded by injection molding, extrusion molding, thermoforming, blow molding or foam molding.   The molded article according to claim 13, which is an automobile part, an electric / electronic part, an electric equipment exterior part, or an OA exterior part.