JP2008156616A - Resin composition and molded product made therefrom - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition excellent in moldability and heat resistance that is formed by blending a resin composition comprising a polylactic acid resin and a phosphonic acid metal salt having an aromatic ring with at least one selected from among a crystallization promotor, a thermoplastic resin except the polylactic acid resin, a filler, a stabilizer, a mold release agent and a reactive terminal sealer. <P>SOLUTION: This resin composition is obtained by blending the resin composition comprising (A) the polylactic acid resin of 100 pts.wt. and (B) the phosphonic acid metal salt having the aromatic ring of 0.05-30 pts.wt. with at least one selected from among (C) a crystallization promotor, (D) a thermoplastic resin except the polylactic acid resin, (E) a filler, (F) a stabilizer, (G) a mold release agent and (H) a reactive terminal sealer, and moreover, preferably (I) a flame retardant. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a resin composition comprising a polylactic acid resin and a phosphonic acid metal salt having an aromatic ring, further a crystallization accelerator, a thermoplastic resin other than the polylactic acid resin, a filler, a stabilizer, and a release agent. And a resin composition excellent in moldability and heat resistance, and in a preferred embodiment, comprising at least one selected from reactive end-blocking agents, and excellent in impact resistance, durability and releasability, and It relates to a molded product.

  In recent years, biodegradable polymers that are decomposed in the natural environment by the action of microorganisms existing in soil or water have attracted attention from the viewpoint of global environmental conservation, and various biodegradable polymers have been developed. Among these, biodegradable polymers that can be melt-formed include, for example, polyhydroxybutyrate, polycaprolactone, aliphatic dicarboxylic acid components such as succinic acid and adipic acid, and glycol components such as ethylene glycol and butanediol. Aliphatic polyesters and polylactic acid are well known. Among these, polylactic acid resin can be produced at low cost by fermentation using microorganisms, using lactic acid as a raw material for lactic acid as a raw material, and has a high melting point of about 170 ° C. It is expected as a possible biopolymer. However, since polylactic acid resin has a low crystallization rate, there is a limit to use it as a molded product after crystallization. For example, when polylactic acid resin is injection-molded, a long molding cycle time or heat treatment after molding is required. In addition, it has a large problem in practical use such as large deformation during molding and heat treatment.

As a method for improving this problem, a method of adding a crystallization accelerator such as a crystal nucleating agent has been studied. Patent Document 1 describes that a resin composition containing a lactic acid resin and a phosphonic acid metal salt having an aromatic ring is excellent in moldability, heat resistance, etc., but the mold temperature is set to 100 ° C. or higher. There is a need for resin compositions and molded products with excellent moldability and heat resistance that can be produced under milder conditions, and resin compositions and molded products with excellent impact resistance and durability. Was strongly desired.
Japanese Patent Laying-Open No. 2006-89587 (page 2-12)

  It is an object of the present invention to provide a resin composition excellent in moldability and heat resistance, and in a preferred embodiment, excellent in impact resistance, durability or flame retardancy, and a molded product comprising the same.

  The present invention employs the following means in order to solve such problems.

That is, the present invention
(1) To (A) 100 parts by weight of polylactic acid resin, and (B) 0.05 to 30 parts by weight of a phosphonic acid metal salt having an aromatic ring, (C) crystallization Contains at least one selected from accelerator, (D) thermoplastic resin other than polylactic acid resin, (E) filler, (F) stabilizer, (G) mold release agent, and (H) reactive endblocker. A resin composition,
(2) The resin composition according to (1), wherein the (C) crystallization accelerator is a plasticizer,
(3) The thermoplastic resin other than (D) polylactic acid resin is at least one selected from polyacetal resin, polyester resin other than polylactic acid resin, polycarbonate resin, polyamide resin, polypropylene resin, and styrene resin (1 The resin composition according to any one of (2) to (2),
(4) The resin composition according to any one of (1) to (3), wherein the filler (E) is a fibrous inorganic filler and / or a plate-like inorganic filler.
(5) The resin composition according to any one of (1) to (4), wherein the (F) stabilizer is a hindered phenol compound and / or a benzotriazole compound.
(6) The resin composition according to any one of (1) to (5), wherein the (G) release agent is a fatty acid partial saponified ester and / or an alkylene bis fatty acid amide,
(7) The resin composition according to any one of (1) to (6), wherein the (H) reactive end-capping agent is an epoxy compound and / or a carbodiimide compound,
(8) The resin composition according to any one of (1) to (7), further comprising (I) a flame retardant.
(9) A molded article comprising the resin composition according to any one of (1) to (8),
It is.

  According to the present invention, it is possible to provide a resin composition excellent in moldability and heat resistance, and in a preferred embodiment, excellent in impact resistance, durability or flame retardancy, and a molded product comprising the same.

  The (A) polylactic acid resin used in the present invention is a polymer mainly composed of L-lactic acid and / or D-lactic acid, but may contain other copolymerization components other than lactic acid. As a polymerization component, it is less than 50 mol%, and it is preferable that it is 30 mol% or less from a heat resistant point, and it is more preferable that it is 10 mol% or less. Examples of such other copolymer component units include polyvalent carboxylic acids, polyhydric alcohols, hydroxycarboxylic acids, lactones, and the like. Specifically, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid , Azelaic acid, sebacic acid, dodecanedioic acid, fumaric acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, anthracene dicarboxylic acid, 5-sodium sulfoisophthalic acid, 5-tetrabutyl Polycarboxylic acids such as phosphonium sulfoisophthalic acid, ethylene glycol, propylene glycol, butanediol, heptanediol, hexanediol, octanediol, nonanediol, decanediol, 1,4-cyclohexanedimethanol, neopentylglyco Glycerin, pentaerythritol, bisphenol A, polyhydric alcohols such as diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc., glycolic acid, Hydroxycarboxylic acids such as 3-hydroxybutyric acid, 4-hydroxybutyric acid, 4-hydroxyvaleric acid, 6-hydroxycaproic acid, hydroxybenzoic acid, and glycolide, ε-caprolactone glycolide, ε-caprolactone, β-propiolactone, δ Lactones such as -butyrolactone, β- or γ-butyrolactone, pivalolactone, and δ-valerolactone can be used.

  In the present invention, from the viewpoint of heat resistance, it is preferable to use a polylactic acid resin having a high optical purity of the lactic acid component. That is, among the total lactic acid components of the polylactic acid resin, it is preferable that the L isomer is contained at 80% or more, or the D isomer is contained at 80% or more, the L isomer is contained at 90% or more, or the D isomer is 90% or more. More preferably, the L-form is contained at 95% or more, or the D-form is more preferably contained at 95% or more, the L-form is contained at 98% or more, or the D-form is contained at 98% or more. It is particularly preferable that the L-form is contained in 99% or more or the D-form is contained in 99% or more. Moreover, the upper limit of the content of L-form or D-form is usually 100% or less.

  (A) The molecular weight or molecular weight distribution of the polylactic acid resin is not particularly limited as long as it can be substantially molded, but the weight average molecular weight is preferably 10,000 from the viewpoint of heat resistance. More preferably, it is 40,000 or more, more preferably 80,000 or more, particularly preferably 100,000 or more, and most preferably 130,000 or more. The upper limit is not particularly limited, but is preferably 500,000 or less, more preferably 300,000 or less, still more preferably 250,000 or less, and particularly preferably less than 200,000 in terms of fluidity. The weight average molecular weight here is a weight average molecular weight in terms of polymethyl methacrylate (PMMA) measured by gel permeation chromatography (GPC) using hexafluoroisopropanol as a solvent.

  (A) Although it does not specifically limit about melting | fusing point of polylactic acid resin, From a point of a moldability and heat resistance, it is preferable that it is 120 degreeC or more, it is more preferable that it is 150 degreeC or more, and 175 degreeC. More preferably, the above is true. The melting point here is the temperature at the peak top of the endothermic peak measured by a differential scanning calorimeter (DSC).

  (A) As a manufacturing method of a polylactic acid resin, a well-known polymerization method can be used, and the direct polymerization method from lactic acid, the ring-opening polymerization method via a lactide, etc. can be used.

  In addition, as the polylactic acid resin (A) used in the present invention, it is preferable to use a polylactic acid stereocomplex in terms of heat resistance and crystallization characteristics. As a method of forming a polylactic acid stereocomplex, for example, L-form is 90 mol% or more, preferably 95 mol% or more, more preferably 98 mol% or more poly-L-lactic acid and D-form is 90 mol% or more, Preferably, 95 mol% or more, more preferably 98 mol% or more of poly-D-lactic acid is mixed by melt kneading, solution kneading or solid phase kneading. In the method of obtaining a polylactic acid stereocomplex by mixing, the poly-L-lactic acid or poly-D-lactic acid may have a weight average molecular weight of 100,000 or more, but the poly-L-lactic acid or poly-D- It is preferable to apply a combination in which the weight average molecular weight of any one of lactic acid is 100,000 or less, preferably 50,000 or less, and the other weight average molecular weight is more than 100,000, preferably 120,000 or more. Another method is a method in which poly-L-lactic acid and poly-D-lactic acid are made into a block copolymer, that is, stereoblock polylactic acid, and a polylactic acid stereocomplex can be easily formed. In this respect, a method using poly-L-lactic acid and poly-D-lactic acid as a block copolymer is preferable.

  The polylactic acid resin (A) used in the present invention may be used alone, but for example, poly-L-lactic acid or poly-D-lactic acid having a high L-form or D-form content and a polylactic acid stereocomplex that forms a polylactic acid stereocomplex. A block copolymer of -L-lactic acid and poly-D-lactic acid can be used in combination.

  The present invention is characterized in that (A) 0.05 to 30 parts by weight of a phosphonic acid metal salt having an aromatic ring is blended with 100 parts by weight of a polylactic acid resin. From the viewpoint of moldability, heat resistance, impact resistance and durability, the blending amount of the phosphonic acid metal salt having an aromatic ring (B) is preferably 0.1 to 20 parts by weight, and 0.3 to 15 parts by weight. More preferably, 0.5 to 10 parts by weight is further preferable, 1 to 7 parts by weight is particularly preferable, and 1.5 to 4 parts by weight is most preferable.

  In the (B) phosphonic acid metal salt having an aromatic ring of the present invention, the aromatic ring may be any of a benzene ring, naphthalene ring, anthracene ring, thiophene ring, furan ring, pyrrole ring, pyrazole ring, pyridine ring, pyran ring, etc. However, in terms of moldability, heat resistance, and cost, a benzene ring, a naphthalene ring, and an anthracene ring are preferable, and a benzene ring is more preferable. (B) Specific examples of the phosphonic acid component having an aromatic ring that forms a phosphonic acid metal salt having an aromatic ring include phenylphosphonic acid, 2-methylphenylphosphonic acid, 3-methylphenylphosphonic acid, and 4-methylphenylphosphone. Acid, 4-ethylphenylphosphonic acid, 2-isopropylphenylphosphonic acid, 2-methoxyphenylphosphonic acid, 4-methoxyphenylphosphonic acid, 2-nitrophenylphosphonic acid, 3-nitrophenylphosphonic acid, 4-nitrophenylphosphonic acid 2-methyl-4-nitrophenylphosphonic acid, 3-methyl-5-nitrophenylphosphonic acid, 2-methoxy-4-nitrophenylphosphonic acid, 2-chloro-5-methylphenylphosphonic acid, 2-fluorophenylphosphonic Acid, 4-chlorophenylphosphonic acid, 4-bromophenyl Nylphosphonic acid, 2-iodophenylphosphonic acid, 2,3-xylylphosphonic acid, 2,4-xylylphosphonic acid, 2,5-xylylphosphonic acid, and the like. You may use together.

(B) In the phosphonic acid metal salt having an aromatic ring, the metal species is not particularly limited, but in terms of moldability, heat resistance and durability, light metals and heavy metals from Group 1A to Group 6B of the periodic table are Preferably, a divalent metal is more preferable in terms of moldability and heat resistance, and among these, any one of magnesium, calcium, iron, copper, and zinc is more preferable, and zinc is particularly preferable. These may be used alone or in combination of two or more. In particular, one or more of magnesium phenylphosphonate, calcium phenylphosphonate and zinc phenylphosphonate are preferred in terms of moldability and heat resistance. From the viewpoint of durability, zinc phenylphosphonate is more preferable. These may be used alone or in combination of two or more.

  The present invention includes (C) a crystallization accelerator, (D) a thermoplastic resin other than a polylactic acid resin, (E) a filler, (F) a stabilizer, (G) a release agent, and (H) a reactive end-capping. It is characterized by blending at least one selected from agents. By blending these in a resin composition obtained by blending 0.05 to 30 parts by weight of a phosphonic acid metal salt having an aromatic ring with respect to 100 parts by weight of (A) polylactic acid resin, moldability and heat resistance are improved. Resin composition having excellent properties, durability, appearance, mechanical properties and surface hardness, and a molded product comprising the same can be obtained.

  In the present invention, it is preferable to blend (C) a crystallization accelerator in terms of moldability, heat resistance, impact resistance, durability, and appearance. (C) By blending a crystallization accelerator, a resin composition excellent in moldability and heat resistance and a molded article comprising the resin composition can be obtained, and in particular, polylactic acid also in injection molding in a temperature range controllable with water. The resin is sufficiently crystallized, and a molded product having excellent heat resistance can be obtained. In addition, a resin composition having an excellent inhibitory effect against a bleed-out or mold deposit, which is a problem when a plasticizer is used as a crystallization accelerator, and a molded product comprising the same are obtained.

  The crystallization accelerator used in the present invention can be selected from a wide variety of compounds. However, the crystal nucleating agent that promotes the formation of polymer crystal nuclei, and the polymer is softened to facilitate movement and promote crystal growth. A plasticizer can be preferably used.

  The blending amount of the crystallization accelerator used in the present invention is preferably 0.01 to 100 parts by weight and more preferably 0.05 to 20 parts by weight with respect to 100 parts by weight of the (A) polylactic acid resin. More preferred.

  As the crystal nucleating agent used as the crystallization accelerator (C) in the present invention, those generally used as polymer crystal nucleating agents can be used without particular limitation, other than phosphonic acid metal salts having an aromatic ring. Any one or more crystal nucleating agents selected from inorganic crystal nucleating agents and organic crystal nucleating agents can be used, and in terms of moldability and heat resistance, inorganic crystal nucleating agents can be used. Is preferred.

  Specific examples of inorganic crystal nucleating agents include talc, kaolinite, mica, synthetic mica, clay, zeolite, silica, carbon black, zinc oxide, magnesium oxide, calcium oxide, titanium oxide, calcium sulfide, magnesium carbonate, calcium carbonate. In addition, talc, kaolinite, mica and synthetic mica are preferable in that the effect of improving heat resistance is large, and talc is more preferable in terms of moldability. These may be used alone or in combination of two or more. These inorganic crystal nucleating agents are preferably modified with an organic substance in order to enhance dispersibility in the composition.

  The blending amount of the inorganic crystal nucleating agent is preferably 0.01 to 100 parts by weight, more preferably 0.05 to 50 parts by weight, and 0.1 to 30 parts by weight with respect to 100 parts by weight of the (A) polylactic acid resin. Is more preferably 1 to 10 parts by weight, and most preferably 1.5 to 5 parts by weight.

  Specific examples of organic crystal nucleating agents include sodium benzoate, potassium benzoate, lithium benzoate, calcium benzoate, magnesium benzoate, barium benzoate, lithium terephthalate, sodium terephthalate, potassium terephthalate, calcium oxalate , Sodium laurate, potassium laurate, sodium myristate, potassium myristate, calcium myristate, sodium octacosanoate, calcium octacosanoate, sodium stearate, potassium stearate, lithium stearate, calcium stearate, magnesium stearate, stearic acid Barium, sodium montanate, calcium montanate, sodium toluate, sodium salicylate, potassium salicylate, zinc salicylate, aluminum Organic carboxylic acid metal salts such as minium dibenzoate, potassium dibenzoate, lithium dibenzoate, sodium β-naphthalate, sodium cyclohexanecarboxylate, organic sulfonates such as sodium p-toluenesulfonate, sodium sulfoisophthalate, Trimesic acid tris Carboxylic acid amides such as (t-butylamide), hydrazide compounds such as adipic acid dihydrazide, phthalic acid dihydrazide and N, N′-dibenzoyl sebacic acid dihydrazide, sodium salts of ethylene / acrylic acid or methacrylic acid copolymers, styrene / Sodium salt or potassium salt of polymer having carboxyl group such as sodium salt of maleic anhydride copolymer (so-called ionomer), benzylidene sorbitol and its Derivatives, phosphorus compound metal salts such as sodium-2,2′-methylenebis (4,6-di-t-butylphenyl) phosphate, sodium 2,2-methylbis (4,6-di-t-butylphenyl), etc. Among them, organic carboxylic acid metal salts, carboxylic acid amides, and hydrazide compounds are preferable in that the effect of improving heat resistance is great. These may be used alone or in combination of two or more.

  The content of the organic crystal nucleating agent is preferably 0.01 to 30 parts by weight, more preferably 0.05 to 10 parts by weight, and 0.1 to 5 parts by weight with respect to 100 parts by weight of the (A) polylactic acid resin. Is more preferable, and 1 to 3 parts by weight is particularly preferable.

  In the present invention, a plasticizer is preferably blended as a crystallization accelerator in terms of improving moldability and heat resistance.

  As the plasticizer used as the crystallization accelerator (C) in the present invention, those generally used as polymer plasticizers can be used without particular limitation. For example, polyester plasticizer, glycerin plasticizer, polyvalent Examples thereof include carboxylic acid ester plasticizers, polyalkylene glycol plasticizers, and epoxy plasticizers.

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

  Specific examples of the glycerin plasticizer include glycerin monoacetomonolaurate, glycerin diacetomonolaurate, glycerin monoacetomonostearate, glycerin diacetomonooleate, and glycerin monoacetomonomontanate.

  Specific examples of the polyvalent carboxylic acid plasticizer include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, diheptyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, trimellitic acid, etc. Tributyl, trimellitic acid ester such as trioctyl trimellitic acid, trihexyl trimellitic acid, diisodecyl adipate, n-octyl-n-decyl adipate, methyldiglycolbutyldiglycol adipic acid, benzylmethyldiglycol adipic acid Citrate esters such as adipic acid esters such as benzyl butyl diglycol adipate, triethyl acetylcitrate, tributyl acetylcitrate and ethoxycarbonylmethyldibutyl citrate , Azelaic acid esters such as di-2-ethylhexyl azelate, sebacic acid esters such as dibutyl sebacate and di-2-ethylhexyl sebacate and the like.

  Specific examples of the polyalkylene glycol plasticizer include polyethylene glycol, polypropylene glycol, poly (ethylene oxide / propylene oxide) block and / or random copolymer, polytetramethylene glycol, ethylene oxide addition polymer of bisphenols, bisphenols And polyoxyalkylene glycols such as propylene oxide addition polymers and bisphenol tetrahydrofuran addition polymers, and end-capped compounds such as terminal epoxy-modified compounds, terminal ester-modified compounds, and terminal ether-modified compounds.

  The epoxy plasticizer generally refers to an epoxy triglyceride composed of an alkyl epoxy stearate and soybean oil, but there are also so-called epoxy resins mainly made of bisphenol A and epichlorohydrin. Can be used.

  Specific examples of other plasticizers include benzoate esters of aliphatic polyols such as neopentyl glycol dibenzoate, diethylene glycol dibenzoate, triethylene glycol di-2-ethylbutyrate, and aliphatic carboxylic acid esters such as butyl oleate. And oxy acid esters such as methyl acetyl ricinoleate and butyl acetyl ricinoleate, pentaerythritol, various sorbitols, polyacrylic acid esters, silicone oils and paraffins.

  The plasticizer used in the present invention is at least selected from glycerin plasticizers, polyvalent carboxylic acid plasticizers, and polyalkylene glycol plasticizers, among those exemplified above in terms of moldability and heat resistance. One type is preferred, and a polyalkylene glycol plasticizer is more preferred. The plasticizer used for this invention may be 1 type, and may use 2 or more types together.

  The blending amount of the plasticizer is preferably in the range of 0.01 to 30 parts by weight with respect to 100 parts by weight of the polylactic acid resin (A) in terms of moldability, heat resistance, impact resistance and durability. The range of -20 weight part is more preferable, and the range of 0.5-10 weight part is further more preferable.

  In the present invention, as the crystallization accelerator (C), a crystal nucleating agent and a plasticizer may be used singly, but it is preferable to use both in combination from the viewpoint of moldability and heat resistance.

  In the present invention, it is preferable to further blend (D) a thermoplastic resin other than the polylactic acid resin in terms of moldability, heat resistance, durability, appearance, and surface hardness.

  (D) Examples of the thermoplastic resin other than polylactic acid resin include polyester resin other than polylactic acid such as polyacetal resin, polyethylene terephthalate resin and polybutylene terephthalate resin, polycarbonate resin, polyamide resin, polyethylene resin, polypropylene resin, polymethyl Polyolefin resins such as pentene resins and cyclic olefin resins, styrene resins such as styrene resins and acrylonitrile / styrene (AS) resins, acrylic resins, cellulose resins such as cellulose acetate, polyphenylene oxide resins, polyarylate resins, polysulfones Resin, polyphenylene sulfide resin, polyether ether ketone resin, polyimide resin, polyether imide resin, polyurethane resin, aromatic and fat Group polyketone resin, fluorine resin, thermoplastic starch resin, polyvinyl chloride resin, polyvinylidene chloride resin, chlorinated polyethylene resin, chlorinated polypropylene resin, vinyl ester resin, polyurethane resin, polyethersulfone resin, phenoxy resin and polyvinyl An alcohol resin etc. can be mentioned, 1 type may be sufficient and 2 or more types may be used together. Of these, polyacetal resins, polyester resins other than polylactic acid, polycarbonate resins, polyamide resins, polypropylene resins, and styrene resins are preferable in terms of moldability, heat resistance, mechanical properties, toughness, durability, and appearance. In terms of heat resistance, one or more of polyacetal resin and polypropylene resin is preferable, and styrenic resin is preferable in terms of appearance.

  In the present invention, the blending amount of the thermoplastic resin other than (D) polylactic acid is preferably 1 to 300 parts by weight with respect to 100 parts by weight of (A) polylactic acid resin in that heat resistance and moldability are improved. 30 to 250 parts by weight is more preferred, and 50 to 200 parts by weight is even more preferred.

  When the thermoplastic resin other than (D) polylactic acid in the present invention is a polyacetal resin, the polyacetal resin is a polymer having an oxymethylene unit as a main repeating unit, and a polymerization reaction using formaldehyde or trioxane as a main raw material. Any of the obtained so-called polyacetal homopolymers and so-called polyacetal copolymers mainly composed of oxymethylene units and containing 15% by weight or less of oxyalkylene units having 2 to 8 adjacent carbon atoms in the main chain. In addition, any of copolymers containing other structural units, that is, block copolymers, terpolymers and cross-linked polymers may be used, and these may be used alone or in combination of two or more, but in terms of thermal stability , 2 adjacents in the main chain A polyacetal copolymer containing 2% by weight or less of oxyalkylene units having carbon atoms or a polyacetal copolymer containing 5% by weight or less of oxyalkylene units having 4 adjacent carbon atoms in the main chain is preferred. Polyacetal copolymer containing 1.4 to 0.2% by weight of oxyalkylene units having 2 adjacent carbon atoms or 3 to 0.5% by weight of oxyalkylene units having 4 adjacent carbon atoms in the main chain The polyacetal copolymer contained is more preferred.

  The viscosity of these polyacetal resins is not particularly limited as long as it can be used as a molding material, but the melt index (MI) can be measured by the ASTM D1238 method, and measured at a temperature of 190 ° C. and a load of 2.16 kg. The MI is preferably in the range of 1.0 to 50 g / 10 min, and particularly preferably in the range of 1.5 to 35 g / 10 min.

  Further, as the polyacetal resin, it is preferable to use a resin containing a heat stabilizer or a generated gas scavenger in advance, and 2,2′-methylenebis (4-methyl-6-tert-butylphenol), calcium ricinolate, Cyanoguanazine, hexamethylene bis (3,5-t-butyl-4-hydroxyhydrocyanate), melamine-formaldehyde resin, nylon 6/66, nylon 66/610/6, nylon 612/6, tetrakis [methylene (3 5-di-t-butyl-4-hydroxyhydrocyanate)] methane, 1,6-hexanediol bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], triethylene glycol [3- (3,5-di-tert-butyl-5-methyl-4-hydroxyphen Le) propionate], preferably contains at least one dihydrazide compound such as adipic dihydrazide.

  When polyacetal resin is used, particularly when 40 parts by weight or more is used, there is a possibility of strongly affecting the properties of the composition itself, such as impairing the durability of the composition by promoting the decomposition of the polyacetal resin. It is preferable not to mix formaldehyde having a high content. Considering the formaldehyde contained in the polyacetal resin itself, it is preferable to keep it at most less than 500 ppm, more preferably less than 250 ppm, and particularly preferably less than 100 ppm with respect to the polyacetal resin. In order to achieve such a formaldehyde content, as described above, after the polymerization of the polyacetal homopolymer, the polymer terminal is acetylated, or after the polymerization of the polyacetal copolymer, the unstable terminal is decomposed and removed. It is preferable to use a polyacetal resin subjected to the above. The formaldehyde content in the resin composition is determined by stirring 1 g of powder obtained by pulverizing the resin composition in 100 ml of water at 50 ° C. for 6 hours, extracting formaldehyde, and quantifying it by the acetylacetone method. Can be measured.

  When the other thermoplastic resin (D) in the present invention is a polyacetal resin, the production method of the polyacetal resin is not particularly limited, and can be produced by a known method. As an example of a typical method for producing a polyacetal homopolymer, high-purity formaldehyde is introduced into an organic solvent containing a basic polymerization catalyst such as an organic amine, an organic or inorganic tin compound, or a metal hydroxide. Examples thereof include a method of polymerizing and filtering the polymer, followed by heating in acetic anhydride in the presence of sodium acetate to acetylate the polymer terminal.

  In addition, as an example of a typical method for producing a polyacetal copolymer, a high purity trioxane and a copolymer component such as ethylene oxide and 1,3-dioxolane are introduced into an organic solvent such as cyclohexane, and boron trifluoride diethyl ether is used. After cationic polymerization using a Lewis acid catalyst such as a complex, a method of manufacturing by deactivating the catalyst and stabilizing the end groups, or into a self-cleaning stirrer without using any solvent Examples thereof include a method in which trioxane, a copolymerization component and a catalyst are introduced and bulk polymerization is performed, and then the unstable terminal is further decomposed and removed.

  In the present invention, a resin composition excellent in moldability, heat resistance, mechanical properties, toughness, and surface appearance can be obtained by blending a polyacetal resin and a molded product comprising the same.

  When the thermoplastic resin other than (D) polylactic acid in the present invention is a polyester resin other than polylactic acid, the polyester resin is (i) a dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof, (B) A thermoplastic polyester resin other than a polylactic acid resin, which is a polymer or copolymer obtained by polycondensation of one or more selected from hydroxycarboxylic acid or an ester-forming derivative thereof and (c) lactone.

  Examples of the dicarboxylic acid or ester-forming derivative thereof include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, Aromatic dicarboxylic acids such as 4,4'-diphenyl ether dicarboxylic acid, 5-tetrabutylphosphonium isophthalic acid, 5-sodium sulfoisophthalic acid, oxalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, malon Examples thereof include aliphatic dicarboxylic acids such as acid, glutaric acid and dimer acid, alicyclic dicarboxylic acid units such as 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, and ester-forming derivatives thereof.

  Examples of the diol or ester-forming derivative thereof include aliphatic glycols having 2 to 20 carbon atoms, that is, ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1, Aroma such as 6-hexanediol, decamethylene glycol, cyclohexanedimethanol, cyclohexanediol, dimer diol or the like, or a long chain glycol having a molecular weight of 200 to 100,000, that is, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, etc. Dioxy compounds such as 4,4′-dihydroxybiphenyl, hydroquinone, t-butylhydroquinone, bisphenol A, bisphenol S, bisphenol F, and the like And La ester forming derivatives.

  Examples of the hydroxycarboxylic acid include glycolic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, hydroxybenzoic acid, p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, and ester formation thereof. Sex derivatives and the like. Examples of the lactone include caprolactone, valerolactone, propiolactone, undecalactone, and 1,5-oxepan-2-one.

  Specific examples of these polymers or copolymers include polybutylene terephthalate, polybutylene (terephthalate / isophthalate) (where "/" indicates copolymerization), polypropylene terephthalate, polypropylene (terephthalate / Isophthalate), polyethylene terephthalate, polyethylene (terephthalate / isophthalate), bisphenol A (terephthalate / isophthalate), polybutylene naphthalate, polybutylene (terephthalate / naphthalate), polypropylene naphthalate, polyethylene naphthalate, polycyclohexanedimethylene Terephthalate, polycyclohexanedimethylene (terephthalate / isophthalate), poly (cyclohexanedimethylene / ethylene) terephthalate, poly (ethylene Aromatic polyesters such as rhohexanedimethylene / ethylene) (terephthalate / isophthalate), polybutylene (terephthalate / isophthalate) / bisphenol A, polyethylene (terephthalate / isophthalate) / bisphenol A, polybutylene (terephthalate / succinate), polyethylene (Terephthalate / succinate), polybutylene (terephthalate / adipate), polyethylene (terephthalate / adipate), polyethylene (terephthalate / sulfoisophthalate / adipate), polybutylene (terephthalate / sebatate), polyethylene (terephthalate / sebatate), polybutylene terephthalate / polyethylene Polyether ester copolymer of glycol, polyethylene terephthalate / Polyethylene glycol polyether ester copolymer, polybutylene terephthalate / poly (tetramethylene oxide) glycol block copolymer, polybutylene terephthalate / isophthalate / poly (tetramethylene oxide) glycol block copolymer, polybutylene terephthalate / Poly (propylene oxide / ethylene oxide) glycol block copolymer, polybutylene terephthalate / isophthalate / poly (propylene oxide / ethylene oxide) glycol block copolymer, polybutylene terephthalate / polybutylene adipate block copolymer, polybutylene terephthalate / Poly-ε-caprolactone copolymer such as polyether or aliphatic polyester copolymerized with aromatic polyester Polyethylene oxalate, polybutylene oxalate, polyneopentyl glycol oxalate, polyisosorbide oxalate, polyethylene succinate, polybutylene succinate, polybutylene adipate, polyethylene adipate, polybutylene (succinate / adipate), polyethylene (succinate) / Adipate), polyhydroxyalkanoates such as polyhydroxybutyric acid and copolymers of β-hydroxybutyric acid and β-hydroxyvaleric acid, aliphatic polyesters such as polycaprolactone, aliphatic polyester carbonates such as polybutylene succinate carbonate, p -Copolyester such as oxybenzoic acid / polyethylene terephthalate, p-oxybenzoic acid / 6-oxy-2-naphthoic acid Like liquid crystalline polyester of.

  Among these, polymers obtained by polycondensation of aromatic dicarboxylic acid or its ester-forming derivative and aliphatic diol or its ester-forming derivative as main components are preferred. Specifically, polybutylene terephthalate, polypropylene terephthalate , Polyethylene terephthalate, poly (cyclohexanedimethylene / ethylene) terephthalate, polybutylene naphthalate, polybutylene terephthalate / isophthalate, polyethylene terephthalate / isophthalate, polybutylene terephthalate / polyethylene glycol polyether ester copolymer, polyethylene terephthalate / polyethylene Polyether ester copolymer of glycol, polybutylene terephthalate poly (tetramethylene oxide) glycol polyether Polyester copolymer, Polyethylene terephthalate / poly (tetramethylene oxide) glycol polyether ester copolymer, Polybutylene terephthalate / isophthalate / poly (tetramethylene oxide) glycol polyether ester copolymer, Polybutylene (terephthalate / adipate) ) And polyethylene (terephthalate / adipate). Ratio of aromatic dicarboxylic acid or ester-forming derivative thereof to total dicarboxylic acid in a polymer obtained by polycondensation of aromatic dicarboxylic acid or ester-forming derivative thereof and aliphatic diol or ester-forming derivative thereof as main components Is more preferably 50 mol% or more, and further preferably 60 mol% or more.

  Further, among these, a polymer obtained by polycondensation containing terephthalic acid or its ester-forming derivative and butanediol or its ester-forming derivative as main components is more preferable. Specifically, polybutylene terephthalate, polybutylene. Terephthalate / isophthalate, polybutylene terephthalate-polyethylene glycol polyether ester copolymer, polybutylene terephthalate-poly (tetramethylene oxide) glycol polyether ester copolymer, polybutylene terephthalate / isophthalate / poly (tetramethylene oxide) ) A polyether ester copolymer of glycol and polybutylene (terephthalate / adipate) can be preferably mentioned. The ratio of terephthalic acid or its ester-forming derivative to the total dicarboxylic acid in the polymer obtained by polycondensation of terephthalic acid or its ester-forming derivative and butanediol or its ester-forming derivative as a main component is 50 mol% or more. More preferably, it is more preferably 60 mol% or more.

  Further, preferred examples of the thermoplastic polyester resin used in the present invention include polyester carbonate, polyhydroxyalkanoate, and polybutylene (terephthalate / adipate). Specifically, polybutylene succinate carbonate, polyhydroxyl Preferable examples include butyric acid and a copolymer of β-hydroxybutyric acid and β-hydroxyvaleric acid. These may be used alone or in combination of two or more.

  In the present invention, a resin composition excellent in moldability, heat resistance, mechanical properties, impact resistance, toughness, and surface appearance can be obtained by blending thermoplastic polyester, and a molded product comprising the same.

  When the thermoplastic resin other than (D) polylactic acid in the present invention is a polyamide resin, the polyamide resin is a thermoplastic polymer having an amide bond starting from an amino acid, lactam or diamine and dicarboxylic acid.

  Examples of amino acids include 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, paraaminomethylbenzoic acid, and the like. Examples of lactam include ε-caprolactam and ω-laurolactam.

  Examples of the diamine include tetramethylene diamine, hexamethylene diamine, undecamethylene diamine, dodecamethylene diamine, 2,2,4-trimethylhexamethylene diamine, 2,4,4-trimethylhexamethylene diamine, 5-methylnonamethylene diamine, 2,4-dimethyloctamethylenediamine, metaxylylenediamine, paraxylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 3, 8-bis (aminomethyl) tricyclodecane, bis (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) ) Piperazine, Ami Such as ethyl piperazine, and the like.

  Dicarboxylic acids include adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5- Examples include sodium sulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, and diglycolic acid.

  Preferred examples of the polyamide used in the present invention include polycaproamide (nylon 6), polytetramethylene adipamide (nylon 46), polyhexamethylene adipamide (nylon 66), polyhexamethylene sebacamide (nylon). 610), polyhexamethylene dodecamide (nylon 612), polyundecane methylene adipamide (nylon 116), polyundecanamide (nylon 11), polydodecanamide (nylon 12), polytrimethylhexamethylene terephthalamide, polyhexa Methylene isophthalamide (nylon 6I), polyhexamethylene terephthalate / isophthalamide (nylon 6T / 6I), polybis (4-aminocyclohexyl) methane dodecamide (nylon PACM12), polybis (3-methyl-4) Aminocyclohexyl) methane dodecamide (nylon dimethyl PACM12), polymetaxylylene adipamide (nylon MXD6), polyundecamethylene terephthalamide (nylon 11T), polyundecamethylene hexahydroterephthalamide (nylon 11T (H)) and These copolyamides, mixed polyamides and the like. Among these, nylon 6, nylon 66, nylon 11, nylon 12, nylon 610, nylon 612, nylon 116 and their copolymerized polyamides and mixed polyamides are preferable, and nylon 6, nylon 11, and nylon 12 are particularly preferable.

  In the present invention, the melting point of the polyamide resin to be used is preferably 90 to 240 ° C, more preferably 100 to 230 ° C, from the viewpoint of thermal stability.

  In the present invention, by blending a polyamide resin, a resin composition excellent in moldability, heat resistance, mechanical properties, toughness, and surface appearance and a molded product comprising the same can be obtained.

  In the present invention, when the thermoplastic resin other than (D) polylactic acid is a polyolefin resin, specific examples include polyethylene resin, polypropylene resin, poly-1-butene resin, poly-1-pentene resin, poly-4-methyl. (Ethylene and / or propylene) and (unsaturated carboxylic acids) such as homopolymers such as -1-pentene resin, ethylene / α-olefin copolymers, ethylene / acrylic acid copolymers and ethylene / methyl acrylate copolymers Acid and / or unsaturated carboxylic acid ester) copolymer, (ethylene and / or propylene) and (unsaturated carboxylic acid and / or unsaturated carboxylic acid ester) copolymer at least part of the carboxyl group (E.g., ethylene and / or propylene) ) And carboxylic acid vinyl esters, ethylene / vinyl alcohol copolymers (ethylene and / or propylene) and vinyl alcohol, or 1,4-hexadiene, dicyclo Non-conjugated dienes such as pentadiene, 2,5-norbornadiene, 5-ethylidene norbornene, 5-ethyl-2,5-norbornadiene, 5- (1′-propenyl) -2-norbornene, vinyl ethers such as vinyl methyl ether, and the like Examples thereof include a vinyl compound derivative, a copolymer obtained by copolymerizing one or more monomers such as acrylonitrile and vinyl alcohol.

  In the present invention, when the thermoplastic resin other than (D) polylactic acid is a polypropylene resin, the polypropylene resin is a resin obtained by polymerizing or copolymerizing propylene and a monomer copolymerizable therewith. .

  In the present invention, when the thermoplastic resin other than (D) polylactic acid is a polypropylene resin, it is preferable to use a polypropylene resin with high stereoregularity, and if a polypropylene resin with high isotacticity is used, moldability A resin composition having excellent heat resistance can be obtained. When a high syndiotactic polypropylene resin is used, a resin composition having excellent impact resistance and transparency can be obtained. As stereoregularity, isotacticity or syndiotacticity is preferably 80% or more, more preferably 90% or more, and still more preferably 95% or more. Syndiotacticity here refers to deuterated o-dichlorobenzene as a solvent and is observed as syndiotacticity, heterotacticity, and isotacticity in 13C-NMR measurement at 110 ° C. This is a value that can be calculated by expressing the percentage of the integrated intensity of each peak as a percentage, with the total integrated intensity of the peaks of the straight chain branched methyl groups of 20.2 ppm, 20.8 ppm, and 21.5 ppm as 100%.

  In the present invention, polypropylene resins having different stereoregularities may be used in combination. For example, it is preferable to use two or more types of polypropylene resins having isotacticity as the main structure, because it is easy to obtain a resin composition excellent in fluidity, moldability, and heat resistance, and a high isotacticity polypropylene resin is preferable. It is preferable to use one or more high syndiotactic polypropylene resins because a resin composition excellent in moldability, heat resistance and impact resistance can be easily obtained.

  In the present invention, the production method of the polypropylene resin is not particularly limited, and a known method can be used. For example, radical polymerization, coordination polymerization using Ziegler-Natta catalyst, anionic polymerization, metallocene catalyst are used. Any method such as coordination polymerization may be used. Among them, high isotacticity polypropylene resin is easily obtained by coordination polymerization using Ziegler-Natta catalyst as a catalyst, and high syndiotactic polypropylene resin is obtained by coordination polymerization using metallocene catalyst as a catalyst. It is easy to be done.

  In the present invention, a resin composition excellent in moldability, heat resistance, and toughness and a molded product comprising the same can be obtained by blending a polypropylene resin. From the viewpoint of impact resistance, it is preferable to use a polypropylene resin in combination with at least one of ethylene / methyl acrylate copolymer and ethylene / vinyl acetate copolymer. At least one of the polymer and the ethylene / vinyl acetate copolymer is a copolymer of a monomer containing a reactive group such as maleic anhydride or glycidyl methacrylate in the molecular chain or as a graft chain. Is more preferable.

  In the present invention, when the thermoplastic resin other than (D) polylactic acid is a styrene resin, the styrene resin includes styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, o- (B) aromatic vinyl monomers such as ethyl styrene, p-ethyl styrene, and pt-butyl styrene and monomers copolymerizable therewith are known bulk polymerization, bulk suspension polymerization, solution polymerization, It is a resin obtained by subjecting it to precipitation polymerization or emulsion polymerization.

  The styrene resin does not include (r) a rubbery polymer obtained by graft polymerization of (b) an aromatic vinyl unit or the like. (R) A rubber polymer obtained by graft polymerization of (b) an aromatic vinyl unit or the like is included in the graft polymer described later.

  Specifically, (b) 0 to 99% by weight of unsaturated carboxylic acid alkyl ester unit, (c) 0 to 50% by weight of vinyl cyanide unit, based on 1 to 100% by weight of aromatic vinyl unit. %, And (d) a vinyl copolymer obtained by copolymerizing 0 to 99% by weight of other vinyl units copolymerizable therewith.

  The (a) unsaturated carboxylic acid alkyl ester monomer used for the styrenic resin is not particularly limited, but acrylic acid esters and / or methacrylic acid esters having an alkyl group having 1 to 6 carbon atoms or a substituted alkyl group may be used. Is preferred.

  Specific examples of (a) unsaturated carboxylic acid alkyl ester monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and n-butyl (meth) acrylate. T-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, chloromethyl (meth) acrylate, 2-chloroethyl (meth) acrylate, 2- (meth) acrylic acid 2- Hydroxyethyl, 3-hydroxypropyl (meth) acrylate, 2,3,4,5,6-pentahydroxyhexyl (meth) acrylate and 2,3,4,5-tetrahydroxypentyl (meth) acrylate Among them, methyl methacrylate is most preferably used. These can be used alone or in combination of two or more thereof.

  The (c) vinyl cyanide monomer used in the styrene resin is not particularly limited, and specific examples include acrylonitrile, methacrylonitrile, ethacrylonitrile, and the like. Among them, acrylonitrile is preferably used. These can use 1 type (s) or 2 or more types.

  (D) Other vinyl monomers copolymerizable with these used in the styrene resin include (a) unsaturated carboxylic acid alkyl ester monomers, (b) aromatic vinyl monomers, ( c) No particular limitation as long as it can be copolymerized with a vinyl cyanide monomer, and specific examples include maleimide monomers such as N-methylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide and the like. Acrylic acid, methacrylic acid, maleic acid, maleic acid monoethyl ester, maleic anhydride, vinyl monomers having a carboxyl group such as phthalic acid and itaconic acid, 3-hydroxy-1-propene, 4 -Hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene, 3-hydro Vinyl monomers having hydroxyl groups such as cis-2-methyl-1-propene, cis-5-hydroxy-2-pentene, trans-5-hydroxy-2-pentene, 4,4-dihydroxy-2-butene , Vinyl monomers having an epoxy group such as glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, allyl glycidyl ether, styrene-p-glycidyl ether and p-glycidyl styrene, acrylamide, methacrylamide, N -Methylacrylamide, butoxymethylacrylamide, N-propylmethacrylamide, aminoethyl acrylate, propylaminoethyl acrylate, dimethylaminoethyl methacrylate, ethylaminopropyl methacrylate, phenyl methacrylate Vinyl monomers having amino groups and derivatives thereof such as minoethyl, cyclohexylaminoethyl methacrylate, N-vinyldiethylamine, N-acetylvinylamine, allylamine, methallylamine, N-methylallylamine, p-aminostyrene, 2- Examples thereof include vinyl monomers having an oxazoline group such as isopropenyl-oxazoline, 2-vinyl-oxazoline, 2-acryloyl-oxazoline and 2-styryl-oxazoline, and these may be used alone or in combination of two or more. it can. In terms of excellent impact resistance, heat resistance, surface appearance, and colorability, for example, a styrene resin copolymerized with methyl methacrylate and a styrene resin not copolymerized with methyl methacrylate are used. It is preferable to use together.

  Although there is no restriction | limiting in the characteristic of a styrene resin, The intrinsic viscosity [(eta)] measured at 30 degreeC using the methyl ethyl ketone solvent is 0.20-2.00 dl / g, especially 0.25-1.50 dl /. Those in the range of g are preferable because a resin composition having excellent impact resistance and molding processability can be obtained.

  The molecular weight of the styrene resin is not limited, but the weight average molecular weight measured by gel permeation chromatography (GPC) using a tetrahydrofuran solvent is in the range of 10,000 to 400,000, particularly in the range of 50,000 to 150,000. Is preferable because a resin composition having excellent impact resistance and molding processability can be obtained.

  Moreover, in this invention, it is especially preferable to mix | blend an impact resistance improving agent as thermoplastic resins other than (D) polylactic acid. A resin composition excellent in impact resistance, toughness, moldability and heat resistance by blending an impact resistance improver with a resin composition comprising a polylactic acid resin and a phosphonic acid metal salt having an aromatic ring, and A molded product comprising the same can be obtained.

  The impact resistance improver used in the present invention is not particularly limited as long as it can be used to improve the impact resistance of a thermoplastic resin, and various impact resistance improvers can be used. In the present invention, a graft polymer is preferred as the impact resistance improver. In the graft polymer used in the present invention, a monomer mixture in which a vinyl monomer and a monomer copolymerizable therewith are added in the presence of (r) a rubbery polymer, a known bulk polymerization, It can be obtained by subjecting it to bulk suspension polymerization, solution polymerization, precipitation polymerization or emulsion polymerization. In addition, the graft polymer is a polymer having a structure in which a copolymer containing a vinyl monomer is grafted to (r) a rubbery polymer, and a copolymer containing a vinyl monomer ( and r) those having a structure non-grafted onto the rubbery polymer.

  Specifically, (r) in the presence of 10 to 80% by weight of rubbery polymer, (a) 20 to 90% by weight of unsaturated carboxylic acid alkyl ester monomer, (b) aromatic vinyl unit 0 Vinyl graft copolymer obtained by copolymerizing ˜70 wt%, (c) 0 to 50 wt% of vinyl cyanide units, and (d) 0 to 70 wt% of other vinyl units copolymerizable therewith. Polymers are preferred.

  The (r) rubbery polymer is not particularly limited, and those having a glass transition temperature of 0 ° C. or lower are suitable, and diene rubber, acrylic rubber, ethylene rubber, and the like can be used. Specific examples of these rubber polymers include polybutadiene, styrene / butadiene copolymer, styrene / butadiene block copolymer, acrylonitrile / butadiene copolymer, butyl acrylate / butadiene copolymer, polyisoprene, butadiene / Methyl methacrylate copolymer, butyl acrylate / methyl methacrylate copolymer, butadiene / ethyl acrylate copolymer, ethylene / propylene copolymer, ethylene / propylene / diene copolymer, ethylene / isoprene copolymer And ethylene / methyl acrylate copolymer. Among these rubbery polymers, polybutadiene, styrene / butadiene copolymer, styrene / butadiene block copolymer and acrylonitrile / butadiene copolymer are particularly preferably used from the viewpoint of impact resistance. It can be used in a mixture of two or more.

  In the present invention, the weight average particle size of the (r) rubbery polymer constituting the graft polymer is not particularly limited, but is 0.05 to 1.0 μm, particularly 0.1 to 0.1 μm in terms of impact resistance. A range of 0.5 μm is preferable. By setting the weight average particle diameter of the rubbery polymer in the range of 0.05 μm to 1.0 μm, excellent impact resistance can be exhibited. Further, as the rubbery polymer, one or more kinds can be used, and it is preferable to use two or more kinds of rubbery polymers having different weight average particle diameters in terms of impact resistance and fluidity. For example, a so-called bimodal rubber using a rubber polymer having a small weight average particle diameter and a rubber polymer having a large weight average particle diameter may be used.

  The weight average particle diameter of the (r) rubbery polymer is sodium alginate described in “Rubber Age, Vol. 88, p. 484 to 490, (1960), by E. Schmidt, PH B. Biddison” Method, that is, by using the fact that the polybutadiene particle size to be creamed differs depending on the concentration of sodium alginate, the particle size of 50% cumulative weight fraction is obtained from the weight proportion of cream and the cumulative weight fraction of sodium alginate concentration. Can be measured.

  (R) The gel content of the rubbery polymer is not particularly limited, but is preferably 40 to 99% by weight and more preferably 60 to 95% by weight in terms of impact resistance and heat resistance. 72 to 88% by weight is particularly preferable. Here, the gel content can be measured by a method in which toluene is extracted at room temperature for 24 hours to obtain the insoluble content.

  In the present invention, the (a) unsaturated carboxylic acid alkyl ester monomer used for the graft polymer is not particularly limited, but an acrylic acid ester having an alkyl group having 1 to 6 carbon atoms or a substituted alkyl group and / or Methacrylic acid esters are preferred. Specific examples of (a) unsaturated carboxylic acid alkyl ester monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and n-butyl (meth) acrylate. T-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, chloromethyl (meth) acrylate, 2-chloroethyl (meth) acrylate, 2- (meth) acrylic acid 2- Hydroxyethyl, 3-hydroxypropyl (meth) acrylate, 2,3,4,5,6-pentahydroxyhexyl (meth) acrylate and 2,3,4,5-tetrahydroxypentyl (meth) acrylate Among them, methyl methacrylate is most preferably used. These can be used alone or in combination of two or more thereof.

  In the present invention, (b) the aromatic vinyl monomer used for the graft polymer is not particularly limited, and specific examples include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, o -Ethyl styrene, p-ethyl styrene, pt-butyl styrene and the like can be mentioned, among which styrene and α-methyl styrene are preferably used. These can use 1 type (s) or 2 or more types.

  In the present invention, the (c) vinyl cyanide monomer used for the graft polymer is not particularly limited, and specific examples include acrylonitrile, methacrylonitrile, ethacrylonitrile, etc., among which acrylonitrile is preferred. Used. These can use 1 type (s) or 2 or more types.

  In the present invention, (d) other vinyl monomers copolymerizable with these used in the graft polymer include (a) unsaturated carboxylic acid alkyl ester monomers and (b) aromatic vinyl monomers. There is no particular limitation as long as it can be copolymerized with a monomer and (c) a vinyl cyanide monomer. Specific examples include N-methylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, and the like. Maleimide monomer, acrylic acid, methacrylic acid, maleic acid, maleic acid monoethyl ester, maleic anhydride, phthalic acid, itaconic acid and other vinyl monomers having a carboxyl group or an anhydrous carboxyl group, 3-hydroxy -1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2 Vinyl having a hydroxyl group such as butene, 3-hydroxy-2-methyl-1-propene, cis-5-hydroxy-2-pentene, trans-5-hydroxy-2-pentene, 4,4-dihydroxy-2-butene Monomers, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, allyl glycidyl ether, vinyl monomers having an epoxy group such as styrene-p-glycidyl ether and p-glycidyl styrene, acrylamide, Methacrylamide, N-methylacrylamide, butoxymethylacrylamide, N-propylmethacrylamide, aminoethyl acrylate, propylaminoethyl acrylate, dimethylaminoethyl methacrylate, ethylaminopropyl methacrylate, Vinyl-based monomer having an amino group such as phenylaminoethyl tacrylate, cyclohexylaminoethyl methacrylate, N-vinyldiethylamine, N-acetylvinylamine, allylamine, methallylamine, N-methylallylamine, p-aminostyrene, and derivatives thereof , Vinyl monomers having an oxazoline group such as 2-isopropenyl-oxazoline, 2-vinyl-oxazoline, 2-acryloyl-oxazoline and 2-styryl-oxazoline, etc., and these are one or more Can be used.

  In the present invention, the graft polymer comprises (r) 10 to 80% by weight, more preferably 30 to 70% by weight of a rubbery polymer, and (a) the unsaturated carboxylic acid alkyl ester monomer is 20%. -90 wt%, more preferably 30-70 wt%, (b) 0-70 wt% aromatic vinyl monomer, more preferably 0-50 wt%, (c) vinyl cyanide monomer 0 to 50% by weight, more preferably 0 to 30% by weight, (d) 0 to 70% by weight, more preferably 0 to 50% by weight, of other vinyl monomers copolymerizable with these. It is obtained by doing. Even if the ratio of the rubbery polymer is less than the above range or exceeds the above range, the impact strength and the surface appearance may be deteriorated.

In the present invention, the graft polymer includes (r) a graft copolymer having a structure in which a monomer or a monomer mixture is grafted to a rubbery polymer, and an ungrafted copolymer. Contains. The graft ratio of the graft polymer is not particularly limited, but in order to obtain a resin composition having a good balance of impact resistance and gloss, it is in the range of 10 to 100% by weight, particularly 20 to 80% by weight. preferable. Here, the graft ratio is a value calculated by the following equation.
Graft rate (%) = [<Amount of vinyl copolymer graft-polymerized to rubbery polymer> / <Rubber content of graft copolymer>] × 100

  The characteristics of the ungrafted copolymer are not particularly limited, but the intrinsic viscosity [η] (measured at 30 ° C.) of the methyl ethyl ketone-soluble component is 0.10 to 1.00 dl / g, particularly 0.20 to 0.00. A range of 80 dl / g is a preferable condition for obtaining an excellent impact-resistant resin composition.

  The graft polymer used in the present invention can be obtained by a known polymerization method. For example, it can be obtained by a method of emulsion polymerization by continuously supplying a mixture of a monomer and a chain transfer agent and a solution of a radical generator dissolved in an emulsifier to a polymerization vessel in the presence of a rubbery polymer latex. .

  In the present invention, the average primary particle diameter of the graft polymer is not particularly limited, but is preferably 10 to 1000 nm and more preferably 20 to 700 nm from the viewpoint of excellent impact resistance. More preferably, it is 50-500 nm, Most preferably, it is 100-200 nm. Further, as the graft polymer, one or more kinds can be used, and it is preferable to use two or more kinds of graft polymers having different average primary particle diameters in terms of impact resistance and fluidity. It is preferable to use a graft polymer having a small average primary particle size and a graft polymer having a large average primary particle size in combination. In the present invention, the average primary particle diameter is a number average primary particle diameter obtained by observing an average of 20,000 times using an electron microscope, measuring the primary particle diameter of 100 arbitrary particles, and averaging them. Can be determined by observing the dispersion form of the graft polymer in the resin composition with an electron microscope.

  In the present invention, the graft polymer includes a multilayer structure polymer. The multi-layer structure polymer is composed of an innermost layer (core layer) and one or more layers (shell layer) covering the innermost layer (core layer), and a so-called core-shell type in which adjacent layers are composed of different polymers. It is a polymer having a so-called structure and is also called a core-shell elastomer.

  In the present invention, when the graft polymer is a multilayer structure polymer, the number of layers constituting the multilayer structure polymer is not particularly limited, and may be two or more layers. There may be four or more layers.

  In the present invention, when the graft polymer is a multilayer structure polymer, the multilayer structure polymer is preferably a multilayer structure polymer having at least one rubber layer therein.

  In the present invention, when the graft polymer is a multilayer structure polymer, the type of the rubber layer in the multilayer structure polymer is not particularly limited, and may be composed of a polymer component having rubber elasticity. That's fine. For example, a rubber composed of a polymer obtained by polymerizing an acrylic component, a silicone component, a styrene component, a nitrile component, a conjugated diene component, a urethane component, an ethylene propylene component, or the like can be given. Preferred rubbers include, for example, acrylic components such as ethyl acrylate units and butyl acrylate units, silicone components such as dimethylsiloxane units and phenylmethylsiloxane units, styrene components such as styrene units and α-methylstyrene units, acrylonitrile units, It is a rubber constituted by polymerizing a nitrile component such as a methacrylonitrile unit or a conjugated diene component such as a butanediene unit or an isoprene unit. Further, a rubber composed of a copolymer obtained by combining two or more of these components is also preferable. For example, (1) acrylic components such as ethyl acrylate units and butyl acrylate units, dimethylsiloxane units, and phenylmethylsiloxane Rubber composed of components copolymerized with silicone components such as units, (2) Components copolymerized with acrylic components such as ethyl acrylate units and butyl acrylate units, and styrene components such as styrene units and α-methylstyrene units (3) rubber composed of a component obtained by copolymerizing an acrylic component such as an ethyl acrylate unit or a butyl acrylate unit and a conjugated diene component such as a butanediene unit or an isoprene unit, and (4) ethyl acrylate. Acrylic components such as units and butyl acrylate units and Rubber composed of a styrene component copolymerized with components such as silicone component and styrene units and α- methylstyrene units such as dimethylsiloxane units or phenylmethylsiloxane units and the like. In addition to these components, a rubber obtained by copolymerizing and crosslinking a crosslinkable component such as a divinylbenzene unit, an allyl acrylate unit, or a butylene glycol diacrylate unit is also preferable.

  In the present invention, when the graft polymer is a multilayer structure polymer, the type of layer other than the rubber layer in the multilayer structure polymer is particularly limited as long as it is composed of a polymer component having thermoplasticity. Although it is not a thing, the polymer component whose glass transition temperature is higher than a rubber layer is preferable. Examples of thermoplastic polymers include unsaturated carboxylic acid alkyl ester units, glycidyl group-containing vinyl units, unsaturated dicarboxylic anhydride units, aliphatic vinyl units, aromatic vinyl units, and vinyl cyanide units. Examples include polymers containing at least one unit selected from units, maleimide units, unsaturated dicarboxylic acid units, and other vinyl units. Among them, unsaturated carboxylic acid alkyl ester units, unsaturated A polymer containing at least one unit selected from glycidyl group-containing units or unsaturated dicarboxylic acid anhydride units is preferred, and at least selected from unsaturated glycidyl group-containing units or unsaturated dicarboxylic acid anhydride units. More preferred are polymers containing one or more units.

  The unsaturated carboxylic acid alkyl ester unit is not particularly limited, but (meth) acrylic acid alkyl ester is preferably used. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, (meth) acrylic N-hexyl acid, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, octadecyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, ( Chloromethyl (meth) acrylate, 2-chloroethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2,3,4,5,6 (meth) acrylic acid -Pentahydroxyhexyl, 2,3,4,5-tetrahydroxypentyl (meth) acrylate, amino acid acrylate Examples include ethyl, propylaminoethyl acrylate, dimethylaminoethyl methacrylate, ethylaminopropyl methacrylate, phenylaminoethyl methacrylate, cyclohexylaminoethyl methacrylate, etc., from the viewpoint that the effect of improving impact resistance is great ( Methyl methacrylate is preferably used. These units can be used alone or in combination of two or more.

  The glycidyl group-containing vinyl-based unit is not particularly limited, and examples thereof include glycidyl (meth) acrylate, glycidyl itaconate, diglycidyl itaconate, allyl glycidyl ether, styrene-4-glycidyl ether, and 4-glycidyl styrene. From the viewpoint that the effect of improving impact resistance is great, glycidyl (meth) acrylate is preferably used. These units can be used alone or in combination of two or more.

  Examples of the unsaturated dicarboxylic acid anhydride unit include maleic anhydride, itaconic anhydride, glutaconic anhydride, citraconic anhydride, or aconitic anhydride. From the viewpoint that the effect of improving impact resistance is great, maleic anhydride Acid is preferably used. These units can be used alone or in combination of two or more.

  The aliphatic vinyl unit may be ethylene, propylene or butadiene, and the aromatic vinyl unit may be styrene, α-methylstyrene, 1-vinylnaphthalene, 4-methylstyrene, 4-propylstyrene, 4-cyclohexyl. Styrene, 4-dodecyl styrene, 2-ethyl-4-benzyl styrene, 4- (phenylbutyl) styrene, halogenated styrene, etc., as vinyl cyanide units, acrylonitrile, methacrylonitrile, ethacrylonitrile, etc. maleimide Units include maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-isopropylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N- (p-bromophenyl) maleimide, N- (chlorophenyl) maleimide and other unsaturated dicarboxylic acid units such as maleic acid, maleic acid monoethyl ester, itaconic acid and phthalic acid, and other vinyl units such as acrylamide, methacrylamide, N-methylacrylamide, Butoxymethylacrylamide, N-propylmethacrylamide, N-vinyldiethylamine, N-acetylvinylamine, allylamine, methallylamine, N-methylallylamine, p-aminostyrene, 2-isopropenyl-oxazoline, 2-vinyl-oxazoline, 2 -Acroyl-oxazoline or 2-styryl-oxazoline can be mentioned, and these units can be used alone or in combination of two or more.

  In the present invention, when the graft polymer is a multilayer structure polymer, the type of outermost layer in the multilayer structure polymer is not particularly limited, and is an unsaturated carboxylic acid alkyl ester-based unit, a glycidyl group-containing vinyl-based polymer. Contains units, aliphatic vinyl units, aromatic vinyl units, vinyl cyanide units, maleimide units, unsaturated dicarboxylic acid units, unsaturated dicarboxylic anhydride units, and / or other vinyl units. Among them, a polymer containing an unsaturated carboxylic acid alkyl ester unit, an unsaturated glycidyl group-containing unit and / or an unsaturated dicarboxylic anhydride unit is preferable, and an unsaturated carboxylic acid alkyl ester is more preferable. A polymer containing a system unit is more preferable. The unsaturated carboxylic acid alkyl ester unit is not particularly limited, but (meth) acrylic acid alkyl ester is preferable, and methyl (meth) acrylate is more preferably used.

  In the present invention, when the graft polymer is a multilayer structure polymer, as a preferred example of the multilayer structure polymer, the core layer is a dimethylsiloxane / butyl acrylate polymer, the outermost layer is a methyl methacrylate polymer, and the core layer is Examples thereof include a butanediene / styrene polymer in which the outermost layer is a methyl methacrylate polymer, the core layer is a butyl acrylate polymer, and the outermost layer is a methyl methacrylate polymer. Furthermore, it is more preferable that either one or both of the rubber layer and the outermost layer is a polymer containing glycidyl methacrylate units.

  In the present invention, when the graft polymer is a multilayer structure polymer, the weight ratio of the core to the shell in the multilayer structure polymer is not particularly limited, but the core layer is based on the entire multilayer structure polymer. Is preferably 50 parts by weight or more and 90 parts by weight or less, and more preferably 60 parts by weight or more and 80 parts by weight or less.

  In the present invention, when the graft polymer is a multilayer structure polymer, as the multilayer structure polymer, commercially available products may be used as those satisfying the above-mentioned conditions, and they can be prepared by a known method. .

  Examples of commercially available products include "Metablen" manufactured by Mitsubishi Rayon, "Kane Ace" manufactured by Kaneka, "Paraloid" manufactured by Rohm and Haas, "Staffroid" manufactured by Gantz Kasei, or "Paraface" manufactured by Kuraray. A single compound or two or more compounds can be used.

  In the present invention, the blending amount of the graft polymer is not particularly limited, but is 1 to 100 parts by weight with respect to 100 parts by weight of the polylactic acid resin (A) in terms of heat resistance and impact resistance. Furthermore, it is more preferably 5 to 70 parts by weight, particularly preferably 7 to 50 parts by weight, and most preferably 10 to 30 parts by weight.

  In the present invention, the graft polymer preferably forms a dispersed phase in the resin composition. As the dispersion form of the graft polymer in the resin composition, the effect of improving the impact resistance is greater as the graft polymer (A) is more finely dispersed in the polylactic acid resin.

  In the present invention, the ratio (X / Y) of the number of aggregated particles (X) and the number of non-aggregated particles (Y) of the graft polymer in the resin composition from the viewpoint of excellent heat resistance and impact resistance. Is preferably 0 to 0.5, and more preferably 0 to 0.3. In the present invention, the number of aggregated particles and the number of non-aggregated particles are observed at a magnification of 20,000 using an electron microscope, and the dispersed particles of the graft polymer are in contact with any 100 dispersed particles. Were determined as agglomerated particles. X represents the total number of dispersed particles involved in aggregation, that is, when three dispersed particles are aggregated to form one aggregate, calculation is made as X = 3.

  In the present invention, from the viewpoint of excellent moldability, heat resistance and impact resistance, the distance between the particle walls of the graft polymer in the resin composition is preferably 1-1000 nm, preferably 1-700 nm. More preferably, it is 1 to 500 nm, more preferably 1 to 300 nm. In the present invention, the distance between the particle walls can be determined by light scattering measurement or transmission electron microscope observation, but light scattering measurement is preferred.

  When the thermoplastic resin other than the (D) polylactic acid resin in the present invention is an acrylic resin, the acrylic resin is a polymethyl methacrylate obtained by using methyl methacrylate as a main component as a vinyl monomer. A polymethyl methacrylate copolymer obtained by copolymerizing another vinyl monomer is more preferable. Other vinyl monomers include aromatic vinyl monomers such as α-methylstyrene, o-methylstyrene, p-methylstyrene, o-ethylstyrene, p-ethylstyrene, and pt-butylstyrene. , Vinyl cyanide monomers such as acrylonitrile, methacrylonitrile, ethacrylonitrile, glycidyl itaconate, allyl glycidyl ether, styrene-p-glycidyl ether, p-glycidyl styrene, maleic anhydride, monoethyl maleate, N-substituted maleimides such as itaconic acid, itaconic anhydride, phthalic acid, N-methylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, acrylamide, methacrylamide, N-methylacrylamide, butoxymethylacrylamido N-propylmethacrylamide, acrylic acid, methyl acrylate, ethyl acrylate, aminoethyl acrylate, propylaminoethyl acrylate, methacrylic acid, cyclohexyl methacrylate, dimethylaminoethyl methacrylate, ethylaminopropyl methacrylate, Phenylaminoethyl methacrylate, cyclohexylaminoethyl methacrylate, methyl 2- (hydroxymethyl) acrylate, ethyl 2- (hydroxymethyl) acrylate, butyl 2- (hydroxymethyl) acrylate, N-vinyldiethylamine, N-acetyl Vinylamine, allylamine, methallylamine, N-methylallylamine, p-aminostyrene, 2-isopropenyl-oxazoline, 2-vinyl-oxazoline, 2-acryloyl-oxazoline and And 2-styryl-oxazoline. These vinyl monomers can be used alone or in combination of two or more. In terms of heat resistance, the polymethyl methacrylate copolymer is particularly preferably a copolymer containing a cyclic structural unit such as maleic anhydride, glutaric anhydride, or maleimide ring in the main chain. More preferably, it is used in combination with methacrylate. Such a polymethylmethacrylate copolymer can be produced according to a known method. The other vinyl monomer component unit amount is preferably a copolymer obtained by copolymerization, preferably 30 mol% or less, more preferably 20 mol% or less.

  The acrylic resin used in the present invention preferably has a weight average molecular weight of 50,000 to 450,000, more preferably 70,000 to 200,000, and even more preferably 90,000 to 150,000, in terms of heat resistance and toughness. The weight average molecular weight here is a weight average molecular weight in terms of polymethyl methacrylate (PMMA) measured by GPC using hexafluoroisopropanol as a solvent.

  The acrylic resin used in the present invention is preferably a glass transition temperature of 80 ° C or higher, more preferably 90 ° C or higher, further preferably 100 ° C or higher, particularly preferably 110 ° C or higher, and 120 ° C or higher in terms of heat resistance. Most preferred. Although an upper limit is not specifically limited, 150 degreeC or less is preferable at the point of a moldability. The glass transition temperature here is a value measured according to the method described in JIS K7121, and is a midpoint glass transition temperature when the temperature is raised at 20 ° C./min by DSC measurement.

  As the acrylic resin used in the present invention, at least one of polymethyl methacrylate is preferably 40% or more, more preferably 45% or more, still more preferably 50% or more, from the viewpoint of heat resistance. % Or more is particularly preferable, and in terms of fluidity, 90% or less is preferable, and 80% or less is more preferable. Further, in terms of excellent heat resistance, at least one of polymethyl methacrylate is preferably 45% or less of heterotacticity, more preferably 40% or less, and further preferably 35% or less. 30% or less is particularly preferable. In terms of excellent heat resistance, at least one polymethyl methacrylate is preferably 20% or less isotacticity, more preferably 15% or less, and even more preferably 10% or less. It is particularly preferably 5% or less. As used herein, syndiotacticity, heterotacticity, and isotacticity are 0.9 ppm, 1.0 ppm, and 1.2 ppm straight lines observed in 1H-NMR measurement using deuterated chloroform as a solvent. This is a value that can be calculated by expressing the percentage of the integrated intensity of each peak as a percentage, where the total integrated intensity of the peaks of the chain-branched methyl groups is 100%.

  The acrylic resin used in the present invention preferably has a glass transition temperature of + 100 ° C. and a melt flow rate (MFR) at a load of 37.2 N of 0.1 to 40 g / 10 min. In this point, it is more preferably 1 to 30 g / 10 minutes, further preferably 2 to 20 g / 10 minutes, and particularly preferably 5 to 15 g / 10 minutes. If the MFR is less than 0.1 g / 10 minutes, the moldability tends to be lowered, and if it exceeds 40 g / 10 minutes, the heat resistance improving effect tends to be lowered.

  In the present invention, it is preferable to further blend (E) a filler in terms of improving heat resistance, and it is more preferable to blend a filler other than an inorganic crystal nucleating agent and a fibrous organic filler. preferable.

  In the present invention, as the filler other than the inorganic crystal nucleating agent, fibers, plates, granules, and powders that are usually used for reinforcement of thermoplastic resins can be used. Specifically, glass fiber, asbestos fiber, carbon fiber, graphite fiber, metal fiber, potassium titanate whisker, aluminum borate whisker, magnesium whisker, silicon whisker, wollastonite, sepiolite, asbestos, slag fiber, zonolite , Elastadite, Gypsum fiber, Silica fiber, Silica / Alumina fiber, Zirconia fiber, Boron nitride fiber, Silicon nitride fiber, Boron fiber and other fibrous inorganic fillers, Polyester fiber, Nylon fiber, Acrylic fiber, Regenerated cellulose fiber, Acetate fiber , Kenaf, ramie, cotton, jute, hemp, sisal, flax, linen, silk, Manila hemp, sugar cane, wood pulp, paper scrap, waste paper and wool, etc., fibrous flakes, glass flakes, graphite, metal foil, ceramic bead 'S, sericite, bentonite, dolomite, fine silicic acid, feldspar powder, potassium titanate, shirasu balloon, aluminum silicate, silicon oxide, gypsum, novaculite, include plate-like or particulate filler, such as such as dawsonite and white clay. In view of moldability, heat resistance and durability, fibrous inorganic fillers are preferable, and glass fiber and wollastonite are particularly preferable. In addition, the use of a fibrous organic filler is also preferable, and it is derived from plants, and natural fibers and regenerated fibers are more preferable from the viewpoint of taking advantage of the biodegradability of the polylactic acid resin. Further, in terms of heat resistance and strength, the aspect ratio (average fiber length / average fiber diameter) of the fibrous filler used for blending is preferably 5 or more, more preferably 10 or more, and 20 or more. More preferably it is.

  The filler may be coated or focused with a thermoplastic resin such as an ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin, or may be a coupling agent such as aminosilane or epoxysilane. It may be processed.

  Moreover, in this invention, it is preferable to mix | blend the layered silicate by which the exchangeable cation which exists between layers was exchanged with the organic onium ion as (E) filler. In the present invention, the layered silicate in which the exchangeable cation existing between the layers is exchanged with the organic onium ion means that the exchangeable cation of the layered silicate having the exchangeable cation between the layers is replaced with the organic onium ion. Inclusion compound.

  A layered silicate having an exchangeable cation between layers has a structure in which plate-like materials having a width of 0.05 to 0.5 μm and a thickness of 6 to 15 angstroms are laminated. Has a cation. The cation exchange capacity is 0.2 to 3 meq / g, and preferably the cation exchange capacity is 0.8 to 1.5 meq / g.

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

  Examples of organic onium ions include ammonium ions, phosphonium ions, and sulfonium ions. Of these, ammonium ions and phosphonium ions are preferred, and ammonium ions are particularly preferred. As the ammonium ion, any of primary ammonium, secondary ammonium, tertiary ammonium, and quaternary ammonium may be used.

  Primary ammonium ions include decyl ammonium, dodecyl ammonium, octadecyl ammonium, oleyl ammonium, benzyl ammonium and the like.

  Secondary ammonium ions include methyl dodecyl ammonium and methyl octadecyl ammonium.

  Examples of tertiary ammonium ions include dimethyl dodecyl ammonium and dimethyl octadecyl ammonium.

  As quaternary ammonium ions, benzyltrialkylammonium ions such as benzyltrimethylammonium, benzyltriethylammonium, benzyltributylammonium, benzyldimethyldodecylammonium, benzyldimethyloctadecylammonium, benzalkonium, trimethyloctylammonium, trimethyldodecylammonium, trimethyloctadecylammonium Alkyltrimethylammonium ions such as dimethyldioctylammonium, dimethyldidodecylammonium, dimethyldialkylammonium ions such as dimethyldioctadecylammonium, trialkylmethylammonium ions such as trioctylmethylammonium and tridodecylmethylammonium, benzene Such as benzethonium ion having two thereof.

  In addition to these, aniline, p-phenylenediamine, α-naphthylamine, p-aminodimethylaniline, benzidine, pyridine, piperidine, 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, amino at the terminal Examples also include ammonium ions derived from polyalkylene glycols having a group.

  Among these ammonium ions, preferred compounds include trioctylmethylammonium, benzyldimethyldodecylammonium, benzyldimethyloctadecylammonium, benzalkonium and the like. These ammonium ions are generally available as a mixture, and the above compound names are representative compound names containing a small amount of analogs. These may be used alone or in combination of two or more.

  Further, those having a reactive functional group and those having high affinity are preferable, and ammonium ions derived from 12-aminododecanoic acid, polyalkylene glycol having an amino group at the terminal, and the like are also preferable.

  The layered silicate in which the exchangeable cation existing in the interlayer used in the present invention is exchanged with the organic onium ion is obtained by reacting the layered silicate having the exchangeable cation between the layer and the organic onium ion by a known method. Can be manufactured. Specifically, a method by an ion exchange reaction in a polar solvent such as water, methanol, ethanol, or a method by directly reacting a layered silicate with a liquid or molten ammonium salt may be used.

  In the present invention, the amount of organic onium ions relative to the layered silicate is determined by the cation exchange of the layered silicate in terms of the dispersibility of the layered silicate, the thermal stability during melting, the gas during molding, the suppression of odor generation, etc. Usually, the amount is in the range of 0.4 to 2.0 equivalents, preferably 0.8 to 1.2 equivalents with respect to the capacity.

  In addition to the above organic onium salts, these layered silicates are preferably pretreated with a coupling agent having a reactive functional group to obtain better mechanical strength. Examples of the coupling agent having a reactive functional group include isocyanate compounds, organic silane compounds, organic titanate compounds, organic borane compounds, and epoxy compounds.

  In this invention, the compounding quantity of (E) filler is 0.1-300 weight part with respect to 100 weight part of polylactic acid resin, 0.5-100 weight part is more preferable, 1-50 weight part Is more preferable, 1 to 30 parts by weight is particularly preferable, and 1 to 20 parts by weight is most preferable.

  In this invention, it is preferable to mix | blend (F) stabilizer. As a stabilizer used by this invention, what is normally used for the stabilizer of a thermoplastic resin can be used. Specific examples include antioxidants and light stabilizers. By blending these, a molded product having excellent mechanical properties, moldability, heat resistance and durability can be obtained.

  Examples of the antioxidant used in the present invention include hindered phenol compounds, phosphite compounds, and thioether compounds.

  Examples of hindered phenol compounds include n-octadecyl-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) -propionate, n-octadecyl-3- (3′-methyl- 5′-t-butyl-4′-hydroxyphenyl) -propionate, n-tetradecyl-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) -propionate, 1,6-hexanediol -Bis- [3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionate], 1,4-butanediol-bis- [3- (3,5-di-t-butyl-4 -Hydroxyphenyl) propionate], 2,2′-methylenebis- (4-methyl-t-butylphenol), triethylene glycol-bis- [3- (3-t-butyl-5- Til-4-hydroxyphenyl) propionate], tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, 3,9-bis [2- {3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] 2,4,8,10-tetraoxaspiro (5,5) undecane, N, N′- Bis-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionylhexamethylenediamine, N, N′-tetramethylene-bis-3- (3′-methyl-5′-t -Butyl-4'-hydroxyphenol) propionyldiamine, N, N'-bis- [3- (3,5-di-t-butyl-4-hydroxyphenol) propionyl] hydrazide N-salicyloyl-N′-salicylidenehydrazine, 3- (N-salicyloyl) amino-1,2,4-triazole, N, N′-bis [2- {3- (3,5-di-t -Butyl-4-hydroxyphenyl) propionyloxy} ethyl] oxyamide and the like. Preferably, triethylene glycol-bis- [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] and tetrakis [methylene-3- (3 ′, 5′-di-t-butyl- 4'-hydroxyphenyl) propionate] methane.

  As the phosphite compound, those in which at least one P—O bond is bonded to an aromatic group are preferable. Specific examples include tris (2,4-di-t-butylphenyl) phosphite, tetrakis ( 2,4-di-t-butylphenyl) 4,4′-biphenylenephosphonite, bis (2,4-di-t-butylphenyl) pentaerythritol-di-phosphite, bis (2,6-di-) t-butyl-4-methylphenyl) pentaerythritol-di-phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, 4,4′-butylidene-bis (3-methyl) -6-tert-butylphenyl-di-tridecyl) phosphite, 1,1,3-tris (2-methyl-4-ditridecyl phosphite-5-tert-butyl-phenyl) Nyl) butane, tris (mixed mono and di-nonylphenyl) phosphite, tris (nonylphenyl) phosphite, 4,4′-isopropylidenebis (phenyl-dialkyl phosphite) and the like, and tris (2, 4-di-t-butylphenyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, bis (2,6-di-t-butyl-4-methylphenyl) Pentaerythritol-di-phosphite, tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylenephosphonite and the like can be preferably used.

  Specific examples of the thioether compound include dilauryl thiodipropionate, ditridecyl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, pentaerythritol tetrakis (3-laurylthiopropioate). Nate), pentaerythritol-tetrakis (3-dodecylthiopropionate), pentaerythritol-tetrakis (3-octadecylthiopropionate), pentaerythritol-tetrakis (3-myristylthiopropionate), pentaerythritol-tetrakis ( 3-stearyl thiopropionate) and the like.

  Examples of the light stabilizer used in the present invention include benzophenone compounds, benzotriazole compounds, aromatic benzoate compounds, oxalic acid anilide compounds, cyanoacrylate compounds and hindered amine compounds.

  Specific examples of benzophenone compounds include benzophenone, 2,4-dihydrobenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and 2,2′-dihydroxy. -4,4'-dimethoxybenzophenone, 2,2'-dihydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4-methoxy-5 Sulfobenzophenone, 5-chloro-2-hydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxy-5-sulfobenzophenone, 2-hydroxy-4-methoxy-2′-carboxybenzophenone, 2-hydroxy -4- (2-hydroxy-3-methyl-acrylic Such as carboxymethyl isopropoxycarbonyl benzophenone and the like.

  Specific examples of the benzotriazole-based compound include 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-tert-amyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butyl-5′-methyl-phenyl) benzotriazole, 2 -(3,5-di-tert-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-tert-isoamyl-2-hydroxyphenyl) benzotriazole, (2-hydroxy- 5-tert-butylphenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis (α, α- Methylbenzyl) phenyl] benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis- (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (2′-hydroxy-4 ′ -Octoxyphenyl) benzotriazole and the like.

  Specific examples of the aromatic benzoate compounds include alkylphenyl salicylates such as pt-butylphenyl salicylate and p-octylphenyl salicylate.

  Specific examples of oxalic acid anilide compounds include 2-ethoxy-2′-ethyloxalic acid bisanilide, 2-ethoxy-5-tert-butyl-2′-ethyloxalic acid bisanilide, 2- And ethoxy-3′-dodecyl oxalic acid bisanilide.

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

  Specific 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-stearyloxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6,6-tetramethylpiperidine, 4-benzyl Oxy-2,2,6,6-tetramethylpiperidine, 4-phenoxy-2,2,6,6-tetramethylpiperidine, 4- (d Rucarbamoyloxy) -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-tetramethyl-4 -Piperidyl) -adipate, bis (2,2,6,6-tetramethyl-4-piperidyl) -terephthalate, 1,2-bis (2,2,6,6-tetramethyl) Ru-4-piperidyloxy) -ethane, α, α′-bis (2,2,6,6-tetramethyl-4-piperidyloxy) -p-xylene, bis (2,2,6,6-tetramethyl) -4-piperidyltolylene-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-tricarboxy 1- [2- {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy} butyl] -4- [3- (3,5-di-t-butyl-4- Hydroxyphenyl) propionyl Xy] 2,2,6,6-tetramethylpiperidine, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and β, β, β ′, Examples include condensates with β ′,-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethanol.

In the present invention, the stabilizer may be used alone or in combination of two or more. Moreover, it is preferable to use a hindered phenol compound and / or a benzotriazole compound as the stabilizer. The blending amount of the stabilizer is (A) polylactic acid resin 100 in terms of mechanical properties, toughness, and durability. 0.01-3 weight part is preferable with respect to a weight part, and 0.03-2 weight part is further more preferable.

  In this invention, it is preferable to mix | blend (G) mold release agent. As the mold release agent used in the present invention, those usually used for a thermoplastic resin mold release agent can be used. Specifically, fatty acids, fatty acid metal salts, oxy fatty acids, fatty acid esters, partially aliphatic saponified esters, paraffin, low molecular weight polyolefins, fatty acid amides, alkylene bis fatty acid amides, aliphatic ketones, fatty acid lower alcohol esters, fatty acid polyhydric alcohols Examples thereof include esters, fatty acid polyglycol esters, and modified silicones. By blending these, a molded product having excellent mechanical properties, moldability, heat resistance and durability can be obtained.

  As the fatty acid, those having 6 to 40 carbon atoms are preferable. Specifically, oleic acid, lauric acid, stearic acid, hydroxystearic acid, behenic acid, arachidonic acid, linoleic acid, linolenic acid, ricinoleic acid, palmitic acid, Examples include stearic acid, montanic acid, and mixtures thereof. The fatty acid metal salt is preferably an alkali metal salt or alkaline 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-oxystearic acid, and examples of the fatty acid ester include stearic acid ester, oleic acid ester, linoleic acid ester, linolenic acid ester, adipic acid ester, behenic acid ester, arachidic acid ester, and montan. Examples of the acid ester, isostearic acid ester, ester of polymerized acid, and aliphatic partially saponified ester include montanic acid partially saponified ester. As the paraffin, those having 18 or more carbon atoms are preferable, and examples thereof include liquid paraffin, natural paraffin, microcrystalline wax, petrolatum, and the like, and the low molecular weight polyolefin preferably has a molecular weight of 5000 or less, specifically, polyethylene wax, Examples thereof include maleic acid-modified polyethylene wax, oxidized type polyethylene wax, chlorinated polyethylene wax, and polypropylene wax. Fatty acid amides preferably have 6 or more carbon atoms, and specifically include oleic acid amide, erucic acid amide, and behen. Examples of the alkylene bis-fatty acid amide include those having 6 or more carbon atoms. Specifically, methylene bis-stearic amide, ethylene bis-stearic amide, N, N-bis (2- Droxyethyl) stearamide and the like, examples of the aliphatic ketone include higher aliphatic ketones, and the fatty acid lower alcohol ester preferably has 6 or more carbon atoms, ethyl stearate butyl stearate, ethyl behenate, Examples of the fatty acid polyhydric alcohol ester include glycerin monostearate, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol adipate stearate, dipentaerythritol adipate stearate, sorbitan monobehe Examples of fatty acid polyglycol esters include polyethylene glycol fatty acid esters and polypropylene glycol fatty acid esters. The cone can be given Chirusuchiriru modified silicone, 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.

  Among the above, fatty acid, fatty acid metal salt, oxy fatty acid, fatty acid ester, fatty acid partial saponified ester, paraffin, low molecular weight polyolefin, aliphatic amide, alkylene bis fatty acid amide are preferred, and fatty acid partial saponified ester and / or alkylene bis fatty acid amide are preferred. More preferred.

  Of these, montanic acid ester, montanic acid partially saponified ester, polyethylene wax, oxidized polyethylene wax, sorbitan fatty acid ester, erucic acid amide, and ethylene bisstearic acid amide are preferable, and particularly, montanic acid partial saponified ester and ethylene bisstearic acid amide are preferable. . One type of release agent may be used, or two or more types may be used in combination.

  Moreover, the compounding quantity of a mold release agent is 0.01-3 weight part with respect to 100 weight part of (A) polylactic acid resin at the point of mechanical characteristics, toughness, and durability, and 0.03-2 weight part is preferable. Is more preferable.

  In this invention, it is preferable to mix | blend (H) reactive terminal blocker from a durable point. The reactive end-capping agent used in the present invention is not particularly limited as long as it is a compound that can block the carboxyl end group or hydroxyl group of the polymer, and those used as the end-capping agent of the polymer may be used. it can. In the present invention, such a reactive end-blocking agent not only blocks the end of the polylactic acid resin but also blocks the carboxyl group of acidic low-molecular compounds such as lactic acid and formic acid generated by thermal decomposition or hydrolysis of the polylactic acid resin. can do. Further, the end-capping agent is more preferably a compound that can also block the hydroxyl end where an acidic low molecular weight compound is generated by thermal decomposition.

  As such a reactive end-capping agent, it is preferable to use at least one compound selected from an epoxy compound, an oxazoline compound, an oxazine compound, a carbodiimide compound, and a compound containing an acid anhydride group. And / or carbodiimide compounds are preferred.

  In this invention, as an epoxy compound which can be used as a reactive terminal blocker, a glycidyl ether compound, a glycidyl ester compound, a glycidyl amine compound, a glycidyl imide compound and an alicyclic epoxy compound can be preferably used. By blending these, a molded product having excellent mechanical properties, moldability, heat resistance and durability can be obtained.

  Examples of glycidyl ether compounds include butyl glycidyl ether, stearyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, o-phenylphenyl glycidyl ether, ethylene oxide lauryl alcohol glycidyl ether, ethylene oxide phenol glycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol Diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane trig Bisphenols such as sidyl ether, pentaerythritol polyglycidyl ether, 2,2-bis- (4-hydroxyphenyl) propane, 2,2-bis- (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) sulfone; Examples thereof include a bisphenol A diglycidyl ether type epoxy resin, a bisphenol F diglycidyl ether type epoxy resin, a bisphenol S diglycidyl ether type epoxy resin obtained from a condensation reaction with epichlorohydrin. Among these, bisphenol A diglycidyl ether type epoxy resin is preferable.

  Examples of glycidyl ester compounds include benzoic acid glycidyl ester, p-toluic acid glycidyl ester, cyclohexanecarboxylic acid glycidyl ester, stearic acid glycidyl ester, lauric acid glycidyl ester, palmitic acid glycidyl ester, versatic acid glycidyl ester, oleic acid glycidyl ester Ester, linoleic acid glycidyl ester, linolenic acid glycidyl ester, terephthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, phthalic acid diglycidyl ester, naphthalene dicarboxylic acid diglycidyl ester, bibenzoic acid diglycidyl ester, methyl terephthalic acid diglycidyl ester , Hexahydrophthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, Hexane dicarboxylic acid diglycidyl ester, adipic acid diglycidyl ester, succinic acid diglycidyl ester, sebacic acid diglycidyl ester, dodecanedioic acid diglycidyl ester, octadecanedicarboxylic acid diglycidyl ester, trimellitic acid triglycidyl ester, pyromellitic acid tetra A glycidyl ester etc. can be mentioned. Among these, benzoic acid glycidyl ester and versatic acid glycidyl ester are preferable.

  Examples of glycidylamine compounds include tetraglycidylaminodiphenylmethane, triglycidyl-paraaminophenol, triglycidyl-metaaminophenol, diglycidylaniline, diglycidyltoluidine, tetraglycidylmetaxylenediamine, diglycidyltribromoaniline, tetraglycidylbisamino Examples include methylcyclohexane, triglycidyl cyanurate, and triglycidyl isocyanurate.

  Examples of glycidylimide compounds include 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-glycidyl succinimide, N-glycidyl hexahydrophthalimide, N-glycidyl-1,2,3,6-tetrahydrophthalimide, N-glycidyl maleimide, N- Glycidyl-α, β-dimethyl Succinimide, N-glycidyl-α-ethylsuccinimide, N-glycidyl-α-propylsuccinimide, N-glycidylbenzamide, N-glycidyl-p-methylbenzamide, N-glycidylnaphthamide, N-glycidylsteramide, etc. be able to. Of these, N-glycidylphthalimide is preferable.

  Examples of alicyclic epoxy compounds include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene diepoxide, 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 imide, and the like.

  Further, as other epoxy compounds, epoxy-modified fatty acid glycerides such as epoxidized soybean oil, epoxidized linseed oil, and epoxidized whale oil, phenol novolac type epoxy resins, cresol nozolac type epoxy resins and the like can be used.

  In the present invention, from the viewpoint of transparency, heat resistance and impact resistance, the reactive end-blocking agent is preferably a polymer containing a glycidyl group-containing vinyl-based unit.

  In the present invention, specific examples of the raw material monomer for forming the glycidyl group-containing vinyl unit include glycidyl esters of unsaturated monocarboxylic acids such as glycidyl (meth) acrylate and glycidyl p-styrylcarboxylate, maleic acid, itaconic acid Monoglycidyl ester or polyglycidyl ester of unsaturated polycarboxylic acid such as, unsaturated glycidyl ether such as allyl glycidyl ether, 2-methylallyl glycidyl ether, styrene-4-glycidyl ether, and the like. Among these, glycidyl acrylate or glycidyl methacrylate is preferably used in terms of radical polymerizability. These can be used alone or in combination of two or more.

  In the present invention, the polymer containing a glycidyl group-containing vinyl-based unit preferably contains a vinyl-based unit other than the glycidyl group-containing vinyl-based unit as a copolymerization component. Depending on the selection, the melting point of the polymer, the glass transition temperature, etc. Can be adjusted. Examples of vinyl units other than glycidyl group-containing vinyl units include acrylic vinyl units, carboxylic acid vinyl ester units, aromatic vinyl units, unsaturated dicarboxylic anhydride units, unsaturated dicarboxylic acid units, and aliphatic types. Examples thereof include vinyl units, maleimide units, and other vinyl units.

  Specific examples of the raw material monomer for forming the acrylic vinyl unit include acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, and n-butyl acrylate. , N-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate , Isobornyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, Roxypropyl, hydroxypropyl methacrylate, acrylic acid ester or methacrylate ester of polyethylene glycol or polypropylene glycol, trimethoxysilylpropyl acrylate, trimethoxysilylpropyl methacrylate, methyldimethoxysilylpropyl acrylate, methyldimethoxysilylpropyl methacrylate, Acrylic vinyl units having amino groups such as acrylonitrile, methacrylonitrile, N, N-dialkylacrylamide, N, N-dialkylmethacrylamide, α-hydroxymethyl acrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate The raw material monomer etc. which form are mentioned, Especially, acrylic acid, methacrylic acid, methyl acrylate, methacrylic acid Methyl, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, t-butyl acrylate, t-butyl methacrylate, Preferred are 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, acrylonitrile, methacrylonitrile, and acrylic acid, methacrylic acid, methyl acrylate, methacrylic acid. Methyl, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, acrylo Tolyl, methacrylonitrile is used. These may be used alone or in combination of two or more.

  Specific examples of the raw material monomer that forms the vinyl carboxylate unit include vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, Monofunctional aliphatic vinyl carboxylates such as vinyl palmitate, vinyl stearate, isopropenyl acetate, 1-butenyl acetate, vinyl pivalate, vinyl 2-ethylhexanoate and vinyl cyclohexanecarboxylate, vinyl benzoate and vinyl cinnamate, etc. And polyfunctional vinyl carboxylates such as vinyl aromatic carboxylate, vinyl monochloroacetate, divinyl adipate, vinyl methacrylate, vinyl crotonic acid and vinyl sorbate. Among them, vinyl acetate is preferably used. These may be used alone or in combination of two or more.

  Specific examples of the raw material monomer for forming the aromatic vinyl unit include styrene, α-methylstyrene, p-methylstyrene, α-methyl-p-methylstyrene, p-methoxystyrene, o-methoxystyrene, 2, 4 -Dimethylstyrene, 1-vinylnaphthalene, chlorostyrene, bromostyrene, divinylbenzene, vinyltoluene and the like can be mentioned, among which styrene and α-methylstyrene are preferably used. These may be used alone or in combination of two or more.

  Examples of the raw material monomer that forms the unsaturated dicarboxylic acid anhydride unit include maleic anhydride, itaconic anhydride, glutaconic anhydride, citraconic anhydride, or aconitic anhydride, among which maleic anhydride is preferably used. . These may be used alone or in combination of two or more.

  Examples of the raw material monomer for forming the unsaturated dicarboxylic acid-based unit include maleic acid, maleic acid monoethyl ester, itaconic acid, phthalic acid and the like. Among these, maleic acid and itaconic acid are preferably used. These may be used alone or in combination of two or more.

  Examples of raw material monomers for forming aliphatic vinyl units include ethylene, propylene, and butadiene. Examples of raw material monomers for forming maleimide units include maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N- As other raw material monomers for forming vinyl units such as isopropylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N- (p-bromophenyl) maleimide, N- (chlorophenyl) maleimide, N-vinyldiethylamine, N- Acetylvinylamine, allylamine, methallylamine, N-methylallylamine, p-aminostyrene and the like can be mentioned, and these can be used alone or in combination of two or more.

  In the present invention, the glass transition temperature of the polymer containing a glycidyl group-containing vinyl-based unit is not particularly limited, but is preferably in the range of 30 to 100 ° C. in terms of excellent handling properties. More preferably, it is in the range of ˜70 ° C., most preferably in the range of 50 to 65 ° C. The glass transition temperature here is an intermediate-point glass transition temperature measured by DSC at a temperature rising temperature of 20 ° C./min by the method of JIS K7121. In addition, the glass transition temperature of the polymer containing a glycidyl group-containing vinyl-based unit can be controlled by adjusting the composition of the copolymerization component. The glass transition temperature can usually be increased by copolymerizing aromatic vinyl units such as styrene, and can be decreased by copolymerizing acrylic ester units such as butyl acrylate.

  In the present invention, the polymer containing a glycidyl group-containing vinyl-based unit usually contains a volatile component because unreacted raw material monomers and solvents remain. The amount of the non-volatile component that is the balance is not particularly limited, but it is preferable that the non-volatile component amount is large from the viewpoint of suppressing the generation of gas. Specifically, it is preferably 95% by weight or more, more preferably 97% by weight or more, further preferably 98% by weight or more, and most preferably 98.5% by weight or more. preferable. In addition, the non-volatile component here represents the remaining amount ratio when the sample 10g is heated at 110 degreeC for 1 hour in nitrogen atmosphere.

  In the present invention, a polymer containing a glycidyl group-containing vinyl-based unit may use a sulfur compound as a chain transfer agent (molecular weight modifier) in order to obtain a low molecular weight product. Contains sulfur. Here, although sulfur content is not specifically limited, From the viewpoint of suppressing unpleasant odor, it is preferable that the sulfur content is small. Specifically, the sulfur atom is preferably 1000 ppm or less, more preferably 100 ppm or less, further preferably 10 ppm or less, and most preferably 1 ppm or less.

  In the present invention, the method for producing a polymer containing a glycidyl group-containing vinyl-based unit is not particularly limited as long as the conditions specified in the present invention are satisfied. Bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc. The known polymerization method can be used. When these methods are used, a polymerization initiator, a chain transfer agent, a solvent, and the like may be used, but these remain as impurities in a polymer containing a vinyl unit containing a glycidyl group finally obtained. There are things to do. The amount of these impurities is not particularly limited, but it is preferable that the amount of impurities is small from the viewpoint of suppressing a decrease in heat resistance and weather resistance. Specifically, the amount of impurities is preferably 10% by weight or less, more preferably 5% by weight or less, further preferably 3% by weight or less, particularly 1% by weight or less, with respect to the finally obtained polymer. Most preferred.

  As a method for producing a polymer containing a glycidyl group-containing vinyl-based unit that satisfies the molecular weight, glass transition temperature, nonvolatile component amount, sulfur content, impurity amount, and the like as described above, a high temperature of 150 ° C. or higher is applied. A method of continuous bulk polymerization under a pressure condition (preferably 1 MPa or more) in a short time (preferably 5 to 30 minutes) is a high polymerization rate, a polymerization initiator or a chain transfer agent that causes impurities and sulfur content And more preferable in that no solvent is used.

  Examples of oxazoline compounds that can be used as the reactive end-capping agent used in the present invention include 2-methoxy-2-oxazoline, 2-ethoxy-2-oxazoline, 2-propoxy-2-oxazoline, and 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-oxy Zolin, 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- Chlohexyl-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, 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), 2,2'-m-pheny Bis (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), 2,2′-cyclohexylenebis ( 2-oxazoline), 2,2′-diphenylenebis (2-oxazoline) and the like. Furthermore, the polyoxazoline compound etc. which contain the above-mentioned compound as a monomer unit can be mentioned.

  Examples of oxazine compounds as reactive endblockers used in the present invention include 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-octyl Oxy-5,6-dihydro-4H-1,3-oxazine, 2-nonyloxy-5,6-dihydro-4H-1,3-oxazine, 2-decyloxy-5,6-dihydro-4H-1, -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, etc. 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'-butylenebi (5,6-dihydro-4H-1,3-oxazine), 2,2′-hexamethylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2′-p-phenylenebis ( 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.

  Among the oxazoline compounds and oxazine compounds, 2,2'-m-phenylenebis (2-oxazoline) and 2,2'-p-phenylenebis (2-oxazoline) are preferable.

  The carbodiimide compound that can be used as the reactive end-capping agent used in the present invention is a compound having at least one carbodiimide group represented by (—N═C═N—) in the molecule. In the presence of a catalyst, the organic isocyanate can be heated and produced by a decarboxylation reaction.

  Examples of carbodiimide compounds include diphenylcarbodiimide, di-cyclohexylcarbodiimide, di-2,6-dimethylphenylcarbodiimide, diisopropylcarbodiimide, dioctyldecylcarbodiimide, di-o-toluylcarbodiimide, di-p-toluylcarbodiimide, di-p- Nitrophenylcarbodiimide, di-p-aminophenylcarbodiimide, di-p-hydroxyphenylcarbodiimide, di-p-chlorophenylcarbodiimide, di-o-chlorophenylcarbodiimide, di-3,4-dichlorophenylcarbodiimide, di-2 , 5-dichlorophenylcarbodiimide, p-phenylene-bis-o-toluylcarbodiimide, p-phenylene-bis-dicyclohexylcarbodiimide, p-phenylene- Su-di-p-chlorophenylcarbodiimide, 2,6,2 ', 6'-tetraisopropyldiphenylcarbodiimide, hexamethylene-bis-cyclohexylcarbodiimide, ethylene-bis-diphenylcarbodiimide, ethylene-bis-dicyclohexylcarbodiimide, N , N′-di-o-triylcarbodiimide, N, N′-diphenylcarbodiimide, N, N′-dioctyldecylcarbodiimide, N, N′-di-2,6-dimethylphenylcarbodiimide, N-triyl-N ′ -Cyclohexylcarbodiimide, N, N'-di-2,6-diisopropylphenylcarbodiimide, N, N'-di-2,6-di-tert-butylphenylcarbodiimide, N-toluyl-N'-phenylcarbodiimide, N, N'-di-p-ni Trophenylcarbodiimide, N, N′-di-p-aminophenylcarbodiimide, N, N′-di-p-hydroxyphenylcarbodiimide, N, N′-di-cyclohexylcarbodiimide, N, N′-di-p-toluyl Carbodiimide, N, N′-benzylcarbodiimide, N-octadecyl-N′-phenylcarbodiimide, N-benzyl-N′-phenylcarbodiimide, N-octadecyl-N′-tolylcarbodiimide, N-cyclohexyl-N′-tolylcarbodiimide, N-phenyl-N′-tolylcarbodiimide, N-benzyl-N′-tolylcarbodiimide, N, N′-di-o-ethylphenylcarbodiimide, N, N′-di-p-ethylphenylcarbodiimide, N, N ′ -Di-o-isopropylphenylcarbodiimide N, N′-di-p-isopropylphenylcarbodiimide, N, N′-di-o-isobutylphenylcarbodiimide, N, N′-di-p-isobutylphenylcarbodiimide, N, N′-di-2,6- Diethylphenylcarbodiimide, N, N′-di-2-ethyl-6-isopropylphenylcarbodiimide, N, N′-di-2-isobutyl-6-isopropylphenylcarbodiimide, N, N′-di-2,4,6 Mono- or dicarbodiimide compounds such as trimethylphenylcarbodiimide, N, N′-di-2,4,6-triisopropylphenylcarbodiimide, N, N′-di-2,4,6-triisobutylphenylcarbodiimide, poly ( 1,6-hexamethylenecarbodiimide), poly (4,4′-methylenebiscyclohexylca) Bodiimide), poly (1,3-cyclohexylenecarbodiimide), poly (1,4-cyclohexylenecarbodiimide), poly (4,4'-diphenylmethanecarbodiimide), poly (3,3'-dimethyl-4,4'- Diphenylmethanecarbodiimide), poly (naphthylenecarbodiimide), poly (p-phenylenecarbodiimide), poly (m-phenylenecarbodiimide), poly (tolylcarbodiimide), poly (diisopropylcarbodiimide), poly (methyl-diisopropylphenylenecarbodiimide), poly ( And polycarbodiimides such as triethylphenylenecarbodiimide) and poly (triisopropylphenylenecarbodiimide). Of these, N, N'-di-2,6-diisopropylphenylcarbodiimide, 2,6,2 ', 6'-tetraisopropyldiphenylcarbodiimide, and polycarbodiimide are preferable.

  In the present invention, examples of the compound containing an acid anhydride group include succinic anhydride, maleic anhydride, and phthalic anhydride. Furthermore, the polymer etc. which contain an above-described compound as a monomer unit can be mentioned.

  As the reactive end-capping agent, one or more compounds can be arbitrarily selected and used.

In the resin composition of the present invention, the carboxyl terminal and the acidic low molecular compound may be appropriately blocked according to the use to be used as a molded product, but the specific carboxyl terminal and acidic low molecular compound are blocked. The acid concentration in the composition is preferably 10 equivalents / 10 ⁶ g or less from the viewpoint of hydrolysis resistance, more preferably 5 equivalents / 10 ⁶ g or less, and more preferably 1 equivalents / 10 ⁶ g or less. It is particularly preferred. The acid concentration in the polymer composition can be measured by dissolving the polymer composition in a suitable solvent and then titrating with an alkali compound solution such as sodium hydroxide having a known concentration, or by NMR.

  In this invention, 0.01-10 weight part is preferable with respect to 100 weight part of (A) polylactic acid resin, and, as for the quantity of a reactive terminal blocker, 0.05-5 weight part is more preferable.

  In the present invention, it is preferable to add a reaction endblocking reaction catalyst. The reaction catalyst referred to here is a compound that has an effect of promoting the reaction between the reactive end-capping agent and the carboxyl end or hydroxyl group of the polymer end or acidic low molecular weight compound, and has the effect of promoting the reaction with a small amount of addition. Certain compounds are preferred. Examples of such compounds include alkali metal compounds, alkaline earth metal compounds, tertiary amine compounds, imidazole compounds, quaternary ammonium salts, phosphine compounds, phosphonium salts, phosphate esters, organic acids, Lewis acids. Specific examples thereof include sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium acetate, potassium acetate, lithium acetate, Sodium stearate, potassium stearate, lithium stearate, sodium borohydride, lithium borohydride, sodium phenyl borohydride, sodium benzoate, potassium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate Dilithium hydrogen phosphate, disodium salt of bisphenol A, dipotassium salt, dilithium salt, phenol sodium salt, potassium salt, lithium salt, cesium salt and other alkali metal compounds, calcium hydroxide, water Alkaline earth such as barium oxide, magnesium hydroxide, strontium hydroxide, calcium bicarbonate, barium carbonate, magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, magnesium stearate, strontium stearate Metal compounds, triethylamine, tributylamine, trihexylamine, triamylamine, triethanolamine, dimethylaminoethanol, triethylenediamine, dimethylphenylamine , Dimethylbenzylamine, 2- (dimethylaminomethyl) phenol, dimethylaniline, pyridine, picoline, tertiary amines such as 1,8-diazabicyclo (5,4,0) undecene-7, 2-methylimidazole, 2- Imidazole compounds such as ethylimidazole, 2-isopropylimidazole, 2-ethyl-4-methylimidazole, 4-phenyl-2-methylimidazole, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium bromide, trimethylbenzylammonium chloride, triethyl Quaternary ammonium salts such as benzylammonium chloride, tripropylbenzylammonium chloride, N-methylpyridinium chloride, trimethylphosphine Phosphine compounds such as triethylphosphine, tributylphosphine, trioctylphosphine, phosphonium salts such as tetramethylphosphonium bromide, tetrabutylphosphonium bromide, tetraphenylphosphonium bromide, ethyltriphenylphosphonium bromide, triphenylbenzylphosphonium bromide, trimethyl phosphate, triethyl Phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, tri (p-hydroxy) phenyl phosphate, tri (p- Methoxy) phenyl phosphate Any phosphoric acid ester, oxalic acid, p-toluenesulfonic acid, dinonylnaphthalenedisulfonic acid, organic acid such as dodecylbenzenesulfonic acid, Lewis acid such as boron trifluoride, aluminum tetrachloride, titanium tetrachloride, tin tetrachloride, etc. These may be used alone or in combination of two or more. Among these, it is preferable to use an alkali metal compound, an alkaline earth metal compound, and a phosphate ester, and particularly an alkali metal or an organic salt of an alkaline earth metal can be preferably used. Particularly preferred compounds are sodium stearate, potassium stearate, calcium stearate, magnesium stearate, sodium benzoate, sodium acetate, potassium acetate, calcium acetate and magnesium acetate. Further, an organic salt of an alkali metal or alkaline earth metal having 6 or more carbon atoms is preferable, and it is preferable to use one or more of sodium stearate, potassium stearate, calcium stearate, magnesium stearate, and sodium benzoate.

  The addition amount of the reaction catalyst is not particularly limited, but is preferably 0.001 to 1 part by weight, more preferably 0.01 to 0.1 part by weight with respect to (A) 100 parts by weight of the polylactic acid resin. 0.02-0.1 part by weight is more preferable.

  In the present invention, in order to impart flame retardancy, (I) a flame retardant may be blended. The flame retardant used in the present invention is at least one selected from brominated flame retardants, chlorine flame retardants, phosphorus flame retardants, nitrogen compound flame retardants, silicone flame retardants and other inorganic flame retardants. A flame retardant can be used.

  Specific examples of the brominated flame retardant used in the present invention include decabromodiphenyl oxide, octabromodiphenyl oxide, tetrabromodiphenyl oxide, tetrabromophthalic anhydride, hexabromocyclododecane, bis (2,4,6-tribromo). Phenoxy) ethane, ethylenebistetrabromophthalimide, 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, tetrabromobis Enol-A, tetrabromobisphenol-A derivative, tetrabromobisphenol-A-epoxy oligomer or polymer, brominated epoxy resin such as brominated phenol novolac epoxy, tetrabromobisphenol-A-carbonate oligomer or polymer, tetrabromobisphenol-A -Bis (2-hydroxydiethyl ether), tetrabromobisphenol-A-bis (2,3-dibromopropyl ether), tetrabromobisphenol-A-bis (allyl ether), tetrabromocyclooctane, ethylenebispentabromodiphenyl, Tris (tribromoneopentyl) phosphate, poly (pentabromobenzylpolyacrylate), octabromotrimethylphenylindane, dibromoneope Chill glycol, pentabromobenzyl polyacrylate, dibromo cresyl glycidyl ether, N, N'ethylene - bis - such as tetrabromo terephthalic imide. Of these, tetrabromobisphenol-A-epoxy oligomer, tetrabromobisphenol-A-carbonate oligomer, and brominated epoxy resin are preferable.

  Specific examples of the chlorinated flame retardant used in the present invention include chlorinated paraffin, chlorinated polyethylene, perchlorocyclopentadecane, and tetrachlorophthalic anhydride.

  The phosphorus-based flame retardant used in the present invention is not particularly limited, and generally used phosphorus-based flame retardants can be used. Typically, phosphate esters, condensed phosphate esters, polyphosphates, etc. Organic phosphorus compounds and red phosphorus.

  Specific examples of the above organic phosphorus compounds include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris ( Isopropylphenyl) phosphate, tris (phenylphenyl) phosphate, trinaphthyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, diphenyl (2-ethylhexyl) phosphate, di (isopropylphenyl) phenyl phosphate, monoisodecyl phosphate, 2- Acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, di- Enyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, triphenylphosphine oxide, tricresylphosphine oxide, diphenyl methanephosphonate, diethyl phenylphosphonate, etc. Phosphoric acid esters, resorcinol poly (di-2,6-xylyl) phosphate, bisphenol A polycresyl phosphate, hydroquinone poly (2,6-xylyl) phosphate and condensates thereof, 9,10 -Cyclic phosphate esters such as dihydro-9-oxa-10-phosphaphenanthrene-10-oxide resorcinol polyphenyl phosphate It is possible. Examples of such commercially available condensed phosphate esters include PX-200, PX-201, PX-202, CR-733S, CR-741, CR747, ADEKA PFR, FP-500, and FP manufactured by Daihachi Chemical Industry. -600, FP-700, T-1317F, and the like.

  Moreover, the polyphosphoric acid salt and the phosphinic acid metal salt which consist of a salt with phosphoric acid, polyphosphoric acid, a periodic table group IA-IVB group metal, ammonia, an aliphatic amine, and an aromatic amine can also be mentioned. As typical salts of polyphosphates, lithium salts, sodium salts, calcium salts, barium salts, iron (II) salts, iron (III) salts, aluminum salts, etc. as metal salts, methylamine salts as aliphatic amine salts, There are ethylamine salt, diethylamine salt, triethylamine salt, ethylenediamine salt, piperazine salt, and aromatic amine salt includes pyridine salt, triazine salt, melamine salt, ammonium salt, etc., and phosphinic acid metal salt includes ethylmethylphosphine Examples include aluminum oxide, aluminum diethylphosphinate, calcium ethylmethylphosphinate, and calcium 1,3-ethane-1,2-bismethylphosphinate.

  In addition to the above, halogen-containing phosphate esters such as trischloroethyl phosphate, trisdichloropropyl phosphate, tris (β-chloropropyl) phosphate, and a structure in which a phosphorus atom and a nitrogen atom are connected by a double bond A phosphazene compound, phosphoric ester amide, melamine polyphosphate, etc. can be mentioned.

  Further, as red phosphorus, not only untreated red phosphorus but also red phosphorus treated with one or more compound films selected from the group consisting of a thermosetting resin film, a metal hydroxide film, and a metal plating film It can be preferably used. The thermosetting resin of the thermosetting resin film is not particularly limited as long as it is a resin capable of coating red phosphorus. For example, phenol-formalin resin, urea-formalin resin, melamine-formalin resin, alkyd resin Etc. The metal hydroxide film is not particularly limited as long as it is a resin capable of coating red phosphorus, and examples thereof include aluminum hydroxide, magnesium hydroxide, zinc hydroxide, and titanium hydroxide. . The metal of the metal plating film is not particularly limited as long as it is a resin capable of coating red phosphorus, and examples thereof include Fe, Ni, Co, Cu, Zn, Mn, Ti, Zr, Al, and alloys thereof. Furthermore, these coatings may be laminated in combination of two or more or in combination of two or more.

  Among the phosphorus-based flame retardants, condensed phosphates, polyphosphates, and red phosphorus are preferable, condensed phosphates are more preferable, and aromatic condensed phosphates are particularly preferable.

  Examples of the nitrogen compound-based flame retardant used in the present invention include aliphatic amine compounds, aromatic amine compounds, nitrogen-containing heterocyclic compounds, cyanide compounds, aliphatic amides, aromatic amides, urea, thiourea and the like. . In addition, nitrogen-containing phosphorus flame retardants such as ammonium polyphosphate as exemplified in the above phosphorus flame retardant are not included in the nitrogen compound flame retardant referred to herein. Examples of the aliphatic amine include ethylamine, butylamine, diethylamine, ethylenediamine, butylenediamine, triethylenetetramine, 1,2-diaminocyclohexane, 1,2-diaminocyclooctane and the like. Examples of the aromatic amine include aniline and phenylenediamine. Examples of nitrogen-containing heterocyclic compounds include uric acid, adenine, guanine, 2,6-diaminopurine, 2,4,6-triaminopyridine, and triazine compounds. Examples of the cyan compound include dicyandiamide. Examples of the aliphatic amide include N, N-dimethylacetamide. Examples of aromatic amides include N, N-diphenylacetamide.

  The triazine compounds exemplified above are nitrogen-containing heterocyclic compounds having a triazine skeleton, and are triazine, melamine, benzoguanamine, methylguanamine, cyanuric acid, melamine cyanurate, melamine isocyanurate, trimethyltriazine, triphenyltriazine, amelin, and amelide. And thiocyanuric acid, diaminomercaptotriazine, diaminomethyltriazine, diaminophenyltriazine, diaminoisopropoxytriazine and the like.

  As melamine cyanurate or melamine isocyanurate, an addition product of cyanuric acid or isocyanuric acid and a triazine compound is preferable, usually an addition having a composition of 1 to 1 (molar ratio) and optionally 1 to 2 (molar ratio). You can list things. Although it is produced by a known method, for example, a mixture of melamine and cyanuric acid or isocyanuric acid is made into a water slurry and mixed well to form both salts into fine particles, and then the slurry is filtered and dried. Later it is generally obtained in powder form. The salt does not need to be completely pure, and some unreacted melamine, cyanuric acid or isocyanuric acid may remain. Moreover, the average particle diameter before blending with the resin is preferably 100 to 0.01 μm, more preferably 80 to 1 μm from the viewpoint of flame retardancy, mechanical strength, and surface property of the molded product.

  Of the nitrogen compound-based flame retardants, nitrogen-containing heterocyclic compounds are preferable, among which triazine compounds are preferable, and melamine cyanurate is more preferable.

  When the dispersibility of the nitrogen compound flame retardant is poor, a dispersant such as tris (β-hydroxyethyl) isocyanurate or a known surface treatment agent such as polyvinyl alcohol or metal oxide may be used in combination. Good.

  Examples of the silicone-based flame retardant used in the present invention include silicone resins and silicone oils. Examples of the silicone resin include resins having a three-dimensional network structure formed by combining structural units of RSiO3 / 2, R2SiO, and R3SiO1 / 2. Here, R represents an alkyl group such as a methyl group, an ethyl group or a propyl group, an aromatic group such as a phenyl group or a benzyl group, or a substituent containing a vinyl group in the above substituent. In the silicone oil, polydimethylsiloxane, and at least one methyl group in the side chain or terminal of polydimethylsiloxane is a hydrogen element, an alkyl group, a cyclohexyl group, a phenyl group, a benzyl group, an amino group, an epoxy group, or a polyether group. , A modified polysiloxane modified with at least one group selected from a carboxyl group, a mercapto group, a chloroalkyl group, an alkyl higher alcohol ester group, an alcohol group, an aralkyl group, a vinyl group, or a trifluoromethyl group, or a mixture thereof Can be mentioned. Further, silsesquioxane forming a cage-type or ladder-type structure and a silicone-based oligomer that is a derivative thereof can be given as preferable examples.

  Other inorganic flame retardants used in the present invention include magnesium hydroxide, aluminum hydroxide, antimony trioxide, antimony pentoxide, sodium antimonate, zinc hydroxystannate, zinc stannate, metastannic acid, first oxide Tin, stannic oxide, tin oxide salt, zinc sulfate, zinc oxide, ferrous oxide, ferric oxide, zinc borate, calcium borate, ammonium borate, ammonium octamolybdate, metal salt of tungstic acid, Examples thereof include complex oxide acids of tungsten and metalloid, ammonium sulfamate, ammonium bromide, zirconium compounds, guanidine compounds, graphite, and swellable graphite. Of these, magnesium hydroxide, aluminum hydroxide, zinc borate, and swellable graphite are preferable, and they may be treated with a known surface treatment agent or the like.

  In the present invention, the flame retardant (I) may be one type, but it is preferable to use two or more types in terms of excellent flame retardancy.

  Among the flame retardants (I), it is preferable to use any two or more of a phosphorus-based flame retardant containing no halogen, a nitrogen compound-based flame retardant, a silicone-based flame retardant, or other inorganic flame retardants. In terms of excellent flammability, it is preferable to use a phosphorus-based flame retardant together with other flame retardants, but among the phosphorus-based flame retardants, when using condensed phosphate ester, polyphosphate, red phosphorus, It is also possible to select and use two or more of these from the viewpoint of excellent flame retardancy. When the flame retardant used in combination with the phosphorus flame retardant is a nitrogen compound flame retardant, a nitrogen-containing heterocyclic compound is preferable, a triazine compound is more preferable, and melamine cyanurate is more preferable. When the flame retardant used in combination with the phosphorus flame retardant is a silicone flame retardant, a silicone resin and a silicone oligomer are preferable. When the flame retardant used in combination with the phosphorus-based flame retardant is other inorganic flame retardant, magnesium hydroxide, aluminum hydroxide, zinc borate, and swellable graphite are preferable, and aluminum hydroxide, zinc borate, swelling Graphite is more preferable, and aluminum hydroxide is more preferable. In the case where a phosphorus flame retardant and other flame retardant are used in combination, the blending ratio is not particularly limited, and any amount can be combined, but in terms of excellent flame retardancy, the phosphorus system in 100% by weight of the flame retardant The amount of the flame retardant is preferably 5% by weight or more, and more preferably 5 to 95% by weight.

  Further, among the flame retardants (I), nitrogen compound flame retardants, silicone flame retardants or other inorganic flame retardants which do not contain any halogen compound and phosphorus compound among the flame retardants (I) in that the load on the environment is easily reduced. One or more flame retardants selected from the above are preferred.

    The blending amount of the flame retardant (I) is preferably 0.5 to 150 parts by weight, more preferably 1 to 100 parts by weight, and 1.2 to 90 parts by weight with respect to 100 parts by weight of the polylactic acid resin. Is more preferable, 2 to 85 parts by weight is particularly preferable, and 3 to 80 parts by weight is most preferable. Further, by using (I) the flame retardant in combination with the (J) fluorine-based resin, there is an effect of improving drip at the time of combustion, and higher flame retardancy can be obtained. Such a fluorine-based resin is a resin containing fluorine in a substance molecule, and specifically includes polytetrafluoroethylene, polyhexafluoropropylene, tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / perfluoroethylene. Fluoroalkyl vinyl ether copolymer, tetrafluoroethylene / ethylene copolymer, hexafluoropropylene / propylene copolymer, polyvinylidene fluoride, vinylidene fluoride / ethylene copolymer, and the like. Among them, polytetrafluoroethylene, Tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / ethylene copolymer, polyvinylidene fluoride In particular, polytetrafluoroethylene and tetrafluoroethylene / ethylene copolymer are preferred, and polytetrafluoroethylene is more preferred, and a polytetrafluoroethylene-containing mixed powder comprising polytetrafluoroethylene particles and an organic polymer. Are also preferably used. The molecular weight of the fluororesin such as polytetrafluoroethylene is preferably in the range of 100,000 to 10,000,000, more preferably in the range of 100,000 to 1,000,000, particularly for the extrudability and flame retardancy of the present invention. effective. Commercially available products of polytetrafluoroethylene include “Teflon (registered trademark)” 6-J, “Teflon (registered trademark)” 6C-J, “Teflon (registered trademark)” 62-J manufactured by Mitsui DuPont Fluorochemicals, “Full-on” CD1 and CD076 manufactured by Asahi IC Fluoropolymers are commercially available. In addition, as a commercial product of a polytetrafluoroethylene-containing mixed powder composed of polytetrafluoroethylene particles and an organic polymer, it is commercially available from Mitsubishi Rayon as the “Metabrene” A series, “Metablene” A-3000, “ METABLEN "A-3800" is commercially available. In addition, polytetrafluoroethylene “Teflon (registered trademark)” 6-J and the like are prone to agglomerate, so if mechanically strongly mixed with other resin compositions with a Henschel mixer, etc., agglomeration may occur due to aggregation. There are problems with handling and dispersibility depending on conditions. On the other hand, a polytetrafluoroethylene-containing mixed powder composed of polytetrafluoroethylene particles and an organic polymer is excellent in handling properties and dispersibility, and is particularly preferably used. The polytetrafluoroethylene-containing mixed powder composed of the polytetrafluoroethylene particles and the organic polymer is not limited, but polytetrafluoroethylene disclosed in Japanese Patent Application Laid-Open No. 2000-226523. Polytetrafluoroethylene-containing mixed powder composed of particles and an organic polymer, and the like. Examples of the organic polymer include aromatic vinyl monomers, acrylate monomers, and vinyl cyanide. An organic polymer containing 10% by weight or more of a monomer, and a mixture thereof may be used. The content of polytetrafluoroethylene in the polytetrafluoroethylene-containing mixed powder is from 0.1% by weight to 90%. It is preferable that it is weight%. Moreover, the compounding quantity of fluorine-type resin is 0.01-5 weight part with respect to 100 weight part of polylactic acid resin, Preferably 0.02-4 weight part is preferable, More preferably, it is 0.03-3. Part by weight is preferable, and if the blending amount of the fluororesin exceeds 3 parts by weight, the fluidity and flame retardancy of the present invention are adversely reduced. .

  As the flame retardancy of the resin composition containing the flame retardant (I), a molded product having a flame retardance of 1.6 mm (1/16 inch) or more in the US UL standard subject 94 (UL-94 standard). Thus, it is possible to obtain a resin composition having flame retardancy of V-2, V-1, and V-0. Here, the flame retardancy of the American UL standard subject 94 (UL-94 standard) will be described. The flame retardancy test method includes a horizontal test and a vertical test, and materials that pass the horizontal test are flame retardancy rank HB. It is evaluated as. In addition, the vertical test, in which the test material is fixed vertically and the flame is applied to the lower part of the material, is more flammable than the horizontal test. Therefore, the material requires a high level of flame retardancy, and the flame retardancy rank is V. -2, V-1, and V-0 are defined, and the smaller the number, the better the flame retardancy. Here, V-0 is the most advanced flame retardance rank.

  In the present invention, a thermosetting resin such as a thermosetting polyester resin, a thermosetting acrylic resin, a silicone resin, or an epoxy resin can be contained within a range not impairing the object of the present invention.

  In the present invention, a branched polymer, a liquid crystal polymer, a low molecular weight linear polyester, a low molecular weight linear polycarbonate, an aromatic low molecular compound, an acrylic compound, three or more, as long as the object of the present invention is not impaired. Additives such as a fluidity improver such as a compound having a hydroxyl group or an amino group, a colorant containing a dye and a pigment, a slidability improver (graphite, a fluororesin, etc.) and an antistatic agent may be contained. These additives can be used alone or in combination of two or more.

  The method for producing the resin composition of the present invention is not particularly limited as long as the requirements specified in the present invention are satisfied. For example, a polylactic acid resin, a phosphonic acid metal salt having an aromatic ring, and other as required After blending the additives in advance, a method of uniformly melting and kneading with a single screw or twin screw extruder or a method of removing the solvent after mixing in a solution is preferably used above the melting point.

  In this invention, it is preferable that the crystallization temperature (Tc) at the time of the temperature fall derived from the polylactic acid resin in a resin composition can be observed at the point which is excellent in a moldability and heat resistance. Here, the crystallization temperature (Tc) at the time of temperature decrease derived from the polylactic acid resin is a crystallization temperature derived from the polylactic acid resin measured at a temperature decrease rate of 20 ° C./min by a differential scanning calorimeter (DSC). The crystallization temperature (Tc) is not particularly limited, but is preferably 100 ° C. or higher, more preferably 105 ° C. or higher, and further preferably 110 ° C. or higher from the viewpoint of moldability.

  In the present invention, the crystallization enthalpy (ΔHc) derived from the polylactic acid resin is 35% or more of the crystal melting enthalpy (ΔHm) derived from the polylactic acid resin, preferably 50% or more, more preferably The value is preferably 70% or more, more preferably 80% or more, and most preferably 100%. Here, the crystallization enthalpy (ΔHc) at the time of temperature decrease derived from polylactic acid resin is the crystallization enthalpy derived from polylactic acid resin measured by DSC at a temperature decrease rate of 20 ° C./min. The crystal melting enthalpy (ΔHm) derived from polylactic acid resin is the crystal melting enthalpy derived from polylactic acid resin measured by DSC at a heating rate of 20 ° C./min, but the heating rate of 20 in the first measurement (1stRUN). After raising the temperature from 30 ° C. to 200 ° C. at a rate of 20 ° C./min, the temperature was lowered to 30 ° C. at a rate of temperature drop of 20 ° C./min. Is the crystal melting enthalpy measured at 2ndRUN when the temperature is raised to.

  The resin composition of the present invention is a composition having unique characteristics, and can be processed and used for various molded products by a method such as injection molding or extrusion molding. The mold temperature in the case of injection molding is preferably 30 ° C. or higher, more preferably 60 ° C. or higher, more preferably 70 ° C. or higher, from the viewpoint of crystallization, and 140 ° C. in that deformation of the test piece can be suppressed. The following is preferable, 120 ° C or lower is more preferable, 110 ° C or lower is further preferable, and lower than 100 ° C is particularly preferable.

  In the present invention, the obtained resin composition can be molded by any method such as generally known injection molding, extrusion molding or blow molding, and can be widely used as a molded product of any shape. Molded products include films, sheets, fibers / clothes, non-woven fabrics, injection molded products, extrusion molded products, vacuum / pressure molded products, blow molded products, or composites with other materials. It can be used for electronic equipment materials, agricultural materials, horticultural materials, fishery materials, civil engineering / architectural materials, stationery, daily necessities, household goods, medical / hygiene products, and other various uses.

  Specifically, air flow meter, air pump, thermostat housing, engine mount, ignition hobbin, ignition case, clutch bobbin, sensor housing, idle speed control valve, vacuum switching valve, ECU housing, vacuum pump case, inhibitor switch, rotation sensor, Accelerometer, Distributor cap, Coil base, Actuator case for ABS, Top and bottom of radiator tank, Cooling fan, Fan shroud, Engine cover, Cylinder head cover, Oil cap, Oil pan, Oil filter, Fuel cap, Fuel strainer, Distribution Turcap, vapor canister housing Air cleaner housing, timing belt cover, brake booster parts, various cases, various tubes, various tanks, various hoses, various clips, various valves, various pipes, automotive underhood parts, torque control levers, safety belt parts, register blades , Washer lever, window regulator handle, window regulator handle knob, passing light lever, sun visor bracket, various motor housings, spare tire covers, door trim and other automotive interior parts, roof rails, fenders, garnishes, bumpers, door mirror stays, spoilers , Hood louver, wheel cover, wheel cap, grill apron cover frame, lamp reflector, lamp bezel Automotive exterior parts such as door handles, mention may be made of wire harness connector, SMJ connector, PCB connector, the auto parts typified by various connector for automobiles such as door grommet connector. Also, notebook computer housings and internal parts, CRT display housings and internal parts, printer housings and internal parts, mobile terminal housings and internal parts such as mobile phones, mobile personal computers and handheld mobiles, recording media (CD, DVD, PD, FDD) Etc.) Electrical and electronic parts represented by drive housings and internal parts, copier housings and internal parts, facsimile housings and internal parts, parabolic antennas and the like. Furthermore, audio equipment parts such as VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, video cameras, audio / laser discs (registered trademark) / compact discs, lighting parts, refrigerator parts, Examples include home and office electrical product parts such as air conditioner parts, typewriter parts, and word processor parts. Also, housings and internal parts of electronic musical instruments, home game machines, portable game machines, various gears, various cases, sensors, LEP lamps, connectors, sockets, resistors, relay cases, motor cases, switches, capacitors, variable capacitors Case, optical pickup, oscillator, various terminal boards, transformer, plug, printed wiring board, tuner, speaker, microphone, headphones, small motor, magnetic head base, power module, semiconductor, liquid crystal, FDD carriage, FDD chassis, motor Electric and electronic parts such as brush holders, transformer members, coil bobbins, sash doors, blind curtain parts, piping joints, curtain liners, blind parts, gas meter parts, water meter parts, water heater parts, roof panels , Heat insulation walls, adjusters, plastic bundles, ceiling fishing gear, stairs, doors, floors and other building materials, fishing lines, fishing nets, seaweed aquaculture nets, fishing bait bags and other fishery related parts, vegetation nets, vegetation mats, grass bags, Weed prevention net, curing sheet, slope protection sheet, fly ash holding sheet, drain sheet, water retention sheet, sludge / sludge dehydration bag, concrete formwork and other civil engineering related members, gears, screws, springs, bearings, levers, key stems, Cams, ratchets, rollers, water supply parts, toy parts, fans, tegs, pipes, cleaning jigs, motor parts, microscopes, binoculars, cameras, clocks, and other mechanical parts, multi-films, tunnel films, bird seats, vegetation Nonwoven fabric for protection, pot for seedling, vegetation pile, seed string tape, germination sheet, house lining sheet, agricultural PVC film stopper, slow-release fertilizer, root prevention , Garden net, insect net, infant tree net, print laminate, fertilizer bag, sample bag, sandbag, animal damage prevention net, inducement string, wind net, etc., paper diaper, sanitary wrapping material, cotton swab, towel , Hygiene items such as toilet seat wipes, medical non-woven fabrics (stitching reinforcements, anti-adhesion membranes, prosthetic repair materials), wound dressings, wound tape bandages, sticker base fabrics, surgical sutures, fracture reinforcements, medical Medical supplies such as film, calendar, stationery, clothing, food packaging film, tray, blister, knife, fork, spoon, tube, plastic can, pouch, container, tank, basket, etc. Fill containers, microwave cooking containers, cosmetic containers, wraps, foam buffers, paper laminates, shampoo bottles, beverage bottles, cups, candy packaging, chestnuts Containers such as link labels, lid materials, envelopes with windows, fruit baskets, hand cut tape, easy peel packaging, egg packs, HDD packaging, compost bags, recording media packaging, shopping bags, wrapping films for electrical and electronic parts, etc. Packaging, natural fiber composites, polo shirts, T-shirts, innerwear, uniforms, sweaters, socks, ties, and other clothing, curtains, chairs, carpets, tablecloths, futons, wallpaper, furoshiki and other interior goods, carrier tape, Print lamination, heat sensitive stencil printing film, release film, porous film, container bag, credit card, cash card, ID card, IC card, paper, leather, non-woven fabric hot melt binder, magnetic material, zinc sulfide, electrode Powder binders for materials, optical elements, conductive Embossed tape, IC tray, golf tee, garbage bag, plastic bag, various nets, toothbrush, stationery, draining net, body towel, hand towel, tea pack, drainage filter, clear file, coating agent, adhesive, bag, chair It is useful as a table, cooler box, kumade, hose reel, planter, hose nozzle, dining table, desk surface, furniture panel, kitchen cabinet, pen cap, gas lighter and so on.

    Hereinafter, the configuration and effects of the present invention will be described in more detail by way of examples. Here, the compounding ratio in an Example shows weight%. Moreover, the raw material used and the code | symbol in a table | surface are shown below.

(A) Polylactic acid resin (A-1) Poly L lactic acid resin (D-form 1.2%, weight average molecular weight 160,000, melting point 172 ° C.)
(A-2) Poly L lactic acid resin (D-form 0.5%, weight average molecular weight 150,000, melting point 180 ° C.)
(A-3) Poly L-lactic acid resin (D-form 1.2%, weight average molecular weight 200,000, melting point 172 ° C.)
(A-4) Polylactic acid stereocomplex (weight average molecular weight 150,000, melting point 210 ° C.) [Reference Example 1].

(B) Phosphonic acid metal salt having an aromatic ring (B-1) Zinc phenylphosphonate [Reference Example 2]
(B-2) Copper phenylphosphonate [Reference Example 3]
(B-3) Calcium phenylphosphonate [Reference Example 4].

(C) Crystallization accelerator (C-1) Talc (Inorganic crystal nucleating agent, “MICRO ACE” P-6, manufactured by Nippon Talc)
(C-2) Polyethylene glycol (PEG6000S manufactured by Sanyo Chemical Industries)
(C-3) Aliphatic ester plasticizer ("DAIFACTY" -101 manufactured by Daihachi Chemical Industry).

(D) Thermoplastic resin other than polylactic acid (D-1) Polyacetal copolymer ("KOCETAL" K300 made by KTP)
(D-2) Polybutylene terephthalate resin ("Toraycon" 1100S manufactured by Toray)
(D-3) Polycarbonate resin (Mitsubishi Gas Chemical "Iupilon" H4000)
(D-4) Polyamide resin ("Amilan" CM4000 manufactured by Toray Industries, Inc.)
(D-5) Styrene resin 1 [Reference Example 5]
(D-6) Polypropylene resin (Prime Polymer J108M)
(D-7) Core shell elastomer (Mitsubrene S2001 from Mitsubishi Rayon)
(D-8) Core shell elastomer ("Kane Ace" M511 made by Kaneka)
(D-9) Graft polymer 1 [Reference Example 6].

(E) Filler (E-1) Glass fiber (Nittobo 3J948)
(E-2) Wollastonite (KAP350 manufactured by Kansai Matec).

(F) Stabilizer (F-1) Triethylene glycol-bis- [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate (“Irganox” 245 manufactured by Ciba Geigy)
(F-2) Tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane (“Irganox” 1010 manufactured by Ciba Geigy).

(G) Mold release agent (G-1) Partially saponified ester of montanic acid ("Licowax" OP made by Clariant)
(G-2) Ethylene bis-stearic acid amide (Nippon Kasei "Slipax" E).

(H) Reactive end-capping agent (H-1) Glycidyl group-containing acrylic / styrene copolymer (Johnson polymer "Johncrill" ADR-4368, Mw7000, epoxy value 3.5 meq / g)
(H-2) Polycarbodiimide (Nisshinbo "Carbodilite" HMV-8CA, Mw2000).

(I) Flame retardant (I-1) Condensed phosphate ester (PX-200 manufactured by Daihachi Chemical Industry)
(I-2) Melamine cyanurate (MC-440 manufactured by Nissan Chemical Industries)

(J) Fluorine resin
(J-1) Tetrafluoroethylene (“Teflon (registered trademark)” 6-J manufactured by Mitsui DuPont Fluorochemicals)
(J-2) Acrylic modified tetrafluoroethylene (Mitsubrene A-3800 manufactured by Mitsubishi Rayon).

[Reference Example 1] (A-4) Production Example of Polylactic Acid Stereocomplex (Stereoblock Polylactic Acid) 100 parts by weight of L-lactide and 0.2 parts by weight of ethylene glycol were added to a nitrogen atmosphere in a reaction vessel equipped with a stirrer. Then, after uniformly dissolving at 170 ° C., 0.01 part by weight of tin octylate was added, followed by polymerization reaction for 2 hours. After completion of the polymerization reaction, the reaction product was dissolved in chloroform and precipitated with stirring in methanol (5 times the amount of chloroform) to completely remove the monomer, and poly-L-lactic acid (P11 having a weight average molecular weight of 40,000). ) The weight average molecular weight of P11 was 50,000.

  Next, 100 parts by weight of the obtained P11 was dissolved in a reaction vessel equipped with a stirrer at 200 ° C. in a nitrogen atmosphere, and then 120 parts by weight of D-lactide was added, and tin octylate 0.01 A part by weight was added and the polymerization reaction was carried out for 3 hours. After completion of the polymerization reaction, the reaction product was dissolved in chloroform, precipitated with stirring in methanol (5 times the amount of chloroform), the monomer was completely removed, and P11 comprising L-lactic acid units was converted into D11 from D-lactic acid units. A stereoblock polylactic acid (P12) having 3 segments to which the following segments were bonded was obtained. P12 had a weight average molecular weight of 150,000 and a melting point of 210 ° C.

Reference Example 2 (B-1) Zinc phenylphosphonate Zinc nitrate hexahydrate 100 parts by weight was dissolved in 1000 parts by weight of water, and then 60 parts by weight of phenylphosphonic acid was dissolved in 600 parts by weight of water. Was added at a rate of 200 parts by weight / minute, and the mixture was stirred at 50 ° C. for 3 hours to be reacted. After the reaction, the precipitate was filtered, washed with 1000 parts by weight of water, and dried at 90 ° C. for 6 hours to obtain 50 parts by weight of zinc phenylphosphonate.

[Reference Example 3] (B-2) Copper phenylphosphonate Copper aqueous solution in which 100 parts by weight of copper acetate monohydrate was dissolved in 1500 parts by weight of water and then 95 parts by weight of phenylphosphonic acid was dissolved in 900 parts by weight of water. Was added at a rate of 300 parts by weight / minute, and the mixture was stirred at 50 ° C. for 3 hours to be reacted. After the reaction, the precipitate was filtered, washed with 1000 parts by weight of water, and dried at 90 ° C. for 6 hours to obtain 100 parts by weight of copper phenylphosphonate.

[Reference Example 4] (B-3) Calcium phenylphosphonate An aqueous solution in which 100 parts by weight of calcium acetate monohydrate was dissolved in 1500 parts by weight of water and then 110 parts by weight of phenylphosphonic acid was dissolved in 1000 parts by weight of water. Was added at a rate of 300 parts by weight / minute, and the mixture was stirred at 50 ° C. for 3 hours to be reacted. After the reaction, the precipitate was filtered, washed with 1000 parts by weight of water, and dried at 90 ° C. for 6 hours to obtain 105 parts by weight of calcium phenylphosphonate.

[Reference Example 5] (D-5) Styrene resin 1
The preparation method of a styrene resin is shown below.

In a stainless steel autoclave having a capacity of 20 L and equipped with a baffle and a foudra-type stirring blade, 0.05 part by weight of methyl methacrylate / acrylamide copolymer (described in Japanese Patent Publication No. 45-24151) is added to 165 parts by weight of ion-exchanged water. The dissolved solution was added and stirred at 400 rpm, and the system was replaced with nitrogen gas. Next, the following mixed substances were added with stirring in the reaction system, and the temperature was raised to 60 ° C. to initiate polymerization.
Styrene 70 parts by weight Acrylonitrile 30 parts by weight t-dodecyl mercaptan 0.2 parts by weight 2,2′-azobisisobutyronitrile 0.4 parts by weight

  After raising the reaction temperature to 65 ° C. over 30 minutes, the temperature was raised to 100 ° C. over 120 minutes. Thereafter, the reaction system was cooled, the polymer was separated, washed, and dried according to the usual method to obtain a bead-shaped polymer. The intrinsic viscosity of the methyl ethyl ketone soluble part of the obtained styrene-based resin was 0.53 dl / g. In addition, the intrinsic viscosity of the obtained polymer was measured by using a Ubbelohde viscometer under a temperature condition of 30 ° C. after preparing a methyl ethyl ketone solution having a concentration of 0.4 g / 100 ml after drying under reduced pressure at 70 ° C. for 5 hours.

[Reference Example 6] (D-9) Graft polymer 1
The method for preparing the graft copolymer is shown below.
Polybutadiene (weight average particle size 0.35 μm) 50 parts by weight (Nipol LX111K, manufactured by Nippon Zeon Co., Ltd.) (solid content conversion)
Potassium oleate 0.5 parts by weight Glucose 0.5 parts by weight Sodium pyrophosphate 0.5 parts by weight Ferrous sulfate 0.005 parts by weight Deionized water 120 parts by weight.

The above substances were charged into a polymerization vessel and heated to 65 ° C. with stirring. The polymerization was started when the internal temperature reached 65 ° C., and 35 parts by weight of methyl methacrylate, 12.5 parts by weight of styrene, 2.5 parts by weight of acrylonitrile, and 0.3 parts by weight of t-dodecyl mercaptan were taken over 5 hours. Continuous dripping. In parallel, an aqueous solution consisting of 0.25 parts by weight of cumene hydroperoxide, 2.5 parts by weight of potassium oleate and 25 parts by weight of pure water was continuously added dropwise over 7 hours to complete the reaction. The obtained graft copolymer latex was coagulated with sulfuric acid, neutralized with caustic soda, washed, filtered and dried to obtain a powder. The graft ratio of the obtained graft copolymer was 40%, and the intrinsic viscosity of methyl ethyl ketone-soluble component was 0.30 dl / g. The graft rate is determined by the following method. Acetone was added to a predetermined amount (m) of the graft copolymer and refluxed for 4 hours. This solution was centrifuged at 8000 rpm (centrifugal force 10,000 G (about 100 × 10 3 m / s 2)) for 30 minutes, and the insoluble matter was filtered off. This insoluble matter was dried under reduced pressure at 70 ° C. for 5 hours, and the weight (n) was measured.
Graft ratio = [(n) − (m) × L] / [(m) × L] × 100
Here, L means the rubber content of the graft copolymer.

  The filtrate of the acetone solution was concentrated with a rotary evaporator to obtain a precipitate (acetone soluble matter). Further, the soluble matter was dried under reduced pressure at 70 ° C. for 5 hours, and then a methyl ethyl ketone solution having a concentration of 0.4 g / 100 ml was prepared, and the intrinsic viscosity was measured using an Ubbelohde viscometer under a temperature condition of 30 ° C.

(1) Formability When a tensile test piece that can be subjected to a tensile test is taken out from the mold, the shortest time for obtaining a solid molded product without deformation was measured as a molding cycle time. It can be said that the shorter the molding cycle time, the better the moldability.

(2) Heat resistance (DTUL)
According to ASTM D648, the deflection temperature under load (load 0.45 MPa) of a molded article of 12.7 mm × 127 mm × 3 mm was measured.

(3) Impact resistance (Izod impact strength)
In accordance with ASTM D256, the Izod impact strength of a 3 mm thick notched strip-shaped product was measured.

(4) Tensile strength and elongation at break A tensile test was conducted according to ASTM D638 using a 3 mm thick ASTM No. 1 dumbbell molded product.

(5) Hydrolysis resistance After the ASTM No. 1 dumbbell molded product was treated in a constant temperature and humidity chamber at 70 ° C. and a relative humidity of 95% for 100 hours, the tensile strength was measured, and the tensile strength retention rate [tensile strength after treatment] / Tensile strength before treatment × 100 (%)]. It can be said that the greater the tensile strength retention, the better the hydrolysis resistance.

(6) Flame retardance A 127mm x 12.7mm x 1.6mm combustion test piece is formed by injection molding, and conforms to the vertical combustion test method of the American UL standard subject 94 (UL94) described in the specification. A flame test was conducted to determine flame retardancy. Materials that did not pass the flame retardancy rank were out of specification.

[Examples 1-20, Comparative Examples 1-3]
As shown in Tables 1 and 2, the raw materials were blended and melt-kneaded under the conditions of a cylinder temperature of 200 ° C. and a rotation speed of 200 rpm using a 30 mm diameter twin screw extruder (TEX-30α manufactured by Nippon Steel) A composition was obtained.

  The obtained resin composition was injection-molded at an injection molding machine (SG75H-MIV manufactured by Sumitomo Heavy Industries, Ltd.) at a cylinder temperature of 200 ° C. and a mold temperature of 90 ° C. to obtain molded products for various evaluations.

  Tables 1 and 2 show the results of various evaluations using the obtained molded product.

  From the results of Tables 1 and 2, it can be seen that the resin composition of the present invention and a molded product comprising the resin composition are excellent in moldability and heat resistance, and in a preferred embodiment, are excellent in impact resistance or mechanical properties.

[Examples 21 to 56]
As shown in Table 3, Table 4 and Table 5, the raw materials were blended, and melt kneading was performed using a 30 mm diameter twin screw extruder (TEX-30α manufactured by Nippon Steel) under conditions of a cylinder temperature of 230 ° C. and a rotation speed of 200 rpm. And a resin composition was obtained.

  The obtained resin composition was injection-molded at an injection molding machine (SG75H-MIV manufactured by Sumitomo Heavy Industries, Ltd.) at a cylinder temperature of 230 ° C. and a mold temperature of 90 ° C. to obtain molded products for various evaluations.

  Tables 3, 4 and 5 show the results of various evaluations using the obtained molded product.

  From the results of Table 3, Table 4 and Table 5, the resin composition of the present invention and the molded article comprising the resin composition are excellent in moldability and heat resistance, and in a preferred embodiment, excellent in impact resistance, mechanical properties or durability. I understand that.

[Examples 57 to 69]
As shown in Table 6, the raw materials were blended and melt-kneaded using a 30 mm diameter twin screw extruder (TEX-30α manufactured by Nippon Steel Works) at a cylinder temperature of 240 ° C. and a rotation speed of 150 rpm to obtain a resin composition. It was.

  The obtained resin composition was injection-molded at an injection molding machine (SG75H-MIV manufactured by Sumitomo Heavy Industries, Ltd.) at a cylinder temperature of 240 ° C. and a mold temperature of 90 ° C. to obtain molded products for various evaluations.

  Table 6 shows the results of various evaluations using the obtained molded product.

  From the results of Table 6, it can be seen that the resin composition of the present invention and a molded product made thereof are excellent in moldability and heat resistance, and in a preferred embodiment, are excellent in impact resistance, mechanical properties, durability or flame retardancy. .

Claims (9)

(A) With respect to 100 parts by weight of the polylactic acid resin, (B) with respect to a resin composition formed by blending 0.05 to 30 parts by weight of a phosphonic acid metal salt having an aromatic ring, (C) a crystallization accelerator, (D) A thermoplastic resin other than polylactic acid resin, (E) a filler, (F) a stabilizer, (G) a mold release agent, and (H) a reactive endblocker are blended. Resin composition. The resin composition according to claim 1, wherein the (C) crystallization accelerator is a plasticizer. The thermoplastic resin other than (D) polylactic acid resin is at least one selected from polyacetal resin, polyester resin other than polylactic acid resin, polycarbonate resin, polyamide resin, polypropylene resin, and styrene resin. The resin composition according to any one of the above. The resin composition according to any one of claims 1 to 3, wherein the (E) filler is a fibrous inorganic filler and / or a plate-like inorganic filler. The resin composition according to any one of claims 1 to 4, wherein the (F) stabilizer is a hindered phenol compound and / or a benzotriazole compound. The resin composition according to claim 1, wherein the release agent (G) is a fatty acid partial saponified ester and / or an alkylene bis fatty acid amide. The resin composition according to claim 1, wherein the (H) reactive end-capping agent is an epoxy compound and / or a carbodiimide compound. Furthermore, the resin composition of any one of Claims 1-7 formed by mix | blending (I) a flame retardant. The molded article which consists of a resin composition of any one of Claims 1-8.