JP2009270090A - Polylactic acid resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polylactic acid resin composition having a good crystallization rate and excellent flame retardancy.
SOLUTION: A polylactic acid resin composition containing a polylactic acid resin, a plasticizer, a crystal nucleating agent, and a phosphorus-based flame retardant excluding phenylphosphonic acid metal salt, wherein the plasticizer has two or more esters in the molecule. A compound in which at least one of the alcohol components constituting the ester is an average of 0.5 to 5 moles of an alkylene oxide having 2 to 3 carbon atoms per hydroxyl group, and the crystal nucleating agent is in the molecule A crystal nucleating agent (1) selected from a compound having a hydroxyl group and an amide group, a metal salt of phenylphosphonic acid, a metal salt of an aromatic sulfonic acid dialkyl ester, a metal salt of a rosin acid, an aromatic carboxylic acid amide, a rosin acid amide, A polylactic acid resin composition which is a mixture of a crystal nucleating agent (2) selected from carbohydrazides, N-substituted ureas, salts of melamine compounds and uracils.
[Selection figure] None

Description

  The present invention relates to a polylactic acid resin composition.

  General-purpose resins made from petroleum such as polypropylene and polyvinyl chloride are used in various fields such as household goods, household appliances, automobile parts, building materials, and food packaging because of their good processability and durability. Has been. However, these resin products have a disadvantage of good durability at the stage of finishing and discarding their functions, and are inferior in degradability in nature, and thus may affect the ecosystem.

  In order to solve such problems, thermoplastic resins and biodegradable resins include polylactic acid and copolymers of lactic acid and other aliphatic hydroxycarboxylic acids, aliphatic polyhydric alcohols and aliphatic polycarboxylic acids. Biodegradable resins, such as aliphatic polyesters, derived from benzene have been developed.

  Among these biodegradable resins, polylactic acid resin is made from a sugar produced from corn, straw, etc., and L-lactic acid is produced in large quantities by fermentation. As the performance of the resulting resin is very strong and transparent, it is expected to be used in the field of agricultural civil engineering materials such as flat yarn, nets and seedling pots, and envelopes with windows. Used for shopping bags, compost bags, stationery, miscellaneous goods, etc. However, in the case of polylactic acid resin, all are limited to the field of hard molded products because they are brittle, hard, and lack flexibility, and when molded into a film, it becomes insufficient in flexibility or whitens when bent. The current situation is that it is not widely spread in the soft or semi-rigid field.

  Various methods for adding a plasticizer have been proposed as techniques for applying polylactic acid resin to soft and semi-rigid fields. For example, a technique of adding a plasticizer such as tributyl acetylcitrate or diglycerin tetraacetate is disclosed. When these plasticizers are added to polylactic acid and a film or sheet is formed by extrusion or the like, good flexibility is obtained, but because the resin is in an amorphous state, flexibility due to temperature changes near the glass transition point is obtained. The property changes markedly (temperature sensitivity) and the heat resistance at high temperatures is insufficient, so that the physical properties change significantly depending on the season, making it difficult to use in a high temperature environment. In order to solve this problem, a method of improving the heat resistance and the like by crystallizing polylactic acid by adding a crystal nucleating agent such as talc (Patent Document 1) has been proposed. However, the crystallization rate due to heat treatment after molding is insufficient, and adding a large amount of crystal nucleating agent such as talc reduces the transparency of the sheet and film after thermoforming, and the molded product is plasticized when left under high temperature and high humidity. There was a problem that the agent bleeds.

  In order to solve these problems, Patent Document 2 discloses a polylactic acid resin containing an aliphatic compound having two or more groups selected from an ester group, a hydroxyl group and an amide group in the molecule as a crystal nucleating agent. A composition is disclosed. Patent Document 3 discloses a polylactic acid resin composition containing a metal salt of a phosphorus compound. However, these compositions are still not fully satisfactory in the crystallization rate, and further improvement of the crystallization rate is required. There is also a need for a polylactic acid resin composition having good flame retardancy.

Japanese Patent No. 3410075 JP 2006-176747 A International Publication No. 2005/097894

  An object of the present invention is to provide a polylactic acid resin composition having a good crystallization rate and excellent flame retardancy.

  The present invention relates to a polylactic acid resin composition containing a phosphorus-based flame retardant excluding a polylactic acid resin, a plasticizer, a crystal nucleating agent, and a phenylphosphonic acid metal salt, wherein the plasticizer has two or more esters in the molecule. And at least one alcohol component constituting the ester is a compound in which an average of 0.5 to 5 moles of alkylene oxide having 2 to 3 carbon atoms per hydroxyl group is added, and the crystal nucleating agent is the following crystal Provided is a polylactic acid resin composition which is a mixture of a nucleating agent (1) and a crystal nucleating agent (2).

Crystal nucleating agent (1): At least one crystal nucleating agent selected from compounds having a hydroxyl group and an amide group in the molecule (2): phenylphosphonic acid metal salt, metal salt of aromatic sulfonic acid dialkyl ester, metal of rosin acid At least one selected from the group consisting of salts, aromatic carboxylic acid amides, rosinic acid amides, carbohydrazides, N-substituted ureas, salts of melamine compounds and uracils

  The polylactic acid resin composition of the present invention has a good crystallization rate, excellent moldability at a low mold temperature, and good flame retardancy.

[Polylactic acid resin]
The polylactic acid resin used in the present invention has biodegradability based on JIS K6953 (ISO 14855) "Aerobic and ultimate biodegradability and disintegration tests under controlled aerobic compost conditions". Polylactic acid resin is preferred.

  The polylactic acid resin used in the present invention is not particularly limited as long as it has a biodegradability capable of being decomposed into a low molecular weight compound due to microorganisms in nature.

  The polylactic acid resin is polylactic acid or a copolymer of lactic acid and hydroxycarboxylic acid. Examples of the hydroxycarboxylic acid include glycolic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxypentanoic acid, hydroxycaproic acid, hydroxyheptanoic acid and the like, and glycolic acid and hydroxycaproic acid are preferable. The molecular structure of polylactic acid is preferably composed of 80 to 100 mol% of either L-lactic acid or D-lactic acid and 0 to 20 mol% of each enantiomer. The copolymer of lactic acid and hydroxycarboxylic acid is composed of 85 to 100 mol% of either L-lactic acid or D-lactic acid and 0 to 15 mol% of hydroxycarboxylic acid units. These polylactic acid resins can be obtained by dehydrating polycondensation using L-lactic acid, D-lactic acid and hydroxycarboxylic acid as a raw material by selecting those having the required structure. Preferably, it can be obtained by ring-opening polymerization by selecting a desired structure from lactide, which is a cyclic dimer of lactic acid, glycolide, which is a cyclic dimer of glycolic acid, and caprolactone. Lactide includes L-lactide which is a cyclic dimer of L-lactic acid, D-lactide which is a cyclic dimer of D-lactic acid, meso-lactide obtained by cyclic dimerization of D-lactic acid and L-lactic acid, and D-lactide. There is DL-lactide, which is a racemic mixture of lactide and L-lactide. Any lactide can be used in the present invention. However, the main raw material is preferably D-lactide or L-lactide.

Further, in the present invention, as polylactic acid, two types obtained by using lactic acid components mainly composed of different isomers from the viewpoint of compatibility of strength and impact resistance of the resin composition, heat resistance, and transparency. Stereocomplex polylactic acid comprising polylactic acid may be used. One polylactic acid constituting the stereocomplex polylactic acid (hereinafter referred to as polylactic acid (A)) contains 90 to 100 mol% of L isomer and 0 to 10 mol% of other components including D isomer. The other polylactic acid (hereinafter referred to as polylactic acid (B)) contains 90 to 100 mol% of D isomer and 0 to 10 mol% of other components including L isomer. In addition, as other components other than L-form and D-form, dicarboxylic acid, polyhydric alcohol, hydroxycarboxylic acid, lactone, etc. having a functional group capable of forming two or more ester bonds are exemplified, and unreacted Polyester, polyether, polycarbonate or the like having two or more of the functional groups in the molecule may be used.
In the stereocomplex polylactic acid, the weight ratio of polylactic acid (A) to polylactic acid (B) [polylactic acid (A) / polylactic acid (B)] is preferably 10/90 to 90/10, and 20/80 to 80 / 20 is more preferable, and 40/60 to 60/40 is more preferable.

The weight average molecular weight of the polylactic acid resin is preferably 100,000 or more from the viewpoint of mechanical properties of the molded body, and preferably 400,000 or less from the viewpoint of fluidity during molding.
The weight average molecular weight of the polylactic acid resin was measured using a gel permeation chromatograph (GPC), chloroform as a solvent, a high-temperature SEC column (GMHHR-H series) manufactured by Tosoh Corporation, a flow rate of 1.0 mL / min, It can be obtained by conversion using a column temperature of 40 ° C., a differential refractive index detector (RI) as a detector, and styrene having a known molecular weight as a reference.

  Examples of commercially available polylactic acid resins include DuPont, trade name Biomax; BASF, trade name Ecoflex; Eastman Chemicals, trade name EsterBio; Showa Polymer Co., Ltd., trade name Bionor; Japan Made by Synthetic Chemical Industry Co., Ltd., trade name: Matterby; Toyota Motor Corporation, trade name: Eco Plastic U'z; Mitsui Chemicals Co., Ltd., trade name: Lacia; Nippon Shokubai Co., Ltd., trade name: Lunare; Chisso Product name Novon, manufactured by Nature Works, Inc., product name Nature works, and the like.

  Among these, preferably, Mitsui Chemicals, Inc., trade name Lacia; Toyota Motor Corporation, trade name Eco Plastic U'z; Nature Works, trade name Nature works, and the like.

[Plasticizer]
The plasticizer used in the present invention has two or more ester groups in the molecule from the viewpoint of plasticization efficiency, and at least one alcohol component constituting the ester has 2 to 3 carbon atoms per hydroxyl group. An average compound of 0.5 to 5 moles of alkylene oxide, having 2 or more ester groups in the molecule, and average of 2 to 3 carbon atoms per hydroxyl group of the alcohol component constituting the ester A compound with 0.5 to 5 mol added is preferable, and a polyhydric alcohol ester or a polycarboxylic acid ether ester having two or more ester groups in the molecule, and ethylene oxide per one hydroxyl group of an alcohol component constituting the ester. A compound with an average addition of 0.5 to 5 mol is more preferred. The alcohol component constituting the ester is preferably an average of 1 to 4 moles of alkylene oxide having 2 to 3 carbon atoms, more preferably 2 to 3 in view of compatibility with polylactic acid resin, plasticization efficiency, and volatile resistance. This is a compound with a molar addition. In view of plasticizing efficiency, the alkylene oxide is preferably ethylene oxide. From the viewpoint of compatibility, the carbon number of hydrocarbon groups such as alkyl groups and alkylene groups contained in the plasticizer, for example, the carbon number of the hydrocarbon group of the polyhydric alcohol or polycarboxylic acid constituting the ester compound is 1-8. Are preferable, 1-6 are more preferable, and 1-4 are more preferable. Moreover, 1-8 are preferable from a compatible viewpoint, as for carbon number of the monocarboxylic acid and monoalcohol which comprise the ester compound of a plasticizer, 1-6 are more preferable, 1-4 are more preferable, and 1-2 are further. More preferred.

  The method for producing the plasticizer used in the present invention is not particularly limited. For example, when the plasticizer used in the present invention is a polyvalent carboxylic acid ether ester, an acid catalyst such as paratoluenesulfonic acid monohydrate or sulfuric acid. Or a saturated dibasic acid having 3 to 5 carbon atoms or an anhydride thereof and a polyalkylene glycol monoalkyl ether in the presence of a metal catalyst such as dibutyltin oxide, or a saturated dibasic acid having 3 to 5 carbon atoms. It can be obtained by transesterification of a lower alkyl ester of a basic acid and a polyalkylene glycol monoalkyl ether. Specifically, for example, polyethylene glycol monoalkyl ether, saturated dibasic acid, and paratoluenesulfonic acid monohydrate as a catalyst, polyethylene glycol monoalkyl ether / saturated dibasic acid / paratoluenesulfonic acid monohydrate. (Molar ratio) = 2 to 4/1 / 0.001 to 0.05, charged in a reaction vessel, in the presence or absence of a solvent such as toluene, at normal pressure or reduced pressure, temperature 100 to 130 It can be obtained by performing dehydration at 0 ° C. A method of performing the reaction under reduced pressure without using a solvent is preferred.

  In the case where the plasticizer used in the present invention is a polyhydric alcohol ester, for example, an alkylene oxide having a carbon number of 2 to 3 at a temperature of 120 to 160 ° C. is used in glycerol with an autoclave in the presence of an alkali metal catalyst. 3 to 9 moles are added. Then, 3 mol of acetic anhydride is added dropwise at 110 ° C. to 1 mol of the glycerin alkylene oxide adduct obtained, and aging is carried out at 110 ° C. for 2 hours after the completion of the addition. The product can be obtained by performing steam distillation under reduced pressure to distill off the acetic acid and unreacted acetic anhydride.

  Further, when the plasticizer used in the present invention is a hydroxycarboxylic acid ether ester, an alkylene oxide having a carbon number of 2 to 3 at a temperature of 120 to 160 ° C. using an autoclave in the presence of an alkali metal catalyst in a hydroxycarboxylic acid such as lactic acid. Is added in an amount of 2 to 5 mol per mol of hydroxycarboxylic acid. Then, 1 mol of acetic anhydride is added dropwise at 110 ° C. to 1 mol of the obtained lactate alkylene oxide adduct, and after completion of the addition, aging is performed at 110 ° C. for 2 hours to perform acetylation. The product is subjected to steam distillation under reduced pressure to distill off the acetic acid and unreacted acetic anhydride. Next, the reaction vessel was charged so that the product / polyalkylene glycol monoalkyl ether / paratoluenesulfonic acid monohydrate (catalyst) (molar ratio) = 1/1 to 2 / 0.001 to 0.05 It can be obtained by performing dehydration at a temperature of 100 to 130 ° C. under normal pressure or reduced pressure in the presence or absence of a solvent such as toluene.

  If the plasticizer used in the present invention has two or more ester groups in the molecule, it is excellent in compatibility with the polylactic acid resin and preferably has 2 to 4 ester groups in the molecule. . Moreover, if at least one of the alcohol components constituting the ester has an average of 0.5 mol or more of alkylene oxide having 2 to 3 carbon atoms per hydroxyl group, sufficient plasticity is imparted to the polylactic acid resin. If an average of 5 moles or less is added, the effect of bleeding resistance is improved. Although not certain, the plasticizer used in the present invention has good moldability when used in combination with a polylactic acid resin having an optical purity of 99% or higher, and exhibits excellent moldability, particularly at a low mold temperature. it can.

  The plasticizer used in the present invention is preferably a compound having 2 or more ester groups in the molecule and an average added mole number of ethylene oxide of 3 to 9, from the viewpoint of moldability, plasticity, and bleed resistance. More preferred is at least one selected from the group consisting of an ester of succinic acid or adipic acid and polyethylene glycol monomethyl ether, and an ester of acetic acid and glycerin or an ethylene oxide adduct of ethylene glycol. Succinic acid or adipic acid and polyethylene glycol are more preferred. More preferred are esters with monomethyl ether.

  Further, from the viewpoint of volatility resistance, an average of 0 to 1.5 of the two or more ester groups in the plasticizer used in the present invention may contain an ester group composed of an aromatic alcohol. Since the aromatic alcohol is more compatible with the polylactic acid resin than the aliphatic alcohol having the same carbon number, the molecular weight can be increased while maintaining the bleed resistance. From the viewpoint of plasticizing efficiency, an average of 0 to 1.2, more preferably 0 to 1 is an ester group composed of an aromatic alcohol. Examples of the aromatic alcohol include benzyl alcohol, and examples of the plasticizer include adipic acid and diethylene glycol monomethyl ether / benzyl alcohol = 1/1 mixed diester.

The average molecular weight of the plasticizer used in the present invention is preferably from 250 to 700, more preferably from 300 to 600, still more preferably from 350 to 550, particularly preferably from the viewpoint of bleed resistance and volatile resistance. Is 400-500. The average molecular weight can be obtained by calculating the saponification value by the method described in JIS K0070 and calculating from the following formula.
Average molecular weight = 56108 × (number of ester groups) / saponification value

  As a plasticizer used in the present invention, from the viewpoint of excellent moldability and impact resistance of the polylactic acid resin composition, an ester of acetic acid and glycerol with an average 3 to 9 mol of ethylene oxide adduct, propylene of acetic acid and diglycerol Alkyl ether esters of polyhydric alcohols such as esters with average oxides of 4 to 12 moles of adduct, esters of acetic acid and ethylene glycol with polyethylene glycol having an average number of moles of addition of 4 to 9, and average addition moles of succinic acid and ethylene oxide Esters of polyethylene glycol monomethyl ether having 2 to 4 numbers, esters of polyethylene glycol monomethyl ether having an average addition mole number of adipic acid and ethylene oxide of 2,3,6-hexanetricarboxylic acid and ethylene oxide The average added mole number is 2-3 Esters of polyvalent carboxylic acids and polyethylene glycol monomethyl ethers such as esters of ethylene glycol monomethyl ether is more preferable. From the viewpoint of excellent moldability, impact resistance and bleed resistance of the plasticizer of the polylactic acid resin composition, an ester of acetic acid and glycerin with an average of 3 to 6 moles of ethylene oxide adduct, an average number of moles of acetic acid and ethylene oxide to be added Is an ester of polyethylene glycol of 4-6, an ester of polyethylene glycol monomethyl ether having an average addition mole number of succinic acid and ethylene oxide of 2-3, an ester of adipic acid and diethylene glycol monomethyl ether, 1,3,6- More preferred are esters of hexanetricarboxylic acid and diethylene glycol monomethyl ether. From the viewpoint of moldability, impact resistance of the polylactic acid resin composition, bleed resistance of the plasticizer, volatilization resistance and irritating odor, an ester of succinic acid and triethylene glycol monomethyl ether is particularly preferable.

  In addition, it is preferable that the ester of this invention is all the esterified saturated ester from a viewpoint of fully exhibiting the function as a plasticizer.

  The reason why the effect of the present invention is improved by a specific plasticizer is not clear, but the plasticizer has two or more ester groups in the molecule, and at least one alcohol component constituting the ester is a hydroxyl group 1. A compound obtained by adding an average of 0.5 to 5 moles of alkylene oxide having 2 to 3 carbon atoms per unit, preferably a polysiloxane having 2 or more ester groups in the molecule and an average added mole number of ethylene oxide of 3 to 9 When it is a compound having an oxyethylene chain (having preferably a methyl group, and preferably having two or more), its heat resistance and compatibility with a polylactic acid resin are improved. Therefore, the bleed resistance is improved and the softening effect of the polylactic acid resin is also improved. It is considered that when the polylactic acid resin is crystallized, the growth rate is also improved by improving the softening of the polylactic acid resin. As a result, since the polylactic acid resin retains flexibility even at a low mold temperature, crystallization of the polylactic acid resin proceeds in a short mold holding time, and good moldability is expected.

[Crystal nucleating agent]
The crystal nucleating agent of the present invention is a mixture of the crystal nucleating agent (1) and the crystal nucleating agent (2). In the present invention, the crystal nucleating agent (1) is preferably an aliphatic amide having a hydroxyl group from the viewpoint of improving the crystallization speed and compatibility with the polylactic acid resin, and has two or more hydroxyl groups in the molecule. An aliphatic amide having two or more groups is more preferable. The melting point of the crystal nucleating agent (1) is preferably 65 ° C. or higher, more preferably 70 to 220 ° C., from the viewpoint of improving the dispersibility of the crystal nucleating agent during kneading and improving the crystallization speed. -190 degreeC is still more preferable.

  Specific examples of the crystal nucleating agent (1) include hydroxy fatty acid monoamides such as 12-hydroxy stearic acid monoethanolamide, methylene bis 12-hydroxy stearic acid amide, ethylene bis 12-hydroxy stearic acid amide, hexamethylene bis 12-hydroxy stearic acid. And hydroxy fatty acid bisamides such as acid amides. From the viewpoint of moldability, heat resistance, impact resistance, and bloom resistance of the polylactic acid resin composition, alkylene bishydroxystearic acid amides such as ethylene bis 12-hydroxystearic acid amide and hexamethylene bis 12-hydroxystearic acid amide are used. Preferably, ethylene bis 12-hydroxystearic acid amide is more preferable.

  Specific examples of the crystal nucleating agent (2) used in the present invention include phenylphosphonic acid metal salts such as phenylphosphonic acid zinc salt; aroma such as dimethyldibarium 5-sulfoisophthalate and dimethyldicalcium 5-sulfoisophthalate. Metal salts of sulfonic acid dialkyl esters; metal salts of rosin acids such as potassium methyldehydroabietic acid; trimesic acid tris (t-butylamide), m-xylylenebis-12-hydroxystearic acid amide, 1,3,5-benzenetricarboxylic acid Aromatic carboxylic acid amides such as tricyclohexylamide; rosinic acid amides such as p-xylylenebisrosinic acid amide; carbohydrazides such as decamethylenedicarbonyldibenzoylhydrazide; N-substituted ureas such as xylenebisstearylurea; Such as melamine cyanurate Salts of Ramin compound; uracils, such as 6-methyl uracil can be mentioned.

Among the crystal nucleating agents (2) used in the present invention, phenylphosphonic acid metal salts are preferable from the viewpoint of crystallization speed. The metal salt of phenylphosphonic acid is a metal salt of phenylphosphonic acid having a phenyl group which may have a substituent and a phosphonic group (—PO (OH) ₂ ). -10 alkyl groups, alkoxycarbonyl groups having 1 to 10 carbon atoms, and the like. Specific examples of phenylphosphonic acid include unsubstituted phenylphosphonic acid, methylphenylphosphonic acid, ethylphenylphosphonic acid, propylphenylphosphonic acid, butylphenylphosphonic acid, dimethoxycarbonylphenylphosphonic acid, and diethoxycarbonylphenylphosphonic acid. And unsubstituted phenylphosphonic acid is preferred.

  Examples of the metal salt of phenylphosphonic acid include salts of lithium, sodium, magnesium, aluminum, potassium, calcium, barium, copper, zinc, iron, cobalt, nickel, and the like, and zinc salts are preferable.

  In the present invention, the ratio between the crystal nucleating agent (1) and the crystal nucleating agent (2) used as the crystal nucleating agent is the crystal nucleating agent (1) / crystal nucleating agent (2) from the viewpoint of expressing the effects of the present invention. (Weight ratio) = 20/80 to 80/20 is preferable, 30/70 to 70/30 is more preferable, and 40/60 to 60/40 is still more preferable.

  The polylactic acid resin composition of the present invention has a special effect that the crystallization rate is good and the flame retardancy is excellent. The reason why the excellent effect of the present invention can be manifested is not clear, but in the presence of a specific plasticizer, the crystal nucleating agent (1) is dissolved during the melt-kneading of the polylactic acid resin composition, and in the cooling step during molding. From the point that a large number of crystal nuclei can be generated and because the crystal nucleating agent (2) has a metal ion, an amide group, an NH group, etc. in the compound, the interaction (adsorption) with the polylactic acid resin is excellent. Synergistically, the crystallization rate of the present invention is good, and it is considered that a special effect of excellent flame retardancy is exhibited.

[Phosphorus flame retardant excluding phenylphosphonic acid metal salts]
As the phosphorus-based flame retardant excluding the phenylphosphonic acid metal salt used in the present invention, from the viewpoint of improving the flame retardancy of the polylactic acid resin composition, phosphate ester, condensed phosphate ester, phosphate salt and condensed phosphoric acid At least one selected from salts is preferred.

  Examples of phosphate esters 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, diphenyl-2-a Liloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, triphenylphosphine oxide, tricresylphosphine oxide, diphenyl methanephosphonate, diethyl phenylphosphonate, resilcinol bis (Diphenyl phosphate), bisphenol A bis (diphenyl phosphate), phosphaphenanthrene and the like can be mentioned. From the viewpoint of improving flame retardancy, triphenyl phosphate and tris (isopropylphenyl) phosphate are preferred.

  Examples of the condensed phosphate ester include trialkyl polyphosphate, resorcinol polyphenyl phosphate, resorcinol poly (di-2,6-xylyl) phosphate, bisphenol A polycresyl phosphate, hydroquinone poly (2,6-xylyl) phosphate, and their A condensed phosphate ester such as a condensate can be mentioned, and resorcinol poly (di-2,6-xylyl) phosphate is preferable from the viewpoint of improving flame retardancy. Examples of commercially available condensed phosphate esters include PX-200 (resorcinol poly (di-2,6-xylyl) phosphate), PX-201 (aromatic condensed phosphate ester), and PX-202 (fragrance) manufactured by Daihachi Chemical Industry. Group condensed phosphate ester), CR-733S (resorcinol polyphenyl phosphate), CR-741 (bisphenol A polycresyl phosphate), CR747 (aromatic condensed phosphate ester), ADEKA ADK STAB PFR (resorcinol polyphenyl phosphate), FP-500 (resorcinol poly (di-2,6-xylyl) phosphate), FP-600 (bisphenol A polycresyl phosphate), FP-700 (bisphenol A polycresyl phosphate), etc. 200, P -201, PX-202 is preferred.

  Examples of phosphates and condensed phosphates include phosphoric acid and / or polyphosphoric acid and at least one metal selected from Group IA to Group IVB metals, ammonia, aliphatic amines, and aromatic amines, or Mention may be made of phosphates and polyphosphates consisting of salts with compounds. Examples of metals in groups IA to IVB of the periodic table include lithium, sodium, calcium, barium, iron (II), iron (III), and aluminum. Examples of aliphatic amines include methylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, Piperazine and the like can be mentioned, and examples of the aromatic amine include pyridine, triazine, melamine and ammonium. Among these, from the viewpoint of improving the flame retardancy, phosphates, polyphosphates, phosphoruss composed of salts of phosphoric acid and / or polyphosphoric acid and metals of group IA to IVB and / or piperazine in the periodic table. A mixture (phosphate complex) of a phosphate and a polyphosphate composed of a salt of an acid and / or polyphosphoric acid and a metal of group IA to IVB of the periodic table and / or piperazine is preferable. Examples of commercially available phosphates and polyphosphates include Taiyen N (ammonium phosphate), Taien L (ammonium polyphosphate), Taien E (aluminum phosphate), Taien S (polyammonium amide), Thaien H (aluminum phosphate), Clariant Clariant AP475 (ammonium polyphosphate complex), Clariant AP750 (ammonium polyphosphate complex), Clariant 1312 (ammonium polyphosphate complex), Clariant 1250 (metal phosphate metal salt), FP-2100 (ADEKA) Phosphate complex), FP-2100J (phosphate complex), FP-2200 (phosphate complex), Suzuhiro Kagaku FCP730 (ammonium polyphosphate complex), Budenheim's BU DIT3167 (ammonium polyphosphate complex), N-6ME (Nitrotris (methylene) phosphonic acid 6-melamine salt) manufactured by Nippon Chemical Industry, PHOSMEL-200 (melamine polyphosphate) manufactured by Nissan Chemical Industries, etc., and FP-2100 manufactured by ADEKA FP-2100J, FP-2200, and PHOSMEL-200 manufactured by Nissan Chemical Industries are preferred.

  Furthermore, in the present invention, from the viewpoint of preventing the drip of the polylactic acid resin composition, for example, a thermosetting resin such as a fluororesin or a phenol resin can be used as the anti-drip agent. Examples of the fluororesin include tetrafluoroethylene, chlorotrifluoroethylene, vinylidene fluoride, hexafluoropropylene, perfluoroalkyl vinyl ether and other fluorine-containing monomers, or copolymers; the above fluorine-containing monomers, ethylene, propylene, (meta ) Copolymers with copolymerizable monomers such as acrylates are included. These anti-drip agents may be used alone or in combination of two or more.

[Polylactic acid resin composition]
The polylactic acid resin composition of the present invention is a polylactic acid resin, an alkylene oxide having 2 or more ester groups in the molecule, and at least one alcohol component constituting the ester having 2 to 3 carbon atoms per hydroxyl group Is a compound in which 0.5 to 5 moles of an average is added, preferably a polyhydric alcohol ester or polycarboxylic acid ether ester having two or more ester groups in the molecule, and ethylene per hydroxyl group of the alcohol component constituting the ester. A compound obtained by adding an average of 0.5 to 5 moles of oxide, more preferably a plasticizer comprising a compound having 2 or more ester groups in the molecule and an average added mole number of ethylene oxide of 3 to 9, and the above crystal nucleus Crystal nucleating agent comprising a mixture of agent (1) and crystal nucleating agent (2), preferably phenylphosphonic acid metal salt, and phenylphosphonic acid metal salt Those containing phosphorus-based flame retardant, excluding. As a particularly preferred combination of a polylactic acid resin, a plasticizer, a crystal nucleating agent, and a phosphorus-based flame retardant excluding a metal salt of phenylphosphonic acid in the polylactic acid resin composition of the present invention, the plasticizer is succinic acid and triethylene glycol monomethyl ether. The ester, the crystal nucleating agent is a mixture of ethylene bis 12-hydroxystearic acid amide and phenylphosphonic acid zinc salt, and the phosphorus flame retardant excluding the phenylphosphonic acid metal salt is phosphate.

  The content of the polylactic acid resin in the polylactic acid resin composition of the present invention is preferably 50% by weight or more, more preferably 70% by weight or more from the viewpoint of achieving the object of the present invention.

  The content of the plasticizer in the polylactic acid resin composition of the present invention is preferably 5 to 30 parts by weight with respect to 100 parts by weight of the polylactic acid resin from the viewpoint of obtaining a sufficient crystallization speed and impact resistance, and 7 to 30. More preferred is 10 parts by weight and even more preferred.

  The content of the crystal nucleating agent (1) in the polylactic acid resin composition of the present invention is preferably 0.1 to 3 parts by weight with respect to 100 parts by weight of the polylactic acid resin from the viewpoint of manifesting the effects of the present invention. 0.1 to 2 parts by weight is more preferable, and 0.2 to 2 parts by weight is particularly preferable.

  The content of the crystal nucleating agent (2) in the polylactic acid resin composition of the present invention is preferably 0.1 to 3 parts by weight with respect to 100 parts by weight of the polylactic acid resin, from the viewpoint of manifesting the effects of the present invention. The amount is more preferably 1 to 2 parts by weight, and particularly preferably 0.2 to 2 parts by weight.

  In the polylactic acid resin composition of the present invention, the content of the phosphorus-based flame retardant excluding the metal salt of phenylphosphonic acid is preferably 5 to 40 parts by weight with respect to 100 parts by weight of the polylactic acid resin from the viewpoint of manifesting the effects of the present invention. 10 to 35 parts by weight is more preferable, and 12 to 30 parts by weight is particularly preferable.

  The polylactic acid resin composition of the present invention can further contain a hydrolysis inhibitor in addition to the phosphorus-based flame retardant excluding the plasticizer, crystal nucleating agent and phenylphosphonic acid metal salt of the present invention. Examples of the hydrolysis inhibitor include carbodiimide compounds such as polycarbodiimide compounds and monocarbodiimide compounds. Polycarbodiimide compounds are preferable from the viewpoint of moldability of the polylactic acid resin composition, and the heat resistance and impact resistance of the polylactic acid resin composition. Monocarbodiimide compounds are preferred from the viewpoints of the properties and the bloom resistance of the crystal nucleating agent.

  Examples of the polycarbodiimide compound include poly (4,4′-diphenylmethanecarbodiimide), poly (4,4′-dicyclohexylmethanecarbodiimide), poly (1,3,5-triisopropylbenzene) polycarbodiimide, and poly (1,3,5). -Triisopropylbenzene and 1,5-diisopropylbenzene) polycarbodiimide and the like, and examples of the monocarbodiimide compound include N, N'-di-2,6-diisopropylphenylcarbodiimide.

  The carbodiimide compounds may be used alone or in combination of two or more in order to satisfy the moldability, heat resistance, impact resistance and bloom resistance of the crystal nucleating agent of the polylactic acid resin composition. Poly (4,4′-dicyclohexylmethanecarbodiimide) is obtained from carbodilite LA-1 (Nisshinbo Co., Ltd.), poly (1,3,5-triisopropylbenzene) polycarbodiimide and poly (1,3,5). -Triisopropylbenzene and 1,5-diisopropylbenzene) polycarbodiimide is stabuxol P and stabuxol P-100 (Rhein Chemie), N, N'-di-2,6-diisopropylphenylcarbodiimide is stabuxol I and stabuxol I LF (manufactured by Rhein Chemie) can be purchased and used.

  From the viewpoint of moldability of the polylactic acid resin composition, the content of the hydrolysis inhibitor in the polylactic acid resin composition of the present invention is preferably 0.05 to 3 parts by weight with respect to 100 parts by weight of the polylactic acid resin. More preferably, it is 1 to 2 parts by weight.

  The polylactic acid resin composition of the present invention preferably further contains an inorganic filler from the viewpoint of improving physical properties such as rigidity. As the inorganic filler used in the present invention, fibers, plates, granules, and powders that are usually used for reinforcing 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, glass flakes, non-swellable mica, swellable mica, graphite, metal foil , Ceramic beads, talc, clay, mica, sericite, zeolite, bentonite, organic modified bentonite, organic modified montmorillonite, dolomite, kaolin, fine powder silicic acid, feldspar powder, potassium titanate, shirasu balloon, calcium carbonate Magnesium carbonate, barium sulfate, calcium oxide, aluminum oxide, titanium oxide, aluminum silicate, silicon oxide, gypsum, novaculite, include plate-like or granular inorganic fillers such as dawsonite and white clay. Among these inorganic fillers, carbon fiber, glass fiber, wollastonite, mica, talc and kaolin are particularly preferable. The aspect ratio of the fibrous filler is preferably 5 or more, more preferably 10 or more, and further preferably 20 or more.

  The inorganic 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 a coupling agent such as aminosilane or epoxysilane. May be processed. Moreover, 1-100 weight part is preferable with respect to 100 weight part of polylactic acid resin, and, as for the compounding quantity of an inorganic filler, 5-50 weight part is more preferable.

  The polylactic acid resin composition of the present invention can further contain a flame retardant other than the phosphorus-based flame retardant except the phenylphosphonic acid metal salt. Specific examples of flame retardants other than phosphorus flame retardants include halogen compounds containing bromine or chlorine, antimony compounds such as antimony trioxide, inorganic hydrates (metal water such as aluminum hydroxide and magnesium hydroxide) Oxide). Metal hydroxides such as aluminum hydroxide and magnesium hydroxide may be treated with a coupling agent such as an isocyanate silane coupling agent, an amino silane coupling agent, or an epoxy silane coupling agent. From the viewpoint of achieving the object of the present invention, the blending amount of the flame retardant other than the phosphorus-based flame retardant is a flame retardant other than the polylactic acid resin / phosphorus-based flame retardant (weight ratio) = 30/70 to 70 / 30 is preferable, and 40/60 to 60/40 is more preferable.

  The polylactic acid resin composition of the present invention may contain other resins from the viewpoint of improving physical properties such as rigidity, flexibility, heat resistance, and durability. Specific examples of other resins include polyethylene, polypropylene, polystyrene, ABS resin, AS resin, acrylic resin, polyamide, polyphenylene sulfide, polyether ether ketone, polyester, polyacetal, polysulfone, polyphenylene oxide, polyimide, polyetherimide, Or thermoplastic resins such as ethylene / glycidyl methacrylate copolymers, polyester elastomers, polyamide elastomers, soft thermoplastic resins such as ethylene / propylene terpolymers, ethylene / butene-1 copolymers, phenol resins, melamine resins, unsaturated Thermosetting resins such as polyester resins, silicone resins, and epoxy resins can be mentioned. Among them, amide bonds and S are preferred from the viewpoint of compatibility with polylactic acid resins. Le coupling, the resin having a bond containing a carbonyl group of a carbonate bond or the like are preferred because structurally polylactic acid resin and affinity tends to be high.

  In the present invention, from the viewpoints of compatibility between moldability, flexibility and rigidity, heat resistance, and wear resistance of the polylactic acid resin composition, a polymer obtained by blending a polylactic acid resin and a resin other than the polylactic acid resin is used. Alloys may be used. Specifically, a polylactic acid resin and a resin other than the polylactic acid resin may be previously melt-kneaded, and the melt-kneaded product and other raw materials may be melt-kneaded. In addition, a polylactic acid resin and a resin other than the polylactic acid resin may be separately prepared by melt-kneading. However, the polylactic acid resin, the resin other than the polylactic acid resin, and other raw materials may be used simultaneously. You may melt-knead.

  Blend ratio of polylactic acid resin and resin other than polylactic acid resin (polylactic acid resin / resin other than polylactic acid resin (weight ratio)) is compatible with moldability, flexibility and rigidity of polylactic acid resin composition. From the viewpoints of heat resistance and wear resistance, 95/5 to 20/80 is preferable, 95/5 to 50/50 is more preferable, and 90/10 to 60/40 is even more preferable.

  In addition to the above, the polylactic acid resin composition of the present invention may further contain a hindered phenol or phosphite antioxidant, a hydrocarbon wax or a lubricant that is an anionic surfactant. The content of each of the antioxidant and the lubricant is preferably 0.05 to 3 parts by weight, more preferably 0.1 to 2 parts by weight with respect to 100 parts by weight of the polylactic acid resin.

  The polylactic acid resin composition of the present invention contains, as components other than those described above, conventional additives such as ultraviolet absorbers (benzophenone compounds, benzotriazole compounds, aromatic benzoates) within the range not impairing the object of the present invention. Compounds, oxalic anilide compounds, cyanoacrylate compounds and hindered amine compounds), heat stabilizers (hindered phenol compounds, phosphite compounds, thioether compounds), antistatic agents, antifogging agents, light stabilizers, One type or two or more types such as a foaming agent, a release agent, a coloring agent including a dye and a pigment, a fungicide, and an antibacterial agent can be further contained.

  Since the polylactic acid resin composition of the present invention has good processability and can be processed at a low temperature of, for example, 200 ° C. or less, there is also an advantage that the plasticizer is hardly decomposed. Can be used for applications. Further, due to the high crystallization speed, it is possible to perform molding at a low mold temperature and in a short time in injection molding.

Examples 1-18, Comparative Examples 1-7
As the polylactic acid resin composition, the products of the present invention (A to R) shown in Table 1 and the comparative products (a to g) shown in Table 2 were 190 using a twin screw extruder (PCM-45 manufactured by Ikegai Co., Ltd.). The mixture was melt-kneaded at 0 ° C., strand cut was performed, and polylactic acid resin composition pellets were obtained.

* 1: Polylactic acid resin (manufactured by Mitsui Chemicals, LACEA H-400)
* 2: Diester of succinic acid and triethylene glycol monomethyl ether (synthetic product)
* 3: Ethylene bis 12-hydroxystearic acid amide (Nippon Kasei Co., Ltd., SLIPAX H)
* 4: Unsubstituted zinc phenylphosphonic acid salt (PPA-Zn manufactured by Nissan Chemical Industries, Ltd.)
* 5: Phosphate (FP-2200, manufactured by ADEKA CORPORATION)
* 6: Carbodilite LA-1 (Nisshinbo Co., Ltd.)
* 7: Phosphate ester (Reophos 65 manufactured by Ajinomoto Fine Techno Co., Ltd.)
* 8: Condensed phosphate ester (PX-200, manufactured by Daihachi Chemical Industry Co., Ltd.)
* 9: Condensed phosphate (PHOSMEL-200, manufactured by Nissan Chemical Industries, Ltd.)
* 10: Decamemethylenedicarbonyldibenzoylhydrazide (T-1287, manufactured by Adeka Corporation)
* 11: Dimethylbarium 5-sulfoisophthalate (synthetic product)
* 12: 1,3,5-benzenetricarboxylic acid tricyclohexylamide (synthetic product)
* 13: 6-methyluracil (Wako Pure Chemical Industries, Ltd., reagent)
* 14: Melamine cyanurate (MC-6000 manufactured by Nissan Chemical Industries, Ltd.)
* 15: Rosin acid metal salt (Arakawa Chemical Co., Ltd., Pine Crystal KM-1500)
* 16: Diisopropylphenylcarbodiimide (Rhein Chemie, Stavaxol I LF)
* 17: Talc (Nippon Talc Co., Ltd., MICRO ACE P6)
* 18: Aluminum hydroxide (manufactured by Nippon Light Metal Co., Ltd., B703)
* 19: Isocyanate-based silane coupling agent (3-isocyanatopropyltriethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., KBE-9007) / aluminum hydroxide (manufactured by Nippon Light Metal Co., Ltd., B703) (weight ratio) = 1. Treatment with a ratio of 0 / 99.0 (this treatment is referred to as treatment 1) Treatment with isocyanate-based silane coupling agent Aluminum hydroxide * 20: Amino-based silane coupling agent (N-phenyl-3-aminopropyltrimethoxysilane, Amino-based silane cup treated at a ratio of Shin-Etsu Chemical Co., Ltd., KBM-573) / aluminum hydroxide (Nihon Light Metal Co., Ltd., B703) (weight ratio) = 1/99 (this treatment is referred to as treatment 2). Ring agent treated aluminum hydroxide * 21: Epoxy silane coupling agent (3-glycidoxypropyltrimethoate) Silane, manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403) / Aluminum hydroxide (manufactured by Nippon Light Metal Co., Ltd., B703) (weight ratio) = 1/99 (this process is referred to as Process 3) Silane coupling agent treated aluminum hydroxide * 22: Glass fiber (manufactured by Nippon Electric Glass Co., Ltd., T187, Φ12μm)

  In the above method, the surface treatment of the silane coupling agent to the metal hydrate is performed by dissolving 5 g of the silane coupling agent in 200 g of an organic solvent (acetone), putting 500 g of the metal hydrate therein, and stirring with a mixer. Then, the organic solvent was removed and the drying was performed.

  About the obtained pellet, the mold holding time and flame retardance required for mold release were evaluated by the following method. These results are shown in Tables 3 and 4.

<Evaluation criteria for mold holding time required for mold release>
The obtained pellets were pulverized with a pulverizer (S-20 manufactured by Daiko Seiki Co., Ltd.) at 40 ° C. or lower to obtain a pulverized product of the polylactic acid resin composition. The obtained pulverized product was dried at 70 ° C. under reduced pressure for 1 day, and the water content was adjusted to 500 ppm or less.
Next, the pulverized product thus obtained was injection molded using an injection molding machine (J75E-D manufactured by Nippon Steel) with a cylinder temperature of 200 ° C., and the mold temperatures shown in Tables 3 and 4 were used. Die holding time required for mold release of test pieces [flat plate (70 mm x 40 mm x 3 mm), prismatic specimen (125 mm x 12 mm x 6 mm) and prismatic specimen (63 mm x 12 mm x 5 mm)] Evaluated by criteria.

At the mold temperatures shown in Tables 3 and 4, the time required until each test piece was not deformed and taken out was determined to be the mold holding time required for mold release. When the mold holding time was required for 240 seconds or more, it was evaluated that mold release was impossible.
Note that the higher the melt crystallization speed of the test piece in the mold and the runner part, the shorter the mold holding time required for mold release.

<Flame retardancy evaluation method>
The obtained pellets were injection-molded using an injection molding machine (J75E-D manufactured by Nippon Steel Works) at a mold temperature of 80 ° C. and mold holding times shown in Tables 3 and 4. Using the test piece of the obtained test piece [square columnar test piece (5 in × 1/2 in × 1/16 in)], based on the safety standard UL94 vertical combustion test procedure of Underwriters Laboratories, the sample held vertically A gas burner flame was brought into contact with the lower end for 10 seconds. When combustion stopped within 30 seconds, an indirect flame was further applied for 10 seconds, and a combustion test was conducted at n = 5. Based on the judgment standard of UL94 vertical combustion test (UL94V), judgment of V-2, V-1, and V-0 was performed. The judgment criteria are shown below.
・ V-0
After any flame contact, no sample continues to burn for more than 10 seconds.
The total combustion time for 10 flames on 5 samples does not exceed 50 seconds.
There is no sample that burns to the position of the clamping clamp.
There is no sample that ignites absorbent cotton placed under the sample and drops burning particles.
After the second flame contact, there is no sample that continues red heat for 30 seconds or more.
・ V-1
No sample continues to burn for more than 30 seconds after any flame contact.
The total burn time for 10 flames on 5 samples does not exceed 250 seconds.
There is no sample that burns to the position of the clamping clamp.
There is no sample that ignites absorbent cotton placed under the sample and drops burning particles.
There is no sample that continues to heat red for more than 60 seconds after the second flame contact ・ V-2
No sample continues to burn for more than 30 seconds after any flame contact.
The total burn time for 10 flames on 5 samples does not exceed 250 seconds.
There is no sample that burns to the position of the clamping clamp.
Falling of burning particles that ignite absorbent cotton placed under the sample is allowed.
After the second flame contact, there is no sample that continues red heat for 60 seconds or more.

Example 19
In Example 13, a polylactic acid resin composition (LACEA H400 / (MeEO3) 2SA / OHC18EB / PPA-Zn / FP-2200 / MCI / talc = 50/10 / 0.5 / 0.5 / 20/1/10) pellets were obtained. The obtained pellets were pulverized with a pulverizer (S-20 manufactured by Daiko Seiki Co., Ltd.) at 40 ° C. or lower to obtain a pulverized product of the polylactic acid resin composition. The obtained pulverized product was dried at 70 ° C. under reduced pressure for 1 day, and the water content was adjusted to 500 ppm or less.
Next, a mixture of 92 parts by weight of the pulverized product thus obtained and 50 parts by weight of polylactic acid resin (LACEA H400) (hereinafter, this mixture is referred to as “resin composition S”) was set to a cylinder temperature of 200 ° C. Test pieces at the mold temperature shown in Table 3 (flat plate (70mm x 40mm x 3mm), prismatic test piece (125mm x 12mm x 6mm) by injection molding using an injection molding machine (J75E-D made by Nippon Steel) And the prism holding test piece (63 mm × 12 mm × 5 mm)] were evaluated according to the same criteria as in Example 1.
Further, the resin composition S was injection molded using an injection molding machine (J75E-D, manufactured by Nippon Steel Works) at a mold temperature of 80 ° C. and a mold holding time shown in Table 3, and the same as in Example 1. The flame retardancy was evaluated.
These results are shown in Table 3.

  From the results of Tables 3 and 4, the polylactic acid resin composition (A to S) of the present invention containing a specific plasticizer, a specific crystal nucleating agent, a phosphorus flame retardant, and a hydrolysis inhibitor was 80. Molding was possible with a short mold holding time even at a mold temperature of ° C. Even at low mold temperatures of 70 ° C. and 60 ° C., molding was possible with a short mold holding time. Furthermore, the polylactic acid resin composition of the present invention was able to achieve flame retardancy of V-2 or higher.

  On the other hand, the comparative polylactic acid resin composition (a to g) containing only a specific plasticizer, a specific crystal nucleating agent, and a hydrolysis inhibitor has a low mold temperature of 80 ° C, 70 ° C and 60 ° C. Although molding was possible at a mold temperature with a short mold holding time, it was impossible to achieve flame retardancy of V-2 or higher.

  From the above results, the polylactic acid resin composition of the present invention using a specific plasticizer and containing a crystal nucleating agent (1) and a crystal nucleating agent (2) as a crystal nucleating agent and a phosphorus flame retardant is a low gold It shows that moldability is excellent at the mold temperature, and that the molded product exhibits excellent flame retardancy.

Claims (6)

A polylactic acid resin composition containing a phosphorus-based flame retardant excluding a polylactic acid resin, a plasticizer, a crystal nucleating agent, and a phenylphosphonic acid metal salt, wherein the plasticizer has two or more ester groups in the molecule , At least one of the alcohol components constituting the ester is a compound obtained by adding an average of 0.5 to 5 moles of alkylene oxide having 2 to 3 carbon atoms per hydroxyl group, and the crystal nucleating agent is the following crystal nucleating agent (1 ) And a crystal nucleating agent (2).
Crystal nucleating agent (1): At least one type of crystal nucleating agent selected from compounds having a hydroxyl group and an amide group in the molecule (2): phenylphosphonic acid metal salt, metal salt of aromatic sulfonic acid dialkyl ester, metal of rosin acid At least one selected from the group consisting of salts, aromatic carboxylic acid amides, rosinic acid amides, carbohydrazides, N-substituted ureas, salts of melamine compounds and uracils   The ratio of crystal nucleating agent (1) and crystal nucleating agent (2) is crystal nucleating agent (1) / crystal nucleating agent (2) (weight ratio) = 20/80 to 80/20. Polylactic acid resin composition.   The polylactic acid resin composition according to claim 1 or 2, wherein the crystal nucleating agent (1) is an aliphatic amide having a hydroxyl group.   The plasticizer is at least one selected from the group consisting of an ester of succinic acid or adipic acid and polyethylene glycol monomethyl ether, and an ester of acetic acid and glycerol or an ethylene oxide adduct of ethylene glycol. A polylactic acid resin composition according to claim 1.   5. The poly according to claim 1, wherein the phosphorus-based flame retardant excluding the metal salt of phenylphosphonic acid is at least one selected from a phosphate ester, a condensed phosphate ester, a phosphate and a condensed phosphate. Lactic acid resin composition.   The content of the plasticizer is 5 to 30 parts by weight, the content of the crystal nucleating agent (1) is 0.1 to 3 parts by weight, and the content of the crystal nucleating agent (2) is 0 with respect to 100 parts by weight of the polylactic acid resin. The polylactic acid resin composition according to any one of claims 1 to 5, wherein the content of the phosphorus-based flame retardant excluding 1 to 3 parts by weight and the metal salt of phenylphosphonic acid is 5 to 40 parts by weight.