JP4687022B2 - Resin composition and molded article comprising the same - Google Patents

Description

  The present invention relates to a resin composition comprising a polylactic acid resin, a flame retardant, and an epoxy compound, excellent in flame retardancy, retention stability, mechanical properties, and hydrolyzability, and a molded article comprising the same.

  Polylactic acid resin is expected as a practically excellent biodegradable polymer because it has a high melting point and can be melt-molded. In the future, it is also expected to be used as a general-purpose polymer made from bio raw materials.

  However, since the polylactic acid resin itself is easily combusted, it cannot be used for members that require flame retardancy, such as electrical and electronic applications. In addition, since the polylactic acid resin has a low crystallization rate, there is a limit to crystallization and use as a molded product.

  Non-Patent Document 1 and Patent Document 1 disclose a method for adsorbing, coating or copolymerizing a specific flame retardant as a method for imparting flame retardancy to polylactic acid fibers, but obtaining excellent hydrolyzability. I couldn't.

  Patent Document 2 discloses a method of blending an epoxy compound as a method for imparting hydrolyzability to a polylactic acid resin, but excellent flame retardancy could not be obtained.

  Patent Document 3 discloses a method of blending a flame retardant additive and a carbodiimide compound as a method for imparting flame retardancy and hydrolyzability to a polylactic acid resin, but has excellent retention stability and mechanical properties. Couldn't get.

  Patent Document 4 and Patent Document 5 disclose a method of blending a flame retardant additive with a carbodiimide compound, an isocyanate compound, and an oxazoline compound as a method for imparting flame retardancy and hydrolyzability to a polylactic acid resin. Excellent residence stability and mechanical properties could not be obtained.

Here, the influence of the retention stability on the product will be described. The polylactic acid resin is molded into various molded product shapes by a method such as extrusion molding or injection molding and then commercialized. However, polylactic acid resins with poor retention stability are easily affected by the residence time in the molding machine, and if the residence time becomes longer, defects such as burrs will occur in the product and mechanical properties will be deteriorated. There has been a problem that the incidence of the increase is high.
Textile Society Journal 55 (7) p. 290-296 (1999) JP 2001-303388 A (page 3-4) JP 2001-335626 A ([0007], [0013] to [0014]) International Publication WO 2004/022650 A1 (Page 2) JP 2003-192925 A (paragraph numbers [0017] to [0026], [0029]) JP 2003-192929 A (paragraph numbers [0018] to [0024], [0027])

  The present invention has been achieved as a result of studying the solution of the problems in the prior art described above as an issue.

  Accordingly, an object of the present invention is to provide a resin composition excellent in flame retardancy, retention stability, mechanical properties and hydrolyzability, and a molded product comprising the same.

  The present inventors have found that a resin composition containing a polylactic acid resin, a flame retardant, and an epoxy compound has excellent characteristics that meet the above-mentioned purpose, and have reached the present invention.

That is, the present invention
(A) One or more flame retardants selected from 100% by weight of one or more flame retardants selected from phosphorus flame retardants, nitrogen compound flame retardants, silicone flame retardants and other inorganic flame retardants per 100 parts by weight of polylactic acid resin Part, epoxy compound 10-0.01 part by weight, and a resin composition comprising 30 to 0.01 part by weight of a crystal nucleating agent selected from carboxylic acid amides (however, excluding a resin composition containing a polyacetal resin) ) ,
(B) One or more flame retardants of 100 to 0.5 weight selected from phosphorus flame retardants, nitrogen compound flame retardants, silicone flame retardants and other inorganic flame retardants with respect to 100 parts by weight of the polylactic acid resin. Parts, epoxy compound 10 to 0.01 parts by weight and polyester elastomer resin, polybutylene terephthalate resin, polyethylene (terephthalate / succinate) resin, aromatic polycarbonate resin, polyamide resin, AS resin, polymethyl methacrylate resin and silicone compound-containing core shell rubber A resin composition comprising 200 to 0.5 parts by weight of one or more thermoplastic resins selected from (excluding a resin composition containing a polyacetal resin) ,
(C) 100 to 0.5 parts by weight of a flame retardant composed of one or more selected from phosphoric acid esters, polyphosphates, silicone flame retardants and other inorganic flame retardants with respect to 100 parts by weight of polylactic acid resin And a resin composition comprising 10 to 0.01 parts by weight of an epoxy compound (excluding a resin composition containing a polyacetal resin) ,
(D) The resin composition according to any one of (i) to (c), wherein the epoxy compound is at least one selected from a glycidyl ester compound, a glycidyl ether compound, and a glycidyl ester ether compound,
(E) The resin composition according to any one of (i) to (d), wherein 10 parts by weight of an alkaline earth metal compound is further blended with 100 parts by weight of the polylactic acid resin.
(F) The resin composition according to (e), wherein the alkaline earth metal compound is at least one alkaline earth metal compound selected from a magnesium compound, a calcium compound, and a barium compound,
(G) Any one of (i) and (c) to (f), wherein 100 to 100 parts by weight of the polylactic acid resin is further blended with 200 to 0.5 parts by weight of one or more thermoplastic resins other than the polylactic acid resin. The resin composition according to item 1,
(H) The thermoplastic resin is selected from a polyester elastomer resin, a polybutylene terephthalate resin, a polyethylene (terephthalate / succinate) resin, an aromatic polycarbonate resin, a polyamide resin, an AS resin, a polymethyl methacrylate resin, and a silicone compound-containing core-shell rubber. The resin composition according to (g), which is at least one thermoplastic resin.
(I) The resin composition according to any one of (i) to (h), which is obtained by further blending 200 to 0.5 parts by weight of a fibrous reinforcing material with respect to 100 parts by weight of the polylactic acid resin.
(Nu) The resin composition according to any one of (i) to (ri), further comprising 40 to 0.1 parts by weight of a layered silicate with respect to 100 parts by weight of the polylactic acid resin,
(L) The resin composition according to any one of (b) to (n), further comprising 30 to 0.01 parts by weight of a crystal nucleating agent with respect to 100 parts by weight of the polylactic acid resin.
(L) The resin composition according to any one of (i) to (l), wherein 30 to 0.1 parts by weight of a plasticizer is further blended with 100 parts by weight of the polylactic acid resin.
(W) A molded article made of the resin composition according to any one of (A) to (W), which is a mechanical mechanism part, an electric / electronic part, or an automobile part.

  The resin composition of the present invention has excellent flame retardancy, residence stability, mechanical properties and hydrolyzability, and the molded product of the present invention comprising this resin composition takes advantage of the above properties, It can be effectively used in various applications such as electrical / electronic parts, building materials, automobile parts, and daily necessities.

  Hereinafter, the present invention will be described in detail.

  The 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. Other monomer units include ethylene glycol, propylene glycol, butanediol, heptanediol, hexanediol, octanediol, nonanediol, decanediol, 1,4-cyclohexanedimethanol, neopentyl glycol, glycerin, pentane. Glycol compounds such as erythritol, bisphenol A, polyethylene glycol, polypropylene glycol and polytetramethylene glycol, oxalic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, malonic acid, glutaric acid, cyclohexanedicarboxylic acid, terephthalic acid , Isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4′-diphenyl ether dicarbohydrate Acids, dicarboxylic acids such as 5-sodium sulfoisophthalic acid, 5-tetrabutylphosphonium isophthalic acid, hydroxycarboxylic acids such as glycolic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, hydroxybenzoic acid, and caprolactone And lactones such as valerolactone, propiolactone, undecalactone, and 1,5-oxepan-2-one. Such other copolymerization component is preferably 0 to 30 mol%, and preferably 0 to 10 mol%, based on all monomer components.

  In the present invention, it is preferable to use a polylactic acid resin having a high optical purity of the lactic acid component from the viewpoint of compatibility. 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. It is particularly preferable that 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. Further preferred.

  It is also preferable to use a polylactic acid containing 80% or more of L-form and a polylactic acid containing 80% or more of D-form. It contains 90% or more of polylactic acid containing 90% or more of L-form and D-form. It is more preferable to use polylactic acid in combination.

  A modified polylactic acid resin may be used. For example, by using a maleic anhydride-modified polylactic acid resin, an epoxy-modified polylactic acid resin, an amine-modified polylactic acid resin, etc., not only heat resistance but also mechanical properties are obtained. It tends to improve, which is preferable.

  As a method for producing the polylactic acid resin, a known polymerization method can be used, and examples thereof include a direct polymerization method from lactic acid and a ring-opening polymerization method via lactide.

  The molecular weight and molecular weight distribution of the polylactic acid resin are not particularly limited as long as it can be substantially molded, but the weight average molecular weight is usually 10,000 or more, preferably 40,000 or more, and further 80,000. The above is desirable. The upper limit is preferably 350,000 or less in view of fluidity during molding. The weight average molecular weight here refers to the molecular weight in terms of polymethyl methacrylate (PMMA) measured by gel permeation chromatography.

  The melting point of the polylactic acid resin is not particularly limited, but is preferably 120 ° C. or higher, and more preferably 150 ° C. or higher. Since the melting point of polylactic acid tends to be higher as the optical purity is higher, polylactic acid having a higher optical purity may be used as the polylactic acid having a higher melting point.

  The flame retardant used in the present invention is not particularly limited as long as it is a substance added for the purpose of imparting flame retardancy to the resin. Specifically, brominated flame retardants, phosphorus flame retardants, Nitrogen compound-based flame retardants, silicone-based flame retardants, and other inorganic flame retardants can be used, and at least one of these can be selected and used.

  The phosphorus-based flame retardant used in the present invention is not particularly limited, and a generally used phosphorus-based flame retardant can be used. Typically, an organic phosphorus compound such as a phosphate ester or a polyphosphate, , Red phosphorus.

  Specific examples of the phosphoric acid ester in 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 acetate Phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, triphenylphosphine oxide, tricresylphosphine oxide, diphenyl methanephosphonate, phenylphosphonic acid Examples include condensed phosphate esters such as diethyl, resorcinol polyphenyl phosphate, resorcinol poly (di-2,6-xylyl) phosphate, bisphenol A polycresyl phosphate, hydroquinone poly (2,6-xylyl) phosphate, and condensates thereof. be able to. Examples of commercially available condensed phosphate esters include PX-200, PX-201, PX-202, CR-733S, CR-741, and CR747 manufactured by Daihachi Chemical Co., Ltd. In particular, the condensed phosphate ester of the following formula (1) can be preferably used from the viewpoint of hydrolyzability.

(In the above formula, Ar ¹ , Ar ² , Ar ³ , Ar ⁴ represent the same or different aromatic groups that do not contain halogen. X is selected from the following formulas (2) to (4): In the following formulas (2) to (4), R ^{1 to} R ⁸ represent the same or different hydrogen atoms or alkyl groups having 1 to 5 carbon atoms, Y represents a direct bond, O, S, SO ₂ , C (CH ₃ ) ₂ , CH ₂ , CHPh, Ph represents a phenyl group, n in the formula (1) is an integer of 0 or more, and k and m in the formula (1) are Each of them is an integer of 0 or more and 2 or less, and (k + m) is an integer of 0 or more and 2 or less.) In addition, such aromatic condensed phosphates are different n or aromatic condensed phosphates having different structures. It may be a mixture of

  In the formula of the formula (1), n is an integer of 0 or more, and the upper limit is preferably 40 or less from the viewpoint of flame retardancy. Preferably it is 0-10, Most preferably, it is 0-5.

  K and m are each an integer of 0 or more and 2 or less, and k + m is an integer of 0 or more and 2 or less, preferably k or m is an integer of 0 or more and 1 or less, particularly preferably k or m. Is 1 respectively.

In the formulas (2) to (4), R ^{1 to} R ⁸ represent the same or different hydrogen or an alkyl group having 1 to 5 carbon atoms. Specific examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, and a neopentyl group. However, hydrogen, a methyl group, and an ethyl group are preferable, and hydrogen is particularly preferable.

Ar ¹ , Ar ² , Ar ³ and Ar ⁴ represent the same or different aromatic groups containing no halogen. Examples of the aromatic group include aromatic groups having a benzene skeleton, a naphthalene skeleton, an indene skeleton, and an anthracene skeleton, and among them, those having a benzene skeleton or a naphthalene skeleton are preferable. These may be substituted with a halogen-free organic residue (preferably an organic residue having 1 to 8 carbon atoms), and the number of substituents is not particularly limited, but may be 1 to 3. preferable. Specific examples include phenyl groups, tolyl groups, xylyl groups, cumenyl groups, mesityl groups, naphthyl groups, indenyl groups, anthryl groups and the like, but phenyl groups, tolyl groups, xylyl groups, cumenyl groups, A naphthyl group is preferable, and a phenyl group, a tolyl group, and a xylyl group are particularly preferable.

  Of these, the following compounds (5) and (6) are preferable, and the compound (5) is particularly preferable.

  Moreover, the polyphosphate which consists 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, Examples include ethylamine salts, diethylamine salts, triethylamine salts, ethylenediamine salts, piperazine salts, and examples of aromatic amine salts include pyridine salts, triazine salts, melamine salts, and ammonium salts.

  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. Examples thereof include phosphazene compounds and phosphoric ester amides.

  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 thermosetting resin coatings, metal hydroxide coatings, and metal plating coatings. 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 coating is not particularly limited as long as it can coat 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 can coat 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.

  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 flame retardant used in the present invention include silicone resins and silicone oils. Examples of the silicone resin include a resin having a three-dimensional network structure formed by combining structural units of SiO ₂ , RSiO _3/2 , R ₂ SiO, and R ₃ SiO _1/2 . 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 at 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.

  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, tin oxide, oxidation Tin salt, zinc sulfate, ferrous oxide, ferric oxide, stannous oxide, stannic oxide, zinc borate, calcium borate, ammonium borate, ammonium octamolybdate, tungstic acid metal salt, tungsten And oxides of metal and metalloid, ammonium sulfamate, ammonium bromide, zirconium compounds, guanidine compounds, fluorine compounds, graphite, swellable graphite, and the like. Among these, aluminum hydroxide, zinc borate, a fluorine compound, and swellable graphite are preferable.

  The above flame retardants may be used alone or in combination of two or more.

  The amount of the flame retardant is 100 to 0.5 parts by weight, and more preferably 80 to 1 parts by weight with respect to 100 parts by weight of the polylactic acid resin.

  Among the above flame retardants, use a combination of at least one selected from phosphorus-based flame retardants containing no halogen, nitrogen compound-based flame retardants, silicone-based flame retardants and other inorganic flame retardants. Is preferred. Thus, when using 2 or more types of flame retardants together, it is preferable to use together a phosphorus flame retardant and another flame retardant. The nitrogen compound flame retardant used in combination with the phosphorus flame retardant is preferably a nitrogen-containing heterocyclic compound, more preferably a triazine compound, and more preferably melamine cyanurate. Moreover, as a silicone type flame retardant used together with a phosphorus type flame retardant, a silicone resin is preferable. Moreover, as other inorganic flame retardants used in combination with phosphorus flame retardants, aluminum hydroxide, zinc borate, fluorine compounds and swellable graphite are preferable. Further, the blending ratio with the phosphorus-based flame retardant can be combined with any amount, and the amount of the phosphorus-based flame retardant in 100% by weight of the flame retardant is particularly preferably 5% by weight or more, and 5 to 95% by weight. It is more preferable that

  As the epoxy compound in the present invention, either a monofunctional epoxy compound or a bifunctional or higher functional epoxy compound can be used, and among them, an epoxy compound having a glycidyl group is preferable. Preferable examples of the epoxy compound having a glycidyl group include a glycidyl ester compound, a glycidyl ether compound, and a glycidyl ester ether compound. One or more of these epoxy compounds can be used.

  Further, the glycidyl ester compound is not limited, but as specific examples, glycidyl benzoate, glycidyl tBu-benzoate, glycidyl P-toluate, glycidyl cyclohexanecarboxylate, glycidyl pelargonate Esters, glycidyl stearate, glycidyl laurate, glycidyl palmitate, glycidyl behenate, glycidyl behenate, glycidyl versatate, glycidyl oleate, glycidyl linoleate, glycidyl linolein, glycidyl behenol, stearolic acid Glycidyl ester, terephthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, phthalic acid diglycidyl ester , Naphthalenedicarboxylic acid diglycidyl ester, bibenzoic acid diglycidyl ester, methyl terephthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, cyclohexanedicarboxylic 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 tetraglycidyl ester, and the like. Two or more kinds can be used.

  The glycidyl ether compound is not limited, but specific examples include phenyl glycidyl ether, P-phenylphenyl glycidyl ether, 1,4-bis (β, γ-epoxypropoxy). ) Butane, 1,6-bis (β, γ-epoxypropoxy) hexane, 1,4-bis (β, γ-epoxypropoxy) benzene, 1- (β, γ-epoxypropoxy) -2-ethoxyethane, 1 Others such as-(β, γ-epoxypropoxy) -2-benzyloxyethane, 2,2-bis- [р- (β, γ-epoxypropoxy) phenyl] propane and bis- (4-hydroxyphenyl) methane Examples include diglycidyl ether obtained by the reaction of bisphenol and epichlorohydrin. These can be used alone or in combination of two or more. .

  Further, the epoxy compound that is preferably used is an epoxy compound in which a monofunctional glycidyl ester compound and a glycidyl ether compound are used in combination or a monofunctional glycidyl ester compound, and more preferably a residence of a composition from which a monofunctional glycidyl ester compound is obtained. Excellent balance between stability and hydrolysis resistance.

  In addition, the epoxy equivalent of the epoxy compound is preferably an epoxy compound of less than 500, and more preferably an epoxy compound of less than 400 epoxy equivalent. Here, the epoxy equivalent is an epoxy compound in which the number of grams of the epoxy compound containing 1 gram equivalent of the epoxy group is less than 500, and the epoxy equivalent is obtained by dissolving the epoxy compound in pyridine and adding 0.05N hydrochloric acid to 45 ° C. After heating, a mixture of thymol blue and cresol red is used as an indicator and back titration with 0.05N caustic soda can be used.

  In addition, the epoxy compound has a great effect on improving the hydrolyzability without impairing the residence stability and mechanical properties, and the compounding amount of the epoxy compound is polylactic acid resin 100 from the standpoint of the residence stability and hydrolyzability. It is 10-0.01 weight part with respect to a weight part, Preferably it is 9-0.05 weight part, More preferably, it is 8-0.1 weight part. The epoxy compound does not include those in which an epoxy compound such as glycidyl methacrylate is grafted or copolymerized on a thermoplastic resin.

Preferred alkaline earth metal compounds in the present invention include alkaline earth metal compounds such as magnesium compounds, calcium compounds, and barium compounds. As examples of the alkaline earth metal compound, alkaline earth metal hydroxides, oxides, carbonates, sulfates, inorganic salts such as-phosphate, acetate, lactate salts. Further, the above specific examples of the alkaline earth metal compound, water calcium oxide, barium hydroxide, magnesium oxide, calcium oxide, barium oxide, magnesium carbonate, calcium carbonate, barium carbonate, magnesium sulfate, calcium sulfate,-phosphate magnesium, calcium, barium phosphate, magnesium acetate, calcium acetate, barium acetate, magnesium lactate, calcium lactate, and etc. lactic barium is. Among them, hydroxides of alkaline earth metals, carbonates are preferably used, yo Ri preferably calcium carbonate is used. Such alkaline earth metals can be used alone or in combination of two or more. In addition, calcium carbonate, light calcium carbonate, heavy calcium carbonate, wet-pulverized fine powder heavy calcium carbonate, wet heavy calcium carbonate (chalk), etc. are known depending on the production method. Included in the invention. These alkaline earth metal compounds may be treated with one or more surface treatment agents such as silane coupling agents, organic substances and inorganic substances, and the shape may be powder, plate or fiber. It is preferable from a dispersibility etc. to use in the powder form of 10 micrometers or less. Further, if the particle size is fine, the effect of improving hydrolyzability is large and preferable.

In addition, as an effect of blending an alkaline earth metal compound, a flame retardant, particularly a phosphorus flame retardant, is easily hydrolyzed, which adversely affects the hydrolyzability of the polylactic acid resin. By adding a metal compound in combination, the hydrolyzability is further improved by neutralizing the phosphoric acid generated from the hydrolyzed phosphorus-based flame retardant with an alkaline earth metal compound. Presumed. In addition, when an alkali metal compound is used instead of the alkaline earth metal compound, the alkali metal compound is not preferred because it often has alkalinity and usually promotes hydrolysis of the polylactic acid resin. The alkaline earth metal compound used in the present invention is preferably insoluble in water in a neutral state and exhibits a neutralizing action by dissolving in an acidic environment when the phosphate ester is decomposed and the system becomes acidic. Used. The solubility in the neutral state is described in, for example, the Handbook of Chemistry, published by Maruzen Co., Ltd. (Showa 41), and the solubility in water is preferably 1 g / 100 g or less, more preferably 10 ⁻¹ g / 100 g water or less. Incidentally, the solubility of calcium carbonate most preferably used in water is 5.2 × 10 ⁻³ g / 100 g water.

  Moreover, the compounding quantity of an alkaline-earth metal compound is 10-0.01 weight part with respect to 100 weight part of polylactic acid resin from the surface of a mechanical characteristic and a hydrolyzability, Preferably it is 9-0.05 weight part, More preferably, it is 8 to 0.1 parts by weight.

  In the present invention, a thermoplastic resin other than polylactic acid can be further blended. Specific examples of thermoplastic resins other than polylactic acid used in the present invention include polyolefin resins such as low density polyethylene resin, high density polyethylene resin, polypropylene resin, polyester resin, polyamide resin, polystyrene resin, polyacetal resin, polyurethane resin, Aromatic and aliphatic polyketone resins, polyphenylene sulfide resins, polyether ether ketone resins, polyimide resins, thermoplastic starch resins, polystyrene resins, acrylic resins, AS resins, ABS resins, AES resins, ACS resins, AAS resins, polyvinyl chloride Resin, polyvinylidene chloride resin, vinyl ester resin, polyurethane resin, MS resin, polycarbonate resin, polyarylate resin, polysulfone resin, polyethersulfone resin, phenoxy resin, polyphenol Two alkylene oxide resin, poly-4-methylpentene-1, polyether imide resin, cellulose acetate resin, and polyvinyl alcohol resins.

  In addition, ethylene-propylene copolymers, ethylene-propylene-nonconjugated diene copolymers, ethylene-butene-1 copolymers, various acrylic rubbers, ethylene-acrylic acid copolymers and alkali metal salts thereof (so-called ionomers) , Ethylene-glycidyl (meth) acrylate copolymer, ethylene-acrylic acid alkyl ester copolymer (for example, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer), acid-modified ethylene-propylene copolymer Copolymers, diene rubbers (for example, polybutadiene, polyisoprene, polychloroprene), copolymers of diene and vinyl monomers (for example, styrene-butadiene random copolymer, styrene-butadiene block copolymer, styrene-butadiene-styrene block copolymer) Polymer Rene-isoprene random copolymer, styrene-isoprene block copolymer, styrene-isoprene-styrene block copolymer, polybutadiene graft copolymerized with styrene, butadiene-acrylonitrile copolymer), polyisobutylene, isobutylene and Copolymers with butadiene or isoprene, natural rubber, thiocol rubber, polysulfide rubber, acrylic rubber, polyurethane rubber, polyether rubber, epichlorohydrin rubber, and the like, and those having various degrees of crosslinking, One having a microstructure such as a cis structure or a trans structure, one having a vinyl group or the like, one having various average particle diameters (in the resin composition), a core layer and one or more shell layers covering the core layer And adjacent layers are different. Of a multilayer structure polymer so-called core-shell rubber consisting of polymers can also be used, it is possible to further core-shell rubber also be used which contains a silicone compound.

  Further, the various (co) polymers mentioned in the above specific examples can be any of random copolymers, block copolymers, graft copolymers and the like.

Moreover, said thermoplastic resin may be used by 1 type, or may be used in combination of 2 or more types .

  Among the above thermoplastic resins, polyester resin, polycarbonate resin, phenoxy resin, polyamide resin, polyetherimide resin, AS resin, polyacetal resin, and silicone compound-containing core shell rubber are more preferable, and polyester resin, polycarbonate resin, polyamide Resin, AS resin, polyacetal resin, and silicone compound-containing core-shell rubber are particularly preferable.

  Moreover, the compounding quantity of thermoplastic resins other than said polylactic acid is 200-0.5 weight part with respect to 100 weight part of polylactic acid resin, Furthermore, it is preferable that it is 150-1 weight part.

  Among the above-mentioned thermoplastic resins other than polylactic acid, polyester resins preferably used are (i) dicarboxylic acid or its ester-forming derivative and diol or its ester-forming derivative, and (b) hydroxycarboxylic acid or its ester formation. It is a polymer or copolymer obtained by polycondensation of at least one selected from a functional derivative, (c) lactone, and is a thermoplastic polyester resin other than polylactic acid resin.

  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 derivatives 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), polypropylene terephthalate, polypropylene (terephthalate / isophthalate), polyethylene terephthalate, polyethylene (terephthalate / isophthalate), bisphenol A (Terephthalate / isophthalate), polybutylene naphthalate, polybutylene (terephthalate / naphthalate), polypropylene naphthalate, polypropylene (terephthalate / naphthalate), polyethylene naphthalate, polycyclohexanedimethylene terephthalate, polycyclohexanedimethylene (terephthalate / isophthalate) Phthalate), poly (cyclohexanedimethylene / ethylene) terephthalate , Aromatic polyesters such as poly (cyclohexanedimethylene / ethylene) (terephthalate / isophthalate), polybutylene (terephthalate / isophthalate) / bisphenol A, polyethylene (terephthalate / isophthalate) / bisphenol A, and polybutylene (terephthalate / succinate) ), Polypropylene (terephthalate / succinate), polyethylene (terephthalate / succinate), polybutylene (terephthalate / adipate), polypropylene (terephthalate / adipate), polyethylene (terephthalate / adipate), polyethylene (terephthalate / sulfoisophthalate / adipate), polyethylene ( Terephthalate / sulfoisophthalate / succinate), polypropylene ( Phthalate / sulfoisophthalate / succinate), polybutylene (terephthalate / sebate), polypropylene (terephthalate / sebate), polyethylene (terephthalate / sebate), polybutylene terephthalate / polyethylene glycol, polypropylene terephthalate / polyethylene glycol, polyethylene terephthalate / polyethylene glycol, poly Butylene terephthalate / poly (tetramethylene oxide) glycol, polypropylene terephthalate / poly (tetramethylene oxide) glycol, polybutylene (terephthalate / isophthalate) / poly (tetramethylene oxide) glycol, polypropylene (terephthalate / isophthalate) / poly (tetramethylene) Oxide) glycol , Polybutylene terephthalate / poly (propylene oxide / ethylene oxide) glycol, Polypropylene terephthalate / poly (propylene oxide / ethylene oxide) glycol, Polybutylene (terephthalate / isophthalate) / Poly (propylene oxide / ethylene oxide) glycol, Polypropylene (terephthalate / isophthalate)・ Poly (propylene oxide / ethylene oxide) glycol, polybutylene (terephthalate / adipate), polypropylene (terephthalate / adipate), polybutylene terephthalate, poly-ε-caprolactone, etc. Blends, polyethylene oxalate, polypropylene oxalate, Butylene oxalate, polyneopentyl glycol oxalate, polyethylene succinate, polypropylene succinate, polybutylene succinate, polybutylene adipate, polypropylene adipate, polyethylene adipate, polybutylene (succinate / adipate), polypropylene (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, polyglycolic acid, fats such as polybutylene succinate carbonate Group polyester carbonate, p-oxybenzoic acid / polyethylene terephthalate, p-oxybenzoic acid / 6- Carboxymethyl-2-liquid crystalline polyesters such as copolyesters, such as naphthoic acid ( "/" indicates copolymerization. same as below. ).

  Among these, a polymer obtained by polycondensation of aromatic dicarboxylic acid or its ester-forming derivative and aliphatic diol or its ester-forming derivative as main components is preferable. Specifically, polybutylene terephthalate, polypropylene terephthalate , Polyethylene terephthalate, poly (cyclohexanedimethylene / ethylene) terephthalate, polypropylene naphthalate, polybutylene naphthalate, polybutylene (terephthalate / isophthalate), polypropylene (terephthalate / isophthalate), polyethylene (terephthalate / isophthalate), polybutylene terephthalate・ Polyethylene glycol, polypropylene terephthalate ・ Polyethylene glycol, polyethylene terephthalate ・ polyethylene glycol Polybutylene terephthalate / poly (tetramethylene oxide) glycol, polypropylene terephthalate / poly (tetramethylene oxide) glycol, polyethylene terephthalate / poly (tetramethylene oxide) glycol, polybutylene (terephthalate / isophthalate) / poly (tetramethylene oxide) glycol, Polypropylene (terephthalate / isophthalate) / poly (tetramethylene oxide) glycol, polybutylene (terephthalate / adipate), polypropylene (terephthalate / adipate), polyethylene (terephthalate / adipate), polybutylene (terephthalate / succinate), polypropylene (terephthalate / succinate) , Polyethylene (terephthalate / succinate It can be mentioned preferably. Ratio of aromatic dicarboxylic acid or its ester-forming derivative to the total dicarboxylic acid in the polymer obtained by polycondensation of the above aromatic dicarboxylic acid or its ester-forming derivative and aliphatic diol or its ester-forming derivative as main components Is more preferably 30 mol% or more, and particularly preferably 40 mol% or more.

  Among these, a polymer obtained by polycondensation of terephthalic acid or an ester-forming derivative thereof and an aliphatic diol selected from ethylene glycol, propylene glycol, or butanediol or an ester-forming derivative thereof as a main component is more preferable. Specifically, polypropylene terephthalate, polybutylene terephthalate, polybutylene (terephthalate / isophthalate), polypropylene (terephthalate / isophthalate), polyethylene terephthalate / polyethylene glycol, polypropylene terephthalate / polyethylene glycol, polybutylene terephthalate / polyethylene glycol, polyethylene terephthalate・ Poly (tetramethylene oxide) glycol, polypropylene terephthalate ・ Poly (teto Methylene oxide) glycol, polybutylene terephthalate / poly (tetramethylene oxide) glycol, polyethylene terephthalate / isophthalate / poly (tetramethylene oxide) glycol, polypropylene (terephthalate / isophthalate) / poly (tetramethylene oxide) glycol, polybutylene (terephthalate) / Isophthalate) poly (tetramethylene oxide) glycol, polyethylene (terephthalate / succinate), polyethylene (terephthalate / adipate), polypropylene (terephthalate / succinate), polypropylene (terephthalate / adipate), polybutylene (terephthalate / succinate), polybutylene ( Terephthalate / adipate) That. 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 30 mol% or more. More preferably, it is particularly preferably 40 mol% or more.

  Preferred examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, polybutylene (terephthalate / isophthalate), polybutylene (terephthalate / adipate), polyethylene (terephthalate / succinate), polybutylene (terephthalate / succinate), polyester elastomer, polypropylene terephthalate. , Polybutylene terephthalate / poly (tetramethylene oxide) glycol, polybutylene succinate, and particularly preferred examples include polybutylene terephthalate, polypropylene terephthalate, polybutylene terephthalate / poly (tetramethylene oxide) glycol, polyethylene ( Terephthalate / succinate), polybutylene sac At least one selected from the acid can be used, and may be used alone or in combination of two or more. By blending a polyester resin, flame retardancy, moldability, heat resistance A resin composition and a molded product with improved properties and mechanical properties can be obtained.

  The polyamide resin used in the present invention is a thermoplastic polymer having an amide bond starting from amino acid, lactam or diamine and dicarboxylic acid.

  Examples of amino acids include 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and paraaminomethylbenzoic acid. 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 polyamides used in the present invention include polycaproamide (nylon 6), polytetramethylene adipamide (nylon 46), polyhexamethylene adipamide (nylon 66), polyhexamethylene sebacamide (nylon). 6/10), polyhexamethylene dodecamide (nylon 6/12), polyundecane adipamide (nylon 11/6), polyundecanamide (nylon 11), polydodecanamide (nylon 12), polytrimethylhexa Methylene terephthalamide, polyhexamethylene isophthalamide (nylon 6I), polyhexamethylene terephthalamide / 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 copolymers thereof with these polyalkylene glycols, mixed polyamides, polyamide elastomers, and the like. Among these, nylon 6, nylon 66, nylon 11, nylon 12, nylon 6/10, nylon 6/12, nylon 11/6 and copolymer polyamides such as copolymerization of these with polyethylene glycol, mixed polyamide, Polyamide elastomer is preferable, nylon 6, nylon 11, nylon 12, nylon 6 / polyethylene glycol, and polyamide elastomer are more preferable, and nylon 6 and nylon 6 / polyethylene glycol are particularly preferable.

  Moreover, from the problem of thermal stability of the polylactic acid resin, the melting point of the polyamide resin to be used is preferably 90 ° C. or higher and 240 ° C. or lower, and preferably 100 ° C. or higher and 230 ° C. or lower.

  Said polyamide resin may be used independently and may be used in mixture of 2 or more types.

  The blending amount of the polyamide resin is preferably 200 to 0.5 parts by weight, more preferably 150 to 10 parts by weight, and particularly preferably 100 to 20 parts by weight with respect to 100 parts by weight of the polylactic acid resin. .

  In the present invention, a resin composition and a molded product excellent in flame retardancy, moldability, mechanical properties, and heat resistance can be obtained by blending a polyamide resin.

  Examples of the polycarbonate resin of the present invention include aromatic polycarbonates such as aromatic homo or copolycarbonates obtained by reacting an aromatic dihydric phenol compound with phosgene or a carbonic acid diester.

  Examples of the aromatic dihydric phenol compound include 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, and bis (4- Hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxy-3,5-diphenyl) butane, 2 , 2-bis (4-hydroxy-3,5-diethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-diethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1-phenyl-1,1-bis (4-hydroxyphenyl) ethane or the like can be used, and these can be used alone or as a mixture.

  The blending amount of the polycarbonate resin is preferably 200 to 0.5 parts by weight, more preferably 150 to 5 parts by weight, and particularly preferably 100 to 10 parts by weight with respect to 100 parts by weight of the polylactic acid resin. .

  In the present invention, a resin composition and a molded product excellent in flame retardancy, mechanical properties and heat resistance can be obtained by blending a polycarbonate resin, and it is difficult to cause a problem particularly when a phosphorus flame retardant is used. Bleeding of the flame retardant can be suppressed.

  The AS resin in the present invention is a copolymer having styrene and acrylonitrile as main components, and is an aromatic vinyl compound such as α-methylstyrene, vinyltoluene, divinylbenzene, a vinyl cyanide compound such as cimethacrylonitrile, methacrylic acid, and the like. (Meth) acrylic acid alkyl esters such as methyl, ethyl methacrylate, n-butyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, stearyl acrylate, maleimide, N-methylmaleimide, N-ethylmaleimide, N -Maleimide monomers such as phenylmaleimide and N-cyclohexylmaleimide, diene compounds, maleic acid dialkyl esters, allyl alkyl ethers, unsaturated amino compounds, and vinyl alkyl ethers may be further copolymerized. .

  The amount of styrene and acrylonitrile as main components in the AS resin is preferably at least 70% by weight or more, and the copolymerization ratio of styrene and acrylonitrile is such that the amount of acrylonitrile is 10% or more and less than 50% by weight. Preferably, the amount of acrylonitrile is 20% by weight or more and less than 40% by weight. When the content of acrylonitrile is in an appropriate range, the following improvement effect is particularly great.

  Further, as the AS resin, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated acid anhydrides or those obtained by graft polymerization or copolymerization of epoxy group-containing vinyl monomers are preferable. More preferred is a graft polymerized or copolymerized epoxy group-containing vinyl monomer.

  Such epoxy group-containing vinyl monomers are compounds that share both radically polymerizable vinyl groups and epoxy groups in one molecule. Specific examples thereof include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, and itacon. Examples thereof include glycidyl esters of unsaturated organic acids such as glycidyl acid, glycidyl ethers such as allyl glycidyl ether, and the above derivatives such as 2-methylglycidyl methacrylate, among which glycidyl acrylate and glycidyl methacrylate can be preferably used. . Moreover, these can be used individually or in combination of 2 or more types.

  Unsaturated acid anhydrides are compounds that share both radically polymerizable vinyl groups and acid anhydrides in one molecule, and preferred examples include maleic anhydride.

  The amount of unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated acid anhydrides or epoxy group-containing vinyl monomers used for graft polymerization or copolymerization is not particularly limited. On the other hand, it is preferably 0.05% by weight or more and 20% by weight or less, more preferably 0.1% by weight or more and 5% by weight or less.

  The blending amount of the AS resin is preferably 200 to 0.5 parts by weight, more preferably 150 to 5 parts by weight, and particularly preferably 100 to 10 parts by weight with respect to 100 parts by weight of the polylactic acid resin. .

  In the present invention, a resin composition and a molded product excellent in flame retardancy, heat resistance, mechanical properties and bleed resistance can be obtained by blending AS resin, particularly when a phosphorus-based flame retardant is used. .

  The polyacetal resin used in the present invention is a polymer having an oxymethylene unit as a main repeating unit, and even a so-called polyacetal homopolymer obtained by polymerization reaction using formaldehyde or trioxane as a main raw material is mainly composed of an oxymethylene unit. Which may be any so-called polyacetal copolymer containing not more than 15% by weight of oxyalkylene units having 2 to 8 adjacent carbon atoms in the main chain, and also containing other structural units, Any of a block copolymer, a terpolymer, and a crosslinked polymer may be used, and these may be used alone or in combination of two or more.

  Among them, a polyacetal copolymer is preferable, and a polyacetal copolymer containing 2% by weight or less of an oxyalkylene unit having 2 adjacent carbon atoms in the main chain or an oxyalkylene unit having 4 adjacent carbon atoms in the main chain More preferably 5% by weight or less of a polyacetal copolymer containing 1.4% by weight or less and 0.2% by weight or more of an oxyalkylene unit having two adjacent carbon atoms in the main chain or in the main chain Particularly preferred is a polyacetal copolymer containing 3% by weight or more and 0.5% or more of an oxyalkylene unit having 4 adjacent carbon atoms.

  There is no restriction | limiting in particular in the manufacturing method of the polyacetal resin in this invention, It can manufacture by a well-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 of the method include polymerizing and filtering the polymer, followed by heating in acetic anhydride in the presence of sodium acetate to acetylate the polymer terminal.

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

  The viscosity of these polymers is not particularly limited as long as it can be used as a molding material, but the melt flow rate (MFR) can be measured by ASTM D1238 method, and the MFR measured at a temperature of 190 ° C. is 1.0. The thing of the range of -70g / 10min is preferable, and the thing of 1.5-50g / 10min is especially preferable.

  The polyacetal resin in the present invention includes 2,2′-methylenebis (4-methyl-6-tert-butylphenol), calcium ricinoleate, cyanoguanazine, hexamethylenebis (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-t-butyl-5-methyl-4- Hydroxyphenyl) propionate] is preferably contained.

  The blending amount of the polyacetal resin is preferably 200 to 0.5 parts by weight, more preferably 150 to 5 parts by weight, and particularly preferably 100 to 10 parts by weight with respect to 100 parts by weight of the polylactic acid resin. .

  In the present invention, by blending the polyacetal resin, the polylactic acid resin and the polyacetal resin are compatible, thereby obtaining unique characteristics that are not seen in the case of a composition that is not normally compatible, and moldability In addition, a resin composition and a molded product excellent in processability, mechanical properties, and heat resistance can be obtained.

  Preferable examples of the silicone compound-containing core-shell rubber include silicone / acrylic composite core-shell rubber.

In the present invention, a fibrous reinforcing material can be further blended. The strengthening material, fibrous used to enhance the normal thermoplastic resins, plate, granular and may be used as powder in the present invention, a fibrous reinforcing material. Specifically, glass fiber, asbestos fiber, carbon fiber, graphite fiber, metal fiber, potassium titanate whisker, aluminum borate whisker, magnesium-based whisker, silicon-based 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 inorganic fibrous reinforcements, polyester fiber, nylon fiber, acrylic fiber, regenerated cellulose fiber, acetate fiber, Organic fibrous reinforcements such as kenaf, ramie, cotton, jute, hemp, sisal, flax, linen, silk, Manila hemp, sugar cane, wood pulp, paper scrap, waste paper and wool, glass flakes, non-swellable mica, graphite, metal foil , Mick beads, clay, mica, sericite, zeolite, bentonite, dolomite, kaolin, fine silicate, feldspar, potassium titanate, shirasu balloon, aluminum oxide, aluminum silicate, silicon oxide, gypsum, novaculite, dosonite and clay And plate-like and granular reinforcements. Among these reinforcing materials, inorganic fibrous reinforcing materials are preferable, in particular glass fibers, are Warasutenai bets preferred. Moreover, use of an organic fibrous reinforcing material is also preferable, and natural fibers and regenerated fibers are more preferable from the viewpoint of taking advantage of the biodegradability of the polylactic acid resin, and kenaf is particularly preferable. Further, the aspect ratio (average fiber length / average fiber diameter) of the fibrous reinforcing material used for blending is preferably 5 or more, more preferably 10 or more, and further preferably 20 or more.

The fibrous reinforcing material 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. It may be processed by.

Moreover, the blending amount of the fibrous reinforcing material is preferably 200 to 0.1 parts by weight, and more preferably 100 to 0.5 parts by weight with respect to 100 parts by weight of the polylactic acid resin.

  In the present invention, a lamellar silicate can be further blended, and it is further preferred to blend a lamellar silicate in which exchangeable cations existing between layers are exchanged with organic onium ions. In the present invention, the layered silicate in which the exchangeable cation existing between the layers is exchanged with the organic onium ion is the exchange of the exchangeable cation of the layered silicate having the exchangeable cation between the layers with the organic onium ion. Inclusion compound. By blending layered silicate, flame retardancy, mechanical properties, and moldability are improved.

  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, and 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.

  Quaternary ammonium ions include benzyltrialkylammonium ions such as benzyltrimethylammonium, benzyltriethylammonium, benzyltributylammonium, benzyldimethyldodecylammonium, benzyldimethyloctadecylammonium, benzalkonium, trimethyloctylammonium, trimethyldodecylammonium, and 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 melted 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 in order 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 the present invention, the amount of the layered silicate is preferably 40 to 0.1 parts by weight, more preferably 30 to 0.5 parts by weight, and particularly preferably 10 to 1 parts by weight with respect to 100 parts by weight of the polylactic acid resin. preferable.

  In the present invention, a crystal nucleating agent can be further blended. As the crystal nucleating agent used in the present invention, those generally used as polymer crystal nucleating agents can be used without particular limitation, and any of inorganic crystal nucleating agents and organic crystal nucleating agents can be used. . Specific examples of the inorganic crystal nucleating agent include talc, kaolinite, montmorillonite, synthetic mica, calcium sulfide, boron nitride, barium sulfate, aluminum oxide, neodymium oxide, and phenylphosphonate metal salts. These inorganic crystal nucleating agents are preferably modified with an organic substance in order to enhance dispersibility in the composition.

  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 oxide, sodium laurate, potassium laurate, sodium myristate, potassium myristate, calcium myristate, sodium octacosanoate, calcium octacosanoate, sodium stearate, potassium stearate, lithium stearate, calcium stearate, magnesium stearate, Barium stearate, sodium montanate, calcium montanate, sodium toluate, sodium salicylate, potassium salicylate, salicylic acid , Metal salts of organic carboxylic acids such as aluminum dibenzoate, potassium dibenzoate, lithium dibenzoate, sodium β-naphthalate, sodium cyclohexanecarboxylate, organic sulfonates such as sodium p-toluenesulfonate, sodium sulfoisophthalate, stearic acid Amides, ethylenebislauric acid amides, palmitic acid amides, hydroxystearic acid amides, erucic acid amides, carboxylic acid amides such as trimesic acid tris (t-butylamide), benzylidenesorbitol and its derivatives, sodium-2,2′-methylenebis Phosphorus compound metal salts such as 4,6-di-t-butylphenyl) phosphate and 2,2-methylbis (4,6-di-t-butylphenyl) sodium be able to.

  As the crystal nucleating agent used in the present invention, among those exemplified above, at least one selected from talc, organic carboxylic acid metal salts, and carboxylic acid amides is particularly preferable. The crystal nucleating agent used in the present invention may be used alone or in combination of two or more.

  The compounding amount of the crystal nucleating agent is preferably 30 to 0.01 parts by weight, more preferably 10 to 0.05 parts by weight, and particularly preferably 5 to 0.1 parts by weight with respect to 100 parts by weight of the polylactic acid resin. preferable.

  In the present invention, it is preferable to add a crystal nucleating agent because moldability, heat resistance and flame retardancy are improved.

The plasticizer used in the present invention, generally can be used without particular limitation for use as a plasticizer for the polymer, glycerin-based plasticizers For example, polycarboxylic acid ester plasticizer, and polyalkylene glycol etc. plasticizers can be mentioned.

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

  Specific examples of polycarboxylic acid plasticizers include phthalates such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, diheptyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, and trimellitic acid. Tributyl ester such as tributyl, trioctyl trimellitic acid, trihexyl trimellitic acid, diisodecyl adipate, n-octyl-n-decyl adipate, methyl diglycol butyl diglycol adipate, benzyl methyl diglycol adipate, adipic acid Adipic acid esters such as benzylbutyl diglycol, citrate esters such as triethyl acetylcitrate and tributyl acetylcitrate, azelaic acid esters such as di-2-ethylhexyl azelate, sebacin Dibutyl, and sebacic acid esters such as 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 Polyalkylene glycols such as propylene oxide addition polymers, tetrahydrofuran addition polymers of bisphenols, or terminal-capped compounds such as terminal epoxy-modified compounds, terminal ester-modified compounds, and terminal ether-modified compounds.

  Specific examples of other plasticizers include benzoic acid esters of aliphatic polyols such as neopentyl glycol dibenzoate, diethylene glycol dibenzoate, triethylene glycol di-2-ethylbutyrate, fatty acid amides such as stearamide, oleic acid Examples thereof include aliphatic carboxylic acid esters such as butyl, oxyacid esters such as methyl acetylricinoleate and butyl acetylricinoleate, pentaerythritol, various sorbitols, polyacrylic acid esters, and paraffins.

The plasticizer used in the present invention, among them those exemplified above, at least one selected from polyalkylene glycol-based plasticizer especially preferred. Only one type of plasticizer may be used in the present invention, or two or more types may be used in combination.

  Moreover, the compounding quantity of a plasticizer has the preferable range of 30-0.01 weight part with respect to 100 weight part of polylactic acid resins, The range of 20-0.1 weight part is more preferable, 10-0.5 weight Part ranges are particularly preferred.

  In the present invention, it is preferable to add a plasticizer because moldability and heat resistance are improved without inhibiting flame retardancy.

  In the present invention, each of the crystal nucleating agent and the plasticizer may be used alone, but it is preferable to use both in combination.

  In the present invention, the resin is adjusted to various colors by adding one or more kinds of pigments and dyes of carbon black, titanium oxide, petal, ultramarine blue, calcined yellow, and various colors, and weather resistance (light) The blending amount of the pigment or dye is 5 to 0.01 parts by weight, preferably 4 to 0.02 parts by weight, based on 100 parts by weight of the polylactic acid resin. Preferably it is 3-0.03 weight part.

Examples of the carbon black include, but are not limited to, channel black, furnace black, acetylene black, anthracene black, oil smoke, pine smoke, and graphite. The average particle diameter is 500 nm or less, and dibutyl phthalate. carbon black oil absorption 50~400cm 3 ^/ 100g is preferably used, aluminum oxide treatment agent, silicon oxide, zinc oxide, zirconium oxide, polyol, may be treated with a silane coupling agent.

  Further, as the above titanium oxide, titanium oxide having a crystal form such as rutile form or anatase form and having an average particle diameter of 5 μm or less is preferably used, and aluminum oxide, silicon oxide, zinc oxide, zirconium oxide, It may be treated with a polyol, a silane coupling agent or the like. In addition, the above-described carbon black, titanium oxide, and various color pigments and dyes may be used in various thermoplastic resins in order to improve dispersibility with the flame retardant resin composition of the present invention and to improve handling during production. And may be used as a blended material that is melt blended or simply blended. In particular, the thermoplastic resin is preferably a polyester resin such as a polylactic acid resin, and a polylactic acid resin is particularly preferably used.

  For the resin composition of the present invention, a stabilizer (antioxidant, ultraviolet absorber, etc.), mold release agent (fatty acid, fatty acid metal salt, oxyfatty acid, fatty acid ester, Aliphatic partially saponified ester, paraffin, low molecular weight polyolefin, fatty acid amide, alkylene bis fatty acid amide, aliphatic ketone, fatty acid lower alcohol ester, fatty acid polyhydric alcohol ester, fatty acid polyglycol ester, modified silicone) can also be added .

  The method for producing the resin composition of the present invention is not particularly limited. For example, after pre-blending a polylactic acid resin, a flame retardant, and other additives as necessary, uniaxially above the melting point of the resin. Or the method of melt-kneading uniformly using a twin-screw extruder, the method of removing a solvent after mixing in a solution, etc. are preferably used rather than the method of containing a flame retardant by copolymerization etc.

  As the flame retardancy of the resin composition of the present invention, the flame retardancy in accordance with UL standards is a molded product having a thickness of 0.8 mm (1/32 inch) and performances of V-2, V-1, V-0, 5V. It is preferable to give V-1, V-0, and 5V performance, and it is particularly preferable to give V-0 and 5V performance. The composition for obtaining the flame retardancy of V-0 is not particularly limited. However, as the flame retardant, it is preferable to use a phosphorus flame retardant and a nitrogen flame retardant or a silicone flame retardant in combination. More preferably, a combination of at least one phosphorus-based flame retardant selected from polyphosphate and red phosphorus and a nitrogen-based flame retardant or a silicone-based flame retardant is used. From a phosphate ester and a nitrogen-based flame retardant or a polyphosphate It is particularly preferred to use at least one selected phosphorus-based flame retardant and nitrogen-based flame retardant in combination.

  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.

  Examples of the molded product of the present invention obtained from the above resin composition include injection molded products, extrusion molded products, blow molded products, films, fibers and sheets, and unstretched films, uniaxially stretched films, and biaxially stretched films. And various fibers such as undrawn yarns, drawn yarns, and super-drawn yarns can be suitably used, and in particular, can be suitably used as an injection molded product. In addition, these molded products can be used for various applications such as electric / electronic parts, mechanical parts, optical devices, building members, automobile parts, and daily necessities, and particularly useful as electric / electronic parts.

  Specific uses of molded products include electrical equipment housings, OA equipment housings, various covers, various gears, various cases, sensors, LED lamps, connectors, sockets, resistors, relay cases, Switch, coil bobbin, condenser, variable capacitor case, optical pickup, oscillator, various terminal boards, transformer, breaker, plug, printed wiring board, tuner, speaker, microphone, headphones, small motor, magnetic head base, power module, housing, Semiconductor, LCD, FDD carriage, FDD chassis, motor brush holder, parabolic antenna, CD tray, cartridge, cassette, sorter, AC adapter, charging stand, switchboard, outlet cover, VTR parts, TV parts, a Ron, hair dryer, rice cooker parts, microwave oven parts, acoustic parts, audio / laser disc / compact disc, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, office computer related parts, telephone related parts, facsimile Related parts and copier-related parts can be listed, and mechanical parts include various types of bearings such as cleaning jigs, oilless bearings, stern bearings, underwater bearings, motor parts, lighters, typewriters, etc. Optical equipment includes microscopes, binoculars, cameras, watches, etc. Automotive parts include precision machine parts, alternator terminals, alternator connectors, IC regulators, exhaust gas valves and other valves, fuel-related Exhaust and intake pipes, air intake nozzle snorkel, intake manifold, fuel pump, engine coolant joint, carburetor main body, carburetor spacer, exhaust gas sensor, coolant sensor, oil temperature sensor, brake pad wear sensor, throttle position Sensor, Crankshaft position sensor, Air flow meter, Thermostat base for air conditioner, Heating hot air flow control valve, Brush holder for radiator motor, Water pump impeller, Turbine vane, Wiper motor related parts, Dust distributor, starter switch, starter Relay, transmission wire harness, window washer nozzle, air conditioner panel switch PCB, fuel-related electromagnetic valve coil, fuse connector, horn terminal, electrical component insulation plate, step motor rotor, lamp socket, lamp reflector, lamp housing, brake piston, solenoid bobbin, engine oil filter, ignition device case, etc. be able to.

  The present invention will be described in more detail below by way of examples, but these examples do not limit the present invention.

[Example 1-14, Comparative Example 1 to 18
Poly-L lactic acid resin having a D-form content of 1.2% and a PMMA equivalent weight average molecular weight of 160,000, various flame retardants shown below, fluorine-based resins, epoxy compounds, alkaline earth metal salts, etc. Resin, reinforcing material, layered silicate, crystal nucleating agent, plasticizer, and other stabilizers were mixed in the proportions shown in Tables 1 to 3, respectively, and the cylinder temperature was 210 ° C. with a 30 mm diameter twin screw extruder. Melting and kneading was performed at a rotation speed of 150 rpm to obtain a resin composition (however, when nylon 6 resin, polycarbonate resin, polybutylene terephthalate resin, polytrimethylene terephthalate resin was used, the cylinder temperature was 235 ° C.) did).

In addition, flame retardant (A), epoxy compound (B), alkaline earth metal salt (C), other resin (D), reinforcing material (E), layered silicate (F), crystal in Tables 1 to 3 The symbols of the nucleating agent (G), the plasticizer (H), and the other stabilizer (I) indicate the following contents.
A-1: Aromatic condensed phosphate ester (“PX-200” manufactured by Daihachi Chemical Industry Co., Ltd.).
A-2: Melamine cyanurate (manufactured by Nissan Chemical Industries, Ltd. “MC-440”).
A-3: Ammonium polyphosphate (“Fire Cut” FCP730 manufactured by Suzuhiro Chemical Co., Ltd.).
A-4: Melamine polyphosphate (“Melpua” 200 manufactured by DSM).
A-5: Aluminum hydroxide ("Hijilite" H-32ST manufactured by Showa Denko KK).
B-1: Versatic acid glycidyl ester (“Cajura E10” manufactured by Japan Epoxy Resin Co., Ltd.).
B-2: Bisphenol A diglycidyl ether (“Epicoat” 828 manufactured by Japan Epoxy Resin).
C-1: Calcium carbonate (“KSS1000” manufactured by Dowa Calfine Co., Ltd.).
C-2: Magnesium hydroxide (“Kisuma 5E” manufactured by Kyowa Chemical Industry Co., Ltd.).
D-1: Nylon 6 resin (“Amilan” CM1010 manufactured by Toray Industries, Inc.).
D-2: Aromatic polycarbonate resin ("Iupilon H4000" manufactured by Mitsubishi Engineering Plastics Co., Ltd.).
D-3: Polybutylene (terephthalate / adipate) resin ("Ecoflex" manufactured by BASF).
D-4: Silicone / acrylic composite core-shell rubber ("METABRENE" SX-005 manufactured by Mitsubishi Rayon Co., Ltd.).
D-5: Polyester elastomer resin (“Hytrel” 4057 manufactured by Toray DuPont Co., Ltd.).
D-6: Polyacetal resin (“Amirasu” S731 manufactured by Toray Industries, Inc.).
D-7: AS resin (styrene / acrylonitrile = 74/26, manufactured by Toray Industries, Inc.).
D-8: Polybutylene terephthalate ("Toraycon" 1401X31 manufactured by Toray Industries, Inc.).
D-9: Polytrimethylene terephthalate resin ("Cortina" manufactured by Shell).
D-10: Polyethylene (terephthalate / succinate) resin ("Biomax" manufactured by DuPont).
D-11: Nylon 6 / polyethylene glycol resin (“Pelestat” manufactured by Sanyo Chemical Industries, Ltd.).
D-12: Polybutylene succinate resin (“Bionore” 1001 manufactured by Showa Polymers).
D-13: Polymethylmethacrylate resin (Sumitex LG35 manufactured by Sumitomo Chemical).
D-14: Polycaprolactone resin ("Placcel" H7 manufactured by Daicel Chemical Industries, Ltd.). E-1: Mica (“Micalet” A-21, manufactured by Yamaguchi Mica Industry Co., Ltd.).
E-2: Glass fiber of chopped strand (CS-3J948 manufactured by Nitto Boseki Co., Ltd.).
F-1: Organized layered silicate (“MTE” manufactured by Coop Chemical Co., Ltd.).
G-1: Talc ("LMS100" manufactured by Fuji Talc Industrial Co., Ltd.).
G-2: Ethylene bis lauric acid amide ("Sripacks L" manufactured by NOF Corporation).
H-1: Polyethylene propylene glycol ("Pluronic" F68 manufactured by Asahi Denka Kogyo Co., Ltd.).
I-1: Polycarbodiimide (“Carbodilite” HMV-8CA manufactured by Nisshinbo Co., Ltd.).
I-2: Polymethylene polyphenyl polyisocyanate (“Millionate” MR manufactured by Nippon Polyurethane Co., Ltd.).
I-3: 1.3 Phenylene-2-oxazoline (“BOX-210” manufactured by Takemoto Yushi Co., Ltd.).

  Further, the obtained resin composition was injection-molded at a cylinder temperature of 210 ° C. and a mold temperature of 80 ° C. (however, nylon 6 resin, polycarbonate resin, polybutylene terephthalate resin, polytrimethylene terephthalate resin) was used. In this case, the cylinder temperature was 235 ° C.). In addition, when polymethyl methacrylate resin was used, it could not be molded at a mold temperature of 80 ° C., so the molding was performed at a mold temperature of 40 ° C., and the characteristics were evaluated by the following methods (1) to (4). .

(1) Mechanical properties Further, using the obtained test piece, a tensile test was conducted according to ASTM method D638, and an Izod impact test (no notch) was conducted according to ASTM method D256.

(2) Flame retardance US UL standard subject 94 (UL94) using a 127 mm × 12.7 mm × 0.8 mm (5 inch × 1/2 inch × 1/32 inch) test piece produced by injection molding. A flame test is performed in accordance with the vertical flame test method, and flame retardancy is evaluated. The evaluation ranks are indicated by V-0, V-1, and V-2 in the order of excellent flame retardancy. Items that did not apply were out of specification.

(3) Hydrolyzability The above tensile test piece was put into a constant temperature and high humidity container of “Humidi Cabinet” LHL-112 manufactured by Tabai Espec. The conditions of the temperature and humidity of the constant temperature and high humidity and the treatment time are 60 ° C. × 95% RH × 200 h, a tensile test is performed according to ASTM method D638, the tensile strength retention is obtained from the following formula, and hydrolyzability is obtained. It was used as an index.
Tensile strength retention rate (%) = (Tensile strength after treatment ÷ Tensile strength of untreated product) × 100

(4) Stability of residence The residence time of the molten polymer in the cylinder of the injection molding machine in the injection molding at the time of making the above-mentioned 127 mm × 12.7 mm × 0.8 mm (5 inch × 1/2 inch × 1/32 inch) test piece Was about 2 minutes. By changing the residence time of this molten polymer to 5 minutes, a 127 mm × 12.7 mm × 0.8 mm (5 inch × 1/2 inch × 1/32 inch) test piece was obtained, and flame retardancy was performed in the same manner as described above. Was measured.

  Moreover, the length of the burr | flash was measured about the said test piece with the Nikon profile projector V-12 universal projector made from Nippon Optical Co., Ltd. The burr was measured at the 12.7 mm width side of the test piece as a gate at the time of injection molding, and finally the burr length of the 12.7 mm width portion on the opposite side to the gate filled with the resin was measured. . The flame retardancy before and after the residence and the burr length were used as indicators of the residence stability.

  These results are shown together in Table 1, Table 2, and Table 3.

From Examples 1 to 14 in Tables 1 to 3, it can be said that the resin composition of the present invention is a molded article composed of a resin composition excellent in flame retardancy, retention stability, mechanical properties and hydrolyzability.

From Comparative Examples 7 to 8 and Comparative Examples 11 to 15 in Table 3, the resin composition in which the epoxy compound is not blended with the poly-L lactic acid resin and the flame retardant resin composition is significantly inferior in hydrolyzability, and in a high temperature and high humidity environment. It can be said that it is a molded article made of a resin composition whose mechanical properties are greatly reduced. Moreover, although the resin composition which mix | blended the epoxy compound in a large quantity beyond the range of this invention was excellent in hydrolyzability, the flame retardance and the mechanical characteristic fell significantly. Comparative Examples 16 to 18 are hydrolysability improvers used in Patent Document 3, Patent Document 4 and Patent Document 5, and some improve hydrolyzability. It can be said that both of them are molded articles made of a flame retardant resin composition having a problem that the flame retardancy after staying and the performance of burr length are greatly reduced and the staying stability is a problem.

Claims (13)

100-0.5 parts by weight of one or more flame retardants selected from phosphorus-based flame retardants, nitrogen compound-based flame retardants, silicone-based flame retardants and other inorganic flame retardants per 100 parts by weight of polylactic acid resin, epoxy A resin composition comprising 10 to 0.01 part by weight of a compound and 30 to 0.01 part by weight of a crystal nucleating agent selected from carboxylic acid amides (excluding a resin composition containing a polyacetal resin) . 100-0.5 parts by weight of one or more flame retardants selected from phosphorus-based flame retardants, nitrogen compound-based flame retardants, silicone-based flame retardants and other inorganic flame retardants per 100 parts by weight of polylactic acid resin, epoxy 10 to 0.01 parts by weight of compound and selected from polyester elastomer resin, polybutylene terephthalate resin, polyethylene (terephthalate / succinate) resin, aromatic polycarbonate resin, polyamide resin, AS resin, polymethyl methacrylate resin and silicone compound-containing core shell rubber A resin composition comprising 200 to 0.5 parts by weight of at least one thermoplastic resin (excluding a resin composition containing a polyacetal resin) . 100 to 0.5 parts by weight of a phosphoric acid ester and 100 or 0.5 parts by weight of a flame retardant comprising at least one selected from polyphosphates, silicone flame retardants and other inorganic flame retardants with respect to 100 parts by weight of a polylactic acid resin A resin composition comprising 10 to 0.01 parts by weight (excluding a resin composition containing a polyacetal resin) . The resin composition according to any one of claims 1 to 3, wherein the epoxy compound is at least one selected from a glycidyl ester compound, a glycidyl ether compound, and a glycidyl ester ether compound. The resin composition according to any one of claims 1 to 4, further comprising 10 to 0.01 parts by weight of an alkaline earth metal compound based on 100 parts by weight of the polylactic acid resin. The resin composition according to claim 5, wherein the alkaline earth metal compound is at least one alkaline earth metal compound selected from a magnesium compound, a calcium compound, and a barium compound. The resin composition according to any one of claims 1 and 3 to 6, further comprising 200 to 0.5 parts by weight of at least one thermoplastic resin other than the polylactic acid resin per 100 parts by weight of the polylactic acid resin. object. The thermoplastic resin is selected from polyester elastomer resin, polybutylene terephthalate resin, polyethylene (terephthalate / succinate) resin, aromatic polycarbonate resin, polyamide resin, AS resin, polymethyl methacrylate resin, and silicone compound-containing core-shell rubber The resin composition according to claim 7, which is the thermoplastic resin described above. The resin composition according to any one of claims 1 to 8, further comprising 200 to 0.5 parts by weight of a fibrous reinforcing material based on 100 parts by weight of the polylactic acid resin. The resin composition according to any one of claims 1 to 9, wherein 40 to 0.1 parts by weight of a layered silicate is further blended with 100 parts by weight of the polylactic acid resin. The resin composition according to any one of claims 2 to 10, wherein 30 to 0.01 parts by weight of a crystal nucleating agent is further blended with 100 parts by weight of the polylactic acid resin. The resin composition according to any one of claims 1 to 11, further comprising 30 to 0.1 parts by weight of a plasticizer based on 100 parts by weight of the polylactic acid resin. It is a molded article which consists of a resin composition of any one of Claims 1-12, Comprising: The molded article which is a mechanical mechanism component, an electrical / electronic component, or a motor vehicle part.