JP2006016447A - Resin composition and molded article comprised of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition excellent in extrusion moldability, high-degree flame retardancy and mechanical properties, and a molded article comprised of the same. <P>SOLUTION: The resin composition comprises 100 pts. wt. of a polylactic acid resin and, incorporated therewith, 100-0.5 pt. wt. of a flame-retardant and 3-0.01 pt. wt. of a fluororesin. The resin composition may further comprise an epoxy compound. The resin composition may further comprise an alkaline earth metal compound. The resin composition may further comprise at least one thermoplastic resin other than the polylactic acid resin. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a resin composition excellent in extrusion moldability, high flame retardancy, and mechanical properties, and a molded article comprising the same, comprising a polylactic acid resin, a flame retardant and a fluorine resin.

  Polylactic acid resin is expected as a practically excellent biodegradable polymer because it has a high melting point and can be melt-molded. Further, it is expected to be used as a general-purpose polymer made from bio raw materials in the future, and various molded products are formed by injection molding, extrusion molding, blow molding (blow molding) and the like.

  However, extrusion molding and blow molding of polylactic acid resin has a large drawdown (property that the falling speed increases due to its own weight), and it is difficult to obtain a thick extruded product or a blow molded product having a uniform thickness. There was a problem. As a general method for improving the moldability, it is possible to use a high-molecular-weight polylactic acid resin having a high melt viscosity, and further to form at a high melt viscosity by reducing the molding temperature of extrusion molding or blow molding as much as possible. Are known. However, the molding temperature condition width is small, and there is a problem that the thickness fluctuation and uneven thickness of the molded product obtained by slight condition fluctuation are likely to occur.

  Moreover, since the polylactic acid resin itself is easily combusted, it cannot be used for a member that needs to be flame retardant.

  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 high flame retardancy. I couldn't.

  Patent Document 2, Patent Document 3 and Patent Document 4 disclose 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. Excellent extrudability and high flame retardancy could not be obtained.

Patent Document 5, Patent Document 6, and Patent Document 7 disclose that a flame retardant and a fluorine-based resin can be blended with a polylactic acid resin as long as the effects of the invention are not impaired. There was no disclosure about the problem of achieving both high flame retardancy and specific means.
Textile Society Journal 55 (7) p. 290-296 (1999) JP 2001-303388 A (page 3-4) 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]) JP 2001-335626 A (page 3) JP 2002-356543 A (page 8) JP 2003-327815 A (page 7)

  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 extrusion moldability, high flame retardancy and mechanical properties, 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 a fluororesin has excellent properties that meet the above-mentioned purpose, and have reached the present invention.

That is, the present invention
(A) A resin composition comprising 100 to 0.5 parts by weight of a polylactic acid resin and 100 to 0.5 parts by weight of a flame retardant and 3 to 0.01 parts by weight of a fluororesin,
(B) The flame retardant is one or more flame retardants selected from brominated flame retardants, phosphorus flame retardants, nitrogen compound flame retardants, silicone flame retardants and other inorganic flame retardants. The resin composition according to the description,
(C) The resin composition according to any one of (i) to (b), wherein the phosphorus-based flame retardant of the flame retardant is a phosphate ester.
(D) The resin composition according to any one of (a) to (c), wherein the fluororesin is tetrafluoroethylene (e) and further comprising an epoxy compound (i) to (d) The resin composition according to any one of the above,
(F) The resin composition according to any one of (a) to (e), further comprising an alkaline earth metal compound.
(G) The resin composition according to any one of (a) to (f), further comprising one or more thermoplastic resins other than the polylactic acid resin.
(H) The resin composition according to (g), wherein the thermoplastic resin is at least one thermoplastic resin selected from a polyester resin, a polycarbonate resin, a polyamide resin, an AS resin, a polyacetal resin, and a silicone compound-containing core-shell rubber. object,
(Li) The resin composition according to any one of (i) to (h), further comprising a reinforcing material,
(Nu) The resin composition according to any one of (i) to (ri), further comprising a layered silicate.
(L) The resin composition according to any one of (i) to (nu), further comprising a crystal nucleating agent,
(O) The resin composition according to any one of (A) to (L), further comprising a plasticizer.
(W) A molded article made of the resin composition according to any one of (A) to (W), wherein the molded article is a mechanical mechanism part, an electric / electronic part, or an automobile part.

  The resin composition of the present invention has excellent extrudability, high flame retardancy and mechanical properties, and the molded product of the present invention comprising this resin composition takes advantage of the above properties to provide a mechanical mechanism. It can be effectively used in various applications such as parts, 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 from the viewpoint 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.

  Specific examples of the brominated flame retardant used in the present invention include decabromodiphenyl oxide, octabromodiphenyl oxide, tetrabromodiphenyl oxide, tetrabromophthalic anhydride, hexabromocyclododecane, bis (2,4,6-tribromo). Phenoxy) ethane, ethylenebistetrabromophthalimide, hexabromobenzene, 1,1-sulfonyl [3,5-dibromo-4- (2,3-dibromopropoxy)] benzene, polydibromophenylene oxide, tetrabromobisphenol-S, Tris (2,3-dibromopropyl-1) isocyanurate, tribromophenol, tribromophenyl allyl ether, tribromoneopentyl alcohol, brominated polystyrene, brominated polyethylene, tetrabromobis Enol-A, tetrabromobisphenol-A derivative, tetrabromobisphenol-A-epoxy oligomer or polymer, tetrabromobisphenol-A-carbonate oligomer or polymer, brominated epoxy resin such as brominated phenol novolac epoxy, tetrabromobisphenol-A -Bis (2-hydroxydiethyl ether), tetrabromobisphenol-A-bis (2,3-dibromopropyl ether), tetrabromobisphenol-A-bis (allyl ether), tetrabromocyclooctane, ethylenebispentabromodiphenyl, Tris (tribromoneopentyl) phosphate, poly (pentabromobenzylpolyacrylate), octabromotrimethylphenylindane, dibromoneope Chill glycol, pentabromobenzyl polyacrylate, dibromo cresyl glycidyl ether, N, N'ethylene - bis - such as tetrabromo phthalic imide. Of these, tetrabromobisphenol-A-epoxy oligomer, tetrabromobisphenol-A-carbonate oligomer, and brominated epoxy resin are preferable.

  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 resins having a three-dimensional network structure formed by combining structural units of SiO2, RSiO3 / 2, R2SiO, and R3SiO1 / 2. Here, R represents an alkyl group such as a methyl group, an ethyl group or a propyl group, an aromatic group such as a phenyl group or a benzyl group, or a substituent containing a vinyl group in the above substituent. In the silicone oil, polydimethylsiloxane, and at least one methyl group 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 Metal of tin salt, zinc sulfate, zinc oxide, ferrous oxide, ferric oxide, stannous oxide, stannic oxide, zinc borate, calcium borate, ammonium borate, ammonium octamolybdate, tungstic acid Examples thereof include salts, complex oxide acids of tungsten and metalloid, ammonium sulfamate, ammonium bromide, zirconium compounds, guanidine compounds, fluorine compounds, graphite, and swellable graphite. Of these, aluminum hydroxide, zinc borate, 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. In the above, when two or more flame retardants are used in combination, it is preferable to use a phosphorus-based flame retardant together with another flame retardant. The nitrogen compound-based flame retardant used in combination with the phosphorus-based flame retardant is preferably a nitrogen-containing heterocyclic compound, more preferably a triazine compound, and further 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 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

  The fluororesin in the present invention is a resin containing fluorine in a substance molecule, specifically, polytetrafluoroethylene, polyhexafluoropropylene, tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene. / Perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene / ethylene copolymer, hexafluoropropylene / propylene copolymer, polyvinylidene fluoride, vinylidene fluoride / ethylene copolymer, etc., among which polytetrafluoro Ethylene, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / ethylene copolymer, polyvinylidene fluoride In particular, polytetrafluoroethylene and tetrafluoroethylene / ethylene copolymers are preferred, and polytetrafluoroethylene is more preferred, and polytetrafluoroethylene-containing mixed powder comprising polytetrafluoroethylene particles and an organic polymer. The body is also preferably used. The molecular weight of the fluororesin such as polytetrafluoroethylene is preferably in the range of 100,000 to 10,000,000, more preferably in the range of 100,000 to 1,000,000, particularly for the extrudability and flame retardancy of the present invention. effective. Commercially available products of polytetrafluoroethylene include “Teflon (registered trademark)” 6-J, “Teflon (registered trademark)” 6C-J, and “Teflon (registered trademark)” 62 manufactured by Mitsui DuPont Fluorochemical Co., Ltd. -J, “Full-on” CD1, CD076 manufactured by Asahi IC Fluoropolymers, Inc. are commercially available. In addition, as a commercial product of a polytetrafluoroethylene-containing mixed powder composed of polytetrafluoroethylene particles and an organic polymer, it is commercially available as “Metabrene (registered trademark)” A series from Mitsubishi Rayon Co., Ltd. METABLEN (registered trademark) “A-3000”, “METABBRENE (registered trademark)” A-3800, and the like are commercially available. In addition, polytetrafluoroethylene “Teflon (registered trademark)” 6-J and the like are prone to agglomerate, so if they are mechanically strongly mixed with other resin compositions using a Henschel mixer or the like, agglomeration may occur due to aggregation. There are problems in handling and dispersibility depending on conditions. On the other hand, a polytetrafluoroethylene-containing mixed powder composed of polytetrafluoroethylene particles and an organic polymer is excellent in handling properties and dispersibility, and is particularly preferably used. The polytetrafluoroethylene-containing mixed powder composed of the polytetrafluoroethylene particles and the organic polymer is not limited, but includes polytetrafluoroethylene particles disclosed in JP-A-2000-226523. Examples thereof include polytetrafluoroethylene-containing mixed powders composed of organic polymers. Examples of the organic polymers include aromatic vinyl monomers, acrylate monomers, and vinyl cyanide monomers. An organic polymer containing 10% by weight or more of a monomer, and a mixture thereof may be used. The content of polytetrafluoroethylene in the mixed powder of polytetrafluoroethylene is 0.1% by weight to 90% by weight. It is preferable that

  Moreover, the compounding quantity of fluorine-type resin is 3-0.01 weight part with respect to 100 weight part of polylactic acid resin, Preferably 2-0.02 weight part is preferable, More preferably, it is 1-0.03. Part by weight is preferred. If the blending amount of the fluorine-based resin exceeds 3 parts by weight, the extrusion moldability and flame retardancy of the present invention are adversely decreased, and if it is less than 0.01, no effect is observed in improving the extrusion moldability and flame retardancy.

  In the present invention, an epoxy compound can be further blended.

  The epoxy compound used in the present invention may be a monofunctional epoxy compound or a bifunctional or higher functional epoxy compound, but is preferably an epoxy compound having a glycidyl group, such as a glycidyl ester compound or a glycidyl ether. Compounds, and glycidyl ester ether compounds. 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 Ester, glycidyl stearate, glycidyl laurate, glycidyl palmitate, glycidyl behenate, glycidyl bersate, 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. .

  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, the viscosity of the 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 viscosity stability and mechanical properties, and the compounding amount of the epoxy compound is polylactic acid resin 100 in terms of the viscosity 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.

  In the present invention, an alkaline earth metal compound can be further blended.

  Preferred alkaline earth metal compounds in the present invention include alkaline earth metal compounds such as magnesium compounds, calcium compounds, and barium compounds. Examples of the alkaline earth metal compounds include inorganic acid salts such as hydroxides, oxides, carbonates, sulfates, acetates, phosphates, acetates, lactates, oleic acids of alkaline earth metals. And organic acid salts such as palmitic acid, stearic acid and montanic acid. Specific examples of the alkaline earth metal compound include magnesium hydroxide, calcium hydroxide, barium hydroxide, magnesium oxide, calcium oxide, barium oxide, magnesium carbonate, calcium carbonate, barium carbonate, magnesium sulfate, calcium sulfate. , Barium sulfate, magnesium phosphate, calcium phosphate, barium phosphate, magnesium acetate, calcium acetate, barium acetate, magnesium lactate, calcium lactate, barium lactate, and also organic acids such as oleic acid, palmitic acid, stearic acid and montanic acid Examples include magnesium salts, calcium salts, and barium salts. Among these, hydroxides and carbonates of alkaline earth metals are preferably used. In particular, magnesium hydroxide and calcium carbonate are preferably used, and calcium carbonate is more preferably 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 the 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 neutral state solubility 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. Less than water. 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.

The thermoplastic resins may be used alone or in combination of two or more. Among the thermoplastic resins, polyester resins, polycarbonate resins, phenoxy resins, polyamide resins, 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 ( Terephthalate / sulfatoisophthalate / 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 used is preferably 90 ° C. or higher and 240 ° C. or lower, and more 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 reinforcing material can be further blended.

  As the reinforcing material used in the present invention, fibrous, plate-like, granular, and powdery materials that are usually used for reinforcement of thermoplastic resins can be used. Specifically, glass fiber, asbestos fiber, carbon fiber, graphite fiber, metal fiber, potassium titanate whisker, aluminum borate whisker, magnesium-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, and glass fiber, wollastonite, mica, and kaolin are particularly preferable. 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 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 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 with a coupling agent such as aminosilane or epoxysilane. It may be processed.

  Further, the compounding amount of the reinforcing material is preferably 200 to 0.1 parts by weight, 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.

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

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

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

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

  The layered silicate in which the exchangeable cation existing in the interlayer used in the present invention is exchanged with the organic onium ion is obtained by reacting the layered silicate having the exchangeable cation between the layer and the organic onium ion by a known method. Can be manufactured. Specifically, a method by an ion exchange reaction in a polar solvent such as water, methanol, ethanol, or a method by directly reacting a layered silicate with a liquid or 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, ethylene bislauric acid amides, palmitic acid amides, hydroxystearic acid amides, erucic acid amides, carboxylic acid amides such as trimesic acid tris (t-butylamide), benzylidene sorbitol 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.

  In the present invention, a plasticizer can be further blended.

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

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

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

  Specific examples of the polyvalent carboxylic acid plasticizer include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, diheptyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, trimellitic acid, etc. Trimellitic acid esters 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, citrates 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.

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

  Specific examples of other plasticizers include 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.

  Among the plasticizers used in the present invention, at least one selected from polyester plasticizers and polyalkylene glycol plasticizers is preferable among those exemplified above. Only one type of plasticizer may be used in the present invention, or two or more types may be used in combination.

  The amount of the plasticizer is preferably 30 to 0.01 parts by weight, more preferably 20 to 0.1 parts by weight, more preferably 10 to 0.5 parts by weight based on 100 parts by weight of the polylactic acid resin. 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 having an oil absorption of 50 to 400 cm 3/100 g is preferably used, and may be treated with aluminum oxide, silicon oxide, zinc oxide, zirconium oxide, polyol, silane coupling agent or the like as a treatment 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) are added as necessary can do.

  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.

  The resin composition of the present invention thus obtained has a flame retardancy according to UL standards of a molded product having a thickness of 0.8 mm (1/32 inch) and gives V-2, V-1, V-0, 5V performance. In a preferred embodiment, V-1, V-0, 5V performance can be provided, and in a more preferred embodiment, V-0, 5V performance can be provided.

  The resin composition of the present invention is a composition having unique characteristics, and various methods are employed by methods such as extrusion molding, injection molding, blow molding, and spinning into various fibers such as undrawn yarn, drawn yarn, and superdrawn yarn. It can be used by processing into product shapes, and can be used for various applications such as mechanical mechanism parts, electrical / electronic parts, automobile parts, optical equipment, building materials and daily necessities, especially mechanical mechanism parts, electrical / electronic parts, Although it can be usefully used as an automobile part, it is preferable to perform extrusion molding or blow molding taking advantage of its excellent extrusion performance.

  Examples of the extrusion-molded product obtained by the above-described extrusion molding include extrusion-molded products such as films, inflation films, sheets, tubes and round bars, and can be used after being stretched. It can be further processed and used in various applications such as electric / electronic parts, automobile parts, optical equipment, building members, and daily necessities. In addition, examples of mechanical parts of injection molded products include various types of bearings such as cleaning jigs, oilless bearings, stern bearings, underwater bearings, motor parts, lighters, typewriters, etc. As electrical and electronic parts, electrical equipment housing, OA equipment housing, various covers, various gears, various cases, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable capacitor cases, 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, liquid crystal, FDD carriage, FDD chassis , Motor brush Rudder, parabolic antenna, CD tray, cartridge, cassette, sorter, AC adapter, charging stand, switchboard, outlet cover, VTR part, TV part, iron, hair dryer, rice cooker part, microwave oven part, acoustic part, audio laser Disc compact discs, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, office computer related parts, telephone related parts, facsimile related parts, copying machine related parts, etc. Parts include precision machinery-related parts, alternator terminals, alternator connectors, IC regulators, various valves such as exhaust gas valves, fuel-related / exhaust / intake system pipes, air intake nozzles -Kel, 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 board, coil for fuel related electromagnetic valve, connector for fuse Horn terminals, electrical component insulation plates, step motor rotors, lamp sockets, lamp reflectors, lamp housings, brake pistons, solenoid bobbins, engine oil filters, ignition device cases, etc. , Microscopes, binoculars, cameras, watches, etc. In addition, blow molded products are molded into the required shape as bellows, boots, bottles and different diameter pipes / cylinders, etc. It can be used for various purposes.

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

[Examples 1-31, Comparative Examples 1-9]
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. did).

In addition, the flame retardant (A), fluorine resin (B), epoxy compound (C), alkaline earth metal salt (D), other resin (E), reinforcing material (F), layered form in Tables 1 to 3 The symbols of silicate (G), crystal nucleating agent (H), plasticizer (I), and other stabilizer (J) 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: Tetrafluoroethylene (“Teflon (registered trademark)” 6-J manufactured by Mitsui DuPont Fluorochemical Co., Ltd.).
B-2: Acrylic modified tetrafluoroethylene (“Metbrene (registered trademark)” A-3800 manufactured by Mitsubishi Rayon Co., Ltd.).
C-1: Versatic acid glycidyl ester (Japan Cardio Resin Co., Ltd. “Cardura E10”).
C-2: Bisphenol A diglycidyl ether (“Epicoat” 828 manufactured by Japan Epoxy Resin).
D-1: Calcium carbonate (“KSS1000” manufactured by Dowa Calfine Co., Ltd.).
D-2: Magnesium hydroxide (“Kisuma 5E” manufactured by Kyowa Chemical Industry Co., Ltd.).
E-1: Nylon 6 resin (“Amilan” CM1010 manufactured by Toray Industries, Inc.).
E-2: Aromatic polycarbonate resin ("Iupilon H4000" manufactured by Mitsubishi Engineering Plastics Co., Ltd.).
E-3: Polybutylene (terephthalate / adipate) resin ("Ecoflex" manufactured by BASF).
E-4: Silicone / acrylic composite core-shell rubber ("METABRENE" SX-005 manufactured by Mitsubishi Rayon Co., Ltd.).
E-5: Polyester elastomer resin (“Hytrel” 4057 manufactured by Toray DuPont Co., Ltd.).
E-6: Polyacetal resin (“Amirasu” S731 manufactured by Toray Industries, Inc.).
E-7: AS resin (styrene / acrylonitrile = 74/26, manufactured by Toray Industries, Inc.).
E-8: Polybutylene terephthalate ("Toraycon" 1401X31 manufactured by Toray Industries, Inc.).
E-9: Polytrimethylene terephthalate resin ("Cortina" manufactured by Shell).
E-10: Polyethylene (terephthalate / succinate) resin (DuPont "Biomax").
E-11: Nylon 6 / polyethylene glycol resin (“Pelestat” manufactured by Sanyo Chemical Industries, Ltd.).
E-12: Polybutylene succinate resin (“Bionore” 1001 manufactured by Showa Polymer).
E-13: Polymethyl methacrylate resin (Sumipex LG35 manufactured by Sumitomo Chemical).
E-14: Polycaprolactone resin (“Placcel” H7 manufactured by Daicel Chemical Industries, Ltd.).
F-1: Mica ("Micalet" A-21 manufactured by Yamaguchi Mica Industry Co., Ltd.).
F-2: Glass fiber of chopped strand (CS-3J948 manufactured by Nitto Boseki Co., Ltd.).
G-1: Organized layered silicate (“MTE” manufactured by Coop Chemical Co., Ltd.).
H-1: Talc ("LMS100" manufactured by Fuji Talc Industrial Co., Ltd.).
H-2: Ethylene bis lauric acid amide ("Sripacks L" manufactured by NOF Corporation).
I-1: Polyethylene propylene glycol ("Pluronic" F68 manufactured by Asahi Denka Kogyo Co., Ltd.).

  The obtained resin composition was evaluated for extrudability using a “lab plast mill” 20 mmφ single screw extruder manufactured by Toyo Seiki Seisakusho Co., Ltd. A full flight screw was used as the kneading screw of the “lab plast mill” 20 mmφ single screw extruder, and a 2.1 mm diameter circular nozzle was attached to the discharge port of the die part for discharging the molten polymer. Extrusion molding was performed at a cylinder temperature of 190 ° C. and a screw rotation speed of 10 rpm (however, when nylon 6 resin, polycarbonate resin, polybutylene terephthalate resin, polytrimethylene terephthalate resin was used, the cylinder temperature was The extrusion moldability was evaluated by the following method (1).

  Further, the obtained resin composition was injection molded at a cylinder temperature of 200 ° C. and a mold temperature of 80 ° C. using an IS55EPN injection molding machine manufactured by Toshiba Machine Co., Ltd. (however, nylon 6 resin, polycarbonate resin, poly In the case of using butylene terephthalate resin or polytrimethylene terephthalate resin, the cylinder temperature was set to 235 ° C.). In addition, when polymethyl methacrylate resin was used, molding was not possible at a mold temperature of 80 ° C., so molding was performed at a mold temperature of 40 ° C., and the characteristics were evaluated by the following methods (2) to (4). .

(1) Extrudability A. Measurement of drawdown 30cm of the molten polymer discharged from the nozzle was sampled, the diameter of the polymer that started out after cooling and the diameter of the 20cm part of the polymer after discharge were measured with calipers, and the rate of change in diameter was calculated from the following equation using the difference in dimensions . In addition, it can be judged that the smaller the dimensional difference (diameter change rate) of the polymer diameter after the start of ejection and 20 cm discharge is, the smaller the drawdown (the property that the falling speed becomes faster due to its own weight), and the wall thickness during extrusion molding. It is an index for materials that are less likely to cause unevenness.
Rate of change in diameter (%) = [(starting polymer diameter−polymer diameter after discharging 20 cm) ÷ starting polymer diameter] × 100

(2) Flame retardance Using test pieces of 127 mm x 12.7 mm x 0.8 mm (5 inches x 1/2 inches x 1/32 inches) produced by injection molding, an American UL standard subject 94 (UL94) Combustion test is performed in accordance with the vertical combustion test method, flame retardancy is evaluated, and the evaluation rank is indicated by V-0, V-1, V-2 in the order of excellent flame retardancy, and corresponds to the above rank What was not done was out of specification.

(3) Mechanical properties Using ASTM No. 1 dumbbell tensile test piece prepared by injection molding, the tensile test is performed according to ASTM method D638, and using the ASTM standard wall thickness impact test piece of 3 mm similarly manufactured by injection molding, according to ASTM method D256. Izod impact test (no notch) was measured.

(4) Hydrolyzability The above tensile test piece was put into a constant temperature and high humidity container of “Humidi Cabinet” LHL-112 manufactured by Tabay 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

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

  From Examples 1 to 31 in Tables 1 to 3, the resin composition of the present invention is excellent in extrusion moldability, flame retardancy, and mechanical properties, and the resin composition of the present invention in which an epoxy compound is further blended has the above performance. It can be said that it is a molded article made of a resin composition excellent in hydrolyzability while maintaining the above.

  From Comparative Examples 1 and 2 and Comparative Examples 5 to 9 in Table 3, the resin composition in which the fluorine-based resin is not blended with the poly-L lactic acid resin and the flame retardant resin composition is inferior in extrusion moldability and has high flame retardancy. It can be said that it is a molded article made of a resin composition from which V-0 cannot be obtained. Further, from Comparative Examples 3 to 4, when the flame retardant is not blended and when the fluororesin is blended beyond the range of the present invention, it falls outside the standard that does not correspond to the standard of the vertical combustion test method of UL94, and flame retardancy is reduced. It can be said that it is a molded article made of a resin composition not shown.

  Moreover, the outlet cover was injection-molded using the resin compositions of Examples 1, 4, and 31 at a cylinder temperature of 220 ° C. and a mold temperature of 80 ° C. Although the obtained outlet cover was used for 5 months, it could be used without any particular problem.

Claims (13)

A resin composition comprising 100 to 0.5 parts by weight of a polylactic acid resin and 100 to 0.5 parts by weight of a flame retardant and 3 to 0.01 parts by weight of a fluororesin. The resin according to claim 1, wherein the flame retardant is one or more flame retardants selected from brominated flame retardants, phosphorus flame retardants, nitrogen compound flame retardants, silicone flame retardants, and other inorganic flame retardants. Composition. The resin composition according to claim 1, wherein the phosphorus-based flame retardant of the flame retardant is a phosphoric ester. The resin composition according to any one of claims 1 to 3, wherein the fluororesin is polytetrafluoroethylene. Furthermore, the resin composition of any one of Claims 1-4 formed by mix | blending an epoxy compound. Furthermore, the resin composition of any one of Claims 1-5 formed by mix | blending an alkaline-earth metal compound. Furthermore, the resin composition of any one of Claims 1-6 formed by mix | blending 1 or more types of thermoplastic resins other than a polylactic acid resin. The resin composition according to claim 7, wherein the thermoplastic resin is one or more thermoplastic resins selected from a polyester resin, a polycarbonate resin, a polyamide resin, an AS resin, a polyacetal resin, and a silicone compound-containing core-shell rubber. Furthermore, the resin composition of any one of Claims 1-8 formed by mix | blending a reinforcing material. Furthermore, the resin composition of any one of Claims 1-9 formed by mix | blending layered silicate. Furthermore, the resin composition of any one of Claims 1-10 formed by mix | blending a crystal nucleating agent. Furthermore, the resin composition of any one of Claims 1-11 formed by mix | blending a plasticizer. It is a molded article which consists of a resin composition of any one of Claims 1-12, Comprising: This molded article is a mechanical mechanism part, an electrical / electronic part, or a motor vehicle part.