JP2010043289A - Resin composition and molded product made thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition excellent in moldability, mechanical properties, heat resistance, and flame retardancy, and to provide a molded article made thereof. <P>SOLUTION: The resin composition includes a polylactic acid resin and a flame retardant of a combination of at least one flame retardant selected from bromine-based flame retardants and nitrogen compound-based flame retardants, with other inorganic flame retardants. The content of the flame retardant is preferably 1-150 pts.wt. based on 100 pts.wt. of the polylactic acid resin. The resin composition optionally contains a reinforcing material, crystal nucleating agent, plasticizer and the like. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a resin composition comprising a polylactic acid resin and a specific flame retardant and having excellent flame retardancy, mechanical properties, and heat resistance, and a molded product comprising the same.

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

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

  Non-Patent Document 1 and Patent Document 1 disclose a method for adsorbing, coating or copolymerizing a specific flame retardant as a method for imparting flame retardancy to polylactic acid fibers, but the effect is insufficient. Moreover, even if these methods are used for injection molded products such as electric and electronic parts, sufficient characteristics cannot be obtained.

JP 2001-303388 A

Textile Society Journal 55 (7) p. 290-296 (1999)

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

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

  The present inventors have found that a resin composition containing a flame retardant using a polylactic acid resin in combination with a brominated flame retardant or a nitrogen compound-based flame retardant and another inorganic flame retardant is excellent in meeting the above-mentioned purpose. As a result, the present invention has been found to have flame retardancy and mechanical properties superior to those of conventional flame retardant resin compositions obtained from aromatic polyesters such as polybutylene terephthalate. .

  That is, the present invention provides a resin composition comprising a polylactic acid resin, a flame retardant using any one selected from a bromine-based flame retardant and a nitrogen compound-based flame retardant, and another inorganic flame retardant. Is to provide.

  In addition, in the resin composition of this invention, it is mentioned as preferable conditions that content of a flame retardant is 1-150 weight part with respect to 100 weight part of polylactic acid resins.

  Moreover, it is mentioned as a preferable condition that the resin composition further contains a reinforcing agent, further contains a layered silicate, further contains a crystal nucleating agent, and further contains a plasticizer.

  Further, it is preferable that the flame retardancy according to the UL94 standard is characterized by giving a V-0 performance to a molded product having a thickness of 0.8 mm (1/32 inch).

  The resin composition of the present invention has excellent flame retardancy, mechanical properties, and heat resistance, and the molded product of the present invention comprising this resin composition takes advantage of the above properties to provide electrical and electronic parts, It can be effectively used for various applications such as 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 dicarboxylic acid Dicarboxylic acids such as 5-sodium sulfoisophthalic acid and 5-tetrabutylphosphonium isophthalic acid, glycolic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, hydroxybenzoic acid and other hydroxycarboxylic acids, and caprolactone, Examples include 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. 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 in 95% or more, or the D-form is more preferably contained in 95% or more, the L-form is contained in 98% or more, or the D-form is contained in 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 also contains 90% or more of polylactic acid containing 90% or more and L-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 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.

  As the flame retardant used in the present invention, any one selected from bromine-based flame retardants and nitrogen compound-based flame retardants and flame retardants in combination with other inorganic flame retardants can be used.

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

  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. . Nitrogen-containing phosphorus-based flame retardants such as ammonium polyphosphate are not included in the nitrogen compound-based flame retardant 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, a known surface treatment agent, or the like may be used in combination.

  Other inorganic flame retardants used in the present invention include magnesium hydroxide, aluminum hydroxide, antimony trioxide, antimony pentoxide, sodium antimonate, zinc hydroxystannate, zinc stannate, metastannic acid, tin oxide, oxidation Tin salt, zinc sulfate, zinc oxide, ferrous oxide, ferric oxide, stannous oxide, stannic oxide, zinc borate, ammonium borate, ammonium octamolybdate, metal salt of tungstic acid, tungsten and Examples thereof include complex oxide acids with metalloids, ammonium sulfamate, ammonium bromide, zirconium compounds, guanidine compounds, fluorine compounds, graphite, and swellable graphite. Of these, magnesium hydroxide, fluorine-based compounds, and swellable graphite are preferable.

  In the present invention, the flame retardant is used as a flame retardant in which any one selected from bromine-based flame retardants and nitrogen compound-based flame retardants and other inorganic flame retardants are used in combination.

  The amount of the flame retardant is not particularly limited, but is preferably 150 to 0.5 parts by weight, more preferably 150 to 1 parts by weight, and more preferably 150 to 1 parts per 100 parts by weight of the polylactic acid resin. More preferably, it is 2 parts by weight, particularly preferably 100 to 1.2 parts by weight, and particularly preferably 80 to 2 parts by weight.

  Among the above flame retardants, it is preferable to use a nitrogen compound-based flame retardant together with other inorganic flame retardants.

  As the nitrogen compound flame retardant, melamine cyanurate and melamine isocyanurate are preferable.

  Of the above flame retardants, one or more selected from brominated flame retardants and one selected from other inorganic flame retardants are used, and brominated flame retardants and other inorganic flame retardants are used. It is preferable to use a flame retardant in combination, and it is particularly preferable to use 100 to 1 part by weight of another inorganic flame retardant with respect to 100 parts by weight of the brominated flame retardant.

  In the present invention, it is preferable to further contain a reinforcing material.

  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, talc, clay, mica, sericite, zeolite, bentonite, dolomite, kaolin, fine silica, feldspar, potassium titanate, shirasu balloon, calcium carbonate, magnesium carbonate, barium sulfate, calcium oxide, aluminum oxide, titanium oxide And plate-like and granular reinforcing materials such as aluminum silicate, silicon oxide, gypsum, novaculite, dosonite and clay. 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 the biodegradability of the polylactic acid resin, and kenaf is particularly preferable. Further, the aspect ratio (average fiber length / average fiber diameter) of the fibrous reinforcing material used for blending is preferably 5 or more, more preferably 10 or more, and further preferably 20 or more.

  The 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.

  Moreover, 200-0.1 weight part is preferable with respect to 100 weight part of polylactic acid resin, and, as for content of a reinforcing material, 100-0.5 weight part is more preferable.

  In the present invention, it is preferable to further contain a lamellar silicate, and it is more 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 containing the 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 saconite, various clay minerals such as vermiculite, halloysite, kanemite, kenyanite, zirconium phosphate, and titanium phosphate, Examples thereof include swelling mica such as Li-type fluorine teniolite, Na-type fluorine teniolite, Na-type tetrasilicon fluorine mica, Li-type tetrasilicon fluorine mica, and the like, which may be natural or synthesized. Among these, smectite clay minerals such as montmorillonite and hectorite, and swellable synthetic mica such as Na-type tetrasilicon fluorine mica and Li-type fluorine teniolite are preferable.

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

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

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

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

Quaternary ammonium ions include benzyltrialkylammonium ions such as benzyltrimethylammonium, benzyltriethylammonium, benzyltributylammonium, benzyldimethyldodecylammonium, benzyldimethyloctadecylammonium, benzalkonium, trimethyloctylammonium, trimethyldodecylammonium, and trimethyloctadecylammonium. Alkyltrimethylammonium ions such as dimethyldioctylammonium, dimethyldidodecylammonium, dimethyldialkylammonium ions such as dimethyldioctadecylammonium, trialkylmethylammonium ions such as trioctylmethylammonium and tridodecylmethylammonium, benzene Such as benzethonium ion having two thereof.
In addition to these, aniline, p-phenylenediamine, α-naphthylamine, p-aminodimethylaniline, benzidine, pyridine, piperidine, 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, amino at the terminal Examples also include ammonium ions derived from polyalkylene glycols having a group.

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

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

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

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

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

  In the present invention, the content of the layered silicate is preferably 40 to 0.1 parts by weight, more preferably 30 to 0.5 parts by weight, particularly 10 to 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 further contain a crystal nucleating agent. As the crystal nucleating agent used in the present invention, those generally used as a polymer crystal nucleating agent can be used without particular limitation, and any of an inorganic crystal nucleating agent and an organic crystal nucleating agent can be used. . Specific examples of inorganic crystal nucleating agents include talc, kaolinite, montmorillonite, synthetic mica, clay, zeolite, silica, graphite, carbon black, zinc oxide, magnesium oxide, titanium oxide, calcium sulfide, boron nitride, calcium carbonate, Examples thereof include metal salts of barium sulfate, aluminum oxide, neodymium oxide, and phenylphosphonate. 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 salt of organic carboxylic acid such as aluminum dibenzoate, potassium dibenzoate, lithium dibenzoate, sodium β-naphthalate, sodium cyclohexanecarboxylate, organic sulfonate such as sodium p-toluenesulfonate, sodium sulfoisophthalate, stearic acid Amide, ethylenebislauric acid amide, palmitic acid amide, hydroxystearic acid amide, erucic acid amide, carboxylic acid amides such as trimesic acid tris (t-butylamide), low density polyethylene, high density polyethylene, polypropylene, polyisopropylene, polybutene Polymers such as poly-4-methylpentene, poly-3-methylbutene-1, polyvinylcycloalkane, polyvinyltrialkylsilane, and high melting point polylactic acid, Sodium salt or potassium salt of a polymer having a carboxyl group such as sodium salt of ethylene-acrylic acid or methacrylic acid copolymer, sodium salt of styrene-maleic anhydride copolymer (so-called ionomer), benzylidene sorbitol and its derivatives, sodium-2, Phosphorus compound metal salts such as 2'-methylenebis (4,6-di-t-butylphenyl) phosphate and 2,2-methylbis (4,6-di-t-butylphenyl) sodium can be exemplified. .

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 content of the crystal nucleating agent is preferably 30 to 0.01 parts by weight, more preferably 10 to 0.05 parts by weight, and even more 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 contain a crystal nucleating agent because moldability, heat resistance and flame retardancy are improved.

  In the present invention, it is preferable to further contain a plasticizer. 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, and 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 polycarboxylic acid plasticizers include phthalates such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, diheptyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, and trimellitic acid. 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, citrate esters such as triethyl acetylcitrate and tributyl acetylcitrate, azelaic acid esters such as di-2-ethylhexyl azelate, sebacin Dibutyl, and sebacic acid esters such as di-2-ethylhexyl sebacate and the like.

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

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, silicone oils, and paraffins.

Among the plasticizers used in the present invention, at least one selected from polyester plasticizers and polyalkylene glycol plasticizers is particularly preferable. Only one type of plasticizer may be used in the present invention, or two or more types may be used in combination.
Further, the content of the plasticizer is preferably in the range of 30 to 0.01 parts by weight, more preferably in the range of 20 to 0.1 parts by weight, with respect to 100 parts by weight of the polylactic acid resin, and 0.5 to 10 parts by weight. A range of parts is more preferred.

  In the present invention, it is preferable to contain a plasticizer because moldability and heat resistance are improved without impairing 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.

  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 preferably added. In addition, coloring agents including dyes and pigments can be added.

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

  As the flame retardancy of the resin composition of the present invention, the flame retardancy in accordance with UL standards is a molded product having a thickness of 0.8 mm (1/32 inch) and performances of V-2, V-1, V-0, 5V. , V-0, V-0, and 5V are more preferable, and V-0 performance is particularly preferable.

  The resin composition of the present invention is a composition having unique characteristics, and can be processed and used for various molded products by a method such as injection molding or extrusion molding.

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

  Specific uses of molded products include electrical equipment housings, OA equipment housings, various covers, various gears, various cases, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches , Coil bobbins, condensers, variable capacitor cases, optical pickups, oscillators, various terminal boards, transformers, breakers, plugs, printed wiring boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, housings, semiconductors , LCD, FDD carriage, FDD chassis, motor brush holder, parabolic antenna, CD tray, cartridge, cassette, sorter, AC adapter, charging stand, switchboard, outlet cover, VTR parts, TV parts, eye Hair dryer, rice cooker parts, microwave oven parts, acoustic parts, audio / laser discs / compact discs, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, telephone related parts, facsimile related parts, copying machines Related parts can be listed, and mechanical parts include various types of bearings such as cleaning jigs, oilless bearings, stern bearings, underwater bearings, motor parts, lighters, typewriters, etc. Examples include microscopes, binoculars, cameras, watches, etc. Automotive parts include precision machine parts, alternator terminals, alternator connectors, IC regulators, various valves such as exhaust gas valves, fuel-related / exhaust systems / intake Various pipes, air Intake nozzle snorkel, intake manifold, fuel pump, engine coolant joint, carburetor main body, carburetor spacer, exhaust gas sensor, coolant sensor, oil temperature sensor, brake pad wear sensor, throttle position sensor, crankshaft position sensor, air Flow meter, Thermostat base for air conditioner, Heating hot air flow control valve, Brush holder for radiator motor, Water pump impeller, Turbine vane, Wiper motor related parts, Dust distributor, Starter switch, Starter relay, Transmission wire harness, Window Oscher nozzle, air conditioner panel switch board, coil for fuel related electromagnetic valve, Examples include a connector for a fuse, a horn terminal, an electrical component insulating plate, a step motor rotor, a lamp socket, a lamp reflector, a lamp housing, a brake piston, a solenoid bobbin, an engine oil filter, and an ignition device case.

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

[Examples 1-3, Comparative Examples 1-3]
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, talc (FMS talc LMS300), plasticizer (polyethylene glycol, PEG4000S manufactured by Sanyo Chemical Co., Ltd.) was mixed in the proportions shown in Table 1 and melt kneaded with a 30 mm diameter twin screw extruder under conditions of a cylinder temperature of 210 ° C. and a rotation speed of 150 rpm to obtain a resin composition.

In addition, the code | symbol of the flame retardant (A) in Table 1 shows the following content.
A-1: Tetrabromobisphenol-A-carbonate oligomer (FG7500 manufactured by Teijin Chemicals)
A-2: Brominated epoxy resin (Sakamoto Yakuhin SR-T1000)
A-3: Antimony trioxide (NA-1030 manufactured by Nissan Chemical Industries)
A-7: Melamine cyanurate (MC-440 manufactured by Nissan Chemical Industries)
A-9: Triphenyl phosphate (manufactured by Daihachi Chemical)
A-10: Magnesium hydroxide (manufactured by Sakai Chemical)

  Further, the obtained resin composition was injection molded at a cylinder temperature of 210 ° C. and a mold temperature of 40 ° C. Further, using the obtained test piece, a tensile test was measured according to ASTM method D638, a bending test was measured according to ASTM method D790, and a thermal deformation temperature (load 0.45 MPa) was measured according to ASTM method D648. Also, vertical combustion test of US UL standard subject 94 (UL94) using a 127 × 12.7 × 0.8 mm (5 inch × 1/2 inch × 1/32 inch) test piece produced by injection molding. A flame test was conducted in accordance with the law to evaluate flame retardancy.

  These results are also shown in Table 1.

Claims (8)

A resin composition comprising a polylactic acid resin, any one selected from a bromine-based flame retardant and a nitrogen compound-based flame retardant, and a flame retardant using another inorganic flame retardant in combination. The resin composition according to claim 1, wherein the content of the flame retardant is 1-150 parts by weight with respect to 100 parts by weight of the polylactic acid resin. Furthermore, the resin composition of any one of Claims 1-2 formed by containing a reinforcing material. Furthermore, the resin composition of any one of Claims 1-3 formed by containing layered silicate. Furthermore, the resin composition of any one of Claims 1-4 formed by containing a crystal nucleating agent. Furthermore, the resin composition of any one of Claims 1-5 formed by containing a plasticizer. The resin composition according to any one of claims 1 to 6, wherein flame retardancy according to UL94 standard gives a performance of V-0 in a molded product having a thickness of 0.8 mm (1/32 inch). . The molded article which consists of a resin composition of any one of Claims 1-7.