WO2008044471A1 - Thermoplastic resin composition - Google Patents

Abstract

A thermoplastic resin composition comprising at least (A) a polylactic acid having a high molecular weight, (B) a plasticity-imparting agent and (C) an inorganic flame retardant agent, wherein the high-molecular-weight polylactic acid (A) contained in the thermoplastic resin composition has a melt flow rate (MFR) of less than 15.

Description

 Specification

 Thermoplastic resin composition

 Technical field

 [0001] The present invention contains a high molecular weight plant-derived resin, a flexibility imparting agent, and an inorganic flame retardant.

Further, the present invention relates to a thermoplastic resin composition containing a plasticizer and achieving excellent toughness and flame retardancy.

 Background art

 [0002] In recent years, plant-derived resins have attracted attention as substitutes for petroleum raw materials, and research into commercialization of resin compositions using various plant-derived resins has been actively conducted. Recently, polylactic acid resins have attracted particular attention as an example of plant-derived resins, and are being commercialized for various uses. Examples of applications of the above-mentioned plant-derived resin are applications for which disposal is expected to be short, such as containers and packaging and films for agricultural use, housings for home appliances, mobile phones and OA equipment, and parts for automobiles. As you can see, there are a wide variety of high-performance applications that can retain the initial characteristics for a long time.

 However, since these plant-derived resins, in particular polylactic acid resins, are inferior in toughness, this property must be enhanced. In addition, when using plant-derived resin in applications that require high flame retardancy beyond toughness alone, such as household appliances and housings of office automation equipment and automotive parts, these properties are simultaneously used. It needs to be achieved. In particular, when a resin composition comprising a plant-derived resin is used for the housing of an electric product, it is necessary to satisfy the flame retardant standards including the US Underwriters Laboratories (UL) standards. Yes. However, the resin composition comprising the existing plant-derived resin can not satisfy the above-mentioned flame retardancy standard.

On the other hand, as a general method, there is a method of achieving high flame retardancy! /, And halogen-containing flame retardants such as bromine compounds in a resin by blending them. However, when a halogen-based flame retardant is added to polycarbonate resin, which is a representative of polyester-based resin, when it is repeatedly melt-kneaded for the purpose of reuse, the resin is degraded and flame resistance, impact resistance, etc. There was a problem that the physical properties decreased. Therefore, as a representative of plant-derived resin, it has an ester bond When a halogen-based flame retardant is used for the polylactic acid resin, there is a concern that the physical properties may deteriorate when it is repeatedly melt-kneaded, as in the case of the polycarbonate resin.

 On the other hand, at least one flame retardant system selected from a polylactic acid resin, y-n compounds, hydroxide compounds (also referred to as metal hydrates and includes aluminum hydroxide), and silica compounds. Patent Document 1 discloses a biodegradable resin composition using an additive. Patent Document 1: Japanese Unexamined Patent Application Publication No. 2003-192925

 Disclosure of the invention

 Problem that invention tries to solve

However, the above-described prior art has the following problems. That is, polylactic acid resin, which is a representative of plant-derived resins (this resin also has biodegradability) is generally a brittle material and has insufficient flame retardancy, so it can be used as a housing for home appliances and OA equipment. There was a problem in applying it.

 Furthermore, the polylactic acid resin composition described in Patent Document 1, that is, a polylactic acid resin composition containing 50% by mass of the illustrated 99.5% by mass of aluminum hydroxide (= Poly lactic acid + aluminum hydroxide + mass ratio to total amount of hydrolysis resistance) is only compliant with V-2 in UL standard, and is required for housing application of home appliances and OA equipment, more advanced There is a problem that can not satisfy the required flame retardancy (V-1 or more).

 In addition, the polylactic acid resin composition containing 50% by mass of aluminum hydroxide described in Patent Document 1 has a bending strain of only about 1% or less in household appliances and OA equipment. There is a problem that the toughness is not enough to apply to

 The present invention has been made in view of power and other problems, and an object of the present invention is to provide a thermoplastic resin composition which is excellent in toughness and flame retardancy and contains a plant-derived resin.

 Means to solve the problem

 The thermoplastic resin composition according to the present invention contains a high molecular weight polylactic acid (A), a flexibility imparting agent (B), and an inorganic flame retardant (C), and the high molecular weight polylactic acid (A The melt flow rate at 190 ° C. is less than 15.

Further, the thermoplastic resin composition according to the present invention is a plasticizer (D) in addition to the above-mentioned high molecular weight polylactic acid (A), a flexibility imparting agent (B) and an inorganic flame retardant (C). Containing Effect of the invention

 The thermoplastic resin composition containing a plant-derived resin according to the present invention has a high molecular weight polylactic acid (A), a flexibility imparting agent (B) and an inorganic flame retardant (C) and further a plastic By containing the agent (D), excellent toughness and flame retardancy can be realized.

 That is, the thermoplastic resin composition according to the present invention, which contains the inorganic flame retardant (C) as an essential component, first contains, simultaneously, high molecular weight polylactic acid (A) and a flexibility imparting agent (B). Show excellent toughness (especially large strain at break). Furthermore, the thermoplastic resin composition according to the present invention, which contains the inorganic flame retardant (C) as an essential component, has the high molecular weight polylactic acid (A), a flexibility imparting agent (B) and a plasticizer (D) At the same time, it contains a synergetic effect that improves the toughness specifically. In particular, the breaking strain is significantly improved.

 Brief description of the drawings

 FIG. 1 is a graph showing the relationship between bending rupture strain and melt flow rate.

 BEST MODE FOR CARRYING OUT THE INVENTION

 Hereinafter, the present invention will be described in more detail.

 The present invention is characterized by containing a high molecular weight polylactic acid (A), a flexibility imparting agent (B) and an inorganic flame retardant (C), and further containing a plasticizer (D). The thermoplastic resin composition.

 The high molecular weight polylactic acid (A) according to the present invention is a polylactic acid having a melt flow rate at 190 ° C. (hereinafter referred to as MFR) of less than 15, and the lower this value is It is effective in improving toughness.

[0018] Here, MFR is an extrusion type plastometer, which measures the mass (g) of resin flowing out in 10 minutes from a nozzle (orifice) with specified dimensions under a constant pressure and a constant temperature. , G / 10 is an index expressed in units of 10 minutes. In general, the smaller the MFR value, the lower the fluidity at the time of melting, that is, the higher the molecular weight of the resin. Here, a method of measuring MFR for polylactic acid in a very general manner, that is, setting the melting temperature to 190 ° C. with an extrusion type plastometer in accordance with ISO (International Stand ardizing Organization) 1133, 2.16 kg Mass of resin that flows out in 10 minutes when the load of water is applied (g / 10 Minutes) as MFR. In the case of high molecular weight polylactic acid having the MFR of less than 15, in the thermoplastic resin composition according to the present invention, an effect of specifically improving the breaking strain is exhibited.

 However, when the MFR of the high molecular weight polylactic acid (A) is too small (that is, the case where the molecular weight of polylactic acid is further increased), the inorganic flame retardant (C) is an essential component. The MFR is preferably 3 or more because the fluidity of the thermoplastic resin composition of the present invention may be reduced and sufficient moldability may not be obtained. The molecular structure of polylactic acid is usually linear, but may be branched.

[0020] The flexibility imparting agent (B) according to the present invention is not particularly limited as long as the elastic modulus at normal temperature is lower than that of polylactic acid, and it is made of an organic material. It is preferable that / is a compound having a structural unit that is compatible with polylactic acid and a structural unit that exhibits flexibility in the same structure. Specific examples of the organic substance constituting the flexibility imparting agent (B) include a copolymer consisting of _three components of polylactic acid, glycols and linear saturated dicarboxylic acid. Examples of the darichles that constitute the copolymer include ethylene glycol, propylene glycol, diethylene glycol and the like. Further, as the above-mentioned linear saturated dicarboxylic acid constituting the above-mentioned copolymer, there can be exemplified succinic acid, dartalic acid, adipic acid, pimelic acid, suberic acid, caseelaic acid, sebacic acid and the like. As specific examples of the organic substance constituting the flexible additive (B), other than the above, polybutylene succinate, copolymer of polybutylene succinate and polylactic acid, polyprotonic agent, polyprogenic agent and polylactic acid Copolymers, natural rubber, acrylic resins such as polymethyl methacrylate (PMMA), polyester segments, polyether segments, and copolymers having a polymer block selected from the group consisting of polyhydroxy carboxylic acid segments Block copolymer in which a polylactic acid segment, an aromatic polyester segment and a polyalkylene ether segment are bonded to each other, a polymer containing an unsaturated carboxylic acid alkyl ester unit as a main component, polyethylene succinate, polyethylene adipate, Polypropylene And aliphatic polyesters such as polybutylene adipate, polyhexamethylene adipate and polybutylene succinate adipate, polyethylene glycol and esters thereof.

The mass ratio of the high molecular weight polylactic acid (A) to the flexibility imparting agent (B) is set to 95: 5 to 50:50. The force that can be preferably is a ratio of 92: 8 to 70:30.

In addition, as the inorganic flame retardant (C) according to the present invention, metal hydrates are particularly preferred. Further, as the flame retardant other than the flame retardant (C), flame retardants other than halogen flame retardants such as nitrogen flame retardant and phosphorus flame retardant may be used in combination. In addition, halogen-based flame retardants interrupt and cut the combustion cycle by capturing and reducing active radicals (······) generated during combustion of plastic by halogen and turning it into a more inactive form. Also, it has a mechanism to generate gaseous halogen compounds and to block the polymer from heat and oxygen, and it simply contains halogen V, not in the sense!

 The flame retardant (C) according to the present invention is an inorganic substance having a content of 0.2% by mass or less of an alkali metal-based substance, and is a metal hydrate which further exhibits thermal absorption effect by thermal decomposition. When used in combination with a plant-derived resin (for example, represented by polylactic acid) having an ester bond having excellent flame retardancy, the molecular weight reduction of the above-mentioned plant-derived resin having an ester bond is Low V, particularly preferred V, (good resistance to hydrolysis).

 As such an inorganic flame retardant (C), aluminum hydroxide, boehmite, magnesium hydroxide, dawsonite, calcium aluminate, hydrated gypsum, calcium hydroxide, zinc borate, barium metaborate, borohydride Examples of such fillers include sand, kaolin clay and calcium carbonate, inorganic fillers surface-treated with various organic substances including epoxy resin and phenolic resin, and inorganic fillers obtained by solidifying metals. Among these, aluminum hydroxide, which is a representative of metal hydrates, is particularly preferable because it is particularly excellent in flame retardancy with high endothermic effect.

 Furthermore, in the present invention, when the 50% by mass particle diameter of the inorganic flame retardant (C) is in the range of 20 111 or less, the plant-derived resin contained in the thermoplastic resin composition of the present invention It is more preferable because the dispersibility is good and the flame retardancy and the mechanical property improvement effect are excellent. When the 50% by mass particle diameter of the inorganic flame retardant (C) is 20 μm or less, the surface properties of the thermoplastic resin composition containing the same are also excellent, and irregularities may be generated on the surface to lower the designability. Absent.

Furthermore, when the weight ratio of the above-mentioned inorganic flame retardant (C) to the total amount of the thermoplastic resin composition of the present invention is X, the above-mentioned X is in the range of 30% by mass to 60% by mass. In addition to a flame retardance and fluidity, it is more preferable because it is excellent in thermal decomposition resistance. The above When the weight ratio X of the inorganic flame retardant (C) is less than 30% by mass, the flame retardance may be insufficient. When the weight ratio X of the above-mentioned inorganic flame retardant (C) exceeds 60% by mass, the fluidity and the thermal decomposition resistance may be lowered.

 In addition, as a flame retardant other than the above-mentioned flame retardant (C) and the halogen-based flame retardant, nitrogen-based flame retardants, phosphorus-based flame retardants and the like can also be used. Examples of these nitrogen-based flame retardants include melamine and isocyanuric acid compounds. Examples of phosphorus-based flame retardants include red phosphorus, phosphoric acid compounds, and organic phosphorus compounds. In particular, when the thermoplastic resin composition of the present invention contains a metal hydrate such as aluminum hydroxide among the inorganic flame retardants (C), the above-mentioned nitrogen based flame retardants and phosphorus based flame retardants may be used. The amount of addition of the flame retardant is small, and deterioration of other physical properties such as moisture resistance, heat resistance, mechanical properties and the like caused by the flame retardant other than the inorganic flame retardant (C) can be suppressed. In addition, the above-mentioned inorganic flame retardant (C) and other flame retardants may be pretreated on high strength fibers and fibers derived from plants for use.

The plasticizer (D) according to the present invention also includes, in a broad sense, a “lubricant” having a releasing effect. The plasticizer (D) is not particularly limited as long as it penetrates between polymer molecules, in particular between polylactic acid molecules to weaken the intermolecular force between the polymers and facilitate movement of the molecular chain. is not. Specific examples of the plasticizer (D) include dimethyl adipate, dibutyl adipate, diisobutyl adipate, bis (2-ethylhexyl) adipate, diisononyl adipate, diisodecyl adipate, bis (butyl diglycol) adipate, bis (butyl ester). Noregi Gliconole) adipate, bis (2-etinole hexinore) gaslate, dimethynoles cenocate, dibutynoresenocate, bis (2-ethinole hexinole) cenocate, bis (2-ethinolehexyl / le) senocate, ge Aliphatic dibasic acid esters such as resuccinate, bismethy / legetylene glycolonaea dipate, and benzyl-2- (2-methoxyethoxy) ethyl adipate, ditridecyl phthalate, dinormalocyl phthalate, diisononyl phthalate, dimethyl Phthalate esters such as tallyte, jetyl phthalate, dibutyl phthalate, bis (2-ethyl nolhexyl) phthalate, di-octyl phthalate, diisodecyl phthalate, butyl benzyl phthalate, diisononyl phthalate, ethyl phthaloyl thalidolate , Trimellitic acid esters such as tolnorroxyl trimellitate, triisodecyl trimellitate and tris (2-ethylhexyl) trimellitate, trimethyl phosphate , Triethyl phosphate, tributyl phosphate, tris (2-ethylhexyl) phosphate, tris (butoxyethyl) phosphate, triphenyl phosphate, tricresyl phosphate, trixylene base phosphate, cresino base resin phosphate, 2- Phosphoric acid esters such as hydroxyethyl oleicyl phosphate, ricinoleic acid esters such as methylacetyl licinolate, aliphatic polyesters such as poly (1, 3-butanediol adipate), polyglycerin acetate, epoxidized soybean oil And other epoxidized polyesters, epoxyxed linseed oil, epoxidized linseed oil, fatty acid butyl, glyceryl triacetate, acetates such as 2-ethylhexyl acetate, sulfones such as N-butyl benzene sulfonamide Liquid paraffin such as chlorinated paraffin, alkyl naphthene hydrocarbon, paraffin wax such as n paraffin, polyethylene wax such as low molecular weight polyethylene, partially oxidized polyethylene, octyl alcohol, decyl alcohol, laurinoleanolec, myristino alano Aliphatic alcohols such as Leconor, cetyl alcohol and stearyl alcohol, linolenic acid, linoleic acid, oleic acid, lauric acid, myristic acid, palmitic acid, fatty acids such as stearic acid and behenic acid, 12-hydroxystearin derived from castor oil Hydroxy fatty acids such as acids, methyl stearate, otatyl stearate, stearyl stearate, ethylene glycol monostearate, fatty acid esters such as ethylene glycol distearate, 12-hydride Hydroxy fatty acid esters such as methyl Hydroxystearate, stearyl 12-hydroxystearate, ethylene glycol mono- 12-hydroxystearate, propylene glycol mono- 12-hydroxystearate, stearylamide, N-hydroxy-glycinoleylamide, N-hydroxy- 12-hydroxy-stearoleamide, N, N, ethylene-bis-bis-oleylamide, N, N, ethylene-bis-bis-cinoleamide, N, N, ethylene-bis-octadecadienyl amide, N, N , 1-bis-bis-12-hydroxystearylamide, N, N, 1-ethylene-bis-bis-stearylamide, N, N, 1-hexamethylene-bis-bisinosylamide, N, N, 1-hexamethylene-bis-one 12-hydroxy stearylamide, N, N, 1 Ren one bis one 12-hydroxystearic acid amides such as Teariruamido include aliphatic stone 鹼等.

When the plasticizer (D) is added to the thermoplastic resin composition of the present invention, it is preferably added so as to be 5% by mass or less based on the total amount of the thermoplastic resin composition. Yes. If this value exceeds 5%, sufficient flame retardance may not be obtained.

[0030] In the thermoplastic resin composition of the present invention, in the case where the high molecular weight polylactic acid (A, hereinafter, high molecular weight polylactic acid) and the flexibility imparting agent (B) are simultaneously contained, the high molecular weight In the case of polylactic acid (A) alone, polylactic acid other than the high molecular weight polylactic acid (A) (hereinafter referred to as low molecular weight polylactic acid ω) alone, the low molecular weight polylactic acid ω is a flexibility imparting agent ( The strain at break is superior to the case where Β) is added. Hereinafter, as high molecular weight polylactic acid (Α) according to the present invention, crystalline high molecular weight polylactic acid with MFR less than 15 (hereinafter referred to as high molecular weight poly L lactic acid (A1). It has a crystalline portion and an amorphous portion. As a flexibility imparting agent (可能 な), a compound having a structural unit capable of compatiblizing with polylactic acid and a structural unit exhibiting flexibility in the same structure, for example, polylactic acid and glycols, and a straight chain The mechanism for improving the toughness, in particular the strain at break, will be described in the case where each of the three component copolymers of the cyclic saturated dicarboxylic acid is used.

 [0031] The above-mentioned flexibility imparting agent (鎖) having a saturated aliphatic chain having a small interaction between molecular chains and polylactic acid as a constitutional unit is a copolymer having flexibility and partially Is compatible with polylactic acid. Therefore, the molecule of the agent for imparting flexibility (Β) is likely to form entanglement of molecular chains with the polylactic acid molecule. In particular, in the case of using the high molecular weight poly L lactic acid (A1) according to the present invention, the molecular chains are easily entangled, and the distance of entanglement is also long. As a result, it is assumed that the toughness is effectively improved as a result of forming a typical crosslink.

 In the thermoplastic resin composition of the present invention, when the plasticizer (D) is further used in combination with the high molecular weight poly (L-lactic acid) (A1) and the flexible additive (Β), the high resin The toughness is remarkably improved as compared with the case where only two components of molecular weight polylactic acid (A1) and the above-mentioned flexibility imparting agent (Β) are contained. A mechanism that synergistically improves toughness, in particular, strain at break, is described for the case where a compound that causes a sliding effect between molecules of polylactic acid, for example, trimellitic acid ester, is used as the plasticizer (D). Do.

In addition to the high molecular weight poly-L-lactic acid (A1) and the flexibility imparting agent (Β), the presence of the plasticizer (D) is presumed to significantly improve the toughness with the following three effects: did. The three effects are [1] The effect of improving the dispersibility of the high molecular weight poly-L-lactic acid (A1) and the flexibility imparting agent (B) in the thermoplastic resin composition of the present invention by the addition of the plasticizer (D) ,

 [2] An effect of increasing the entanglement V of the molecular chains of the high molecular weight poly-L-lactic acid (A1) and the moldability imparting agent (B) by the dispersion improvement effect of the above [1],

 [3] Addition of plasticizer (D) reduces the intermolecular force, resulting in the effect of causing slippage between molecular chains

 It is.

 That is, since the dispersibility of the high molecular weight poly-L-lactic acid (A1) and the flexibility imparting agent (B) is improved by the addition of the plasticizer (D), the (A1) and (B) can be obtained. As the molecular chains of the polymer chains become entangled, the (A1) has a high molecular weight, so that the distance between the molecular chains is longer than in the case where only low molecular weight polylactic acid (a) is used. Therefore, when the thermoplastic resin composition of the present invention is deformed by stress, stress relaxation due to the flexibility of the flexibility imparting agent (Β) is more than that when the low molecular weight polylactic acid (a) is solely composed. While the effect is effectively developed, a large amount of energy is consumed to break up the entanglement between molecular chains, and the effect of slipping between the molecular chains is also exhibited because the plasticizer intervenes between molecules, and stress is generated. It was speculated that the effect would be alleviated more than expected. As a result, I think that it showed an unexpected improvement in strength and breaking strain. Furthermore, crystals of polylactic acid which are hard, brittle and difficult to deform become "crystals having flexibility" which are easily deformed by stress due to the addition effect of the plasticizer (D), and the thermoplastic resin of the present invention It is estimated that it contributed to the increase in the toughness of the composition.

The thermoplastic resin composition according to the present invention may contain an organic substance derived from a plant other than polylactic acid, and the structure thereof is not particularly limited. As plant-derived organic substances other than polylactic acid, for example, as a plant-derived resin based on succinic acid which can be obtained using saccharides contained in corn and corn as starting materials, esters such as polybutylene succinate are usable. is there. In addition, starch, amylose, cellulose, cellulose ester, chitin, chitosan, gellan gum, carboxyl group-containing cellulose, carboxyl group-containing starch, pectinic acid, polysaccharides such as alginic acid and the like are also plant-derived organic substances. When using polybutylene succinate as “organic matter derived from plants other than polylactic acid”, Excluded from the above-mentioned flexibility imparting agent (B) of the invention.

[0036] Also, polybetahydroxyalkanoate (Zeneca, trade name: biopore, etc.), which is a polymer of hydroxybutyrate and / or hydroxyvalerate synthesized by microorganisms, is not derived from plants, but It can be used because it has the same meaning as plant-derived resin in that it does not require petroleum resources.

[0037] Lignin is a dehydrogenation polymer of coniferyl alcohol and sinapyl alcohol which is contained in 20 to 30% of wood, and a modified product thereof is also a plant-derived resin. That is, thermosetting resins using plant materials such as lignin, hemicellulose and cellulose may also be used.

 [0038] Among the above-mentioned plant-derived resins, artificially synthesized biodegradable oligomers and polymers, modified products of artificially synthesized biodegradable oligomers and polymers, and modified products of naturally synthesized biodegradable oligomers and polymers Since the bonding strength between molecules is appropriate, the thermoplastic resin is excellent, and the viscosity at the time of melting is preferably not significantly increased, because it has good moldability and processing ability. Among them, aliphatic polyesters and modified polyesters which are crystalline polyesters and modified polyesters are more preferable. Furthermore, aliphatic polyamino acids and aliphatic polyamino acids modified with polyamino acids and modified polyamino acids are more preferable. In addition, modified products of polyols and polyols are preferable, and modified products of aliphatic polyols and aliphatic polyols are more preferable.

In addition, petroleum-derived resins can also be mixed with plant-derived resins. As resins derived from petroleum, for example, polypropylene, polystyrene, ABS, nylon, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, urea resin, melamine resin, alkoxide resin, acrylic resin, unsaturated polyester resin, diaryle phthalate resin, Epoxy resin, silicone resin, cyanate resin, isocyanate resin, furan resin, furan resin, ketone resin, thermosetting resin, thermosetting polyimide, thermosetting polyamide, styrylpyridine resin, nitrile terminal resin, addition curing resin Examples include thermosetting resins such as quinoxaline, addition-curable polyquinoxaline resin, and the like, and the plant-derived resin. When a thermosetting resin is used, a curing agent and a curing accelerator necessary for the curing reaction can be used. Further, the thermoplastic resin composition according to the present invention may contain a core forming agent (E). The above-mentioned heat forming agent (E) is excellent in thermal decomposition resistance and is not particularly limited as long as it is a compound which easily forms a carbonized component (also referred to as a heat generating agent)! As the above-mentioned chain forming agent (E), phenols, silicone compounds, boron compounds and the like are particularly preferable in view of flame retardancy and flowability.

 The phenols are generally used as curing agents for epoxy resins, as long as they are not particularly limited unless they volatilize or decompose at the kneading temperature or molding temperature of the resin. A phenolic resin is available. These phenol resins are exemplified by phenol nopolac resin, cresol nopolac resin, p-cresol nopolac resin, phenol xylene alaryl type resin, phenol biphenyl dilenalallyl type resin, bis phenol A type phenol resin, bis phenol F-type phenol resin, bis-phenol S-type phenol resin, biphenyl isomer dihydroxy ether-type phenol resin, naphthalene diol-type phenol resin, phenol diphenol ether resin, naphthalene-containing nopolac resin, anthracene-containing nopolac resin Resin, biscresol fluorene, fluorene-containing nopolac resin, bisphenol fluorene-containing novolak resin, bisphenol F-containing nopolac phenol resin, bisphenol A-containing nopolac phenol resin, phenol biphenyl triazine resin, phenol xylylene triazine resin, phenol triazine resin, trisphenyl dirole ethane resin, tetrafluorodi roll ethane resin, polyphenol resin, aromatic ester pheno resin Resin, cyclic aliphatic ester-containing phenolic resin, ether ester type phenolic resin and phenoxy resin, furan ring-containing phenolic resin and the like. Also, as other phenols, biphenyl, xylenol, bisphenol A, bisphenol 1? And bisphenol S, catechol and catechol resins. Furthermore, catechol biphenyl alkyal resins, catechol xylene alaryl resins and the like obtained by copolymerizing catechol and derivatives of aromatics can also be used. In addition, lignin and its analogues (for example, lignophenols) may be used.

However, since phenols are easily oxidized! /, In applications where design is required, it is generally more preferable to use in combination with a compound used as an antioxidant. Or Since p-cresol nopolac resin and biscresol fluorene are relatively good in flame retardancy and at the same time difficult to take a quinone structure which is a cause of coloring, use of these is preferable because the designability is good. In addition, compounds obtained by dalysylated or ethylene oxided phenolic hydroxyl groups in the structure of phenols do not change to the quinone structure that causes coloring, so if these compounds are used, the thermoplastic resin composition of the present invention The design of the object is good.

 The silicone compound is an organosilane containing an aromatic ring, which is branched or linear unless it volatilizes or decomposes at the kneading temperature or molding temperature of the resin. The structure is not limited. Among these, as a silicone compound of a branched structure, it is preferable that it is a thing containing the unit (T unit) shown by Formula RSiO 2. Furthermore, the formula SiO

 1.5

 You may contain the unit (Q unit) shown by these. Furthermore, the branched structure of the silicone compound

2.0

 Is a unit represented by the formula RSi o (T unit), a unit represented by the formula R SiO 2 (D unit), the formula

 1.5 2 1.0

 Composed of units (M units) represented by R SiO! /, And particularly preferred in terms of improvement of flame retardancy

3 0.5

 Yes. Here, R represents a monovalent aliphatic hydrocarbon group or an aromatic hydrocarbon group, at least one of which is a group containing an aromatic ring. Even if all R's are different, all R's may be the same. The subscripts "2" and "3" in R indicate the number of substitutions. With such a structure, the flame retardancy can be further improved. In addition, the silicone compound having a linear structure has a unit represented by the formula R SiO (D unit), a unit represented by the formula R SiO (M unit

 2 1.0 3 0.5

 It refers to what consists of. Furthermore, such silicone compounds are effective in improving impact resistance in addition to the improvement of flame retardancy and fluidity.

 In addition, when the weight ratio of the above-mentioned key forming agent (E) to the total amount of the thermoplastic resin composition of the present invention is Y, the Y is not less than 0.5% by mass and not more than 20% by mass. Within the above range, even if the amount of use of the inorganic flame retardant (C) is reduced, it is more preferable because the flame retardancy and the heat resistance which is superior to the fluidity alone are excellent. If the weight ratio Y of the above-mentioned core-forming agent (E) is less than 0.5% by mass, the effect of improving the flame retardancy and the fluidity may be insufficient. In addition, when the weight ratio Y of the above-mentioned core-forming agent (E) exceeds 20% by mass, the heat resistance (in particular, the load deflection temperature <HDT>) may be reduced.

[0045] The above-described carrier-forming agent (E) can be treated with high molecular weight polylactic acid (A), a flexibility imparting agent (B), an inorganic type It has been discovered that, when used in combination with the thermoplastic resin composition of the present invention comprising the flame retardant (C) and the plasticizer (D), there is an excellent flame retardancy improvement effect which is reduced by the flowability improvement effect alone. . Although the cause of this effect is not necessarily clear, it can be caused when the resin composition containing the above-mentioned chain forming agent (E) is ignited especially when metal hydrate is used as the inorganic flame retardant (C). The carbide (including the molten resin) is complexed with the above-mentioned metal hydrate (including the formed metal oxide) to form a unique composite layer (carbide, molten resin, metal hydrate and this oxide). Forming a composite layer), and the composite layer contains water generated by thermal decomposition of metal hydrate and decomposition gas (including combustible gas) of resin components in the resin composition. It is thought that the flame retardancy is improved as a result of the formation of a heat insulating layer that can expand and shut off the heat of ignition efficiently. Furthermore, it is assumed that this heat insulation layer also has an effect of capturing the decomposition gas of the resin and diffusing the decomposition gas to the outside to spread the fire of the resin.

Furthermore, it is preferable to add a crystal nucleating agent (F) to the thermoplastic resin composition of the present invention.

 As the nucleating agent (F), an inorganic nucleating agent or an organic nucleating agent can be used. Examples of inorganic crystal nucleating agents include clay minerals, calcium carbonate, boron nitride, synthetic silicic acid, silicates, silica, carbon black, zinc flower, basic magnesium carbonate, quartz powder, glass fiber, glass powder, green algae, It is possible to cite dolomite powder, titanium oxide, zinc oxide, antimony oxide, barium sulfate, calcium sulfate, alumina, calcium silicate, boron nitride and the like. Here, the clay mineral refers to a hydrous cayrate produced as a main component of clay. Specific examples of clay minerals include alophen, hisingerite, phyllosilicate, neurophyllite, talc, ummo (also called my power) group, montmorillonite group, vermiculite group, liyotadi group, kaolin group, inokeyic acid Salt, norigorskite group, etc.

Further, as an organic crystal nucleating agent,

(1) Organic carboxylic acids, for example, octylic acid, toluic acid, heptanoic acid, heptanoic acid, pelargonic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, cerotic acid, montanic acid, melisic acid, benzoic acid Acid, p-tert-butylbenzoic acid, terephthalic acid, terephthalic acid monomethyl ester, isophthalic acid, isophthalic acid monomethyl ester, rosin acid, 12-hydroxystearic acid, cholic acid, etc. (2) Organic carboxylic acid alkali (earth) metal salts, such as alkaline (earth) metal salts of the above organic carboxylic acids,

 (3) Polymeric organic compounds having metal salts of carboxyl groups, for example, carboxyl group-containing polyethylene obtained by oxidation of polyethylene, carboxyl group-containing polypropylene obtained by oxidation of polypropylene, ethylene, propylene, butene-1 etc. Copolymers of acrylic acid or methacrylic acid, copolymers of styrene and acrylic acid or methacrylic acid, copolymers of olefins and maleic anhydride, styrene and maleic anhydride Metal salts such as copolymers, etc.

(4) Amide compounds, for example, foreic acid amide, stearic acid amide, erucic acid amide, behenic acid amide, N-oleyl palmitamide, N stearyl yl acid amide, N, N'- methylene bis ( Stearyl amide), methylol 'stearyl amide, ethylene bis behenic acid amide, ethylene bis lauric acid amide, hexamethylene bis oleic acid amide, hexamethylene bis stearic acid amide, butylene bis stearic acid amide, N, N'— Dioleyl sebacic acid amide, N, N, -Dioleyl adipic acid amide, N, N,-Distearyl adipic acid amide, N, N,-Distearyl sebacic acid amide, m- xylylene bis-stearic acid amide, N , N 'distearyl isophthalic acid amide, N, N' distearyl terephthalic acid amide, N Acid amide, N-stearyloleic acid amide, N-stearyl acetate, N-oleyl stearamide, N-stearyl-stearic amide, N-butyl-N-stearyl-urea, N-propyl-N, stearyl-acid-urea, N-aryl- N'-stearyl urea, N phenyl N, mono stearyl urea, N stearyl N, mono stearyl urea, dimethitol oil amide, dimethyl lauric acid amide, dimethyl stearic acid amide, etc., N hydroxyl ethylicyclic amide, N Hydroxyethyl-12-hydroxycystearylamide, N, N, monoethylene mono bis mono oleyl amide, N, N, mono ethylene mono bis ricinoleyl amide, N, N, mono ethylene bis-octadecadienyl amide, N , N'-Ethylene-bis-bis- 12-hydroxy stearinoleamide, N, N, ethylene Mono-bis-styramide, N, N, hexamethylene-bis-ricinoleyl amide, N, N, hexa-methylene-bis-one 12-hydroxystearylamide, N, N, mono-xylylene-bis-one 12- Hydroxystearylamide, N, N, monocyclohexane bis (stear opening amide), N lauroyl —L-glutamic acid mono-a, γ-n-butyroreamide, trimesic acid tris (t-butylamide), trimesic acid tris (2-methylcyclohexylene amide), trimesic acid trippenzinoleamide, 1,4-cyclohexanedicarboxylic acid dianilide, 1, 4 Cyclohexanedicarboxylic acid bis (p toluidine amide), 2,6 naphthalenedicarboxylic acid dicyclohexylamide, adipate diisocyanate, adipate bis (4-cyclohexylanilide), butanetetracarboxylic acid tetradicyclohexylamide, butanetetracarboxylic acid tetra-cyclodicarboxylic acid (2-Methylcyclohexyl amide), terephthalic acid dibenzylamide, N, N'-dibenzil 1, 4-diaminocyclohexane, N, N'- dicyclohexanecarbodione 1, 4-diaminocyclohexane, N, N '— To dicyclo Sankarubo two Lou 1, 5-§ amino naphthalene, N, N '- Jibenzoi Honoré one p-phenylene Renjiamin, N, New' - Jibenzoiru 1, 4-Jiaminobutan like,

(5) A high molecular weight organic compound, for example, 3,3 dimethylbutene 1,3 methylbutene 1,3 -methylpentene 1,3-methylhexene 1,3,5,5-trimethylhexene 1 etc. Polymers of 3- or 3-position branched α-olefene having carbon atoms, as well as bulcycloalkanes such as bulcyclopentane, vinylorethene hexane, bulnorbornane, polyalkylene glycols such as polyethylene glycol and polypropylene glycol, polyglycorenoic acid, cenolellose , Cenolerose Estenole, Cenolerose Etenole, Polyestenore, Polycarbonate etc.,

 (6) Phosphoric acid or phosphorous acid and an organic compound thereof or metal salt thereof, for example, diphenyl phosphite, diphenyl phosphite, sodium bis (4-tert butylphenyl) phosphate, methylene phosphate (2, 4-tert-butyl (biphenyl) sodium etc.,

 (7) Sorbitol derivatives, for example, bis (p methyl benzylidene) sorbitol, bis (p ethyl benzylidene) sorbitol,

 (8) Cholesterol derivatives, for example, cholesteryl stearate, cholesteryloxys thearamide,

 (9) Thioglycolic anhydride, paratoluenesulfonic acid, paratoluenesulfonic acid amide and metal salts thereof and the like can be mentioned.

[0049] In addition to the above, metal phenylphosphonates such as zinc phenylphosphonate, calcium phenylphosphonate and magnesium phenylphosphonate, melamine cyanurate and melami Melamine compounds such as monopolyphosphate and bis (benzidrazino carbonyl) octaneate can also be used.

 Among the organic crystal nucleating agents, some of them exert effects as a plasticizer (D), but when used as a crystal nucleating agent (F), the plasticizer (D) may be used. Excluded from).

 [0051] The organic crystal nucleating agent is used for injection molding, etc./ It is compatible with the resin in the high temperature molten state, or dissolved or finely dispersed, and it is deposited in the mold cooling stage in the mold. An organic crystal nucleating agent which phase-separates and acts as a crystal nucleus is preferably used. In addition, the inorganic crystal nucleating agent functions efficiently as a crystal nucleus by highly dispersing the inorganic substance of the fine particles in the resin. The surface of the inorganic crystal nucleating agent is compatibilized (coating treatment using a resin or compound having a compatibilizing action, or ion-exchange treatment, surface treatment with a coupling agent, etc.) S-preferable. Yes. The inorganic crystal nucleating agent whose surface is compatibilized is enhanced in the interaction with the resin to improve the dispersibility, and the aggregation of the nucleating agent can be prevented.

 Alternatively, a masterbatch may be used in which a crystal nucleating agent (F) is previously dissolved or dispersed in a plant-derived resin such as polylactic acid. In addition, when using the crystal nucleating agent (F), when the weight ratio to the total amount of the thermoplastic resin composition of this invention is set to Z, Z is more than 0. 05 mass% and 20 mass% or less These are particularly preferable because the crystallization rate of a crystalline resin such as polylactic acid can be increased to improve the productivity and the impact resistance is good. That is, if the weight ratio Z of the crystal nucleating agent (F) is more than 0.05 mass%, the crystallization proceeds rapidly and the production rate is improved. In addition, when the weight ratio Z of the crystal nucleating agent (F) is 20% by mass or less, particularly when using an inorganic crystal nucleating agent, the growth of cracks starting from the inorganic crystal nucleating agent is suppressed. The impact resistance of the thermoplastic resin composition of the present invention is improved.

The anti-drip agent (G) may be used in combination with the thermoplastic resin composition of the present invention. Examples of the drip inhibitor (G) include organic fibers such as polytetrafluoroethylene (PTFE) and acryl-modified PTFE. In particular, in the case of using these anti-drip agents, it is preferable that the weight ratio to the total amount of the thermoplastic resin composition of the present invention is 1% by mass or less. When the proportion by weight of these anti-drip agents is 1% by mass or less, the granulation property is good when making pellets. Furthermore, when the plant-derived resin has an ester bond in the structure, generally, it is easily hydrolysed by hydrolysis, and thus a known hydrolysis inhibitor (H 2) is used for the purpose of improving hydrolysis resistance. You may use together. As the above-mentioned hydrolysis inhibitor, compounds having reactivity with active hydrogen in a plant-derived resin can be used. Here, as active hydrogen, hydrogen in a carboxyl group, a hydroxyl group, an amino group, an amide group, etc. in a plant-derived resin can be mentioned. As a compound having reactivity with these active hydrogens, a carpodiimide compound, an isocyanate compound and a oxazoline compound can be applied. Although not particularly limited to these, from the viewpoint of achieving both hydrolysis resistance and flame retardancy, aromatic polycarpimides are particularly preferable.

 In addition, high strength fibers (I) can be used as a method for improving heat resistance (particularly heat deformation temperature) and impact strength. High-strength fibers (I) include polyamide fibers such as aramid fibers and nylon fibers, polyester fibers such as polyarylate fibers and polyethylene terephthalate fibers, ultra-high-strength polyethylene fibers, polypropylene fibers, carbon fibers, metal fibers, glass fibers, etc. Such as, high aspect ratio! /, Organic matter and inorganic matter can be mentioned.

 [0056] Aramid fibers and polyarylate fibers are aromatic compounds and have higher heat resistance and higher strength than other fibers, and because they are light in color, they do not impair the designability even when added to a resin. Because of its low specific gravity, it is particularly desirable.

 In addition, the shape of the high strength fiber (I) is a polygon having a round fiber cross section, an irregular shape, or a shape having irregularities, and having a high aspect ratio or a small fiber diameter. The bonding area with force resin increases. As a result, the debonding effect between the fiber and the matrix is increased, and the impact relaxation effect due to the drawing of the fiber is also increased, so that the impact strength is improved. In addition, fibers having irregularities formed on the surface of the fiber, fibers having a kind of wedge shape in which both end portions of the fibers are made thicker than the central portion, those having a narrow part in the fibers, or non-linear By using fibers of a crimped shape, friction at the time of pulling out of the fibers is increased, and impact resistance is improved.

In addition, the high-strength fiber (I) can be subjected to a surface treatment, as necessary, in order to enhance the affinity with the resin as the base material or the entanglement between the fibers. As the surface treatment method, treatment with a coupling agent such as silane or titanate, ozone or plasma treatment, Treatment with an alkyl phosphate ester type surfactant is effective. However, treatment methods that can usually be used to modify the surface of the filler, which is not particularly limited to these, are possible.

 When the average fiber length of the high strength fiber (I) is in the range of 1 mm to 10 mm, it is particularly effective for improving the impact resistance. When the average fiber length of the high strength fiber (I) is lmm or more, sufficient impact resistance can be obtained to enhance the energy absorption effect by pulling out the fiber. In addition, it is preferable to set the average fiber length of the high strength fiber (I) to 10 mm or less because the moldability is good. When high strength fibers (I) are used, when the weight ratio of high strength fibers (I) to the total amount of the thermoplastic resin composition of the present invention is 10% by mass or less, impact resistance is obtained. Preferred because the properties and formability are particularly excellent.

 In addition to the high-strength fiber (I) described above, vegetable fibers such as kenaf and flax can also be used.

 In the present invention, plant fibers refer to fibers derived from plants, and specific examples include fibers obtained from wood, kenaf, bamboo, hemp and the like. The fibers preferably have an average fiber length of 10 mm or less. Also, pulps etc. obtained by delignifying / de-pecting these plant fibers are particularly preferable because they are less likely to be degraded by heat, discoloration, and deterioration. Kenaf and bamboo can absorb a large amount of carbon dioxide because they have high photosynthetic rate and fast growth, and they are excellent as one of the means to solve global problems such as global warming and deforestation by carbon dioxide at the same time. In addition, high-strength fibers (I) and organic fibers among the above-mentioned plant fibers act as crystal nucleating agents for resins, and the heat resistance of the thermoplastic resin composition of the present invention (especially deflection temperature under load) Effect that can improve the <HDT>.

In addition to the thermoplastic resin composition of the present invention, if necessary, a reinforcing material, a coloring agent (such as titanium oxide), a stabilizer (such as a radical scavenger or an antioxidant), an antibacterial agent or an antimicrobial agent Can be used together with mold materials. As a reinforcing material, silica, alumina, sand, clay, slag and the like can be used. Further, as the antibacterial agent, silver ion, copper ion, zeolite containing these, etc. can be used.

The thermoplastic resin composition of the present invention as described above is not particularly limited, and known injection molding methods, injection / compression molding, compression molding methods, film molding methods, blow molding methods, foam molding methods, etc. According to the method described above, it can be processed into molded articles such as electrical and electronic equipment applications such as housings of electric appliances, building materials applications, automobile parts applications, daily necessities applications, medical applications, agricultural applications and the like.

The mixing method of the various compounding components of the thermoplastic resin composition in the present invention is not particularly limited, and mixing and extrusion using known mixers such as a tumbler, ribbon blender, single- or twin-screw kneader, etc. Melt mixing by machine, roll etc. is mentioned.

With regard to the temperature at the time of these melt mixing and molding, it is possible to set a range which is equal to or higher than the melting temperature of the resin as the base material and in which the plant fibers and the plant-derived resin are not thermally deteriorated.

 Example

 Hereinafter, the present invention will be described in more detail by way of specific examples.

 First, raw materials used in the invention examples and the comparative examples will be described. High molecular weight polylactic acid (A), low molecular weight polylactic acid (a), flexibility imparting agent (B), inorganic type flame retardant (C), plasticizer (D), as shown in Table 1 below. A forming agent (Ε), a crystal nucleating agent (F), an anti-drip agent (G) and a hydrolysis inhibitor (Η) were used.

[0067] [Table 1]

Component Content

 High molecular weight polylactic acid (A-1) Melt flow resin (M F R) "= 3

High molecular weight polylactic acid (A-2) MFR ¹ = 9

High molecular weight polylactic acid (A-3) MFR * ¹ = 1 4

Low molecular weight polylactic acid (a-1) MFR * ¹ = 1 6

 Flexibility agent (B-1) Copolymer of propylene glycol, sebacic acid and polylactic acid

 (Dainippon Ink Chemical Industries, Inc.,

 Product name Platelet P D-1 50 ") Inorganic flame retardant (C-1) Aluminum hydroxide

 (Product name Γ H P— 350 *, made by Showa Denko:

N a ₂ 0 * ^z = 0. 05 mass ⁰ / o,

 50% by mass particle size = 3 ju m)

 Inorganic flame retardant (C-1) fine particle aluminum hydroxide

 (The above ground product of "H P-35 0 *":

 50 mass% particle size = 1 jU m)

 Plasticizer (D-1) Benzyl 1-2 (2-Metoxytoxy)

 Fertility Adipate

 (Made by Daihachi Chemical Industry,

 Brand name "D A I F A T T Y-1 0 1") Plasticizer (D-2) Bis (butyl diglycol) Adipate

 (Dahachi Chemical Industry Co., Ltd., trade name "B X A") Plasticizer (D-3) Tris (2-Ethyl Hexyl) Trimelliate

 (Made by Daihachi Chemical Industry Co., Ltd., trade name "Ο Ο Μ 可塑") Plasticizer (D-4)

 (Made by Kao, trade name "Trimex Ν-08") Chain forming agent (E-1) Fueno 1 novolac resin

 (Meiwa Chemical Co., Ltd., trade name "H F-45") Crystal nucleating agent (F-1) N, N '-Ethylene-bis-one 1-2 2-hydroxy stearylamide

 (Ito Oil Co., Ltd.

 Product name r i T Q HWA X J— 530 ”) Anti-drip agent (G-1) Poly trafluorecilene

 (Made by Daikin Industries,

 Brand name “Polyflon M P A F A— 500”) Hydrolysis inhibitor (H-1) Mixture of aromatic polycarboximide 9 5 ° / o and 5% silica

 (Line Chemie, brand name Γ Stabacuzole P ”)

* 1 Melt flow rate (MFR) is shellfish IJ in IS01133 and using an extrusion type plastometer, when the temperature of the resin composition is 190 ° C, a load of 2.16 kg is applied for 10 minutes. The mass (g) of the resin composition flowing out of a nozzle (orifice) having a prescribed size was measured and calculated (unit: g / 10 min). * 2 As total amount of alkali metal based materials in aluminum hydroxide, Table 1 shows total amount of Na 2 O.

 Next, evaluation methods of bending characteristics and flame retardancy in the examples of the present invention and the comparative examples will be shown.

 (1) Kneading of resin composition

 A kneader (biaxial type) in which each material for thermoplastic resin compositions shown in Examples (which may be represented as Examples) and Comparative Examples is set so that the temperature of this composition is about 180 ° C. The mixture was melt mixed to make pellets for injection molding.

 (2) Preparation of a sample for evaluation 1 (molding with a low temperature mold)

 Using the pellets dried at 100 ° C for 7 hours or longer, and setting the mold temperature to 25 ° C, the injection molding machine is 13 cm long, 13 mm wide, and 1.6 mm or 3.2 mm thick. Two types of molded bodies were created. Next, these molded bodies were heated at 100 ° C. for 4 hours to crystallize the resin component, and then used as samples for various evaluations. By the way, the temperature of the barrel of the injection molding machine is 190. I was jealous.

 (3) Preparation of evaluation sample 2 (Molding with high temperature mold)

 Using the pellets dried at 100 ° C. for 7 hours or longer, the mold surface temperature is set to 110 ° C., and the injection molding machine is 13 cm long, 13 mm wide, and 1.6 mm thick. Two types of molded articles of 2 mm were prepared and used as samples for various evaluations. Incidentally, the temperature of the barrel of the injection molding machine was set to 190 ° C., and the sample holding time in the mold was 180 seconds.

(4) Evaluation of bending characteristics

 For molded articles with a plate thickness of 3.2 mm obtained by the above method (2) or (3), the distance between fulcrums is set to 5 cm, the push speed is set to 1.6 mm / min, and three points complying with JIS K7171. A bending test was conducted to determine bending stress (MPa), flexural modulus (GPa), and bending strain (%).

(5) Evaluation of flame retardancy

 UL (Und erwriters) for samples (plate thickness 1.6 mm) molded by the above method (2) or (3)

Laboratories In) A 94 standard vertical fire test was conducted to evaluate flame retardancy. The evaluation criteria for flame retardancy are as shown in Table 2. [Table 2]

 [0076] In the case of combustion forms other than the above classification, it was classified as NOT. By the way, if the flame resistance is arranged in order from good to bad, it becomes V-0, V-1 and (V-2 or NOT).

(Example 1)

 50% by mass of polylactic acid (A-1) having an MFR of 3 as high molecular weight polylactic acid (A), and 5% by mass of (B-1) shown in Table 1 as a flexible additive (B) A mixture containing 45% by mass of aluminum hydroxide (C 1) shown in Table 1 as the flame retardant (C) was melt mixed in a kneader to prepare pellets of a resin composition. The temperature of the kneader was set such that the temperature of the above-mentioned resin composition in the kneader was about 180 ° C.

 Next, using the obtained pellet, a sample for evaluation was prepared according to the method of the above (2) Preparation of evaluation sample 1 (molding with a low temperature mold).

 (Example 2-11), (Comparative Example 1 7)

 Various evaluation samples were prepared in the same manner as in Example 1 except that the resin compositions of the formulations shown in Tables 3 to 6 were used. The resin composition of the formulation shown in Table 7 was used to prepare an evaluation sample according to the method of (3) Preparation of evaluation sample 2 (molding with a high temperature mold). The evaluation results are shown in Tables 3 to 6.

[Table 3] Comparative Example 1 Comparative Example 2 Comparative Example 3 Example 1 High Molecular Weight Polylactic Acid (A-1) 5 5 5 0 Low Molecular Weight Polylactic Acid (a-1) 5 5 5 0 Flexibility Agent (B-1) 5 5 Inorganic Flame Retardant (C-1) 4 5 4 5 4 5 4 5 Flexural Properties Bending Stress (MPa) 7 2 7 5 6 5 6 9 Flexural Modulus (GPa) 7 7 8 6 2 6 1 Bending fracture strain (%) 1. 0 1 1. 6 2. 9

[Table 4]

[Table 5]

Comparative Example 4 Example 5 Example 6 Example 2 High Molecular Weight Polylactic Acid (A-1) 48

 (A-2) 48

 (A— 3) 48

 Low molecular weight polylactic acid (a- 1) 48

 Flexibility agent (B-1) 5 5 5 5 Inorganic flame retardant (C-1) 45 45 45 45 Plasticizer (D-1) 2 2 2 2

 (D-2)

 (D-3)

 Flexural properties Flexural stress (MPa) 55 56 56 58 Flexural modulus (GPa) 5.4 5.3 5.2 5.0 Flexural strain, 1.5 6.0 6.5 7.3

Based on the results in Table 5, the relationship between MFR and bending strain is shown in FIG.

[Table 6]

[Table 7] Comparative Example 例 Example 8 Example 9 Example L0 Example 1 L Example 12 Example 13 High Molecular Weight Polylactic Acid (A-1) 43 38 36 33 32

 (A-2) 36

 (A- 3) 36

 Low molecular weight polylactic acid (a-1)

 Flexibility agent (B-1) 5 5 5 5 10 10 Inorganic flame retardant (c-i) 49.5 49.5 49.5 49.5 49.5 49.5 Plasticizer (D-1)

 (D-2)

 (D-3) 2 2 2 1 Carrier forming agent (E-1) 5 5 5 5 5 5 5 Crystal nucleating agent (F-1) 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Anti-drip agent (G-1) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Hydrolysis inhibitor (H-1) 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Flexural property Bending fracture stress

 72 78 54 52 50 60 50

(MPs)

 Flexural modulus

 9.6 7.3 5.4 5.4 5.3 5.1 4.3

(GPa)

 Bending fracture

 0.8 1.8 5.0 4.5 4.3 3.3 6.0 Strain «)

 Flame Retardant U mm 941.6 mm V-0 v-i v-i v-i V-1 v-i

[Table 8]

From the results shown in Tables 3 to 8 above, the thermoplastic resin composition of the present invention was compared to the prior art. It is apparent that the resin composition of each of the related comparative examples is superior in toughness in which the bending fracture strain is larger. In particular, when simultaneously containing the three components of high molecular weight polylactic acid (A), flexibility imparting agent (B) and plasticizer (D), it is known that extremely high bending rupture strain is exhibited.

As apparent from the comparison between Inventive Example 1 shown in Table 3 and Comparative Examples 1 to 3, the high-molecular-weight polylactic acid (A) is used in combination with the flexibility imparting agent (B). The breaking strain is improved, and a thermoplastic resin composition having good toughness can be obtained.

 Further, as is clear from the comparison between Inventive Example 2 and Comparative Example 4 shown in Table 4 and the comparison between Example 3 and Comparative Example 5, high molecular weight polylactic acid (A), flexibility was imparted. By simultaneously containing the three components of the agent (B) and the plasticizer (D), the breaking strain is specifically improved, and a thermoplastic resin composition having excellent toughness can be obtained.

 [0090] In addition, high molecular weight polylactic acid having an MFR of less than 15 (A), as is apparent from comparisons between Inventive Examples 2, 5 and 6 shown in Table 5 and Comparative Example 4 and also from FIG. In the case where is used, the strain at break is specifically improved, and a thermoplastic resin composition excellent in toughness is obtained.

 [0091] In addition, as shown in Table 6, the comparative power of Example 4 of the present invention with Example 7 and Comparative Example 6, and as apparent, the high molecular weight polylactic acid (A) and the flexibility imparting agent (B) Strain) is specifically improved by using the plasticizer (D) in combination, and a thermoplastic resin composition having excellent toughness can be obtained.

Yes

 Further, as is also apparent from the comparison between the invention examples 8 to 16 shown in Tables 7 to 8 and the comparative example 7, the high molecular weight polylactic acid (A) and the flexibility imparting agent (B) By using the plasticizer (D) in combination, a thermoplastic resin composition excellent in toughness and having a specifically improved breaking strain can be obtained.

 Although the present invention has been described above with reference to the examples, the present invention is not limited to the above examples. The configurations and details of the present invention can be modified in various ways that can be understood by those skilled in the art within the scope of the present invention.

 Industrial applicability

The thermoplastic resin composition of the present invention can be used for electric / electronic devices, construction materials, automobile parts, etc. by methods such as injection molding, film molding, blow molding, foam molding and the like. This application is processed into molded articles for daily use, medical use, agricultural use, toy use, and entertainment use etc. (October 2006, 10 Claim priority and incorporate all of its disclosure here.

Claims

The scope of the claims

 [1] A thermoplastic resin composition comprising at least a high molecular weight polylactic acid (A), a flexibility imparting agent (B) and an inorganic flame retardant (C),

 The thermoplastic resin composition, wherein the melt flow rate of the high molecular weight polylactic acid (A) at 190 ° C. is less than 15.

[2] The thermoplastic resin composition according to claim 1, which contains a plasticizer (D).

[3] The thermoplastic resin composition according to claim 1 or 2, wherein the inorganic flame retardant (C) is a metal hydrate.