JP2007100068A - Thermoplastic resin composition and molded product thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition and molded products, comprising polyamide resin and polylactic acid resin, and much improved in mechanical properties, moldability and heat resistance, which are defects of polylactic acid resin. <P>SOLUTION: The thermoplastic resin composition is obtained by compounding 15-50 wt.% polyamide resin (a) and 50-85 wt.% polylactic acid resin (b), and forming a phase structure, wherein, in resin phase separation structure observed by an electron microscope, the polyamide resin (a) forms a continuous phase and the polylactic acid resin (b) forms a continuous phase or a dispersed phase. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention provides specific mechanical properties, moldability and heat resistance obtained by forming a phase structure with the characteristics by controlling the resin phase separation structure of a thermoplastic resin composition comprising a polyamide resin and a polylactic acid resin. The present invention relates to a thermoplastic resin composition and a molded product obtained by processing the same.

  Conventional polymers are mostly made from petroleum resources, but carbon dioxide that has been stored in the ground since the geological era due to the fact that petroleum resources will be depleted in the future and that large amounts of petroleum resources are consumed. Is released into the atmosphere, and there is concern that global warming will become more serious. However, if a polymer can be synthesized using plant resources that grow by taking in carbon dioxide from the atmosphere, it is possible not only to suppress global warming by carbon dioxide circulation, but also to solve the problem of resource depletion at the same time. . For this reason, attention has been focused on polymers using plant resources as raw materials, that is, polymers using biomass.

  In view of the above, biomass-utilizing polymers are attracting great attention and are expected to replace conventional polymers made from petroleum resources. However, biomass-utilizing polymers generally have problems such as low mechanical properties and heat resistance and high cost. Currently, polylactic acid, which is a kind of aliphatic polyester, has attracted the most attention as a biomass-utilizing polymer that can solve these problems. Polylactic acid is a polymer made from lactic acid obtained by fermenting starch extracted from a plant, and among the biomass-using polymers, it has an excellent balance of mechanical properties, heat resistance, and cost. Development of resin products, fibers, films, sheets, and the like using this has been performed at a rapid pitch.

However, even the most promising polylactic acid has several drawbacks compared to conventional petroleum-based polymers. Among these, a large thing is that mechanical properties and heat resistance are low. For this reason, studies have been made to blend polylactic acid and polyamide to compensate for the above-mentioned drawbacks. Patent Documents 1 and 2 disclose a resin composition in which polyamide is dispersed in polylactic acid. However, since polylactic acid forms a continuous phase, further improvement in mechanical properties and heat resistance is required. Further, Patent Document 3 discloses a resin composition in which polylactic acid is dispersed in polyamide, but the polylactic acid content is small and further improvement is required from the viewpoint of low environmental load. Patent Document 4 discloses a method of controlling a resin phase separation structure in a resin composition of polylactic acid and a thermoplastic resin other than polylactic acid to a two-phase continuous structure having a structural period of 0.001 to 2 μm using spinodal decomposition. However, in this case, it is necessary to uniformly dissolve the two components once, and the resin used is limited in terms of molecular weight and the like.
JP 2003-238775 A (Claims) JP 2004-51835 A (Claims) JP-A-5-148418 (Claims) JP 2004-250549 A (Claims)

  The present invention controls the resin phase separation structure of a thermoplastic resin composition comprising a polyamide resin and a polylactic acid resin to form a characteristic phase structure, thereby reducing the mechanical properties, moldability, The object is to greatly improve the heat resistance.

  Therefore, the present inventors have studied to solve the above problems, and as a result, in a thermoplastic resin composition obtained by blending a specific amount of a polyamide resin and a polylactic acid resin, the polyamide is used in a resin phase separation structure observed with an electron microscope. The inventors have found that the above problems can be solved by controlling the dispersion structure so that the resin phase forms a continuous phase, and have reached the present invention.

That is, the present invention
(1) A resin phase-separated structure which is a thermoplastic resin composition comprising 15 to 50% by weight of a polyamide resin (a) and 50 to 85% by weight of a polylactic acid resin (b) and which is observed with an electron microscope A thermoplastic resin composition characterized by forming a phase structure in which the polyamide resin (a) is a continuous phase and the polylactic acid resin (b) is a dispersed phase,
(2) The thermoplastic resin composition according to (1), comprising 25 to 45% by weight of polyamide resin (a) and 55 to 75% by weight of polylactic acid resin (b),
(3) A resin phase separation structure which is a thermoplastic resin composition comprising 15 to 50% by weight of a polyamide resin (a) and 50 to 85% by weight of a polylactic acid resin (b) and which is observed with an electron microscope A thermoplastic resin composition characterized in that both the phase comprising the polylactic acid resin (b) and the phase comprising the polyamide resin (a) form a phase structure which is a substantially continuous phase,
(4) The thermoplastic resin composition according to (3), wherein the phase structure does not have a structural period,
(5) 0.01 to 10 parts by weight of the compatibilizer (c) is added to 100 parts by weight of the thermoplastic resin composition, according to any one of (1) to (4), Thermoplastic resin composition,
(6) The compatibilizer (c) is at least one selected from the group consisting of bisphenol-glycidyl ether-based epoxy compounds, carbodiimide compounds, ethylene / glycidyl (meth) acrylate-g- (meth) acrylate copolymers. (5) The thermoplastic resin composition according to (5).
(7) The heat according to any one of (1) to (6), wherein 0.01 to 30 parts by weight of the plasticizer (f) is added to 100 parts by weight of the thermoplastic resin composition. Plastic resin composition.
(8) The thermoplastic resin composition as described in (7), wherein the plasticizer (f) is a polyalkylene glycol plasticizer.
(9) The thermoplastic resin composition according to any one of (1) to (8), wherein a main component of the polyamide resin (a) is a nylon 6 resin,
(10) It is characterized by being produced by applying a kneading energy of 0.15 kWh / kg or more to a molten mixture of the resin constituting the thermoplastic resin composition while controlling the resin temperature to 260 ° C. or less ( 1) to a method for producing a polyamide resin composition according to any one of (9),
(11) A molded product obtained by processing the thermoplastic resin composition according to any one of (1) to (9), and (12) a method selected from injection molding, injection compression molding, and compression molding The molded product according to (11) obtained,
Is to provide.

  ADVANTAGE OF THE INVENTION According to this invention, the thermoplastic resin composition which consists of a polyamide resin and polylactic acid resin in which the mechanical characteristics, the moldability, and heat resistance which were the faults of the polylactic acid resin were improved significantly can be obtained.

  Embodiments of the present invention will be described below. In the present invention, “weight” means “mass”.

  The polyamide resin (a) used in the present invention is a polyamide mainly composed of amino acids, lactams or diamines and dicarboxylic acids. Representative examples of the main constituents include amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and paraaminomethylbenzoic acid, lactams such as ε-caprolactam and ω-laurolactam, and tetramethylenediamine. Hexamerenediamine, 2-methylpentamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, Metaxylylenediamine, paraxylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, Bis (4-aminosic (Rohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, aminoethylpiperazine, aliphatic, alicyclic, aromatic Diamines, and adipic acid, speric acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid Examples include aliphatic, alicyclic, and aromatic dicarboxylic acids such as acids, 2,6-naphthalenedicarboxylic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid. In the present invention, nylon derived from these raw materials Homopolymers or copolymers each alone or in the form of a mixture It is possible to have.

  In the present invention, particularly useful polyamide resin (a) is a polyamide resin having a melting point of 150 ° C. or more and excellent in heat resistance and strength. Specific examples include polycaproamide (nylon 6), polyhexamethylene. Adipamide (nylon 66), polytetramethylene adipamide (nylon 46), polyhexamethylene sebamide (nylon 610), polyhexamethylene dodecane (nylon 612), polyundecanamide (nylon 11), polydodecane Amide (nylon 12), polycaproamide / polyhexamethylene terephthalamide copolymer (nylon 6 / 6T), polyhexamethylene adipamide / polyhexamethylene terephthalamide copolymer (nylon 66 / 6T), polyhexamethylene adipamide / Polyhexamethylene isof Luamide copolymer (nylon 66 / 6I), polyhexamethylene adipamide / polyhexamethylene isophthalamide / polycaproamide copolymer (nylon 66 / 6I / 6), polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon) 6T / 6I), polyhexamethylene terephthalamide / polydodecanamide copolymer (nylon 6T / 12), polyhexamethylene adipamide / polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6T / 6I), Polyxylylene adipamide (nylon XD6), polyhexamethylene terephthalamide / poly-2-methylpentamethylene terephthalamide copolymer (nylon 6T / M5T) and this Mixtures of the like.

  In general, since the melting point of polylactic acid resin is about 170 ° C., the melting point of polyamide is more preferably 250 ° C. or less, particularly preferably 230 ° C. or less in consideration of lowering the blending temperature as much as possible. . Moreover, in order to improve the moldability of the blend polymer resin obtained by blending polyamide with polylactic acid resin and the dimensional stability of the molded body, the blend polymer resin is preferably crystalline. For this reason, it is preferable that the polyamide to be blended is also crystalline. If a melting peak can be observed by differential scanning calorimetry (DSC) measurement, the polymer can be judged to be crystalline.

  Particularly preferred polyamide resins (a) include nylon 6, nylon 610, nylon 612, nylon 11 and nylon 12. Furthermore, these polyamide resins are required characteristics such as impact resistance, molding processability and compatibility. It is also practically suitable to use as a mixture according to the above. In particular, in the present invention, the main component of the polyamide resin (a) is preferably a nylon 6 resin.

  The degree of polymerization of these polyamide resins is not particularly limited, but the relative viscosity measured at 25 ° C. in a 98% concentrated sulfuric acid solution having a sample concentration of 0.01 g / ml is preferably in the range of 2.0 to 5.0, Particularly preferred is a polyamide resin in the range of 2.0 to 4.0. When the relative viscosity is less than 2.0, it is difficult to develop the excellent mechanical properties that are characteristic of the thermoplastic resin composition of the present invention. When the relative viscosity is greater than 5.0, the polyamide resin that is the feature of the present invention is difficult. However, it is difficult to form a resin phase separation structure in which a continuous phase is formed, and the melt viscosity of the thermoplastic resin composition is remarkably increased and the fluidity is lowered.

  Moreover, in order to improve long-term heat resistance, the copper compound is preferably blended with the polyamide resin (a) of the present invention. Specific examples of copper compounds include cuprous chloride, cupric chloride, cuprous bromide, cupric bromide, cuprous iodide, cupric iodide, cupric sulfate, nitric acid. Cupric, copper phosphate, cuprous acetate, cupric acetate, cupric salicylate, cupric stearate, cupric benzoate and inorganic copper halides and xylylenediamine, 2-mercaptobenzimidazole And complex compounds such as benzimidazole. Of these, monovalent copper compounds, particularly monovalent copper halide compounds are preferred, and cuprous acetate, cuprous iodide, and the like can be exemplified as particularly suitable copper compounds. The addition amount of the copper compound is usually preferably 0.01 to 2 parts by weight, more preferably 0.015 to 1 part by weight with respect to 100 parts by weight of the polyamide resin. If the amount added is too large, metal copper is liberated during melt molding, and the value of the product is reduced by coloring. In the present invention, an alkali halide can be added in combination with a copper compound. Examples of the alkali halide compound include lithium chloride, lithium bromide, lithium iodide, potassium chloride, potassium bromide, potassium iodide, sodium bromide and sodium iodide. Sodium chloride is particularly preferred.

  The polylactic acid resin (b) referred to in the present invention is a polymer containing L-lactic acid and / or D-lactic acid as a main constituent component, but may contain other copolymerization components other than lactic acid. Other copolymerization components include ethylene glycol, propylene glycol, butanediol, heptanediol, hexanediol, octanediol, nonanediol, decanediol, 1,4-cyclohexanedimethanol, neopentylglycol, glycerin, Glycol compounds such as pentaerythritol, 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, terephthalate Acid, isophthalic acid, phthalic acid, naphthalene dicarboxylic 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. As such a copolymer component, it is preferable to set it as content of 30 mol% or less normally in all the monomer components, and it is preferable that it is 10 mol% or less. Further, it may contain additives other than polylactic acid, particles, flame retardants, antistatic agents and the like as long as the properties of polylactic acid are not impaired.

  In the present invention, polylactic acid having a high optical purity of the lactic acid component is preferably used as the polylactic acid resin (b) from the viewpoint of compatibility. That is, among the total lactic acid components of polylactic acid, 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 contained at 90% or more. It is particularly preferable that the L-form is contained at 95% or more or the D-form is contained at 95% or more. In addition, in this invention, it is a preferable aspect to use polylactic acid with high optical purity which has L body or D body as a main component, and to use those mixtures individually.

  The molecular weight and molecular weight distribution of the polylactic acid resin (b) 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, Furthermore, it is desirable that it is 80,000 or more. 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 (b) is not particularly limited, but is preferably 120 ° C. or higher, and more preferably 150 ° C. or higher.

  As a method for producing the polylactic acid resin (b), 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 blending ratio of the polyamide resin (a) and the polylactic acid resin (b) in the thermoplastic resin composition of the present invention is 15 to 50% by weight of the polyamide resin (a) and 50 to 85% by weight of the polylactic acid resin (b). , Preferably 25 to 45% by weight of polyamide resin and 55 to 75% by weight of polylactic acid resin. If the polylactic acid resin (b) is less than 50% by weight, it is not preferable because the low environmental load due to the use of the biomass-utilizing polymer, which is a feature of the thermoplastic resin composition of the present invention, becomes poor. When the polylactic acid resin (b) exceeds 85% by weight, it becomes difficult to form a resin phase separation structure in which the polyamide resin, which is a feature of the thermoplastic resin composition of the present invention, forms a continuous phase. This is not preferable because it causes a decrease in heat resistance.

  The thermoplastic resin composition of the present invention forms a resin phase separation structure in which the polyamide resin (a) forms a continuous phase. Usually, in the case of a two-component polymer blend, a resin phase separation structure is formed in which the major component is the continuous phase and the minor component is the dispersed phase. In the thermoplastic resin composition of the present invention, the polyamide resin (a) 15-50 The polyamide resin / polylactic acid resin melt viscosity ratio satisfies the following formula (1) even if the polyamide resin (a) component is a minor component such as 50% by weight and 50% to 85% by weight of the polylactic acid resin (b). By appropriately controlling the temperature, a phase structure in which the polyamide resin takes a continuous phase can be formed.

  In the thermoplastic resin composition of the present invention, the polyamide resin (a) and the polylactic acid resin (b) together form a substantially continuous phase. Even when the polyamide resin (a) component and the polylactic acid resin (b) component have a phase structure (for example, sea-sea structure) that forms a substantially continuous phase, the polyamide resin (a) is 15 to 50% by weight, In the composition range of 50 to 85% by weight of the lactic acid resin (b), it is important to control the melt viscosity and the compatibility of the polyamide resin and the polylactic acid resin. In realizing this phase separation structure, a composition of polyamide resin (a) of 25 to 45% by weight and polylactic acid resin (b) of 55 to 75% by weight is preferable. If the polylactic acid resin (b) is less than 50% by weight, it is not preferable because the low environmental load due to the use of the biomass-utilizing polymer, which is a feature of the thermoplastic resin composition of the present invention, becomes poor. Further, when the polylactic acid resin (b) exceeds 85% by weight, the polyamide resin and the polylactic acid resin, which are the characteristics of the thermoplastic resin composition of the present invention, may form a resin phase separation structure in which a continuous phase is formed together. It becomes difficult, and mechanical characteristics and heat resistance are deteriorated.

Unlike the phase structure formed using spinodal decomposition, the resin phase separation structure of the thermoplastic resin composition of the present invention preferably has no structural period after it is once compatibilized. The term “structure period” as used herein refers to a repeating period of a regular continuous structure obtained when a phase-separated structure is formed using spinodal decomposition, and scattering measurement performed using a light scattering device or a small-angle X-ray scattering device. The existence of a structural period can be confirmed by showing the scattering maximum (peak) in FIG. 1. The period is determined by using the wavelength λ in the scattering medium of the scattered light and the scattering angle θm that gives the scattering maximum. (Structure period) = (λ / 2) / sin (θm / 2)
Can be calculated.

  The absence of a structural period can be determined from the fact that no clear peak is exhibited when the resin composition of the present invention is subjected to light scattering measurement. A composition in which a phase structure is formed using spinodal decomposition is not preferable because it becomes difficult to exhibit the excellent mechanical properties that are characteristic of the thermoplastic resin composition of the present invention.

  A compatibilizing agent (c) can be added to the thermoplastic resin composition of the present invention for the purpose of improving the compatibility between the thermoplastic resins. Here, the compatibilizing agent may be either a low molecular compound or a polymer which is a high molecular compound. Among them, preferred examples include a carboxyl group reactive compound, a carboxyl group, an epoxy group or an acid. Examples thereof include a polymer having an anhydride group.

  In the present invention, the carboxyl group-reactive compound is not particularly limited as long as it is a compound reactive with the carboxyl end group of the polylactic acid resin, but it is generated by thermal decomposition or hydrolysis of the polylactic acid resin. It is more preferable if it is reactive with the carboxyl group of the acidic low molecular compound, and it is more preferable that the compound is also reactive with the hydroxyl group end group of the acidic low molecular compound produced by thermal decomposition.

  Examples of such carboxyl group-reactive compounds include bisphenol A, resorcinol, hydroquinone, pyrocatechol, bisphenol F, saligenin, 1,3,5-trihydroxybenzene, bisphenol S, trihydroxy-diphenyldimethylmethane, 4,4 ′. -Bisphenol-glycidyl ether type epoxy compounds such as dihydroxybiphenyl, 1,5-dihydroxynaphthalene, cashew phenol, 2,2,5,5-tetrakis (4-hydroxyphenyl) hexane, glycidyl ester type epoxy such as glycidyl phthalate Compounds, glycidylamine-based epoxy compounds such as N-glycidylaniline, glycidylimide compounds, alicyclic epoxy compounds, epoxy group-containing compounds, 2,2′-m-phenylenebis (2 Oxazoline), oxazoline compounds such as 2,2′-p-phenylenebis (2-oxazoline), oxazine compounds, N, N′-di-2,6-diisopropylphenylcarbodiimide, 2,6,2 ′, 6′- From carbodiimide compounds such as tetraisopropyldiphenylcarbodiimide and polycarbodiimide, and organic silane compounds such as alkoxysilane having at least one functional group selected from epoxy group, amino group, isocyanate group, hydroxyl group, mercapto group and ureido group It is preferable to use at least one selected compound, and among them, a bisphenol-glycidyl ether epoxy compound, an epoxy group, an organic silane compound having an isocyanate group, and a carbodiimide compound are preferable. As the carboxyl group-reactive compound, one or more compounds can be arbitrarily selected and used.

  In the present invention, examples of the polymer having a carboxyl group, an epoxy group, or an acid anhydride group include ethylene / (meth) acrylate glycidyl copolymer, ethylene / (meth) acrylate ethyl-g-maleic anhydride copolymer. ("G" represents a graft, the same shall apply hereinafter), ethylene / glycidyl (meth) acrylate-g- (meth) methyl acrylate copolymer, ethylene / ethyl (meth) acrylate / maleic anhydride copolymer -G- (Meth) acrylic acid methyl copolymer, epoxy group-containing polymer compound obtained by epoxidizing a double bond part of a polymer having a double bond, novolac epoxy resin obtained by reacting novolac phenol resin with epichlorohydrin And so on.

  The blending ratio of the compatibilizing agent (c) is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the thermoplastic resin composition. When the addition amount is less than 0.01 parts by weight, a sufficient compatibility improving effect cannot be obtained, and when it exceeds 10 parts by weight, the melt viscosity of the thermoplastic resin composition is remarkably increased and the fluidity is lowered.

  In the present invention, it is preferable to further add a reaction catalyst of the compatibilizer (c). The reaction catalyst mentioned here is a compound that has an effect of promoting the reaction between the compatibilizing agent and the terminal of the resin or the carboxyl group or hydroxyl group of the acidic low molecular weight compound. Certain compounds are preferred, for example, alkali metal compounds, alkaline earth metal compounds, and phosphate esters. The addition amount of the reaction catalyst is not particularly limited, but is preferably 0.001 to 1 part by weight, more preferably 0.01 to 0.2 part by weight with respect to 100 parts by weight of the thermoplastic resin composition. Most preferred is 0.02 to 0.1 parts by weight.

  The thermoplastic resin composition obtained by the method of the present invention can be used by blending a filler (d) within the range not impairing the effects of the present invention for the purpose of improving mechanical strength. Specific examples of the filler (d) include glass fiber, carbon fiber, potassium titanate whisker, zinc oxide whisker, calcium carbonate whisker, wollastonite whisker, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber, ceramic fiber, Fibers such as asbestos fiber, stone-kow fiber, metal fiber, cotton fiber, hemp fiber, bamboo fiber, wood fiber, kenaf fiber, jute fiber, banana fiber, coconut fiber, animal fiber such as silk, wool, Angola, cashmere or camel Swellable layered silicates such as talc, wollastonite, zeolite, sericite, mica, kaolin, clay, pyrophyllite, bentonite, asbestos, alumina silicate, montmorillonite, synthetic mica, oxidation Silicon, magnesium oxide, aluminum Metal compounds such as sodium, zirconium oxide, titanium oxide and iron oxide, carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, calcium hydroxide, magnesium hydroxide and aluminum hydroxide Hydroxide, glass beads, glass flakes, glass powder, ceramic beads, boron nitride, silicon carbide, carbon black and silica, graphite, paper powder, wood powder, bamboo powder, cellulose powder, rice husk powder, fruit shell powder, chitin powder Non-fibrous fillers such as chitosan powder, protein, starch, rice husk, wood chips, okara, waste paper pulverized material, clothing pulverized material, etc. may be used, and these may be hollow. It is possible to use more than one type together. These fillers may be used after pretreatment with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, and an epoxy compound. Among the fillers, PAN-based carbon fibers are preferably used when glass fibers and conductivity are required. The type of glass fiber is not particularly limited as long as it is generally used for reinforcing a resin, and can be selected from, for example, a long fiber type, a short fiber type chopped strand, a milled fiber, or the like. Moreover, said filler can also be used in combination of 2 or more types. In addition, the surface of the filler used in the present invention is a known coupling agent (for example, silane coupling agent, titanate coupling agent, etc.), other surface treatment agents, and swellable layered silicates. Pretreatment with an organic onium ion is preferable in terms of obtaining a higher mechanical strength. The glass fiber may be coated or bundled with a thermoplastic resin such as an ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin.

  The blending amount of the filler (d) is preferably 0.5 to 100 parts by weight with respect to 100 parts by weight of the thermoplastic resin composition of the present invention. More preferably, it is 5 to 80 parts by weight. If the blending amount is less than 0.5 parts by weight, the reinforcing effect is small, which is not preferable. On the other hand, if the blending amount exceeds 100 parts by weight, the fluidity at the time of molding is impaired.

  Moreover, it is preferable that the thermoplastic resin composition of the present invention contains an antioxidant in order to maintain thermal stability. As such a heat-resistant agent and antioxidant, it is preferably used to contain one or more antioxidants selected from phenolic and phosphorus compounds. As the phenolic antioxidant, a hindered phenolic compound is preferably used. Specific examples include triethylene glycol-bis [3-t-butyl- (5-methyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide), tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate ] Methane, pentaerythrityltetrakis [3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-t-butyl- 4-hydroxybenzyl) -s-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,1,3-tris (2-methyl-4 Hydroxy-5-tert-butylphenyl) butane, 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), n-octadecyl-3- (3,5-di-tert-butyl-4-hydroxy-) Phenyl) propionate, 3,9-bis [2- (3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethylethyl] -2,4,8,10 -Tetraoxaspiro [5,5] undecane, 1,3,5-trimethyl-2,4,6-tris- (3,5-di-t-butyl-4-hydroxybenzyl) benzene and the like.

  Among them, tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, N, N′-hexamethylenebis (3,5-di-t-butyl- 4-hydroxy-hydrocinnamide), pentaerythrityltetrakis [3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate], 3,9-bis [2- (3- (3- (3- t-Butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane and the like are preferably used.

  Next, phosphorus antioxidants include bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite, bis (2,4-di-t-butylphenyl). ) Pentaerythritol di-phosphite, bis (2,4-di-cumylphenyl) pentaerythritol di-phosphite, tris (2,4-di-t-butylphenyl) phosphite, tetrakis (2,4-di-t-butylphenyl) -4,4'-bisphenylene phosphite, di-stearyl pentaerythritol di-phosphite, triphenyl phosphite, 3,5-dibutyl-4-hydroxybenzyl phosphite Examples include phonate diethyl ester. The blending amount of the heat stabilizer and the antioxidant is 0.01 parts by weight or more, particularly 0.02 parts by weight or more with respect to 100 parts by weight of the total thermoplastic resin composition from the viewpoint of the heat resistance improving effect. From the viewpoint of gas components generated during molding, it is preferably 5 parts by weight or less, particularly preferably 1 part by weight or less. In addition, the combined use of phenolic and phosphorus antioxidants is particularly preferable because of their large heat resistance, thermal stability and fluidity retention effect.

  Furthermore, a resin (e) other than a polyamide resin or a polylactic acid resin can be added to the thermoplastic resin composition of the present invention as long as the effects of the present invention are not impaired. Specific examples of the resin (e) include aromatic polyester resins, ABS resins, polyolefin resins, polyalkylene oxide resins, modified polyphenylene ether resins, polysulfone resins, polyketone resins, polyphenylene sulfide resins, poly Etherimide resin, polyarylate resin, polyethersulfone resin, polyetherketone resin, polythioetherketone resin, polyetheretherketone resin, polyimide resin, polyamideimide resin, polyethylene tetrafluoride Resin, and a multilayer structure polymer having a multilayer structure. When the blending ratio exceeds 30 parts by weight with respect to 100 parts by weight of the entire thermoplastic resin composition of the present invention, the original characteristics of the thermoplastic resin composition are included. Is not preferable, particularly 2 The addition of the following parts by weight are preferably used. Of these, olefin resins and multilayer polymers are preferably used for improving impact resistance and toughness.

  Olefin resins include olefin polymer elastomers and / or olefin polymer elastomers and / or conjugated diene-aromatics obtained by graft reaction or copolymerization of unsaturated carboxylic acids and / or their derivatives and vinyl monomers. A hydrogenated block copolymer elastic body in which a part or all of the conjugated diene block portion of the vinyl hydrocarbon block copolymer is hydrogenated is preferable, and an unsaturated carboxylic acid and / or a derivative thereof, which is grafted or copolymerized, The amount of the vinyl monomer is preferably 0.01 to 20% by weight. Examples of the unsaturated carboxylic acid used in the graft reaction or copolymerization include (meth) acrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, and butenedicarboxylic acid. In addition, examples of the derivatives include alkyl esters, glycidyl esters, esters having a di- or tri-alkoxysilyl group, acid anhydrides, imides, etc., and glycidyl esters, di- or tri-alkoxysilyl groups having no glycidyl ester. Saturated carboxylic acid esters, acid anhydrides and imides are preferred.

  Preferred examples of the unsaturated carboxylic acid or its derivative include maleic acid, fumaric acid, glycidyl (meth) acrylate, itaconic acid diglycidyl ester, citraconic acid diglycidyl ester, butenedicarboxylic acid diglycidyl ester, butenedicarboxylic acid monoglycidyl Examples thereof include esters, maleic anhydride, itaconic anhydride, citraconic anhydride, maleic imide, itaconic imide, citraconic imide and the like, and glycidyl methacrylate, maleic anhydride, itaconic anhydride and maleic imide are particularly preferred. Examples of vinyl monomers include aromatic vinyl compounds such as styrene, vinyl cyanide compounds such as acrylonitrile, vinylsilane compounds such as vinyltrimethoxysilane, and these unsaturated carboxylic acids or their derivatives or Two or more vinyl monomers may be used in combination. In addition, about the method of grafting these unsaturated carboxylic acid or its derivative (s), or a vinyl monomer, a well-known method can be used. Two or more of these can be used in combination.

  Specific examples include ethylene / methacrylic acid copolymers and those in which some or all of the carboxylic acid moieties in these copolymers are salts with sodium, lithium, potassium, zinc, calcium, ethylene / (meth) acrylic Ethyl acrylate-g-maleic anhydride copolymer, ethylene / ethyl acrylate-g-maleimide copolymer, ethylene / ethyl acrylate-g-N-phenylmaleimide copolymer and partially saponified products of these copolymers, Ethylene / (meth) acrylic acid copolymer, ethylene / vinyl acetate / (meth) acrylic acid copolymer, ethylene / methyl (meth) acrylate / glycidyl (meth) acrylate, ethylene / glycidyl ether copolymer Polymer, ethylene / propylene-g-maleic anhydride copolymer, ethylene / butene-1-g-none Maleic acid copolymer, ethylene / propylene / 1,4-hexadiene-g-maleic anhydride copolymer, ethylene / propylene / dicyclopentadiene-g-maleic anhydride copolymer, ethylene / propylene / 2,5- Norbornadiene-g-maleic anhydride copolymer, ethylene / propylene-gN-phenylmaleimide copolymer, ethylene / butene-1-gN-phenylmaleimide copolymer, hydrogenated styrene / butadiene / styrene-g -Maleic anhydride copolymer, hydrogenated styrene / isoprene / styrene-g-maleic anhydride copolymer, and the like. Among them, ethylene / methacrylic acid copolymers and some or all of the carboxylic acid moieties in these copolymers as salts with sodium, lithium, potassium, zinc, calcium, ethylene / propylene-g-anhydrous Maleic acid copolymers, ethylene / butene-1-g-maleic anhydride copolymers, hydrogenated styrene / butadiene / styrene-g-maleic anhydride copolymers are preferred, and ethylene / methacrylic acid copolymers and these A part or all of the carboxylic acid moiety in the copolymer made into a salt with sodium, lithium, potassium, zinc, calcium, ethylene / propylene-g-maleic anhydride copolymer, ethylene / butene-1-g -Maleic anhydride copolymers are preferred.

  The multi-layer structure polymer is composed of an innermost layer (core layer) and one or more layers (shell layer) covering the innermost layer (core layer), and a so-called core-shell type in which adjacent layers are composed of different polymers. The number of layers constituting the multi-layered polymer is not particularly limited, and may be two or more, and may be three or more or four or more. A multilayer structure polymer having at least one rubber layer therein is preferable. The type of the rubber layer is not particularly limited as long as it is composed of a polymer component having rubber elasticity. For example, rubber composed of a polymer obtained by polymerizing an acrylic component, a silicone component, a styrene component, a nitrile component, a conjugated diene component, a urethane component, an ethylene propylene component, or the like can be given. Preferred rubbers include, for example, acrylic components such as ethyl acrylate units and butyl acrylate units, silicone components such as dimethylsiloxane units and phenylmethylsiloxane units, styrene components such as styrene units and α-methylstyrene units, acrylonitrile units, It is a rubber constituted by polymerizing a nitrile component such as a methacrylonitrile unit or a conjugated diene component such as a butanediene unit or an isoprene unit. Further, a rubber composed of a copolymer obtained by combining two or more of these components is also preferable. For example, (1) acrylic components such as ethyl acrylate units and butyl acrylate units, dimethylsiloxane units, and phenylmethylsiloxane Rubber composed of components copolymerized with silicone components such as units, (2) Components copolymerized with acrylic components such as ethyl acrylate units and butyl acrylate units, and styrene components such as styrene units and α-methylstyrene units (3) rubber composed of a component obtained by copolymerizing an acrylic component such as an ethyl acrylate unit or a butyl acrylate unit and a conjugated diene component such as a butanediene unit or an isoprene unit, and (4) ethyl acrylate. Acrylic components such as units and butyl acrylate units and Rubber composed of a styrene component copolymerized with components such as silicone component and styrene units and α- methylstyrene units such as dimethylsiloxane units or phenylmethylsiloxane units and the like. In addition to these components, a rubber obtained by copolymerizing and crosslinking a crosslinkable component such as a divinylbenzene unit, an allyl acrylate unit, or a butylene glycol diacrylate unit is also preferable.

  In the multilayer structure polymer, the type of layer other than the rubber layer is not particularly limited as long as it is composed of a polymer component having thermoplasticity, but a polymer having a glass transition temperature higher than that of the rubber layer. Ingredients are preferred. Polymers having thermoplastic properties include unsaturated carboxylic acid alkyl ester units, glycidyl group-containing vinyl units, unsaturated dicarboxylic anhydride units, aliphatic vinyl units, aromatic vinyl units, and vinyl cyanide units. Examples include polymers containing at least one unit selected from units, maleimide units, unsaturated dicarboxylic acid units, and other vinyl units, among which unsaturated carboxylic acid alkyl ester units, unsaturated A polymer containing at least one unit selected from glycidyl group-containing units or unsaturated dicarboxylic acid anhydride units is preferred, and at least selected from unsaturated glycidyl group-containing units or unsaturated dicarboxylic acid anhydride units. More preferred are polymers containing one or more units.

  The unsaturated carboxylic acid alkyl ester unit is not particularly limited, but (meth) acrylic acid alkyl ester is preferably used. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, (meth) acrylic N-hexyl acid, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, octadecyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, ( Chloromethyl (meth) acrylate, 2-chloroethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2,3,4,5,6 (meth) acrylic acid -Pentahydroxyhexyl, 2,3,4,5-tetrahydroxypentyl (meth) acrylate, amino acid acrylate Examples include ethyl, propylaminoethyl acrylate, dimethylaminoethyl methacrylate, ethylaminopropyl methacrylate, phenylaminoethyl methacrylate, cyclohexylaminoethyl methacrylate, etc., from the viewpoint that the effect of improving impact resistance is great ( Methyl methacrylate is preferably used. These units can be used alone or in combination of two or more.

  The glycidyl group-containing vinyl-based unit is not particularly limited, and examples thereof include glycidyl (meth) acrylate, glycidyl itaconate, diglycidyl itaconate, allyl glycidyl ether, styrene-4-glycidyl ether, and 4-glycidyl styrene. From the viewpoint that the effect of improving impact resistance is great, glycidyl (meth) acrylate is preferably used. These units can be used alone or in combination of two or more.

  Examples of the unsaturated dicarboxylic acid anhydride unit include maleic anhydride, itaconic anhydride, glutaconic anhydride, citraconic anhydride, or aconitic anhydride. From the viewpoint that the effect of improving impact resistance is great, maleic anhydride Acid is preferably used. These units can be used alone or in combination of two or more.

  The aliphatic vinyl unit may be ethylene, propylene or butadiene, and the aromatic vinyl unit may be styrene, α-methylstyrene, 1-vinylnaphthalene, 4-methylstyrene, 4-propylstyrene, 4-cyclohexyl. Styrene, 4-dodecyl styrene, 2-ethyl-4-benzyl styrene, 4- (phenylbutyl) styrene, halogenated styrene, etc., as vinyl cyanide units, acrylonitrile, methacrylonitrile, ethacrylonitrile, etc. maleimide Units include maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-isopropylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N- (p-bromophenyl) maleimide, N- (chlorophenyl) maleimide and other unsaturated dicarboxylic acid units such as maleic acid, maleic acid monoethyl ester, itaconic acid and phthalic acid, and other vinyl units such as acrylamide, methacrylamide, N-methylacrylamide, Butoxymethylacrylamide, N-propylmethacrylamide, N-vinyldiethylamine, N-acetylvinylamine, allylamine, methallylamine, N-methylallylamine, p-aminostyrene, 2-isopropenyl-oxazoline, 2-vinyl-oxazoline, 2 -Acroyl-oxazoline or 2-styryl-oxazoline can be mentioned, and these units can be used alone or in combination of two or more.

  In the multilayer polymer, the type of the outermost layer is not particularly limited, and is an unsaturated carboxylic acid alkyl ester unit, a glycidyl group-containing vinyl unit, an aliphatic vinyl unit, an aromatic vinyl unit, cyanide. Examples include polymers containing vinyl units, maleimide units, unsaturated dicarboxylic acid units, unsaturated dicarboxylic acid anhydride units and / or other vinyl units, among which unsaturated carboxylic acid alkyl ester systems A polymer containing a unit, an unsaturated glycidyl group-containing unit and / or an unsaturated dicarboxylic anhydride-based unit is preferred, and a polymer containing an unsaturated carboxylic acid alkyl ester-based unit is more preferred. The unsaturated carboxylic acid alkyl ester unit is not particularly limited, but (meth) acrylic acid alkyl ester is preferable, and methyl (meth) acrylate is more preferably used.

  As a preferred example of the multilayer structure polymer, the core layer is a dimethylsiloxane / butyl acrylate polymer, the outermost layer is a methyl methacrylate polymer, the core layer is a butanediene / styrene polymer, and the outermost layer is a methyl methacrylate polymer. Examples include a butyl acrylate polymer layer and an outermost methyl methacrylate polymer. Furthermore, it is more preferable that either one or both of the rubber layer and the outermost layer is a polymer containing glycidyl methacrylate units.

  The particle diameter of the multilayer polymer is not particularly limited, but is preferably 0.01 μm or more and 1000 μm or less, more preferably 0.02 μm or more and 100 μm or less, and particularly preferably Most preferably, it is not less than 05 μm and not more than 10 μm.

  In the multilayer structure polymer, the weight ratio of the core and the shell is not particularly limited, but the core layer is preferably 50 parts by weight or more and 90 parts by weight or less with respect to the entire multilayer structure polymer. Further, it is more preferably 60 parts by weight or more and 80 parts by weight or less.

  Examples of the multilayer polymer include “Metablen” manufactured by Mitsubishi Rayon, “Kaneace” manufactured by Kaneka Chemical Industry, “Paraloid” manufactured by Kureha Chemical Industry, “Acryloid” manufactured by Rohm and Haas, “Staffroid” manufactured by Takeda Pharmaceutical Kuraray "parapet SA" and the like can be mentioned, and these can be used alone or in combination of two or more.

  A plasticizer (f) can be added to the thermoplastic resin composition of the present invention. The addition of a plasticizer is preferable because it has the effect of softening the polymer and facilitating movement and promoting crystal growth, and improves mechanical properties, moldability and heat resistance. As the plasticizer (f) used in the present invention, generally known plasticizers can be used. For example, polyester plasticizer, glycerin plasticizer, polyvalent carboxylic ester plasticizer, phosphate ester. Examples thereof include a plasticizer, a polyalkylene glycol plasticizer, and an epoxy plasticizer.

  Specific examples of polyester plasticizers include acid components such as adipic acid, sebacic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, propylene glycol, 1,3-butanediol, 1,4-butane. Examples thereof include polyesters composed of diol components such as diol, 1,6-hexanediol, ethylene glycol and diethylene glycol, and polyesters composed of hydroxycarboxylic acid 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, sebacic acid esters such as diisodecyl adipate, n-octyl-n-decyl adipate adipate, triethyl acetylcitrate, tributyl acetylcitrate, etc. Citrate esters, azelaic acid esters such as di-2-ethylhexyl azelate, sebacic acid esters such as dibutyl sebacate, and di-2-ethylhexyl sebacate.

  Specific examples of phosphate plasticizers include phosphate esters such as tributyl phosphate, tri-2-ethylhexyl phosphate, trioctyl phosphate, triphenyl phosphate, diphenyl-2-ethylhexyl phosphate, and tricresyl phosphate. Mention may be made of aliphatic and aromatic condensed phosphates.

  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 include aliphatic carboxylic acid esters such as butyl, oxyacid esters such as methyl acetylricinoleate and butyl acetylricinoleate, pentaerythritol, various sorbitols, polyacrylic acid esters, polycarboxylic acid vinyl esters, silicone oils, and paraffins. be able to.

  The molecular weight of the plasticizer used in the present invention is preferably 100 or more and 30,000 or less, more preferably 500 or more and 20,000 or less, and particularly preferably 1000 or more and 10,000 or less.

  In addition, the above plasticizer obtained by block or graft copolymerization of polylactic acid can be usefully used as a plasticizer.

  Among the plasticizers used in the present invention, at least one selected from polyester plasticizers and polyalkylene glycol plasticizers is particularly preferable. Also, at least one selected from a copolymer of polylactic acid and an aliphatic polyester plasticizer or a copolymer of polylactic acid and a polyalkylene glycol plasticizer can be preferably used. Only one type of plasticizer may be used in the present invention, or two or more types may be used in combination.

    The blending amount of the plasticizer is preferably in the range of 0.01 to 30 parts by weight, more preferably in the range of 0.1 to 20 parts by weight, with respect to 100 parts by weight of the thermoplastic resin composition of the present invention. The range of 5 to 10 parts by weight is more preferable, and the range of 0.1 to 5 parts by weight is particularly preferable.

  A crystal nucleating agent that promotes the formation of polymer crystal nuclei can be added to the thermoplastic resin composition of the present invention.

  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 both inorganic crystal nucleating agents and organic crystal nucleating agents can be used. it can. Specific examples of the inorganic crystal nucleating agent 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. The average particle size of the inorganic crystal nucleating agent is preferably 10 μm or less, more preferably 5 μm or less, and particularly preferably 3 μm or less. Specific examples of the organic crystal nucleating agent include sodium benzoate, potassium benzoate, lithium benzoate, calcium benzoate, magnesium benzoate, barium benzoate, lithium terephthalate, sodium terephthalate, potassium terephthalate, and calcium oxalate. , Sodium laurate, potassium laurate, sodium myristate, potassium myristate, calcium myristate, sodium octacosanoate, calcium octacosanoate, sodium stearate, potassium stearate, lithium stearate, calcium stearate, magnesium stearate, stearic acid Barium, sodium montanate, calcium montanate, sodium toluate, sodium salicylate, potassium salicylate, zinc salicylate, aluminum Organic carboxylic acid metal salts such as minium dibenzoate, potassium dibenzoate, lithium dibenzoate, sodium β-naphthalate, sodium cyclohexanecarboxylate, organic sulfonates such as sodium p-toluenesulfonate, sodium sulfoisophthalate, lauric acid amide , Stearic acid amide, ethylene bis lauric acid amide, ethylene bis stearic acid amide, palmitic acid amide, hydroxy stearic acid amide, erucic acid amide, trimesic acid tris (t-butylamide), organic carboxylic acid amides such as terephthalic acid dianilide, low Density polyethylene, high density polyethylene, polypropylene, polyisopropylene, polybutene, poly-4-methylpentene, poly-3-methylbutene-1, polyvinyl Sodium or potassium salt of a polymer having a carboxyl group such as a polymer such as loalkane, polyvinyltrialkylsilane, high melting point polylactic acid, sodium salt of ethylene-acrylic acid or methacrylic acid copolymer, sodium salt of styrene-maleic anhydride copolymer (So-called ionomers), benzylidene sorbitol and derivatives thereof, phosphorus compound metal salts such as sodium-2,2′-methylenebis (4,6-di-t-butylphenyl) phosphate, and 2,2-methylbis (4,6 -Di-t-butylphenyl) sodium and the like.

  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 organic carboxylic acid amides is particularly preferable. Preferable talc includes talc having an average particle size of 0.5 to 7 μm and a ratio of SiO 2 and MgO in the component excluding a loss during combustion of 93% by weight or more. The crystal nucleating agent used in the present invention may be used alone or in combination of two or more.

  The compounding amount of the crystal nucleating agent is preferably in the range of 0.01 to 30 parts by weight, more preferably in the range of 0.05 to 20 parts by weight, with respect to 100 parts by weight of the thermoplastic resin composition of the present invention. The range of 0.1 to 15 parts by weight is more preferable.

  In addition, for the purpose of modification, other components such as weathering agents (resorcinol-based, salicylate-based, benzotriazole-based, benzophenone-based, hindered amine-based, etc.), mold release agents and lubricants (Montan) are used as long as the effects of the present invention are not impaired. Acids and their metal salts, their esters, their half esters, stearyl alcohol, stearamide, various bisamides, bisureas, polyethylene waxes, etc.), pigments (cadmium sulfide, phthalocyanine, carbon black, etc.), dyes (eg, nigrosine), crystal nucleating agents (Talc, silica, kaolin, clay, etc.), plasticizers (octyl p-oxybenzoate, N-butylbenzenesulfonamide, etc.), antistatic agents (alkyl sulfate type anionic antistatic agents, polyoxyethylene sorbitan monostearate) Non-io like Antistatic agents, betaine amphoteric antistatic agents, etc.), flame retardants (eg, red phosphorus, melamine cyanurate, magnesium hydroxide, aluminum hydroxide and other hydroxides, ammonium polyphosphate, brominated polystyrene, brominated polyphenylene) Ethers, brominated polycarbonates, brominated epoxy resins or combinations of these brominated flame retardants and antimony trioxide), and other polymers can be added.

  The kneading machine used for the production of the thermoplastic resin composition of the present invention is supplied to a generally known melt kneader such as a single-screw or twin-screw extruder, a Banbury mixer, a kneader, or a mixing roll. A representative example is a method of kneading at a processing temperature equal to or higher than the melting point. Among these, an extruder, particularly a twin screw extruder is preferable in terms of productivity. It is also preferred to provide a vent port for the purpose of removing moisture generated during melt kneading and low molecular weight volatile components. In order to control the resin phase separation structure of the thermoplastic resin composition of the present invention as described above using a twin-screw extruder, kneading energy during extrusion (extruder work amount per discharge amount (kW / (kg / H))) needs to be increased. Preferable kneading energy is 0.15 or more and 0.65 or less, and particularly preferably 0.25 or more. As a result, good melt-kneading can be performed, and the intended resin phase separation structure can be formed. However, increasing the kneading energy usually increases the resin temperature due to heat generated by shearing, causing thermal decomposition of polylactic acid resin with poor melt heat resistance and changing the melt viscosity ratio with polyamide resin. It becomes difficult to form. The resin temperature here refers to a temperature obtained by measuring, for example, a molten resin discharged from an extruder die with a thermometer. Therefore, the resin temperature at the time of extrusion is preferably not less than the melting point of the higher melting point resin of the polyamide resin and the polylactic acid resin and not more than 260 ° C., more preferably not more than 250 ° C. By controlling the kneading energy and the resin temperature in this way, it is possible to form a target resin phase separation structure.

  In melt-kneading using a twin-screw extruder, a method in which the cylinder temperature is set to a low temperature and the screw rotation speed is set to a high rotation speed is preferable because high shear can be obtained and high kneading energy can be achieved. However, in this case, when a conventional kneading disk is used for the screw element of the kneading part, the amount of heat generated by shearing is large, and it is difficult to control the resin temperature during extrusion as described above. On the other hand, it is preferable to use a low exothermic kneading element for the screw element of the kneading part because heat generation due to shearing can be suppressed and a resin temperature of 260 ° C. or less during extrusion can be achieved. The low heat generation element mentioned here includes a screw element or the like in which the flight tip portions arranged in parallel in the conventional kneading disc are inclined within a range of the spiral angle of 0 to 90 degrees or 90 to 180 degrees, By introducing these into the kneading part of the screw, it is possible to obtain the effect of suppressing the temperature rise of the resin which is insufficient in the conventional kneading disk. A method of introducing supercritical carbon dioxide or supercritical nitrogen into the kneading part is also preferable because heat generation due to shearing can be suppressed.

  When the cylinder temperature of the twin screw extruder is divided into a plasticizing part for plasticizing the resin charged in the twin screw extruder and a kneading part for melting and kneading the plasticized molten resin, the plasticizing part is made of a polyamide resin ( Of the polylactic acid resin (b), it is preferable that the temperature of the resin having a high melting point is the melting point to the melting point + 20 ° C., and the cylinder temperature of the kneading part is preferably in the range of 100 to 210 ° C. At this time, the mixing order of the raw materials is not particularly limited, and a method in which all raw materials are blended and then melt-kneaded by the above method, a part of the raw materials are blended and melt-kneaded by the above method, and the remaining raw materials are further blended Any method may be used such as a method of melt kneading or a method of mixing a part of raw materials and mixing the remaining raw materials using a side feeder during melt kneading with a single or twin screw extruder. In addition, as for the small amount additive component, other components may be kneaded and pelletized by the above-described method or the like, and then added before molding and used for molding.

  There is no limitation on the molding method of the thermoplastic resin composition of the present invention, and known methods (injection molding, extrusion molding, blow molding, press molding, etc.) can be used. Molding, injection compression molding, and compression molding. Further, the molding temperature is usually selected from a temperature range 5 to 50 ° C. higher than the melting point of the thermoplastic resin composition, and is generally a single layer, but may be multi-layered by a two-color molding method. . The arrangement of each layer when performing two-color molding is not particularly limited, and all layers may be composed of the thermoplastic resin composition of the present invention, or other layers may be composed of other thermoplastic resins. May be. The thermoplastic resin used as a layer other than the thermoplastic resin composition of the present invention used here is a saturated polyester, polysulfone, tetrafluoropolyethylene, polyetherimide, polyamideimide, polyamide, polyketone copolymer, polyphenylene ether. , Polyimide, polyethersulfone, polyetherketone, polythioetherketone, polyetheretherketone, thermoplastic polyurethane, polyolefin, ABS, polyamide elastomer, polyester elastomer, etc., and if necessary, one or more of these thermoplastic resins These can be used in combination, or various additives can be added to them to impart desired physical properties. Further, the obtained molded products may be bonded or welded to each other or other molded products, and the method is not particularly limited, and a general technique can be used.

  Since the thermoplastic resin composition of the present invention is excellent in mechanical properties and heat resistance, it is an automobile part (interior / exterior part), mechanical part, electrical / electronic part (various housings, gears, gears, etc.), building member, civil engineering. It can be used for various purposes such as materials, agricultural materials, medical care, food, household / office supplies, furniture parts and daily necessities.

  Hereinafter, although an example is given and the present invention is explained in detail, the gist of the present invention is not limited only to the following examples.

(1) Observation of resin phase separation structure The resin phase separation structure was observed as follows. SG75H-MIV manufactured by Sumitomo Heavy Industries, Ltd. was used, a thin piece having a thickness of 80 nm was cut from the inside of the molding surface of ASTM No. 1 dumbbell molded at a cylinder temperature of 230 ° C. and a mold temperature of 80 ° C., and a magnification of 10,000 with a transmission electron microscope. Observed at double.

(2) Melt viscosity ratio Using a Toyo Seiki Capillograph Model 1C, the melt viscosity was measured under the conditions of 230 ° C and a shear rate of 100 seconds- ¹ and melted from [melt viscosity of polylactic acid resin / melt viscosity of polyamide resin]. The viscosity ratio was determined.

(3) Resin temperature When melt-kneading in a twin-screw extruder, the molten resin discharged from the extruder die was measured with a thermometer.

(4) Material strength It measured according to the following standard methods.
Tensile strength, tensile elongation: ASTM D638
Flexural modulus: ASTM D790

(5) Formability Regarding the formability, when the tensile test piece was taken out from the mold, the shortest time during which a solidified molded product without deformation was obtained was measured as the molding cycle time. It can be said that the shorter the molding cycle time, the better the moldability.

(6) Heat resistance Using a bending test piece (1/4 inch thick), a deflection temperature under load (0.45 MPa) was measured according to ASTM method D648.

Examples 1-11, Comparative Examples 1-5
After dry blending each component shown below at each ratio shown in Table 1, with a TEX30 type twin screw extruder manufactured by Nippon Steel Works, set the cylinder temperature and screw rotation speed to the conditions shown in Table 1, Examples 1-9 and Comparative Examples 2-4 use a screw with a low heat generation kneading element introduced into the screw kneading part, and Comparative Example 5 uses a screw with a conventional kneading disk introduced into the screw kneading part. The gut discharged from the die was immediately cooled in a water bath and pelletized with a strand cutter. The pellet of this example was heat-treated at 240 ° C. for 1 minute with a heating press, and then a light-scattering measurement was performed by cutting out a 100 μm-thick section from a 0.5-mm-thick sheet that was quenched and fixed in structure. No peak was found. From this, it was suggested that the resin phase separation structure of the sample of the present invention was not formed by spinodal decomposition through a compatibility process.

  The obtained pellets were vacuum-dried at 80 ° C. for 12 hours, and test pieces were prepared by injection molding (SG75H-MIV, Sumitomo Heavy Industries, Ltd., cylinder temperature 230 ° C., mold temperature 80 ° C.). The results of evaluating the mechanical properties, moldability, and heat resistance of each sample are as shown in Table 1. Comparative Examples 2 and 3 could not achieve a resin phase separation structure in which the target polyamide resin was a continuous phase, and were inferior in moldability and heat resistance. In Comparative Example 4, melt kneading was performed under the conventional cylinder temperature conditions, but sufficient kneading energy was not obtained, and the desired resin phase separation structure could not be achieved, so that the moldability and heat resistance were poor. there were. In Comparative Example 5, melt kneading was carried out with the cylinder temperature of the kneading part being low, but since a conventional kneading disk screw was used in the screw kneading part, heat generation was large, the resin temperature increased, and the polylactic acid resin was decomposed. Therefore, the target resin phase separation structure could not be achieved, and the moldability and heat resistance were poor. In this example, compared with Comparative Examples 1 to 5, it was excellent in balance between mechanical properties, moldability and heat resistance.

Examples 12-13, Comparative Example 6
Each component shown below was dry blended with polyamide resin, polylactic acid resin and compatibilizing agent in the proportions shown in Table 2, and then introduced into the main feeder of a TEX30 twin screw extruder manufactured by Nippon Steel Co., Ltd. The screw rotation speed was set to the conditions shown in Table 2, melt kneading was performed using a screw having a low heat generation kneading element introduced into the screw kneading section, and glass fibers were introduced from a side feeder downstream of the extruder. The gut discharged from the die was immediately cooled in a water bath and pelletized with a strand cutter. The obtained pellets were vacuum-dried at 80 ° C. for 12 hours, and test pieces were prepared by injection molding (SG75H-MIV, Sumitomo Heavy Industries, Ltd., cylinder temperature 230 ° C., mold temperature 80 ° C.). The results of evaluating the mechanical properties, moldability, and heat resistance of each sample are as shown in Table 2. Compared with Comparative Example 6, Examples 12 and 13 were excellent in moldability and heat resistance in order to achieve a resin phase separation structure in which the polyamide resin is a continuous phase.

Example 14 and Comparative Example 7
Each component shown below was dry blended with polyamide resin (a), polylactic acid resin (b), compatibilizer (c) and talc in the proportions shown in Table 2, and then TEX30 type twin screw extruder manufactured by Nippon Steel Co., Ltd. This is introduced into the main feeder, the cylinder temperature and the screw speed are set to the conditions shown in Table 2, melt kneading is carried out using a screw having a low exothermic kneading element in the screw kneading part, and it is discharged from the die. The gut was immediately cooled in a water bath and pelletized with a strand cutter. The obtained pellets were vacuum-dried at 80 ° C. for 12 hours, and test pieces were prepared by injection molding (SG75H-MIV, Sumitomo Heavy Industries, Ltd., cylinder temperature 230 ° C., mold temperature 80 ° C.). The results of evaluating the mechanical properties, moldability, and heat resistance of each sample are as shown in Table 2. Compared with Comparative Example 7, Example 14 was excellent in moldability and heat resistance in order to achieve a resin phase separation structure in which the polyamide resin is a continuous phase.

Examples 15-20, comparative example 8
After dry blending each component shown below at each ratio shown in Table 3, with a TEX30 type twin screw extruder manufactured by Nippon Steel Works, set the cylinder temperature and screw rotation speed to the conditions shown in Table 3, Melting and kneading were performed using a screw having a low exothermic kneading element introduced into the screw kneading section, and the gut discharged from the die was immediately cooled in a water bath and pelletized by a strand cutter. The obtained pellets were vacuum-dried at 80 ° C. for 12 hours, and test pieces were prepared by injection molding (SG75H-MIV, Sumitomo Heavy Industries, Ltd., cylinder temperature 230 ° C., mold temperature 80 ° C.). The results of evaluating the mechanical properties, moldability, and heat resistance of each sample are as shown in Table 3. Comparative Example 8 cannot achieve a resin phase separation structure in which the target polyamide resin is a continuous phase, and is inferior in moldability and heat resistance, while Examples 15 to 20 have mechanical properties and molding. The heat resistance and heat resistance were particularly excellent.

The polyamide resin (a) used in the examples and comparative examples is as follows.
(A-1): Nylon 6 resin having a melting point of 225 ° C. and a relative viscosity of 2.30.
(A-2): Nylon 6 resin having a melting point of 225 ° C. and a relative viscosity of 2.80.
(A-3): Nylon 12 resin having a melting point of 180 ° C. and a relative viscosity of 2.50.
(A-4): Nylon 610 resin having a melting point of 225 ° C. and a relative viscosity of 2.70.

Similarly, the polylactic acid resin (b) is as follows.
(B-1): Poly L lactic acid resin having a weight average molecular weight (PMMA conversion) of 210,000 and a D-form content of 1.2%.
(B-2): Poly L lactic acid resin having a weight average molecular weight (PMMA conversion) of 160,000 and a D-form content of 1.2%.

Similarly, the compatibilizer (c) is as follows.
(C-1): A bisphenol A type epoxy resin having an epoxy equivalent of 600 to 700 and a molecular weight of 1060.
(C-2): Polycarbodiimide (“Carbodilite” LA-1 manufactured by Nisshinbo).
(C-3): Ethylene / Glycidyl methacrylate-g-polymethyl methacrylate (“Modiper” A-4200 manufactured by NOF Corporation).

Similarly, the filler (d) is as follows.
(D-1): Glass fiber having an average fiber diameter of 13 μm (T-289 manufactured by Nippon Electric Glass Co., Ltd.).
(D-2): Talc (Nihon Talc SG-200).

Similarly, the resin (e) added in addition to the polyamide resin and the polylactic acid resin is as follows.
(E-1): A part of the carboxylic acid moiety in the ethylene / methacrylic acid copolymer is zinc salt (“High Milan” 1706, manufactured by Mitsui DuPont Polychemicals).
(E-2): Multi-layer structure polymer (“METABRENE” S2001, manufactured by Mitsubishi Rayon) in which the core layer is a silicone / acrylic polymer and the shell layer is a methyl methacrylate polymer.

Similarly, the plasticizer (f) is as follows.
(F-1): Polyoxyethyleneoxypropylene block copolymer (Asahi Denka Co., Pluronic F68)
(F-2): Polyoxyethyleneoxypropylene block copolymer (Asahi Denka Co., Pluronic L101)
(F-3): Polyoxyethyleneoxypropylene block copolymer (Asahi Denka Co., Pluronic P85)
(F-4): Polypropylene glycol (Asahi Denka Co., Adeka Polyether P-3000)
(F-5): Polyethylene glycol-polylactic acid block copolymer The polyethylene glycol-polylactic acid block copolymer of (F-5) was produced by the method of Production Example 1 below.
(Production Example 1) 71 parts by weight of polyethylene glycol having an average molecular weight of 10000 and 29 parts by weight of L-lactide were mixed with 0.025 parts by weight of tin octylate, and in a reaction vessel equipped with a stirrer at 140 ° C. in a nitrogen atmosphere. Polymerization was carried out for 30 minutes at 180 ° C. for 60 minutes to obtain a block copolymer of polyethylene glycol and polylactic acid having a polylactic acid segment having an average molecular weight of 2,000.

Claims (12)

Polyamide resin (a) is a thermoplastic resin composition comprising 15 to 50% by weight and polylactic acid resin (b) 50 to 85% by weight, and in a resin phase separation structure observed with an electron microscope, polyamide resin A thermoplastic resin composition characterized by forming a phase structure in which (a) is a continuous phase and polylactic acid resin (b) is a dispersed phase. The thermoplastic resin composition according to claim 1, comprising 25 to 45% by weight of polyamide resin (a) and 55 to 75% by weight of polylactic acid resin (b). A thermoplastic resin composition comprising 15 to 50% by weight of a polyamide resin (a) and 50 to 85% by weight of a polylactic acid resin (b), and polylactic acid in a resin phase separation structure observed with an electron microscope A thermoplastic resin composition characterized in that both the phase consisting of the resin (b) and the phase consisting of the polyamide resin (a) form a phase structure which is a substantially continuous phase. The thermoplastic resin composition according to claim 3, wherein the phase structure does not have a structural period. The thermoplastic resin composition according to any one of claims 1 to 4, wherein 0.01 to 10 parts by weight of the compatibilizer (c) is added to 100 parts by weight of the thermoplastic resin composition. . The compatibilizer (c) is at least one selected from the group consisting of a bisphenol-glycidyl ether epoxy compound, a carbodiimide compound, and an ethylene / glycidyl (meth) acrylate-g- (meth) acrylate copolymer. The thermoplastic resin composition according to claim 5. The thermoplastic resin composition according to any one of claims 1 to 6, wherein 0.01 to 30 parts by weight of the plasticizer (f) is added to 100 parts by weight of the thermoplastic resin composition. 8. The thermoplastic resin composition according to claim 7, wherein the plasticizer (f) is a polyalkylene glycol plasticizer. The thermoplastic resin composition according to any one of claims 1 to 8, wherein a main component of the polyamide resin (a) is a nylon 6 resin. The resin mixture constituting the thermoplastic resin composition is produced by applying kneading energy of 0.15 kWh / kg or more while controlling the resin temperature to 260 ° C or lower. The manufacturing method of the polyamide resin composition in any one of 9. A molded product obtained by processing the thermoplastic resin composition according to claim 1. The molded article according to claim 11, obtained by a method selected from injection molding, injection compression molding, and compression molding.