JP6668587B2 - Resin composition and molded resin - Google Patents

Description

  The present invention relates to a resin composition and a resin molded article.

  For electrical products and electronic / electric device parts, polymer materials such as polystyrene, polystyrene-ABS resin copolymer, polycarbonate, polyester, polyphenylene sulfide, polyacetal, etc. Are used because they are excellent in maintaining mechanical strength against environmental changes.

  In recent years, from the viewpoint of environmental issues and the like, a resin composition containing a polylactic acid resin, which is a kind of biodegradable polymer, and a molded article obtained using the resin composition are known.

  For example, Patent Document 1 contains a biodegradable resin and a filler whose surface is coated with the biodegradable resin, and the filler is at least one selected from mica, talc, and montmorillonite, A biodegradable resin composition in which the biodegradable resin is polylactic acid is described.

  Patent Document 2 discloses that, based on 100 parts by weight of a mixture of (A) 60 to 95% by weight of a polylactic acid resin and (B) 40 to 5% by weight of a copolymerized polyester resin having a melting point of 75 to 160 ° C, (C) ) 0.5 to 10 parts by weight of a modified olefin resin having a functional group, and (D) a nucleating agent such as a metal soap of montanic acid, a sorbitol compound, a sodium salt of fosphosin oxide, or talc. A polylactic acid composition containing 0 parts by weight and having excellent heat resistance and molding cycle properties is described.

JP 2004-075722 A JP 2008-143989 A

  An object of the present invention is to provide, in a resin composition containing an aliphatic polyester resin, a resin composition having excellent heat resistance, flame retardancy and impact resistance when formed into a molded article, and a resin molding obtained using the resin composition. Is to provide the body.

The invention according to claim 1 comprises a resin component containing an aliphatic polyester resin, and a surface-treated red phosphorus surface-treated with at least one of aluminum hydroxide, magnesium hydroxide, and titanium oxide, wherein the resin The composition further includes an alloyed resin of a polycarbonate resin and an acrylonitrile-butadiene rubber-styrene resin, and the content of the surface-treated red phosphorus is 1% by mass or more and 30% by mass or less based on the content of the resin component. range der of is, the content of the aliphatic polyester resin, the total content of the alloying resin content of the aliphatic polyester resin ranges der of 10 wt% to 50 wt% Resin composition.

  The invention according to claim 2 is the resin composition according to claim 1, wherein the aliphatic polyester resin includes a polylactic acid resin.

The invention according to claim 3 is a resin molded article obtained by using the resin composition according to claim 1 or 2, and having a relative crystallinity of 50 or more.

According to the invention according to claims 1 and 2, in the resin composition containing the aliphatic polyester resin, the content of the surface-treated red phosphorus is out of the above range, and the relative crystallinity of the molded article is less than 50. As compared with a certain case, a molded article is superior in heat resistance, flame retardancy and impact resistance.

According to the invention according to claim 3 , in the molded article containing the aliphatic polyester resin, the content of the surface-treated red phosphorus is out of the above range, and the heat resistance is higher than when the relative crystallinity is less than 50. Excellent in flame retardancy and impact resistance.

  An embodiment of the present invention will be described below. The present embodiment is an example for implementing the present invention, and the present invention is not limited to the present embodiment.

  The resin composition according to the embodiment of the present invention contains a resin component containing an aliphatic polyester resin and red phosphorus. The content of red phosphorus is in the range of 1% by mass or more and 30% by mass or less with respect to the content of the resin component, and the relative crystallinity of the molded article is 50 or more. Thereby, when it is formed into a molded product, it is excellent in heat resistance, flame retardancy and impact resistance.

  In a resin composition containing an aliphatic polyester resin such as a polylactic acid resin, a nucleating agent such as talc or a filler such as mica is added in order to improve heat resistance when formed into a molded product. Although studies have been made to improve the crystallinity of aliphatic polyester resins such as resins, flame retardancy and impact resistance were not sufficient. The present inventors, in a resin composition containing an aliphatic polyester resin, by including red phosphorus in a specific amount range, by making the relative crystallinity of the molded body 50 or more, the molded body, It has been found that when this is done, it is excellent in heat resistance, flame retardancy and impact resistance.

  In the present specification, "relative crystallinity" refers to a relative crystallinity when the crystallinity when all aliphatic polyester resins are crystallized is 100 when formed into a molded article. Refers to In the resin composition according to the present embodiment, the relative crystallinity when formed into a molded product is 50 or more, preferably 70 or more, and more preferably 100. If the relative crystallinity of the molded body is less than 50, the heat resistance is insufficient. As a method of making the relative crystallinity of the molded body 50 or more, the amount of red phosphorus is adjusted to be in a range of 1% by mass or more and 30% by mass or less with respect to the content of the resin component. Examples include a method of increasing the mold temperature during molding (for example, 100 ° C. or higher), and a method of performing an annealing treatment (for example, 80 ° C. or higher) after molding.

<Aliphatic polyester resin>
The resin composition according to the present embodiment contains an aliphatic polyester resin as a resin component. Aliphatic polyester resins are roughly classified into microorganism-produced polymers, synthetic polymers, and semi-synthetic polymers. Examples of the microorganism-producing polymer include polyhydroxybutyric acid and polyhydroxyvaleric acid. Examples of the synthetic polymer include polycaprolactone, a condensate of an aliphatic dicarboxylic acid and an aliphatic diol, and the like. Examples of the semi-synthetic polymer include a polylactic acid-based polymer (polylactic acid resin). One of these aliphatic polyester resins may be used alone, or two or more thereof may be used in combination.

Among these aliphatic polyester resins, a semi-synthetic polymer is preferable, and a polylactic acid polymer (polylactic acid resin) is more preferable from the viewpoint of processability, biodegradability, and the like. In particular, since polylactic acid resin can synthesize lactic acid from a non-petroleum raw material such as sweet potato or corn, it is possible to cope with a movement to replace a resin that does not use petroleum resources with a resin that uses petroleum resources. As described above, the polylactic acid resin is derived from a plant, and has an effect of reducing the environmental load, specifically, reducing the amount of CO ₂ emission and the amount of petroleum used.

  The polylactic acid resin is not particularly limited as long as it is a condensate of lactic acid, and examples thereof include polylactic acid or a copolymer of lactic acid and another monomer. One of these polylactic acid resins may be used alone, or two or more thereof may be used in combination. The content of such other monomer may be usually 1 mol% or more and 50 mol% or less in all monomer components. Further, as the polylactic acid resin, a modified resin may be used. For example, maleic anhydride-modified polylactic acid, epoxy-modified polylactic acid, amine-modified polylactic acid, or the like may be used.

  The other monomer may be any compound having two or more ester bond-forming functional groups, such as dicarboxylic acid, polyhydric alcohol, hydroxycarboxylic acid, and lactone.

  Examples of the dicarboxylic acid include succinic acid, azelaic acid, sebacic acid, terephthalic acid, and isophthalic acid.

  Examples of the polyhydric alcohol include aromatic polyhydric alcohols such as a compound obtained by addition reaction of bisphenol with ethylene oxide; ethylene glycol, propylene glycol, butanediol, hexanediol, octanediol, glycerin, sorbitan, trimethylolpropane, neopentyl Aliphatic polyhydric alcohols such as glycol; ether glycols such as diethylene glycol, triethylene glycol, polyethylene glycol, and polypropylene glycol.

  Examples of the hydroxycarboxylic acid include glycolic acid, hydroxybutylcarboxylic acid, and the hydroxycarboxylic acid described in JP-A-6-184417.

  Examples of the lactone include glycolide, ε-caprolactone glycolide, ε-caprolactone, β-propiolactone, δ-butyrolactone, β- or γ-butyrolactone, pivalolactone, δ-valerolactone, and the like.

  As a method for synthesizing the polylactic acid resin, a known synthesis method can be used. Examples of the method for synthesizing the polylactic acid resin include, for example, the synthesis method described in JP-A-7-33861; the synthesis method described in JP-A-59-96123; And the synthesis methods described on pages 3198 to 3199, and the like. Specific examples include a synthesis method by direct dehydration condensation of lactic acid and a synthesis method by ring-opening polymerization of lactide.

  Examples of the lactide include L-lactide, D-lactide, DL-lactide, meso-lactide and the like. One of these lactides may be used alone, or two or more of them may be used in combination.

  Examples of the lactic acid include L-lactic acid, D-lactic acid, and DL-lactic acid. One of these lactic acids may be used alone, or two or more thereof may be used in combination.

  Regarding the polylactic acid resin, whether it is poly-L-lactic acid (hereinafter also referred to as "PLLA") or poly-D-lactic acid (hereinafter also referred to as "PDLA"), they are mixed by copolymerization or blending. It is a mixture of poly-L-lactic acid and poly-D-lactic acid, and is a highly heat-resistant stereocomplex polylactic acid (hereinafter referred to as "SC-PLA") in which these helical structures are interlocked. ").

  The component ratio (molar ratio%) of poly-L-lactic acid and poly-D-lactic acid in the copolymer or mixture is not particularly limited, but from the viewpoint of heat resistance and the like, L-lactic acid / D-lactic acid is used. , 50/50 or more and 99.99 / 0.01 or less. If the ratio of L-lactic acid / D-lactic acid is less than 50/50, the mechanical properties may deteriorate when formed into a molded article, and if it exceeds 99.99 / 0.01, the cost may increase. is there.

  As the polylactic acid resin, a synthesized product may be used, or a commercially available product may be used. Commercially available products include, for example, “Terramac TE4000”, “Terramac TE2000”, “Terramac TE7000” manufactured by Unitika Ltd., “Ingeo3251D”, “Ingeo3001D”, “Ingeo4032D” manufactured by NatureWorks, and Zhejiang Sea Biological Materials. "REVODE110", "REVODE190", and the like.

  The molecular weight of the polylactic acid resin is not particularly limited, but in the present embodiment, the weight average molecular weight of the polylactic acid resin is preferably in the range of 50,000 to 300,000, and 70,000 or more. More preferably, it is in the range of 250,000 or less. When the weight average molecular weight of the polylactic acid resin is less than 50,000, the mechanical properties may be reduced when formed into a molded article, and when the weight average molecular weight of the polylactic acid resin exceeds 300,000, the processability may decrease. It may be defective.

  The glass transition temperature of the polylactic acid resin is not particularly limited, but is preferably in the range of 100 ° C to 250 ° C, more preferably in the range of 120 ° C to 200 ° C. If the glass transition temperature of the polylactic acid resin is less than 100 ° C., the mechanical properties may be reduced when formed into a molded body, and if the glass transition temperature of the polylactic acid resin exceeds 250 ° C., the workability is poor. May be.

  The polylactic acid resin may contain a lactone compound such as a cyclic lactone such as butyrolactone and 1,6-dioxacyclodecane-2,7-dione as an impurity in production. It is preferable that the content of such impurities such as a lactone compound is small. Specifically, the content is preferably less than 10% by mass, more preferably less than 5% by mass, based on the amount of polylactic acid. When the content of impurities such as a lactone compound is 10% by mass or more, it reacts with a polycarbonate / epoxy compound or the like, and the reactivity with the polyamide is reduced. As a result, the mechanical properties of a molded article are reduced. May be.

<Thermoplastic resin>
The resin composition according to the present embodiment preferably contains a thermoplastic resin as a resin component in addition to the aliphatic polyester resin. By including a thermoplastic resin, impact resistance, heat resistance, and the like are improved. Examples of the thermoplastic resin include a polycarbonate resin, a styrene-based resin, a polyphenylene ether resin, a polyethylene resin, a methacrylic resin, and a thermoplastic elastomer resin. The thermoplastic resin may be an alloyed resin in which at least two of these are combined.

  Although the molecular weight of the thermoplastic resin is not particularly limited, in the present embodiment, the weight average molecular weight of the thermoplastic resin is preferably in the range of 5,000 to 30,000, and more preferably 10,000 or more. More preferably, it is in the range of 25,000 or less. If the weight average molecular weight of the thermoplastic resin is less than 5,000, the processability may be reduced due to excess fluidity, and if the weight average molecular weight of the thermoplastic resin exceeds 30,000, the processability may be reduced due to insufficient flowability. May decrease.

  The glass transition temperature of the thermoplastic resin is not particularly limited, but is preferably in the range of 100 ° C to 200 ° C, more preferably in the range of 120 ° C to 180 ° C. When the glass transition temperature of the thermoplastic resin is less than 100 ° C., heat resistance may be insufficient, and when the glass transition temperature of the thermoplastic resin exceeds 200 ° C., workability may be insufficient.

  The polycarbonate resin may be obtained by polycondensation of one or more monomers, and is not particularly limited as long as it is a polymer having at least one carbonate group. For example, aromatic polycarbonate resins such as bisphenol A type polycarbonate, bisphenol S type polycarbonate and biphenyl type polycarbonate are exemplified.

  As the polycarbonate resin, a synthesized resin may be used, or a commercially available product may be used. Examples of commercially available products include “L-1250Y” and “AD5503” manufactured by Teijin Chemicals Limited, “A2200” manufactured by Idemitsu Kosan Co., Ltd., and “Iupilon S2000” (aromatic polycarbonate resin) manufactured by Mitsubishi Engineering-Plastics Corporation. Can be The polycarbonate resin may be used alone or in combination of two or more.

  Examples of the styrene resin include a GPPS resin (general polystyrene resin), a HIPS resin (impact polystyrene), an SBR resin (styrene butadiene rubber), an ABS resin (acrylonitrile-butadiene rubber-styrene copolymer), and an AES resin ( Acrylonitrile-ethylene propylene rubber-styrene copolymer), AAS resin (acrylonitrile-acryl rubber-styrene copolymer), MBS resin (methyl methacrylate-butadiene rubber-styrene copolymer), AS resin (acrylonitrile-styrene copolymer) And MS resin (methyl methacrylate-styrene copolymer). Among them, HIPS resin, ABS resin, AS resin and the like are preferable from the viewpoint of compatibility with aliphatic polyester resins such as polylactic acid resin.

  As the thermoplastic resin, it is preferable to include at least one of a polycarbonate resin, a styrene-based resin, and an alloyed resin thereof, and the polycarbonate resin, an acrylonitrile-butadiene rubber-styrene resin, and an alloyed resin thereof. More preferably, at least one of

  As the polycarbonate / styrene-based alloyed resin, a synthesized product or a commercially available product may be used. Examples of commercially available products include “TN7300” (polycarbonate / ABS alloyed resin) manufactured by Teijin Chemicals. Further, the polycarbonate / styrene-based alloyed resin may be used alone or in combination of two or more.

  Although the molecular weight of the polycarbonate / styrene-based alloyed resin is not particularly limited, in the present embodiment, the weight average molecular weight of the polycarbonate / styrene-based alloyed resin is in the range of 5,000 to 300,000. Preferably, it is more preferably in the range of 10,000 or more and 150,000 or less. When the weight average molecular weight of the polycarbonate / styrene-based alloyed resin is less than 5,000, workability may be reduced due to excessive fluidity, and when the weight-average molecular weight of the polycarbonate / styrene-based alloyed resin exceeds 300,000 In some cases, workability may be reduced due to insufficient fluidity.

  The glass transition temperature of the polycarbonate / styrene-based alloyed resin is not particularly limited, but is preferably in the range of 80 ° C to 200 ° C, more preferably in the range of 90 ° C to 180 ° C. . When the glass transition temperature of the polycarbonate / styrene-based alloyed resin is less than 80 ° C., the heat resistance may be insufficient, and when the glass transition temperature of the polycarbonate / styrene-based alloyed resin exceeds 200 ° C., the workability is insufficient. May be.

  The content of the aliphatic polyester resin is in the range of 10% by mass or more and 50% by mass or less, and 20% by mass or more and 40% by mass or less based on the total content of the aliphatic polyester resin and the content of the thermoplastic resin. Is preferably within the range. When the content of the aliphatic polyester resin is less than 10% by mass with respect to the sum of the content of the aliphatic polyester resin and the content of the thermoplastic resin, the contribution to reducing the environmental load is reduced, and exceeds 50% by mass. , The heat resistance decreases.

  The content of the thermoplastic resin is in the range of 50% by mass or more and 90% by mass or less with respect to the total content of the aliphatic polyester resin and the content of the thermoplastic resin, and is 60% by mass or more and 80% by mass or less. It is preferably within the range. If the content of the thermoplastic resin is less than 50% by mass with respect to the sum of the content of the aliphatic polyester resin and the content of the thermoplastic resin, the heat resistance is reduced, and if it exceeds 90% by mass, the environmental load is reduced. The contribution to is reduced.

<Red phosphorus>
Red phosphorus is a mixture with other allotropes containing purple phosphorus as a main component. By adding red phosphorus, the crystallinity of an aliphatic polyester resin such as a polylactic acid resin is increased, and the heat resistance and the flame retardancy of a molded article are improved. The red phosphorus is preferably a surface-treated red phosphorus obtained by surface-treating red phosphorus from the viewpoints of chemical safety, electrical properties, moisture and heat resistance and the like.

  Examples of the surface treatment agent for red phosphorus include aluminum hydroxide, magnesium hydroxide, and titanium oxide.

  The red phosphorus content of the surface-treated red phosphorus is not particularly limited, but is preferably 50% by mass or more, and more preferably 80% by mass or more. The red phosphorus content of the surface-treated red phosphorus is adjusted, for example, by adjusting the surface treatment amount of the red phosphorus.

  The average particle diameter of the surface-treated red phosphorus and red phosphorus is preferably 50 μm or less, more preferably 20 μm or less. If the average particle diameter of the surface-treated red phosphorus exceeds 50 μm, appearance may be poor when formed into a molded product.

  As the surface-treated red phosphorus, a synthesized product or a commercially available product may be used. Examples of commercially available products include "Hishigard White" (manufactured by Nippon Chemical Co., Ltd.) and "NOVA EXCEL 140" (manufactured by Rin Kagaku Kogyo Co., Ltd.) surface-treated with titanium oxide. The surface-treated red phosphorus may be used alone or in combination of two or more. Red phosphorus and surface-treated red phosphorus may be used in combination.

  The content of red phosphorus is in the range of 1% by mass to 30% by mass, and preferably in the range of 3% by mass to 10% by mass, based on the content of the resin component. If the content of red phosphorus is less than 1% by mass with respect to the content of the resin component, the heat resistance of the molded article will be insufficient, and if it exceeds 30% by mass, the mechanical strength will decrease.

<Other additives>
As additives other than the plasticizer having an ester bond and the foaming agent, a flame retardant, an antioxidant, a filler, an anti-drip agent and the like may be used as necessary. The content of these other components is preferably 10% by mass or less, based on the total solid content of the resin composition.

  By containing a flame retardant, the flame retardancy is improved when formed into a molded article. The flame retardant may be one generally used as a resin flame retardant, and is not particularly limited. For example, inorganic flame retardants and organic flame retardants are exemplified. Specific examples of inorganic flame retardants include magnesium hydroxide, aluminum hydroxide, silicon dioxide, silica-based flame retardants such as low-melting glass, and specific examples of organic flame retardants include phosphate compounds and phosphate esters. And the like. As the flame retardant used in the present embodiment, among those exemplified above, a phosphate compound, particularly ammonium polyphosphate, is preferable from the viewpoint of flame retardant efficiency and the like. The flame retardants may be used alone or in combination of two or more.

  Examples of the antioxidant include phenol-based, amine-based, phosphorus-based, sulfur-based, hydroquinone-based, and quinoline-based antioxidants. Antioxidants may be used alone or in combination of two or more.

  Examples of the filler include clays such as kaolin, bentonite, kibushi clay and gairome clay, talc, mica, and montmorillonite. One type of filler may be used alone, or two or more types may be used in combination.

  By including the anti-drip agent, the anti-drip (melt dripping) property is improved when the molded article is formed. As the anti-drip agent, a synthesized one or a commercially available one may be used. Examples of commercially available products include polytetrafluoroethylene "PTFE CD145" manufactured by Asahi Glass Co., Ltd., and "FA500H" manufactured by Daikin Industries, Ltd. The anti-drip agent may be used alone or in combination of two or more.

<Various measurement methods>
The contents of the aliphatic polyester resin and the thermoplastic resin in the resin composition are measured by ¹ H-NMR analysis. The content of impurities such as a lactone compound contained in polylactic acid in the resin composition is measured by the same method. The contents of the aliphatic polyester resin and the thermoplastic resin in the resin molded product obtained by using the resin composition are measured by ¹ H-NMR analysis. From the contents of the aliphatic polyester resin and the thermoplastic resin in the resin molded body thus measured, the contents of the aliphatic polyester resin and the thermoplastic resin in the resin composition are estimated.

  The weight average molecular weight of the aliphatic polyester resin and the thermoplastic resin in the resin composition is determined by dissolving the polymer in a solvent and measuring the weight average molecular weight of the solution by size exclusion chromatography (GPC). Tetrahydrofuran (THF) is dissolved and analyzed by molecular weight distribution measurement (GPC). The weight average molecular weight of the aliphatic polyester resin and the thermoplastic resin in the resin molded product obtained by using the resin composition is determined by dissolving the polymer in a solvent, and measuring the weight average molecular weight by size exclusion chromatography (GPC). Determine the molecular weight. Dissolve in tetrahydrofuran (THF) and analyze by molecular weight distribution measurement (GPC).

  The glass transition temperature of the aliphatic polyester resin and the thermoplastic resin in the resin composition is measured by a method according to JIS K 7121 using a thermal analyzer (DSI Nano Technology, DSC6000 type). The glass transition temperature of the aliphatic polyester resin and the thermoplastic resin in the resin molded product obtained by using the resin composition is measured by a method according to JIS K 7121 using a thermal analyzer (DSI Nano Technology, model DSC6000). Measure.

  By measuring the structure and composition ratio of each material for the resin composition and the resin molded product obtained using the resin composition using an elemental analyzer, an NMR device, an IR device, etc., the resin composition and the resin The content of red phosphorus and the like in the molded article is measured. Further, the content of red phosphorus or the like having an ester bond in the resin composition is estimated from the content of red phosphorus or the like in the resin molded product.

  The content of red phosphorus in the resin composition is measured by a pyrolysis gas chromatograph mass spectrometry. The content of red phosphorus in the resin molded product obtained by using the resin composition is measured by the same method.

  The identification of the surface treatment of the red phosphorus surface is measured by NMR and IR.

  The red phosphorus content of the surface-treated red phosphorus in the resin composition is measured by a colorimetric analysis method. The red phosphorus content of the surface-treated red phosphorus in the resin molded product obtained using the resin composition is measured by SEM-EDX.

  The average particle diameter of red phosphorus in the resin composition is measured by a laser Raman spectrometer LabRAM ARAMIS manufactured by Horiba, Ltd., laser wavelength: 633 nm. The average particle diameter was measured by Raman chemical imaging of the component distribution by principal component analysis, which is one of the multivariate analysis methods, using OMNIC At 1 μs software, and the circle equivalent diameter was measured. The average value of the particle diameter D50 is determined as the average particle diameter. The average particle diameter of red phosphorus in the resin molded product is measured by the same method.

  The relative crystallinity when the resin composition is formed into a molded article is measured using a differential scanning calorimeter (DSC-8500, manufactured by PerkinElmer). A sample (10 mg) is weighed, and the temperature is raised from 30 ° C. to 230 ° C. at a rate of temperature rise of 10 ° C./min, and kept at 230 ° C. for 5 minutes. Next, the temperature is lowered to 30 ° C. at a temperature decreasing rate of 10 ° C./min. Note that the measurement is performed in an atmosphere of a nitrogen flow rate of 50 mL / min, and an Al container is used. The crystallization heat (ΔHc) during the differential scanning calorimetry is calculated. Assuming that ΔHc in an uncrystallized state is a relative crystallinity of 100, the crystallinity is calculated relative to a sample in another crystallized state.

<Production method of resin composition>
The resin composition according to the present embodiment may be prepared by kneading, for example, an aliphatic polyester resin, red phosphorus, a thermoplastic resin if necessary, and other components.

  The kneading may be performed by using a known kneading device such as a biaxial kneading device (manufactured by Toshiba Machine Co., Ltd., TEM58SS), a simple kneader (manufactured by Toyo Seiki Co., Ltd., Labo Plast Mill). Here, the kneading temperature condition (cylinder temperature condition) is, for example, preferably in the range of 170 ° C to 220 ° C, more preferably in the range of 180 ° C to 220 ° C, and further in the range of 190 ° C to 220 ° C. More preferred. This makes it easier to obtain a molded article having excellent heat resistance, flame retardancy, and impact resistance.

<Resin molded body>
The resin molded body according to the present embodiment is obtained, for example, by molding the above-described resin composition according to the present embodiment.

  For example, the resin molded body according to the present embodiment is obtained by molding by a molding method such as injection molding, extrusion molding, blow molding, and hot press molding. For reasons such as productivity, the resin composition according to the present embodiment is preferably obtained by injection molding.

  Injection molding may be performed using a commercially available device such as “NEX150” manufactured by Nissei Plastics Industries, “NEX70000” manufactured by Nissei Plastics Industries, and “SE50D” manufactured by Toshiba Machine Co., Ltd. At this time, the cylinder temperature is preferably in the range of 170 ° C to 250 ° C, more preferably in the range of 180 ° C to 240 ° C, from the viewpoint of suppressing decomposition of the resin. The mold temperature is preferably in the range of 30 ° C. or more and 100 ° C. or less, and more preferably in the range of 30 ° C. or more and 60 ° C. or less, from the viewpoint of productivity and the like.

  Further, after molding at a low mold temperature of, for example, 30 ° C. or more and 60 ° C. or less, annealing treatment may be performed at, for example, 80 ° C. or more and 110 ° C. or less.

  The resin molded article according to the present embodiment has excellent heat resistance, flame retardancy, and impact resistance.

<Electronic and electrical components>
Since the resin molded article according to the present embodiment can have excellent mechanical strength (impact resistance, tensile modulus, etc.), it is suitable for applications such as electronic / electric devices, home appliances, containers, and automobile interior materials. Used for More specifically, housings for home appliances and electronic / electric devices, various parts, such as wrapping films, storage cases for CD-ROMs and DVDs, tableware, food trays, beverage bottles, chemical wrapping materials, and the like. Especially, it is suitable for parts of electronic and electric equipment. Many parts of electronic / electric devices have complicated shapes and are heavy, so high impact resistance is required as compared with non-heavy ones. According to the resin molded body, such required characteristics are sufficiently satisfied. The resin molded body according to the present embodiment is particularly suitable for a housing of an image forming apparatus, a copying machine, or the like.

  Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to the following examples.

<Examples , Reference Examples and Comparative Examples>
The raw materials are blended with the compositions (parts by mass) shown in Tables 1 and 2, and the raw materials are put into a biaxial kneader (TEM58SS, manufactured by Toshiba Machine Co., Ltd.) and kneaded at a cylinder temperature of 200 ° C. to obtain a resin composition (compound). Obtained. Next, the obtained resin composition was molded at a cylinder temperature of 200 ° C. and a mold temperature of 40 ° C. using an injection molding apparatus (NEX150E, manufactured by Nissei Plastics Industries), and then annealed at 90 ° C. for 1 hour. Performed to obtain evaluation pieces. In Example 5, annealing was performed at 90 ° C. for 0.5 hour to obtain an evaluation piece. For each component shown in Tables 1 and 2, Table 3 shows the product name, manufacturer name and the like.

(Evaluation method)
[Relative crystallinity]
For the evaluation piece after annealing, the relative crystallinity was measured by a method described above using a differential scanning calorimeter (DSC-8500, manufactured by PerkinElmer).

[Flame retardance]
For the evaluation piece after the annealing treatment, a V test specified in UL94 was performed at a test piece thickness of 1.0 mm. In addition, the result of a combustion test is a high level in order of V-0, V-1, V-2, and notV.

[Deflection temperature under load (heat resistance evaluation)]
With respect to the test pieces before and after annealing, as a heat resistance index, the temperature of the test piece was increased under a load (0.45 MPa) specified in the test method standard of ASTM D648, and the magnitude of the deflection was defined. (The deflection temperature under load: DTUL) was measured. Evaluation was made according to the following criteria. The results are shown in Tables 1 and 2.
：: 70 ° C or higher △: 60 ° C or higher and lower than 70 ° C ×: lower than 60 ° C

[Impact strength (impact resistance)]
For the evaluation piece after the annealing treatment, a notch-processed ISO multipurpose dumbbell test piece was used, and a Charpy impact strength (kJ) was measured by an impact tester (DG-5, manufactured by Toyo Seiki Co., Ltd.) according to the method specified in ISO-179. / M ² ) was measured. Evaluation was made according to the following criteria. The results are shown in Tables 1 and 2.
：: 5.0 or more Δ: 2.0 or more and less than 5.0 ×: less than 2.0

  From Comparative Example 1, the resin composition comprising the polylactic acid resin had low flame retardancy and low heat resistance. In Comparative Examples 2 and 3, the heat resistance tends to be improved by adding mica as a nucleating agent, but the flame retardancy and impact resistance were not sufficient. In Comparative Example 4, heat resistance was improved by adding an alloyed resin of a polycarbonate resin and an acrylonitrile / butadiene rubber / styrene resin to the polylactic acid resin, but the flame retardancy was not sufficient. In Comparative Example 5, red phosphorus was added to the resin composition of Comparative Example 4 at 0.5% by mass, but the heat resistance was not sufficient. It can be seen that the resin compositions of the examples have characteristics excellent in flame retardancy and also excellent characteristics in heat resistance and impact resistance as compared with the resin compositions of the comparative examples.

  As described above, the resin composition of the example was superior to the resin composition of the comparative example in heat resistance, flame retardancy, and impact resistance when formed into a molded product.

Claims (3)

A resin component containing an aliphatic polyester resin, aluminum hydroxide, magnesium hydroxide, and a surface-treated red phosphorus surface-treated with at least one of titanium oxide,
As the resin component, further includes an alloyed resin of polycarbonate resin and acrylonitrile butadiene rubber styrene resin,
The relative content of the resin component, Ri range der content below 30 wt% 1 mass% or more of the surface treatment of red phosphorus,
The content of the aliphatic polyester resin, the total content of the alloying resin content of the aliphatic polyester resin, and wherein the range der Rukoto of 10 wt% to 50 wt% Resin composition.   The resin composition according to claim 1, wherein the aliphatic polyester resin contains a polylactic acid resin. Obtained using the resin composition according to claim 1 or 2,
A resin molded product having a relative crystallinity of 50 or more.