Thermoplastic resin composition and molded article, and methods for producing them

Abstract

To provide: a resin composition and a molded article, which enable efficient reuse of a resin waste and have excellent processability with reduced gas emission during processing; and methods for producing them.SOLUTION: A thermoplastic resin composition comprises: a resin composition (A) comprising at least a thermoplastic resin; a resin waste (B); and a gas adsorbent (C) as essential components. The thermoplastic resin is an engineering plastic or a super engineering plastic. The content of the resin waste (B) is 0.1 to 100 pts.mass relative to 100 pts.mass of the resin composition (A). The gas adsorbent (C) is at least one selected from the group consisting of activated carbon, silica, zeolite, and hydrotalcite.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a thermoplastic resin composition, a thermoplastic resin molded article, and methods for producing them.

Background Art

[0002] In recent years, in order to realize a sustainable society, technological development related to the recycling of various materials has been accelerating. Among them, industrial waste collected from automobiles and home appliances is discharged in large quantities, so efficient reuse is required. Usually, such industrial waste is composed of multiple materials, and it is difficult to use it directly as a raw material for new products. Therefore, the collected industrial waste is generally disassembled by part, crushed, and the iron-based metal is separated by magnetic separation, and then landfilled as resin waste (so-called shredder dust or mixed residue).

[0003] It is preferable to reuse such resin waste as a resin material as much as possible. For example, Patent Document 1 discloses a waste plastic mixture for melt-kneading containing different types of waste plastics and a molded article obtained by melt-molding the mixture. However, when such resin waste is recycled alone as a material, the molded article obtained due to the deterioration of the resin has poor mechanical strength, so it is generally used by mixing with virgin materials. In particular, when a material with a high processing temperature such as engineering plastic or super engineering plastic is used as the virgin material, a large amount of decomposition gas of the low melting point component is generated, which may have an adverse effect on processability and physical properties.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] Therefore, the problem to be solved by the present invention is to provide a resin composition, a molded article, and a method for producing the same, which can recycle resin waste, suppress the generation of gas during processing, and have excellent processability.

Means for Solving the Problem

[0006] As a result of intensive studies to solve the above problems, the present inventors have completed the following present invention.

[0007] That is, the present disclosure is a thermoplastic resin composition obtained by blending at least a resin composition (A) containing a thermoplastic resin, a resin waste (B), and a gas adsorbent (C) as essential components, wherein the thermoplastic resin is an engineering plastic or a super engineering plastic, the blending amount of the resin waste (B) is 0.1 to 100 parts by mass with respect to 100 parts by mass of the resin composition (A), and the gas adsorbent (C) is at least one selected from the group consisting of activated carbon, silica, zeolite, and hydrotalcite.

[0008] The present disclosure also relates to a molded article obtained by melt-molding the resin composition described above.

[0009] The present disclosure also relates to a method for producing a thermoplastic resin composition, which comprises blending at least a resin composition (A) containing a thermoplastic resin, a resin waste (B), and a gas adsorbent (C) as essential components, and melt-kneading at a temperature equal to or higher than the softening flow temperature of the thermoplastic resin, wherein the thermoplastic resin is an engineering plastic or a super engineering plastic, the blending amount of the resin waste (B) is 0.1 to 100 parts by mass with respect to 100 parts by mass of the resin composition (A), and the gas adsorbent (C) is at least one selected from the group consisting of activated carbon, silica, zeolite, and hydrotalcite.

[0010] The present disclosure also relates to a method for manufacturing a molded article, which includes a step of manufacturing a thermoplastic resin composition by the manufacturing method described above, and a step of melt-molding the obtained thermoplastic resin composition.

Effects of the Invention

[0011] According to the present invention, it is possible to provide a resin composition and a molded article in which resin waste can be reused, the generated gas during processing is suppressed, and the processability is excellent, and methods for manufacturing them.

Modes for Carrying Out the Invention

[0012] Hereinafter, embodiments of the present invention will be described in detail. However, the scope of the present invention is not limited to the embodiments described herein, and various modifications can be made without departing from the spirit of the present invention. Also, when a plurality of upper limit values and lower limit values are described for specific parameters, any combination of an upper limit value and a lower limit value can be used to form a suitable numerical range.

[0013] The PAS resin composition according to the present embodiment is a thermoplastic resin composition obtained by blending, as essential components, a resin composition (A) containing at least a thermoplastic resin, a resin waste (B), and a gas adsorbent (C), wherein the thermoplastic resin is an engineering plastic or a super engineering plastic, the blending amount of the resin waste (B) is 0.1 to 100 parts by mass with respect to 100 parts by mass of the resin composition (A), and the gas adsorbent (C) is at least one selected from the group consisting of activated carbon, silica, zeolite, and hydrotalcite. The following will be described.

[0014] <Resin Composition (A) Containing at Least a Thermoplastic Resin> The thermoplastic resin composition according to the present embodiment is formed by blending, as an essential component, a resin composition (A) containing at least a thermoplastic resin (hereinafter sometimes simply referred to as resin composition (A)). The thermoplastic resin contained in the resin composition (A) used in this embodiment may be an engineering plastic or a super engineering plastic. For example, polyarylene sulfide resin (hereinafter referred to as PAS resin), polyamide resin, modified polyphenylene ether resin, polyether ether ketone resin, polyether ketone resin, polyketone resin, polyarylate resin, polyimide resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polycarbonate resin, polyacetal resin, polysulfone resin, polyether sulfone resin, polyamideimide resin, polyetherimide resin, polytetrafluoroethylene resin, and liquid crystalline polyester resin are preferable. From the viewpoints of chemical resistance, heat resistance, and mechanical properties, PAS resin is more preferable, and among PAS resins, polyphenylene sulfide resin (hereinafter referred to as PPS resin) is particularly preferable.

[0015] PAS resin has a resin structure having a structure in which an aromatic ring and a sulfur atom are bonded as a repeating unit. Specifically, the following general formula (1)

[0016]

Chemical formula

[0017]

Chemical formula

[0018] Here, the structural part represented by the general formula (1) is particularly R in the formula1 and R 2 is preferably a hydrogen atom from the viewpoint of the mechanical strength of the PAS resin. In that case, those bonded at the para position represented by the following formula (3) and those bonded at the meta position represented by the following formula (4) can be mentioned.

[0019]

Chemical formula

[0020] Further, the PAS resin contains not only the structural parts represented by the general formulas (1) and (2), but also the following structural formulas (5) to (8)

[0021]

Chemical formula

[0022] Further, the PAS resin may have a naphthyl sulfide bond or the like in its molecular structure, but it is preferably 3 mol% or less, particularly preferably 1 mol% or less, based on the total number of moles with other structural parts.

[0023] Further, the physical properties of the PAS resin are not particularly limited as long as the effects of the present invention are not impaired, but are as follows.

[0024] (Melt viscosity) The melt viscosity of the PAS resin used in this embodiment is in the range of 200 Pa·s or less as measured at 300°C because the balance between processability and toughness is good. Further, it is preferably in the range of 2 Pa·s or more, more preferably in the range of 30 Pa·s or more. And it is preferably in the range of 180 Pa·s or less, more preferably in the range of 160 Pa·s or less. However, the measurement of the melt viscosity (V6) is performed using a flow tester, CFT-500D, manufactured by Shimadzu Corporation on the PAS resin, and the measured value of the melt viscosity measured after holding for 6 minutes at 300°C, load: 1.96×10 6 Pa, L / D = 10 (mm) / 1 (mm).

[0025] (Manufacturing method) The method for producing the PAS resin is not particularly limited. For example, (Production Method 1) a method of polymerizing a dihalogenoaromatic compound in the presence of sulfur and sodium carbonate, and adding a polyhalogenoaromatic compound or other copolymerization components if necessary; (Production Method 2) a method of polymerizing a dihalogenoaromatic compound in a polar solvent in the presence of a sulfidizing agent or the like, and adding a polyhalogenoaromatic compound or other copolymerization components if necessary; (Production Method 3) a method of self-condensing p-chlorothiophenol and adding other copolymerization components if necessary; (Production Method 4) a method of melt-polymerizing a diiodoaromatic compound and elemental sulfur under reduced pressure in the presence of a polymerization inhibitor which may have a functional group such as a carboxyl group or an amino group, etc. These methods include, among others, the method of (Production Method 2) which is general and preferred. During the reaction, an alkali metal salt of a carboxylic acid or a sulfonic acid, or an alkali hydroxide may be added to adjust the degree of polymerization. Among the above (Production Method 2) methods, a hydrous sulfidizing agent is introduced into a mixture containing a heated organic polar solvent and a dihalogenoaromatic compound at a rate at which water can be removed from the reaction mixture, and the dihalogenoaromatic compound and the sulfidizing agent are added, if necessary, with a polyhalogenoaromatic compound in the organic polar solvent and reacted, and the water content in the reaction system is controlled within the range of 0.02 to 0.5 mol per 1 mol of the organic polar solvent to produce a PAS resin (see JP-A-07-228699). Also, a method in which a dihalogenoaromatic compound and, if necessary, a polyhalogenoaromatic compound or other copolymerization components are added in the presence of a solid alkali metal sulfide and an aprotic polar organic solvent, and an alkali metal hydrosulfide and an alkali metal organic acid salt are reacted while controlling the alkali metal organic acid salt in the range of 0.01 to 0.9 mol per 1 mol of the sulfur source and the water content in the reaction system within the range of 0.02 mol or less per 1 mol of the aprotic polar organic solvent (see WO2010 / 058713 pamphlet) is particularly preferred.Specific examples of the dihalogenoaromatic compound include p-dihalobenzene, m-dihalobenzene, o-dihalobenzene, 2,5-dihalotoluene, 1,4-dihalonaphthalene, 1-methoxy-2,5-dihalobenzene, 4,4'-dihalobiphenyl, 3,5-dihalobenzoic acid, 2,4-dihalobenzoic acid, 2,5-dihalonitrobenzene, 2,4-dihalonitrobenzene, 2,4-dihaloanisole, p,p'-dihalodiphenyl ether, 4,4'-dihalobenzophenone, 4,4'-dihalodiphenyl sulfone, 4,4'-dihalodiphenyl sulfoxide, 4,4'-dihalodiphenyl sulfide, and compounds having an alkyl group with 1 to 18 carbon atoms in the aromatic ring of each of the above compounds. Examples of the polyhalogenoaromatic compound include 1,2,3-trihalobenzene, 1,2,4-trihalobenzene, 1,3,5-trihalobenzene, 1,2,3,5-tetrachlorobenzene, 1,2,4,5-tetrachlorobenzene, 1,4,6-trihalonaphthalene, and the like. Further, the halogen atom contained in each of the above compounds is preferably a chlorine atom or a bromine atom.

[0026] As a method for post-treating the reaction mixture containing the PAS resin obtained by the polymerization process, there are no particular restrictions, but for example, (Post-treatment 1) after the polymerization reaction is completed, first, the reaction mixture is left as it is, or after adding an acid or a base, the solvent is distilled off under reduced pressure or normal pressure, and then the solid matter after solvent distillation is washed one or more times with solvents such as water, the reaction solvent (or an organic solvent having the same solubility as the low molecular polymer), acetone, methyl ethyl ketone, alcohols, etc., and further neutralized, washed with water, filtered, and dried; or (Post-treatment 2) after the polymerization reaction is completed, a solvent such as water, acetone, methyl ethyl ketone, alcohols, ethers, halogenated hydrocarbons, aromatic hydrocarbons, aliphatic hydrocarbons (a solvent that is soluble in the polymerization solvent used and is a poor solvent at least for PAS) is added as a precipitant to precipitate solid products such as PAS and inorganic salts, and these are filtered off, washed, and dried; or (Post-treatment 3) after the polymerization reaction is completed, a reaction solvent (or an organic solvent having the same solubility as the low molecular polymer) is added to the reaction mixture and stirred, then filtered to remove the low molecular weight polymer, and then washed one or more times with solvents such as water, acetone, methyl ethyl ketone, alcohols, etc., and then neutralized, washed with water, filtered, and dried; (Post-treatment 4) after the polymerization reaction is completed, water is added to the reaction mixture for washing with water, filtering, and if necessary, an acid is added during washing with water for acid treatment, and then dried; (Post-treatment 5) after the polymerization reaction is completed, the reaction mixture is filtered, and if necessary, washed one or more times with the reaction solvent, and further washed with water, filtered, and dried, etc. Among these methods, the method of (Post-treatment 4) is preferable because a PAS resin having a carboxyl group at the molecular end of the PAS resin can be obtained.

[0027] In addition, in the post-treatment methods exemplified in the above (Post-treatment 1) to (Post-treatment 5), the drying of the PAS resin may be carried out in a vacuum, or in air or an inert gas atmosphere such as nitrogen.

[0028] The blending amount of the resin composition (A) in the present embodiment is not particularly limited, but it is preferable to adjust the blending amount of the resin composition (A) so that the amount of the thermoplastic resin is preferably 20 to 90 parts by mass, more preferably 40 to 70 parts by mass, in 100 parts by mass of the resulting resin composition. In such a range, it is preferable because the resin composition has good processability and the molded product is excellent in chemical resistance, toughness, etc.

[0029] In addition, as the resin composition (A) used in the present embodiment, a resin composition containing a newly polymerized thermoplastic resin (virgin thermoplastic resin) can be used, or a resin composition containing a thermoplastic resin recovered from a resin composition or a molded product can also be used. In addition, those obtained by mechanically pulverizing the recovered resin composition or molded product can also be used. Specifically, there are examples such as sprues or runners generated during the production of molded products, those recovered as off-specification molded products, and those obtained by pulverizing molded products that have been used as products once.

[0030] The resin composition (A) used in the present embodiment contains at least the above-mentioned thermoplastic resin as an essential component, and in addition, as optional components, known and commonly used additives such as colorants, antistatic agents, antioxidants, heat stabilizers, ultraviolet stabilizers, ultraviolet absorbers, foaming agents, flame retardants, flame retardant aids, rust preventives, and mold release agents, antibacterial agents, antiviral agents, fillers, coupling agents, etc. may be blended as necessary.

[0031] <Resin waste (B)> The thermoplastic resin composition according to the present embodiment is formed by blending resin waste (B) as an essential component.

[0032] The resin waste in the present disclosure is industrial waste mainly composed of resin, and examples thereof include used resin products, fragments of resin compositions or resin molded products generated during product manufacturing, defective products, losses, and the like. The resin waste (B) applicable to the present embodiment may contain wood, metal, glass, rubber, paper, fiber, filler, additive, moisture, sand, etc. in addition to thermoplastic resin and thermosetting resin. However, from the viewpoint of processability, the content of the resin component is preferably 30 to 100 parts by mass, and more preferably 50 to 100 parts by mass.

[0033] The resin waste (B) applicable to the present embodiment is preferably a pulverized product from the viewpoints of mixability and processability. For example, the major axis is preferably 0.3 to 7 mm, and more preferably 1 to 5 mm. After the resin waste (B) is pulverized, it can be sieved and used so that the major axis falls within the above range. Also, shredder dust is preferable as the resin waste (B), and it is particularly preferable to use Automobile Shredder Residue.

[0034] In the present embodiment, the blending amount of the resin waste (B) is preferably 0.1 to 100 parts by mass, more preferably 10 to 75 parts by mass, and still more preferably 10 to 45 parts by mass with respect to 100 parts by mass of the resin composition (A). Such a range is preferable because of excellent recycling efficiency and processability.

[0035] <Gas adsorbent (C)> The thermoplastic resin composition according to the present embodiment is formed by blending a gas adsorbent (C) as an essential component.

[0036] The gas adsorbent (C) in the present disclosure is at least one selected from the group consisting of activated carbon, silica, zeolite, and hydrotalcite, and adsorbs gases generated during melt processing (for example, decomposition gases derived from the resin waste (B), etc.), and suppresses the gases generated in the heating and melting process during the production of the resin composition or the production of the molded product.

[0037] When silica is used as the gas adsorbent (C), examples include silica gel and mesoporous silica (porous silica with a mesopore size having an average pore diameter of 2 to 50 nm). When zeolite is used as the gas adsorbent (C), any natural or synthetic zeolite can be used, and they can also be used in combination. Examples of natural zeolite include natrolite, wairakite, sodalite, mesolite, thomsonite, gonardite, scolecite, edingtonite, gismondine, dachiardite, mordenite, nigawaraite, erionite, ashcroftine, chabazite, clinoptilolite, tapazite, hakushite, dachiardite, kaijuzudite, juzudite, gmelinite, ryoite, faujasite, etc. Examples of synthetic zeolite include A-type, X-type, Y-type, L-type, beta-type, mordenite, chabazite, ferrierite, MCM-22, etc. When hydrotalcite is used as the gas adsorbent (C), any natural or synthetic hydrotalcite compound having a hydrotalcite structure can be used, and they can also be used in combination. Further, the hydrotalcite compounds can be used without being limited by their crystal structure, crystal particles, etc. Hydrotalcite compounds are inorganic compounds having a layered crystal structure of hydroxides of divalent metal ions and trivalent metal ions and having a structure containing anions between the layers of the layered crystal structure, or calcined products thereof. Examples of the divalent metal ions constituting such hydrotalcite compounds include Mg2 + 、Mn2 + 、Fe2 + 、Co2 + 、Ni2 + 、Cu2 + 、and Zn2 + ; examples of the trivalent metal ions include Al3 + 、Fe3 + 、Cr3 + 、Co3 + 、and In3 + . Also, examples of the anions include OH - 、F - 、Cl - 、Br- , NO3 - , CO3 - , SO4 2- , Fe(CN)6 3- and CH3COO - , molybdate ions, polymolybdate ions, vanadate ions, and polyvanadate ions can be mentioned.

[0038] In this embodiment, the blending amount of the gas adsorbent (C) is preferably 0.1 to 40 parts by mass, more preferably 1 to 30 parts by mass, and still more preferably 5 to 10 parts by mass with respect to 100 parts by mass of the resin composition (A). In such a range, it is preferable because it is excellent in gas adsorbability and moldability. Also, with respect to 100 parts by mass of the resin waste (B), it is preferably 1 to 500 parts by mass, more preferably 5 to 300 parts by mass, and still more preferably 10 to 200 parts by mass.

[0039] The gas adsorbent (C) is preferably porous from the viewpoint of gas adsorption ability. For example, the specific surface area is preferably 50 m 2 / g or more, more preferably 100 m 2 / g or more, still more preferably 250 m 2 / g or more, and particularly preferably 500 m 2 / g or more. The upper limit is not particularly limited, but when it is 2000 m 2 / g or less, the stability is excellent.

[0040] Furthermore, in addition to the above essential components, the thermoplastic resin composition according to the present embodiment may further contain, depending on the application, resins other than engineering plastics or super engineering plastics, for example, virgin materials of synthetic resins such as polyester resins, polyethylene resins, polypropylene resins, polyhexafluoropropylene resins, polystyrene resins, ABS resins, epoxy resins, phenolic resins, urethane resins, liquid crystal polymers, and thermoplastic elastomers (hereinafter simply referred to as synthetic resins) as optional components. In the present invention, the synthetic resin is not an essential component, but when it is blended, the blending ratio is not particularly limited as long as the effects of the present invention are not impaired, and it varies depending on each purpose and cannot be generally defined. However, as the ratio of the synthetic resin blended in the resin composition according to the present embodiment, for example, about 5 to 15 parts by mass with respect to 100 parts by mass of the thermoplastic resin can be mentioned.

[0041] In addition, the thermoplastic resin composition according to the present embodiment may also contain, as optional components, known and commonly used additives such as colorants, antistatic agents, antioxidants, heat stabilizers, ultraviolet stabilizers, ultraviolet absorbers, foaming agents, flame retardants, flame retardant aids, rust preventives, and mold release agents, antibacterial agents, antiviral agents, fillers, coupling agents, etc., as required. These additives are not essential components. For example, with respect to 100 parts by mass of the thermoplastic resin, it is preferably in the range of 0.01 part by mass or more, and preferably 1000 parts by mass or less, more preferably 100 parts by mass or less, and still more preferably 10 parts by mass or less, and is appropriately adjusted according to the purpose and application so as not to impair the effects of the present invention and then used.

[0042] <Manufacturing Method of Thermoplastic Resin Composition> The manufacturing method of the thermoplastic resin composition according to the present embodiment comprises a step of blending, as essential components, a resin composition (A) containing at least a thermoplastic resin, a resin waste (B), and a gas adsorbent (C), and melt-kneading in a temperature range equal to or higher than the temperature at which the thermoplastic resin becomes in a softened and fluid state by heating (which may be the melting point in the case of a crystalline resin or the glass transition point in the case of an amorphous resin. Hereinafter, simply referred to as "softening flow temperature"). Details are described below.

[0043] The method for producing a thermoplastic resin composition according to this embodiment includes a step of blending the above essential components and melt-kneading them in a temperature range equal to or higher than the softening flow temperature of the thermoplastic resin. More specifically, the thermoplastic resin composition according to this embodiment is obtained by blending each essential component and, if necessary, other optional components. The method for producing the resin composition used in the present invention is not particularly limited, but a method of blending essential components and, if necessary, optional components and then melt-kneading them is used. More specifically, a method of uniformly dry-blending using a tumbler or a Henschel mixer as needed and then charging the mixture into a twin-screw extruder for melt-kneading can be mentioned.

[0044] The melt-kneading can be carried out by heating to a temperature range in which the resin temperature is equal to or higher than the softening flow temperature of the thermoplastic resin, preferably a temperature range of the softening flow temperature + 10°C or higher, more preferably the softening flow temperature + 10°C or higher, still more preferably the softening flow temperature + 20°C or higher, and preferably up to the softening flow temperature + 100°C or lower, more preferably up to the softening flow temperature + 50°C or lower.

[0045] From the viewpoints of dispersibility and productivity, a twin-screw kneading extruder is preferable as the melt-kneading machine. For example, it is preferable to perform melt-kneading while appropriately adjusting the range of the discharge amount of the resin component of 5 to 500 (kg / hr) and the range of the screw rotation speed of 50 to 500 (rpm), and it is more preferable to perform melt-kneading under the condition that the ratio (discharge amount / screw rotation speed) is in the range of 0.02 to 5 (kg / hr / rpm). In addition, the addition and mixing of each component to the melt-kneading machine may be performed simultaneously or separately. For example, when adding a fibrous filler among the above components, it is preferable to charge it into the extruder from the side feeder of the twin-screw kneading extruder from the viewpoint of dispersibility. The position of such a side feeder is preferably such that the ratio of the distance from the resin charging part (top feeder) of the twin-screw kneading extruder to the side feeder to the total length of the screw of the extruder is 0.1 or more, more preferably 0.3 or more. Further, such a ratio is preferably 0.9 or less, more preferably 0.7 or less.

[0046] The thermoplastic resin composition according to this embodiment obtained by melt-kneading as described above is a melt mixture containing the above essential components, optional components added as necessary, and components derived therefrom. Therefore, the thermoplastic resin composition according to this embodiment has a morphology in which the thermoplastic resin forms a continuous phase and other essential components and optional components are dispersed.

[0047] After the melt-kneading, the thermoplastic resin composition according to this embodiment is preferably processed into forms such as pellets, chips, granules, and powders by a known method, for example, by extruding the resin composition in a molten state into strands, and then pre-dried in a temperature range of 100 to 150 °C as necessary.

[0048] <Resin molded article, method for manufacturing resin molded article> The molded article according to this embodiment is obtained by melt-molding the above thermoplastic resin composition. Further, the method for manufacturing the molded article according to this embodiment includes a step of melt-molding the thermoplastic resin composition manufactured by the above method. Therefore, the molded article according to this embodiment has a morphology in which the thermoplastic resin forms a continuous phase and other essential components and optional components are dispersed. By having such a morphology, a molded article excellent in thermal conductivity and mechanical strength can be obtained.

[0049] The thermoplastic resin composition according to this embodiment can be used for various molding methods such as injection molding, compression molding, composite, sheet, pipe extrusion molding, drawing molding, blow molding, and transfer molding. In particular, due to its excellent mold release property, it is suitable for injection molding applications. When molding by injection molding, various molding conditions are not particularly limited, and it can be molded by a generally common method. For example, in an injection molding machine, after passing through a step of melting the thermoplastic resin composition in a temperature range where the resin temperature is equal to or higher than the softening flow temperature of the thermoplastic resin, preferably in a temperature range of the softening flow temperature + 10°C or higher, more preferably in a temperature range of the softening flow temperature + 10°C to the softening flow temperature + 100°C, and even more preferably in a temperature range of the softening flow temperature + 20°C to the softening flow temperature + 50°C, it can be injected into the mold from the resin discharge port and molded. At that time, the mold temperature can also be set within a known temperature range, for example, room temperature (23°C) to 300°C, preferably 130 to 190°C.

[0050] The manufacturing method of the molded product according to this embodiment may include a step of annealing the molded product. The annealing conditions are selected according to the use or shape of the molded product. The annealing temperature is in a temperature range equal to or higher than the glass transition temperature of the thermoplastic resin, preferably in a temperature range of the glass transition temperature + 10°C or higher, and more preferably in a temperature range of the glass transition temperature + 30°C or higher. On the other hand, it is preferably in a range of 260°C or lower, and more preferably in a range of 240°C or lower. The annealing time is not particularly limited, but it is preferably in a range of 0.5 hours or more, and more preferably in a range of 1 hour or more. On the other hand, it is preferably in a range of 10 hours or less, and more preferably in a range of 8 hours or less. In such a range, it is preferable because the strain of the obtained molded product is reduced, the crystallinity of the resin is improved, and the thermal conductivity and mechanical strength are further improved. The annealing treatment may be performed in air, but it is preferably performed in an inert gas such as nitrogen gas.

[0051] The molded article according to this embodiment includes a remolded article obtained by recycling a molded article formed by melt-molding the thermoplastic resin composition. Specifically, for example, sprues or runners generated during the production of molded articles, articles recovered as off-specification molded articles, or molded articles that have been used as products once are washed as necessary and then pulverized and remelted at a temperature equal to or higher than the softening flow temperature of the thermoplastic resin to obtain molded articles. When recycling, it is preferable from the viewpoint of mechanical strength to mix and use the pulverized molded article with the thermoplastic resin composition. The size of the molded article when pulverized is not particularly limited, but from the viewpoints of mixability and processability, it is preferably about the same size as the thermoplastic resin composition to be mixed. Further, the mixing ratio is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and even more preferably 20 parts by mass or less of the pulverized molded article with respect to 100 parts by mass of the thermoplastic resin composition. Within such a range, recyclability can be improved without impairing the effects exhibited by the thermoplastic resin composition of the present disclosure.

[0052] <Use> Since the resin composition and the resin molded article of the present invention are characterized by excellent low gas permeability and moldability, they are suitable for various parts such as in-vehicle parts, electric and electronic parts, and water-related parts. Specifically, for example, protective and support members for box-shaped electric and electronic component integrated modules, a plurality of individual semiconductors or modules, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, varicon cases, optical pickups, oscillators, various terminal boards, transformers, plugs, printed circuit boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, terminal blocks, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, computer-related parts, etc., which are representative of electric and electronic parts; VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, audio parts, audio, laser disk, compact disk, DVD disk, Blu-ray disk, etc., which are representative of audio and video equipment parts, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, or water-related equipment parts such as hot water supply machines, hot water amount and temperature sensors in bathtubs, etc., which are representative of home and office electrical product parts; office computer-related parts, telephone-related parts, facsimile-related parts, copier-related parts, cleaning jigs, motor parts, lighters, typewriters, etc., which are representative of machine-related parts: optical instruments, precision machine-related parts such as microscopes, binoculars, cameras, watches, etc.Alternator terminals, alternator connectors, brush holders, slip rings, IC regulators, light dimming potentiometer bases, relay blocks, inhibitor switches, various valves such as exhaust gas valves, various pipes for fuel-related, exhaust, and intake systems, air intake nozzle snorkels, intake manifolds, engine coolant joints, carburetor main bodies, carburetor spacers, exhaust gas sensors, coolant sensors, oil temperature sensors, brake pad wear sensors, throttle position sensors, crankshaft position sensors, temperature sensors, air flow meters, brake pad wear sensors, air conditioner thermostat bases, heating warm air flow control valves, brush holders for radiator motors, water pump impellers, turbine vanes, wiper motor-related parts, distributors, starter switches, ignition coils and their bobbins, motor insulators, motor rotors, motor cores, starter relays, wire harnesses for transmissions, window washer nozzles, air conditioner panel switch substrates, coils for fuel-related solenoid valves, connectors for fuses, horn terminals, insulating boards for electrical components, stepper motor rotors, lamp sockets, lamp reflectors, lamp housings, brake pistons, solenoid bobbins, engine oil filters, ignition device cases, bumpers, and other automotive and vehicle-related parts are listed, and it is also applicable to various other uses.;

Example

[0053] Hereinafter, examples and comparative examples will be used for explanation, but the present invention is not limited to these examples. In the following, unless otherwise specified, “%” and “parts” are based on mass.

[0054] <Examples 1 to 10 and Comparative Examples 1 to 12> The respective materials were blended according to the composition components and blending amounts described in Table 1. Thereafter, these blended materials were charged into a twin-screw extruder "TEX-30α (product name)" with a vent, manufactured by Japan Steel Works, Ltd., and melt-kneaded at a resin component discharge rate of 30 kg / hr, a screw rotation speed of 200 rpm, and a set resin temperature of 310°C to obtain pellets of the resin composition. The glass fiber and polyamide fiber were charged from a side feeder (S / T ratio 0.5), and the other materials were uniformly mixed in advance with a tumbler and charged from a top feeder. The obtained pellets of the resin composition were dried in a gear oven at 140°C for 2 hours and then the following tests were conducted.

[0055] <Evaluation>

[0056] (1) Measurement of weight loss rate (amount of generated gas) A pellet sample of the resin composition was weighed into an aluminum petri dish of 4.00 g using an analytical balance. After the sample was left standing in a dryer set at 150°C for 1 hour, the petri dish was taken out, allowed to cool to room temperature, and then weighed. Next, the same petri dish was left standing in a dryer set at 320°C for 1 hour, the petri dish was taken out, allowed to cool to room temperature, and then weighed. The weight loss rate of each sample was calculated from the following formula. The results are shown in Tables 1 and 2. Weight loss rate [wt%] = (weight value [g] after heating at 150°C - weight value [g] after heating at 320°C) / weight value [g] after heating at 150°C × 100

[0057] (2) Molding property evaluation The moldability when injection molding pellet samples of the resin composition was evaluated. They were supplied to an injection molding machine (SE-75D-HP) manufactured by Sumitomo Heavy Industries, Ltd. with the cylinder temperature set at 310°C, and injection molding was performed using a mold for ISO Type-A dumbbell piece molding with the mold temperature controlled at 140°C. After holding for 15 seconds or more to solidify, the presence or absence of sticking of the dumbbell piece to the mold when the mold was opened was confirmed. Note that it was made by injecting the resin from a single-point gate so as to obtain a test piece without a weld part. Injection molding was carried out 20 times and evaluated according to the following criteria. The evaluation results are shown in Tables 1 and 2. 〇: Does not stick to the mold and continuous molding can be performed △: Stuck to the mold 1 to 10 times and unable to perform continuous molding ×: Stuck to the mold 10 to 20 times and unable to perform continuous molding

[0058]

Table 1

[0059]

Table 2

[0060] In addition, the compounding ratios of the compounding components in Tables 1 and 2 are as follows. · Resin composition containing at least a thermoplastic resin A-1: Virgin material of polyarylene sulfide resin composition, manufactured by DIC Corporation, "DIC.PPS Z-230 BLACK" A-2: Virgin material of aromatic polyamide resin composition, manufactured by DuPont Corporation, "Zytel HTN51g35EFBK083" A-3: Virgin material of polybutylene terephthalate resin composition, manufactured by Toray Industries, Inc., "Trelcon 8207X01" · Resin waste B-1: Pellets with an average particle size of 5 mm obtained by mechanically pulverizing and sieving waste ECU housing. Composition: 78 wt% polybutylene terephthalate, 23 wt% polyarylene sulfide · Gas adsorbent C-1: Activated carbon, manufactured by Osaka Gas Chemical Co., Ltd., "Shirasagi A" C-2: Mesoporous silica, manufactured by Taiyo Chemical Co., Ltd., "TMPS-4R" C-3: Zeolite Ca-A type, manufactured by Nippon Chemical Industry Co., Ltd., "Zeostar CA-100P" C-4: Zeolite Ca-X type, manufactured by Tosoh Corporation, "F-9" C-5: Hydrotalcite, manufactured by Kyowa Chemical Industry Co., Ltd., "DHT-4A-2" c-6: Lithium carbonate, manufactured by Nippon Chemical Industry Co., Ltd. c-7: Zinc carbonate, manufactured by Junsei Chemical Co., Ltd. c-8: Zinc Phosphate, Junsei Chemical Co., Ltd. c-9: Zinc Hydroxide, Junsei Chemical Co., Ltd. c-10: Organic Phosphite, manufactured by ADEKA Corporation, "ADEKA STAB PEP-36"

Claims

1. A thermoplastic resin composition comprising as essential components a resin composition (A) containing at least a thermoplastic resin, a resin waste (B), and a gas adsorbent (C), wherein the thermoplastic resin is an engineering plastic or a super engineering plastic, the blending amount of the resin waste (B) is 0.1 to 100 parts by mass with respect to 100 parts by mass of the resin composition (A), and the gas adsorbent (C) is at least one selected from the group consisting of activated carbon, silica, zeolite, and hydrotalcite.

2. The thermoplastic resin composition according to Claim 1, wherein the thermoplastic resin is a polyarylene sulfide resin.

3. The thermoplastic resin composition according to Claim 1 or 2, wherein the resin waste (B) is shredder dust.

4. The thermoplastic resin composition according to Claim 1 or 2, wherein the resin content of the resin waste (B) is 50 to 100 parts by mass.

5. The specific surface area of the gas adsorbent (C) is 50 m ２ / g or more, a thermoplastic resin composition.

6. A thermoplastic resin composition, wherein the blending amount of the gas adsorbent (C) is 0.1 to 50 parts by mass with respect to 100 parts by mass of the resin composition (A).

7. A thermoplastic resin composition having a weight loss rate of 1.0 wt% or less when heated at 320 °C for 60 minutes.

8. A molded article obtained by melt-molding the resin composition according to Claim 1 or 2.

9. A method for producing a thermoplastic resin composition, comprising blending as essential components a resin composition (A) containing at least a thermoplastic resin, a resin waste (B), and a gas adsorbent (C), and melt-kneading at a temperature equal to or higher than the softening flow temperature of the thermoplastic resin, wherein the thermoplastic resin is an engineering plastic or a super engineering plastic, the blending amount of the resin waste (B) is 0.1 to 100 parts by mass with respect to 100 parts by mass of the resin composition (A), and the gas adsorbent (C) is at least one selected from the group consisting of activated carbon, silica, zeolite, and hydrotalcite.

10. The method for producing a thermoplastic resin composition according to Claim 9, wherein the thermoplastic resin is a polyarylene sulfide resin.

11. The method for producing a thermoplastic resin composition according to Claim 9 or 10, wherein the resin waste (B) is shredder dust.

12. The method for producing a thermoplastic resin composition according to claim 9 or 10, wherein the resin content of the resin waste (B) is 50 to 100 parts by mass.

13. A method for producing a molded article, comprising a step of producing a thermoplastic resin composition by the production method according to claim 9 or 10, and a step of melt-molding the obtained thermoplastic resin composition.

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