JP2011153251A - Regenerated polyolefinic resin composition and regenerated polystyrene resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a regenerated polyolefinic or a regenerated polystyrene resin composition, excel in heat stability, under consideration of a degradation of reinforcement during recycling, in the degradation of resin composition caused because an inorganic filler or a surface treatment agent of titanium oxide or the like causes a decomposition of a base material of a resin composition comprising a metal composition of titanium oxide or the like when a used resin composition is recycled. <P>SOLUTION: The regenerated resin composition comprises 0.05-10 ps.wt. of a metal scavenger based on 100 ps.wt. of a recovered polyolefinic resin composition or 100 ps.wt. of recycled polystyrene composition. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to the regeneration and production method of polyolefin resins and polystyrene resins, and particularly to the regeneration of used polyolefin and polystyrene resin compositions.

  At present, thermoplastic resin compositions such as olefin-based, styrene-based, acrylonitrile-based, and polycarbonate-based resins are generally used as housings and parts of OA equipment and computers such as home appliances and copying machines. When these products are used up and discarded, they are treated as waste, and many of them have been incinerated, landfilled and treated as fuel. However, in recent years, in response to the situation that environmental pollution caused by incineration and landfilling and a shortage of landfill disposal sites have become a social problem, the home appliance industry and OA equipment industry are from the viewpoint of reducing environmental impact and effective use of resources. Material recycling, which is crushed as it is, remelted and processed into various molded products, is being promoted, and application of material recycled materials to products is being promoted.

  Used home appliances are mostly polyolefin (polypropylene, polyethylene), polystyrene (HIPS (High Impact Polystyrene), GPPS (General Purpose Polystyrene)), acrylonitrile (ABS (Acrylonitrile-Butadiene-Styrene), AS (Acrylonitrile-) Styrene)) resin composition, and used OA equipment and computers are acrylonitrile (ABS, AS), polycarbonate (PC), polycarbonate / acrylonitrile, and flame retardant resin compositions.

  The above-mentioned various resin compositions gradually deteriorate over time due to external forces, chemical changes, and the like in a use environment (see FIG. 1). In order to recycle the used resin composition, it is necessary to grasp the degree of deterioration of the resin composition and improve characteristics such as mechanical properties and thermal oxidation stability against the deterioration.

  A method for improving the above-described characteristics when recycling a used resin composition is proposed for each component of the resin composition. The component of the resin composition is a base material of the resin composition that is the main component of the resin composition, a reinforcing material mainly composed of an inorganic compound, an additive for imparting functionality, a stabilizer such as an antioxidant, etc. are categorized.

  For example, as a method for regenerating the lowered mechanical properties due to deterioration of the base material of the resin composition, in Patent Document 1, a monomer that is the same as or similar to the monomer that constitutes the thermoplastic resin in the thermoplastic resin A method has been proposed in which olefin rubber and acrylic rubber imparted with compatibility with the resin are added to the resin as an equivalent regeneration improver by graft polymerization of the resin to effect equivalent regeneration. In addition, a method of additionally adding a consumed amount is generally proposed for the deterioration of additives such as an additive for imparting functionality and a stabilizer such as an antioxidant. Reinforcing materials mainly composed of inorganic compounds are mainly composed of inorganic compounds, so in the case of fibrous reinforcing agents such as glass fibers and carbon fibers, the fiber length is shortened due to external forces in the usage environment or crushing during the recycling process. Therefore, it is said that the mechanical properties are deteriorated due to the reduction of the reinforcing effect, and in the case of recycling, a method of adding a fibrous reinforcing material is common.

  Further, titanium oxide added for the purpose of improving the white colorant and strength has a strong oxidizing power due to the photocatalytic action. In Patent Document 2, as a polybutylene terephthalate resin composition having excellent recycling characteristics, the amount of titanium compound added to the resin is set to titanium atoms in order to suppress hydrolysis caused by titanium oxide when the resin composition is recycled. There has been proposed a method for regulating the conversion to 10 ppm or more and 80 ppm or less. In addition, since titanium oxide usually has a strong oxidizing power due to photocatalytic action, when added to the resin composition, surface treatment is performed to prevent deterioration of the resin due to the added titanium oxide. However, there is a problem that the surface treatment agent deteriorates due to a heat history in recycling.

To solve the above problem, in Patent Document 3, when recycling a polyolefin resin containing an inorganic filler, a hydrotalcite compound (eg, hydrotalcite) and a general formula R—CO—NH— (CH ₂ ) By blending a compound represented by _n- NH-CO-R (eg ethylene bisstearylamide) with phenolic and phosphorus antioxidants, thermal oxidation stability, odor and hue stability are good. Certain thermoplastic resin compositions are described.

JP 2002-105332 A JP 2007-284533 A JP 2001-302809 A

  When the resin composition is recycled, it is necessary to grasp not only the base material of the resin composition and additives such as a stabilizer, but also the degree of deterioration of the reinforcing material that is an inorganic compound. Since titanium oxide used as a white colorant has a strong oxidizing power due to the photocatalytic action as described above, surface treatment is applied when it is added to the resin composition in order to suppress this oxidizing power. In this surface treatment, in order to enhance the affinity with the resin composition in addition to the suppression of the oxidizing power, a hydrous oxide of Al or Si or the like is used as the surface treatment agent. In particular, when the surface treatment agent is aluminum hydroxide, the melting point is around 300 ° C., and when it reaches a temperature of 200 ° C. or higher, crystal water dissociation occurs and decomposes into alumina and crystal water. (180 to 250 ° C.) induces deterioration of the surface treatment agent, causing decomposition of the base material of the resin composition by the titanium oxide from which the surface treatment agent was peeled off and the metal component of the decomposed aluminum compound, and the resin composition Things will deteriorate.

  Further, in the method of Patent Document 3, it is considered that the added antioxidant alone is insufficient to prevent deterioration due to the photocatalytic action of titanium oxide. In other words, the antioxidant only suppresses radical reaction and acts as a scavenger, and suppresses the oxidative degradation promotion reaction to the titanium oxide and the metal components of the aluminum compound generated by thermal degradation of the above-mentioned surface treatment agent. It is thought that it cannot be done.

In order to solve this problem and suppress the deterioration reaction of titanium oxide and the aluminum compound due to thermal deterioration of titanium oxide and the surface treatment agent, it is necessary to suppress the oxidation deterioration promoting reaction of the metal component. For example, the photocatalytic action of titanium oxide having a strong oxidizing power is OH ⁻ (hydroxide ion) or OH · generated by reaction of moisture and holes by electrons and holes generated on the surface of titanium oxide by light absorption. (Hydroxide radical) is to decompose organic matter and finally oxidize to oxygen dioxide and water. Therefore, in order to suppress the photocatalytic action of titanium oxide, it is required to inactivate electrons and holes generated on the titanium oxide surface.

  The present invention has been made to solve the above-described problems, and in consideration of deterioration of a reinforcing material that occurs during recycling, a recycled polyolefin-based and recycled polystyrene-based resin composition having excellent thermal stability. The purpose is to obtain.

  In order to solve the above problems and obtain a regenerated polyolefin resin composition and a regenerated polystyrene resin composition having excellent heat stability, the metal components of titanium oxide and aluminum compounds generated by thermal deterioration of titanium oxide and the surface treatment agent It is necessary to suppress the oxidative degradation promoting reaction, and it is required to inactivate electrons and holes generated on the surface of the metal component.

  The present invention is characterized in that, as a means for solving the above problems, first, 0.05 to 10 parts by weight of a metal scavenger is added to 100 parts by weight of the recovered polyolefin resin composition. This is a recycled polyolefin resin composition.

  2ndly, it is the reproduction | regeneration polystyrene resin composition characterized by adding 0.05-10 weight part of metal capture agents with respect to 100 weight part of collection polystyrene resin compositions.

  Third, the metal scavenger added to the recovered polyolefin resin composition or the recovered polystyrene resin composition is one of ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylethylenediaminetriacetic acid, and tocopherol acetate. It is characterized by including the above.

  Fourthly, a fatty acid having 8 to 24 carbon atoms is added as a stabilizer to the regenerated polyolefin resin composition or the regenerated polystyrene resin composition.

  According to this invention, by adding a specific amount of the metal scavenger to the recovered polyolefin resin composition or the recovered polystyrene resin composition, electrons and holes generated on the surface of the metal component contained in the recovered resin composition Since the chelate is formed and inactivated, the oxidative degradation promoting reaction of the metal component can be suppressed. As a result, the regenerated resin composition can obtain a thermal stability equivalent to or higher than that of a new polyolefin resin composition or a new polystyrene resin composition.

(A)-(e) is a figure explaining the degradation reaction of a polypropylene resin over time. It is a figure explaining the inactivation mechanism by the capture | acquisition of the metal component of ethylenediaminetetraacetic acid which is a metal scavenger in this invention.

  Hereinafter, the present invention will be described in detail. The recycled resin composition of the present invention is characterized in that each of the recovered polyolefin resin composition or the recovered polystyrene resin composition contains a specific amount of a metal scavenger.

[Recovered polyolefin resin composition]
The polyolefin resin constituting the recovered polyolefin resin composition in the present invention is polyethylene, homopolypropylene, propylene-ethylene block copolymer, propylene-butene block copolymer, propylene-α-olefin block copolymer, propylene- Examples thereof include an ethylene random copolymer, a propylene-butene random copolymer, a propylene-α-olefin random copolymer, and a propylene-α-olefin graft copolymer. Such recovered polyolefin resin composition also includes recycled polyolefin resin recovered from used home appliances and the like. These polyolefin resins include known resins such as ethylene-α-olefin copolymers and styrene elastomers, talc, mica, wollastonite, calcium carbonate, barium sulfate, magnesium carbonate, clay , Alumina, silica, calcium sulfate, carbon fiber, glass fiber, metal fiber, silica sand, feldspar, carbon black, titanium oxide, magnesium hydroxide, asbestos, zeolite, molybdenum, diatomaceous earth, sericite, shirasu, calcium hydroxide, Those containing inorganic fillers such as calcium sulfite, sodium sulfate, bentonite, and graphite are also included. Such a recovered polyolefin resin composition generally contains 0.1 to 10 parts by weight of an inorganic filler with respect to 100 parts by weight of the resin composition.

  In the present invention, the “recovered resin composition” is not only the resin recovered from the used home appliances as described above, but also various additives, etc., as raw materials even in an unused state. Resins that cannot be reused as they are, such as scraps added to the resin and produced during processing. The same applies to the recovered polystyrene resin composition.

[Recovered polystyrene resin composition]
Examples of the polystyrene resin constituting the recovered polystyrene resin composition in the present invention include monomers composed of monovinyl aromatic monomers such as styrene, α-methylstyrene, p-methylstyrene, and p-t-butylstyrene. A rubber-modified styrenic polymer produced by dissolving a typical polystyrene (GPPS) or rubber-like substance in a styrenic monomer and polymerizing by bulk or bulk suspension polymerization. As the material, polybutadiene (PBD), styrene-butadiene copolymer (SBR) or the like is used, and representative examples include high impact polystyrene (HIPS), middle impact polystyrene (MIPS) and the like. In addition, acrylonitrile-styrene copolymer (AS resin), which is a polymer obtained by polymerizing a monomer composed of acrylonitrile vinyl cyanide monomer having cyano group, and polybutadiene with acrylonitrile and styrene. And an ABS (acrylonitrile-butadiene-styrene copolymer) resin composition obtained by polymerizing. An MBS resin composition in which methyl methacrylate and styrene are polymerized on polybutadiene is also included. In addition, recycled polystyrene resins recovered from used home appliances and the like are also included. These polystyrene resins include known resins such as styrene elastomers, talc, mica, wollastonite, calcium carbonate, barium sulfate, magnesium carbonate, clay, alumina, silica, calcium sulfate, carbon fiber, glass fiber, metal fiber, Contains inorganic fillers such as silica sand, silica, carbon black, titanium oxide, magnesium hydroxide, asbestos, zeolite, molybdenum, diatomaceous earth, sericite, shirasu, calcium hydroxide, calcium sulfite, sodium sulfate, bentonite, graphite Also included. Such a recovered polystyrene resin composition generally contains 0.1 to 10 parts by weight of an inorganic filler with respect to 100 parts by weight of the resin composition.

[Metal scavenger]
In the present invention, the metal scavenger is added to suppress the oxidative degradation promotion reaction of titanium oxide and aluminum compounds generated by thermal degradation of the titanium oxide and surface treatment agent contained in the recovered resin composition. It is a compound that inactivates electrons and holes generated on the surface of the metal component. Examples of such metal scavengers include ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylethylenediaminetriacetic acid, and tocopherol acetate. The above metal scavenger may contain one or more of the above. By adding the metal scavenger, the thermal stability of the recovered polyolefin resin composition or recovered polystyrene resin composition is increased to a level equivalent to or higher than that of the new polyolefin resin composition or new polystyrene resin composition. Can be improved.

This is because ethylenediaminetetraacetic acid, which is a metal scavenger, has an amide group (NR ₂ group) or a carbonyl group (CO group), and thus the deactivation mechanism of the metal component shown in FIG. Since the amide group (NR ₂ group) or carbonyl group (CO group) of the metal and the electrons and holes generated on the surface of the metal component are inactivated by forming a chelate, the oxidative degradation promoting reaction of the metal component can be suppressed. is there. Suppression of such oxidative degradation promoting reaction can be obtained with nitrilotriacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylethylenediaminetriacetic acid, and tocopherol acetate, which are metal scavengers. Tocopherol acetate does not have an amide group (NR ₂ group), but forms a chelate with a carbonyl group (CO group) and electrons and holes generated on the surface of the metal component, thereby inactivating the metal component. Suppresses oxidative degradation promotion reaction.

  Among the chelating agents used as the metal scavenger, when the above-exemplified compounds are used, the ability to form a chelate with titanium oxide contained in the recovered resin composition and aluminum oxide which is a surface treatment agent for the titanium oxide is high. Therefore, the heat resistance improvement effect is excellent.

  In the present invention, the content of the metal scavenger is 0.05 to 10 parts by weight with respect to 100 parts by weight of the recovered resin composition. When the content of the metal scavenger is 0.05 parts by weight or more and 10 parts by weight or less with respect to 100 parts by weight of the recovered resin composition, it forms chelate with electrons and holes generated on the surface of the metal component. The effect of improving thermal stability by activation can be obtained. Further, when the content of the metal scavenger exceeds 10 parts by weight, the effect of improving the thermal stability is great, but rigidity (for example, flexural modulus) and strength (for example, bending strength and tensile strength) and viscosity, There is a tendency that the mechanical properties required as a resin composition are difficult to be maintained.

[Stabilizer]
In the present invention, better thermal stability can be obtained by adding a fatty acid having 8 to 24 carbon atoms as a stabilizer to the metal scavenger contained in the recovered resin composition.

  In the present invention, the stabilizer is added in order to suppress the decomposition of the metal scavenger, and when the stabilizer is added, the regenerated resin composition has better thermal stability. Become. As such a stabilizer, it is preferable to use a fatty acid having 8 to 24 carbon atoms. This is because the decomposition temperature of the metal scavenger is 250 ° C for ethylenediaminetetraacetic acid, 247 ° C for nitrilotriacetic acid, 175-188 ° C for diethylenetriaminepentaacetic acid, 288-290 ° C for hydroxyethylethylenediaminetriacetic acid, and 200-220 for tocopherol acetate. Since it is C and near the processing temperature (180 to 250 ° C.) during recycling of the recovered polyolefin resin composition and the recovered polystyrene resin composition, the metal scavenger may be decomposed. In order to suppress the decomposition, by adding a fatty acid having 8 to 24 carbon atoms, reducing the processing temperature during recycling, increasing the fluidity of the resin, and improving the dispersibility of the metal scavenger, A remarkable effect of suppressing the oxidative degradation promoting reaction of the metal component is obtained.

  As fatty acids having 8 to 24 carbon atoms, octanoic acid (alias: caprylic acid, carbon number 8), decanoic acid (capric acid, carbon number 10), lauric acid (carbon number 12), myristic acid (carbon number 14), Palmitic acid (16 carbon atoms), palmitoleic acid (16 carbon atoms), stearic acid (18 carbon atoms), oleic acid (18 carbon atoms), elaidic acid (18 carbon atoms), paxenoic acid (18 carbon atoms), linoleic acid (18 carbon atoms), α-linolenic acid (18 carbon atoms), γ-linolenic acid (18 carbon atoms), dihomo-γ-linolenic acid (20 carbon atoms), arachidic acid (20 carbon atoms), eicosatrienoic acid (20 carbon atoms), arachidonic acid (20 carbon atoms), icosapentaenoic acid (20 carbon atoms), behenic acid (22 carbon atoms), docosenoic acid (also known as erucic acid, 22 carbon atoms), docosapentaenoic acid (charcoal) Number 22), docosahexaenoic acid (22 carbon atoms), such as lignoceric acid (24 carbon atoms).

[Heat resistance stabilizer]
In the case of the recovered polyolefin-based and recovered polystyrene-based resin composition according to the present invention, which is selected and recovered from plastic residues derived from used home appliances, the heat stabilizer added to the new material is significantly consumed, It is desirable to add an agent. The heat stabilizer here includes at least one hindered phenol-based, phosphite-based, sulfur-based antioxidant and metal deactivator, and the composition ratio of the heat stabilizer is particularly limited. However, it is desirable to adjust each time according to the required physical properties. The amount of the heat stabilizer added to the recovered polyolefin resin and the recovered polystyrene resin composition is preferably 0.05 to 10 parts by weight.

  Examples of the antioxidant constituting the heat stabilizer added to the recovered polyolefin resin and recovered polystyrene resin composition in the present invention include 2,6-di-t-butyl-p-cresol, tetrakis [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, stearyl β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl- 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, triethylene glycol bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] Phenols such as tris (2,4-di-t-butylphenyl) phosphite, tetrakis (2,4-di-t-butylphenyl) [1,1-biphe L] -4,4′-diylbisphosphonite, bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester phosphorous acid, bis (2,4-di-t -Butylphenyl) pentaerythritol diphosphite, triallyl phosphite, tri (monononylphenyl) phosphite, etc. phosphorus, dilauryl-3,3'-thiodipropionate, dioctadecyl-3,3'-thiodipro Known compounds such as sulfur-based compounds such as piionate are used. Among these, in terms of heat resistance stability, the phenol type is tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, and the phosphorus type is tris (2, 4-Di-t-butylphenyl) phosphite and sulfur are preferably dioctadecyl-3,3′-thiodipropionate.

  As the metal deactivator constituting the heat stabilizer added to the recovered polyolefin resin and recovered polystyrene resin composition in the present invention, 2 ′, 3-bis [[3- [3,5-di-t-butyl- 4-hydroxyphenyl] propionyl]] propionohydrazide, 3- (N-salicyloyl) amino-1,2,4-triazole, decamethylenedicarboxylic acid disalicyloyl hydrazide, N-formylsalicyloyl hydrazine, benzotriazole , Methylbenzotriazole, methylbenzotriazole potassium salt, N, N-dibenzal (oxalyl hydrazide), N, N-bis (3,5-di-t-butyl-4-hydroxyhydrocinnamate), etc. Used. Among these, decamethylene dicarboxylic acid disalicyloyl hydrazide is preferable in terms of heat resistance stability.

[Other additives]
In the present invention, additives such as a plasticizer, a release agent, a flame retardant, a flame retardant aid, a dye, a pigment, and an antistatic agent can be blended as long as the object of the present invention is not impaired. In addition, about each of these, only the 1 type can be used individually or in combination of 2 or more types.

  As a plasticizer, it can be arbitrarily selected from known ones such as polyethylene glycol, polyamide oligomer, ethylene bisstearoamide, phthalic acid ester, adipic acid ester, polystyrene oligomer, polyethylene wax, silicone oil and mineral oil. it can.

  The release agent can be arbitrarily selected from known ones such as polyethylene wax, silicone oil, long chain carboxylic acid, and long chain carboxylic acid metal salt.

  Examples of the flame retardant include phosphorus flame retardants such as tricresyl phosphate, triphenyl phosphate, tris-3-chloropropyl phosphate, 2,2-bis [4- (2,3-dibromopropoxyl) -3,5- Brominated flame retardants such as dibromophenyl] propane, bis (3,5-dibromo-4-dibromopropyloxyphenyl) sulfone, ethylene bispentabromobenzene, hexabromocyclododecane, silicone flame retardants, magnesium hydroxide and hydroxide It can be arbitrarily selected from known ones such as hydroxide flame retardants such as aluminum.

  The flame retardant aid can be arbitrarily selected from antimony compounds such as antimony trioxide and others.

[Production of Recycled Polyolefin Resin Composition and Recycled Polystyrene Resin Composition]
The metal scavenger and stabilizer added to the regenerated polyolefin resin composition and polystyrene resin composition of the present invention are usually provided as powder or granules. A metal scavenger or a metal scavenger and a stabilizer are added to the recovered resin composition, and if desired, the above additives are added and kneaded to obtain a molding material. As a kneading method, kneading is performed using a physical blend such as melt kneading, solvent cast blending, latex blending, polymer complex, etc., and melt kneading method is particularly preferable.

  As a device for kneading the material, a tumbler, a Henschel mixer, a rotary mixer, a super mixer, a ribbon tumbler, a V blender, and the like are used. After the materials are uniformly dispersed by the kneading device, and then melt-kneaded, Pelletize. In general, a single-screw or multi-screw extruder is used for melt-kneading pelletization. In addition to the above-mentioned extruder, a Banbury mixer, a roller, a co-kneader, a blast mill, a Plavender brow graph, etc. should be used. They can be run batchwise or continuously. In addition, a so-called mold is used in which resin pellets, metal scavengers, stabilizers, and other additives are mixed without melting and kneading, and the mixture is used as a molding resin to melt and knead in a molding machine heating cylinder. A blend can also be implemented.

  About the manufacturing method of the molded article concerning this invention, when performing by injection molding, there is no restriction | limiting in particular, It can shape | mold by a well-known shaping | molding method.

  The regenerated polyolefin resin composition and the regenerated polystyrene resin composition of the present invention produced as described above contain a specific amount of metal scavenger with respect to the recovered resin composition, so that the heat stability in the resin composition The agent can be improved and can be reused as a resin composition having the same physical properties as the new material.

  EXAMPLES Next, although an Example and a comparative example demonstrate this invention in detail, this invention is not limited to these Examples.

  In the examples and comparative examples of the present invention, the polyolefin resin composition selected and collected from used home appliances is, for example, a resin selected and collected by a method called wet specific gravity selection using water (specific gravity 1.0) as a specific gravity liquid. In addition, the composition of the polyolefin resin is 90% by weight or more, and the polystyrene resin composition selected and collected from used home appliances is a wet type liquid with a specific gravity liquid of water (specific gravity 1.0) and salt water (specific gravity 1.1). A resin selected and collected by a specific gravity sorting method and a method called electrostatic sorting using frictional electrification of the resin and having a composition of 90% by weight or more of polystyrene resin was used.

  In the examples, comparative examples, and reference examples of the present invention, evaluations were made by adding a general antioxidant in advance. The antioxidant added to the polyolefin resin composition was tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane and tris (2,4- Di-t-butylphenyl) phosphite 0.05 parts by weight, polystyrene resin composition includes stearyl β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate and tris (2,4 0.05 parts by weight of each of -di-t-butylphenyl) phosphite was added. For physical property evaluation, in order to evaluate the degree of thermal oxidative degradation of recycled polyolefin-based and polystyrene-based resin compositions, by using an injection molding machine, a multi-purpose test piece A type resin composition conforming to JIS standard K7139 is prepared, The tensile elongation at break by a tensile test was measured. The tensile elongation at break of the test piece of the resin composition deteriorated by the thermal oxidation stability test was compared with the initial value.

  The tensile test was performed by a method according to JIS standard K7161. The test was performed using a universal testing machine at a test speed of 50 mm / min to obtain the tensile elongation at break. With respect to the obtained tensile breaking elongation, the tensile breaking elongation retention rate (%) relative to the initial tensile breaking elongation was obtained. The thermal oxidation stability test of the polyolefin-based resin composition was performed by a method based on JIS standard K7368. The test was conducted at 140 ° C. for 0, 1500 and 3000 hours, and the tensile breaking elongation retention rate was determined by a tensile test. The thermal oxidation stability test of the polystyrene resin composition was conducted at 90 ° C. for 0, 1500 and 3000 hours. Here, the criterion for determining the deterioration of the resin was the case where the tensile elongation at break retention ratio was reduced to 50%.

Example 1
For 100 parts by weight of a polypropylene resin composition selected and collected from used home appliances, 0.05 parts by weight of ethylenediaminetetraacetic acid as a metal scavenger and tetrakis [methylene-3- (3 ′, a general antioxidant] , 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane and 0.05 parts by weight of tris (2,4-di-t-butylphenyl) phosphite were added and mixed. The mixture was kneaded in an extruder while being heated and melted at 200 ° C. to produce 3 to 5 mm pellets. Next, a multipurpose test piece A was molded by an injection molding machine under the conditions of a resin temperature (molding temperature) of 200 ° C. and a mold temperature of 50 ° C. Table 1 shows the results obtained by conducting a thermal oxidative degradation test at 140 ° C. for 0, 1500 and 3000 hours using the obtained test pieces and measuring the tensile elongation at break (%) by a tensile test. As a result, the recycled polypropylene resin composition of the present invention had a good appearance, the tensile elongation at break after the thermal oxidative degradation test was 100% after 1500 hours, and 58% after 3000 hours, and the tensile elongation at break retention rate. Is 50% or more, compared to before the addition of the metal scavenger (corresponding to Reference Example 3), the effect of improving the thermal stability is seen, and the thermal stability to the equivalent of the new material polypropylene resin (corresponding to Reference Example 1) It was found that sex could be improved.

(Example 2)
10 parts by weight of ethylenediaminetetraacetic acid as a metal scavenger and tetrakis [methylene-3- (3 ′, 5), a general antioxidant, with respect to 100 parts by weight of a polypropylene resin composition selected and collected from used home appliances. '-Di-t-butyl-4'-hydroxyphenyl) propionate] methane and 0.05 parts by weight of tris (2,4-di-t-butylphenyl) phosphite were added and mixed. Then, the mixture was kneaded in an extruder while being heated and melted to produce 3 to 5 mm pellets. Next, a multipurpose test piece A was molded by an injection molding machine under the conditions of a resin temperature (molding temperature) of 200 ° C. and a mold temperature of 50 ° C. Table 1 shows the results obtained by conducting a thermal oxidative degradation test at 140 ° C. for 0, 1500 and 3000 hours using the obtained test pieces and measuring the tensile elongation at break (%) by a tensile test. As a result, the recycled polypropylene resin composition of the present invention has a good appearance, and the tensile elongation at break after the thermal oxidative degradation test is 100% after 1500 hours and 100% after 3000 hours. Compared to before adding the metal scavenger (corresponding to Reference Example 3), the effect of improving the thermal stability is seen, and heat up to the equivalent of the new polypropylene resin (corresponding to Reference Example 1). It was found that the stability can be improved.

(Example 3)
With respect to 100 parts by weight of a polypropylene resin composition selected and collected from used home appliances, 0.05 parts by weight of ethylenediaminetetraacetic acid and 5 parts by weight of stearic acid as stabilizers and a general antioxidant as a metal scavenger Tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate] methane and tris (2,4-di-tert-butylphenyl) phosphite 0.05 each The mixture obtained by adding parts by weight was kneaded in an extruder while being heated and melted at 200 ° C. to produce 3 to 5 mm pellets. Next, a multipurpose test piece A was molded by an injection molding machine under the conditions of a resin temperature (molding temperature) of 200 ° C. and a mold temperature of 50 ° C. Table 1 shows the results obtained by conducting a thermal oxidative degradation test at 140 ° C. for 0, 1500 and 3000 hours using the obtained test pieces and measuring the tensile elongation at break (%) by a tensile test. As a result, the recycled polypropylene resin composition of the present invention had a good appearance, the tensile elongation at break after thermal oxidation degradation test was 100% after 1500 hours, and 72% after 3000 hours, and the tensile elongation at break retention rate was Compared to before adding the metal scavenger (corresponding to Reference Example 3), the effect of improving the thermal stability is seen, and heat up to the equivalent of the new polypropylene resin (corresponding to Reference Example 1). It was found that the stability can be improved.

Example 4
As a metal scavenger, 0.1 part by weight of nitrile triacetic acid, tetrakis [methylene-3- (3 ′), a general antioxidant, with respect to 100 parts by weight of a polypropylene resin composition selected and collected from used home appliances. , 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane and 0.05 parts by weight of tris (2,4-di-t-butylphenyl) phosphite were added and mixed. The mixture was kneaded in an extruder while being heated and melted at 200 ° C. to produce 3 to 5 mm pellets. Next, a multipurpose test piece A was molded by an injection molding machine under the conditions of a resin temperature (molding temperature) of 200 ° C. and a mold temperature of 50 ° C. Table 1 shows the results obtained by conducting a thermal oxidative degradation test at 140 ° C. for 0, 1500 and 3000 hours using the obtained test pieces and measuring the tensile elongation at break (%) by a tensile test. As a result, the recycled polypropylene resin composition of the present invention has a good appearance, the tensile elongation at break after the thermal oxidative degradation test is 100% after 1500 hours, and 80% after 3000 hours, and the tensile elongation at break retention rate. Compared to before adding the metal scavenger (corresponding to Reference Example 3), the effect of improving the thermal stability is seen, and heat up to the equivalent of the new polypropylene resin (corresponding to Reference Example 1). It was found that the stability can be improved.

(Example 5)
100 parts by weight of polypropylene resin composition selected and collected from used home appliances, 0.5 parts by weight of diethylenetriaminepentaacetic acid as a metal scavenger and 1 part by weight of oleic acid as a stabilizer, general antioxidant Tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate] methane and tris (2,4-di-tert-butylphenyl) phosphite 0.05 each The mixture obtained by adding parts by weight was kneaded in an extruder while being heated and melted at 200 ° C. to produce 3 to 5 mm pellets. Next, a multipurpose test piece A was molded by an injection molding machine under the conditions of a resin temperature (molding temperature) of 200 ° C. and a mold temperature of 50 ° C. Table 1 shows the results obtained by conducting a thermal oxidative degradation test at 140 ° C. for 0, 1500 and 3000 hours using the obtained test pieces and measuring the tensile elongation at break (%) by a tensile test. As a result, the recycled polypropylene resin composition of the present invention has a good appearance, the tensile elongation at break after the thermal oxidative degradation test is 100% after 1500 hours, and 100% after 3000 hours, and the tensile elongation at break is maintained. When the rate is 50% or more, compared with before adding the metal scavenger (corresponding to Reference Example 3), the effect of improving the thermal stability is observed, and the heat is increased to a level equivalent to the new polypropylene resin (corresponding to Reference Example 1). It was found that the stability can be improved.

(Example 6)
100 parts by weight of a polypropylene resin composition selected and collected from used home appliances, 0.1 parts by weight of hydroxyethylethylenediaminetriacetic acid as a metal scavenger and 10 parts by weight of palmitic acid as a stabilizer, general oxidation Tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane and tris (2,4-di-t-butylphenyl) phosphite each 0 The mixture obtained by adding 0.05 parts by weight was kneaded in an extruder while being heated and melted at 200 ° C. to produce 3 to 5 mm pellets. Next, a multipurpose test piece A was molded by an injection molding machine under the conditions of a resin temperature (molding temperature) of 200 ° C. and a mold temperature of 50 ° C. Table 1 shows the results obtained by conducting a thermal oxidative degradation test at 140 ° C. for 0, 1500 and 3000 hours using the obtained test pieces and measuring the tensile elongation at break (%) by a tensile test. As a result, the recycled polypropylene resin composition of the present invention had a good appearance, the tensile elongation at break after the thermal oxidative degradation test was 100% after 1500 hours, and 81% after 3000 hours, and the tensile elongation at break retention rate. Compared to before adding the metal scavenger (corresponding to Reference Example 3), the effect of improving the thermal stability is seen, and heat up to the equivalent of the new polypropylene resin (corresponding to Reference Example 1). It was found that the stability can be improved.

(Example 7)
To 100 parts by weight of a polypropylene resin composition selected and collected from used home appliances, 1.0 parts by weight of tocopherol acetate as a metal scavenger, tetrakis [methylene-3- (3 ′, 3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane and 0.05 parts by weight of tris (2,4-di-t-butylphenyl) phosphite were added and mixed. The mixture was kneaded in an extruder while being heated and melted at 3 ° C. to produce 3 to 5 mm pellets. Next, a multipurpose test piece A was molded by an injection molding machine under the conditions of a resin temperature (molding temperature) of 200 ° C. and a mold temperature of 50 ° C. Table 1 shows the results obtained by conducting a thermal oxidative degradation test at 140 ° C. for 0, 1500 and 3000 hours using the obtained test pieces and measuring the tensile elongation at break (%) by a tensile test. As a result, the recycled polypropylene resin composition of the present invention had a good appearance, the tensile elongation at break after the thermal oxidative degradation test was 100% after 1500 hours, and 82% after 3000 hours, and the tensile elongation at break retention rate. Compared to before adding the metal scavenger (corresponding to Reference Example 3), the effect of improving the thermal stability is seen, and heat up to the equivalent of the new polypropylene resin (corresponding to Reference Example 1). It was found that the stability can be improved.

(Example 8)
For 100 parts by weight of a polyethylene resin composition selected and collected from used home appliances, 0.05 parts by weight of ethylenediaminetetraacetic acid as a metal scavenger and tetrakis [methylene-3- (3 ′, a general antioxidant] , 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane and 0.05 parts by weight of tris (2,4-di-t-butylphenyl) phosphite were added and mixed. The mixture was kneaded in an extruder while being heated and melted at 180 ° C. to produce 3 to 5 mm pellets. Next, a multipurpose test piece A was molded by an injection molding machine under conditions of a resin temperature (molding temperature) of 180 ° C. and a mold temperature of 50 ° C. Table 1 shows the results obtained by conducting a thermal oxidative degradation test at 140 ° C. for 0, 1500 and 3000 hours using the obtained test pieces and measuring the tensile elongation at break (%) by a tensile test. As a result, the recycled polyethylene resin composition of the present invention has a good appearance, the tensile elongation at break after the thermal oxidative degradation test is 100% after 1500 hours, and 60% after 3000 hours. Is 50% or more, compared to before the addition of the metal scavenger (corresponding to Reference Example 5), the effect of improving the thermal stability is seen, and stable to the new material polyethylene resin (corresponding to Reference Example 2) It was found that sex could be improved.

(Reference Example 1)
Tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate which is a general antioxidant, based on 100 parts by weight of a general new material polypropylene resin composition ] 0.05 parts by weight of methane and tris (2,4-di-t-butylphenyl) phosphite were added and mixed with an injection molding machine using a resin temperature (molding temperature) of 200 ° C. and a mold temperature. A multipurpose specimen A type was molded under the condition of 50 ° C. Table 2 shows the results obtained by conducting a thermal oxidative degradation test at 140 ° C. for 0, 1500 and 3000 hours using the obtained test pieces and measuring the tensile elongation at break (%) by a tensile test. As a result, the new polypropylene resin composition has a good appearance, the tensile elongation at break after thermal oxidation degradation test is 100% after 1500 hours, 60% after 3000 hours, and the tensile elongation at break is 50%. % Or more.

(Reference Example 2)
Tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate, which is a general antioxidant, with respect to 100 parts by weight of a general new polyethylene resin composition ] 0.05 parts by weight of methane and tris (2,4-di-t-butylphenyl) phosphite were added and mixed with an injection molding machine using a resin temperature (molding temperature) of 180 ° C. and a mold temperature. A multipurpose specimen A type was molded under the condition of 50 ° C. Table 2 shows the results obtained by conducting a thermal oxidative degradation test at 140 ° C. for 0, 1500 and 3000 hours using the obtained test pieces and measuring the tensile elongation at break (%) by a tensile test. As a result, the new polyethylene resin composition has a good appearance, the tensile elongation at break after the thermal oxidative degradation test is 100% after 1500 hours, 65% after 3000 hours, and the tensile elongation at break retention is 50%. % Or more.

(Comparative Example 1)
Tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxy), which is a general antioxidant, with respect to 100 parts by weight of the polypropylene resin composition selected and collected from used home appliances. Phenyl) propionate] methane and tris (2,4-di-t-butylphenyl) phosphite 0.05 parts by weight of each were added and mixed using an injection molding machine, resin temperature (molding temperature) 200 ° C., A multi-purpose specimen A type was molded under the condition of a mold temperature of 50 ° C. Table 2 shows the results obtained by conducting a thermal oxidative degradation test at 140 ° C. for 0, 1500 and 3000 hours using the obtained test pieces and measuring the tensile elongation at break (%) by a tensile test. As a result, the recycled polypropylene resin composition had a brown appearance and cracks, and the tensile elongation at break after thermal oxidation degradation test was 32% after 1500 hours and 0% after 3000 hours. After 1500 hours, the tensile elongation at break was 50% or less, and it was determined that the deterioration occurred.

(Comparative Example 2)
Tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxy), which is a general antioxidant, with respect to 100 parts by weight of the polypropylene resin composition selected and collected from used home appliances. Phenyl) propionate] Methane and tris (2,4-di-t-butylphenyl) phosphite added with 5 parts by weight of each resin composition were injected with an injection molding machine at a resin temperature (molding temperature) of 200 ° C. and a mold temperature. A multipurpose specimen A type was molded under the condition of 50 ° C. Table 2 shows the results obtained by conducting a thermal oxidative degradation test at 140 ° C. for 0, 1500 and 3000 hours using the obtained test pieces and measuring the tensile elongation at break (%) by a tensile test. As a result, the recycled polypropylene resin composition had a brown appearance and cracks, and the tensile elongation at break after thermal oxidation degradation test was 49% after 1500 hours and 0% after 3000 hours. After 1500 hours, the tensile elongation at break was 50% or less, and it was determined that the deterioration occurred.

(Comparative Example 3)
A multi-purpose specimen A type was molded from 100 parts by weight of a polyethylene resin composition selected and collected from used home appliances under the conditions of a resin temperature (molding temperature) of 180 ° C. and a mold temperature of 50 ° C. by an injection molding machine. Table 2 shows the results obtained by conducting a thermal oxidative degradation test at 140 ° C. for 0, 1500 and 3000 hours using the obtained test pieces and measuring the tensile elongation at break (%) by a tensile test. As a result, the recycled polyethylene resin composition has a brown appearance and cracks, and the tensile elongation at break after thermal oxidation degradation test is 57% after 1500 hours and 0% after 3000 hours. After 3000 hours, the tensile elongation at break retention was 50% or less, and it was determined that the deterioration occurred.

(Comparative Example 4)
100 parts by weight of a polypropylene resin composition selected and collected from used home appliances and mixed with 0.01 parts by weight of ethylenediaminetetraacetic acid as a metal scavenger are extruded while being heated and melted at 200 ° C. It knead | mixed in the machine and produced the 3-5 mm pellet. Next, a multipurpose test piece A was molded by an injection molding machine under the conditions of a resin temperature (molding temperature) of 200 ° C. and a mold temperature of 50 ° C. Table 2 shows the results obtained by conducting a thermal oxidative degradation test at 140 ° C. for 0, 1500 and 3000 hours using the obtained test pieces and measuring the tensile elongation at break (%) by a tensile test. As a result, the recycled polypropylene resin composition had a brown appearance and cracks, and the tensile elongation at break after the thermal oxidation degradation test was 39% after 1500 hours and 0% after 3000 hours. After 1500 hours, the tensile elongation at break was 50% or less, and it was determined that the deterioration occurred.

Example 9
To 100 parts by weight of polystyrene resin composition selected and collected from used home appliances, 0.05 parts by weight of ethylenediaminetetraacetic acid as a metal scavenger was added and mixed at 220 ° C. while heating and melting. It knead | mixed in the machine and produced the 3-5 mm pellet. Next, the multipurpose test piece A was molded by an injection molding machine under the conditions of a resin temperature (molding temperature) of 220 ° C. and a mold temperature of 55 ° C. Table 3 shows the results obtained by performing the thermal oxidative deterioration test at 90 ° C. for 0, 1500 and 3000 hours using the obtained test pieces and measuring the tensile elongation at break (%) by the tensile test. As a result, the recycled polystyrene resin composition of the present invention has a good appearance, the tensile elongation at break after the thermal oxidative degradation test is 100% after 1500 hours, and 52% after 3000 hours, and the tensile elongation at break retention rate. Is 50% or more, compared to before the addition of the metal scavenger (corresponding to Comparative Example 5), the effect of improving the thermal stability is seen, and the thermal stability to the equivalent of new polystyrene resin (corresponding to Reference Example 3) It was found that sex could be improved.

(Example 10)
What is obtained by adding 10 parts by weight of ethylenediaminetetraacetic acid as a metal scavenger to 100 parts by weight of a polystyrene resin composition selected and collected from used home appliances and mixing them at 220 ° C. while heating and melting is used. It knead | mixed in and produced the 3-5 mm pellet. Next, the multipurpose test piece A was molded by an injection molding machine under the conditions of a resin temperature (molding temperature) of 220 ° C. and a mold temperature of 55 ° C. Table 3 shows the results obtained by performing the thermal oxidative deterioration test at 90 ° C. for 0, 1500 and 3000 hours using the obtained test pieces and measuring the tensile elongation at break (%) by the tensile test. As a result, the regenerated polystyrene resin composition of the present invention has a good appearance, and the tensile elongation at break after the thermal oxidative degradation test is 100% after 1500 hours and 100% after 3000 hours, and the tensile elongation at break retention is 100%. Is 50% or more, compared to before the addition of the metal scavenger (corresponding to Comparative Example 5), an effect of improving the thermal stability is observed, and heat is increased to a level equivalent to the new polystyrene resin (corresponding to Reference Example 3). It was found that the stability can be improved.

(Example 11)
100 parts by weight of polystyrene resin composition selected and collected from used home appliances and mixed with 0.05 parts by weight of ethylenediaminetetraacetic acid as a metal scavenger and 5 parts by weight of stearic acid as a stabilizer Was kneaded in an extruder while being heated and melted at 220 ° C. to produce 3 to 5 mm pellets. Next, the multipurpose test piece A was molded by an injection molding machine under the conditions of a resin temperature (molding temperature) of 220 ° C. and a mold temperature of 55 ° C. Table 3 shows the results obtained by performing the thermal oxidative deterioration test at 90 ° C. for 0, 1500 and 3000 hours using the obtained test pieces and measuring the tensile elongation at break (%) by the tensile test. As a result, the regenerated polystyrene resin composition of the present invention has a good appearance, and the tensile elongation at break after the thermal oxidative degradation test is 100% after 1500 hours and 65% after 3000 hours. Is 50% or more, compared to before the addition of the metal scavenger (corresponding to Comparative Example 5), an effect of improving the thermal stability is observed, and heat is increased to a level equivalent to the new polystyrene resin (corresponding to Reference Example 3). It was found that the stability can be improved.

(Example 12)
100 parts by weight of polystyrene resin composition selected and collected from used home appliances and mixed with 0.1 parts by weight of nitrile triacetic acid as a metal scavenger and extruded at 220 ° C. while being heated and melted It knead | mixed in the machine and produced the 3-5 mm pellet. Next, the multipurpose test piece A was molded by an injection molding machine under the conditions of a resin temperature (molding temperature) of 220 ° C. and a mold temperature of 55 ° C. Table 3 shows the results obtained by performing the thermal oxidative deterioration test at 90 ° C. for 0, 1500 and 3000 hours using the obtained test pieces and measuring the tensile elongation at break (%) by the tensile test. As a result, the recycled polystyrene resin composition of the present invention has a good appearance, the tensile elongation at break after the thermal oxidative degradation test is 100% after 1500 hours, and 70% after 3000 hours, and the tensile elongation at break retention rate. Is 50% or more, compared to before the addition of the metal scavenger (corresponding to Comparative Example 5), an effect of improving the thermal stability is observed, and heat is increased to a level equivalent to the new polystyrene resin (corresponding to Reference Example 3). It was found that the stability can be improved.

(Example 13)
100 parts by weight of polystyrene resin composition selected and collected from used home appliances and mixed with 0.5 parts by weight of diethylenetriaminepentaacetic acid as a metal scavenger and 1 part by weight of oleic acid as a stabilizer Was kneaded in an extruder while being heated and melted at 220 ° C. to produce 3 to 5 mm pellets. Next, the multipurpose test piece A was molded by an injection molding machine under the conditions of a resin temperature (molding temperature) of 220 ° C. and a mold temperature of 55 ° C. Table 3 shows the results obtained by performing the thermal oxidative deterioration test at 90 ° C. for 0, 1500 and 3000 hours using the obtained test pieces and measuring the tensile elongation at break (%) by the tensile test. As a result, the recycled polystyrene resin composition of the present invention has a good appearance, and the tensile elongation at break after thermal oxidation degradation test is 100% after 1500 hours and 89% after 3000 hours, and the tensile elongation at break retention is Is 50% or more, compared to before the addition of the metal scavenger (corresponding to Comparative Example 5), an effect of improving the thermal stability is observed, and heat is increased to a level equivalent to the new polystyrene resin (corresponding to Reference Example 3). It was found that the stability can be improved.

(Example 14)
Add 100 parts by weight of hydroxyethylethylenediaminetriacetic acid as a metal scavenger and 10 parts by weight of palmitic acid as a stabilizer to 100 parts by weight of a polystyrene resin composition selected and collected from used home appliances. The obtained product was kneaded in an extruder while being heated and melted at 220 ° C. to produce 3 to 5 mm pellets. Next, the multipurpose test piece A was molded by an injection molding machine under the conditions of a resin temperature (molding temperature) of 220 ° C. and a mold temperature of 55 ° C. Table 3 shows the results obtained by performing the thermal oxidative deterioration test at 90 ° C. for 0, 1500 and 3000 hours using the obtained test pieces and measuring the tensile elongation at break (%) by the tensile test. As a result, the recycled polystyrene resin composition of the present invention has a good appearance, and the tensile elongation at break after the thermal oxidative degradation test is 100% after 1500 hours and 72% after 3000 hours, and the tensile elongation at break retention rate is 72%. Is 50% or more, compared to before the addition of the metal scavenger (corresponding to Comparative Example 5), an effect of improving the thermal stability is observed, and heat is increased to a level equivalent to the new polystyrene resin (corresponding to Reference Example 3). It was found that the stability can be improved.

(Example 15)
Extruder that heats and melts at 220 ° C a mixture of 1.0 part by weight of tocopherol acetate as a metal scavenger added to 100 parts by weight of a polystyrene resin composition selected and collected from used home appliances. The mixture was kneaded in 3 to 5 mm pellets. Next, the multipurpose test piece A was molded by an injection molding machine under the conditions of a resin temperature (molding temperature) of 220 ° C. and a mold temperature of 55 ° C. Table 3 shows the results obtained by performing the thermal oxidative deterioration test at 90 ° C. for 0, 1500 and 3000 hours using the obtained test pieces and measuring the tensile elongation at break (%) by the tensile test. As a result, the regenerated polystyrene resin composition of the present invention has a good appearance, and the tensile elongation at break after thermal oxidation degradation test is 100% after 1500 hours and 74% after 3000 hours, and the tensile elongation at break retention is 74%. Is 50% or more, compared to before the addition of the metal scavenger (corresponding to Comparative Example 5), an effect of improving the thermal stability is observed, and heat is increased to a level equivalent to the new polystyrene resin (corresponding to Reference Example 3). It was found that the stability can be improved.

(Example 16)
Extruded at 240 ° C while heating and melting, mixed with 0.05 parts by weight of ethylenediaminetetraacetic acid as a metal scavenger, to 100 parts by weight of ABS resin composition selected and collected from used home appliances It knead | mixed in the machine and produced the 3-5 mm pellet. Next, the multipurpose test piece A was molded by an injection molding machine under the conditions of a resin temperature (molding temperature) of 240 ° C. and a mold temperature of 60 ° C. Table 3 shows the results obtained by performing the thermal oxidative deterioration test at 90 ° C. for 0, 1500 and 3000 hours using the obtained test pieces and measuring the tensile elongation at break (%) by the tensile test. As a result, the recycled ABS resin composition of the present invention has a good appearance, and the tensile elongation at break after thermal oxidation degradation test is 100% after 1500 hours and 64% after 3000 hours, and the tensile elongation at break retention is Is 50% or more, compared to before the addition of the metal scavenger (corresponding to Comparative Example 7), an effect of improving the thermal stability is seen, and the thermal stability up to the equivalent of the new ABS resin (corresponding to Reference Example 4) It was found that sex could be improved.

(Reference Example 3)
A general purpose polystyrene resin composition (100 parts by weight) was molded using an injection molding machine under the conditions of a resin temperature (molding temperature) of 220 ° C. and a mold temperature of 55 ° C. to form a multipurpose test piece A type. Table 4 shows the results obtained by conducting a thermal oxidative degradation test at 90 ° C. for 0, 1500 and 3000 hours using the obtained test pieces and measuring the tensile elongation at break (%) by a tensile test. As a result, the new polystyrene resin composition has a good appearance, the tensile elongation at break after the thermal oxidative degradation test is 100% after 1500 hours, 61% after 3000 hours, and the tensile elongation at break retention is 50%. % Or more.

(Reference Example 4)
A general purpose ABS resin composition (100 parts by weight) was molded into a multipurpose test piece A using an injection molding machine under conditions of a resin temperature (molding temperature) of 240 ° C. and a mold temperature of 60 ° C. Table 4 shows the results obtained by conducting a thermal oxidative degradation test at 90 ° C. for 0, 1500 and 3000 hours using the obtained test pieces and measuring the tensile elongation at break (%) by a tensile test. As a result, the new ABS resin composition has a good appearance, the tensile elongation at break after thermal oxidation degradation test is 100% after 1500 hours, 60% after 3000 hours, and the tensile elongation at break retention is 50%. % Or more.

(Comparative Example 5)
A multi-purpose test piece A was molded from a polystyrene resin composition selected and collected from used home appliances with an injection molding machine under conditions of a resin temperature (molding temperature) of 220 ° C. and a mold temperature of 55 ° C. Table 4 shows the results obtained by conducting a thermal oxidative degradation test at 90 ° C. for 0, 1500 and 3000 hours using the obtained test pieces and measuring the tensile elongation at break (%) by a tensile test. As a result, the recycled polystyrene resin composition has a brown appearance and cracks, and the tensile elongation at break after thermal oxidation degradation test is 20% after 1500 hours and 0% after 3000 hours. After 1500 hours, the tensile elongation at break was 50% or less, and it was determined that the deterioration occurred.

(Comparative Example 6)
Tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxy), which is a general antioxidant, with respect to 100 parts by weight of the polystyrene resin composition selected and collected from used home appliances. Phenyl) propionate] By an injection molding machine to which 5 parts by weight of methane and tris (2,4-di-t-butylphenyl) phosphite are added, the resin temperature (molding temperature) is 220 ° C. and the mold temperature is 55 ° C. Under the conditions, a multipurpose specimen A type was molded. Table 4 shows the results obtained by conducting a thermal oxidative degradation test at 90 ° C. for 0, 1500 and 3000 hours using the obtained test pieces and measuring the tensile elongation at break (%) by a tensile test. As a result, the recycled polystyrene resin composition has a brown appearance and cracks, and the tensile elongation at break after thermal oxidation degradation test is 25% after 1500 hours and 0% after 3000 hours. After 1500 hours, the tensile elongation at break was 50% or less, and it was determined that the deterioration occurred.

(Comparative Example 7)
A multi-purpose specimen A type was molded from 100 parts by weight of the ABS resin composition selected and collected from used home appliances with an injection molding machine under conditions of a resin temperature (molding temperature) of 240 ° C. and a mold temperature of 60 ° C. Table 4 shows the results obtained by conducting a thermal oxidative degradation test at 90 ° C. for 0, 1500 and 3000 hours using the obtained test pieces and measuring the tensile elongation at break (%) by a tensile test. As a result, the recycled ABS resin composition had a brown appearance and cracks, and the tensile elongation at break after the thermal oxidative degradation test was 60% after 1500 hours and 10% after 3000 hours. After 3000 hours, the tensile elongation at break retention was 50% or less, and it was determined that the deterioration occurred.

(Comparative Example 8)
To 100 parts by weight of polystyrene resin composition selected and collected from used home appliances, 0.03 parts by weight of ethylenediaminetetraacetic acid as a metal scavenger was added and mixed at 220 ° C. while heating and melting. It knead | mixed in the machine and produced the 3-5 mm pellet. Next, the multipurpose test piece A was molded by an injection molding machine under the conditions of a resin temperature (molding temperature) of 220 ° C. and a mold temperature of 55 ° C. Table 4 shows the results obtained by conducting a thermal oxidative degradation test at 90 ° C. for 0, 1500 and 3000 hours using the obtained test pieces and measuring the tensile elongation at break (%) by a tensile test. As a result, the recycled polystyrene resin composition has a brown appearance and cracks, and the tensile elongation at break after thermal oxidation degradation test is 20% after 1500 hours and 0% after 3000 hours. After 1500 hours, the tensile elongation at break was 50% or less, and it was determined that the deterioration occurred.

(Example 17)
200 parts by weight of ethylene resin tetraacetic acid 0.05 parts by weight and tocopherol acetate 0.05 parts by weight were added as a metal scavenger to 100 parts by weight of a polypropylene resin composition selected and collected from used home appliances. The mixture was kneaded in an extruder while being heated and melted at 3 ° C. to produce 3 to 5 mm pellets. Next, a multipurpose test piece A was molded by an injection molding machine under the conditions of a resin temperature (molding temperature) of 200 ° C. and a mold temperature of 50 ° C. Table 5 shows the results obtained by conducting a thermal oxidative degradation test at 140 ° C. for 0, 1500 and 3000 hours using the obtained test pieces and measuring the tensile elongation at break (%) by the tensile test. As a result, the recycled polypropylene resin composition of the present invention has a good appearance, the tensile elongation at break after the thermal oxidative degradation test is 100% after 1500 hours, and 80% after 3000 hours, and the tensile elongation at break retention rate. Is 50% or more, compared to before the addition of the metal scavenger (corresponding to Comparative Example 1), the effect of improving the thermal stability is seen, and heat up to the equivalent of the new polypropylene resin (corresponding to Reference Example 1) It was found that the stability can be improved.

(Example 18)
For 100 parts by weight of the polypropylene resin composition selected and collected from used home appliances, 0.1 parts by weight of nitrilotriacetic acid, 0.1 parts by weight of hydroxyethylethylenediamine triacetic acid and stearin as a metal scavenger. The mixture obtained by adding 5 parts by weight of the acid was kneaded in an extruder while being heated and melted at 200 ° C. to produce 3 to 5 mm pellets. Next, a multipurpose test piece A was molded by an injection molding machine under the conditions of a resin temperature (molding temperature) of 200 ° C. and a mold temperature of 50 ° C. Table 5 shows the results obtained by conducting a thermal oxidative degradation test at 140 ° C. for 0, 1500 and 3000 hours using the obtained test pieces and measuring the tensile elongation at break (%) by the tensile test. As a result, the recycled polypropylene resin composition of the present invention has a good appearance, and the tensile elongation at break after the thermal oxidative degradation test is 100% after 1500 hours and 100% after 3000 hours. Is 50% or more, compared to before the addition of the metal scavenger (corresponding to Comparative Example 1), the effect of improving the thermal stability is seen, and heat up to the equivalent of the new polypropylene resin (corresponding to Reference Example 1) It was found that the stability can be improved.

(Example 19)
As a metal scavenger, 0.05 parts by weight of ethylenediaminetetraacetic acid, 0.05 parts by weight of diethylenetriaminepentaacetic acid and 0.05 parts by weight of tocopherol acetate are used as a metal scavenger for 100 parts by weight of the polypropylene resin composition selected and collected from used home appliances. What was added and mixed was kneaded in an extruder while heating and melting at 200 ° C. to produce 3 to 5 mm pellets. Next, a multipurpose test piece A was molded by an injection molding machine under the conditions of a resin temperature (molding temperature) of 200 ° C. and a mold temperature of 50 ° C. Table 5 shows the results obtained by conducting a thermal oxidative degradation test at 140 ° C. for 0, 1500 and 3000 hours using the obtained test pieces and measuring the tensile elongation at break (%) by the tensile test. As a result, the recycled polypropylene resin composition of the present invention has a good appearance, and the tensile elongation at break after the thermal oxidative degradation test is 100% after 1500 hours and 100% after 3000 hours. Is 50% or more, compared to before the addition of the metal scavenger (corresponding to Comparative Example 1), the effect of improving the thermal stability is seen, and heat up to the equivalent of the new polypropylene resin (corresponding to Reference Example 1) It was found that the stability can be improved.

(Example 20)
To 100 parts by weight of polyethylene resin composition selected and collected from used home appliances, as a metal scavenger, 0.05 parts by weight of ethylenediaminetetraacetic acid and 0.05 parts by weight of diethylenetriaminepentaacetic acid were added and mixed. The mixture was kneaded in an extruder while being heated and melted at 180 ° C. to produce 3 to 5 mm pellets. Next, a multipurpose test piece A was molded by an injection molding machine under conditions of a resin temperature (molding temperature) of 180 ° C. and a mold temperature of 50 ° C. Table 5 shows the results obtained by conducting a thermal oxidative degradation test at 140 ° C. for 0, 1500 and 3000 hours using the obtained test pieces and measuring the tensile elongation at break (%) by the tensile test. As a result, the regenerated polyethylene resin composition of the present invention has a good appearance, and the tensile elongation at break after the thermal oxidative degradation test is 100% after 1500 hours and 92% after 3000 hours. Is 50% or more, compared to before the addition of the metal scavenger (corresponding to Comparative Example 3), the effect of improving the thermal stability is seen, and heat up to the equivalent of the new polyethylene resin (corresponding to Reference Example 2) It was found that the stability can be improved.

(Example 21)
As a metal scavenger, 0.05 parts by weight of nitrilotriacetic acid, 0.05 parts by weight of tocopherol acetate, and 5 parts by weight of oleic acid as a stabilizer for 100 parts by weight of a polyethylene resin composition selected and collected from used home appliances. The parts added and mixed were kneaded in an extruder while being heated and melted at 180 ° C. to produce 3 to 5 mm pellets. Next, a multipurpose test piece A was molded by an injection molding machine under conditions of a resin temperature (molding temperature) of 180 ° C. and a mold temperature of 50 ° C. Table 5 shows the results obtained by conducting a thermal oxidative degradation test at 140 ° C. for 0, 1500 and 3000 hours using the obtained test pieces and measuring the tensile elongation at break (%) by the tensile test. As a result, the recycled polyethylene resin composition of the present invention has a good appearance, and the tensile elongation at break after thermal oxidation degradation test is 100% after 1500 hours and 100% after 3000 hours, and the tensile elongation at break retention is 100%. Is 50% or more, compared to before the addition of the metal scavenger (corresponding to Comparative Example 3), the effect of improving the thermal stability is seen, and heat up to the equivalent of the new polyethylene resin (corresponding to Reference Example 2) It was found that the stability can be improved.

(Example 22)
As a metal scavenger, 0.05 parts by weight of ethylenediaminetetraacetic acid and 0.05 parts by weight of tocopherol acetate were added to and mixed with 100 parts by weight of a polystyrene resin composition selected and collected from used home appliances. The mixture was kneaded in an extruder while being heated and melted at 3 ° C. to produce 3 to 5 mm pellets. Next, the multipurpose test piece A was molded by an injection molding machine under the conditions of a resin temperature (molding temperature) of 220 ° C. and a mold temperature of 55 ° C. Table 5 shows the results obtained by conducting the thermal oxidative degradation test at 90 ° C. for 0, 1500 and 3000 hours using the obtained test pieces and measuring the tensile elongation at break (%) by the tensile test. As a result, the recycled polystyrene resin composition of the present invention has a good appearance, and the tensile elongation at break after the thermal oxidative degradation test is 100% after 1500 hours and 72% after 3000 hours, and the tensile elongation at break retention rate is 72%. Is 50% or more, compared to before the addition of the metal scavenger (corresponding to Comparative Example 5), an effect of improving the thermal stability is observed, and heat is increased to a level equivalent to the new polystyrene resin (corresponding to Reference Example 3). It was found that the stability can be improved.

(Example 23)
As a metal scavenger, 0.05 parts by weight of ethylenediaminetetraacetic acid, 0.05 parts by weight of nitrilotriacetic acid and 0.05 parts of hydroxyethylethylenediaminetriacetic acid are used as metal scavengers with respect to 100 parts by weight of the polystyrene resin composition selected and collected from used home appliances. The mixture obtained by adding parts by weight was kneaded in an extruder while being heated and melted at 220 ° C. to produce 3 to 5 mm pellets. Next, the multipurpose test piece A was molded by an injection molding machine under the conditions of a resin temperature (molding temperature) of 220 ° C. and a mold temperature of 55 ° C. Table 5 shows the results obtained by conducting the thermal oxidative degradation test at 90 ° C. for 0, 1500 and 3000 hours using the obtained test pieces and measuring the tensile elongation at break (%) by the tensile test. As a result, the regenerated polystyrene resin composition of the present invention has a good appearance, and the tensile elongation at break after thermal oxidation degradation test is 100% after 1500 hours and 74% after 3000 hours, and the tensile elongation at break retention is 74%. Is 50% or more, compared to before the addition of the metal scavenger (corresponding to Comparative Example 5), an effect of improving the thermal stability is observed, and heat is increased to a level equivalent to the new polystyrene resin (corresponding to Reference Example 3). It was found that the stability can be improved.

(Example 24)
5 parts by weight of ethylenediaminetetraacetic acid, 5 parts by weight of tocopherol acetate and 5 parts by weight of stearic acid as a metal scavenger are added to 100 parts by weight of a polystyrene resin composition selected and collected from used home appliances. The mixture was kneaded in an extruder while being heated and melted at 220 ° C. to produce 3 to 5 mm pellets. Next, the multipurpose test piece A was molded by an injection molding machine under the conditions of a resin temperature (molding temperature) of 220 ° C. and a mold temperature of 55 ° C. Table 5 shows the results obtained by conducting the thermal oxidative degradation test at 90 ° C. for 0, 1500 and 3000 hours using the obtained test pieces and measuring the tensile elongation at break (%) by the tensile test. As a result, the regenerated polystyrene resin composition of the present invention has a good appearance, and the tensile elongation at break after the thermal oxidative degradation test is 100% after 1500 hours and 100% after 3000 hours, and the tensile elongation at break retention is 100%. Is 50% or more, compared to before the addition of the metal scavenger (corresponding to Comparative Example 5), an effect of improving the thermal stability is observed, and heat is increased to a level equivalent to the new polystyrene resin (corresponding to Reference Example 3). It was found that the stability can be improved.

(Example 25)
What added and mixed 0.05 parts by weight of ethylenediaminetetraacetic acid and 0.05 parts by weight of hydroxyethylethylenediaminetriacetic acid as metal scavengers to 100 parts by weight of ABS resin composition selected and collected from used home appliances Was kneaded in an extruder while being heated and melted at 240 ° C. to produce 3 to 5 mm pellets. Next, the multipurpose test piece A was molded by an injection molding machine under the conditions of a resin temperature (molding temperature) of 240 ° C. and a mold temperature of 60 ° C. Table 5 shows the results obtained by conducting the thermal oxidative degradation test at 90 ° C. for 0, 1500 and 3000 hours using the obtained test pieces and measuring the tensile elongation at break (%) by the tensile test. As a result, the recycled ABS resin composition of the present invention has a good appearance, and the tensile elongation at break after thermal oxidation degradation test is 100% after 1500 hours and 73% after 3000 hours, and the tensile elongation at break retention is 73%. Is 50% or more, compared to before the addition of the metal scavenger (corresponding to Comparative Example 7), an effect of improving the thermal stability is seen, and heat up to the equivalent of the new ABS resin (corresponding to Reference Example 4). It was found that the stability can be improved.

(Example 26)
5 parts by weight of nitrilotriacetic acid, 5 parts by weight of hydroxyethylethylenediamine triacetic acid and 5 parts by weight of oleic acid as a metal scavenger for 100 parts by weight of ABS resin composition selected and collected from used home appliances The mixture was added and mixed at 240 ° C. while being heated and melted, and kneaded in an extruder to produce 3 to 5 mm pellets. Next, the multipurpose test piece A was molded by an injection molding machine under the conditions of a resin temperature (molding temperature) of 240 ° C. and a mold temperature of 60 ° C. Table 5 shows the results obtained by conducting the thermal oxidative degradation test at 90 ° C. for 0, 1500 and 3000 hours using the obtained test pieces and measuring the tensile elongation at break (%) by the tensile test. As a result, the recycled ABS resin composition of the present invention has a good appearance, and the tensile elongation at break after the thermal oxidative degradation test is 100% after 1500 hours and 100% after 3000 hours. Is 50% or more, compared to before the addition of the metal scavenger (corresponding to Comparative Example 7), an effect of improving the thermal stability is seen, and heat up to the equivalent of the new ABS resin (corresponding to Reference Example 4). It was found that the stability can be improved.

  Although the embodiments and examples of the present invention have been described as described above, it is also planned from the beginning to appropriately combine the configurations of the above-described embodiments and examples.

  It should be understood that the embodiments and examples disclosed herein are illustrative and non-restrictive in every respect. The scope of the present invention is defined by the terms of the claims, rather than the description above, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.

  The resin is not limited to regeneration of the polyolefin-based resin composition and the polystyrene-based resin composition, and the resin can be regenerated by adding a metal scavenger to a resin containing titanium oxide surface-treated with titanium oxide or aluminum oxide.

Claims (6)

  A recycled polyolefin resin composition comprising 0.05 to 10 parts by weight of a metal scavenger with respect to 100 parts by weight of a recovered polyolefin resin composition.   The regenerated polyolefin resin composition according to claim 1, wherein the metal scavenger is at least one of ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylethylenediaminetriacetic acid, and tocopherol acetate.   The regenerated polyolefin resin composition according to claim 1 or 2, wherein the regenerated polyolefin resin composition contains a fatty acid having 8 to 24 carbon atoms.   A recycled polystyrene resin composition comprising 0.05 to 10 parts by weight of a metal scavenger with respect to 100 parts by weight of a recovered polystyrene resin composition.   The regenerated polystyrene resin composition according to claim 4, wherein the metal scavenger is at least one of ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylethylenediaminetriacetic acid, and tocopherol acetate.   The regenerated polystyrene resin composition according to claim 4 or 5, wherein the regenerated polystyrene resin composition contains a fatty acid having 8 to 24 carbon atoms.

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