JP2013245301A - Thermoplastic resin molded product, method for producing the same, and method for recycling thermoplastic resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an olefinic thermoplastic resin composition molded product having a high degree of characteristics and high quality and using olefinic thermoplastic resin compositions with mutually different melt flow rates (MFR) as materials, a method for producing the thermoplastic resin composition molded product, and a method for recycling the thermoplastic resin composition molded product.SOLUTION: An olefinic thermoplastic resin molded product includes: an olefinic thermoplastic resin mixture formed by compounding an olefinic resin composition (A) and an olefinic resin composition (B) having melt flow rates different from each other with a compounding ratio (A)/(B) of 1/3 to 3/1; and an impact modification material (C) of 1 to 10 pts.wt. based on 100 pts.wt. of the olefinic thermoplastic resin mixture.

Description

  The present invention relates to a thermoplastic resin molded body and a method for producing the same. Furthermore, this invention relates to the recycling method of the thermoplastic resin molded object collect | recovered from the waste.

  In recent years, the constituent materials in various product members such as home appliances have changed, the number of metal members including iron has decreased, and the proportion of plastic members made of thermoplastic resin has been increasing. Many thermoplastic resins are synthesized using crude fossil and other embedded fossil fuels as the basic raw material, and can provide properties suitable for each component by preparing components and using additives, compared to metals. This is due to the high degree of freedom in design. For this reason, the amount of plastic components discarded has been increasing year by year, but because fossil fuels are used as raw materials, environmental destruction such as global warming and acid rain due to the release of carbon dioxide and sulfur oxides from combustion, and chlorine There are serious and urgent problems such as environmental pollution such as dioxin generation and scattering caused by incineration of plastics containing compounds, and a shortage of landfill disposal sites due to the increase in bulky plastic waste.

  In view of this, research and development have been conducted on a recycling method for material recycling in which a virgin material is added to a waste material of a thermoplastic resin molded body separated and recovered for each system of the thermoplastic resin composition, and is heated and melted to be molded. A so-called thermoplastic resin waste material is used as a raw material for a plastic member having low required characteristics.

  For example, in Patent Document 1, a thermoplastic resin molding is manufactured by mixing and melting a waste material of a thermoplastic resin and a virgin material. A method for producing a high-quality thermoplastic resin molded article by suppressing the amount of virgin material used for a thermoplastic resin biomaterial has been disclosed.

JP 2000-159900 A

  However, since the virgin material of 70% or more must be used in the recycling method of Patent Document 1, not only is the effect of recycling the waste material extremely low, but also a thermoplastic resin molded body made only from the virgin material. Since the characteristics are lower than the above, it can only be used for low-grade applications.

  In addition, even for thermoplastic resin compositions of the same system, it is possible to ensure the properties of thermoplastic resin molded articles produced using a plurality of types of thermoplastic resin compositions having different properties such as physical properties and fluidity. Although it is difficult, it does not disclose a method for combining and recycling thermoplastic resin compositions having different characteristics. For this reason, the material composition is complicated, such as home appliances, and it is difficult to use it for waste materials that are difficult to recycle by unifying characteristics, particularly melt flow rate (hereinafter referred to as “MFR”). It is.

  For example, the characteristics of a plastic member recovered from a washing tub requiring relatively high strength are as low as about 14 g / min for MFR. On the other hand, there is a case where a plastic member recovered from a refrigerator that does not require relatively high strength has a high MFR of about 42 g / min. For this reason, when the collected plastic member is simply mixed and recycled, a plastic member having desired strength and characteristics cannot be obtained.

  The present invention has been made in view of the above-mentioned problems. A thermoplastic resin composition molded article having high properties and quality using a thermoplastic resin composition having a different MFR as a material, and a method for producing a thermoplastic resin composition molded article And a method for recycling a molded thermoplastic resin composition.

  In the present specification, the “thermoplastic resin molded product” is obtained by melting and molding a thermoplastic resin composition. The “thermoplastic resin composition” refers to a pulverized material that is a material of a molded body, and the pulverized material includes a virgin material or a pulverized material of waste material.

  The “thermoplastic resin” is used as an expression including a thermoplastic resin composition and a thermoplastic resin molded article. Furthermore, the waste material of the thermoplastic resin molded body is described as “thermoplastic resin waste material”. The “virgin material” means an unused resin composition.

  One embodiment of the olefinic thermoplastic resin molded article of the present invention is an olefinic thermoplastic resin molded article composed of thermoplastic resin compositions having different melt flow rates. The mixing ratio (A) / (B) of the resin composition (B) is 1/3 or more and 3/1 or less, and the olefinic thermoplastic resin mixture is 100 weights. An olefinic thermoplastic resin molded article comprising 1 part by weight or more and 10 parts by weight or less of an impact modifier (C), the melt of the olefinic resin composition (A) and the olefinic resin composition (B) The difference in flow rate is that there is a difference of 25 g / 10 min or more.

  The melt flow rate of the olefinic thermoplastic resin composition (A) is 10 g / 10 min or more and 20 g / 10 min or less, and the melt flow rate of the olefinic resin composition (B) is 35/10 min or more and 50 g / 10 min. It is good also as follows.

  The impact modifier (C) may be an elastomer containing ethylene and a copolymer of olefins having 3 or more carbon atoms.

  A dialkyl peroxide organic peroxide (D) may be further blended.

  The compounding ratio (C / A) of component A and component C may be 0.036 or more and 0.145 or less.

An olefin-based thermoplastic resin molded article characterized in that a relationship between d which is a blending part of component D and a which is a blending part of component A satisfies formula (1) below.
(0.0005a−0.02) ≦ d ≦ (0.0005a + 0.014) (1)
The olefin-based thermoplastic resin composition (A) or the olefin-based thermoplastic resin composition (B) may be produced by pulverizing a thermoplastic resin molded body recovered as waste.

  ADVANTAGE OF THE INVENTION According to this invention, the thermoplastic resin composition molded object which has the high characteristic and quality by using the thermoplastic resin composition from which MFR differs, the manufacturing method of a thermoplastic resin composition molded object, and a thermoplastic resin composition molded object It is to provide a recycling method.

It is a flowchart which shows the manufacturing method of the thermoplastic resin molding of this invention. It is a flowchart which shows the 1st recycling method of the thermoplastic resin molding of this invention. It is a flowchart which shows the 2nd recycling method of the thermoplastic resin molding of this invention. It is a figure of the measurement result of the physical property which measured the thermoplastic resin molding of this invention. It is a figure of the measurement result of the physical property which measured the thermoplastic resin molding of this invention. It is a figure of the measurement result of the physical property which measured the thermoplastic resin molding of this invention. It is a figure of the measurement result of the physical property which measured the thermoplastic resin molding of this invention. Component C and component A mixing ratio (C / A) and surface added to 100 weights of olefin resin mixture in which component A and component B mixing ratio (A) / (B) is 1/3 It is the figure which showed the relationship between impact height and a bending elastic modulus. Component C and Component A Mixing Ratio (C / A) and Plane with respect to 100 Weight of Olefin Resin Mixture Mixed at a Ratio of Component A and Component B (A) / (B) 1/1 It is the figure which showed the relationship between impact height and a bending elastic modulus. Component C and component A mixing ratio (C / A) and surface added to 100 weights of the olefin resin mixture in which the mixing ratio (A) / (B) of component A and component B is 3/1 It is the figure which showed the relationship between impact height and a bending elastic modulus. It is a figure of the measurement result of the physical property which measured the thermoplastic resin molding of this invention. It is the figure which showed the relationship between the addition amount of the component D of the olefin resin composition of this invention, and MFR. It is the figure which showed the relationship between the compounding ratio of the component A of the olefin resin composition of this invention, and the addition amount of the component D. FIG.

  Hereinafter, the present invention will be described in more detail with reference to embodiments.

≪Thermoplastic resin molding≫
The thermoplastic resin molded article of the present invention comprises an olefinic thermoplastic resin composition (A), an olefinic thermoplastic resin composition (B) having different MFRs, and an elastomer (C) as an impact modifier. It is a waste.

Here, the olefinic thermoplastic resin composition (A), and an olefin-based thermoplastic resin composition and (B), chain unsaturated hydrocarbons having a double bond represented by a general formula C _n H _2n Indicates hydrogen. Typical examples include polyethylene (PE) using ethylene (C ₂ H ₂ ) as a monomer and polypropylene (PP) using propylene (C ₃ H ₆ ) as a monomer. Polyethylene includes linear low density polyethylene (LLDPE), low density polyethylene (LDPE), high density polyethylene (HDPE), and ethylene vinyl acetate copolymer (EVA), which is a copolymer with vinyl acetate. It is.

In addition to an atactic polymer that does not crystallize, there are polypropylenes having different arrangements of methyl groups (CH ₃ ) such as isotactic and syndiotactic due to differences in stereoregularity. Most of the industrial polypropylenes are mainly composed of isotactic polymers. Polypropylene is classified into a homopolymer, a random copolymer, and a block copolymer in the form of comonomer copolymerization. Generally, propylene-ethylene random copolymer excellent in low-temperature impact property is used for polypropylene used for injection molding of home appliances. In the present invention, the propylene-ethylene random copolymer is mentioned and described, but a homopolymer or a random copolymer may be used depending on the application.

  On the other hand, MFR depends on the molecular weight of the polymer, and the higher the MFR, the smaller the molecular weight. Polypropylene with a high MFR is suitable for injection molding because it can be easily filled into a mold, and a polypropylene with a low MFR is suitable for extrusion molding because the molten resin does not easily sag during molding. In general, a material having a high MFR deteriorates physical properties such as impact characteristics.

  In general, an injection molded product having an MFR of 10 g / min or more and 50 g / min or less is frequently used. In the present invention, depending on the range of MFR, the olefin-based thermosetting resin composition (A) and the olefin-based thermosetting are used. The resin composition (B) is properly used. The resin having a relatively low MFR value will be described as an olefinic thermosetting resin composition (A), and the resin having a relatively high MFR value will be described as an olefinic thermosetting resin composition (B).

  Further, the olefin resin composition (A) and the olefin resin composition (B) do not need to be formed of one kind of thermoplastic resin composition, and are each constituted by a plurality of kinds of thermoplastic resins. It doesn't matter. For example, a thermoplastic resin composition having a certain range of MFR values may be adjusted by mixing thermoplastic resin compositions having different MFRs.

  In addition to the elastomer (C) and dialkyl peroxide organic peroxide (D) containing the copolymer of ethylene and an olefin having 3 or more carbon atoms, the additive is a heat stabilizer, light stabilizer, antistatic agent. Additives such as agents, lubricants, fillers, copper damage inhibitors, antibacterial agents, and colorants may be added as necessary.

  Further, the present invention provides an olefin resin composition in which the difference in MFR value between the olefin resin composition (A) and the olefin resin composition (B) is 25 g / 10 min or more from the viewpoint of efficient recycling. The present invention relates to an olefin-based resin molded body molded from a product.

  In one embodiment, the MFR of the olefin resin composition (A) is preferably 10 g / 10 min or more and 20 g / 10 min or less, and the MFR of the olefin resin composition (B) is 35 g / 10 min. It is good that it is above 50g / 10min.

  The elastomer is added as an impact modifier and contains a copolymer of ethylene and an olefin having 3 or more carbon atoms. For example, an elastomer (C) containing a copolymer of ethylene and an olefin having 3 or more carbon atoms is an α-olefin copolymer having 3 or more ethylene-carbon atoms such as an ethylene-propylene copolymer elastomer or an ethylene-butene copolymer elastomer. An elastomer may be used. Further, an elastomer hydrogenated to a styrene-diene copolymer such as an elastomer hydrogenated to a styrene-butadiene copolymer or a styrene-isoprene copolymer may be used.

  Here, the elastomer (C) is a mixture in which the blending ratio (A) / (B) of the olefin resin composition (A) and the olefin resin composition (B) is 1/3 or more and 3/1 or less. It is preferable that 1 part by weight or more and 10 parts by weight or less are included with respect to 100 parts by weight of a certain olefin-based thermoplastic resin mixture. Further, when the amount of component C added is 1 part by weight or less, the surface impact height is inferior, and when it exceeds 10 parts by weight, the flexural modulus decreases and the predetermined physical properties cannot be obtained.

  Moreover, in order to improve the melt viscosity (fluidity) of the thermoplastic resin molded article of the present invention, a dialkyl peroxide organic peroxide (D) may be further blended. The dialkyl peroxide organic peroxide (D) generates radicals by an addition reaction to an unsaturated double bond, a hydrogen abstraction reaction from an alkyl group, etc., and as a result, the molecular weight of the polymer (polymer) decreases, It is possible to improve fluidity.

  The dialkyl peroxide organic peroxide (D) blended here is dicumyl peroxide, 2.5-dimethyl-2.5-di (t-butyl peroxy), 1.3-bis (t-butyl peroxy isopropyl). ), T-butyl cumyl peroxide, di-t-butyl peroxide, 2.5-dimethyl-2,5-di (t-butyl peroxy), and the like are preferably used.

≪Shape of thermoplastic resin molding≫
The shape of the thermoplastic resin molded body of the present invention is not particularly limited as long as it is manufactured from the thermoplastic resin composition constituting the thermoplastic resin molded body. That is, the shape of the thermoplastic resin molded body of the present invention includes a shape formed to be a shape used as a member of various products, and a pellet shape that is a shape of a precursor used in the step of forming the member. It includes shapes such as sheet, film, and pipe.

≪Method for producing thermoplastic resin molded article≫
FIG. 1 is a flowchart showing an embodiment of a method for producing a thermoplastic resin molded body according to the present invention. Details of each process will be described with reference to FIG.

  One embodiment of the method for producing a thermoplastic resin molded body of the present invention is a method of mixing a plurality of types of thermoplastic resin compositions, which are materials for a thermoplastic resin molded body, and an additive by melting and mixing them. Completion based on the process (Step 101), the precursor material creation process (Step 102) for creating a precursor material for forming a finished member from the molten mixture obtained in the mixing process, and the precursor as the material And a completed member forming step (step 103) for forming the member.

  In the mixing step, the thermoplastic composition (A) and the thermoplastic composition (B) having a predetermined size and a predetermined additive are blended, and then melted by heating and uniformly mixed (step 101).

  Here, as the predetermined additive, an elastomer (C) as an impact modifier and a dialkyl peroxide organic peroxide (D) as a fluidity modifier are mixed. Further, the mixing method is not particularly limited, but when the thermoplastic resin composition is melt-mixed, it is preferable that the thermoplastic resin components are uniformly mixed using a tumbler mixer or the like. In addition, the thermoplastic resin molded article of the present invention appropriately contains additives such as a heat stabilizer, a light stabilizer, an antistatic agent, a lubricant, a filler, a heavy metal deactivator, an antibacterial agent, and a colorant. It may be added during the mixing step.

  In the next precursor material preparation step, a thermoplastic resin molded body having a certain shape as a precursor material for forming a molten mixture containing the thermoplastic resin composition uniformly melt-mixed in the mixing step into a finished member Is created (step 102).

  Here, the certain shape of the precursor material may be, for example, a pellet shape. Examples of the method for forming into a fixed shape include an extrusion molding method, an injection molding method, a compression molding method, a vacuum molding method, a transfer molding method, a powder molding method, and a blow molding method.

  Of these molding methods, the extrusion molding method and the injection molding method are preferably employed. When the extrusion molding method is employed, the extrusion molding apparatus is not particularly limited, and examples thereof include a single-screw extruder, a biaxial extruder, and a multi-screw extruder. When the injection molding method is adopted, the injection molding machine is not particularly limited, and examples thereof include a screw inline type injection molding machine and a plunger type injection molding machine.

  In the next finished member molding process, the precursor material created in the precursor material creating process is put into an injection molding machine, and after melting and heating, a thermoplastic resin molded body as a finished member is injection molded (step 103). .

  Although it does not specifically limit as an injection molding machine used here, For example, a screw in-line type injection molding machine, a plunger type injection molding machine, etc. are mentioned. In the flowchart according to the present invention, the precursor material is created as the material of the completed member. However, the completed member forming process may be performed after the mixing process to simplify the process.

  The simplified flowchart includes a mixing step similar to the step in FIG. 1 and a finished member forming step, and in the mixing step, a plurality of types of thermoplastic resin compositions that are materials for the thermoplastic resin molded body, and addition After the product is melted and mixed to create a molten mixture, the molten mixture containing the thermoplastic resin composition is crushed and put into an extrusion molding machine or injection molding machine in the finished member process, and the thermoplastic resin A molded body will be manufactured.

≪Recycling method of thermoplastic resin moldings≫
In the method for producing a thermoplastic resin molded article of the present invention, the thermoplastic resin composition can use as a material a thermoplastic resin molded article recovered from waste.

  Here, the waste is not particularly limited as long as a member containing a thermoplastic resin is used. For example, household appliances, OA equipment, electrical and electronic parts, and the like can be cited as suitable examples of waste, and extremely effective recycling of thermoplastic resin molded articles can be realized.

  That is, if the thermoplastic resin composition (A) contained in the thermoplastic resin molded article of the present invention or the thermoplastic resin composition recovered from waste is used for the thermoplastic resin composition (B), the environment In consideration, extremely efficient material recycling can be established.

  The first recycling method of the thermoplastic resin composition waste material according to the present invention is a method of classifying waste thermoplastic resin composition molded bodies composed of thermoplastic resin compositions of the same system according to characteristics into waste. The crushing process (step 202) which crushed each thermoplastic resin molded object obtained by the process (step 201) and the classification process to create a crushed material made of the thermoplastic resin composition, and the created thermoplastic resin composition A washing step (step 203) for washing each crushed material comprising a product, and a dehydrating and drying step for producing a thermoplastic resin composition as a material for the thermoplastic resin molded article by dehydrating and drying the washed thermoplastic resin composition (Step 204), a mixing step (Step 205) in which various additives are added to a plurality of types of thermoplastic resin compositions obtained in the dehydration drying step, and melt-mixed to create a molten mixture; Precursor material preparation step (step 206) for forming a precursor material for forming a finished member from the molten mixture obtained in the process, and finished member molding for forming a finished member based on the precursor material to be a material Process (step 207).

  Here, an embodiment of a method for recycling a thermoplastic resin molded body according to the present invention will be described with reference to FIG. FIG. 2 is a flowchart showing a first recycling method for creating a thermoplastic resin molded body from a washing machine and a refrigerator recovered as a waste of the thermoplastic resin molded body. Each step will be described in detail with reference to FIG.

  In addition, you may add the recycling method of the thermoplastic resin molding of this invention as needed about the process which is not shown by FIG. Moreover, since the mixing step of the recycling method, the precursor material creation step, and the finished member molding step are the same as the method of manufacturing the thermoplastic resin molded body, detailed description thereof is omitted.

  In the recycling method shown in FIG. 2, firstly, in the classification process, the waste including the thermoplastic resin molded body collected after use at home or the like is dismantled, and each member composed of the thermoplastic resin composition of the same system Are classified according to the characteristics (step 201).

  In FIG. 2, a dehydration tank of a washing machine as a waste for preparing a thermoplastic resin composition (A) as a material from a plurality of types of waste, and a thermoplastic resin composition (B) as a material. Refrigerator vegetable cases are selectively categorized as waste for creating.

  Here, in the present invention, for example, an olefinic thermoplastic resin composition is selectively classified as a thermoplastic resin composition of the same system, but it is preferable to selectively classify systems of the same composition. . Moreover, the system | strain of the same composition means that divisions, such as a polypropylene-type resin, a polyethylene-type resin, a thermoplastic polyester resin, are the same, for example. For example, for vegetable cases in refrigerators, not only polypropylene resins but also polystyrene resins may be used. By selectively classifying polypropylene resins, the thermoplastic resin composition is classified from waste. , Mixing of thermoplastic resin compositions having different compositions is reduced. For this reason, the characteristics of the thermoplastic resin composition molded body obtained by heating and melting are stable, and the characteristics of the material or material made of the recycled polypropylene-based thermoplastic resin composition or its material can be greatly improved. Can be expanded.

  Moreover, the same part means the member which uses the same thing, for example, means a washing machine water tank, a washing machine dewatering tank, a washing machine housing | casing, a refrigerator vegetable case, etc. The characteristic of the waste thermoplastic resin composition molded article to be classified refers to, for example, MFR.

  In one embodiment of FIG. 2, the thermoplastic resin moldings are classified into the same parts, but the properties of the thermoplastic resin composition obtained by classification, in particular, MFR is classified within a certain range. If possible, it may be recovered from different parts.

  For example, in the embodiment of FIG. 2, the dehydrating tub of the washing machine or the refrigerator in which the MFR value has a certain width so that the characteristics of the thermoplastic resin composition to be recovered, in particular, the MFR is in the same range. It is classified by the same parts such as vegetable cases. In addition, a plurality of types of thermoplastic resin members having a constant width of MFR and a plurality of types of thermoplastic resin members having a constant width of MFR may be classified and recovered, and the same member It is not limited to. In addition, regarding the method for disassembling waste, it may be disassembled using a general dismantling apparatus, and dismantling by hand may be performed.

  Next, in the pulverization step, a thermoplastic resin molded body composed of the selectively classified thermoplastic resin compositions is crushed to create a crushed material composed of the thermoplastic resin composition. (Step 202). In FIG. 2, the dewatering tank of the washing machine classified by the classification process is pulverized to produce a crushed product of the thermoplastic resin composition (A). Similarly, the vegetable case of the refrigerator classified by the classification | category process is grind | pulverized, and the crushed material of the thermoplastic resin composition (B) is obtained. Here, as a crushing method, a conventionally known method can be used. For example, a hammer crusher, a uniaxial crusher, a biaxial crusher, or a cutting machine can be used, but is not limited thereto. .

  In addition, in the recycling method of this invention, the workability | operativity of a subsequent process improves by including a crushing process. For example, in the precursor material preparation process described later, when using an extruder or the like, the biting of the crushed resin by the screw is stabilized, and the workability is improved. Further, the size of the pulverized product is not particularly limited, but the pulverization was performed so as to be in the range of 10 mm to 80 mm.

  Next, in the washing process, the crushed material which is the thermoplastic resin composition of the same system obtained by the crushing process is mixed and washed (step 203). In FIG. 2, the thermoplastic resin composition (A) obtained in the crushing step is uniformly mixed and washed. Similarly, the thermoplastic resin composition (B) obtained in the crushing step is uniformly mixed and washed. Here, foreign substances adhering to the thermoplastic resin composition can be removed, and there is an advantage that the physical properties of the molded thermoplastic resin composition are improved. As a cleaning method, a conventionally known general method can be used.

  Next, in the dehydration washing process, the thermoplastic resin composition obtained in the washing process is dehydrated and dried (step 204). In FIG. 2, the thermoplastic resin composition (A) washed in the washing step is dehydrated and dried. Similarly, the thermoplastic resin composition (B) obtained in the washing step is dehydrated and dried. By including this step, the water content of the thermoplastic resin composition is reduced, and there is an advantage that workability is improved when the thermoplastic resin composition in the subsequent procedure is uniformly mixed. As a cleaning method, a conventionally known general method can be used.

  The thermoplastic composition (A) and the thermoplastic composition (B), which are materials for the thermoplastic resin molded body, are prepared through the above-described washing step and dehydration drying step. Note that the cleaning step (step 202) and the dehydration step (step 203) can be omitted as appropriate, for example, when a thermoplastic resin molded body is used for an application that is less affected by foreign matter contamination.

  Next, in the mixing step, the thermoplastic composition (A) formed in a predetermined size, the thermoplastic composition (B), and a predetermined additive are blended and then heated and melted, uniformly mixed, and melted. A mixture is created (step 205). Here, as the predetermined additive, an elastomer (C) as an impact modifier and a dialkyl peroxide organic peroxide (D) as a fluidity modifier are mixed.

  In the next precursor material preparation step, a thermoplastic resin molded body having a certain shape as a precursor material for forming a molten mixture containing the thermoplastic resin composition uniformly melt-mixed in the mixing step into a finished member Is created (step 206).

  In the next finished member molding process, the precursor material created in the precursor material creating process is put into an injection molding machine, and after melting and heating, a thermoplastic resin molded body as a finished member is injection molded (step 207). . FIG. 2 is a diagram showing the steps of the first recycling method for the thermoplastic resin molded article of the present invention. However, the method for recycling the thermoplastic resin molded article of the present invention is limited to the steps of FIG. Instead, the second recycling method of FIG. 3 may be performed.

  FIG. 3 shows a flowchart of the second recycling method of the thermoplastic resin molding of the present invention. The second recycling method of the thermoplastic resin composition waste material of the present invention is a method of selectively classifying waste thermoplastic resin composition molded bodies composed of the same series of thermoplastic resin compositions as waste. Classification and blending step (step 301) for blending so as to have a blending ratio of the thermoplastic resin molded product of (2), and a crushing step for crushing the thermoplastic resin molded body blended by the classification and blending step to create a crushed material ( Step 302), a washing step for washing the crushed material composed of the crushed thermoplastic resin composition (Step 303), and dehydration and drying of the washed thermoplastic resin composition to obtain heat that becomes a material of the thermoplastic resin molded body A dehydrating and drying step (step 304) for producing a plastic resin composition, and a mixing step (spinning step) for adding a variety of additives to the thermoplastic resin composition obtained in the dehydrating and drying step and melt-mixing them. 305), a precursor material preparation step (step 306) for forming a precursor material for forming a finished member from the molten mixture obtained in the mixing step, and completion based on the precursor material as a material A completed member forming step (step 307) for forming the member.

  In the classification and blending process, waste containing thermoplastic resin moldings collected after use at home etc. is dismantled and selectively classified according to the characteristics for each component made of the same series of thermoplastic resin composition To do. Then, the classified waste thermoplastic resin moldings are blended so as to obtain a desired blending ratio of the thermoplastic resin moldings (step 301).

  Here, the thermoplastic resin composition of the same system indicates that the olefinic thermoplastic resin composition is selectively classified, but it is preferable to selectively classify the system of the same composition. Moreover, the system | strain of the same composition means that divisions, such as a polypropylene-type resin, a polyethylene-type resin, a thermoplastic polyester resin, are the same, for example. Moreover, the same part means the member which uses the same thing, for example, means a washing machine water tank, a washing machine dewatering tank, a washing machine housing | casing, a refrigerator vegetable case, etc. The characteristic of the waste thermoplastic resin composition molded article to be classified refers to MFR.

  In one embodiment of FIG. 3, the thermoplastic resin moldings are classified into the same parts, but are classified so that the properties of the thermoplastic resin composition obtained by classification, in particular, MFR is in a certain range. If possible, it may be recovered from different parts. In FIG. 3, after classifying the washing machine dewatering tank as the waste thermoplastic resin molding (A) and the vegetable case of the refrigerator as the waste thermoplastic resin molding (B) from the waste, the desired thermoplastic resin molding The waste thermoplastic resin molded product (A) and the waste thermoplastic resin molded product (B), which are classified so as to have a blending ratio, are blended after adjusting the blending ratio.

  Next, in the crushing step, the blended waste thermoplastic resin molded body (A) and the waste thermoplastic resin molded body (B) are crushed to create a crushed product made of the thermoplastic resin composition (step 302).

  Next, in the washing process, the crushed material that is the thermoplastic resin composition obtained in the crushing process is mixed and washed (step 303).

  Next, in the dehydration washing process, the thermoplastic resin composition obtained in the washing process is dehydrated and dried (step 304).

  Next, in the mixing step, a predetermined additive is blended with the mixture of the thermoplastic composition (A) and the thermoplastic composition (B), and then heated and melted, uniformly mixed to prepare a molten mixture ( Step 305). Here, as the predetermined additive, an elastomer (C) as an impact modifier and a dialkyl peroxide organic peroxide (D) as a fluidity modifier are mixed.

  In the next precursor material preparation step, a thermoplastic resin molded body having a certain shape as a precursor material for forming a molten mixture containing the thermoplastic resin composition uniformly melt-mixed in the mixing step into a finished member Is created (step 306).

  In the next finished member molding process, the precursor material created in the precursor material creating process is put into an injection molding machine, and after melting and heating, a thermoplastic resin molded body as a finished member is injection molded (step 307). . Note that the crushing step, the washing step, the dehydration drying step, the mixing step, the precursor material creation step, and the finished member forming step in FIG. 3 can be performed in the same steps as in FIG. Description is omitted.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these.
≪Creating specimens≫
Each test piece used as the thermoplastic resin molded body of this example and comparative example is an olefin resin composition (A) having a low MFR (hereinafter also referred to as component A) and an olefin resin composition having a high MFR. (B) (hereinafter also referred to as component B), elastomer component (C) (hereinafter also referred to as component C), and dialkyl peroxide organic peroxide (D) (hereinafter also referred to as component D). Were uniformly mixed according to the blending amounts shown in FIGS. 4 to 13, and after extrusion molding, were molded under injection molding conditions of a molding temperature of 230 ° C. and a mold temperature of 40 ° C. Each test piece was prepared as an ASTM-compliant physical property measurement test piece.

  In addition, the value described in the component A and the component B of FIGS. 4 to 7 and FIG. 11 indicates the mixing ratio of the component A and the component B, and the value described in the component C and the component D is the olefinic thermoplasticity. The value of the weight part of each component with respect to 100 weight of the olefinic thermoplastic resin mixture which is a mixture of the resin composition (A) and the olefinic thermoplastic resin composition (B) is shown.

  Component A is an olefinic thermoplastic resin composition adjusted to have an MFR of 10 g / min in order to compare olefinic resin compositions having a low MFR value. Component A-1 and MFR are 18 g / min. Two types of component A-2 which are the olefin type thermoplastic resin compositions adjusted so that it might become min were prepared. The olefinic thermoplastic resin composition having a low MFR including both is referred to as component A.

  Component B is an olefinic thermoplastic resin composition adjusted to have an MFR of 35 g / min in order to compare olefinic resin compositions having a high MFR value. Two types of component B-2 which are the olefin type thermoplastic resin compositions adjusted so that it might be set to min were prepared. The olefinic thermoplastic resin composition having a high MFR including both is referred to as Component B.

  In addition, component A-1 and component A-2 are waste olefin-based resin molded bodies recovered from the dehydration tank of the washing machine, and component B-1 and component B-2 are waste olefin-based recovered from the vegetable case of the refrigerator. The resin molded body is adjusted by crushing, washing, dehydrating and drying using a general crusher. Component C uses product name JSREP01P manufactured by JSR Corporation as an elastomer component. For component D, dialkyl peroxide manufactured by Kayaku Akzo Co., Ltd. was used as the dialkyl peroxide organic peroxide.

  Moreover, the sample was created using the component between the value of two MFR as described in this embodiment (between component A-1 and component A-2, and between component B-1 and component B-2). In some cases, the inventors have already found that similar physical property values can be obtained.

≪Characteristic evaluation method≫
The characteristic evaluation method for each test piece of Example 101 to Example 124, Example 202 to Example 209, Comparative Example 101 to Comparative Example 120, and Comparative Example 201 to Comparative Example 206 conforms to the provisions of the JIS standard shown below. And measured.
(1) The “tensile yield strength” and “tensile elongation at break” in FIGS. 4 to 7 and 11 were measured in accordance with JIS K7113.
(2) “Bending strength” and “flexural modulus” in FIGS. 4 to 11 were measured according to JIS K7203.
(3) “Izod impact value” in FIGS. 4 to 7 and 11 was measured in accordance with JIS K7110.
(4) “Surface impact height” in FIGS. 4 to 11 was measured in accordance with JIS K5400 by measuring the 50% fracture height under the conditions of a radius of struck tip of 1/2 inch and a bell of 1 kg. .
(5) “MFR” in FIGS. 4 to 13 was measured according to JIS K7210.

  Here, as for a general olefin-based thermoplastic resin molded body, a molded body having a flexural modulus of about 850 MPa to 1300 MPa is often used, and a molded body lower than 850 MPa has low rigidity and uses are limited. . For this reason, it is good to produce the olefin type thermoplastic resin molding which has a value whose bending elastic modulus is 850 Mpa or more.

  Further, when molding a large component, it is preferable to prepare an olefin-based thermoplastic resin molded body having a flexural modulus of 950 MPa or more from the viewpoint of deflection and strain. A large part refers to a solid having a side length of 50 cm or more, and includes shapes such as a cube, a rectangular parallelepiped, a polygonal column, a cylinder, an ellipse, and a sphere, but is not limited to the shape.

  On the other hand, the surface impact height is an important factor for the practical strength of the product. The surface impact height is less than 20 cm, and the parts using olefin-based thermoplastic resin moldings are hard when the package is dropped. Crazes and cracks occur due to daily impact of the product, such as bumping. For this reason, it is generally preferable to use an olefin-based thermoplastic resin molded body having a surface impact height of 50 cm or more.

  In addition, it is preferable to use an olefin-based resin molded body having a surface impact height of 50 cm or more for a component that requires higher strength.

  Both the flexural modulus and the surface impact height are required to have high performance, but since the rigidity and impact strength are in a trade-off relationship, there is also a balance regarding the relationship between the flexural modulus and the surface impact height. It becomes important. For this reason, the values of the flexural modulus and the surface impact height were evaluated based on the minimum standards necessary for the thermoplastic resin molded body.

<< Comparative Example 101 to Comparative Example 113 >>
The measurement result of the test piece prepared by blending component A and component B will be described. FIG. 4 is a diagram showing the measurement results of a test piece prepared by blending component A and component B. FIG.

  First, measurement results of test pieces (Comparative Example 101, Comparative Example 102, Comparative Example 103, and Comparative Example 104) prepared by blending only Component A or Component B will be described. As understood from FIG. 4, the values of the flexural modulus and the surface impact height measured for the test pieces (Comparative Example 103 and Comparative Example 104) generated using only the component B having a high MFR value are as follows. A value higher than the reference value could be obtained. On the other hand, the test pieces (Comparative Example 101 and Comparative Example 102) generated using only the component A having a low MFR have a low value of the surface impact height and cannot be used as a thermoplastic resin molded product. It was.

  Next, test pieces (Comparative Example 105 to Comparative Example 113) prepared by using only Component A and Component B and changing the mixing ratio of Component A and Component B will be described. As for the characteristics of each test piece, the surface impact height was low, and the standard physical property values could not be obtained. It became clear that an appropriate physical property value could not be obtained by simply blending components having greatly different MFRs.

<< Example 101 to Example 124 >>
Next, the test piece which mix | blended component A, component B, and component C is demonstrated. FIG. 5 to FIG. 7 are diagrams showing measurement results of test pieces prepared by blending predetermined amounts of component A, component B, and component C. FIG.

  First, the blending ratio is blended so that component A is 75% and component B is 25%, and component C is blended in a predetermined amount shown in FIG. 5 with respect to 100 parts by weight of the mixture of component A and component B. The test pieces (Example 101 to Example 109) prepared in FIG. 5 will be described in comparison with a comparative example.

  With respect to 100 parts by weight of the mixture of the olefinic thermoplastic resin composition blended so that the blending ratio is 75% for component A and 25% for component B, the addition amount of component C is gradually increased from 0 parts by weight. Measurements were made on the increased specimens. As a result, the value of the surface impact height of the test piece (Comparative Example 105 to Comparative Example 107) in which the addition amount of Component C is 0 parts by weight and the test piece of 0.5 part by weight (Comparative Example 114, Comparative Example 115) is As a result, the result was not usable as a thermoplastic resin molding.

  Furthermore, the test piece (Example 101-Example 109) which added the component C gradually and added the component C 2.5 weight part showed the value of a surface impact height of 50 cm or more and a bending elastic modulus of 950 Mpa or more, Both exceeded the standard value.

  Therefore, 2.5 parts by weight or more of component C is added to 100 parts by weight of the mixture of the olefinic thermoplastic resin composition blended so that the blending ratio is 75% for component A and 25% for component B. It is preferable to make it.

  In addition, the specimens (Example 108, Example 109) to which component C was gradually added and 12.5 parts by weight of component C were added had a flexural modulus exceeding 850 Mpa but the reference value of 950 Mpa. The result was lower.

  Therefore, in order to mold a large component, the component is 100 parts by weight with respect to 100 parts by weight of the mixture of the olefin-based thermoplastic resin composition blended so that the blending ratio is 75% for component A and 25% for component B. The addition amount of C is preferably 2.5 or more and less than 12.5. In addition, Example 108 and Example 109 can also be used as members having required characteristics of medium to low quality. Moreover, the test piece to which component C was further added resulted in a gradual decrease in the value of flexural modulus.

  Next, the mixing ratio is 50% for component A and 50% for component B, and component C is mixed in a predetermined amount shown in FIG. 6 with respect to 100 parts by weight of the mixture of component A and component B. The test pieces (Example 110 to Example 117) prepared in FIG. 6 will be described in comparison with comparative examples.

  With respect to 100 parts by weight of the mixture of the olefinic thermoplastic resin composition blended so that the blending ratio is 50% for component A and 50% for component B, the addition amount of component C is gradually increased from 0 parts by weight. Measurements were made on the increased specimens. As a result, the surface impact height values of the test pieces (Comparative Example 108 to Comparative Example 110) in which the amount of component C added is 0 parts by weight and the test pieces of 0.5 parts by weight (Comparative Examples 116 and 117). As a result, it was not possible to use as a thermoplastic resin molding.

  Further, test pieces (Example 110 to Example 117) in which Component C was gradually added and Component C was added by 2.5 parts by weight or more showed values of a surface impact height of 50 cm or more and a flexural modulus of 950 Mpa or more. Both exceeded the standard value.

  Therefore, 2.5 parts by weight or more of component C is added to 100 parts by weight of the mixture of the olefinic thermoplastic resin composition blended so that the blending ratio is 50% for component A and 50% for component B. It is preferable to make it.

  In addition, the specimens (Example 116, Example 117) in which Component C was gradually added and 12.5 parts by weight of Component C were added, the flexural modulus exceeded 850 Mpa but below the standard value of 950 Mpa. .

  Therefore, in order to mold a large component, the component is 100 parts by weight with respect to 100 parts by weight of the mixture of the olefinic thermoplastic resin composition blended so that the blending ratio is 50% for component A and 50% for component B. The addition amount of C is preferably 2.5 parts by weight or more and less than 12.5 parts by weight. It should be noted that Example 117 can also be used as a member having required characteristics of medium to low quality. Further, when component C was further added, the value of the flexural modulus gradually decreased.

  Next, the compounding ratio is 25% for component A and 75% for component B, and component C is mixed in a predetermined amount shown in FIG. 7 with respect to 100 parts by weight of the mixture of component A and component B. The test pieces (Example 118 to Example 124) created in FIG. 7 will be described in comparison with comparative examples.

  With respect to 100 parts by weight of the mixture of the olefin-based thermoplastic resin composition blended so that the blending ratio is 25% for Component A and 75% for Component B, the addition amount of Component C is gradually increased from 0 parts by weight. Measurements were made on the increased specimens.

  As a result, the value of the surface impact height of the test piece (Comparative Example 111 to Comparative Example 113) in which the addition amount of Component C is 0 parts by weight and the test piece of 0.5 part by weight (Comparative Example 118 to Comparative Example 120) is As a result, the result was not usable as a thermoplastic resin molding.

  Furthermore, the test piece (Example 118-Example 124) which added the component C gradually and added 1 weight part or more of component C showed the value of 50 cm or more of surface impact heights, and a bending elastic modulus of 950 Mpa or more. The reference value was exceeded.

  Therefore, 1 part by weight or more of component C is added to 100 parts by weight of the mixture of the olefinic thermoplastic resin composition blended so that the blending ratio is 25% for component A and 75% for component B. Is preferred.

  From the experimental results of the olefinic thermoplastic resin moldings in which the blending ratios of component A, component B and component C are changed, 25 to 75 parts by weight of olefinic resin moldings (component A) having a low MFR are obtained. It can be seen that it is better to further add 2 parts by weight or more of an elastomer (component C) to an olefin thermoplastic resin composition containing 75 to 25 parts by weight of a high olefin resin molded product (component B).

  Further, particularly preferably, an olefinic thermoplastic comprising 25 to 75 parts by weight of an olefinic resin molded product having a low MFR (component A) and 75 to 25 parts by weight of an olefinic resin molded product having a high MFR (component B). It is preferable to add 2 parts by weight or more and less than 12.5 parts by weight of the elastomer (component C) to the resin composition.

  FIG. 8 to FIG. 10 show the surface impact height and the flexural modulus of an olefin-based resin molded body prepared by mixing component A, component B, and component C, and the mixing ratio of component C and component A (C / A) is plotted in each case. The solid line shows the surface impact height and the dotted line shows the transition of the flexural modulus.

  The olefin-based resin molded body of FIG. 8 is further added to 100 parts by weight of a mixture of the olefin-based thermoplastic resin composition blended so that the blending ratio is 75% for component A and 25% for component B. A plurality of test pieces prepared by changing the amount of component C added were measured.

  Further, the olefin-based resin molded body of FIG. 9 is further added to 100 parts by weight of a mixture of the olefin-based thermoplastic resin composition blended so that the blending ratio is 50% for component A and 50% for component B. A plurality of test pieces prepared by changing the amount of component C added were measured.

  Further, the olefin-based resin molded body of FIG. 10 is further added to 100 parts by weight of a mixture of the olefin-based thermoplastic resin composition blended so that the blending ratio is 25% for component A and 75% for component B. A plurality of test pieces prepared by changing the amount of component C added were measured.

  From the experimental result of FIG. 8, the compounding ratio (C / A) of the component C and the component A having a surface impact height exceeding 50 cm is 2.33 ≦ (C / A) × 100, and the flexural modulus exceeds 950 MPa. The blending ratio (C / A) between component C and component A is (C / A) × 100 ≦ 15.4, and the blending ratio (C / A) is 2.33 ≦ (C / A) × 100 ≦ 15. It can be seen that a range of 4 is preferred.

  Further, from the experimental results of FIG. 9, the compounding ratio (C / A) of the component C and the component A having a surface impact height exceeding 50 cm is 3.57 ≦ (C / A) × 100, and the flexural modulus is 950 MPa. The compounding ratio (C / A) of component C and component A exceeding is (C / A) × 100 ≦ 15.0, and the compounding ratio (C / A) is 3.57 ≦ (C / A) × 100 ≦ 15. It can be seen that a range of 0.0 is preferred.

  Further, from the experimental results of FIG. 10, the compounding ratio (C / A) of the component C and the component A having a surface impact height exceeding 50 cm is 2.67 ≦ (C / A) × 100, and the flexural modulus is 950 MPa. The compounding ratio (C / A) of component C and component A exceeding is (C / A) × 100 ≦ 14.5, and the compounding ratio (C / A) is 2.67 ≦ (C / A) × 100 ≦ 14. It can be seen that a range of .5 is preferred.

  For this reason, 100 weight of the olefin resin mixture in which the mixing ratio (A) / (B) of the olefin resin composition (A) and the olefin resin composition (B) is 1/3 or more and 3/1 or less. The relationship between the compounding ratio (C / A) of component C to component A added to the surface impact height and flexural modulus is preferably in the range of 0.036 ≦ (C / A) ≦ 0.145. Understandable.

Moreover, when the compounding ratio of component C and component A (C / A) is a surface impact height of less than 50 cm and a flexural modulus of less than 950 MP, the use of the thermoplastic resin molded article is a low-grade member. It is limited.
<< Example 201 to Example 209, Comparative Example 201 to Comparative Example 206 >>
The measurement result of the test piece which mix | blended the component A, the component B, the component C, and the component D is demonstrated. FIG. 11 shows the measurement results of a test piece prepared by blending a predetermined amount of Component A, Component B, Component C, and Component D. 11 is blended so that the blending ratio of component A and component B is the blending ratio shown in FIG. It is a measurement result of the test piece (Example 201-Example 209, Comparative Example 201-Comparative Example 206) created by adding and adding the compounding amount.

  About Example 201-Example 209, in any case, the bending elastic modulus and the surface impact height are exceeded, and the fluidity is also satisfied. For Comparative Examples 201 to 206, appropriate physical properties and fluidity cannot be obtained. It turns out that the addition amount of the component D influences the compounding ratio of the component A and the component B.

  Next, the relationship between the added amount of component D constituting the olefin-based resin molded body and MFR will be described with reference to FIG. FIG. 12 shows the relationship between the amount of component D added and MFR for an olefin-based resin molded body prepared by blending component A, component B, and component D. The olefin-based resin molded body of FIG. 12 was prepared by blending Component A and Component B at a predetermined blending ratio, and further adding Component D to 100 parts by weight of the mixture of Component A and Component B. The blending ratio of component A and component B (A / B) is 100% / 0%, 75% / 25%, 50% / 50%, 25% / 75%, 0% / 100%. It measured by changing the addition amount of the component D to add with respect to the sample of ratio.

  For example, the plot of “A = 75%, B = 25%” shows that the blend ratio is 75% for component A and 25% for component B, and further component D is 0, 0.02 , 0.04, 0.06, and 0.08 parts by weight of each sample are shown. From the results shown in FIG. 12, the MFR value increased as the amount of component D increased in all the blending ratios.

  Next, the relationship between the compounding ratio of component A and the amount of component D constituting the olefin-based resin molded body will be described with reference to FIG. FIG. 13 shows the relationship between the blending ratio of component A and the added amount of component D in an olefin resin molded product having an MFR value of 30 and an olefin resin molded product having an MFR value of 60.

  The olefin-based resin molded body of FIG. 13 is prepared by mixing component A and component B at a predetermined mixing ratio, and further adding component D to 100 parts by weight of the mixture of component A and component B. It is a thing. Here, a in FIG. 13 shows the ratio (%) of the blending ratio of component A to the mixture of component A and component B. It is prepared by further adding component D to 100 parts by weight of the mixture of the olefinic thermoplastic resin composition blended at the blending ratio shown in FIG.

  In a general injection molded product, when the MFR is in the range of 30 g / min to 60 g / min, the moldability can be maintained regardless of the shape and size of the molded product. For this reason, the data comparison of the olefin resin molded products having MFR values of 30 and 60 was performed in FIG.

As a result, in both samples with MFR 60 and MFR 30, plotted on a linear function, the following approximate expression (2) and approximate expression (3) were obtained. 014 (2)
For MFR30 d = 0.0005a-0.02 (3)
Here, a indicates the ratio (%) of the mixing ratio of component A in the mixture of component A and component B, and d indicates the amount of component D added in 100 parts by weight of the mixture of component A and component B. .

As a result, it was found that an olefin-based resin molded body prepared by mixing component A, component B, and component D can obtain good physical property values by the following formula (1).
0.005a−0.02 ≦ d ≦ 0.0005a + 0.014 (1)
In the examples of the present specification, examples in which the compounding ratios of Component A, Component B, Component C, and Component D are changed have been described. Additives such as light stabilizers, antistatic agents, lubricants, fillers, copper damage inhibitors, antibacterial agents, and coloring agents may be added as necessary.

Claims (8)

In the olefin-based thermoplastic resin molded body composed of thermoplastic resin compositions having different melt flow rates,
An olefinic thermoplastic resin mixture in which the blending ratio (A) / (B) of the olefinic resin composition (A) and the olefinic resin composition (B) is blended at a ratio of 1/3 to 3/1;
An olefinic thermoplastic resin molded article containing 1 to 10 parts by weight of impact modifier (C) with respect to 100 parts by weight of the olefinic thermoplastic resin mixture,
An olefinic thermoplastic resin molded article, wherein the difference in melt flow rate between the olefinic resin composition (A) and the olefinic resin composition (B) is 25 g / 10 min or more. The olefin-based thermoplastic resin composition (A) has a melt flow rate of 10 g / 10 min or more and 20 g / 10 min or less,
The olefinic thermoplastic resin molded article according to claim 1, wherein the olefinic resin composition (B) has a melt flow rate of 35/10 min or more and 50 g / 10 min or less.   The olefin-based thermoplastic resin molded article according to claim 2, wherein the impact modifier (C) is an elastomer containing ethylene and a copolymer of olefins having 3 or more carbon atoms.   The olefinic thermoplastic resin molded article according to claim 3, further comprising a dialkyl peroxide organic peroxide (D). In the olefin type thermoplastic resin molding in any one of Claim 1 to 4,
The compounding ratio (C / A) of the component A and the component C is 0.036 or more and 0.145 or less, The olefin type thermoplastic resin molding characterized by the above-mentioned. The olefinic thermoplastic resin molded article according to claim 4, wherein the relationship between d, which is the blending part of component D, and a, which is the blending part of component A, satisfies the following formula (1). An olefin-based thermoplastic resin molded article characterized by being made.
(0.0005a−0.02) ≦ d ≦ (0.0005a + 0.014) (1) In the olefinic thermoplastic resin composition molded article according to any one of claims 1 to 6,
The olefinic thermoplastic resin composition (A) or the olefinic thermoplastic resin composition (B) is produced by pulverizing a thermoplastic resin molded body recovered as a waste product. Molded body. In the manufacturing method of the thermoplastic resin molding in any one of Claim 1 to 6,
A method for recycling a thermoplastic resin composition waste material, comprising using the olefinic thermoplastic resin composition (A) or the olefinic thermoplastic resin composition (B) recovered from waste.