JP2007284495A - Recycling method of thermoplastic resin, and, raw material of thermoplastic resin, thermoplastic resin member and manufacturing method thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an efficient and low-cost recycling method of a thermoplastic resin comprising a thermoplastic resin composition derived from fossil resources and a thermoplastic resin composition derived from biomass, and a raw material of a thermoplastic resin and a thermoplastic resin member manufactured by the recycling method. <P>SOLUTION: The recycling method of the thermoplastic resin (A), comprising the thermoplastic resin composition derived from fossil resources and the thermoplastic resin composition derived from biomass, comprises at least a molded article-manufacturing process for manufacturing the raw material of a thermoplastic resin (A) and the thermoplastic resin member from the thermoplastic resin (A), where the molded article-manufacturing process comprises a mixing step of adding a second thermoplastic resin (B) to the thermoplastic resin (A) and mixing them. The raw material of a thermoplastic resin and the thermoplastic resin member are manufactured by the recycling method. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for recycling a thermoplastic resin. More specifically, the present invention relates to a method for recycling a thermoplastic resin containing a fossil resource-derived thermoplastic resin composition and a biomass-derived thermoplastic resin composition. The present invention also relates to a thermoplastic resin material and a thermoplastic resin member obtained by the recycling method of the present invention.

  In general, many members made of a thermoplastic resin are synthesized using a buried fossil resource such as crude oil as a basic raw material. However, from the viewpoint of effective use of resources, the use of thermoplastics synthesized from biomass, especially plants, as a basic raw material, and the promotion of resource recycling of products equipped with components made of these thermoplastic resins have been strongly promoted in recent years. It has been requested.

  In addition, plant-derived thermoplastic resin absorbs carbon dioxide in the process of plant growth, so it is said that the concentration of carbon dioxide in the environment does not increase even when incinerated at the time of disposal. The expansion of its use has become an important issue.

  However, biomass-derived thermoplastic resins are inferior in mechanical properties such as impact resistance, so there are problems such as breakage and deformation when used as members with high required properties such as home appliances and office equipment. Many are limited to materials with relatively low required properties such as packaging materials and films for horticultural materials.

  In order to improve these characteristic problems of the biomass-derived thermoplastic resin, a molded body composed of a resin composition of an aliphatic polyester resin and polycaprolactone (for example, see Patent Document 1), or polylactic acid is mainly used. A biodegradable polyester composition in which a compound in which a saturated alkyl and an aliphatic polyester are bonded to a polyester resin as a component is mixed has been proposed (see, for example, Patent Document 2).

  However, although these molded articles and compositions have improved mechanical characteristics to some extent, they are not sufficient for use as members having high required characteristics such as home appliances and office equipment.

  In order to overcome such problems, by mixing a plant-derived thermoplastic resin composition and a fossil resource-derived thermoplastic resin composition, the properties of the resulting thermoplastic resin are improved, and a member with high required properties is obtained. A lot of research and development has been done to reach a usable level.

  For example, in Patent Document 3, mechanical properties are improved by mixing 1 to 15% by weight of syndiotactic polypropylene with an aliphatic polyester containing lactic acid as a main component. In Patent Document 4, the appearance and heat resistance are improved by mixing 3 to 70 parts by weight of a polylactic acid resin, 25 to 92 parts by weight of a crystalline polypropylene resin composition, and 1 to 40 parts by weight of an inorganic filler. A lactic acid resin composition having excellent dispersibility and a molded article comprising the resin composition are provided.

  Furthermore, in patent document 5, the polylactic acid resin composition excellent in impact resistance is provided by mixing a polylactic acid resin and an impact-resistant polystyrene resin. As described above, in order to use a plant-derived thermoplastic resin for a member having high required characteristics such as home appliances and office equipment, a plant-derived thermoplastic resin composition and a fossil resource-derived thermoplastic resin composition are used. Mixing is one of the effective means, and it is considered that many such mixed resins will be produced in the future.

  On the other hand, in recent years, with the improvement in income levels in Japan, air conditioners (also simply referred to as air conditioners in this specification), television receivers (also simply referred to as TVs in this specification), refrigerators, freezers, laundry Household appliances such as machines, information devices such as personal computers and word processors, office equipment such as printers and fax machines, and various other furniture, stationery, and toys are now being provided at a high penetration rate in general households. Convenience in home life has been dramatically improved.

  However, as a result, the amount of discarded products such as home appliances tends to increase year by year. Conventionally, the recycling of waste products such as home appliances has often been performed through the iron scrap collection route. In contrast, in recent years, the constituent materials of various products such as home appliances have changed, the number of members made of metals such as iron has decreased, and the proportion of members made of thermoplastic resin compositions has increased. Tend to. Thermoplastic resins have a greater degree of design freedom than metals such as iron, and can provide various properties that are difficult to achieve with metals by preparing components and using additives, and are lightweight and durable. This is because it has many advantages such as high performance.

  In response to the above situation, the Home Appliance Recycling Law was enforced in April 2001. According to the Home Appliance Recycling Law, as of March 2006, recycling of four home appliances such as air conditioners, televisions, refrigerators, and washing machines is obligatory. Legal reference values of 55% or more, refrigerator 50% or more, and washing machine 50% or more are set.

  And, following the enforcement of the Home Appliance Recycling Law, the recovery of thermoplastic resin waste is progressing. As a method for recycling the recovered thermoplastic resin waste, Many methods related to so-called thermal recycling, in which waste materials are used as fuel, are used as in the past. However, according to such thermal recycling, it is possible to recycle the waste material of the thermoplastic resin, but there is a problem such as generation of carbon dioxide gas due to combustion, so this method is sufficiently in line with social demands. That's not true.

  There is also a so-called chemical recycling method in which the recovered thermoplastic resin waste is reacted and decomposed at a high temperature to recycle it into raw materials for chemical substances such as monomers. However, most chemical recycling requires some kind of catalyst, and in order to produce a desired chemical substance from a chemical raw material obtained by reaction and decomposition at a high temperature, it is necessary to perform a chemical reaction again. Since energy is consumed, it cannot be said that the environment is fully considered, and it is disadvantageous in terms of cost.

  Therefore, the thermoplastic resin composition is separated from the thermoplastic resin waste material thus recovered by a method such as manual disassembly, and the thermoplastic resin composition is separated for each thermoplastic resin system. There has been proposed a method of recycling a waste material of a thermoplastic resin which is used by processing the member again into a product member or its raw material. Such a recycling method is called material recycling in contrast to the thermal recycling and chemical recycling described above.

  And the member which consists of a thermoplastic resin composition isolate | separated for every system | strain of a thermoplastic resin as mentioned above can be material-recycled comparatively easily by heat-melting and shape | molding again.

  On the other hand, regarding the recycling of biomass-derived thermoplastic resins, as described above, it is desired to expand the use of biomass-derived thermoplastic resins as materials that are harmonized with the environment. Many research and development efforts have been made in various fields regarding methods of recycling biomass-derived thermoplastic resins.

  For example, Patent Document 5 discloses a method for recovering lactide by heating and mixing a polylactic acid product in the presence of water and a catalyst in a screw extruder. Similarly, Patent Documents 6 to 8 disclose a method for recovering lactide from polylactic acid by thermal decomposition in the presence of a catalyst.

  Patent Document 9 discloses a method of decomposing into a monomer by treating a molded body mainly composed of a biodegradable resin having an ester bond such as polylactic acid with a solution containing alcohols. . Patent Documents 10 to 11 disclose a method for recovering a monomer by hydrolyzing polylactic acid at a high temperature. Patent Document 12 discloses a method for recovering a monomer by treating a mixture of a plurality of types of thermoplastic resins containing at least 10% or more of a biodegradable polyester together with moisture at a high temperature.

However, these are all related to chemical recycling, and as described above, chemical recycling is not a method that is sufficiently harmonized with the environment. In addition, the recycling method disclosed in the above-mentioned patent document includes a thermoplastic resin composed solely of a biomass-derived thermoplastic resin composition, or a thermoplastic resin composed solely of a biomass-derived thermoplastic resin composition and other simple units. It is a recycling method for a mixture with a thermoplastic resin composed of one component, and a method for recycling a thermoplastic resin containing a biomass-derived thermoplastic resin composition and a fossil resource-derived thermoplastic resin composition Not touched. Here, the “mixed product” means a product in which a plurality of types of resins having different resin components are mixed.
JP 2000-226501 A Japanese Patent No. 3385329 JP-A-10-251498 JP-A-2005-307128 Japanese Patent Laid-Open No. 7-309863 JP-A-9-77904 JP-A-9-241417 International Publication No. 2003/091238 Pamphlet JP-A-8-253619 JP 2003-3000927 A Japanese Patent Application Laid-Open No. 2004-269566 Japanese Patent Laying-Open No. 2005-330211

  Therefore, in spite of the strong demand for the development of a method for recycling the thermoplastic resin containing the thermoplastic resin composition derived from fossil resources and the thermoplastic resin composition derived from biomass by material recycling, Such a recycling method is not yet known.

  The present invention has been made in view of such circumstances, and the object of the present invention is a thermoplastic resin containing a thermoplastic resin composition derived from fossil resources and a thermoplastic resin composition derived from biomass. It is to provide an efficient and low cost recycling method.

  Moreover, another subject of this invention is providing the manufacturing method of the thermoplastic resin raw material and a thermoplastic resin member using the said recycling method. Furthermore, another subject of this invention is providing the thermoplastic resin raw material and thermoplastic resin member which are obtained by the said manufacturing method.

  The recycling method of the present invention is a recycling method of a thermoplastic resin (A) containing a thermoplastic resin composition derived from a fossil resource and a thermoplastic resin composition derived from a biomass. ) At least a molded body manufacturing process for manufacturing a thermoplastic resin raw material or a thermoplastic resin member, and the molded body manufacturing process adds the second thermoplastic resin (B) to the thermoplastic resin (A), It includes a mixing step of mixing.

  The recycling method of the present invention further includes a resin recovery step of separating and recovering the thermoplastic resin from the waste, and the thermoplastic resin (A) is a thermoplastic resin recovered through the resin recovery step. It is preferable that

  Here, the thermoplastic resin (B) is a thermoplastic resin containing a fossil resource-derived thermoplastic resin, a biomass-derived thermoplastic resin, a fossil resource-derived thermoplastic resin composition, and a biomass-derived thermoplastic resin composition. One or two or more thermoplastic resins selected from the group consisting of:

Furthermore, the thermoplastic resin (B) may be a thermoplastic resin recovered from waste.
The biomass-derived thermoplastic resin composition contained in the thermoplastic resin (A) is preferably a polylactic acid polymer mainly composed of L-lactic acid and / or D-lactic acid.

  The fossil resource-derived thermoplastic resin composition contained in the thermoplastic resin (A) is preferably a polyolefin-based thermoplastic resin composition or a polystyrene-based thermoplastic resin composition.

  In the resin recovery step, the thermoplastic resin (A) is another heat containing a thermoplastic resin composition of the same type as the fossil resource-derived thermoplastic resin composition contained in the thermoplastic resin (A). You may collect | recover with a plastic resin.

  Here, the resin recovery step utilizes a specific gravity difference using a specific gravity liquid, and is derived from a fossil resource contained in the thermoplastic resin (A) and / or the thermoplastic resin (A) from a crushed material made of plastic. It is preferable to include a specific gravity separation step of separating and recovering another thermoplastic resin containing the same type of thermoplastic resin composition as the thermoplastic resin composition. The specific gravity liquid is preferably water.

In the mixing step, an additive that imparts hydrolysis resistance may be further added.
Here, the additive imparting hydrolysis resistance is a carbodiimide compound, and the sum of the thermoplastic resin recovered in the resin recovery step and the second thermoplastic resin (B) mixed in the mixing step. It is preferable to add 0.01 to 10 parts by weight with respect to 100 parts by weight.

  In the mixing step, a compatibilizer and / or an antioxidant may be further added.

  Here, at least one of the compatibilizers is preferably a block copolymer obtained by bonding a polylactic acid polymer mainly composed of L-lactic acid and / or D-lactic acid and an aliphatic polyester.

  Here, the block copolymer obtained by bonding a polylactic acid polymer mainly composed of L-lactic acid and / or D-lactic acid and an aliphatic polyester is mixed with the thermoplastic resin recovered in the resin recovery step and the above mixture. It is preferable to add 0.01 to 30 parts by weight with respect to 100 parts by weight as a total with the second thermoplastic resin (B) mixed in the process.

  Moreover, in addition to the block copolymer which combined the polylactic acid polymer which has L-lactic acid and / or D-lactic acid as a main component, and aliphatic polyester, it has a 1 type, or 2 or more types of reactive functional group A compatibilizing agent may be further added. The compatibilizing agent having a reactive functional group is a copolymer having a reactive functional group in a side chain and composed of an olefinic thermoplastic resin component and a styrene thermoplastic resin component, and / or an olefinic type. A copolymer composed of a thermoplastic resin component and a styrene-based thermoplastic resin component, comprising a structural unit containing a carboxylic acid group or a derivative group thereof in the main chain or side chain of the olefin-based thermoplastic resin component A modified polymer is preferred.

  Here, the copolymer having a reactive functional group in the side chain and composed of an olefin-based thermoplastic resin component and a styrene-based thermoplastic resin component is 100 parts by weight of the thermoplastic resin recovered in the resin recovery step. It is preferable to add 0.1-20 weight part with respect to this.

  The copolymer is composed of an olefinic thermoplastic resin component and a styrene thermoplastic resin component, and contains a carboxylic acid group or a derivative group in the main chain or side chain of the olefinic thermoplastic resin component. The modified polymer containing a structural unit is preferably added in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the thermoplastic resin recovered in the resin recovery step.

  The antioxidant is a phenol-based antioxidant and / or a phosphorus-based antioxidant, and a second thermoplastic resin mixed in the mixing step with the thermoplastic resin recovered in the resin recovery step ( It is preferable to add 0.01 to 5 parts by weight with respect to 100 parts by weight as a sum of B).

  The waste is preferably one or more kinds of waste selected from the group consisting of home appliances, OA equipment, and electrical / electronic components.

  Moreover, this invention provides the manufacturing method of a thermoplastic resin raw material and the manufacturing method of a thermoplastic resin member which used the said recycling method. Furthermore, the present invention relates to a thermoplastic resin material produced by the method for producing a thermoplastic resin material, and a thermoplastic resin member produced by the method for producing the thermoplastic resin member. Also provide. Here, the thermoplastic resin raw material is preferably in the form of pellets.

The thermoplastic resin raw material and the thermoplastic resin member preferably contain a polyolefin resin composition, and the specific gravity is preferably less than 1.0 g / cm ^{3. In} this case, an alternative to the resin member made of the polyolefin resin composition Is preferably used.

The thermoplastic resin material and the thermoplastic resin member contains a polystyrene-based resin composition, it is preferable that the specific gravity is greater than 1.1 g / cm ³ than 1.0 g / cm ^3, in this case polystyrene resin It is suitably used as an alternative to a resin member made of a composition.

  The thermoplastic resin raw material and the thermoplastic resin member can be used in any of an air conditioner, a television, a refrigerator, and a washing machine.

  According to the thermoplastic resin recycling method of the present invention, a high-grade thermoplastic resin raw material and / or a thermoplastic resin containing a fossil resource-derived thermoplastic resin composition and a biomass-derived thermoplastic resin composition, and / or Or a thermoplastic resin member can be manufactured at low cost. In addition, the thermoplastic resin raw material and the thermoplastic resin member manufactured by the manufacturing method using the recycling method of the present invention include an air conditioner, a television, a refrigerator, a washing machine (hereinafter, sometimes referred to as four items of home appliances), and the like. It can also be suitably used as a member having high required characteristics such as home appliances, OA equipment, and electric / electronic parts.

  Further, the thermoplastic resin raw material and the thermoplastic resin member manufactured by the manufacturing method using the recycling method of the present invention can be recycled any number of times according to the thermoplastic resin recycling method of the present invention. Therefore, the usage-amount of the thermoplastic resin synthesize | combined by using a buried fossil resource as a basic raw material can be reduced.

<Recycling method of thermoplastic resin>
The present invention relates to a method for recycling a thermoplastic resin (A) comprising a fossil resource-derived thermoplastic resin composition and a biomass-derived thermoplastic resin composition, wherein the thermoplastic resin (A) is converted into a thermoplastic resin. It has at least a molded body manufacturing process for manufacturing a raw material or a thermoplastic resin member, and the molded body manufacturing process includes a mixing process in which the second thermoplastic resin (B) is added to the thermoplastic resin (A) and mixed. It is characterized by including. Here, the “composition” means one polymer component constituting the thermoplastic resin when the thermoplastic resin is composed of one or a mixture of two or more polymer components.

  “Fossil resources” include natural gas as well as crude oil and coal. The “fossil resource-derived thermoplastic resin composition” means a thermoplastic resin produced by polymerization reaction of various compounds obtained using such a fossil resource as a raw material.

  In addition, “a biomass-derived thermoplastic resin composition” refers to a thermoplastic resin produced by a polymerization reaction of various compounds obtained from plants or microorganisms, as well as directly extracted from such plants or microorganisms. Is included.

Hereinafter, the present invention will be described in detail with reference to embodiments.
The recycling method of the present invention is preferably roughly divided into two steps:
(A) Thermoplastic resin (A) containing a thermoplastic resin composition derived from a fossil resource and a thermoplastic resin composition derived from biomass and / or a thermoplastic derived from a fossil resource contained in the thermoplastic resin (A) A resin recovery step of separating and recovering from the waste other thermoplastic resin containing a thermoplastic resin composition of the same system as the resin composition;
(B) Contains the thermoplastic resin (A) recovered in step (a) and / or the same series of thermoplastic resin composition as the fossil resource-derived thermoplastic resin composition contained in the thermoplastic resin (A) The second thermoplastic resin (B) is added to and mixed with another thermoplastic resin to be heated and melted to produce a thermoplastic resin raw material or a thermoplastic resin member, and a molded body production process. Hereafter, the said resin collection | recovery process and a molded object manufacturing process are demonstrated in detail.

(Resin recovery process)
FIG. 1 is a schematic flowchart showing a preferred example of the resin recovery step of the recycling method of the present invention. Hereinafter, the resin recovery step will be described with reference to FIG. In addition, when using a virgin material or a process waste material as a thermoplastic resin (A), the said resin recovery process is not necessarily required. Here, “virgin material” means an unused resin material that is not recovered from waste, and “process waste material” is a scrap material generated in the process of molding resin. , Means something that never comes to market as a product.

  In the resin recovery step of the recycling method of the present invention, first, a product including a thermoplastic resin (A) containing a thermoplastic resin composition derived from fossil resources and a thermoplastic resin composition derived from biomass is used as waste. Collect (step 101). As described above, the thermoplastic resin (A) is not limited to those recovered from waste, but may be virgin material or process waste, but from the viewpoint of a recycling method for effective use of resources, It is preferable that the resin (A) is recovered from waste.

  The waste is not particularly limited as long as it is a waste containing a thermoplastic resin (A) containing a thermoplastic resin composition derived from a fossil resource and a thermoplastic resin composition derived from biomass. Home appliances, OA equipment, electrical and electronic parts, and the like can be given. The recovered waste is not limited to one type, and two or more types of waste may be recovered and used for one resin recovery step.

  As described above, the fossil resource-derived thermoplastic resin composition contained in the thermoplastic resin (A) means a thermoplastic resin produced by a polymerization reaction of various compounds obtained from fossil resources. However, as such, for example, polyolefin, polystyrene, polyester, polyurethane, polycarbonate, polyamide, acrylic, acrylonitrile, polyvinyl chloride, polyether, polyvinyl alcohol, polyvinyl acetate Examples thereof include thermoplastic resins of a series such as a fluororesin and a fluororesin.

  Here, in Table 1, a typical example of the composition ratio of the resin composition constituting the member in the member made of plastic included in the four home appliances is shown. In the present specification, the term “plastic” means a broad concept including a thermoplastic resin and a polymer such as a thermosetting resin or rubber.

  As shown in Table 1, in a member made of plastic included in four household appliances, the total composition ratio of the polyolefin-based thermoplastic resin composition and the polystyrene-based thermoplastic resin composition is 95.1% by weight for television. The refrigerator is 67.3 wt%, the washing machine is 85.7 wt%, and the air conditioner is 68.1 wt%. Therefore, in the four items of home appliances, it is effective to recycle the members made of plastic containing the polyolefin-based thermoplastic resin composition and / or the polystyrene-based thermoplastic resin composition among the members made of plastic. This is particularly important from the viewpoint of use.

  The thermoplastic resin composition derived from biomass contained in the thermoplastic resin (A) is, as described above, a thermoplastic resin produced by polymerization reaction of various compounds obtained from plants or microorganisms, Examples include those directly extracted from such plants and microorganisms, such as polybutylene succinate, polytrimethylene terephthalate, polylactic acid polymer, polyhydroxyalkanoate, cellulose acetate. And thermoplastic resins such as esterified starch and bacterial cellulose. Examples of the polylactic acid-based polymer include polylactic acid polymers containing L-lactic acid and / or D-lactic acid as a main component. A polylactic acid polymer mainly composed of L-lactic acid and / or D-lactic acid has excellent mechanical properties and the like among the biomass-derived thermoplastic resins.

  In the subsequent process, the collected waste is roughly disassembled, and a member made of thermoplastic resin, a large metal member such as a compressor, a heat exchanger, or the like is taken out (step 102). As a method of dismantling, a conventionally known appropriate method can be adopted, and for example, dismantling by a human hand can be exemplified. For example, when the waste is a washing machine, the member made of the thermoplastic resin is a case for a vegetable room or the like when the waste is a refrigerator. Note that step 102 is not an essential step in the recycling method of the present invention, and may be omitted depending on the type of waste.

  In the subsequent process, the remaining members of the waste from which the members made of thermoplastic resin, large metal members and the like are taken out are roughly crushed (step 103a). As the rough crushing method, a conventionally known appropriate method can be adopted, and examples thereof include a method using a large crusher such as an impact crusher or a shear crusher.

  The particle size of the crushed material produced by crushing is not particularly limited, but is preferably 10 mm or more, and more preferably 40 mm or more. Moreover, it is preferable that the particle size of a crushed material is 80 mm or less, and it is more preferable that it is 60 mm or less. When the particle size of the crushed material is less than 10 mm or more than 80 mm, the metal selection accuracy in the next process tends to decrease. Further, when the particle size of the crushed material is less than 10 mm, it takes a long time for crushing, so that the plastic contained in the waste tends to be deteriorated by melting or thermal oxidation. Furthermore, when the particle size of the crushed material exceeds 80 mm, the bulk specific gravity tends to be small, and the workability in the subsequent processes tends to be adversely affected. Therefore, it is particularly preferable to crush so that the particle diameter is about 60 mm.

  In the case where the step 102 is provided and the member made of thermoplastic resin is taken out from the waste, the remaining member of the waste from which the member is taken out separately, or the member made of the thermoplastic resin or the large metal member is taken out. It is preferable to roughly pulverize together with the members (step 103b when separately crushed separately, 103a when roughly crushed together with the remaining members of the waste). Hereinafter, the roughly crushed crushed material is referred to as a “crushed crushed material”.

  In the subsequent process, a metal-based coarsely crushed material made of iron, copper, aluminum, etc. is selected and removed from the roughly crushed material obtained in step 103a (step 104). As a method for selectively removing the metal-based coarsely crushed material, a conventionally known appropriate method can be employed. For example, iron-based coarsely crushed materials can be selected and removed using a magnet. In addition, aluminum-based and copper-based coarsely crushed materials can be selectively removed using eddy currents.

  In addition, although not shown in figure, you may provide the process of classifying and removing a low bulk specific gravity crushed material before or after step 104. Here, the low bulk specific gravity crushed material means a crushed material having a bulk specific gravity of 0.3 or less, and examples thereof include a polyurethane-based heat-insulated material and a foamed styrene-based material. By providing this process, workability of the subsequent processes is improved.

  For the selective removal of the low-bulk specific gravity crushed material, a conventionally known appropriate method can be adopted, for example, a method using wind power can be mentioned. In this way, when a process for selectively removing crushed materials with low bulk specific gravity is provided, and further, when selecting and removing metal-based crushed materials using magnets and selecting and removing metal-based crushed materials using eddy currents, The order is not particularly limited, but from the viewpoint of sorting efficiency, first, iron-based coarsely crushed materials are sorted and removed by magnetic force, then aluminum-based and copper-based crushed materials are sorted and removed by eddy current, and finally It is preferable to screen and remove the low bulk specific gravity crushed material by wind power. Through the above steps, the metal-based crushed material is removed from the waste, and the crushed material made of plastic is sorted and recovered.

  In a subsequent process, heat containing a specific thermoplastic resin crushed material, that is, a fossil resource-derived thermoplastic resin composition and a biomass-derived thermoplastic resin composition, from a crude crushed material made of plastic using a specific gravity difference. The crushed material of the plastic resin (A) is separated and recovered (step 105). Here, usually, other thermoplastic resin containing the thermoplastic resin composition of the same system as the thermoplastic resin composition derived from the fossil resource contained in the thermoplastic resin (A) together with the thermoplastic resin (A). Crushed material is also collected. Hereinafter, this process is referred to as “specific gravity separation process”. The crushed material used in this process is a roughly crushed material made of plastic obtained in step 104, but if necessary, a member made of a thermoplastic resin taken out in step 102 and separately crushed in step 103b. You may perform this process with it. Or it is also possible to perform this process only about the member which consists of the said thermoplastic resin separately coarsely crushed.

  Specifically, in the specific gravity separation step, the roughly crushed material made of the plastic and / or the member made of the separately crushed thermoplastic resin is put into a liquid (hereinafter referred to as specific gravity liquid) put in a container. The coarse crushed material floating in the liquid of the specific gravity liquid or on the surface of the specific gravity liquid in order to have a specific gravity smaller than the specific gravity of the specific gravity liquid is scooped out from the specific gravity liquid using, for example, a mesh or from the container together with the specific gravity liquid. After overflowing, it is recovered by a method such as separation from the specific gravity liquid. Crushed material having a specific gravity greater than the specific gravity of the specific gravity liquid settles toward the bottom of the container.

  The specific gravity separation step (step 105) will be described in more detail. First, a roughly crushed material made of plastic and / or a member made of the above-mentioned roughly crushed thermoplastic resin is dispersed in a specific gravity liquid contained in a container. At this time, the coarsely crushed material having a specific gravity smaller than the specific gravity of the specific gravity liquid floats in the liquid of the specific gravity liquid or on the surface of the specific gravity liquid. After overflowing with the specific gravity liquid, it is recovered by a method such as separation from the specific gravity liquid. The recovered coarsely crushed material is a crushed material of the thermoplastic resin (A), or the thermoplastic resin composition of the same system as the thermoplastic resin composition derived from the fossil resource contained in the crushed material and the thermoplastic resin (A). It is a mixture with other thermoplastic resin crushed material containing the product (hereinafter referred to as a recycled thermoplastic resin raw material).

By performing this process, other types of thermoplastic resins, such as soft vinyl chloride resins and polyacetal resins, that are not included in the recycled thermoplastic resin raw material contained in the coarsely crushed material charged into the specific gravity liquid are removed. can do. As shown in Table 2 below, the specific gravity range of a thermoplastic resin made of, for example, a soft vinyl chloride resin is generally included in the range of 1.16 to 1.35 g / cm ³ , High value.

  Here, Table 2 shows a typical example of the range of the specific gravity of the plastic for each system of the resin composition constituting the plastic.

As can be seen from Table 2, the specific gravity range of the thermoplastic resin composed of the polyolefin resin composition is generally included in the range of 0.89 to 0.91 g / cm ³ , and the heat composed of the polystyrene resin composition. It can be seen that the specific gravity range of the plastic resin is generally included in the range of 1.04 to 1.05 g / cm ³ .

  On the other hand, the specific gravity of the thermoplastic resin (A) contained in the coarsely crushed material charged into the specific gravity liquid varies depending on the contents of the fossil resource-derived thermoplastic resin composition and the biomass-derived thermoplastic resin composition.

Table 3 shows that the fossil resource-derived thermoplastic resin composition is polypropylene with a specific gravity of 0.89 g / cm ³ , and the biomass-derived thermoplastic resin composition has a specific gravity of 1.25 g / cm ^3. The relationship between the specific gravity of a thermoplastic resin (A) and the content rate (weight%) of both components in the thermoplastic resin (A) which is a polymer is shown.

Table 4 shows that the fossil resource-derived thermoplastic resin composition is a polypropylene having a specific gravity of 0.91 g / cm ³ , and the biomass-derived thermoplastic resin composition has a specific gravity of 1.29 g / cm ³ . The relationship between the specific gravity of a thermoplastic resin (A) and the content rate (weight%) of both components in the thermoplastic resin (A) which is a lactic acid-type polymer is shown.

As can be seen from Tables 3 and 4, when the thermoplastic resin composition derived from the fossil resource of the thermoplastic resin (A) is a polyolefin resin and the content of the polyolefin resin composition is relatively high, When the content of the polyolefin resin composition is 70% or more, more preferably 77% or more, the specific gravity of the thermoplastic resin (A) is less than 1.0 g / cm ³ . As described above, by using the specific gravity liquid having a specific gravity of about 1.0 g / cm ^{3 by} setting the specific gravity of the thermoplastic resin (A) to less than 1.0 g / cm ³ , the coarsely crushed material charged into the specific gravity liquid. From the recycled thermoplastic resin raw material, that is, the thermoplastic resin comprising the polyolefin resin composition and the thermoplastic resin (A) containing the polyolefin resin composition can be selectively separated and recovered, It becomes possible to remove certain polystyrene resin compositions and other types of thermoplastic resins.

Table 5 shows that the fossil resource-derived thermoplastic resin composition is polystyrene having a specific gravity of 1.04 g / cm ³ , and the biomass-derived thermoplastic resin composition has a specific gravity of 1.25 g / cm ^3. The relationship between the specific gravity of a thermoplastic resin (A) and the content rate (weight%) of both components in the thermoplastic resin (A) which is a polymer is shown.

Table 6 shows that the thermoplastic resin composition derived from fossil resources is polystyrene having a specific gravity of 1.05 g / cm ³ , and the thermoplastic resin composition derived from biomass is a polycrystal having a specific gravity of 1.29 g / cm ³ . The relationship between the specific gravity of a thermoplastic resin (A) and the content rate (weight%) of both components in the thermoplastic resin (A) which is a lactic acid-type polymer is shown.

As can be seen from Table 5 and Table 6, when the thermoplastic resin composition derived from the fossil resource of the thermoplastic resin (A) is a polystyrene resin, and the content of the polystyrene resin composition is relatively high, concrete When the content of the polystyrene resin composition is 72% or more, more preferably 80% or more, the specific gravity of the thermoplastic resin (A) is less than 1.1 g / cm ³ . Thus, the specific gravity of the thermoplastic resin (A) by less than 1.1 g / cm ^3, by using the specific gravity liquid having a specific gravity of approximately 1.1 g / cm ^3, crude crushed product was placed in a solution of specific gravity From a recycled thermoplastic resin raw material, that is, a thermoplastic resin comprising a polyolefin resin composition and a thermoplastic resin (A) containing a polyolefin resin composition, and a thermoplastic resin comprising a polystyrene resin composition and a polystyrene resin The mixture with the thermoplastic resin (A ′) containing the thermoplastic resin composition can be selectively separated and recovered, and other types of thermoplastic resins such as vinyl chloride resins can be removed. Become. Thereafter, by using a specific gravity liquid having a specific gravity of about 1.0 g / cm ^3, a thermoplastic resin comprising the polyolefin resin composition, a thermoplastic resin (A1) containing the polyolefin resin composition, and a polystyrene resin. The thermoplastic resin comprising the composition and the thermoplastic resin (A2) containing the polystyrene resin composition can be separated and recovered.

  That is, the specific gravity separation step included in the thermoplastic resin recycling method of the present invention preferably comprises the following two specific gravity separation steps. First, by the first specific gravity separation, the thermoplastic resin (A) and other thermoplastics containing the same type of thermoplastic resin composition as the fossil resource-derived thermoplastic resin composition contained in the thermoplastic resin (A) The resin is separated and recovered from the other series of thermoplastic resins. Next, another heat containing a thermoplastic resin composition of the same system as the thermoplastic resin composition derived from the fossil resource contained in the thermoplastic resin (A) and the thermoplastic resin (A) by the second specific gravity separation. A thermoplastic resin comprising a thermoplastic resin (A1) containing a polyolefin resin composition and a thermoplastic resin comprising a polyolefin resin composition, and a thermoplastic resin (A2) containing a polystyrene resin composition and a polystyrene resin composition Separated into thermoplastic resin. Here, the order of the first specific gravity separation and the second specific gravity separation is not particularly limited. Moreover, when the thermoplastic resin containing a polystyrene-type resin composition is not contained in a crushed material, the specific gravity separation process of 2 times is not necessarily required.

  The specific gravity liquid having a desired specific gravity can be adjusted, for example, as follows. That is, when the desired specific gravity is less than 1.0, water is added to a solvent having a specific gravity of less than 1.0, such as alcohol such as ethanol, until the desired specific gravity is obtained. If the desired specific gravity is greater than 1.0, a salt such as sodium chloride is added to water to obtain the desired specific gravity. If the desired specific gravity is 1.0, water is used. Although the solvent used as the main ingredient of the specific gravity liquid is not necessarily water, the solvent used as the main ingredient of the specific gravity liquid is preferably water in consideration of the ease of adjusting the specific gravity and the treatment after using the specific gravity liquid.

  As described above, the recycled thermoplastic resin raw material can be separated and recovered from waste such as home appliances through the resin recovery step. This recycled thermoplastic resin raw material is subjected to the next molded body manufacturing process.

(Molded body manufacturing process)
FIG. 2 is a schematic flowchart showing a preferable example of a molded body manufacturing process of the recycling method of the present invention. Hereinafter, the said molded object manufacturing process is demonstrated according to FIG.

  First, the recycled thermoplastic resin raw material recovered in the resin recovery step is finely crushed (step 201). As a fine crushing method, a conventionally known appropriate method can be adopted, and for example, a method using a large crusher such as a shear crusher can be mentioned. Hereinafter, the finely crushed material is referred to as “finely crushed material”.

  The size of the finely crushed material is not particularly limited, but the maximum length of the finely crushed material is about 5 to 20 mm so that it can be sufficiently melted and mixed with other substances in a subsequent process. It is preferable that it is about 10 mm. In addition, this process is performed as needed and may be omitted.

  In the subsequent process, the finely crushed material is washed to remove foreign matters such as dust and detergent residue (step 202). As a cleaning method, a conventionally known appropriate method can be employed, and examples thereof include a wet water cleaning method using a blade rotor, a dewatering screen type cleaning dehydration dryer, and the like. In addition, this process is performed as needed and may be omitted.

  In the subsequent process, the second thermoplastic resin (B) and various additives as necessary are added to the finely crushed material after washing and mixed uniformly (step 203). In addition, there is no restriction | limiting in the addition order of a thermoplastic resin (B) and an additive. As described above, the second thermoplastic resin (B) is preferably mixed as a material for a high-quality thermoplastic resin, particularly a plastic member for home appliances and office equipment that require high required characteristics. This is because a thermoplastic resin that can be used is obtained.

<Thermoplastic resin (B)>
The type of the thermoplastic resin (B) is a thermoplastic resin containing a fossil resource-derived thermoplastic resin, a biomass-derived thermoplastic resin, or a fossil resource-derived thermoplastic resin composition and a biomass-derived thermoplastic resin composition. Or any combination of two or more thereof. As the thermoplastic resin (B), a thermoplastic resin recovered from waste can be used. In addition, the thermoplastic resin containing the fossil resource-derived thermoplastic resin composition and the biomass-derived thermoplastic resin composition as the thermoplastic resin (B) is recovered from waste according to the recycling method of the present invention. A finely crushed crushed material can be preferably used. Resources can be effectively used by using the thermoplastic resin (B) recovered from waste.

  Here, when the thermoplastic resin (B) includes a fossil resource-derived thermoplastic resin, and a thermoplastic resin containing a fossil resource-derived thermoplastic resin composition and a biomass-derived thermoplastic resin composition, It is preferable that the resin composition of the thermoplastic resin derived from the fossil resource of the plastic resin (B) is the same system as the thermoplastic resin composition derived from the fossil resource mainly contained in the thermoplastic resin (A). In the case of thermoplastic resin compositions of different systems, the thermoplastic resin (A) and the thermoplastic resin (B) may not be compatible with each other.

There is no restriction | limiting in particular in the mixing amount of the thermoplastic resin (B) with respect to the finely crushed material after washing | cleaning. However, when considering that the thermoplastic resin raw material or the thermoplastic resin member obtained by the recycling method of the present invention is used again for the recycling method of the present invention, the mixing amount of the thermoplastic resin (B) is It is preferable to determine the specific gravity of the obtained thermoplastic resin raw material or thermoplastic resin member to be a preferable value for each system of the thermoplastic resin composition derived from fossil resources mainly contained in the plastic resin (A). That is, when the system of the thermoplastic resin composition derived from fossil resources mainly contained in the thermoplastic resin (A) is a polyolefin, the specific gravity of the obtained thermoplastic resin raw material or thermoplastic resin member is 1.0 g / Preferably it is less than cm ³ . When the specific gravity is less than 1.0 g / cm ³ , the obtained thermoplastic resin raw material or product using the thermoplastic resin member is discarded, and the recycling method of the present invention is applied to the waste. In the specific gravity separation step, it can be easily separated and recovered together with the thermoplastic resin composed of the polyolefin-based resin composition again, so that repeated material recycling is possible. Here, from Table 3 and Table 4, in order to set the specific gravity of the thermoplastic resin raw material or the thermoplastic resin member to less than 1.0 g / cm ³ , the polysiloxane contained in the thermoplastic resin raw material or the thermoplastic resin member is used. The type and mixing of the thermoplastic resin (B) so that the content of the lactic acid-based thermoplastic resin is, for example, 30% by weight or less in the case of the resin of Table 3 and 23% by weight or less in the case of the resin of Table It can be seen that the amount should be set.

Moreover, when the system of the thermoplastic resin composition derived from fossil resources mainly contained in the thermoplastic resin (A) is a polystyrene type, the specific gravity of the obtained thermoplastic resin raw material or thermoplastic resin member is 1.0 g / it is preferably greater than 1.1 g / cm ³ than cm ^3. By setting the specific gravity in such a range, the product using the obtained thermoplastic resin raw material or thermoplastic resin member is discarded, and when the recycling method of the present invention is applied to the waste, the specific gravity separation is performed. In the process, since it can be easily separated and recovered together with the thermoplastic resin composed of the polystyrene resin composition again, material recycling can be repeated. In this way, the amount of thermoplastic resin derived from fossil resources can be reduced by repeatedly recycling the material. Here, from Table 5 and Table 6, the specific gravity of the thermoplastic resin material or thermoplastic resin member obtained in order to increase 1.1 g / cm less than ³ than 1.0 g / cm ³ is the thermoplastic resin material Alternatively, the content of the polylactic acid-based thermoplastic resin contained in the thermoplastic resin member is, for example, 28% by weight or less in the case of the resin in Table 5, and 20% by weight or less in the case of the resin in Table 6. It turns out that what is necessary is just to set the kind and mixing amount of a thermoplastic resin (B).

  Moreover, you may add various additives to the finely crushed material after washing | cleaning. By adding an additive, various properties can be imparted to the thermoplastic resin raw material or the thermoplastic resin member. Examples of the additive include an additive that imparts hydrolysis resistance, a compatibilizing agent, an antioxidant, and the like, and one or more of these may be used in combination. Moreover, you may add other additives, such as a conventionally well-known heat stabilizer, a light stabilizer, an antistatic agent, a lubricant, a filler, a copper damage inhibitor, an antibacterial agent, and a coloring agent, as needed. Hereinafter, additives, compatibilizers and antioxidants that impart hydrolysis resistance will be described in detail.

<Additives imparting hydrolysis resistance>
In the method for recycling the thermoplastic resin of the present invention, it is preferable to add an additive imparting hydrolysis resistance. In general, polylactic acid polymers are hydrolyzable, and thus have a drawback of low long-term reliability. Therefore, when the thermoplastic resin (A) and / or the thermoplastic resin (B) contains a polylactic acid polymer as a biomass-derived thermoplastic resin composition, by adding an additive that imparts hydrolysis resistance Can overcome this drawback.

  As an additive that imparts hydrolysis resistance, an oxazoline compound, an epoxy compound, a carbodiimide compound, or the like can be preferably used, but a carbodiimide compound that imparts higher hydrolysis resistance is more preferable. As the carbodiimide compound, for example, Carbodilite (registered trademark) LA-1 manufactured by Nisshinbo Co., Ltd. can be suitably used. When a carbodiimide compound is used as an additive for imparting hydrolysis resistance, the carbodiimide compound is added in an amount of 0.01 to 10 parts by weight with respect to 100 parts by weight of the total of the recycled thermoplastic resin raw material and the thermoplastic resin (B). It is preferable to do. If the added amount is less than 0.01 parts by weight, sufficient hydrolysis resistance tends to be not provided, and if it exceeds 10 parts by weight, the mechanical properties are lowered, the viscosity is lowered, and the molding processability is deteriorated. Tend.

<Compatibilizer>
In the method for recycling the thermoplastic resin of the present invention, it is preferable to add at least one compatibilizing agent. “Compatibilizer” means an agent for improving the miscibility of resins having different compositions contained in the recycled thermoplastic resin raw material and the thermoplastic resin (B), and any compound having such a function can be used. For example, a block copolymer obtained by bonding a polylactic acid polymer mainly composed of L-lactic acid and / or D-lactic acid and an aliphatic polyester can be preferably used. . Here, the aliphatic polyester is not particularly limited, and examples thereof include an aliphatic polyester composed of glycol and aliphatic dicarboxylic acid such as polybutylene succinate, polyethylene succinate, polybutylene succinate adipate, and the like. .

  Such a block copolymer obtained by bonding a polylactic acid polymer containing L-lactic acid and / or D-lactic acid as a main component and an aliphatic polyester functions as a compatibilizing agent. And the aliphatic part of the aliphatic dicarboxylic acid is compatible with the thermoplastic resin composition derived from fossil resources, and the polylactic acid polymer part is compatible with the thermoplastic resin composition derived from biomass. Conceivable.

  A block copolymer obtained by bonding a polylactic acid polymer mainly composed of L-lactic acid and / or D-lactic acid and an aliphatic polyester is a total of 100 weights of the recycled thermoplastic resin raw material and the thermoplastic resin (B). It is preferable to add 0.01 to 30 parts by weight with respect to parts. When the addition amount is less than 0.01 parts by weight, sufficient compatibility tends not to be exhibited, and when it exceeds 30 parts by weight, mechanical properties tend to be lowered.

  In addition to the above-described block copolymer obtained by bonding a polylactic acid polymer mainly composed of L-lactic acid and / or D-lactic acid and an aliphatic polyester, a compatibilizing agent having a reactive functional group is added. Also good. By adding such a compatibilizing agent having a reactive functional group, the miscibility of resins having different compositions contained in the recycled thermoplastic resin raw material and the thermoplastic resin (B) can be further improved.

  Although it does not specifically limit as a reactive functional group, For example, an acid anhydride group, a carboxyl group, an epoxy group, an oxazoline group, an imide group etc. can be mentioned. The compatibilizing agent having a reactive functional group is not particularly limited as long as it has at least the reactive functional group as described above, but its main chain is composed of, for example, an olefin-based thermoplastic resin component and a styrene-based thermoplastic. A copolymer composed of a resin component is preferred. In this case, the reactive functional group exists as a side chain. As the copolymer having such a reactive functional group, a conventionally known copolymer can be appropriately used. For example, imide group-modified styrene-butylene-butadiene-styrene copolymer (SBBS), maleic acid-modified styrene- And ethylene / butylene-styrene block copolymer (SEBS). In particular, maleic acid-modified SEBS is preferable in that it is excellent in heat resistance and weather resistance.

  For example, a copolymer having a maleic anhydride group as a reactive functional group, the main chain of which is composed of an olefinic thermoplastic resin component and a styrenic thermoplastic resin component, functions as a compatibilizing agent. This is probably because the portion is compatible with the fossil resource-derived thermoplastic resin composition, and the maleic anhydride group reacts with the ester portion of the thermoplastic resin composition derived from biomass to be compatible.

  The copolymer having a reactive functional group is preferably added in an amount of 0.01 to 20 parts by weight with respect to 100 parts by weight of the recycled thermoplastic resin raw material. If the added amount is less than 0.01 parts by weight, the effect of improving the miscibility tends not to be obtained. If the added amount exceeds 20 parts by weight, it is disadvantageous in terms of cost. , There is a tendency that strength and rigidity are lowered and physical properties cannot be balanced.

  The compatibilizing agent is a copolymer composed of an olefinic thermoplastic resin component and a styrenic thermoplastic resin component, and a carboxylic acid group or a derivative group thereof is added to the main chain or side chain of the olefinic thermoplastic resin component. It may be a modified polymer containing a structural unit containing. Even with such a modified polymer, the miscibility of resins having different compositions contained in the recycled thermoplastic resin raw material and the thermoplastic resin (B) can be further improved. The modified polymer compatibilizer is preferably added in an amount of 0.01 to 10 parts by weight with respect to 100 parts by weight of the recycled thermoplastic resin raw material. If the added amount is less than 0.01 parts by weight, the effect of improving the miscibility tends not to be obtained. If the added amount exceeds 10 parts by weight, it is disadvantageous in terms of cost. There is a tendency to be unbalanced.

  The above-mentioned compatibilizers may be used alone or in combination of two or more. A polylactic acid polymer mainly composed of L-lactic acid and / or D-lactic acid and an aliphatic polyester are used. More preferably, it comprises a block copolymer that has been bonded.

<Antioxidant>
In the method for recycling the thermoplastic resin of the present invention, it is preferable to add an antioxidant. The antioxidant may be added together with at least one compatibilizing agent or may be added alone. The antioxidant is not particularly limited, and examples thereof include at least one selected from a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, and the like. By using an antioxidant, long-term reliability can be improved. Among them, it is preferable to use a phenolic antioxidant and / or a phosphorus antioxidant because of its excellent thermal stability and color tone stability. The total of the recycled thermoplastic resin raw material and the thermoplastic resin (B) is 100. It is preferable to add 0.01 to 5 parts by weight with respect to parts by weight. If the addition amount is less than 0.01 parts by weight, a sufficient effect cannot be obtained, and if it exceeds 5 parts by weight, there is a possibility that the cost is disadvantageous.

  In step 203, it is preferable that the finely crushed material after washing, the thermoplastic resin (B), and the additive added as necessary are mixed so that they are uniform. Such mixing can be performed by a conventionally known method such as a method using a tumbler mixer or the like.

  In the subsequent process, the mixture obtained in step 203 is heated and melted (step 204), and further molded if necessary (step 205) to obtain a thermoplastic resin raw material.

  Here, the heating temperature at the time of heat melting and molding is preferably T ° C. or higher when the lowest temperature at which the whole mixture obtained in Step 203 is melted is T ° C., and is (T + 10) ° C. or higher. More preferably. Moreover, it is preferable that it is (T + 120) degrees C or less, and it is more preferable that it is (T + 60) degrees C or less. This is because when the heating temperature at the time of heat melting and molding is less than T ° C., the whole mixture obtained in Step 203 tends to be difficult to be molded because it is not sufficiently melted. This is because if the heating temperature at the time of molding exceeds (T + 120) ° C., the resin composition tends to be thermally deteriorated.

  The shape of the thermoplastic resin material is not particularly limited. That is, for example, the thermoplastic resin raw material may have a pellet shape, a sheet shape, a film shape, a pipe shape, or the like as a precursor used in the step of forming into the shape of the member. Among these, a pellet shape is particularly preferable. In this case, the particle size of the pellet is not particularly limited, but is preferably 1 mm or more, and more preferably 2 mm or more. Moreover, it is preferable that the particle size of a pellet is 8 mm or less, and it is more preferable that it is especially 5 mm or less. When the particle size of the pellet is less than 1 mm, there is a tendency that the workability is lowered due to floating, and when the particle size of the pellet exceeds 8 mm, it is not sufficiently melted in the cylinder of the molding machine, so it is uniformly mixed. There is a tendency not to be refined.

  A conventionally known method can be used as a method for forming a pellet, sheet, film, pipe, or the like as a precursor, such as a single screw extruder or a multi-screw extruder. A method using an extrusion molding machine such as can be used. When forming into a pellet form, methods such as sheet cutting, strand cutting, hot air cutting, underwater cutting, and the like can be used. Among these methods, when molding into a specific shape by injection molding later, an underwater cut that can smoothly supply the resin raw material and can cope with a large amount of processing is particularly preferable.

  Furthermore, the shape of the thermoplastic resin raw material is not limited to the above-mentioned shapes, and after being melted by heating, it is simply agglomerated or crushed into an indefinite shape, particularly through a molding step (step 205). Some are not included.

  The thermoplastic resin raw material thus produced is heated and melted (step 206) and molded (step 207) to produce thermoplastic resin members for various products. Examples of such products include home appliances, OA equipment (including information equipment such as personal computers and office equipment such as printers and copiers), and electrical and electronic parts. Examples of home appliances include air conditioners. , TV, refrigerator, washing machine and the like. A conventionally known method can be used as a method for forming a precursor shape from a pellet shape, a sheet shape, a film shape, a pipe shape, or the like into a shape used as a member of various products, for example, a screw. A method using an injection molding machine such as an inline type injection molding machine or a plunger type injection molding machine can be used. In manufacturing the thermoplastic resin member, the thermoplastic resin member may be directly manufactured by the molding process in step 205 without going through the thermoplastic resin raw material.

<Method for producing thermoplastic resin raw material and thermoplastic resin member>
This invention also provides the manufacturing method of the said thermoplastic resin raw material and a thermoplastic resin member. In producing the thermoplastic resin raw material and the thermoplastic resin member, the thermoplastic resin recycling method of the present invention can be suitably used.

<Raw material of thermoplastic resin and thermoplastic resin member>
The present invention also provides a thermoplastic resin raw material and a thermoplastic resin member obtained by the thermoplastic resin raw material and the method for producing a thermoplastic resin member. That is, the thermoplastic resin raw material and the thermoplastic resin member of the present invention include a thermoplastic resin (A) containing a fossil resource-derived thermoplastic resin composition and a biomass-derived thermoplastic resin composition, and a thermoplastic resin (B And preferably further includes the above-described additives. In addition, about the shape of a thermoplastic resin raw material and a thermoplastic resin member, it is as having mentioned above.

The specific gravity of the thermoplastic resin raw material and the thermoplastic resin member is, as described above, the thermoplastic resin composition derived from the fossil resource of the thermoplastic resin (A) used in producing the thermoplastic resin raw material and the thermoplastic resin member. When is a polyolefin type, it is preferably less than 1.0 g / cm ³ . When the specific gravity is less than 1.0 g / cm ³ , the obtained thermoplastic resin raw material and the product using the thermoplastic resin member are discarded, and the recycling method of the present invention is applied to the waste. In the specific gravity separation step, it can be easily separated and recovered together with the thermoplastic resin composed of the polyolefin-based resin composition again, so that repeated material recycling is possible.

As described above, the thermoplastic resin material and the thermoplastic resin member containing the polyolefin resin composition and having a specific gravity of less than 1.0 g / cm ³ are suitably used as an alternative to the resin member made of the polyolefin resin composition. be able to.

The specific gravity of the thermoplastic resin raw material and the thermoplastic resin member is, as described above, the thermoplastic resin derived from the fossil resource of the thermoplastic resin (A) used for manufacturing the thermoplastic resin raw material and the thermoplastic resin member. when the composition is a polystyrene is preferably greater than 1.1 g / cm ³ than 1.0 g / cm ^3. By the specific gravity greater 1.1 g / cm less than ³ than 1.0 g / cm ^3, products using the obtained thermoplastic resin material and the thermoplastic resin member is discarded, re of the present invention to the waste When the resource recycling method is applied, it can be easily separated and recovered together with the thermoplastic resin composed of the polystyrene resin composition again in the specific gravity separation step, so that material recycling can be repeated.

Thus, it contains polystyrene resin composition, a thermoplastic resin material and a thermoplastic resin member specific gravity of greater than 1.1 g / cm ³ than 1.0 g / cm ³ is formed of a polystyrene resin composition It can be suitably used as an alternative to the resin member.

  In addition, the thermoplastic resin raw material and the thermoplastic resin member of the present invention can be used for members made of a thermoplastic resin of various products, as well as those requiring high required characteristics, such as four items of home appliances. It can also be applied to members of household appliances.

  When plastics are material recycled, it is essential to sort and collect plastics for each system, but a method for sorting and collecting plastics for each system using the difference in specific gravity of plastics is widely used. On the other hand, as described above, it is important to expand the use of biomass-derived thermoplastic resin compositions, particularly polylactic acid polymers, because of their good harmony with the environment. In order to improve, a method of mixing with a fossil resource-derived thermoplastic resin composition is effective. However, the specific gravity of the polylactic acid polymer is relatively large as 1.25 to 1.29 as shown in Table 2, and the thermoplastic produced by mixing with a polyolefin-based thermoplastic resin composition or a polystyrene-based thermoplastic resin composition. When the resin composition (A) is sorted and recovered using the specific gravity difference, there is a possibility that plastics of a system different from the polyolefin system or the polystyrene system may be mixed. Such thermoplastic resin compositions and thermoplastic resin crushed materials in which different types of plastics are mixed are very difficult to recycle materials due to problems in their characteristics. Accordingly, not only the recycled thermoplastic resin composition by the recycling method of the present case is widely spread to the world, but also when the specific gravity is selected in the material design stage of the thermoplastic resin composition (A), different systems are selected. It is extremely effective to design so that no plastics are mixed in from the viewpoint of suppressing the use of petroleum resources and preventing global warming.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these.

<Example 1>
First, a material corresponding to a thermoplastic resin (thermoplastic resin (A)) recovered from waste to be recycled was produced by the following method. That is, polypropylene (Prime Polypro J-3057HP manufactured by Prime Polymer Co., Ltd.) as a thermoplastic resin composition derived from fossil resources, and L-lactic acid and / or D-lactic acid as a biomass-derived thermoplastic resin composition are the main components. Polylactic acid polymer (Laisia (registered trademark) H-100J, manufactured by Mitsui Chemicals, Inc.), polylactic acid polymer and aliphatic polyester mainly composed of L-lactic acid and / or D-lactic acid as a compatibilizing agent A block copolymer (Plamate (registered trademark) PD-150, manufactured by Dainippon Ink and Co., Ltd.) and a carbodiimide compound as an additive that imparts hydrolysis resistance (Carbodilite (registered by Nisshinbo Industries, Ltd.)) (Trademark) LA-1) was uniformly mixed using a normal tumbler mixer at a weight ratio shown in Table 7, and the screw diameter was 30 m. With melt mixing at 200 ° C. using a twin-screw extruder, by extruding to be molded into a particular shape, to produce a pellet-shaped molded product having a diameter of 2 mm, length 3 mm. When the formed body was put into water, the entire amount floated on the surface of the water, indicating that the specific gravity was less than 1.0 g / cm ³ .

  Subsequently, the pellet-shaped molded body obtained as described above is put into a hopper of a 10-ton injection molding machine, and is used for measuring physical properties in accordance with ASTM under injection molding conditions of a molding temperature of 210 ° C. and a mold temperature of 40 ° C. A test piece was prepared. Then, in order to simulate the recycled thermoplastic resin raw material recovered from the waste, it was left for 300 hours under constant temperature and humidity conditions of a temperature of 65 ° C. and a humidity of 95%.

A test piece (corresponding to the thermoplastic resin (A)) simulating the recycled thermoplastic resin raw material collected from the waste thus produced was again crushed to a diameter of about 2 mm and a length of about 3 mm to form a pellet. Next, polypropylene (Prime Polymer Co., Ltd. Prime Polypro J-3057HP) and a carbodiimide compound (Nisshinbo Co., Ltd. Carbodilite (registered trademark) LA-) in the weight ratio shown in Table 7 were used. 1) is added, uniformly mixed using a normal tumbler mixer, melt mixed at 200 ° C. using a twin screw extruder with a screw diameter of 30 mm, and extruded to form a specific shape. A pellet-shaped thermoplastic resin material having a diameter of 2 mm and a length of 3 mm was produced. When the prepared thermoplastic resin raw material was put into water, the entire amount floated on the water surface, indicating that the specific gravity was less than 1.0 g / cm ³ . Furthermore, the obtained pellet-shaped thermoplastic resin material is put into a hopper of a 10-ton injection molding machine, and a test piece for measuring physical properties in accordance with ASTM is produced under injection molding conditions of a molding temperature of 210 ° C. and a mold temperature of 40 ° C. did.

<Example 2>
Instead of adding polypropylene as the thermoplastic resin (B), a polylactic acid polymer containing L-lactic acid and / or D-lactic acid as a main component in a weight ratio shown in Table 7 (Laisia (registered by Mitsui Chemicals, Inc.)) (Trademark) A thermoplastic raw material and a test piece were prepared in the same manner as in Example 1 except that H-100J) was added. When the prepared thermoplastic resin raw material was put into water, it was found that the specific gravity was larger than 1.0 g / cm ³ because the whole amount was settled in water.

<Example 3>
Instead of adding polypropylene as the thermoplastic resin (B), polypropylene (Prime Polypro J-3057HP manufactured by Prime Polymer Co., Ltd.) resin composition and L-lactic acid and / or D-lactic acid were mixed at a weight ratio shown in Table 7. A thermoplastic resin raw material and a thermoplastic resin raw material in the same manner as in Example 1 except that a thermoplastic resin comprising a polylactic acid polymer (Lacia (registered trademark) H-100J, manufactured by Mitsui Chemicals, Inc.) as a main component is added. A test piece was prepared. When the prepared thermoplastic resin raw material was put into water, the entire amount floated on the water surface, indicating that the specific gravity was less than 1.0 g / cm ³ .

  In Examples 1 to 3, the thermoplastic resin composition constituting the thermoplastic resin to be recycled, the weight ratio and the thermoplastic resin added to produce the thermoplastic resin raw material, the type of additive, and the weight ratio The summary is shown in Table 7.

<Comparative example>
Tests for measuring physical properties in compliance with ASTM under injection molding conditions of molding temperature of 230 ° C and mold temperature of 40 ° C, using polypropylene virgin material used in 4 items of household appliances and being injected into the hopper of a 10-ton injection molding machine Created a piece.

<Measuring method of various characteristics>
About each test piece obtained by Examples 1-3 and the comparative example, the following characteristics were measured with the following measuring methods. Table 8 shows the measurement results.
(I) “Tensile strength” and “elongation” were measured according to JIS K7113 as tensile yield strength and tensile elongation at break, respectively.
(Ii) “Bending strength” and “flexural modulus” were measured according to JIS K7203.
(Iii) “Izod impact strength” was measured according to JIS K7110.
(Iv) “Surface impact strength” was measured according to JIS K7211.
(V) "specific gravity" is a thermoplastic resin material whether settle or float when placed in water, or is less than 1.0 g / cm ^3, or greater than 1.0 g / cm ³ It was judged.

<Evaluation of test piece characteristics>
The test pieces of Examples 1 to 3 showed high values comparable to or higher than those of the comparative example using the virgin material, particularly in tensile strength and bending strength. However, the elongation, Izod impact strength and surface impact strength are not sufficiently satisfactory when compared with the test piece of the comparative example. That is, it is a very hard material that is not balanced in physical properties, and does not satisfy the required characteristics of a high-quality thermoplastic resin composition used for durable consumer goods such as home appliances.

When Examples 1 to 3 are compared, the impact properties and elongation of the test pieces of Examples 1 and 3 are greatly improved as compared with the test piece of Example 2. The test pieces of Examples 1 and 3 have a specific gravity of less than 1.0 g / cm ^3, which is a preferable value when the recycling method of the present invention is applied again as described above. Therefore, it can be said that it is a resin molded product that meets social demands for reducing the amount of petroleum used as a depleted resource because it can be repeatedly recycled. On the other hand, the test piece of Example 2 is inferior to the test pieces of Examples 1 and 3 in impact resistance characteristics (Izod impact strength and surface impact strength), and the elongation is not good. This is considered to be because only the polylactic acid polymer was added as the thermoplastic resin (B) in Example 2. Furthermore, in Example 2, as a result of adding only 25 parts by weight of the polylactic acid polymer as the thermoplastic resin (B), the content of the polylactic acid resin composition contained in the produced thermoplastic resin raw material is increased, and the specific gravity is increased. Is 1.0 g / cm ³ or more.

<Example 4>
Furthermore, a block copolymer (Plamate manufactured by Dainippon Ink Co., Ltd.) in which a polylactic acid polymer mainly composed of L-lactic acid and / or D-lactic acid and an aliphatic polyester are combined at a weight ratio shown in Table 9. A thermoplastic resin material and a test piece were prepared in the same manner as in Example 3 except that (registered trademark) PD-150) was added. When the prepared thermoplastic resin raw material was put into water, the entire amount floated on the water surface, indicating that the specific gravity was less than 1.0 g / cm ³ .

<Example 5>
Furthermore, the modified polymer containing a structural unit containing a carboxylic acid group or a derivative group thereof in the main chain or side chain of the olefinic thermoplastic resin component as a compatibilizing agent which is a modified polymer at a weight ratio shown in Table 9 A thermoplastic resin material and a test piece were prepared in the same manner as in Example 4 except that (Yomex 1010 manufactured by Sanyo Chemical Industries, Ltd.) was added. When the prepared thermoplastic resin raw material was put into water, the entire amount floated on the water surface, indicating that the specific gravity was less than 1.0 g / cm ³ .

<Example 6>
Further, maleic acid-modified styrene-ethylene-butylene-styrene block copolymer (SEBS) (Tuftec (registered trademark) M1943 manufactured by Asahi Kasei Chemicals Corporation) is added as a compatibilizing agent at a weight ratio shown in Table 9. A thermoplastic resin material and a test piece were prepared in the same manner as in Example 4 except that. When the prepared thermoplastic resin raw material was put into water, the entire amount floated on the water surface, indicating that the specific gravity was less than 1.0 g / cm ³ .

  Thermoplastic resin composition, weight ratio and thermoplasticity added to produce thermoplastic resin raw materials constituting the recycled thermoplastic resin in Examples 4 to 6 (and Example 3 for comparison) Table 9 summarizes the types of resins and additives and the weight ratio.

  In addition, Table 10 shows measurement results of various characteristics measured by the measurement method.

<Evaluation of test piece characteristics>
It can be seen that the impact resistance of the test piece of Example 4 is improved compared to the test piece of Example 3. However, compared with the comparative example, it does not meet the required characteristics of a high-quality thermoplastic resin composition. On the other hand, both the test pieces of Examples 5 and 6 have greatly improved impact resistance characteristics, and the characteristics other than the elongation are the same values as the test pieces of the comparative example. Therefore, if a part where the required characteristic of elongation is not so high is selected, it can be used for a member of durable consumer goods such as home appliances. Particularly, in the test piece of Example 5, all the characteristics are improved as compared with the test piece of Example 4. Further, the test piece of Example 5 shows high rigidity while maintaining the impact resistance characteristics as compared with the test piece of Example 6, and development to a member requiring high rigidity is conceivable. On the other hand, the test piece of Example 6 shows a property superior to that of the test piece of Example 5 in terms of elongation, and development to a member that requires high viscosity is conceivable. Thus, by adding a small amount of a compatibilizing agent having a reactive functional group, it is possible to greatly improve the properties of the produced thermoplastic resin molded article, and material recycling can be performed at low cost. Each formula is adjusted to have a specific gravity of less than 1.0 g / cm ³ , meets the conditions for repeated material recycling, and has a social requirement to reduce the amount of petroleum used as a depleted resource. It conforms to.

<Example 7>
As shown in Table 11, the polypropylene as the fossil resource-derived thermoplastic resin composition contained in the recycled thermoplastic resin is a polypropylene that is recovered by manual dismantling from the waste of household electrical appliances. Except for the above, the same procedure as in Examples 1 to 5 was performed, and hereinafter, a thermoplastic resin material and a test piece were prepared in the same manner as in Example 5. When the prepared thermoplastic resin raw material was put into water, the entire amount floated on the water surface, indicating that the specific gravity was less than 1.0 g / cm ³ . The prepared specimen was subjected to a constant temperature and humidity test under conditions of a temperature of 65 ° C. and a humidity of 95%. Further, another test piece was subjected to a thermal oxidation deterioration acceleration test under the condition of a temperature of 140 ° C.

<Example 8>
As shown in Table 11, polypropylene as a fossil resource-derived thermoplastic resin composition contained in a thermoplastic resin to be recycled is made from plastic obtained according to the flow of FIG. The crude crushed material is the same as in Examples 1 to 5 except that it is a crushed thermoplastic resin that floats on the water surface when subjected to the specific gravity separation step in Step 105 (specific gravity liquid is water). Similarly, a thermoplastic resin material and a test piece were prepared. When the prepared thermoplastic resin raw material was put into water, the entire amount floated on the water surface, indicating that the specific gravity was less than 1.0 g / cm ³ .

<Example 9>
Furthermore, except that styrene-butylene-butadiene-styrene block copolymer (SBBS) (Tuftec (registered trademark) P2000 manufactured by Asahi Kasei Chemicals Corporation) is added as a compatibilizing agent at a weight ratio shown in Table 11, In the same manner as in Example 8, a thermoplastic resin material and a test piece were prepared. When the prepared thermoplastic resin raw material was put into water, the entire amount floated on the water surface, indicating that the specific gravity was less than 1.0 g / cm ³ .

  Thermoplastic resin composition, weight ratio and thermoplasticity added to produce thermoplastic resin raw materials constituting the recycled thermoplastic resin in Examples 7-9 (and Example 5 for comparison) Table 11 summarizes the types of resins, additives, and weight ratio.

  In addition, Table 12 shows measurement results of various characteristics measured by the measurement method.

<Evaluation of test piece characteristics>
The test piece of Example 7 in which the polypropylene as the fossil resource-derived thermoplastic resin composition contained in the thermoplastic resin to be recycled is polypropylene recovered by manual dismantling from the waste of household electrical appliances is recycled. Compared with the test piece of Example 5 in which the polypropylene in the thermoplastic resin composition to be made is a virgin material, the tensile strength, elongation and bending strength are poor, but the impact resistance characteristics are still high. Development to durable consumer goods such as is possible.

  On the other hand, polypropylene as a fossil resource-derived thermoplastic resin composition contained in a thermoplastic resin to be recycled is a coarsely crushed product made of plastic obtained by using four household appliances as waste and following the flow of FIG. The test piece of Example 8, which is a crushed thermoplastic resin that floats on the water surface when subjected to the specific gravity separation step of Step 105 (the specific gravity liquid is water), stretches compared to the test piece of Example 5, and has an impact resistance. The deterioration of the characteristics is so severe that it is difficult to develop into durable consumer goods such as home appliances. This is considered to be due to foreign substances such as a polystyrene-based thermoplastic resin composition and urethane foam slightly contained in the crushed material.

On the other hand, in the test piece of Example 9 to which styrene-butylene-butadiene-styrene block copolymer (SBBS) was added, the elongation and impact resistance characteristics were greatly improved, and it can be applied to durable consumer goods such as home appliances. It is. Thus, by adding a small amount of a compatibilizing agent having a reactive functional group, a thermoplastic resin molded article containing a thermoplastic resin recovered from wastes such as waste home appliances as a main component is again used for home appliances and the like. It is possible to expand to durable consumer goods, and material recycling can be performed at low cost. Moreover, by adding a small amount of SBBS in addition to a small amount of a compatibilizing agent having a reactive functional group, it is possible to recycle even a thermoplastic resin separated and recovered from a coarsely crushed product made of plastic. I understand that Therefore, the amount of the thermoplastic resin to be material recycled can be increased. Furthermore, all formulas are adjusted to have a specific gravity of less than 1.0 g / cm ³ , meet the conditions for repeated material recycling, and social demands to reduce the consumption of petroleum as a depleted resource It conforms to.

<Example 10>
Instead of the carbodiimide compound (Nisshinbo Co., Ltd. Carbodilite (registered trademark) LA-1) added when preparing the thermoplastic resin raw material, the phenolic antioxidant and the phosphorus-based compound are mixed at a weight ratio shown in Table 13. A thermoplastic resin material and a test piece were prepared in the same manner as in Example 7, except that an antioxidant blended with an antioxidant (Adeka Stub A-612 manufactured by Asahi Denka Co., Ltd.) was added. When the prepared thermoplastic resin raw material was put into water, the entire amount floated on the water surface, indicating that the specific gravity was less than 1.0 g / cm ³ . The prepared specimen was subjected to a constant temperature and humidity test under conditions of a temperature of 65 ° C. and a humidity of 95%. Further, another test piece was subjected to a thermal oxidation deterioration acceleration test under the condition of a temperature of 140 ° C.

<Example 11>
Furthermore, Example 7 is added except that an antioxidant (Adeka Stub A-612 manufactured by Asahi Denka Co., Ltd.) blended with a phenolic antioxidant and a phosphorus antioxidant at a weight ratio shown in Table 13 is added. Similarly, a thermoplastic resin material and a test piece were prepared. When the prepared thermoplastic resin raw material was put into water, the entire amount floated on the water surface, indicating that the specific gravity was less than 1.0 g / cm ³ . The prepared specimen was subjected to a constant temperature and humidity test under conditions of a temperature of 65 ° C. and a humidity of 95%. Further, another test piece was subjected to a thermal oxidation deterioration acceleration test under the condition of a temperature of 140 ° C.

  Thermoplastic resin composition, weight ratio, and thermoplastic added to make thermoplastic resin material in Examples 10 and 11 (and Example 7 for comparison) constituting the recycled thermoplastic resin Table 13 summarizes the types of resins and additives and the weight ratio.

  Table 14 shows the results of the constant temperature and humidity test, and Table 15 shows the results of the thermal oxidation deterioration acceleration test.

<Evaluation of test piece characteristics>
In the constant temperature and humidity test conducted under the conditions of a temperature of 65 ° C. and a humidity of 95%, the test piece of Example 7 and Example 11 to which a carbodiimide compound (Carbodilite (registered trademark) LA-1 manufactured by Nisshinbo Industries, Ltd.) was added. The test piece maintained good physical properties even after 600 hours had passed, and there was no noticeable abnormality in the appearance. In contrast, in the test piece of Example 10 to which no carbodiimide compound (Nisshinbo Co., Ltd. Carbodilite (registered trademark) LA-1) was added, lactide bleed was observed on the surface of the test piece after 300 hours had passed. As seen, after 450 hours, the bleed is severe, and the physical properties are severely degraded. From this, it can be seen that by adding an additive imparting hydrolysis resistance such as a carbodiimide compound, the physical properties and appearance are well maintained even under high temperature and high humidity. In addition, the physical property retention here represents the retention with respect to the initial physical property value of bending strength.

  As a result of the thermal oxidation degradation acceleration test conducted at a temperature of 140 ° C., the test piece of Example 10 and the test piece of Example 11 to which an antioxidant was added maintained good physical properties even after 2000 hours. Also, there was no noticeable abnormality in the appearance. On the other hand, in the test piece of Example 7 in which the antioxidant was not added, the physical properties were maintained until 1000 hours passed, and no abnormal appearance was observed, but when 1250 hours passed. Local deterioration was observed occasionally, and physical properties began to decline greatly. Thereafter, the number of local deteriorations rapidly increased with the passage of time, and the physical properties dropped sharply. By the time 1750 hours passed, the test piece was severely brittle and deteriorated so that the physical properties could not be measured. From this, it can be seen that the addition of an antioxidant is preferable for the method for recycling the thermoplastic resin of the present invention. In addition, the physical property retention rate here represents the retention rate with respect to the initial physical property value of tensile strength.

  The embodiments and examples disclosed herein are illustrative in all respects and should not be construed as being restrictive. 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.

It is a schematic flowchart which shows a preferable example of the resin collection process of the recycling method of this invention. It is a schematic flowchart which shows a preferable example of the molded object manufacturing process of the recycling method of this invention.

Claims (30)

A method for recycling a thermoplastic resin (A) containing a thermoplastic resin composition derived from fossil resources and a thermoplastic resin composition derived from biomass,
Having at least a molded body production process for producing a thermoplastic resin raw material or a thermoplastic resin member from the thermoplastic resin (A),
The method for recycling a thermoplastic resin (A), wherein the molded body manufacturing step includes a mixing step of adding and mixing the second thermoplastic resin (B) to the thermoplastic resin (A). . A resin recovery step of separating and recovering the thermoplastic resin from the waste,
The recycling method according to claim 1, wherein the thermoplastic resin (A) is a thermoplastic resin recovered through the resin recovery step.   The thermoplastic resin (B) comprises a thermoplastic resin containing a fossil resource-derived thermoplastic resin, a biomass-derived thermoplastic resin, a fossil resource-derived thermoplastic resin composition, and a biomass-derived thermoplastic resin composition. The recycling method according to claim 1 or 2, which is one or more thermoplastic resins selected from a group.   The recycling method according to claim 3, wherein the thermoplastic resin (B) is a thermoplastic resin recovered from waste.   The biomass-derived thermoplastic resin composition contained in the thermoplastic resin (A) is a polylactic acid polymer mainly composed of L-lactic acid and / or D-lactic acid. 5. The recycling method according to any one of 4 above.   The resource recycling according to any one of claims 1 to 5, wherein the fossil resource-derived thermoplastic resin composition contained in the thermoplastic resin (A) is a polyolefin-based thermoplastic resin composition. Method.   The resource recycling according to any one of claims 1 to 5, wherein the fossil resource-derived thermoplastic resin composition contained in the thermoplastic resin (A) is a polystyrene-based thermoplastic resin composition. Method.   In the resin recovery step, the thermoplastic resin (A) is another heat containing a thermoplastic resin composition of the same type as the fossil resource-derived thermoplastic resin composition contained in the thermoplastic resin (A). It is collect | recovered with a plastic resin, The recycling method in any one of Claims 2-7 characterized by the above-mentioned.   The resin recovery step utilizes a specific gravity difference using a specific gravity liquid, and the thermoplastic resin (A) and / or a thermoplastic derived from a fossil resource contained in the thermoplastic resin (A) from a crushed material made of plastic. The recycling method according to any one of claims 2 to 8, further comprising a specific gravity separation step of separating and recovering another thermoplastic resin containing a thermoplastic resin composition of the same system as the resin composition. .   The recycling method according to claim 9, wherein the specific gravity liquid is water.   The recycling method according to any one of claims 1 to 10, wherein an additive imparting hydrolysis resistance is further added in the mixing step.   The additive for imparting hydrolysis resistance is a carbodiimide compound, and the total of 100 parts by weight of the thermoplastic resin recovered in the resin recovery step and the second thermoplastic resin (B) mixed in the mixing step The recycling method according to claim 11, wherein 0.01 to 10 parts by weight are added.   The recycling method according to any one of claims 1 to 12, wherein a compatibilizing agent and / or an antioxidant is further added in the mixing step.   The at least one kind of the compatibilizer is a block copolymer obtained by bonding a polylactic acid polymer mainly composed of L-lactic acid and / or D-lactic acid and an aliphatic polyester. 14. The recycling method according to 13.   The block copolymer obtained by bonding a polylactic acid polymer mainly composed of L-lactic acid and / or D-lactic acid and an aliphatic polyester is combined with the thermoplastic resin recovered in the resin recovery step and the mixing step. The recycling method according to claim 14, wherein 0.01 to 30 parts by weight is added to 100 parts by weight of the total of the second thermoplastic resin (B) to be mixed.   The recycling method according to claim 14 or 15, further comprising adding a compatibilizing agent having one or more reactive functional groups.   At least one of the compatibilizers having the reactive functional group is a copolymer having a reactive functional group in a side chain and composed of an olefin-based thermoplastic resin component and a styrene-based thermoplastic resin component, The recycling method according to claim 16, wherein 0.1 to 20 parts by weight is added to 100 parts by weight of the thermoplastic resin recovered in the resin recovery step.   At least one of the compatibilizers having a reactive functional group is a copolymer composed of an olefinic thermoplastic resin component and a styrene thermoplastic resin component, and the main chain of the olefinic thermoplastic resin component or A modified polymer containing a structural unit containing a carboxylic acid group or a derivative group thereof in the side chain, and added in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the thermoplastic resin recovered in the resin recovery step The recycling method according to claim 16 or 17, characterized in that:   The antioxidant is a phenol-based antioxidant and / or a phosphorus-based antioxidant, and the second thermoplastic resin (B) mixed in the mixing step with the thermoplastic resin recovered in the resin recovery step. The recycling method according to any one of claims 13 to 18, wherein 0.01 to 5 parts by weight is added to 100 parts by weight of the total.   The recycling method according to any one of claims 2 to 19, wherein the waste is one or more kinds of waste selected from the group consisting of home appliances, OA equipment, and electrical and electronic parts.   The manufacturing method of the thermoplastic resin raw material using the recycling method in any one of Claims 1-20.   The manufacturing method of the thermoplastic resin member using the recycling method in any one of Claims 1-20.   A thermoplastic resin raw material produced by the method according to claim 21.   The thermoplastic resin material according to claim 23, which is in a pellet form.   A thermoplastic resin member manufactured by the method according to claim 22. Contains a polyolefin resin composition, a thermoplastic resin material or a thermoplastic resin members according to any one of claims 23 to 25 a specific gravity of less than 1.0 g / cm ^3.   The thermoplastic resin raw material or thermoplastic resin member according to any one of claims 23 to 25, which is used as an alternative to a resin member comprising a polyolefin-based resin composition. Containing polystyrene resin composition, a thermoplastic resin material or a thermoplastic resin members according to any one of claims 23 to 25 a specific gravity of greater than 1.1 g / cm ³ than 1.0 g / cm ^3.   The thermoplastic resin raw material or thermoplastic resin member according to any one of claims 23 to 25, which is used as an alternative to a resin member comprising a polystyrene resin composition.   The thermoplastic resin material or thermoplastic resin member according to any one of claims 23 to 29, which is used in any of an air conditioner, a television, a refrigerator, and a washing machine.

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