WO2014017072A1

WO2014017072A1 - Regenerated thermoplastic resin material

Info

Publication number: WO2014017072A1
Application number: PCT/JP2013/004457
Authority: WO
Inventors: 中島　啓造; 公美子大久保; 章浩野末; 西田　博史; 憲一徳弘
Original assignee: パナソニック株式会社
Priority date: 2012-07-24
Filing date: 2013-07-22
Publication date: 2014-01-30
Also published as: JP6327470B2; CN103797057A; JPWO2014017072A1

Abstract

A regenerated thermoplastic resin material according to the present invention can be obtained by: recovering a thermoplastic resin waste, which is a mixture consisting of multiple kinds of resin materials, from ground waste electrical appliances; from this thermoplastic resin waste, selecting a thermoplastic resin material of a specific kind by using a material sorting device, followed by dry washing; and then mixing the thermoplastic resin material of the specific kind with resin modifiers, said resin modifiers including a phenol-based antioxidant, a sulfur-based antioxidant, a metal-inactivating agent, a thermoplastic elastomer or a bromine-based flame retardant and an antimony-based auxiliary flame retardant.

Description

Thermoplastic recycled resin material

The present invention is a heat obtained by recycling a specific type of synthetic resin material (target resin material) from waste including a plurality of types of synthetic resins, such as used home appliances (waste home appliances). The present invention relates to a plastic recycled resin material. In particular, the present invention relates to a thermoplastic recycled resin material capable of suppressing or avoiding a decrease in physical properties and realizing a quality superior to the conventional one when selecting and recycling a target resin material from the waste.

Recent economic activities of mass production, mass consumption, and mass disposal are causing environmental problems on a global scale such as global warming or resource depletion. Under such circumstances, the Home Appliance Recycling Law has been fully enforced since April 2001 in Japan to build a recycling society. Under the Home Appliance Recycling Law, recycling of used air conditioners, TVs, refrigerators, freezers, and washing machines is obligatory.

Conventionally, household electrical appliances (waste household electrical appliances) that have been collected when they are no longer needed are crushed at a household appliance recycling plant, and then separated and collected according to the type of material, and then recycled as necessary. Yes. Generally, magnetic collection, wind power, and / or vibration is used for fractional collection or sorting. Among various materials, in particular, metal materials (for example, iron, copper, or aluminum) can be accurately sorted by metal type by using a specific gravity sorting device and / or a magnetic sorting device. Therefore, the metal material can be recycled with high purity, and a high recycling rate can be realized.

On the other hand, in the selection of synthetic resin materials (resin materials), it is possible to select relatively high precision for some types. For example, polypropylene (PP) is a typical thermoplastic resin material, but its specific gravity is smaller (lighter) than other resin materials. Therefore, a specific gravity sorting method using water (for convenience, the “water specific gravity sorting method”). Therefore, it is possible to sort and recover from a resin material having a large specific gravity (heavy) with relatively high accuracy.

In addition, the resin material before sorting for each specific type (that is, a mixture of a plurality of types of resin materials) is referred to as “resin waste material” for convenience of explanation, and the resin material after sorting (that is, A specific type of resin material) is referred to as “recycled resin material” for convenience of explanation.

Here, the following problems are known in the water specific gravity sorting method. For example, in the water specific gravity sorting method, a large amount of wastewater is generated because water is used to sort PP from resin waste. In addition, for example, among the thermoplastic resin materials that are widely used, polystyrene (PS) and ABS resin (acrylonitrile-butadiene-styrene copolymer) are close to each other in specific gravity, so that they can be selected with higher accuracy than PP. It has become difficult.

When sorting PS or ABS resin by the water specific gravity sorting method, it is possible to sort to some extent by using water with adjusted specific gravity such as salt water. However, even a water specific gravity sorting method using salt water or the like cannot be sorted with the same accuracy as PP. In order to sort PS or ABS resin with higher accuracy, equipment different from the equipment for performing the water specific gravity sorting method is required. Furthermore, in recent years, the demand for PP containing a filler (filler) has increased, but this PP containing filler cannot be well sorted by the conventional water specific gravity sorting method. Therefore, depending on the type of resin material, high-precision sorting is difficult only by the water specific gravity sorting method.

For example, a sorting method disclosed in Patent Document 1 or Patent Document 2 has been proposed as a technique that takes into account such a problem relating to the water specific gravity sorting method. In this sorting method, a specific type of resin material (target resin material) is sorted from resin waste using near infrared rays.

Specifically, for example, in the case of the technique disclosed in Patent Document 2, first, the resin waste (sorting target) is transported by a transport device. Next, the materials of various resin materials are identified by a near infrared identification device (material identification device). Thereafter, when the resin waste material falls from the carry-out end of the conveying device, high-pressure air is discharged from below the dropping path toward the detected resin material of the specific material. Thereby, the resin material of a specific material can be blown away from the natural fall position of other resin materials (mixtures). Therefore, it becomes possible to select a resin material of a specific material from other resin materials.

With the screening methods disclosed in these patent documents, it is possible to select not only PP but also PS and ABS resin having similar specific gravity, and it is also possible to select filler-containing PP having a large specific gravity. Further, with these sorting methods, it is possible to sort a specific resin material as a high-purity recycled resin material having a purity of 99% or more.

However, when the selected resin material is used as it is as a recycled resin material, that is, when a molded product is produced only from the recycled resin material obtained by sorting, in the obtained molded product, the physical properties or There is a risk of quality degradation.

First, if the resin waste material is shredder dust that crushes waste home appliances, even if the above-mentioned thermoplastic resin material such as PP, PS, or ABS resin can be selected with high accuracy, a small amount of foreign matter should be avoided. I can't. Such a recycled resin material mixed with foreign matter has lower strength and / or impact resistance than a virgin material (unused resin material) or a recycled resin material almost free of foreign matter.

For example, urethane foam used as a heat insulating material (urethane resin is generally known as a thermosetting resin material), various sealing materials, elastomer materials (rubber etc.), other resin materials, And various metal materials (iron, copper, aluminum, etc.). In many cases, these foreign substances adhere to or adhere to the recycled resin material after sorting. If the foreign matter is simply attached to the resin material, it can be removed by a known dry cleaning or the like. However, if the foreign matter adheres strongly to the recycled resin material via a sealing material or the like, the foreign matter cannot be completely removed even by washing.

Next, resin waste recovered from waste home appliances often depends on the usage environment of home appliances, but in many cases, has deteriorated over time. Additives (eg, antioxidants, light stabilizers, weathering agents, etc.) intended to maintain durability are usually added to resin materials used in household appliances. The resin material is consumed with the aging of the resin material. Therefore, even if it is a high-purity recycled resin material, the durability of a molded product manufactured using the recycled resin material as it is decreases.

Furthermore, depending on the type of additive, there is a possibility of some influence on the recycled resin material. As an additive added to the resin material, an additive such as a filler or a pigment is also added in addition to the above-described one that improves the durability. Here, the filler or the pigment may contain metal components, and these metal components may affect the thermal deterioration of the recycled resin material. In addition, the foreign matter described above may affect the deterioration or durability of the recycled resin material, or may accelerate the deterioration.

Therefore, for example, a technique for suppressing or avoiding a decrease in physical properties or a variation in physical properties of the recycled resin material by blending a recycled resin material with a virgin material is known. For example, the technique disclosed in Patent Document 3 describes that the physical properties of a recycled resin material can be improved by mixing a recycled resin material (recycled plastic material) and a virgin material.

Further, Patent Document 4 proposes a laminate having a recycled polypropylene resin as an intermediate layer and a polypropylene virgin resin containing a flame retardant as a surface layer and a back layer. According to this document, it is said that a flame-retardant polypropylene excellent in strength and appearance can be obtained by using the laminate having the above-described configuration.

Japanese Patent Laid-Open No. 2002-263587 JP 2011-104461 A JP 2011-089026 A JP 2001-009995 A

However, as disclosed in Patent Document 3, there is a case where the physical properties cannot be sufficiently improved even by a method of mixing a virgin material with a recycled resin material.

For example, if a recycled resin material obtained by mixing a virgin material is referred to as a “mixed recycled resin material” for convenience, this mixed recycled resin material is certainly more than the original recycled resin material that is not mixed with a virgin material. Physical properties are improved. However, the physical properties of the mixed recycled resin material do not reach the physical properties of the virgin material after all. Therefore, the use of the mixed recycled resin material is limited to a field where physical properties lower than those of the virgin material are sufficient.

Moreover, in order to bring the physical properties of the mixed recycled resin material close to those of the virgin material, it is necessary to mix a large amount of virgin material with the original recycled resin material. In order to recycle the target resin material, mixing a large amount of virgin material does not lead to an improvement in recycling. Therefore, it is difficult to say that it is sufficiently meeting social demands for achieving a high recycling rate (requests for a recycling-oriented society).

Furthermore, depending on the type of the resin material, there is a possibility that the lowered physical properties cannot be recovered sufficiently even when the virgin material is mixed. For example, a crystallized resin such as PP can recover the lowered physical properties to some extent by mixing a virgin material. On the other hand, since the styrene resin material is a non-crystallized resin, the physical properties may not be sufficiently recovered even when the virgin material is mixed.

In addition, if the above-mentioned foreign matter is contained in the original recycled resin material, the physical properties may be further lowered by the action of the foreign matter. Therefore, even if a large amount of virgin material is mixed or a large amount of the same kind of consumed additive (antioxidant, light stabilizer, weathering agent, etc.) is added, the physical properties of the mixed recycled resin material May not be improved sufficiently.

In addition, as disclosed in Patent Document 4, in the method of laminating the virgin material on the surface instead of mixing the virgin material, a laminating process is essential. Therefore, a separate laminating process is required to obtain a molded product of the recycled resin material, and the total man-hour is increased. As a result, this method not only complicates the manufacturing process but also increases the manufacturing cost. Moreover, since it is necessary to use a virgin material for a surface layer and a back surface layer in patent document 4, the usage-amount of a recycled resin material cannot be increased more.

The present invention was made to solve such problems, and from a mixture of a plurality of types of resin materials derived from waste home appliances, a specific type of thermoplastic resin material is selected, An object of the present invention is to provide a technique capable of realizing good physical properties of a thermoplastic recycled resin material without mixing a large amount of virgin material when recycled as a thermoplastic recycled resin material.

In order to solve the above-mentioned problems, the thermoplastic recycled resin material according to the present invention is obtained from a waste material of a thermoplastic resin mixed with a plurality of types of resin materials obtained from crushed waste home appliances using a material identification device. (1) A phenol-based antioxidant and a sulfur-based antioxidant are blended with a specific type of thermoplastic resin material obtained after being screened and dry-cleaned, or (2) the heat The metal deactivator is blended in the range of 0.01 to 1 part by weight with respect to 100 parts by weight of the plastic resin material, (3) the thermoplastic elastomer is blended, or (4) bromine-based difficulty. A proper amount of a flame retardant and an antimony flame retardant aid are blended.

According to the above configuration, deterioration or deterioration of the physical properties of the thermoplastic recycled resin material is effectively suppressed. Therefore, the thermoplastic recycled resin material can be effectively reused as a molded product. Further, since the promotion of deterioration of physical properties can be effectively suppressed, the reused molded product can be used stably over a long period of time. In addition, when recycling recycled thermoplastic resin materials, good physical properties (durability, strength, impact resistance, etc.) can be realized without adding a large amount of virgin material. Can be improved. Therefore, it is possible to further promote the development of home appliances in consideration of the environment.

The above object, other objects, features, and advantages of the present invention will become apparent from the following detailed description of preferred embodiments with reference to the accompanying drawings.

In the present invention, with the above configuration, a specific type of thermoplastic resin material is selected from a mixture of a plurality of types of resin materials derived from waste home appliances, and recycled as a thermoplastic recycled resin material. At this time, there is an effect that it is possible to provide a technique capable of realizing good physical properties of the thermoplastic recycled resin material without mixing a large amount of virgin material.

It is an example of the manufacturing process (recycling process of a thermoplastic resin material) of the thermoplastic recycled resin material which concerns on Embodiment 1 of this invention, Comprising: It is process drawing which shows the process until it selects the resin material of a specific material ( In FIG. 1, the order of wind power, magnetic force, and eddy current selection does not matter. FIG. 2 is a continuation of the manufacturing process of the thermoplastic recycled resin material shown in FIG. 1 and is a process diagram showing a process until a specific type of selected resin material is modified and molded. It is a typical perspective view which shows an example of the near-infrared identification system used in order to select the thermoplastic resin material of a specific material in the manufacturing process of the thermoplastic recycled resin material shown in FIG. It is an example of the manufacturing process of the thermoplastic reproduction | regeneration resin material which concerns on Embodiment 2 of this invention, Comprising: It is process drawing which shows the process until it modifies and shape | molds the selected specific kind of resin material. It is an example of the manufacturing process of the thermoplastic reproduction | regeneration resin material which concerns on Embodiment 3 of this invention, Comprising: It is process drawing which shows the process until it modifies and shape | molds the selected specific kind of resin material. It is an example of the manufacturing process of the thermoplastic reproduction | regeneration resin material which concerns on Embodiment 4 of this invention, Comprising: It is process drawing which shows the process until it modifies and shape | molds the selected specific kind of resin material.

In order to solve the above-mentioned problem, a first thermoplastic recycled resin material according to the present invention is a material identification device obtained from a waste thermoplastic resin mixed with a plurality of types of resin materials obtained from crushed waste home appliances. This is a structure in which a phenolic antioxidant and a sulfur-based antioxidant are blended with a specific type of thermoplastic resin material obtained after being screened and dry-cleaned.

According to the above configuration, two kinds of antioxidants are added in combination to the specific kind of thermoplastic resin material subjected to the dry cleaning treatment. Thereby, even if the thermoplastic resin material has deteriorated over time or the deterioration of the thermoplastic resin material has progressed due to the inclusion of foreign matter, the acceleration of deterioration can be effectively suppressed. Therefore, the durability of the obtained thermoplastic recycled resin material can be improved satisfactorily. As a result, since the selected thermoplastic recycled resin material can be reused as a part of home appliances, the recycling rate can be improved.

Further, in order to solve the above-mentioned problem, the second thermoplastic recycled resin material according to the present invention is obtained from a thermoplastic resin waste material obtained from a crushed material of waste home appliances and containing a plurality of types of resin materials. With respect to 100 parts by weight of the thermoplastic resin material, the metal deactivator is 0.01 to 1 with respect to a specific type of thermoplastic resin material obtained after being selected using an identification device and dry-cleaned. It is the structure formed by mixing within the range of parts by weight.

According to the above configuration, an appropriate amount of a metal deactivator is added to a specific type of thermoplastic resin material that has undergone a dry cleaning treatment. The metal deactivator forms a complex with a metal-based foreign matter derived from waste home appliances or a metal component contained in the additive in the thermoplastic resin material. Thereby, the catalytic action by a metal component can be reduced effectively, and progress of deterioration of a thermoplastic resin material can be controlled effectively. Therefore, the durability of the obtained thermoplastic recycled resin material can be improved satisfactorily. As a result, since the selected thermoplastic recycled resin material can be reused as a part of home appliances, the recycling rate can be improved.

Further, in order to solve the above problems, the third thermoplastic recycled resin material according to the present invention is obtained from a thermoplastic resin waste material obtained from a crushed material of waste home appliances and containing a plurality of types of resin materials. This is a configuration in which a thermoplastic elastomer is blended with a specific kind of thermoplastic resin material obtained after being sorted using an identification device and subjected to a dry cleaning process.

According to the above configuration, a compatible thermoplastic elastomer is added to a specific type of thermoplastic resin material that has undergone a dry cleaning treatment. Thereby, in the thermoplastic resin material after selection, it is possible to improve the adhesion between resin molecules. Therefore, the physical properties (especially impact resistance) of the thermoplastic recycled resin material obtained can be improved. As a result, since the selected thermoplastic recycled resin material can be reused as a part of home appliances, the recycling rate can be improved.

In addition, the fourth thermoplastic recycled resin material according to the present invention is obtained from a waste material of a thermoplastic resin mixed with a plurality of types of resin materials obtained from crushed waste home appliances, using a material identification device, In the range of 18 to 25 parts by weight of a brominated flame retardant and an antimony flame retardant aid with respect to 100 parts by weight of the thermoplastic resin material with respect to a specific type of thermoplastic resin material obtained after the dry cleaning treatment. It is the structure which is mix | blended in the inside.

Alternatively, the fifth thermoplastic recycled resin material according to the present invention is obtained from a crushed material of waste home appliances, from a thermoplastic resin waste material in which a plurality of types of resin materials are mixed, using a material identification device, More than 30 parts by weight of a recycled resin material of the same material with a lower sorting accuracy is blended with respect to 100 parts by weight of the thermoplastic resin material, with respect to 100 parts by weight of the thermoplastic resin material obtained after the dry cleaning treatment, In addition, the composition may be such that bromine-based flame retardant and antimony-based flame retardant aid are blended within a range of 13 to 17 parts by weight with respect to 100 parts by weight of the thermoplastic resin material.

According to the above configuration, a bromine-based flame retardant and an antimony-based flame retardant aid are added in appropriate amounts to a specific type of thermoplastic resin material that has undergone a dry cleaning treatment. Thereby, even if a foreign material is contained in the thermoplastic resin material, the same degree of flame retardancy as when a flame retardant is added to the virgin material can be realized. Therefore, physical properties such as flame retardancy of the obtained thermoplastic recycled resin material can be improved satisfactorily. As a result, since the selected thermoplastic recycled resin material can be reused as a part of home appliances, the recycling rate can be improved.

In the first thermoplastic recycled resin material having the above structure, the total amount of the phenolic antioxidant and the sulfurous antioxidant is 0.01 to 2 with respect to 100 parts by weight of the thermoplastic resin material. It may be within the range of 0.0 part by weight.

In the first thermoplastic recycled resin material having the above-described structure, the blending ratio of the phenolic antioxidant and the sulfurous antioxidant is within a range of 1: 1 to 1: 4 by weight. Also good.

Further, in the second thermoplastic recycled resin material having the above-described structure, at least a compound selected from the group consisting of an oxalic acid derivative, a salicylic acid derivative, a hydrazide derivative, a triazole derivative, and an imidazole derivative is used as the metal deactivator. The structure by which 1 type is mix | blended may be sufficient.

In the third thermoplastic recycled resin material having the above-described configuration, the blending amount of the thermoplastic elastomer may be in the range of 3 to 20 parts by weight with respect to 100 parts by weight of the thermoplastic resin material. .

In the fourth and fifth thermoplastic recycled resin materials having the above-described structure, at least tetrabromobisphenol A-bis (2,3-dibromopropyl ether) is used as the brominated flame retardant. Also good.

In the first to fifth thermoplastic recycled resin materials having the above-described configuration, the thermoplastic resin material may be a styrene resin material or a polyolefin.

Further, in the first to fifth thermoplastic recycled resin materials having the above-described configuration, the styrenic resin material may be at least one of general-purpose polystyrene and high-impact polystyrene.

Further, in the third thermoplastic recycled resin material having the above-described configuration, when the thermoplastic resin material is a styrene resin material, the thermoplastic elastomer may be a styrene elastomer.

Further, the third thermoplastic recycled resin material having the above-described configuration may further include a general-purpose polystyrene blended with the styrene-based elastomer.

Moreover, in the 3rd thermoplastic recycled resin material of the said structure, the said general purpose polystyrene is a recycled material obtained from a waste household appliance, The compounding quantity of the said general purpose polystyrene is with respect to 100 weight part of the said thermoplastic resin materials. And may be in the range of 10 to 50 parts by weight.

Further, in the first to fifth thermoplastic recycled resin materials having the above-described configuration, the material identifying device may be a near infrared identifying device.

In the first to fifth thermoplastic recycled resin materials having the above-described configuration, the waste home appliance is at least one home appliance selected from the group consisting of a refrigerator, a freezer, an air conditioner, and a washing machine. There may be.

In addition, the present invention includes a specially-classified thermoplastic resin material that is selected from a waste material of a thermoplastic resin mixed with a plurality of types of resin materials obtained from crushed waste home appliances using a material identification device. As a resin modifier, a phenolic antioxidant and a sulfur-based antioxidant, a metal deactivator, or a thermoplastic elastomer The manufacturing method of the thermoplastic reproduction | regeneration resin material which mix | blends is also included.

Hereinafter, preferred embodiments of the present invention will be described with reference to the drawings. In the following description, the same or corresponding elements are denoted by the same reference symbols throughout the drawings, and redundant description thereof is omitted.

(Embodiment 1)
[Example of recycling thermoplastic resin materials]
First, the manufacturing process of the thermoplastic recycled resin material according to the present invention will be specifically described with reference to FIGS. 1 and 2 are process diagrams showing an example of a process for producing a thermoplastic recycled resin material according to the first embodiment (in other words, a resin material regeneration process or a recycling process).

First, as shown in FIG. 1, a thermoplastic resin waste material (shredder dust) is obtained by carrying out five steps on waste home appliances, and a sorting step is performed on this thermoplastic resin waste material. By doing so, the selected specific kind of thermoplastic resin material is obtained. If this thermoplastic resin material is referred to as a “resin material after sorting” for convenience, the thermoplastic recycled resin according to the present invention is obtained by performing four steps on the resin material after sorting as shown in FIG. A material is obtained. This thermoplastic recycled resin material can be molded by, for example, injection molding. Moreover, in FIG. 1 and FIG. 2, what is removed in the said process is connected and shown with the broken line with respect to the frame which shows each process.

Examples of the waste home appliance include, but are not limited to, a used refrigerator, a freezer, an air conditioner, or a washing machine. These waste home appliances include household products and commercial products. Therefore, the waste home appliances in the present invention are not limited to household appliances, and widely include consumer electronics. As shown in FIG. 1, a disassembly and disassembly process is performed on the waste home appliance. At this time, the waste home appliances to be disassembled and disassembled may be only one type or two or more types of the plurality of types of used electrical products. Moreover, even if it is the same kind of waste home appliances, electric products from different manufacturers may be mixed, or different models may be mixed.

Describing a refrigerator as an example of waste home appliances, in the disassembly and disassembly process, the used refrigerator is manually disassembled to remove the compressor and remove the refrigerant. Thereafter, the case or shelf is manually removed from the vegetable compartment, freezer compartment, refrigerator compartment, etc. inside the refrigerator. The compressor or the like removed at this time corresponds to the manually recovered metal waste material shown in FIG. 1, and the case or the shelf corresponds to the manually recovered resin waste material.

As shown in FIG. 1, a crushing process is performed on the refrigerator that has undergone the disassembly and disassembly processes. In the crushing process, a known crusher is used.

For the crushed material obtained in the crushing step, as shown in FIG. 1, a wind force sorting step, a magnetic force sorting step, and an eddy current sorting step are performed. The wind sorting process, the magnetic sorting process, and the eddy current sorting process may be performed in the order shown in FIG. 1, may be performed in a different order, or some sorting processes may be omitted. That is, after the crushing process, at least one sorting process selected from a wind sorting process, a magnetic sorting process, and an eddy current sorting process may be performed, and two sorting processes or three sorting processes are performed. Even in that case, the order is not particularly limited.

In the wind sorting process, urethane foam or fine foreign matters contained in the crushed material are sucked and removed by wind force using a known suction device. At this time, the refrigerant contained in the urethane foam is also removed. In FIG. 1, the urethane waste material is illustrated as what is removed by a wind-power selection process.

In this embodiment, the magnetic force sorting process is performed after the wind sorting process. In the magnetic separation process, the iron waste material is removed by a known electromagnet or the like. An eddy current sorting process is performed after the magnetic sorting process. In the eddy current sorting step, non-ferrous metal waste materials such as copper and aluminum are removed by a known eddy current sorter or the like.

After the eddy current selection process, the crushed material is sieved as necessary. Therefore, although not shown in FIG. 1, a sieving step may be performed in the present embodiment. Thereby, the thermoplastic resin waste material (shredder dust) comprised by the crushing piece (resin piece) of the magnitude | size of the predetermined range is obtained. When sieving is performed, the size of the crushed pieces is set within a range of 5 to 150 mm, but is not particularly limited.

The obtained thermoplastic resin waste material is subjected to a resin material sorting step as shown in FIG. In the resin material sorting step, for example, a near-infrared identification system 20 as shown in FIG. 3 is used, and a specific kind of resin material and another resin material are sorted. The near infrared identification system 20 will be described later. In addition, the identification method performed in the resin material sorting step is not limited to the method using near infrared rays, and a known method that can identify the material of the resin material can be appropriately employed. For example, an identification method using near infrared rays and a water specific gravity sorting method may be used in combination.

A specific kind of thermoplastic resin material (resin material after sorting) is obtained by the resin material sorting process. As shown in FIG. 2, a dry cleaning process is performed on the sorted resin material. In the dry cleaning process, the surface adhering matter (surface dirt) of the resin pieces constituting the resin material after sorting is removed using a known dry cleaning apparatus. Examples of the dirt on the surface include, but are not limited to, dust, a sealing material, and powder. Also, as a dry cleaning device, a type equipped with a hammer blade that rotates at high speed (removes surface deposits by striking the hammer blade), or a type in which resin pieces are rubbed together (removes surface deposits by rubbing) Is not particularly limited.

As a method for cleaning the resin material after sorting, there are various methods such as a wet cleaning process as well as a dry cleaning process. In the present invention, a dry cleaning process is employed. This is because the dry cleaning process does not use water for cleaning, and thus the influence on the environment can be reduced as compared with the wet cleaning process or the like.

However, the dry cleaning treatment tends to increase the residual amount of deposits after cleaning as compared with the wet cleaning treatment. Therefore, in this embodiment, as necessary, as shown in FIG. 2, the above-described wind sorting process, magnetic sorting process, electrostatic sorting process (sorting using an electrostatic separator), or the like is appropriately performed. Also good. This sorting step is referred to as a “post-washing sorting step” for convenience.

By performing the post-cleaning sorting step, foreign matters (impurities) such as iron, non-metal, and powder that could not be removed by the dry cleaning step can be removed as much as possible. Therefore, the post-cleaning sorting step is not an essential step but an optional step in the present embodiment. In addition, the post-cleaning sorting process may be performed by at least one of a wind sorting process, a magnetic sorting process, and an electrostatic sorting process, or all of these sorting processes may be performed, or other than these. The sorting step may be performed.

Next, in this embodiment, as shown in FIG. 2, a phenol-based antioxidant and a sulfur-based antioxidant are added as a resin modifier to the washed resin material after sorting. This step is referred to as “antioxidant addition step”. The method of adding the antioxidant in the antioxidant addition step is not particularly limited. For example, a predetermined amount of phenolic antioxidant and sulfur antioxidant is added to the resin material after sorting after washing, and a tumbler or The method of mixing homogeneously using well-known mixing apparatuses, such as a Henschel mixer, can be mentioned.

The mixing device for mixing the antioxidant is not necessarily limited to a tumbler or a Henschel mixer. However, if the resin material after sorting is sufficiently mixed with these mixing devices, not only the antioxidant can be dispersed in the resin material after sorting, but also the resin material after sorting can be homogenized well, so there is less variation in physical properties. can do. Therefore, it is preferable to set the mixing time by the mixing apparatus to a length that takes into account the homogenization of the resin material after sorting. In addition, when mixing the antioxidant, a predetermined amount of spreading agent may be added. Thereby, antioxidant becomes easy to adhere to the surface of the resin piece which comprises the resin material after a selection.

Further, as described later, in the antioxidant addition step, a phosphorus antioxidant may be added in addition to the phenol antioxidant and the sulfur antioxidant. In addition, additives other than antioxidants can be added as appropriate. Examples of additives other than antioxidants include heat stabilizers, light stabilizers, antistatic agents, lubricants, fillers (fillers), copper damage inhibitors, antibacterial agents, colorants, and other antioxidants. It is done. As these additives, known additives can be appropriately selected and used according to various conditions such as durability, mechanical properties and appearance required for the thermoplastic recycled resin material.

Further, additives other than the phenolic antioxidant and the sulfurous antioxidant may be added to the resin material after selection together with the phenolic antioxidant and the sulfurous antioxidant in the antioxidant addition step, It may be added at any stage of the production process shown in FIGS. Furthermore, in addition to the additive, a resin material other than the resin material after sorting may be blended. This resin material may be a virgin material blended within a range that does not lower the recycling rate, or may be a waste material other than the resin material after sorting in order to realize desired physical properties. Accordingly, the thermoplastic recycled resin material according to the present invention may be composed of only a specific type of resin material, or may be a polymer blend in which another resin material is blended.

After the antioxidant addition step, a heating kneading and extrusion step is performed as shown in FIG. In the heat-kneading and extruding step, using a known extruder, the resin material after selection (the phenolic antioxidant and the sulfur-based antioxidant have been added) is heat-kneaded under predetermined conditions and extruded from the extruder. Here, the extruder is preferably provided with a mesh filter.

Even if the resin material after sorting has removed foreign matters (impurities) by the dry cleaning process, a small amount of foreign matters such as urethane waste, other resin materials (including silicon resin, rubber, etc.), iron waste, metal waste, etc. remain. There is a risk. For example, if the waste home appliance is a refrigerator, a large amount of foreign materials such as urethane foam, seals, other resin materials, rubbers, metal pieces, coated copper wire, etc., adhere to the crushed material of the refrigerator. Yes.

These foreign substances often adhere strongly to the surface of the resin material after sorting. Therefore, even if the dry cleaning process or the post-cleaning sorting process is performed, these foreign substances cannot be completely removed. If these foreign substances are finally mixed in the thermoplastic recycled resin material, the molded product molded using this thermoplastic recycled resin material has a decrease in initial physical properties, variation in physical properties, deterioration in durability, etc. May occur. Moreover, the fall of an initial physical property originates also in aged deterioration accompanying long-term use of household appliances.

Therefore, by extruding the post-sorting resin material that has been heat-kneaded through a mesh filter, foreign substances (impurities) that could not be removed in the dry cleaning process (or post-cleaning screening process) can be removed. Moreover, since the phenol-based antioxidant and the sulfur-based antioxidant are added to the heat-kneaded post-selection resin material, by passing through a mesh filter, these antioxidants (and other additives) It can be kneaded homogeneously in the resin component.

The specific configuration of the extruder is not particularly limited, and examples thereof include a single screw extruder, a twin screw extruder, and a multi-screw extruder. In general, from the viewpoint of improving the kneading conditions, a multi-screw extruder having two or more screws is preferably used. The number of axes may be uniaxial depending on various conditions such as screw shape, screw rotation speed, extrusion diameter, and cylinder length.

The conditions for heating and kneading the resin material after sorting with an extruder are not particularly limited, and the resin material after sorting melts well, and the phenolic antioxidant and sulfur antioxidant and the resin material after sorting are well Conditions for kneading can be set as appropriate. If the heating temperature (cylinder temperature and die temperature) is too high, the resin component is deteriorated. Therefore, it is preferable to set a suitable temperature range according to the type of the resin material after sorting. For example, if the resin material after selection is polypropylene (PP), the heating temperature is preferably within a range of 170 to 270 ° C., and if polystyrene (PS) is preferably within a range of 160 to 280 ° C., it may be an ABS resin. For example, the temperature is preferably within the range of 160 to 270 ° C.

Also, the specific configuration of the mesh filter provided in the extruder is not particularly limited. By making the mesh of the mesh filter finer, the effect of removing foreign substances can be enhanced, and various physical properties such as impact characteristics and elongation characteristics of the obtained thermoplastic recycled resin material can be easily improved.

In the heating and kneading and extrusion steps, it is preferable to pelletize the extruded thermoplastic recycled resin material. The method of pelletization is not particularly limited, and a known method is preferably used. For example, there is a method (strand cut) in which a thermoplastic recycled resin material is extruded from an extruder into a strand shape, cooled in a water tank, and then cut into a pellet of an appropriate size by a pelletizer. Moreover, the method (hot cut) cut | judged immediately after extruding a thermoplastic recycled resin material in water may be sufficient.

Further, the pelletized thermoplastic recycled resin material may be mixed by stirring with the mixing apparatus (such as the tumbler or Henschel mixer described above) described in the antioxidant addition step. Thereby, since the pellets of the thermoplastic recycled resin material obtained can be homogenized, variation in physical properties can be further reduced.

As shown in FIG. 2, the thermoplastic recycled resin material thus obtained is reused as a home appliance such as an air conditioner or a general molded product by performing an injection molding process. can do.

[Example of selection of thermoplastic resin material]
Next, an example of the near-infrared identification system 20 used in the resin material selection step described above will be specifically described with reference to FIG. FIG. 3 is a perspective view schematically showing the near-infrared identification system 20 used in the present embodiment. As shown in FIG. 3, the near-infrared identification system 20 according to the present embodiment includes a transport device 1, a near-infrared identification device 4, a sorting plate 6, a tubular body 8, an electromagnetic valve 10, a control unit 14, and an air pressure source. 15 etc.

The conveying apparatus 1 conveys the thermoplastic resin waste material 11, and a known belt conveyor is used in the present embodiment. The transport direction of the transport apparatus 1 is the −y direction in FIG. 3, the height direction is the z direction, and the direction orthogonal to the transport direction (transverse direction) is the x direction.

The near-infrared identification device 4 is provided on the transport path of the transport device 1 and selects a specific type of thermoplastic resin material from the transported resin waste 11 using near-infrared spectroscopy. Although not shown in FIG. 3, various processing apparatuses that perform the above-described wind sorting process, magnetic sorting process, or eddy current sorting process may be provided in the transport path of the transport apparatus 1. In this case, the resin material conveyed by the conveying apparatus 1 is not the thermoplastic resin waste material 11 but a crushed material of waste home appliances.

The near infrared spectroscopy will be described. Organic compounds have different light absorption wavelength bands depending on the types of atomic groups (organic groups) contained in the molecular structure. Therefore, if an organic compound is irradiated with near infrared rays, a unique near infrared absorption spectrum can be obtained according to the molecular structure of the organic compound. Therefore, the near-infrared absorption spectrum is measured by irradiating an unknown resin material with near-infrared radiation, and the resin material is compared with the spectrum (or registered spectrum) obtained from other resin materials. Can be identified. This is the near infrared spectroscopy. The near-infrared identification device 4 uses this near-infrared spectroscopic analysis method to select a specific type of thermoplastic resin material from the resin waste material 11.

In the near-infrared absorption spectrum, the peak position, peak width, absorption intensity (absorbance), etc. change due to hydrogen bonding and / or intermolecular interaction. Therefore, according to the near-infrared spectroscopic analysis method, it is possible to identify a resin material containing halogen such as bromine.

The tube 8 is provided in the transverse direction (x direction) at the downstream end in the transport direction of the transport device 1 and has a plurality of discharge ports 5 that discharge high-pressure air toward the downstream side. The sorting plate 6 is provided so as to stand upright in the transverse direction further downstream in the transport direction when viewed from the tube body 8 (and the downstream end of the transport device 1). A predetermined interval is provided between the sorting plate 6 and the downstream end of the transport device 1. The air pressure source 15 is a mechanism that supplies high-pressure air to the tube body 8, and the electromagnetic valve 10 is a valve body that controls the flow of high-pressure air from the air pressure source 15 to the tube body 8. The control unit 14 controls the operations of the near-infrared identification device 4 and the air pressure source 15.

The specific configurations of the sorting plate 6, the tube 8, the electromagnetic valve 10, the control unit 14, the pneumatic pressure source 15 and the like are not particularly limited, and a known configuration can be suitably used. For example, the pipe body 8 is exemplified by a metal pipe. Moreover, as the electromagnetic valve 10, a known solenoid valve is exemplified. Moreover, as the control part 14, a well-known computer (processor) or a controller is illustrated. Examples of the air pressure source 15 include a compressor that supplies air at a constant pressure.

Next, the resin material selection step by the near infrared identification system 20 will be specifically described by giving a case where the resin waste material 11 is derived from a refrigerator.

First, it is assumed that the thermoplastic resin material to be reused is polystyrene (PS). The resin waste material 11 derived from the refrigerator includes general-purpose polystyrene (GPPS) and high-impact polystyrene (HIPS) as a plurality of resin materials. Therefore, in the near-infrared identification device 4, GPPS and HIPS are preset as specific types of resin materials to be selected.

In the example shown in FIG. 3, the resin waste material 11 includes a thermoplastic resin material 2 shown as a shaded resin piece and another resin material 3 shown as a non-shaded resin piece. In the present embodiment, GPPS or HIPS corresponds to the thermoplastic resin material 2.

At the upstream end of the transport device 1 in the transport direction, the resin waste material 11 is dispersed on the transport surface of the transport device 1 so that the resin waste material 11 is dispersed (a plurality of resin pieces constituting the resin waste material 11 do not overlap each other). This spraying may be performed manually or automatically using a known spraying device. The transport apparatus 1 transports the resin waste material 11 at a speed of about 2 m / second, for example. Since the near-infrared identification device 4 is located on the downstream side when viewed from the upstream end of the conveyance device 1, the resin waste material 11 moves toward the near-infrared identification device 4 by the conveyance of the conveyance device 1.

When the resin waste material 11 reaches the position of the near-infrared identifying device 4, the near-infrared identifying device 4 irradiates the resin waste material 11 with near-infrared light and measures a near-infrared absorption spectrum. Then, the material of the resin material is identified based on the difference between the near-infrared absorption spectrum from the thermoplastic resin material 2 and the near-infrared absorption spectrum of the other resin material 3. Further, the near-infrared identification device 4 captures an image of the resin waste material 11 to acquire an image, and based on the analysis result of this image and the identification result by the near-infrared absorption spectrum, the resin piece that is the thermoplastic resin material 2 is obtained. Get location information. The position information of the resin piece may be position information in the x direction of the transport device 1.

The control unit 14 controls to open the electromagnetic valve 10 based on the position information obtained from the near infrared identification device 4. Thereby, high-pressure air is discharged (injected) from the discharge port 5 of the tubular body 8 toward the thermoplastic resin material 2 (resin to be selected) falling from the downstream end of the conveying device 1. Although the discharge pressure at this time is not specifically limited, For example, 5 bar can be mentioned. As a result, the thermoplastic resin material 2 is blown obliquely upward on the downstream side (−y direction), so that the thermoplastic resin material 2 jumps over the sorting plate 6.

On the other hand, when the resin piece which is the other resin material 3 falls from the downstream end of the transport apparatus 1, the control unit 14 keeps the electromagnetic valve 10 closed. Therefore, when the other resin material 3 passes over the discharge port 5, high-pressure air is not injected from the discharge port 5. Therefore, the other resin material 3 falls without jumping over the sorting plate 6.

Thus, resin pieces that become the other resin material 3 are accumulated on the upstream side of the sorting plate 6, and resin pieces that become the thermoplastic resin material 2 are accumulated on the downstream side of the sorting plate 6. Therefore, the thermoplastic resin material 2 and the other resin material 3 other than the resin waste material 11 can be selected. As a result, the thermoplastic resin material 2 can be recovered efficiently and with high accuracy. Moreover, not only the selection of metal materials, but also thermoplastic resin materials (and other resin materials) can be selected well, so it is possible to promote the reuse of various materials used in waste home appliances, The recycling rate can be further improved.

In particular, the near-infrared identification system 20 according to the present embodiment can improve the purity after selection of a specific thermoplastic resin material, and requires a large amount of water at the time of sorting, such as a water specific gravity sorting method. It is possible to simplify the resin material sorting process. In addition, resin materials that are difficult to be sorted by the water specific gravity sorting method (for example, filler-containing PP, etc.), and resin materials that are close in specific gravity difference such as ABS and PS can be suitably sorted. Therefore, the mixing amount of different types of resin materials can be greatly reduced.

[Modification of thermoplastic resin material after selection]
Next, in order to improve the physical properties of the resin material after sorting selected by the near-infrared identification system 20, it is added in the method of modifying the resin material after sorting, that is, in the antioxidant addition step described above. Two types of antioxidants will be specifically described.

In the present invention, the type of the thermoplastic resin material to be selected is not particularly limited, and may be various resin materials widely used for home appliances. Typical thermoplastic resin materials include styrene resin materials and polyolefins. Examples of the polyolefin include various polyethylenes and various polypropylenes. Styrene resin materials include general-purpose polystyrene (GPPS), high impact polystyrene (HIPS), styrene-butadiene copolymer, styrene-acrylonitrile copolymer (SAN), and acrylonitrile-butadiene-styrene copolymer (ABS). Etc.

Therefore, the resin waste material obtained from the waste home appliance includes at least one type of resin material selected from the group consisting of the plurality of thermoplastic resin materials described above, and preferably includes at least two types of resin material. .

In the present embodiment, when these thermoplastic resin materials are selected from the resin waste material and reused, as described above, the phenol-based antioxidant and the sulfur-based antioxidant are blended. By using these antioxidants in combination, the physical properties, particularly durability, of the resulting thermoplastic recycled resin material can be greatly improved. In particular, if the thermoplastic resin material is a styrene resin material, the effect of improving the durability due to the blending of the phenol-based antioxidant and the sulfur-based antioxidant tends to be large. Furthermore, among styrene resin materials, it has been clarified that the greatest improvement effect can be obtained at the present time for HIPS.

The specific types of added phenolic antioxidant and sulfur antioxidant are not particularly limited. If it is a phenolic antioxidant, a phenyl group or a derivative thereof is included in the chemical structure, and any compound having an antioxidant action may be used. If it is a sulfur-based antioxidant, a sulfur atom is included in the chemical structure. Any compound having an antioxidant action may be used. In the present invention, the phenol-based antioxidant or the sulfur-based antioxidant is an “antioxidant” in which various known solvents or additives are mixed in a predetermined range in addition to the above-mentioned compounds. It may be a “composition”.

In the present invention, compounds or compositions that are particularly preferred as phenolic antioxidants and sulfur antioxidants can be mentioned depending on the type of thermoplastic resin material.

First, preferred compounds for the phenolic antioxidant will be exemplified. If the thermoplastic resin material is polystyrene, preferred phenolic antioxidants include, for example, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (for example, trade name from BASF) IRGANOX 1076), bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionic acid] (2,4,8,10-tetraoxaspiro [5,5] undecane-3,9-diyl ) Bis (2,2-dimethyl-2,1-ethanediyl) (for example, Sumitizer GA-80 manufactured by Sumitomo Chemical Co., Ltd.), triethylene glycol bis [3- (3-t-butyl-5-methyl-4) -Hydroxyphenyl) propionate] (for example, trade name IRGANOX245 manufactured by BASF), 2,6-di-t-butyl-p-cresol (BHT), pentaerythro Tritoltetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane (for example, trade name ADK STAB AO-60 manufactured by ADEKA), 2,4,6- And tris (3 ′, 5′-di-tert-butyl-4′-hydroxybenzyl) mesitylene (for example, trade name IRGANOX1330 manufactured by BASF). Only one type of these compounds may be used, or two or more types may be used in appropriate combination.

Among these, bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionic acid] (2, 4, 8, 10-tetraoxaspiro [5,5] undecane-3,9-diyl) bis (2,2-dimethyl-2,1-ethanediyl), triethylene glycol-bis [3- (3-t-butyl-5- Methyl-4-hydroxyphenyl) propionate] and the like are more preferable.

If the thermoplastic resin material is an ABS resin, preferred phenolic antioxidants include, for example, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, triethylene glycol- Bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionic acid] (2,4 , 8,10-Tetraoxaspiro [5,5] undecane-3,9-diyl) bis (2,2-dimethyl-2,1-ethanediyl, 2,6-di-t-butyl-p-cresol, penta Erythritol tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, 2,4,6-tris ( 3 ', 5'-di-tert-butyl-4'-hydroxybenzyl) mesitylene, 4,4'-butylidenebis (6-tert-butyl-3-methylphenol) (for example, trade name Sumitizer BBM- manufactured by Sumitomo Chemical) S), poly (dicyclopentadiene-co-p-cresol) (for example, trade name Wingstay L manufactured by Eliokem), etc. These compounds may be used alone or in combination of two or more. May be used in appropriate combination.

If the thermoplastic resin material is polypropylene, a preferable phenolic antioxidant is, for example, pentaerythritol tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl). Propionate] methane, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionic acid] ( 2,4,8,10-tetraoxaspiro [5,5] undecane-3,9-diyl) bis (2,2-dimethyl-2,1-ethanediyl), triethylene glycol-bis [3- (3- t-butyl-5-methyl-4-hydroxyphenyl) propionate], 2,6-di-t-butyl-p-cresol, 2,4,6-to Examples thereof include squirrel (3 ′, 5′-di-tert-butyl-4′-hydroxybenzyl) mesitylene. Only one type of these compounds may be used, or two or more types may be used in appropriate combination.

Of these, pentaerythritol tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane is preferred because the thermoplastic recycled resin material obtained has excellent heat stability. Etc. are preferred.

Next, preferred compounds for the sulfur-based antioxidant will be exemplified. Whether the thermoplastic resin material is polystyrene, ABS resin or polypropylene, for example, dilauryl-3,3′-thiodipropionate (DLTDP), distearyl-3,3′-thiodipropionate (DSTDP) Dimyristyl-3,3′-thiodipropionate (DMTDP), bis [3- (dodecylthio) propionic acid] 2,2-bis [[3- (dodecylthio) -1-oxopropyloxy] methyl] -1, 3-propanediyl, bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionic acid] (2,4,8,10-tetraoxaspiro [5,5] undecane-3,9 -Diyl) bis (2,2-dimethyl-2,1-ethanediyl) (for example, trade name Sumitizer TP-D manufactured by Sumitomo Chemical). Only one type of these compounds may be used, or two or more types may be used in appropriate combination.

Among these, since the heat-resistant stability of the obtained thermoplastic recycled resin material is excellent, bis [3- (3-tert-butyl-4-－hydroxy-5-methylphenyl) propionic acid] (2,4,8, 10-tetraoxaspiro [5,5] undecane-3,9-diyl) bis (2,2-dimethyl-2,1-ethanediyl) and the like are preferable.

Furthermore, the combination of the above-described phenolic antioxidant and sulfur antioxidant is not particularly limited. However, as a preferred combination, for example, the phenolic antioxidant is bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionic acid] (2,4,8,10-tetraoxa Spiro [5,5] undecane-3,9-diyl) bis (2,2-dimethyl-2,1-ethanediyl) and triethylene glycol-bis [3- (3-tert-butyl-5-methyl-) 4-hydroxyphenyl) propionate] and the sulfur-based antioxidant is bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionic acid] (2,4,8, List the combinations that are 10-tetraoxaspiro [5,5] undecane-3,9-diyl) bis (2,2-dimethyl-2,1-ethanediyl) Can. According to this combination, it is possible to further improve the heat resistance stability of the obtained thermoplastic recycled resin material.

The total blending amount of the phenolic antioxidant and the sulfurous antioxidant is not particularly limited, but is preferably in the range of 0.01 to 2.0 parts by weight with respect to 100 parts by weight of the thermoplastic resin material. The content is preferably in the range of 0.1 to 0.5 parts by weight. If the blending amount is less than 0.01 parts by weight, the content in the thermoplastic recycled resin material may become insufficient due to bleeding out or the like. Moreover, when it exceeds 2.0 weight part, the durable improvement effect corresponding to a compounding quantity cannot be expected.

Further, the blending ratio (mixing ratio) of the phenolic antioxidant and the sulfur-based antioxidant is not particularly limited, but is preferably in the range of 1: 1 to 1: 4 by weight, and is preferably 1: 2 to 1. : More preferably within the range of 3. If the blending ratio is within this range, the durability can be effectively improved by blending these antioxidants.

Furthermore, in this embodiment, a phosphorus antioxidant may be used in combination with the phenol antioxidant and the sulfur antioxidant. There are many thermoplastic recycled resin materials when blended with a phenol-based antioxidant and a sulfur-based antioxidant (antioxidant addition step, heat-kneading and extrusion step) and during injection molding (injection molding step). Receive heat history. Therefore, in order to improve the heat resistance stability during blending or injection molding, it is preferable to blend a phosphorus-based antioxidant.

The specific phosphorus-based antioxidant is not particularly limited as long as it is a compound that contains a phosphorus atom in the chemical structure and has an antioxidant action. As a preferable phosphorus-based antioxidant, for example, tris (2,4-di-t-butylphenyl) phosphite (for example, manufactured by BASF) is used regardless of whether the thermoplastic resin material is polystyrene, ABS resin, or polypropylene. Trade name IRGFOS168), tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylphosphonite (for example, trade name IRGFOS PEP-Q manufactured by BASF), bis (2,4di-tert -Butyl-6-methylphenyl) = ethyl = phosphite (eg, trade name IRGFOS 38 from BASF), bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite (eg, product from ADEKA) Name ADK STAB PEP-24G), 2,2′-methylenebis (4,6-di-t-butylphenyl) octyl phosphite (eg, ADEKA Product name ADK STAB HP-10), 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide (for example, trade name SANKO-HCA manufactured by Sanko), triallyl phosphite, tris (nonyl-phenyl) ) Phosphite and the like. Only one type of these compounds may be used, or two or more types may be used in appropriate combination.

Among these, since the heat-resistant stability of the obtained thermoplastic regenerated resin material is excellent, among these, tris (2,4-di-t-butylphenyl) phosphite is more preferable in terms of excellent heat-resistant stability. preferable.

The amount of the phosphorus antioxidant is not particularly limited, but is preferably in the range of 0.01 to 0.2 parts by weight with respect to 100 parts by weight of the thermoplastic resin material. If the blending amount is less than 0.01 parts by weight, there is a possibility that a sufficient heat stability improvement effect cannot be obtained even if a phosphorus-based antioxidant is blended. On the other hand, if the blending amount exceeds 0.1 parts by weight, an effect of improving the heat stability corresponding to the blending amount cannot be expected.

As described above, the thermoplastic recycled resin material according to the present embodiment is selected from the thermoplastic resin waste obtained by pulverizing waste home appliances and containing a plurality of types of resin materials, using a material identification device. The phenol-type antioxidant and the sulfur-type antioxidant are blended with a specific type of thermoplastic resin material obtained after the dry cleaning treatment.

When recycling thermoplastic resin materials from waste home appliances, the thermoplastic resin materials used in waste home appliances may deteriorate over time, or foreign substances may be mixed into the thermoplastic resin material selected for reuse. There is a risk that the physical properties such as the above will decrease, or the deterioration of physical properties may be promoted. On the other hand, in the present embodiment, deterioration of physical properties (or promotion of deterioration) is effectively suppressed by blending a phenol-based antioxidant and a sulfur-based antioxidant into the thermoplastic recycled resin material. . Thereby, the thermoplastic recycled resin material can be reused as a molded article of the recycled resin material through a molding process such as injection molding. Further, since the promotion of deterioration of physical properties can be effectively suppressed, the reused molded product can be used stably over a long period of time. In addition, when recycling recycled thermoplastic resin materials, good physical properties (durability, strength, impact resistance, etc.) can be realized without adding a large amount of virgin material. Can be improved.

[Modification]
In the present embodiment, the near-infrared identification system 20 shown in FIG. 3 is used in the resin material selection step shown in FIG. 1, but the present invention is not limited to this, and other known selection methods are also suitably used. be able to. For example, a specific type of thermoplastic resin material may be selected from the thermoplastic resin waste material by a water specific gravity selection method. For example, polyolefin such as polypropylene (PP) or polyethylene (PE) has a specific gravity lighter than water. If these polyolefins are used as resin materials for waste home appliances, these resin materials can be selected by a water specific gravity sorting method in the resin material sorting step.

Further, in the resin material sorting step, a specific type of thermoplastic resin material may be sorted from the thermoplastic resin waste material by using an electrostatic sorting method. For example, ABS resin and polystyrene (PS) are relatively close in specific gravity and cannot be sufficiently sorted by the water specific gravity sorting method, but these resin materials are different in the order of charge trains (charge permutation difference). Therefore, it is possible to sort these styrenic resins by electrostatic sorting using the difference between the charged columns. Therefore, in the resin material sorting step, the resin material may be sorted using at least one of the water specific gravity sorting method and the electrostatic sorting method, or a combination thereof, without using near infrared rays.

Note that it is difficult to eliminate the resin material containing bromine by the electrostatic sorting method. Therefore, when resin materials containing bromine are contained in waste home appliances, for example, a resin material can be sorted using a measuring device that can identify the bromine content, such as an X-ray sorting device. preferable.

In addition, as a method for selecting the ABS resin and PS, a water specific gravity selecting method using salt water or the like can be used. Compared with the waste plastic materials derived from waste home appliances, the specific gravity of polystyrene contained in the waste resin material is about 1.03 to 1.04, and the specific gravity of ABS resin is about 1.05 to 1.07. Many. Therefore, it is possible to sort ABS resin and PS with relatively high accuracy by using water with adjusted specific gravity such as salt water. However, even with a water specific gravity sorting method using salt water or the like, it is difficult to exclude a resin material containing bromine. Therefore, for example, it is preferable to use an X-ray sorting apparatus or the like together.

Further, in the present embodiment, the dry cleaning process is performed on the resin material after sorting obtained by the resin material sorting process without performing any other process. However, the present invention is not limited to this, and for example, the resin material after sorting may be further crushed with a crusher in the previous stage of the dry cleaning process.

As described above, if the sieving step is performed after the eddy current selection step, the size of the thermoplastic resin waste material (crushed pieces) is in the range of, for example, 5 to 150 mm. Thereafter, if the crushing step is performed again after performing the resin material selection step, the size of the resin material (resin piece) after the selection can be in the range of 2 to 50 mm. Thereby, since the variation in the size of the resin material after sorting is reduced, the antioxidant can be mixed more homogeneously in the subsequent antioxidant addition step (or the step of adding other additives or the like). . As a result, it is possible to reduce variations in physical properties of the obtained thermoplastic recycled resin material.

In the present embodiment, after the dry cleaning process is performed on the resin material after sorting, the sorting process after washing may be performed as necessary (that is, the sorting process after cleaning may not be performed). Good). In this post-cleaning sorting step, sorting steps such as wind sorting, magnetic sorting, electrostatic sorting and the like may be performed at least once. This also applies to the wind sorting process, magnetic sorting process, eddy current sorting process, and the like for producing thermoplastic resin waste.

That is, if there is little foreign matter mixed in the disassembly and disassembly process of the household electrical appliance and the subsequent crushing process, or if it is biased toward a specific type of foreign matter, the wind sorting process, the magnetic sorting process, and the vortex At least one of the current selection steps may not be performed. On the contrary, when foreign substances that cannot be removed by the wind sorting process, the magnetic sorting process, or the eddy current sorting process are included, other known sorting processes may be performed.

Further, in the present embodiment, the used refrigerator is exemplified as the waste home appliance, but the waste home appliance to which the present invention is applied is not limited to this. As described above, examples of the waste home appliance include a freezer, an air conditioner, or a washing machine in addition to the refrigerator. Therefore, the crushed material before the sorting step may be obtained from waste home appliances other than the refrigerator, or may be obtained from a plurality of types of waste home appliances including the refrigerator.

Also, for example, even if the type or model of the waste home appliance is different, the basic flow of the resin material regeneration process (or recycling process) shown in FIGS. 1 and 2 is the same. However, if the types or models of waste home appliances are different, the types of metal wastes and resin wastes that are collected separately are different. Therefore, some processes can be omitted from the regeneration process of FIGS. 1 and 2 or a new process can be added. For example, if the waste home appliance is a washing machine, since a heat insulating material such as urethane foam is unnecessary, there is no need for a wind-power sorting step for sorting urethane waste material. In addition, unlike a refrigerator, a washing machine does not use a refrigerant, so that it is not necessary to remove the refrigerant in the disassembly and disassembly processes.

(Embodiment 2)
In the first embodiment, a phenol-based antioxidant and a sulfur-based antioxidant are blended in the thermoplastic recycled resin material in order to avoid deterioration of physical properties of the thermoplastic recycled resin material or promotion of deterioration of physical properties. However, in Embodiment 2, a predetermined amount of metal deactivator is blended. This point will be specifically described with reference to FIG. FIG. 4 is a process diagram showing an example of a thermoplastic recycled resin material manufacturing process (resin material recycling process or recycling process) according to the second embodiment.

The process shown in FIG. 4 is the same as the process shown in FIG. 2 described in the first embodiment, and the “selected specific type of thermoplastic resin material” (resin material after selection) in FIG. Obtained by the same process. Moreover, since the dry cleaning process, the post-cleaning selection process, the heat-kneading and extrusion process, and the injection molding process in FIG. 4 are the same as those in the first embodiment, description thereof is omitted.

In the present embodiment, a metal deactivator addition step is performed in which a metal deactivator is added as a resin modifier after the dry cleaning step or the post-cleaning sorting step. In this metal deactivator addition step, the metal deactivator is added within a range of 0.01 to 1 part by weight with respect to 100 parts by weight of the resin material after sorting.

The metal deactivator added in the metal deactivator addition step is not particularly limited, but a known compound or composition can be suitably used. Specific examples of the metal deactivator include at least one compound selected from the group consisting of oxalic acid derivatives, salicylic acid derivatives, hydrazide derivatives, triazole derivatives, and imidazole derivatives.

Among these compounds, as the oxalic acid derivative, for example, as the oxalic acid derivative, oxalo-bis-1,2-hydroxybenzylidene hydrazide (trade name Eastman inhibitor OABH manufactured by Eastman Kodak), 2,2′- Oxamidobis (ethyl 3- (3,5-tert-butyl-4-hydroxyphenyl) propionate) (trade name Naugard® XL-1 manufactured by Shiraishi Calcium Co., Ltd.) and the like can be mentioned, but not particularly limited. Only one type of these compounds may be used, or two or more types may be used in appropriate combination.

Examples of the salicylic acid derivative include 3- (N-salicyloyl) amino-1,2,4-triazole (trade name Adeka Stab CDA-1 manufactured by ADEKA), decamethylenedicarboxylic acid disalicyloyl hydrazide (ADEKA). Examples thereof include, but are not limited to, the product name ADK STAB CDA-6) and salicylidene salicyloylhydrazine (trade name Chel-180 manufactured by BASF). Only one type of these compounds may be used, or two or more types may be used in appropriate combination.

Examples of the hydrazide derivative include N, N′-bis ((3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl)) propionohydrazide (trade name CDA- manufactured by ADEKA). 10), trade name Qunox manufactured by Mitsui Toatsu Fine Co. Only one type of these compounds may be used, or two or more types may be used in appropriate combination.

Examples of triazole derivatives include benzotriazole, 3-amino-1,2,4-triazole, 2-mercaptobenzotriazole, 2,5-dimercaptobenzotriazole, 4-alkylbenzotriazole, and 5-alkylbenzotriazole. 4,5,6,7-tetrahydrobenzotriazole, 5,5′-methylenebisbenzotriazole, 1- [di (2-ethylhexyl) aminomethyl] -1,2,4-triazole, 1- (1-butoxy Ethyl) -1,2,4-triazole, acylated 3-amino-1,2,4-triazole, and the like, but are not particularly limited. Only one type of these compounds may be used, or two or more types may be used in appropriate combination.

Examples of imidazole derivatives include 4,4′-methylenebis (2-undecyl-5-methylimidazole), bis [(N-methyl) imidazol-2-yl] carbinol octyl ether, and the like. Only one type of these compounds may be used, or two or more types may be used in appropriate combination.

In addition, among the compounds exemplified as the oxalic acid derivative, salicylic acid derivative, hydrazide derivative, triazole derivative, or imidazole derivative described above, one or more different types of derivatives can be used in combination as appropriate.

In this embodiment, the type of the thermoplastic resin material (resin material after sorting) to be sorted is not particularly limited, and may be various resin materials widely used in home appliances. As a typical thermoplastic resin material, as described in the first embodiment, a styrenic resin material or a polyolefin can be used. Since the specific types of polyolefin or styrene resin material are the same as those in the first embodiment, description thereof is omitted.

In this embodiment, when such a thermoplastic resin material is selected from the resin waste material and reused, the metal deactivator is blended in the range of 0.01 to 1 part by weight. By blending the metal deactivator in this amount, the physical properties, particularly durability, of the resulting thermoplastic recycled resin material can be greatly improved. In particular, if the thermoplastic resin material is a styrene resin material, the effect of improving the durability of the metal deactivator tends to be large.

The method for blending the metal deactivator in a predetermined blending amount in the metal deactivator adding step is not particularly limited. In the present embodiment, as in the first embodiment, for example, a metal deactivator is added to the resin material after sorting after washing, and a known mixing device such as a tumbler or a Henschel mixer is used. And a homogeneous mixing method.

After the metal deactivator addition step, the metal deactivator is dispersed in the resin material after selection in the heat-kneading and extruding steps as in the first embodiment. At this time, using a known extruder, the resin material after selection is heat-kneaded under predetermined conditions and extruded from the extruder, or it is preferable that the extruder is provided with a mesh filter. This is the same as the first embodiment.

Here, in the present embodiment, the heating temperature (cylinder temperature, die temperature, etc.) in the extruder is set to a temperature range of 180 to 240 ° C., for example, if the resin material after sorting is a styrene resin material. An example can be given. Further, the mesh filter mesh is preferably a mesh within the range of 40 to 200 mesh in the present embodiment.

As described above, the thermoplastic recycled resin material according to the present embodiment is selected from the thermoplastic resin waste obtained by pulverizing waste home appliances and containing a plurality of types of resin materials, using a material identification device. The metal deactivator is blended in the range of 0.01 to 1 part by weight with respect to 100 parts by weight of the thermoplastic resin material with respect to a specific type of thermoplastic resin material obtained after the dry cleaning treatment. It is the composition which consists of.

Generally, it is known that the deterioration of the resin material proceeds by auto-oxidation. Here, when a metal atom or metal ion is present in the resin material, the metal atom or metal ion acts as, for example, a redox catalyst. Thereby, since generation | occurrence | production of a radical increases in a resin material, the auto-oxidation of a resin material is accelerated | stimulated. Therefore, it is necessary to suppress the auto-oxidation of the resin material after sorting and to improve the durability. In addition, the filler or pigment that is an additive in the resin material may contain a metal component. These metal components can also deteriorate the resin material by the catalytic oxidation action.

In this embodiment, as described above, an appropriate amount of a metal deactivator is blended in the thermoplastic recycled resin material. Thereby, the metal deactivator can form a complex with a metal atom or metal ion and reduce its catalytic action. Therefore, the metal deactivator can suppress various deterioration reactions caused by the foreign matters contained in the resin component, and can also greatly delay the progress of the deterioration reaction. Therefore, a high-quality thermoplastic recycled resin material having good durability and stability can be obtained.

Thereby, the thermoplastic recycled resin material can be reused as a molded article of the recycled resin material through a molding process such as injection molding. Further, since the promotion of deterioration of physical properties can be effectively suppressed, the reused molded product can be used stably over a long period of time. In addition, when recycling recycled thermoplastic resin materials, good physical properties (durability, strength, impact resistance, etc.) can be realized without adding a large amount of virgin material. Can be improved.

Furthermore, in the present embodiment, an antioxidant may be used in combination as a resin modifier (resin modifying component) in addition to the metal deactivator. Examples of the antioxidant that can be used in combination include the phenol-based antioxidant described in the first embodiment, and both a phenol-based antioxidant and a sulfur-based antioxidant may be used in combination. Thereby, it becomes possible to improve the effect by the metal deactivator.

(Embodiment 3)
In the first embodiment, a phenol-based antioxidant and a sulfur-based antioxidant are blended with the thermoplastic recycled resin material. In the second embodiment, an appropriate amount of a metal deactivator is blended with the thermoplastic recycled resin material. On the other hand, in this Embodiment 3, the thermoplastic elastomer corresponding to a thermoplastic reproduction resin material is mix | blended. This point will be specifically described with reference to FIG. FIG. 5 is a process diagram showing an example of a thermoplastic recycled resin material manufacturing process (resin material recycling process or recycling process) according to the third embodiment.

The process shown in FIG. 5 is the same as the process shown in FIG. 2 described in the first embodiment or the process shown in FIG. 4 described in the second embodiment. The “thermoplastic resin material” (resin material after sorting) is obtained in the same process as in FIG. In addition, the dry cleaning process, the post-cleaning selection process, the heat-kneading and extrusion process, and the injection molding process in FIG.

In this embodiment, an elastomer addition step is performed in which a thermoplastic elastomer is added as a resin modifier after the dry cleaning step or the post-cleaning sorting step. In the elastomer addition step, as will be described later, a general-purpose resin material of the same system as the post-selection resin material can be added together with the thermoplastic elastomer.

The specific kind of the thermoplastic elastomer to be added is not particularly limited, but if the resin material after selection is a styrene resin material, it may be a styrene thermoplastic elastomer. The styrenic thermoplastic elastomer may be a polymer using styrene or a derivative thereof as a monomer and may be a rubber-like elastic body. Examples of the thermoplastic elastomer that is specifically affected by the present embodiment include a structure in which the molecular structure includes a polystyrene-based structure as a hard segment and a polydiene structure as a soft segment, or a combination of styrene and a diene monomer. Examples thereof include a hydrogenated product of a polymer.

Here, the polystyrene structure may be a polymer using styrene or a derivative thereof as a monomer. Specifically, for example, a homopolymer using only one kind of styrene or a derivative thereof, a copolymer using two or more kinds of styrene or a derivative thereof, or a styrene or a derivative thereof. It may be a copolymer obtained by polymerizing a derivative and another monomer. Moreover, the polydiene structure should just be a polymer containing a diene structure. Specifically, for example, polybutadiene (1,3-butadiene homopolymer), polyisoprene (2-methyl-1,3-butadiene (isoprene) homopolymer), butadiene and other monomers Examples thereof include a copolymer and a copolymer of isopylene and another monomer. Examples of the hydrogenated product of a copolymer of styrene and a diene monomer include a hydrogenated product of a styrene-butadiene block copolymer and a hydrogenated product of a styrene-isoprene block copolymer.

Further, the addition amount (blending amount) of the thermoplastic elastomer is not particularly limited. Depending on the physical properties of the resin material after sorting (thermoplastic resin material before modification), the specific type of thermoplastic elastomer, the physical properties required for the thermoplastic recycled resin material to be obtained, etc. Different. Therefore, it is preferable to appropriately adjust the addition amount according to the type of the resin material after selection and the type of the thermoplastic elastomer. Generally, the addition amount of the thermoplastic elastomer may be in the range of 3 to 20 parts by weight with respect to 100 parts by weight of the resin material after sorting.

If the addition amount of the thermoplastic elastomer is within the above range, the resulting thermoplastic recycled resin material can obtain good impact resistance. On the other hand, although depending on the type of thermoplastic elastomer and the like, if the added amount exceeds 20 parts by weight, for example, further improvement in impact resistance of the thermoplastic recycled resin material can be expected, but the strength tends to decrease. Moreover, if it is less than 3 weight part, the effect corresponding to the addition amount cannot be expected. Note that only one type of thermoplastic elastomer may be added, or two or more types may be added in appropriate combination.

Furthermore, in the present embodiment, general-purpose polystyrene (GPPS) may be added to the resin material after sorting together with the thermoplastic elastomer. This GPPS is preferably a recycled material. Specifically, for example, if the waste home appliance is a used refrigerator, GPPS derived from a vegetable compartment case, a refrigerator compartment case, a shelf and the like of the refrigerator can be cited. As described above, these can be obtained as a manually recovered resin waste material in the decomposition and dismantling process (see FIG. 1), and the manually recovered resin waste material crushed by a crusher may be used as the recycled GPPS.

The addition amount (blending amount) of GPPS is not particularly limited, the physical properties of the resin material after sorting (thermoplastic resin material before modification), the specific type of thermoplastic elastomer used together, and the thermoplastic recycled resin material obtained The amount of GPPS added varies depending on conditions such as physical properties required for the above. However, generally, it may be in the range of 10 to 50 parts by weight with respect to 100 parts by weight of the resin material after sorting.

When the amount of GPPS added exceeds 50 parts by weight, the strength of the thermoplastic recycled resin material can be expected to be further improved, but the impact resistance tends to decrease. On the other hand, if the amount is less than 10 parts by weight, an effect commensurate with the amount added cannot be expected. Therefore, the typical blending amount is preferably in the range of 3 to 20 parts by weight of the thermoplastic elastomer and in the range of 10 to 50 parts by weight of GPPS with respect to 100 parts by weight of the resin material after sorting. This makes it possible to achieve both good impact resistance and good strength in the resulting thermoplastic recycled resin material.

In addition, the styrene resin material selected by the near infrared identification system 20 shown in FIG. 3 may contain GPPS and high impact polystyrene (HIPS). If the waste home appliance is a used refrigerator and the selected styrenic resin material is composed of GPPS and HIPS, the proportions are, for example, 10 to 30% by weight of GPPS and 70 to 90% by weight of HIPS. As described above, if the GPPS ratio is large, the tensile strength and the bending strength are increased, but the impact resistance is decreased.

In this case, the physical properties of the resin material after sorting are measured in advance, and the addition amount of the thermoplastic elastomer and the addition amount of GPPS may be adjusted according to the obtained physical property results. Thereby, the addition amount of a thermoplastic elastomer or GPPS (or both) can be suitably adjusted according to the physical property requested | required of a thermoplastic reproduction resin material (or its molded article). Moreover, if the thermoplastic recycled resin material contains both GPPS and HIPS, it becomes easy to realize good strength and impact resistance.

In addition, in the phenol-based antioxidant and the sulfur-based antioxidant in the first embodiment as well as in the metal deactivator in the second embodiment, the addition amount can be adjusted by measuring the physical properties in advance. The point is the same as in the present embodiment.

Note that GPPS is not limited to a recycled material, and may be a virgin material. However, when a virgin material is used, the amount of GPPS added is preferably as small as possible. When there is too much addition amount of GPPS of a virgin material, the use ratio of a recycled material will fall. On the other hand, if GPPS is a recycled material as described above, the use ratio of the recycled material can be increased by setting the addition amount within the above range.

In the present embodiment, the type of thermoplastic resin material (resin material after sorting) to be selected is not particularly limited to the above-described styrenic resin material, and may be various resin materials widely used for home appliances such as polyolefin. May be. If the resin material after selection is a polyolefin, a polyolefin-based thermoplastic elastomer may be added, and a polyolefin recycled material may be used in the same manner as GPPS. In addition, since the kind of specific polyolefin or styrene resin material is the same as that of the said Embodiment 1, the description is abbreviate | omitted.

In the present embodiment, the method of blending the thermoplastic elastomer (and general-purpose polystyrene or the like) with a predetermined blending amount in the elastomer adding step is not particularly limited. In the present embodiment, as in the first embodiment, for example, a thermoplastic elastomer or the like is added to the resin material after sorting after washing, and a known mixing device such as a tumbler or a Henschel mixer is used. The method of mixing uniformly can be mentioned.

After the elastomer addition step, as in the first embodiment, a thermoplastic elastomer or the like is dispersed in the post-selection resin material in a heat-kneading and extrusion step. At this time, using a known extruder, the resin material after selection is heat-kneaded under predetermined conditions and extruded from the extruder, or it is preferable that the extruder is provided with a mesh filter. This is the same as the first embodiment.

Here, in the present embodiment, the heating temperature (cylinder temperature, die temperature, etc.) in the extruder is set to a temperature range of 200 to 220 ° C., for example, if the resin material after sorting is a styrene resin material. An example can be given. In the present embodiment, the mesh filter mesh is also preferably within the range of 30 to 100 mesh.

As described above, the thermoplastic recycled resin material according to the present embodiment is selected from the thermoplastic resin waste obtained by pulverizing waste home appliances and containing a plurality of types of resin materials, using a material identification device. In this configuration, at least a thermoplastic elastomer is blended with a specific type of thermoplastic resin material obtained after the dry cleaning treatment.

In the above configuration, at least a thermoplastic elastomer is blended with the thermoplastic recycled resin material, and preferably a general-purpose resin material similar to a specific type of thermoplastic resin material is blended. Thereby, the various deterioration reaction which the foreign material contained in a resin component, especially a metal atom or a metal ion causes can be suppressed. Specifically, if the resin material after sorting is a styrene resin material, the impact resistance of the resulting thermoplastic recycled resin material can be improved by adding a styrene thermoplastic elastomer. Moreover, the intensity | strength of the thermoplastic reproduction resin material obtained can be raised by adding general purpose polystyrene (GPPS). Therefore, a high-quality thermoplastic recycled resin material having good durability and stability can be obtained.

Thus, the thermoplastic recycled resin material can be reused as a molded product of the recycled resin material through a molding process such as injection molding. Further, since the promotion of deterioration of physical properties can be effectively suppressed, the reused molded product can be used stably over a long period of time. Furthermore, when the thermoplastic recycled resin material is reused, good physical properties (durability, strength, impact resistance, etc.) can be realized without adding a large amount of virgin material. And if the general purpose resin material used together is a recycled resin material, it is not necessary to mix | blend a virgin material. Therefore, the usage rate of recycled resources can be improved.

(Embodiment 4)
In the first embodiment, a phenol-based antioxidant and a sulfur-based antioxidant are blended with the thermoplastic recycled resin material. In the second embodiment, an appropriate amount of a metal deactivator is blended with the thermoplastic recycled resin material. On the other hand, in this Embodiment 4, in order to maintain or improve the flame retardancy among various physical properties, an appropriate amount of a brominated flame retardant and an auxiliary agent for several years are blended in the thermoplastic recycled resin material. This point will be specifically described with reference to FIG. FIG. 6 is a process diagram showing an example of a thermoplastic recycled resin material manufacturing process (resin material recycling process or recycling process) according to the fourth embodiment.

The process shown in FIG. 6 is the process shown in FIG. 2 described in the first embodiment, the process shown in FIG. 4 described in the second embodiment, or the process shown in FIG. 5 described in the third embodiment. The “sorted specific kind of thermoplastic resin material” (resin material after sorting) in FIG. 6 is obtained in the same process as in FIG. Further, since the dry cleaning process, the post-cleaning selection process, the heat-kneading and extrusion process, and the injection molding process in FIG. 6 are the same as those in the first embodiment, description thereof is omitted.

In the present embodiment, after the dry cleaning process or the post-cleaning selection process, a flame retardant addition process is performed in which a brominated flame retardant and an antimony flame retardant aid are added as resin modifiers. In this flame retardant addition step, the total amount of brominated flame retardant and antimony flame retardant aid is added within the range of 18 to 25 parts by weight with respect to 100 parts by weight of the resin material after sorting.

The brominated flame retardant added in the flame retardant addition step is not particularly limited, and a known compound can be suitably used as the flame retardant. Among these, preferable brominated flame retardants include decabromodiphenyl ether, tetrabromobisphenol A-bis (2,3-dibromopropyl ether), ethylene bis (tetrabromophthalimide), bis (pentabromophenyl) ethane, and the like. it can. One type of these brominated flame retardants may be used, or two or more types may be used in appropriate combination. Among these, tetrabromobisphenol A-bis (2,3-dibromopropyl ether) is particularly preferably used.

Also, the antimony flame retardant auxiliary added together with the brominated flame retardant in the flame retardant addition step is not particularly limited, and for example, antimony trioxide, antimony pentoxide, and the like are preferably used. Only one kind of these antimony flame retardant aids may be used, or two or more kinds may be used in appropriate combination.

The blending ratio of brominated flame retardant and antimony flame retardant aid is not particularly limited, but the weight of antimony flame retardant aid is in the range of 1/5 to 1/2 with respect to the total weight of brominated flame retardant. If it is in, it is preferable. In other words, the weight of brominated flame retardant: weight of antimony flame retardant aid = 4: 1 to 2: 1 is preferable.

In the present embodiment, a recycled resin material with lower sorting accuracy (referred to as “lower recycled resin material” for convenience) may be mixed with the sorted resin material. At this time, 30 parts by weight or more of the lower recycled resin material can be mixed with 100 parts by weight of the resin material after sorting. As a result, since the lower recycled resin material with low sorting accuracy can be reused together with the post-sorting resin material with high sorting accuracy, the recycling rate of the thermoplastic recycled resin material can be improved.

Here, when 30 parts by weight or more of the lower recycled resin material is mixed with the resin material after sorting, the total amount of brominated flame retardant and antimony flame retardant auxiliary added (blended) in the flame retardant addition step is The amount may be in the range of 13 to 17 parts by weight relative to 100 parts by weight of the resin material after sorting. That is, the preferred range of the addition amount of brominated flame retardant and antimony flame retardant aid is different between the case where only the resin material after sorting is regenerated and the case where the lower recycled resin material is used in combination.

In the present embodiment, the kind of thermoplastic resin material (resin material after sorting) to be selected can be either styrene resin material or polyolefin, as in the first to third embodiments. . One preferred type of resin is polypropylene, but the present invention is not particularly limited thereto.

In the resin material sorting step described above, various sorts of foreign matter may remain even in the resin material after sorting from which foreign matter (impurities) has been removed by the dry cleaning step. In addition, these foreign substances include flammable substances. If the thermoplastic recycled resin material contains a flame retardant, the thermoplastic recycled resin material is difficult to ignite even if it comes into contact with flames, but if flammable foreign matter is mixed in, the foreign matter may ignite. is there. Therefore, the presence of foreign matters not only affects various physical properties and durability of the thermoplastic recycled resin material, but also affects flame retardancy.

In contrast, in the present embodiment, an appropriate amount of bromine-based flame retardant and antimony-based flame retardant aid are blended in the flame retardant addition step. Thereby, the flame retardance of the resin material after sorting can be improved to the same extent as the flame retardancy of the virgin material. Thereby, the thermoplastic recycled resin material can be reused as a molded article of the recycled resin material through a molding process such as injection molding. Further, when the recycled thermoplastic resin material is reused, good flame retardancy can be realized without mixing a virgin material.

The present invention will be described more specifically based on examples, comparative examples, and reference examples, but the present invention is not limited thereto. Those skilled in the art can make various changes, modifications, and alterations without departing from the scope of the present invention. In addition, measurement / evaluation of physical properties and the like in the following examples, comparative examples, and reference examples were performed as follows.

(Measurement method of physical properties)
The tensile strength and the tensile elongation at break of each test piece obtained in each example, each comparative example, or reference example were measured according to JIS K7161 and JIS K7162. Similarly, the Izod impact value of each test piece was measured according to JIS K7110. Similarly, the bending test and bending elastic modulus of each test piece were measured according to JIS K7171.

In Example 15 and Comparative Examples 17 and 18, a boss strength test, which is an original evaluation method for verifying the strength of the molded product, was performed on each test piece. In this boss strength test, a male screw and a female screw portion screwed into the male screw were formed on the test piece. Then, the male screw was screwed and fastening and removal were repeated a predetermined number of times, and the number of times until the male screw could not be fastened (the number of times of fastening) was measured.

In Examples 16 and 17 and Comparative Examples 19 and 20, the flame retardancy of each test piece was evaluated according to the UL94V standard 20 mm vertical combustion test.

(Example 1)
As shown in FIG. 1, the collected used refrigerator was used as a waste home appliance. Each process shown in FIG. 1 (disassembly and dismantling process, crushing process, wind power sorting process, magnetic force sorting process, eddy current sorting process, etc.) shown in FIG. 1 is performed on this refrigerator to produce thermoplastic resin waste (shredder dust). did. From this thermoplastic resin waste material, high-impact polystyrene (HIPS) was selected using a near-infrared identification system 20 shown in FIG. 3 (resin material selection step). Then, the dry cleaning process shown in FIG. 2 was performed on this HIPS (resin material after sorting) (dry cleaning process). The washed HIPS was used as a raw material.

100 parts by weight of HIPS after washing, 0.1 part by weight of Sumilizer GA-80 (trade name, manufactured by Sumitomo Chemical Co., Ltd.) as a phenol-based antioxidant, and Sumilizer TP-D (commodity as a sulfur-based antioxidant) Name, manufactured by Sumitomo Chemical Co., Ltd.) and 0.1 part by weight of IRGAFOS168 (trade name, manufactured by BASF) as a phosphorus-based antioxidant were added and mixed (antioxidant addition step shown in FIG. 2). .

Then, while heating at 200 ° C. with an extruder, HIPS and each antioxidant were kneaded and extruded using a mesh filter of mesh size 60. In this way, pellets of HIPS as a thermoplastic recycled resin material were produced (heating kneading and extrusion process shown in FIG. 2). This pellet (thermoplastic recycled resin material) was injection molded under molding conditions of a molding temperature of 200 ° C. and a mold temperature of 30 ° C. to produce a test piece as a molded product (injection molding process shown in FIG. 2).

The physical properties (initial physical properties) of the obtained test pieces were measured. Thereafter, the test piece was left in an oven at 80 ° C. for 2000 hours (endurance test), and the subsequent physical properties (physical properties after the endurance test) were also measured and evaluated. Table 1 shows the rate of change between the initial physical properties and the physical properties after the durability test.

(Example 2)
0.067 parts by weight of Sumilizer GA-80 (trade name, manufactured by Sumitomo Chemical Co., Ltd.) as a phenolic antioxidant and 100 parts by weight of HIPS after cleaning, Sumizer TP-D (trade name, Sumitomo) as a sulfur-based antioxidant A test piece was produced in the same manner as in Example 1 except that 0.133 part by weight of Chemical) was added. About this test piece, it carried out similarly to Example 1, and measured the initial physical property and the physical property after an endurance test. Table 1 shows the rate of change of these physical properties.

(Example 3)
0.05 parts by weight of Sumilizer GA-80 (trade name, manufactured by Sumitomo Chemical Co., Ltd.) as a phenol-based antioxidant and 100 parts by weight of HIPS after cleaning, Sumizer TP-D (trade name, Sumitomo) as a sulfur-based antioxidant A test piece was produced in the same manner as in Example 1 except that 0.15 part by weight of Chemical) was added. About this test piece, it carried out similarly to Example 1, and measured the initial physical property and the physical property after an endurance test. Table 1 shows the rate of change of these physical properties.

Example 4
0.125 parts by weight of Sumilizer GA-80 (trade name, manufactured by Sumitomo Chemical) as a phenolic antioxidant and 100 parts by weight of HIPS after cleaning, Sumizer TP-D (trade name, Sumitomo) as a sulfur-based antioxidant A test piece was produced in the same manner as in Example 1 except that 0.375 part by weight of Chemical) was added. About this test piece, it carried out similarly to Example 1, and measured the initial physical property and the physical property after an endurance test. Table 1 shows the rate of change of these physical properties.

(Example 5)
For 100 parts by weight of HIPS after washing, 0.1 part by weight of IRGANOX245 (trade name, manufactured by BASF) is used as a phenolic antioxidant, and Sumizer TP-D (trade name, manufactured by Sumitomo Chemical) is used as a sulfur-based antioxidant. A test piece was produced in the same manner as in Example 1 except that 0.1 part by weight was added. About this test piece, it carried out similarly to Example 1, and measured the initial physical property and the physical property after an endurance test. Table 1 shows the rate of change of these physical properties.

(Example 6)
For 100 parts by weight of HIPS after washing, 0.1 part by weight of IRGANOX 1076 (trade name, manufactured by BASF) is used as a phenol-based antioxidant, and Sumizer TP-D (trade name, manufactured by Sumitomo Chemical) is used as a sulfur-based antioxidant. A test piece was produced in the same manner as in Example 1 except that 0.1 part by weight was added. About this test piece, it carried out similarly to Example 1, and measured the initial physical property and the physical property after an endurance test. Table 1 shows the rate of change of these physical properties.

(Example 7)
For 100 parts by weight of HIPS after washing, 0.05 parts by weight of IRGANOX 1076 (trade name, manufactured by BASF) is used as a phenol-based antioxidant, and Sumilizer TP-D (trade name, manufactured by Sumitomo Chemical) is used as a sulfur-based antioxidant. A test piece was produced in the same manner as in Example 1 except that 0.15 part by weight was added. About this test piece, it carried out similarly to Example 1, and measured the initial physical property and the physical property after an endurance test. Table 1 shows the rate of change of these physical properties.

(Example 8)
With respect to 100 parts by weight of HIPS after washing, 0.25 parts by weight of IRGANOX 1076 (trade name, manufactured by BASF) is used as a phenol-based antioxidant, and Sumilizer TP-D (trade name, manufactured by Sumitomo Chemical) is used as a sulfur-based antioxidant. A test piece was produced in the same manner as in Example 1 except that 0.25 part by weight was added. About this test piece, it carried out similarly to Example 1, and measured the initial physical property and the physical property after an endurance test. Table 1 shows the rate of change of these physical properties.

(Comparative Example 1)
Rather than using HIPS virgin material (trade name: H9152, manufactured by PS Japan) as a raw material, instead of selecting HIPS from thermoplastic resin waste (shredder dust) derived from waste home appliances and using it as a resin material after sorting Produced a test piece in the same manner as in Example 1. About this test piece, it carried out similarly to Example 1, and measured the initial physical property and the physical property after an endurance test. Table 1 shows the rate of change of these physical properties.

(Comparative Example 2)
Phenol antioxidant and sulfur antioxidant were not added to 100 parts by weight of HIPS after washing (that is, only IRGAFOS168 (trade name, manufactured by BASF), which is a phosphorus antioxidant, as an antioxidant) A test piece was produced in the same manner as in Example 1 except that 0.05 part by weight of (A) was added. About this test piece, it carried out similarly to Example 1, and measured the initial physical property and the physical property after an endurance test. Table 1 shows the rate of change of these physical properties.

(Comparative Example 3)
Example 1 except that 0.2 parts by weight of IRGANOX 1076 (trade name, manufactured by BASF) was added as a phenol-based antioxidant without adding a sulfur-based antioxidant to 100 parts by weight of HIPS after washing. A test piece was produced in the same manner. About this test piece, it carried out similarly to Example 1, and measured the initial physical property and the physical property after an endurance test. Table 1 shows the rate of change of these physical properties.

(Comparative Example 4)
Example 1 except that 0.5 parts by weight of IRGANOX 1076 (trade name, manufactured by BASF) was added as a phenol-based antioxidant without adding a sulfur-based antioxidant to 100 parts by weight of HIPS after washing. A test piece was produced in the same manner. About this test piece, it carried out similarly to Example 1, and measured the initial physical property and the physical property after an endurance test. Table 1 shows the rate of change of these physical properties.

(Comparative Example 5)
Example 1 with the exception that 1.0 part by weight of IRGANOX 1076 (trade name, manufactured by BASF) was added as a phenol-based antioxidant without adding a sulfur-based antioxidant to 100 parts by weight of HIPS after washing. A test piece was produced in the same manner as described above. About this test piece, it carried out similarly to Example 1, and measured the initial physical property and the physical property after an endurance test. Table 1 shows the rate of change of these physical properties.

(Comparative Example 6)
Except for adding 100 parts by weight of HIPS after washing, 0.2 parts by weight of Sumilizer GA-80 (trade name, manufactured by Sumitomo Chemical Co., Ltd.) was added as a phenolic antioxidant without adding a sulfur-based antioxidant. A test piece was produced in the same manner as in Example 1. About this test piece, it carried out similarly to Example 1, and measured the initial physical property and the physical property after an endurance test. Table 1 shows the rate of change of these physical properties.

(Comparative Example 7)
Except for adding 100 parts by weight of HIPS after washing without adding a sulfur-based antioxidant and adding 0.5 parts by weight of Sumilizer GA-80 (trade name, manufactured by Sumitomo Chemical) as a phenol-based antioxidant. A test piece was produced in the same manner as in Example 1. About this test piece, it carried out similarly to Example 1, and measured the initial physical property and the physical property after an endurance test. Table 1 shows the rate of change of these physical properties.

(Comparative Example 8)
The collected home air conditioner was used as a waste home appliance. A test piece was produced in the same manner as in Example 1 except that HIPS was recovered as a manually recovered resin waste material from this air conditioner and used as a raw material. About this test piece, it carried out similarly to Example 1, and measured the initial physical property and the physical property after an endurance test. Table 1 shows the rate of change of these physical properties.

(Comparative Example 9)
Except that the HIPS virgin material (trade name: H9152, manufactured by PS Japan) used in Comparative Example 1 and the thermoplastic recycled resin material obtained in Comparative Example 3 were mixed at 5: 5 to obtain raw materials. A test piece was produced in the same manner as in Example 1. About this test piece, it carried out similarly to Example 1, and measured the initial physical property and the physical property after an endurance test. Table 1 shows the rate of change of these physical properties.

(Comparative Example 10)
Example except that HIPS virgin material (trade name: H9152, manufactured by PS Japan) used in Comparative Example 1 and the thermoplastic recycled resin material obtained in Comparative Example 3 were mixed at 7: 3 to obtain raw materials. A test piece was produced in the same manner as in Example 1. About this test piece, it carried out similarly to Example 1, and measured the initial physical property and the physical property after an endurance test. Table 1 shows the rate of change of these physical properties.

(Contrast of Examples 1 to 8 and Comparative Examples 1 to 10)
From the results shown in Table 1, Examples 1 to 8 and Comparative Examples 1 to 10 are compared. First, in the test piece (virgin material) of Comparative Example 1, the elongation at break and the Izod impact value of the measured physical properties are hardly lowered. Moreover, the test piece of Comparative Example 2 (without adding a phenolic antioxidant and a sulfurous antioxidant) has a significantly reduced elongation at break and Izod impact value. Further, even in the test piece of Comparative Example 3 (in which an antioxidant contained in general HIPS is added in a general addition amount), the elongation at break and the Izod impact value are significantly reduced. From the results of these comparative examples, it is determined that the deterioration of physical properties of HIPS (thermoplastic recycled resin material) selected from the thermoplastic resin waste material of waste home appliances is accelerated.

Although the test piece of Comparative Example 8 (using HIPS manually collected from a domestic air conditioner) is not equivalent to the test piece of Comparative Example 1 (virgin material), the test of Comparative Example 2 or Comparative Example 3 It can be seen that the deterioration of the physical properties is small compared to the piece. From the results of these comparative examples, it is determined that hand-collected HIPS is less deteriorated in physical properties than HIPS selected using the near-infrared identification system 20.

The blending amount (addition amount) of the antioxidant contained in the test piece of Comparative Example 8 is about 60% of the antioxidant contained in the test piece of Comparative Example 3. From the results of these comparative examples, it is suggested that the HIPS selected using the near-infrared identification system 20 is greatly deteriorated, and therefore, foreign matter or the like may have an influence as a deterioration accelerating factor.

In addition, in the test piece of Comparative Example 9 and the test piece of Comparative Example 10 (the thermoplastic recycled resin material of Comparative Example 3 blended with 50% or more virgin material), the initial physical properties were improved. However, the physical properties after the durability test were greatly reduced compared to the initial physical properties. Therefore, from the results of Comparative Examples 3, 9, and 10, it is determined that the HIPS selected by the near infrared identification system 20 cannot sufficiently improve the decrease in durability even when the virgin material is blended.

In Comparative Examples 2 to 5, the amount of phenolic antioxidant added is gradually increased. In Comparative Examples 6 and 7, the addition amount of different types of phenolic antioxidants is changed (increased). From the physical properties of the test pieces of these comparative examples, it is judged that the decrease in physical properties tends to be suppressed if the amount of the phenolic antioxidant added is increased. Further, from the results of Comparative Examples 2 to 5 and Comparative Examples 6 and 7, even if the type of phenolic antioxidant is changed, the decrease in physical properties can be suppressed to the same extent, and it was used in Comparative Examples 6 and 7. The phenolic antioxidant (trade name Sumilizer GA-80 manufactured by Sumitomo Chemical) improves the deterioration of physical properties more than the phenolic antioxidant used in Comparative Examples 2 to 6 (trade name IRGANOX1076 manufactured by BASF). It is judged that the effect tends to be high.

Particularly, from the results of Comparative Example 5, by adding 1 part by weight of a phenolic antioxidant, deterioration of its physical properties is effectively suppressed although it is not equivalent to Comparative Example 1 (virgin material). Therefore, the durability can be greatly improved by adding a large amount of phenolic antioxidant. However, as an addition amount of the antioxidant to HIPS, the addition amount of 1 part by weight is generally judged to be considerably large.

In the test piece of Example 1, a phenol-based antioxidant and a sulfur-based antioxidant are added. Therefore, the test piece of Comparative Example 3 (in which an antioxidant contained in general HIPS is added in a general addition amount) or the test piece of Comparative Example 6 (in which only a phenolic antioxidant is added) ), The deterioration of physical properties is improved satisfactorily. Furthermore, in the test pieces of Example 2 and Example 3, the addition amount (blending amount) of the sulfur-based antioxidant is increased. In the test pieces of these Examples, even when compared with the test piece of Comparative Example 5 (one added with 1 part by weight of a phenolic antioxidant), the decrease in physical properties is improved more favorably.

Moreover, in the test piece of Example 4, although the total addition amount of a phenolic antioxidant and sulfur type antioxidant is increased, by this, to the same extent as the test piece (virgin material) of the comparative example 1, The decrease in physical properties has been greatly improved.

Further, in the test pieces of Examples 5 to 8, even when the type of phenolic antioxidant or sulfur antioxidant is changed or the amount of addition is changed, the physical properties are decreased as in Examples 1 to 4. It has been improved well. In particular, in the test piece of Example 8, even if the total amount of phenolic antioxidant or sulfur-based antioxidant was 0.5 parts by weight, the physical properties were the same as those of the test piece (virgin material) of Comparative Example 1. The decline has been improved. Further, from the physical properties of the test pieces of Examples 6 and 7, even if the raw material (resin material after sorting) is the same, there is a difference in the effect of improving the decrease in physical properties depending on the kind of the sulfur-based antioxidant. Therefore, in the sulfur-based antioxidant (or phenol-based antioxidant), the addition amount may be increased according to various conditions.

Example 9
As shown in FIG. 1, the collected used refrigerator was used as a waste home appliance. Each process shown in FIG. 1 (disassembly and dismantling process, crushing process, wind power sorting process, magnetic force sorting process, eddy current sorting process, etc.) shown in FIG. 1 is performed on this refrigerator to produce thermoplastic resin waste (shredder dust). did. From this thermoplastic resin waste material, an ABS resin was sorted using a near infrared ray identification system 20 shown in FIG. 3 (resin material sorting step). Then, the dry cleaning process shown in FIG. 2 was performed on this HIPS (resin material after sorting) (dry cleaning process). The washed ABS resin was used as a raw material.

100 parts by weight of the ABS resin after washing is phenolic antioxidant, 0.05 parts by weight of Sumilizer GA-80 (trade name, manufactured by Sumitomo Chemical Co., Ltd.) and Sumilyzer TP-D (product of sulfur-based antioxidants) Name, manufactured by Sumitomo Chemical Co., Ltd.) and 0.05 parts by weight of IRGAFOS168 (trade name, manufactured by BASF) as a phosphorus-based antioxidant were added and mixed (antioxidant addition step shown in FIG. 2). .

Then, while heating at 220 ° C. with an extruder, the ABS resin and each antioxidant were kneaded and extruded using a mesh filter of mesh size 60. This produced pellets of ABS resin as a thermoplastic recycled resin material (heating kneading and extruding steps shown in FIG. 2). This pellet (thermoplastic recycled resin material) was injection molded under molding conditions of a molding temperature of 230 ° C. and a mold temperature of 50 ° C. to produce a test piece as a molded product (injection molding process shown in FIG. 2).

The physical properties (initial physical properties) of the obtained test pieces were measured. Thereafter, the test piece was left in an oven at 80 ° C. for 3000 hours (endurance test), and the subsequent physical properties (physical properties after the endurance test) were also measured and evaluated. Table 2 shows the rate of change between the initial physical properties and the physical properties after the durability test.

(Comparative Example 11)
Rather than selecting ABS resin from waste thermoplastic resin (shredder dust) derived from waste home appliances and using it as a resin material after sorting, ABS resin virgin material (trade name: 700-X01, manufactured by Toray) is used as a raw material. A test piece was produced in the same manner as in Example 9 except that it was used. About this test piece, it carried out similarly to Example 9, and measured the initial physical property and the physical property after an endurance test. Table 2 shows the rate of change of these physical properties.

(Comparative Example 12)
Phenol antioxidant and sulfur antioxidant were not added to 100 parts by weight of ABS resin after washing (that is, IRGAFOS168 (trade name, manufactured by BASF, which is a phosphorus antioxidant as an antioxidant). A test piece was produced in the same manner as in Example 9 except that 0.05 part by weight of only) was added. About this test piece, it carried out similarly to Example 9, and measured the initial physical property and the physical property after an endurance test. Table 2 shows the rate of change of these physical properties.

(Comparative Example 13)
Without adding a sulfur-based antioxidant to 100 parts by weight of the ABS resin after washing, 0.1 part by weight of IRGANOX 1076 (trade name, manufactured by BASF) as a phenol-based antioxidant, as a phosphorus-based antioxidant A test piece was produced in the same manner as in Example 9 except that 0.05 part by weight of IRGAFOS168 (trade name, manufactured by BASF) was added. About this test piece, it carried out similarly to Example 9, and measured the initial physical property and the physical property after an endurance test. Table 2 shows the rate of change of these physical properties.

(Comparative Example 14)
For 100 parts by weight of the washed ABS resin, 0.1 part by weight of Sumilizer GA-80 (trade name, manufactured by Sumitomo Chemical Co., Ltd.) is added as a phenolic antioxidant without adding a sulfur-based antioxidant. A test piece was produced in the same manner as in Example 9, except that 0.05 part by weight of IRGAFOS168 (trade name, manufactured by BASF) was added as an antioxidant. About this test piece, it carried out similarly to Example 9, and measured the initial physical property and the physical property after an endurance test. Table 2 shows the rate of change of these physical properties.

(Contrast of Example 9 and Comparative Examples 11 to 14)
From the results shown in Table 2, Example 9 and Comparative Examples 11 to 14 (and the results of Table 1) are compared. In the test pieces of Comparative Examples 12 to 14 as well, the physical properties are deteriorated as in Comparative Examples 2 to 7 of Table 1, but the test pieces of Comparative Examples 13 and 14 and the test piece of Comparative Example 12 are used. In comparison, it is judged that the decrease in physical properties is improved by adding a phenolic antioxidant.

Furthermore, in the test piece of Example 9, since the phenolic antioxidant and the sulfur-based antioxidant are added, the deterioration of physical properties is improved as compared with the test pieces of Comparative Example 13 and Comparative Example 14. Moreover, in the test piece of Example 9, the physical properties are improved to the same extent as the test piece (virgin material) of Comparative Example 11.

(Example 10)
As shown in FIG. 1, the collected used refrigerator was used as a waste home appliance. Each process shown in FIG. 1 (disassembly and dismantling process, crushing process, wind power sorting process, magnetic force sorting process, eddy current sorting process, etc.) shown in FIG. 1 is performed on this refrigerator to produce thermoplastic resin waste (shredder dust). did. From this thermoplastic resin waste material, HIPS was selected using a near-infrared identification system 20 shown in FIG. 3 (resin material selection step). Then, the dry cleaning process shown in FIG. 4 was performed on this HIPS (resin material after sorting) (dry cleaning process). The washed HIPS was used as a raw material.

0.1 parts by weight of ADK STAB CDA-10 (trade name, manufactured by ADEKA) is added as a metal deactivator to 100 parts by weight of HIPS after washing, and IRGAFOS168 (trade name, BASF) is used as a phosphorus antioxidant. 0.05 part by weight was added and mixed (metal deactivator addition step shown in FIG. 4).

Then, while heating at 200 ° C. with an extruder, HIPS and each additive were kneaded and extruded using a mesh filter of mesh size 60. In this way, pellets of HIPS as a thermoplastic recycled resin material were produced (heat kneading and extrusion process shown in FIG. 4). This pellet (thermoplastic recycled resin material) was injection molded under molding conditions of a molding temperature of 200 ° C. and a mold temperature of 30 ° C. to produce a test piece as a molded product (injection molding process shown in FIG. 4).

The physical properties (initial physical properties) of the obtained test pieces were measured. Thereafter, the test piece was left in a constant temperature oven at 80 ° C. for 1000 hours (durability test), and the subsequent physical properties (physical properties after the durability test) were also measured and evaluated. Table 3 shows the rate of change between the initial physical properties and the physical properties after the durability test.

(Example 11)
A test piece was produced in the same manner as in Example 10, except that 0.1 part by weight of Adeka Stub CDA-1 (trade name, manufactured by ADEKA) was added as a metal deactivator to 100 parts by weight of HIPS after washing. did. About this test piece, it carried out similarly to Example 10, and measured the initial physical property and the physical property after an endurance test. Table 3 shows the rate of change of these physical properties.

Example 12
0.1 parts by weight of ADEKA STAB CDA-10 (trade name, manufactured by ADEKA) is added as a metal deactivator to 100 parts by weight of HIPS after washing, and IRGANOX 1076 (trade name, BASF) is used as a phenolic antioxidant. A test piece was produced in the same manner as in Example 10 except that 0.1 part by weight of the product was added. About this test piece, it carried out similarly to Example 10, and measured the initial physical property and the physical property after an endurance test. Table 3 shows the rate of change of these physical properties.

(Example 13)
0.1 parts by weight of ADK STAB CDA-1 (trade name, manufactured by ADEKA) as a metal deactivator is added to 100 parts by weight of HIPS after washing, and IRGANOX 1076 (trade name, A test piece was produced in the same manner as in Example 10 except that 0.1 part by weight of BASF was added. About this test piece, it carried out similarly to Example 10, and measured the initial physical property and the physical property after an endurance test. Table 3 shows the rate of change of these physical properties.

(Comparative Example 15)
Rather than using HIPS virgin material (trade name: H9152, manufactured by PS Japan) as a raw material, instead of selecting HIPS from thermoplastic resin waste (shredder dust) derived from waste home appliances and using it as a resin material after sorting Produced a test piece in the same manner as in Example 10. About this test piece, it carried out similarly to Example 10, and measured the initial physical property and the physical property after an endurance test. Table 3 shows the rate of change of these physical properties.

(Comparative Example 16)
No metal deactivator was added to 100 parts by weight of HIPS after washing (that is, 0.05 parts by weight of only IRGAFOS168 (trade name, manufactured by BASF) which is a phosphorus-based antioxidant as an antioxidant). A test piece was produced in the same manner as in Example 10 except that (added) was performed. About this test piece, it carried out similarly to Example 10, and measured the initial physical property and the physical property after an endurance test. Table 3 shows the rate of change of these physical properties.

(Contrast of Examples 10 to 13 and Comparative Examples 15 and 16)
From the results shown in Table 3, Examples 10 to 13 and Comparative Examples 15 and 16 are compared. First, in the test piece (virgin material) of Comparative Example 15, the elongation at break and the Izod impact value of the measured physical properties are hardly lowered. In addition, the tensile strength at break and the Izod impact value of the test piece of Comparative Example 16 (without the addition of a metal deactivator) are greatly reduced. From the results of these comparative examples, similar to the results of Comparative Examples 1 to 3 described above, HIPS (thermoplastic recycled resin material) selected from the waste thermoplastic resin materials of waste home appliances has greatly reduced (deteriorated) physical properties. It is judged that

On the other hand, the test pieces of Example 10 and Example 11 (those with 0.1 parts by weight of a metal deactivator) were compared with the test pieces of Comparative Example 16 (those without the addition of a metal deactivator). The drop is improved satisfactorily. In addition, in the test pieces of Example 12 and Example 13 (in which a metal deactivator and a phenolic antioxidant are used in combination), the deterioration of physical properties is further improved. Therefore, from the results of these examples, a more excellent effect can be achieved by using a metal deactivator and a phenolic antioxidant together as the resin modifier. In addition, it is expected that even more excellent effects can be achieved by using a metal deactivator, a phenolic antioxidant, and a sulfurous antioxidant in combination.

(Example 14)
As shown in FIG. 1, the collected used refrigerator was used as a waste home appliance. Each process shown in FIG. 1 (disassembly and dismantling process, crushing process, wind power sorting process, magnetic force sorting process, eddy current sorting process, etc.) shown in FIG. 1 is performed on this refrigerator to produce thermoplastic resin waste (shredder dust). did. From this thermoplastic resin waste material, HIPS was selected using a near-infrared identification system 20 shown in FIG. 3 (resin material selection step). Then, the dry cleaning process shown in FIG. 5 was performed on this HIPS (resin material after sorting) (dry cleaning process). The washed HIPS was used as a raw material.

6 parts by weight of TR2000 (trade name, manufactured by JSR) as a thermoplastic elastomer was added to and mixed with 100 parts by weight of HIPS after washing (elastomer addition step shown in FIG. 5).

Then, while heating at 200 ° C. with an extruder, HIPS and thermoplastic elastomer were kneaded and extruded using a mesh filter of mesh size 60. In this way, pellets of HIPS as a thermoplastic recycled resin material were produced (heating kneading and extrusion process shown in FIG. 5). This pellet (thermoplastic recycled resin material) was injection molded under molding conditions of a molding temperature of 200 ° C. and a mold temperature of 30 ° C. to produce a test piece as a molded product (injection molding step shown in FIG. 5).

The physical properties (initial physical properties) of tensile strength, tensile breaking elongation, Izod impact value, bending strength, and bending elastic modulus were measured for the obtained test pieces. The results are shown in Table 4.

(Reference example)
A test piece was produced in the same manner as in Example 14 except that 30 parts by weight of general-purpose polystyrene (GPPS) manually collected from the refrigerator was added to 100 parts by weight of HIPS after washing. Each physical property of this test piece was measured in the same manner as in Example 14. The results are shown in Table 4.

(Example 15)
6 parts by weight of TR2000 (trade name, manufactured by JSR) as a thermoplastic elastomer is added to 100 parts by weight of HIPS after washing, and 30 parts by weight of general-purpose polystyrene (GPPS) manually collected from the refrigerator is added. Produced a test piece in the same manner as in Example 14. Each physical property of this test piece was measured in the same manner as in Example 14. The results are shown in Table 4. A boss strength test was also performed on the test piece of Example 15. The results are shown in Table 5.

(Comparative Example 17)
Rather than using HIPS virgin material (trade name: H9152, manufactured by PS Japan) as a raw material, instead of selecting HIPS from thermoplastic resin waste (shredder dust) derived from waste home appliances and using it as a resin material after sorting Produced a test piece in the same manner as in Example 14. Each physical property of this test piece was measured in the same manner as in Example 14. The results are shown in Table 4. A boss strength test was also performed on the test piece of Comparative Example 17. The results are shown in Table 5.

(Comparative Example 18)
Test piece in the same manner as in Example 14 except that the thermoplastic elastomer was not added to 100 parts by weight of HIPS after washing (that is, only HIPS selected by the near infrared identification system 20 was used as a raw material). Manufactured. About this test piece, it carried out similarly to Example 14, and measured the initial physical property and the physical property after an endurance test. Table 4 shows the rate of change of these physical properties. A boss strength test was also performed on the test piece of Comparative Example 18. The results are shown in Table 5.

(Comparison of Examples 14 and 15, Reference Examples and Comparative Examples 17 and 18)
From the results shown in Tables 4 and 5, Examples 14, 15 and Reference Examples and Comparative Examples 17, 18 are compared. The test piece of Comparative Example 18 (HIPS selected by the near-infrared identification system 20) has a lower Izod impact value than the test piece of Comparative Example 17 (virgin material). In addition, the test piece of Example 14 (added with a thermoplastic elastomer) has a lower Izod impact value than the test piece of Comparative Example 1, although the tensile strength and bending strength are low. In addition, the test piece of the reference example (with the manually collected GPPS added) has higher tensile strength and bending strength than the test piece of Comparative Example 1.

Furthermore, although the impact resistance of the test piece of Example 15 (added with the thermoplastic elastomer and GPPS) is slightly lower than that of the test piece of Example 14, it is lower than that of the test piece of Comparative Example 1. It is high. In addition, the test piece of Example 15 has higher tensile strength and bending strength than the test piece of Example 14.

In addition, when the result of the boss strength test is seen, the test piece of Comparative Example 18 is compared with the test piece of Comparative Example 17 (virgin material) and the test piece of Comparative Example 18 (HIPS selected by the near infrared identification system 20). The male screw cannot be fastened with a significantly smaller number of times than the test piece of Comparative Example 17. On the other hand, in the test piece of Example 15, fastening is not impossible even if the male screw is repeated 10 times or more. Therefore, the thermoplastic recycled resin material to which the thermoplastic elastomer and GPPS are added can have a boss strength equal to or higher than that of the virgin material.

Thus, by adding a small amount of thermoplastic elastomer, the impact resistance of the thermoplastic recycled resin material is improved satisfactorily, and by adding an appropriate amount of GPPS, each physical property including impact resistance is balanced overall. Well improved. Therefore, at least by improving the impact resistance (preferably by improving each physical property in a well-balanced manner), it is possible to reuse the thermoplastic recycled resin material as a resin material of the same level as the virgin material. Become.

Also, the boss strength is improved in the thermoplastic recycled resin material modified by adding thermoplastic elastomer and GPPS. Therefore, the thermoplastic recycled resin material can be reused as a component that requires boss strength. For example, in an air conditioner for home use, a good boss strength is required for an air filter frame of an indoor unit. Therefore, the modified thermoplastic recycled resin material can also be used for molded products that could not be conventionally used.

(Example 16)
As shown in FIG. 1, the collected used refrigerator was used as a waste home appliance. Each process shown in FIG. 1 (disassembly and dismantling process, crushing process, wind power sorting process, magnetic force sorting process, eddy current sorting process, etc.) shown in FIG. 1 is performed on this refrigerator to produce thermoplastic resin waste (shredder dust). did. From this thermoplastic resin waste material, polypropylene was sorted using the near infrared ray identification system 20 shown in FIG. 3 (resin material sorting step). Thereafter, the polypropylene (resin material after sorting) was subjected to a dry cleaning process shown in FIG. 6 (dry cleaning process). This washed polypropylene was used as a raw material.

15 parts by weight of tetrabromobisphenol A-bis (2,3-dibromopropyl ether) is added as a brominated flame retardant to 100 parts by weight of the washed polypropylene, and trioxide as an antimony flame retardant aid. 5 parts by weight of antimony was added (total amount of flame retardant and flame retardant aid: 20 parts by weight) and mixed (flame retardant addition step shown in FIG. 6).

Thereafter, the polypropylene and each additive were kneaded while being heated at 200 ° C. by an extruder, and extruded using a mesh filter having a mesh size of 60. Thus, polypropylene pellets as a thermoplastic recycled resin material were produced (heating kneading and extruding steps shown in FIG. 6). This pellet (thermoplastic recycled resin material) was injection molded under molding conditions of a molding temperature of 220 ° C. and a mold temperature of 40 ° C., and a test piece (length 125 mm × width 13 mm × thickness 0.8 mm) as a molded product was obtained. Manufactured (injection molding step shown in FIG. 6). About the obtained test piece, the flame retardance evaluation mentioned above was performed. The results are shown in Table 6.

(Example 17)
40 parts by weight of polypropylene extrusion molding waste (lower recycled resin material) is mixed with 100 parts by weight of the polypropylene resin material after sorting and tetrabromobisphenol A-bis (2,3-dibromopropyl ether). A test piece was produced in the same manner as in Example 16 except that 10 parts by weight and 4 parts by weight of antimony trioxide were added (total amount of flame retardant and flame retardant aid: 14 parts by weight). This test piece was evaluated for flame retardancy in the same manner as in Example 16. The results are shown in Table 6.

(Comparative Example 19)
Rather than selecting polypropylene from waste thermoplastic resin waste material (shredder dust) derived from waste home appliances and using it as a resin material after selection, polypropylene virgin material (trade name: J750HP, manufactured by Prime Polymer Co., Ltd.) is used as a raw material. Test piece as in Example 16, except that bromine-based flame retardant and antimony-based flame retardant auxiliary were added in the same amount as in Example 17 (total amount of flame retardant and flame retardant auxiliary: 14 parts by weight) Manufactured. This test piece was evaluated for flame retardancy in the same manner as in Example 16. The results are shown in Table 6.

(Comparative Example 20)
Example 1 except that 10 parts by weight of tetrabromobisphenol A-bis (2,3-dibromopropyl ether) and 4 parts by weight of antimony trioxide were added (total amount of flame retardant and flame retardant aid: 14 parts by weight). A test piece was produced in the same manner as in FIG. This test piece was evaluated for flame retardancy in the same manner as in Example 16. The results are shown in Table 6.

(Contrast of Examples 16 and 17 and Comparative Examples 19 and 20)
From the results shown in Table 6, Examples 16 and 17 and Comparative Examples 19 and 20 are compared. In both the test pieces of Examples 16 and 17, it is possible to achieve the flame resistance of the UL94V standard. In addition, the test piece of Comparative Example 20 in which the addition amount (blending amount) of the flame retardant and the flame retardant aid is less than the appropriate amount (18 to 25 parts by weight) is more flame retardant than the test piece of Example 16 to which the appropriate amount was added. The sex is inferior. Therefore, when the flame retardant and the flame retardant aid are added at the same ratio as the virgin material (Comparative Example 19), the amount of addition is increased even if the same level of flame retardancy as the virgin material cannot be realized (Comparative Example 20). If it is made, it is possible to implement | achieve the flame retardance comparable as a virgin material (Example 16).

Furthermore, when the test piece of Example 17 and the test piece of Comparative Example 19 are compared, the amounts of the flame retardant and the flame retardant aid are the same, and 40 parts by weight of the lower recycled resin material is mixed (implementation) Even in Example 18), it can be seen that flame retardancy comparable to that of the virgin material (Comparative Example 19) can be realized.

From the above description, many modifications and other embodiments of the present invention are apparent to persons skilled in the art. Accordingly, the foregoing description should be construed as illustrative only and is provided for the purpose of teaching those skilled in the art the best mode of carrying out the invention. The details of the structure and / or function may be substantially changed without departing from the spirit of the invention.

The present invention can be widely and suitably used in the field of recycling specific types of thermoplastic resin materials from waste home appliances.

DESCRIPTION OF SYMBOLS 1 Conveying device 2 Thermoplastic resin material 3 Other resin material 4 Near infrared identification device (material identification device)
5 Discharge port 6 Sorting plate 8 Tube 11 Waste thermoplastic resin 14 Control section (control means)
15 Air pressure source 20 Near infrared identification system

Claims

A specific type of thermoplastic resin material obtained from a waste plastic product obtained from crushed waste home appliances, which is mixed with a plurality of types of resin materials, selected using a material identification device and dry-cleaned. On the other hand, a phenolic antioxidant and a sulfur antioxidant are blended,
Thermoplastic recycled resin material.
A specific type of thermoplastic resin material obtained from a waste plastic product obtained from crushed waste home appliances, which is mixed with a plurality of types of resin materials, selected using a material identification device and dry-cleaned. for,
A metal deactivator is blended within a range of 0.01 to 1 part by weight with respect to 100 parts by weight of the thermoplastic resin material.
Thermoplastic recycled resin material.
A specific type of thermoplastic resin material obtained from a waste plastic product obtained from crushed waste home appliances, which is mixed with a plurality of types of resin materials, selected using a material identification device and dry-cleaned. In contrast, a thermoplastic elastomer is blended.
Thermoplastic recycled resin material.
A specific type of thermoplastic resin material obtained from a waste plastic product obtained from crushed waste home appliances, which is mixed with a plurality of types of resin materials, selected using a material identification device and dry-cleaned. for,
A bromine-based flame retardant and an antimony-based flame retardant aid are blended within a range of 18 to 25 parts by weight with respect to 100 parts by weight of the thermoplastic resin material.
Thermoplastic recycled resin material.
A specific type of thermoplastic resin material obtained from a waste plastic product obtained from crushed waste home appliances, which is mixed with a plurality of types of resin materials, selected using a material identification device and dry-cleaned. for,
30 parts by weight or more of the same recycled resin material with lower sorting accuracy is blended with 100 parts by weight of the thermoplastic resin material, and with respect to 100 parts by weight of the thermoplastic resin material, a brominated flame retardant and Antimony flame retardant aid is blended in the range of 13 to 17 parts by weight,
Thermoplastic recycled resin material.
The total amount of the phenolic antioxidant and the sulfur antioxidant is in the range of 0.01 to 2.0 parts by weight with respect to 100 parts by weight of the thermoplastic resin material.
The thermoplastic recycled resin material according to claim 1.
The mixing ratio of the phenolic antioxidant and the sulfurous antioxidant is in the range of 1: 1 to 1: 4 by weight.
The thermoplastic recycled resin material according to claim 1 or 6.
As the metal deactivator, at least one compound selected from the group consisting of oxalic acid derivatives, salicylic acid derivatives, hydrazide derivatives, triazole derivatives, and imidazole derivatives is blended,
The thermoplastic recycled resin material according to claim 2.
The amount of the thermoplastic elastomer is in the range of 3 to 20 parts by weight with respect to 100 parts by weight of the thermoplastic resin material.
The thermoplastic recycled resin material according to claim 3.
As the brominated flame retardant, at least tetrabromobisphenol A-bis (2,3-dibromopropyl ether) is used.
The thermoplastic recycled resin material according to claim 4 or 5.
The thermoplastic resin material is a styrenic resin material or a polyolefin,
The thermoplastic recycled resin material according to any one of claims 1 to 10.
Furthermore, the styrenic resin material is at least one of general-purpose polystyrene and high-impact polystyrene.
The thermoplastic recycled resin material according to claim 11.
When the thermoplastic resin material is a styrene resin material, the thermoplastic elastomer is a styrene elastomer.
The thermoplastic recycled resin material according to claim 11.
Furthermore, general-purpose polystyrene is blended with the styrene-based elastomer,
The thermoplastic recycled resin material according to claim 13.
The general-purpose polystyrene is a recycled material obtained from the waste home appliance,
The blending amount of the general-purpose polystyrene is in the range of 10 to 50 parts by weight with respect to 100 parts by weight of the thermoplastic resin material.
The thermoplastic recycled resin material according to claim 14.
The material identification device is a near infrared identification device,
The thermoplastic recycled resin material according to any one of claims 1 to 15.
The waste home appliance is at least one home appliance selected from the group consisting of a refrigerator, a freezer, an air conditioner, and a washing machine;
The thermoplastic recycled resin material according to any one of claims 1 to 16.
Using a material identification device, select from thermoplastic resin waste material that is obtained from crushed waste home appliances and contains multiple types of resin materials.
The selected specially-designed thermoplastic resin material is dry-cleaned,
For the thermoplastic resin material after dry cleaning, a phenol-based antioxidant and a sulfur-based antioxidant, or a metal deactivator, or a thermoplastic elastomer is blended as a resin modifier.
A method for producing a thermoplastic recycled resin material.