JP2021014532A - Product including resin part and recycle system thereof - Google Patents

Abstract

To provide a product including resin parts and a recycle system without influencing characteristics of the resin part in recycling and with means for easily determining deterioration state of the collected resin from production to collection.SOLUTION: A product including resin parts includes resin parts collected and reused after use. Fluorescent is applied to the resin parts forming a jacket surface of the product. The fluorescent emits light when light of a specified wavelength is irradiated and the light emitting volume decreases with time by ultraviolet rays exposure.SELECTED DRAWING: Figure 1

Description

The present invention relates to a product including resin parts and a recycling system thereof. More specifically, the present invention relates to a product containing a resin part and a recycling system thereof, which does not affect the characteristics of the resin part at the time of recycling and has a means for easily determining the deterioration state from the time of production to the time of recovery of the recovered resin. ..

The state of deterioration of the recovered resin parts differs depending on the usage status of the product. For example, those used outdoors for a long period of time are severely deteriorated by ultraviolet rays, whereas those used indoors for a short period of time far from the window are less deteriorated. Since it is difficult to visually determine the state of deterioration of these parts, if the resin parts that are severely deteriorated are recycled, the strength of the recycled resin and parts will be reduced. On the other hand, if the degree of deterioration is to be investigated for each resin part in advance, it is necessary to measure the molecular weight of the resin and evaluate the strength, which requires a great deal of time and cost, and a recycling system cannot be established.

Therefore, there is a need for a means for easily determining the deteriorated state of the recovered resin.

Patent Document 1 discloses a recycling treatment method in which data for determining a disposal treatment method and a treatment method is displayed on a product in advance, and as the means, numbers, letters, and barcodes are used with dyes and pigments. -It is a method of recording information by color. Although the labeling method using a fluorescent agent is also described, the type of fluorescent agent and the coating method are not specified, and the deterioration of the product from the time of production to the time of collection should be grasped and the treatment method should be selected accordingly. It is not a deterioration evaluation method and a recycling system.

In Patent Document 2, the information presenting substance is mixed (kneaded) in the resin at the time of recycling, and the content of the information presenting substance is detected at the time of the next recycling, thereby increasing the number of reproductions and A system that detects the usage rate of recycled parts and selects a resin recycling method including modification is disclosed. Fluorescent substances are mentioned as information presenting substances, and light intensity measurement is mentioned as a detection method.

However, the technique disclosed in the above patent document mainly aims to grasp what kind of material (for example, the number of times of regeneration, the usage rate of recycled parts, etc.) is used for the recovered material. Is. When an information presenting substance is detected in the resin, one of the reforming treatments determined in advance in several stages is selected according to the content of the information presenting substance, and the selected modification is applied to the resin. It is a system that controls the reforming means.

Therefore, the above-mentioned patent document is not a recycling system that individually grasps the deterioration of resin parts from the time of production to the time of collection and selects a treatment method according to the deterioration. In particular, the fluorescent agent as the information presenting substance does not take into consideration the deterioration of the fluorescent agent (change in the amount of light emitted) when the product is used. In addition, the information presenting substance is added at the time of kneading in the recycling process, and it is expected that the amount of the information presenting substance is large so that it can be detected after recovery. Therefore, for example, the information presenting substance such as a fluorescent agent is mixed. It does not take into account the deterioration of the characteristics of resin parts due to the above.

Therefore, the emergence of products containing resin parts and their recycling systems, which do not affect the characteristics of resin parts during recycling and have a means for easily determining the deterioration state of the resin from the time of production to the time of collection, is awaited. There is.

Japanese Unexamined Patent Publication No. 8-323337 JP-A-2007-112017

The present invention has been made in view of the above problems and situations, and the solution to the problem is to simplify the deterioration state of the recovered resin from the time of production to the time of recovery without affecting the characteristics of the resin parts at the time of recycling. It is to provide a product containing a resin part having a means for making a judgment and a recycling system thereof.

In order to solve the above problems, the present inventor is a product containing resin parts that are collected and reused after use in the process of examining the cause of the above problems, and constitutes the exterior surface of the product. A fluorescent agent is applied to the resin parts, and when the resin parts are irradiated with light of a specific wavelength, the fluorescent agent emits light, and the amount of light emitted decreases with time due to exposure to ultraviolet rays, so that the characteristics of the resin parts during recycling It was found that a product containing resin parts and a recycling system thereof can be obtained without affecting the above-mentioned conditions and having a means for easily determining the deterioration state from the time of production to the time of recovery of the recovered resin.

That is, the above problem according to the present invention is solved by the following means.

1. 1. A product containing resin parts that are collected and reused after use.
A fluorescent agent is applied to the resin parts constituting the exterior surface of the product.
A product containing a resin component, characterized in that the fluorescent agent emits light when irradiated with light of a specific wavelength, and the amount of light emitted decreases with time due to exposure to ultraviolet rays.

2. 2. The fluorescent agent is applied to any of the resin parts constituting the upper surface, the corner surface, and the exterior surface within the range of the side surface of the product, which is irradiated with ambient light when the product is used. A product containing the resin parts according to the first item.

3. 3. The fluorescent agent is applied to all of the resin parts constituting the upper surface, the corner surface, and the exterior surface within the range of the side surface of the product, which is irradiated with ambient light when the product is used. A product containing the resin parts according to the first or second paragraph.

4. The fluorescent agent is applied to all a plurality of places of the resin parts constituting the upper surface, the corner surface and the exterior surface within the range of the side surface of the product to which ambient light is irradiated when the product is used. A product containing the resin parts according to any one of the items 1 to 3, characterized by the above.

5. The amount of fluorescent light emitted by the fluorescent agent after a light irradiation test corresponding to outdoor exposure for 10 years using a xenon arc light source is in the range of 10 to 80% as compared with the amount of fluorescent light emitted before light irradiation. A product containing the resin parts according to any one of the items 1 to 4, which is characterized by the above.

6. A product containing the resin component according to any one of items 1 to 5, wherein the coating amount of the fluorescent agent is 0.0005 g or more per 1 cm ² .

7. A product containing the resin component according to any one of items 1 to 6, wherein the application range of the fluorescent agent is 0.5 cm × 0.5 cm or more.

8. A product containing the resin component according to any one of items 1 to 7, wherein the fluorescent agent is transparent under visible light.

9. A product containing the resin component according to any one of items 1 to 8, wherein the fluorescent agent emits visible light when irradiated with ultraviolet rays.

10. A recycling system for products containing resin parts, which recycles products containing the resin parts according to any one of paragraphs 1 to 9.
A product containing a resin part, which comprises a step of evaluating the degree of deterioration of the resin part by irradiating the fluorescent agent applied to the resin part with ultraviolet rays and measuring the amount of fluorescence emission. Recycling system.

11. The method for recycling a product containing a resin part according to Item 10, wherein the step following the step of evaluating the degree of deterioration includes a step of removing the fluorescent agent and other impurities from the resin.

12. When the resin parts are coated with fluorescent agents at a plurality of places and the evaluation results of the respective deterioration degrees are different, the resin parts are characterized by having a step of determining the evaluation results having a large degree of deterioration as the deterioration degree of the parts. A method for recycling a product containing the resin parts according to item 10.

A product containing a resin part provided with a means for easily determining the deterioration state from the time of production to the time of recovery of the recovered resin without affecting the characteristics of the resin part during recycling by the above means of the present invention. A recycling system can be provided.

In the recycling system of the present invention, when a used product is collected from the market and decomposed into a single component, the amount of light emitted by the fluorescent agent pre-applied to the exterior surface by irradiating with ultraviolet rays (also referred to as fluorescence emission amount). It is considered that the degree of deterioration of the resin part can be determined from the correlation data between the amount of light emitted and the degree of deterioration of the resin part prepared in advance by measuring.).

That is, as compared with the methods disclosed in Patent Documents 1 and 2 described above, the fluorescent agent according to the present invention is mainly used for grasping the degree of deterioration of resin parts from the time of production to the time of recovery. It is intended and does not enter information that is known in advance at the time of production.

Further, in the recycling system of the present invention, since the fluorescent agent is selectively applied to a part of the surface of the component, the amount of light emitted can be secured with a small amount of the fluorescent agent, and the resin component is not mixed (kneaded). Resin parts are made of resin because the physical properties do not deteriorate, the fluorescent agent is removed after the evaluation, so that foreign matter is hardly mixed in the recycled resin, and the fluorescent agent that could not be completely removed also adds a metal stabilizer during kneading. It has advantages such as being able to suppress deterioration of physical properties of.

Schematic diagram showing the application position of the fluorescent agent Schematic diagram showing the process flow of the recycling system of the present invention An example of a measuring device that measures the amount of fluorescent light emitted by irradiating the fluorescent agent of the recovered resin with ultraviolet rays. Schematic diagram explaining the principle of the resin deterioration evaluation test method

The product containing the resin parts of the present invention is a product containing the resin parts that are collected and reused after use, and the resin parts constituting the exterior surface of the product are coated with a fluorescent agent. The fluorescent agent emits light when irradiated with light of a specific wavelength, and the amount of light emitted decreases with time due to exposure to ultraviolet rays. This feature is a technical feature common to or corresponding to the following embodiments.

In an embodiment of the present invention, from the viewpoint of exhibiting the effect of the present invention, the resin constituting the outer surface within the range of the upper surface, the corner surface and the side surface of the product to which ambient light is irradiated when the product is used. It is preferable that the fluorescent agent is applied to any of the manufactured parts from the viewpoint of improving the evaluation accuracy of the degree of deterioration.

In addition, the fluorescent agent is applied to all of the resin parts constituting the upper surface, the corner surface, and the exterior surface within the range of the side surface of the product, which is irradiated with ambient light when the product is used. However, it is preferable from the viewpoint of improving the accuracy of evaluation.

The fluorescent agent is applied to all a plurality of places of the resin parts constituting the upper surface, the corner surface and the exterior surface within the range of the side surface of the product which is irradiated with ambient light when the product is used. This is preferable from the viewpoint of improving the evaluation accuracy of the degree of deterioration.

The amount of fluorescent light emitted by the fluorescent agent after a light irradiation test corresponding to outdoor exposure for 10 years using a xenon arc light source is in the range of 10 to 80% as compared with the amount of fluorescent light emitted before light irradiation. This is preferable from the viewpoint of improving the evaluation accuracy of the degree of deterioration.

The viewpoint that the coating amount of the fluorescent agent is 0.0005 g or more per 1 cm ² and the coating range of the fluorescent agent is 0.5 cm × 0.5 cm or more improves the evaluation accuracy of the degree of deterioration. Therefore, it is preferable.

It is preferable that the fluorescent agent is transparent under visible light from the viewpoint of not affecting the appearance of the product during use.

It is preferable that the fluorescent agent emits visible light by irradiating it with ultraviolet rays from the viewpoint of expanding the selection of evaluation equipment.

The recycling system for products containing resin parts of the present invention includes a step of evaluating the degree of deterioration of resin parts by irradiating a fluorescent agent applied to the resin parts with ultraviolet rays and measuring the amount of fluorescent light. It is characterized by.

Further, it is preferable to have a step of removing the fluorescent agent and other impurities from the resin in the next step of the step of evaluating the degree of deterioration from the viewpoint of obtaining a high quality recycled resin.

Further, when the resin parts are coated with fluorescent agents at a plurality of places and the evaluation results of the respective deterioration degrees are different, it is possible to have a step of determining the evaluation results having a large degree of deterioration as the deterioration degree of the parts. It is preferable from the viewpoint of accurately reflecting the evaluation result in the production of the recycled resin and obtaining a high-quality recycled resin.

Hereinafter, the present invention, its constituent elements, and modes and modes for carrying out the present invention will be described in detail. In the present application, "~" is used to mean that the numerical values described before and after the value are included as the lower limit value and the upper limit value.

<< Outline of the product including the resin part of the present invention >>
The product containing the resin parts of the present invention is a product containing the resin parts that are collected and reused after use, and the resin parts constituting the exterior surface of the product are coated with a fluorescent agent. The fluorescent agent emits light when irradiated with light having a specific wavelength, and the amount of the light emitted decreases with time due to exposure to ultraviolet rays.

In the recycling system of the present invention, utilizing the above-mentioned characteristics, when a used product is collected from the market and decomposed into a single part, the amount of light emitted by the fluorescent agent pre-applied to the exterior surface by irradiating ultraviolet rays is measured. By measuring, the "deterioration degree evaluation test method for resin parts" is used to determine the deterioration degree of the resin parts from the correlation data between the light emission amount and the deterioration degree of the resin parts prepared in advance. Is preferable.

Hereinafter, the "deterioration degree evaluation test method for resin parts" will be described. However, the present invention is not limited to the following methods.

≪Overview of deterioration evaluation test method for resin parts≫
The "deterioration evaluation test method for resin parts (hereinafter, also simply referred to as" resin ")" used in the present invention is a resin deterioration evaluation test method using a fluorescent agent, and is at least the following step (1). ), (2) and (3) are preferably included.
(1) A step of applying a fluorescent agent to the resin parts constituting the exterior surface of the product.
(2) A step of irradiating the fluorescent agent of the resin with ultraviolet rays using a resin coated with the fluorescent agent on the exterior surface to measure the amount of fluorescence emission.
(3) A step of evaluating the degree of deterioration of the resin from the amount of fluorescent light emitted.

With such a configuration, it is not necessary to measure the molecular weight or evaluate the strength of each resin, time and cost can be saved, and the degree of deterioration of the resin can be evaluated more accurately and quantitatively by measuring the amount of fluorescence emission. ..

Here, "deterioration of resin" means that the properties and characteristics of a resin such as mechanical properties, thermal properties, electrical properties, flame retardancy, fluidity at the time of melting, odor, color, and molecular weight are the properties and characteristics of the resin before shipment. It means changing from the state.

[1] Resin Deterioration Evaluation Test Method and Product Recycling System Using the Resin Deterioration Evaluation Test Method The details of the resin deterioration evaluation test method of the present invention are described below with reference to the process flow chart of the product recycling system shown in FIG. explain. Further, the repellet step in the following description refers to the steps from "recovery" to "repelletization" in FIG.

[Steps (1) and (2)]: Fluorescent agent coating step and fluorescence emission amount measuring step In the production step of a product using a resin, the step (1) is applied to the resin parts constituting the exterior surface of the product. This is the step of applying a fluorescent agent.

In the present invention, a resin part coated with a fluorescent agent is targeted for a step of irradiating an ultraviolet ray described later to measure the amount of fluorescence emitted, and a resin having a sheet coated with the fluorescent agent attached to the surface thereof. Including manufactured parts. Hereinafter, a step of applying the fluorescent agent, which is a preferred embodiment of the present invention, to resin parts will be mainly described.

In an embodiment of the present invention, from the viewpoint of exhibiting the effect of the present invention, the resin constituting the outer surface within the range of the upper surface, the corner surface and the side surface of the product to which ambient light is irradiated when the product is used. It is preferable that the fluorescent agent is applied to any of the manufactured parts from the viewpoint of improving the evaluation accuracy of the degree of deterioration.

Further, the fluorescent agent is applied to all of the resin parts constituting the upper surface, the corner surface and the outer surface within the range of the side surface of the product to which ambient light is irradiated when the product is used. However, it is preferable from the viewpoint of improving the accuracy of evaluation.

Further, the fluorescent agent is applied to all the plurality of places of the resin parts constituting the upper surface, the corner surface and the exterior surface within the range of the side surface of the product which is irradiated with ambient light when the product is used. It is preferable from the viewpoint of improving the evaluation accuracy of the degree of deterioration.

FIG. 1 is a schematic view showing a coating position of a fluorescent agent, and is a cross-sectional view of a product including resin parts when viewed from the side.

When the outside of the part to be irradiated with the ambient light 2 when the resin part 1 is used is the "exterior surface" and the inside of the part is the "non-exterior surface", the "ambient light is irradiated when the product is used" in the present invention. The "exterior surface within the range of the upper surface, the corner surface and the side surface" of the product is the "upper surface" and the "corner portion" described as "OK" in the "exterior surface" in FIG. Refers to "face" and "side". The portion described as "NG" in FIG. 1 is a portion where the ambient light 2 is not directly irradiated on the "non-exterior surface" or the portion which is the "exterior surface" but the amount of light is weak even if it is irradiated. , It is an unfavorable place for applying the fluorescent agent according to the present invention.

The step (2) is a step of irradiating the fluorescent agent of the resin part with ultraviolet rays and measuring the amount of fluorescence emission by using the resin part coated with the fluorescent agent on the surface.

<Fluorescent agent>
The fluorescent agent according to the present invention is a substance to which energy such as ultraviolet rays is applied to excite and emit the excitation energy as light, and is classified into an organic fluorescent agent and an inorganic fluorescent agent. In the case of an organic fluorescent agent, one that is transparent in the visible light region is preferable in order to maintain the appearance of the product. Inorganic fluorescent agents are generally more durable than organic fluorescent agents. In addition, the fluorescent agent has a light emitting center that generates fluorescence, and examples thereof include rare earth metal compounds such as europium (Eu), cerium (Ce), samarium (Sm), and ytterbium (Yb).

Examples of the organic fluorescent agent include a stillben-based fluorescent agent, a distylben-based fluorescent agent, a benzoxazole-based fluorescent agent, a styryl-oxazole-based fluorescent agent, a pyrene-oxazole-based fluorescent agent, a coumarin-based fluorescent agent, an imidazole-based fluorescent agent, and a benzoimidazole. Examples thereof include a system fluorescent agent, a pyrazoline system fluorescent agent, an aminocoumarin system fluorescent agent, a distyryl-biphenyl system fluorescent agent, and a naphthalimide system fluorescent agent.

Examples of the inorganic fluorescent agent include zinc oxide (ZnO), zinc sulfide (ZnS), zinc selenide (ZnSe), cadmium sulfide (CdS), and Er ³⁺ , Yb ³⁺ , Tm ³⁺ , Ho ³⁺ , Pr ³⁺ , Eu. ^Examples thereof include inorganic fluorescent agents such as rare earth-containing YAG (yttrium aluminum garnet) containing rare earth elements such as ³⁺ .

Among these fluorescent agents, it is excited by irradiating with ultraviolet rays (light wavelength range of 10 to 400 nm), and this excitation energy is emitted as visible light, which corresponds to outdoor exposure for 10 years using a xenon arc light source. It is preferable to use one in which the amount of fluorescence emitted after the light irradiation test is within the range of 10 to 80% of the amount of fluorescence emitted before light irradiation from the viewpoint of improving the evaluation accuracy. When the amount of fluorescent light emitted is within the range of 10 to 80%, the deterioration rate of the fluorescent agent is appropriate, and the degree of deterioration of the resin and the degree of deterioration of the fluorescent agent can be easily correlated. For example, if a fluorescent agent has a fluorescence emission amount of 0% after 10 years of outdoor exposure, it is difficult to prepare a calibration curve in the first place. Further, if the fluorescent agent exceeds 80%, the deterioration rate is too slow, and the accuracy of the correlation between the deterioration degree of the resin and the deterioration degree of the fluorescent agent is insufficient.

Here, the measurement of "the amount of fluorescence emitted after 10 years of outdoor exposure" is a value obtained by an accelerated test by a xenon light irradiation test using a xenon arc lamp, which will be described later.

Among them, as the rare earth metal compound used as a preferable fluorescent agent, for example, europium chloride (EuCl ₃ ), europium oxide (Eu ₂ O ₃ ) and the like can be mentioned as typical examples, and further, lantern (La), samarium (La), samarium ( Ce), Praseodymium (Pr), Neodymium (Nd), Samarium (Sm), Gadolium (Ga), Terbium (Tb), Disposorium (Dy), Holmium (Ho), Elbium (Er), Tulum (Tm), Ytterbium It is a compound (oxide, sulfide, organic oxide, etc.) such as Yb), lutethium (Lu), ytterbium (Y), and samarium (Sc), and it is preferable to add one or more compounds. .. In particular, the metal compounds Eu, Sm, and Tb have a strong fluorescence emission amount and are preferable for determining the degree of deterioration.

The method for applying the rare earth metal compound is not particularly limited, but an inkjet printing method, a spray coating method, a brush coating method, etc. are used so that the rare earth metal compound is appropriately dissolved or dispersed in an organic solvent at a concentration suitable for coating and the coating amount is uniform. Alternatively, it is preferable to adopt a method of attaching a sticker coated with a fluorescent agent in advance.

Above all, the inkjet printing method in which the rare earth metal compound is dissolved or dispersed in an organic solvent and used as an ink is preferable because it can be applied to parts with high accuracy by a simple device.

Examples of organic solvents applicable to ink include methanol, ethanol, n-propanol, ethylene glycol, cyclopentan, o-xylene, toluene, hexane, tetraline, mesitylene, benzene, methylcyclohexane, as general alcohols. Examples thereof include ethylbenzene, 1,3-diethylbenzene, isophorone, 2-hexanol, triethylamine, cyclohexanone, diisopropylamine, isopropyl alcohol, pyridine, acetophenone, 2-butoxyethanol, 1-butanol, 1-pentanol, and dioxane. it can.

In addition, polyhydric alcohol ethers (for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobuty ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, ethylene Glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, etc.), amines (for example, ethanolamine, diethanolamine, tri) Ethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenediamine, triethylenetetramine, tetraethylenepentamine, polyethyleneimine, pentamethyldiethylenetriamine, tetramethylpropylenediamine, etc.), amides (For example, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, etc.), heterocyclics (for example, 2-pyrrolidone, N-methyl-2-pyrrolidone, cyclohexylpyrrolidone, 2-oxazolidone, 1,3- Examples thereof include dimethyl-2-imidazolidinone), sulfoxides (eg, dimethylsulfoxide, etc.), sulfones (eg, sulfolane, etc.), urea, acetonitrile, acetone, and the like.

Examples of the inkjet printing method include Japanese Patent Application Laid-Open No. 2012-140017, Japanese Patent Application Laid-Open No. 2013-010227, Japanese Patent Application Laid-Open No. 2014-058171, JP-A-2014-097644, JP-A-2015-142979, and JP-A-2015-142979. It is described in JP-A-2015-142980, JP-A-2016-002675, JP-A-2016-002682, JP-A-2016-107401, JP-A-2017-109476, JP-A-2017-177626, etc. The inkjet printing method having the above-mentioned configuration can be appropriately selected and applied.

As for the coating area of the fluorescent agent, it is preferable that the coating range on the resin substrate is 0.5 cm × 0.5 cm or more from the viewpoint of improving the evaluation accuracy of the degree of deterioration. From the viewpoint of maintaining the physical properties of the resin, the residual amount of the fluorescent agent after removing the fluorescent agent is preferably 0.05% by mass or less with respect to the mass of the component. For example, the mass of the component is 10 g and the coating amount is 0.05 g / cm. ^2. Assuming that the removal rate is 95%, the coating area is preferably about 3 cm × 3 cm or less.

The coating amount is preferably 0.0005 g or more per 1 cm ² , and the upper limit is preferably 0.05 g or less per 1 cm ² . Within this range, it is preferable because it is transparent under visible light and does not affect the surface properties and gloss of the parts.

The thickness of the fluorescent agent layer after coating is preferably in the range of 1 to 50 μm, more preferably in the range of 10 to 40 μm, and most preferably in the range of 20 to 30 μm because it is preferably transparent in order to maintain the appearance of the product. The range.

The degree of deterioration of the resin can be determined by irradiating the fluorescent agent with ultraviolet rays or the like and measuring the emission intensity from the fluorescent agent.

In the step (1), in the production process of the product using the resin, the resin part coated with the fluorescent agent is used in the market after the product is assembled, appropriately collected and disassembled, and returned to the resin part.

In the step (2), the amount of fluorescence emitted is measured by irradiating the fluorescent agent of the resin with ultraviolet rays with respect to the resin having the fluorescent agent on the surface of the resin component when irradiated with ultraviolet rays.

The "ratio of the amount of fluorescent light emitted" in the present invention means the ratio of the amount of fluorescent light emitted by the fluorescent agent after deterioration when the amount of fluorescent light emitted when the fluorescent agent before deterioration is exposed to ultraviolet rays is 100%.

FIG. 3 shows an example of a measuring device (also referred to as a fluorescence measuring device) that measures the amount of fluorescence emitted by irradiating the fluorescent agent of the recovered resin with ultraviolet rays.
The fluorescence emission measuring device 10 includes an ultraviolet light source unit 13 which is a UV lamp that mainly irradiates the fluorescent agent 12 coated on the resin 11 with ultraviolet rays, and a camera unit 14 that measures the amount of light emitted by the fluorescence emission. ..

Examples of the ultraviolet light source include VL-6 manufactured by VILBER. Use LC. The distance from the irradiation surface of the light source to the fluorescent agent-coated surface of the target component is 5 cm, and irradiation is performed at an angle of 45 °.

For the measurement of the amount of fluorescence, for example, a Nikon camera D850 uses AF-S NIKKOR 35 mm f / 1.4 G as the lens unit, the distance from the front surface of the lens to the surface coated with the fluorescent agent is 10 cm, and the angle is 90 ° (true). Above). The shooting conditions on the camera side are fixed, and the shot image is processed by image processing software to calculate the amount of fluorescence.

[Step (3)]: Resin Deterioration Degree Evaluation Step Step (3) is a step of evaluating the deterioration degree of the resin from the amount of fluorescence emitted. Hereinafter, the principle of evaluating the degree of deterioration of the resin will be described.

FIG. 4 is a schematic diagram illustrating the principle of the resin deterioration degree evaluation test method.

FIG. 4A is a schematic diagram showing the degree of deterioration of the characteristics of the resin, and FIG. 4B is a schematic diagram showing the degree of deterioration of the fluorescent agent itself. The horizontal axis is the degree of deterioration, and the vertical axis is the vertical axis as the degree of deterioration is shown. The characteristics of the resin (for example, molecular weight, impact strength, etc.) and the amount of fluorescent light emitted by the fluorescent agent are reduced. Based on this characteristic, a xenon light irradiation test using a xenon arc lamp (for example, based on the exposure test method using a JIS K735-2: 2008 plastic laboratory light source) was performed as a deterioration acceleration test for resins and fluorescent agents. , The characteristics of the resin and the degree of deterioration of the amount of light emitted by the fluorescent agent are measured.

When monitoring fluctuations in molecular weight or impact strength as a characteristic of the resin, it is preferable to measure the weight average molecular weight or impact strength of the resin by the following method with respect to the irradiation time of the xenon light irradiation test.

<Measurement of molecular weight>
The molecular weight measurement by gel permeation (GPC) is performed as follows. After adding the solvent solution to the resin, ultrasonic waves were applied for 30 minutes, and the melted portion was used for the measurement of the GPC device. For the number average molecular weight (Mn) (in terms of polystyrene), an HLC-8120GPC or SC-8020 apparatus manufactured by Tosoh Corporation was used as the GPC apparatus, and a TSKgei, SuperHM-H (6.0 mm ID x 15 cm x 2) was used as the column. As the eluent, THF (tetrahydrofuran) for chromatograph manufactured by Wako Pure Chemical Industries, Ltd. was used. The measurement conditions were a flow velocity of 0.6 mL / min, a sample injection volume of 10 μL, a measurement temperature of 40 ° C., and an RI detector. The calibration curve is "polystylene standard sample TSK standard" manufactured by Tosoh Corporation: A-500, F-1, F-10, F-80, F-380, A-2500, F-4, F-40, F- It was prepared from 10 samples of 128 and F-700. The data collection interval in the sample analysis was set to 300 ms. In addition, depending on the type of resin, measurement is performed under appropriate conditions (change the solvent used, the type of column, and the measuring device) as necessary.

<Impact strength>
Measure after leaving the test piece at a temperature of 23 ° C. and a humidity of 50% RH for 16 hours under the test conditions of JIS K7110 (1999) with an impact tester. For example, the impact tester uses PST-300 manufactured by Shinyei Testing Machinery under the conditions of a temperature of 23 ° C. and a humidity of 55% RH.

The amount of light emitted from the fluorescent agent is measured with respect to the irradiation time of the xenon light irradiation test by the apparatus and method described in step (2).

The figure on the left side of FIG. 4C schematically shows the degree of deterioration of polycarbonate (PC), acrylonitrile-butadiene-styrene resin (ABS), and high-impact (impact-resistant) polystyrene (HIPS) as resins.

The right side view of FIG. 4C shows the correlation between the characteristics of the resin and the amount of light emitted from the fluorescent agent for each irradiation time of the xenon light irradiation test. The horizontal axis is the measurement data of the amount of light emitted from the fluorescent agent, and the vertical axis is the measurement data of the characteristics of the resin. By measuring the amount of light emitted from the fluorescent agent applied to the resin from this correlation diagram, the degree of deterioration of the resin (variation from before deterioration) can be estimated accurately.

Further, in step (3), when the resin parts are coated with fluorescent agents at a plurality of places and the evaluation results of the respective deterioration degrees are different, the evaluation results having a large degree of deterioration are determined as the deterioration degree of the parts. It is preferable to have a step (3 *) of By adding the step (3 *), sorting for obtaining a higher quality recycled resin can be performed by the next step (4).

[Step (4)]: Resin Separation Step This step is a step of separating the resin according to the degree of deterioration evaluated in the step (3). For example, the degree of deterioration of the resin is divided into several stages, and the resin parts within the range are sorted. For example, a range of deterioration degree of 0% or more and less than 5%, a range of deterioration degree of 5% or more and less than 10%, a range of deterioration degree of 10% or more and less than 15%, a range of deterioration degree of 15% or more are set, and the resin is prepared. Sort. Considering the work process, it is preferable to separate into 3 to 4 stages.

[Step (5)]: Unnecessary resin removing step This step is a step of removing (discarding) unnecessary resin according to the degree of deterioration evaluated in step (3).

For example, by taking measures such as excluding resin with a degree of deterioration of 15% or more from the recycling system, it is possible to prevent the resin parts that are severely deteriorated from being recycled and the strength of the recycled resin and parts from being lowered. be able to.

[Step (6)]: Fluorescent Agent and Impurity Removal Step In the recycling system of the present invention, it is preferable to add a step of removing the fluorescent agent and other impurities.

Since the seal and other impurities coated with the fluorescent agent and the fluorescent agent are removed after the evaluation, almost no foreign matter is mixed in the recycled resin, and even if the fluorescent agent cannot be completely removed, a metal stabilizer is added at the time of kneading. , Deterioration of recycled resin can be suppressed.

Impurities are stains adhering to the separated resin from "molding" to step (4). Specifically, dust, pollen and yellow sand, substances contained in tobacco smoke, nitrogen oxides, and the like. Examples include sulfur oxides and sebum.

The removal of the fluorescent agent and other impurities is preferably carried out by washing with water, and in addition to water, an alcohol solvent such as methanol or ethanol can be used alone or in combination, and is inorganic. Impurities and low molecular weight organic impurities can be removed. It is also preferable to use a surfactant to enhance the detergency.

It is also preferable to polish and remove the fluorescent agent from the resin part. For example, a polishing jig such as a brass brush can be attached to the tip of the drill and rotated to remove the fluorescent agent by hitting the surface coated with the fluorescent agent.

[Step (7)]: Blending ratio determination step In the above step (6), the washed resin is pulverized in a separated state, a compounding ratio is determined for each pulverized product according to the purpose, and repellets are used. Mix for conversion.

[Step (8)]: Repelletization step Repelletization is performed using the mixture whose compounding ratio has been determined in step (7).

For repelletization, a method of producing resin pellets by applying a shearing force to a resin as a host material and, if necessary, other resin components with a melt-kneading device is preferably used.

Specific kneading machines include KRC kneader (manufactured by Kurimoto Iron Works); Polylab system (manufactured by HAAKE); Labplast mill (manufactured by Toyo Seiki Seisakusho); Nauter mixer Busco kneader (manufactured by Buss). ); TEM type extruder (manufactured by Toshiba Machine Co., Ltd.); TEX twin-screw kneader (manufactured by Japan Steel Works); PCM kneader (manufactured by Ikekai Iron Works); three roll mill, mixing roll mill, kneader (manufactured by Inoue Seisakusho) ); Needex (manufactured by Mitsui Mining Co., Ltd.); MS type pressurized kneader, Nidarruder (manufactured by Moriyama Seisakusho); Banbury mixer (manufactured by Kobe Steel Works), etc. The size of the pellet is appropriately determined, but it is preferably in the form of particles having a major axis of about 3 to 5 mm.

Step (8) is a step of adding a metal stabilizer at the time of the repelling.

Examples of metal stabilizers include oxalic acid derivatives, salicylic acid derivatives, hydrazide derivatives, triazole derivatives, and imidazole derivatives.

Examples of oxalic acid derivatives include oxalobis-1,2-hydroxybenzylidenehydrazide (Eastman inhibitor OABH; Eastman Kodak), 2,2'-oxamidbis (ethyl 3- (3,5-tert-butyl-4). -Hydroxyphenyl) propionate) (Naugard XL-1; Shiraishi Calcium Co., Ltd., "Naugard" is a registered trademark of the company) is included.

Examples of salicylic acid derivatives include 3- (N-salicyloyl) amino-1,2,4-triazole (ADEKA STAB CDA-1; ADEKA Corporation, "ADEKA STAB" is a registered trademark of the company), disalicylo decamethylenedicarboxylic acid. Ilhydrazide (ADEKA STAB CDA-6; ADEKA Corporation), salicylidene salicyloylhydrazine (Chel-180; BASF) are included.

Examples of hydrazide derivatives include N, N'-bis ((3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl)) propionohydrazide (CDA-10; ADEKA Corporation, Qunox; Mitsui Toatsu Fine Co., Ltd. and "Quant" are registered trademarks of the company).

Examples of triazole derivatives include benzotriazole, 3-amino-1,2,4-triazole, 2-mercaptobenzotriazole, 2,5-dimercaptobenzotriazole, 4-alkylbenzotriazole, 5-alkylbenzotriazole, 4 , 5,6,7-Tetrahydrobenzotriazole, 5,5'-methylenebisbenzotriazole, 1- [di (2-ethylhexyl) aminomethyl] -1,2,4-triazole, 1- (1-butoxyethyl) -1,2,4-triazole and acylated 3-amino-1,2,4-triazole are included.

Examples of imidazole derivatives include 4,4'-methylenebis (2-undecyl-5-methylimidazole) and bis [(N-methyl) imidazol-2-yl] carbinol octyl ether.

The metal stabilizer is preferably 0.01% by mass or more, and more preferably 0.1% by mass or more, from the viewpoint of inactivating the metal contained in the recovered material. Further, the metal stabilizer is preferably 1% by mass or less from the viewpoint of saturating the effect of inactivating the metal contained in the recovered material.

In the recycling system of the present invention, the above steps (5), (6) and (8) are not necessarily essential steps and can be omitted.

[2] Resin used in the product of the present invention The resin used in the product of the present invention is preferably a thermoplastic resin, specifically, polycarbonate (PC), polypropylene (PP) or polystyrene (PS) -based resin. It is preferably a resin. However, it is not limited to these.
[2.1] Polycarbonate The polycarbonate referred to in the present invention is a polymer having a basic structure having a carbonic acid bond represented by the formula:-[-O-X-OC (= O)-]-. In the formula, X represents a linking group and is generally a hydrocarbon, but a heteroatom or an X having a heterobond introduced may be used to impart various properties.

Generally, as polycarbonate, aliphatic polycarbonate and aromatic polycarbonate are known. Aliphatic polycarbonate has a low thermal decomposition temperature and a low temperature at which it can be molded, so a method for improving heat resistance is usually taken. For example, the thermal decomposition temperature is improved by reacting the terminal hydroxyl group of the aliphatic polycarbonate with the isocyanate compound. In addition, aliphatic polycarbonate, which copolymerizes carbon dioxide and epoxide in the presence of a metal catalyst, has excellent properties such as impact strength, light weight, transparency, and heat resistance, and is also biodegradable. It has a low environmental load and is an important resin as an engineering plastic material and a medical material due to its characteristics.

On the other hand, aromatic polycarbonate resins have excellent physical properties such as heat resistance, transparency, hygiene, and mechanical strength (for example, impact strength), and are widely used in various applications. The "aromatic polycarbonate" refers to a polycarbonate in which the carbon directly bonded to the carbonic acid bond is an aromatic carbon. For example, examples of the diol component constituting the polycarbonate include polycarbonate using a diol component containing an aromatic group such as bisphenol A. In particular, polycarbonate using only a diol component containing an aromatic group is preferable. The production method includes a method of reacting an aromatic dihydroxy compound such as bisphenol A with phosgene (interfacial method), or an aromatic dihydroxy compound such as bisphenol A or a derivative thereof and a carbonic acid diester compound such as diphenyl carbonate. , A method of performing a transesterification reaction in a molten state (melting method or transesterification method) and the like are known.

In the present invention, it is preferable to use aromatic polycarbonate from the viewpoints of heat resistance, mechanical properties, electrical characteristics and the like.

As the aromatic polycarbonate, a linear polycarbonate and a branched polycarbonate are known, but it is preferable to use them properly or use them in combination depending on the purpose. For example, branched polycarbonate tends to have lower fluidity than linear polycarbonate having the same molecular weight, so linear polycarbonate may be selected or mixed with linear polycarbonate to increase fluidity. can do.

In order to obtain a branched aromatic polycarbonate, for example, a polyfunctional compound having three or more functional groups reactive with a carbonic acid diester described in JP-A-2006-89509 and International Publication No. 2012/005250. Transesterification of a binder containing a branched aromatic polycarbonate having a branch of origin or a trifunctional or higher functional aliphatic polyol compound described in International Publication No. 2014/024904 under reduced pressure conditions in the presence of a transesterification catalyst. A method for producing a branched aromatic polycarbonate by reacting the compounds can be referred to.

Aromatic polycarbonate is obtained by reacting divalent phenol with a carbonate precursor. Examples of the reaction method include an interfacial polymerization method, a molten transesterification method, a solid phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound.

Typical examples of the dihydric phenol used here are hydroquinone, resorcinol, 4,4'-biphenol, 1,1-bis (4-hydroxyphenyl) ethane, and 2,2-bis (4-hydroxyphenyl). ) Propane (commonly known as bisphenol A), 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl)- 1-phenylethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxyphenyl) Pentan, 4,4'-(p-phenylenediisopropyridene) diphenol, 4,4'-(m-phenylenediisopropylidene) diphenol, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane , Bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) ketone Hydroxyphenyl) ester, bis (4-hydroxy-3-methylphenyl) sulfide, 9,9-bis (4-hydroxyphenyl) fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, etc. Be done. The preferred dihydric phenol is bis (4-hydroxyphenyl) alkane, and among them, bisphenol A (hereinafter, may be abbreviated as "BPA") is particularly preferable and widely used from the viewpoint of impact strength.

In the present invention, it is possible to use a special polycarbonate produced by using other divalent phenols in addition to the bisphenol A-based polycarbonate which is a general-purpose polycarbonate.

For example, 4,4'-(m-phenylenediisopropyridene) diphenol (hereinafter sometimes abbreviated as "BPM"), 1,1-bis (4-), as a part or all of the dihydric phenol component. Hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (hereinafter sometimes abbreviated as "Bis-TMC"), 9,9-bis (4-hydroxy) Polycarbonates (homopolymers or copolymers) using phenyl) fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (hereinafter sometimes abbreviated as "BCF") are It is suitable for applications where dimensional changes due to water absorption and morphological stability requirements are particularly strict.

These polycarbonates may be used alone or in admixture of two or more. Further, these can also be used by mixing them with a widely used bisphenol A type polycarbonate.

The production method and characteristics of these polycarbonates are described in detail in, for example, JP-A-6-172508, JP-A-8-27370, JP-A-2001-55435, JP-A-2002-117580 and the like. ..

The glass transition temperature Tg of polycarbonate is 160 to 250 ° C., preferably 170 to 230 ° C.

Tg (glass transition temperature) is a value obtained by differential scanning calorimetry (DSC) measurement according to JIS K7121.

As the carbonate precursor, carbonyl halide, carbonic acid diester, haloformate and the like are used, and specific examples thereof include phosgene, diphenyl carbonate and dihaloformate of divalent phenol.

In producing aromatic polycarbonate by the interfacial polymerization method of the divalent phenol and the carbonate precursor, a catalyst, a terminal terminator, an antioxidant for preventing the dihydric phenol from being oxidized, etc., if necessary, etc. May be used. Further, the aromatic polycarbonate resin according to the present invention is a branched polycarbonate resin obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound, or an aromatic or aliphatic (including alicyclic) bifunctional carboxylic acid. It contains a polyester carbonate, a copolymerized polycarbonate obtained by copolymerizing a bifunctional alcohol (including an alicyclic group), and a polyester carbonate obtained by copolymerizing such a bifunctional carboxylic acid and a bifunctional alcohol together. Further, it may be a mixture of two or more kinds of the obtained aromatic polycarbonates.

The branched polycarbonate can increase the melt tension of the resin and improve the moldability in extrusion molding, foam molding and blow molding based on such characteristics. As a result, a molded product obtained by these molding methods, which is superior in dimensional accuracy, can be obtained.

Examples of trifunctional or higher polyfunctional aromatic compounds used in branched polycarbonate resins include 4,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) heptene, 2,2,4,6-trimethyl. -2,4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1, 1-Tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, and 4- {4- [1,1-bis) Trisphenols such as (4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol are preferably exemplified.

Other polyfunctional aromatic compounds include fluoroglucolcin, fluorochloroside, tetra (4-hydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone, and 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene. , And trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid and their acid chlorides are exemplified. Of these, 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are preferable, and 1,1,1-tris (4-hydroxyphenyl) ethane is particularly preferable. Hydroxyphenyl) ethane is preferred.

The structural unit derived from the polyfunctional aromatic compound in the branched polycarbonate resin is 0 in a total of 100 mol% of the structural unit derived from the dihydric phenol and the structural unit derived from the polyfunctional aromatic compound. It is 0.03 to 1 mol%, preferably 0.07 to 0.7 mol%, and particularly preferably 0.1 to 0.4 mol%.

Further, the branched structural unit is not only derived from the polyfunctional aromatic compound, but also can be derived without using the polyfunctional aromatic compound, such as a side reaction during the melt transesterification reaction. Good. The ratio of such a branched structure can be calculated by 1H-NMR measurement.

The aliphatic bifunctional carboxylic acid is preferably α, ω-dicarboxylic acid. Examples of the aliphatic bifunctional carboxylic acid include linear saturated aliphatic dicarboxylic acids such as sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, and icosandioic acid, and cyclohexanedicarboxylic acid. Such as alicyclic dicarboxylic acid is preferably mentioned. As the bifunctional alcohol, an alicyclic diol is more preferable, and examples thereof include cyclohexanedimethanol, cyclohexanediol, and tricyclodecanedimethanol.

Further, it is also possible to use a polycarbonate-polyorganosiloxane copolymer obtained by copolymerizing a polyorganosiloxane unit.

The reaction by the interfacial polymerization method is usually a reaction between divalent phenol and phosgene, and is reacted in the presence of an acid binder and an organic solvent. As the acid binder, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, pyridine and the like are used.

As the organic solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used.

Further, for promoting the reaction, for example, a catalyst such as a tertiary amine or a quaternary ammonium salt can be used, and as a molecular weight modifier, for example, phenol, p-tert-butylphenol, p-cumylphenol and the like are simply used. It is preferable to use functional phenols. Further, examples of the monofunctional phenols include decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol, docosylphenol, and triacontylphenol. These monofunctional phenols having a relatively long-chain alkyl group are effective when improvement in melt flow rate and hydrolysis resistance is required.

The reaction temperature is usually 0 to 40 ° C., the reaction time is preferably several minutes to 5 hours, and the pH during the reaction is usually kept at 10 or more.

The reaction by the melt transesterification method is usually a transesterification reaction of dihydric phenol and carbonic acid diester, in which dihydric phenol and carbonic acid diester are mixed in the presence of an inert gas and reacted at 120 to 350 ° C. under reduced pressure. .. The degree of decompression is changed stepwise, and finally the phenols produced at 133 Pa or less are removed from the system. The reaction time is usually about 1 to 4 hours.

Examples of the carbonic acid diester include diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate and dibutyl carbonate, and diphenyl carbonate is preferable.

A polymerization catalyst can be used to increase the polymerization rate, and the polymerization catalyst includes, for example, hydroxides of alkali metals and alkaline earth metals such as sodium hydroxide and potassium hydroxide, and hydroxides of boron and aluminum. Alkali metal salts, alkaline earth metal salts, quaternary ammonium salts, alkali metal and alkaline earth metal alkoxides, alkali metal and alkaline earth metal organic acid salts, zinc compounds, boron compounds, silicon compounds, germanium compounds, Examples thereof include catalysts usually used for esterification reactions and ester exchange reactions of organic tin compounds, lead compounds, antimony compounds, manganese compounds, titanium compounds, zirconium compounds and the like. The catalyst may be used alone or in combination of two or more. The amount of these polymerization catalysts used is preferably 1 × ^10-9 to 1 × ^10-5 equivalents, more preferably 1 × ^{10-8 to} 5 × ^10-6 equivalents, relative to 1 mol of the raw material divalent phenol. Selected by range.

In the reaction by the melt ester exchange method, for example, 2-chlorophenylphenyl carbonate, 2-methoxycarbonylphenylphenyl carbonate and 2-ethoxycarbonylphenylphenyl carbonate are used in order to reduce the phenolic terminal groups at the late stage or after the completion of the polycondensation reaction. And other compounds can be added.

Further, in the molten transesterification method, it is preferable to use a deactivating agent that neutralizes the activity of the catalyst. The amount of the deactivator is preferably 0.5 to 50 mol with respect to 1 mol of the remaining catalyst. Further, it is used at a ratio of 0.01 to 500 ppm, more preferably 0.01 to 300 ppm, and particularly preferably 0.01 to 100 ppm, based on the polymerized aromatic polycarbonate resin. Preferred examples of the deactivator include a phosphonium salt such as tetrabutylphosphonium salt of dodecylbenzenesulfonic acid and an ammonium salt such as tetraethylammonium dodecylbenzyl sulfate.

Details of reaction types other than the above are also well known in various documents and patent gazettes.

The weight average molecular weight of the polycarbonate is not particularly limited, but is preferably in the range of 20000 to 60,000, more preferably in the range of 30,000 to 57,000, and further in the range of 35,000 to 55,000 according to the GPC measurement method.

[2.2] Polypropylene-based resin Examples of the polypropylene-based resin include homopolypropylene, propylene-ethylene block copolymer, propylene-butene block copolymer, propylene-α-olefin block copolymer, and propylene-ethylene random copolymer. , Polypropylene-butene random copolymer, propylene-α-olefin random copolymer, propylene-α-olefin graft copolymer and the like. Polypropylene-based resins also include known resins such as ethylene-α-olefin copolymers and styrene-based elastomers, and fillers such as talc, mica, wallastonite, and glass fiber.

[2.3] Polystyrene-based resin As the polystyrene-based resin, a monomer composed of a monovinyl-based aromatic monomer such as styrene, α-methylstyrene-p-methylstyrene, and pt-butylstyrene is polymerized. The obtained polymer is a rubber-modified styrene-based polymer produced by dissolving typical polystyrene (GPPS) or a rubber-like substance in a styrene-based monomer by a massive or massive suspension polymerization method, and the rubber-like substance is Polybutadiene (PBD), styrene-butadiene copolymer (SBR) and the like are used, and typical examples thereof include high impact polystyrene (HIPS) and middle impact polystyrene (MIPS).

Further, an acrylonitrile-styrene copolymer (AS resin), which is a typical polymer obtained by polymerizing a monomer composed of vinyl cyanide-based monomers such as acrylonitrile having a cyano group as a polar group and methacrylonitrile. And ABS (acrylonitrile-butadiene-styrene copolymer) resin in which acrylonitrile and styrene are polymerized on polybutadiene can be mentioned. Methyl methacrylate (MMA) resin or polybutadiene, which is a typical polymer obtained by polymerizing a monomer composed of a carboxylated vinyl-based monomer such as methacrylic acid having a carboxyl group with another polar group. MBS resin obtained by polymerizing methyl and styrene is also included. Not only the new styrene resin material mentioned above, but also recycled styrene resin recovered from used home appliances is included. Further, these polystyrene-based resins also include those containing a resin such as a styrene-based elastomer and a filler such as talc, mica, wallastonite, and glass fiber.

[2.4] Other Resin Components The resin according to the present invention may be blended with a thermoplastic polyester resin. For example, polyethylene terephthalate resin (PET), polypropylene terephthalate resin (PPT), polybutylene terephthalate resin (PBT), polyhexylene terephthalate resin, polyethylene naphthalate resin (PEN), polybutylene naphthalate resin (PBN), poly (1). , 4-Cyclohexanedimethylene terephthalate) resin (PCT), polycyclohexylcyclohexylate (PCC) and the like. Of these, polyethylene terephthalate resin (PET) and polybutylene terephthalate resin (PBT) are preferable from the viewpoint of melt flow rate and impact resistance.

It is also preferable to further add an elastomer to the resin according to the present invention. By blending an elastomer, the impact strength of the obtained resin can be further improved.

The elastomer used in the present invention is an IPN composed of polybutadiene rubber, butadiene-styrene copolymer, polyalkyl acrylate rubber, polyorganosiloxane rubber, polyorganosiloxane rubber and polyalkylacrylate rubber in terms of mechanical properties and surface appearance. (Interpentrating Polymer Network) type composite rubber is preferable.

Further, it is also preferable to appropriately use other resin additives in the resin according to the present invention, for example, a heat stabilizer (for example, a phosphorus compound, etc.), an antioxidant (for example, a hindered phenol-based antioxidant, etc.). ), Release agent (for example, aliphatic carboxylic acid, ester of aliphatic carboxylic acid and alcohol, aliphatic hydrocarbon compound, polysiloxane-based silicone oil, etc.), filler, ultraviolet absorber, dye pigment (carbon black) Included), titanium oxide, antistatic agents, antifogging agents, antiblocking agents, melt flow rate improvers, plasticizers, dispersants, antibacterial agents and the like. One type of resin additive may be blended, or two or more kinds may be blended in any combination and ratio.

Above all, it is preferable to add a heat-resistant stabilizer. The amount of the heat-resistant stabilizer added is preferably in the range of 0.05 to 1 part by mass with respect to 100 parts by mass of the resin composition.

An example of using an antioxidant as a heat-resistant stabilizer is given below.

2,6-di-t-butyl-p-cresol, tetrakis [methylene-3- (3', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, stearyl β- (3,5) -Di-t-Butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, triethylene glycol Phenolic compounds such as bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], tris (2,4-di-t-butylphenyl) phosphite, tetrakis (2,4-di) -T-Butylphenyl) [1,1-4,4'-diylbisphosphonite, bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester phosphite, bis (2,4-di-t-Butylphenyl) Pentaerythritol diphosphite, triallylphosphite, tri (monononylphenyl) phosphite and other phosphorus-based, dilauryl-3,3'-thiodipropionate, dioctadecyl Sio-based materials such as -3,3'-thiodipropionate can be used. Among these, in terms of heat stability, the phenol type is tetrakis [methylene-3- (3', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, and the phosphorus type is tris (2, For 4-di-t-butylphenyl) phosphite and sulfur, dioctadecyl-3,3'-thiodipropionate is preferable.

The molded product made of the resin mixture formed by the resin recycling system of the present invention can be suitably used for various purposes such as electric / electronic parts, home appliance parts, automobile parts, various building materials, containers, and miscellaneous goods.

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In the examples, the indication of "parts" or "%" is used, but unless otherwise specified, it indicates "parts by mass" or "% by mass".
[Example A]
(1) Selection of fluorescent agent The following two types of fluorescent agents were selected.

A: Sunluminis SP Blue; Central Techno Co., Ltd. B: Sunluminis SP Red; Central Techno Co., Ltd. Fluorescence emission amount of the selected fluorescent agent after 10 years of outdoor exposure using a xenon arc light source. And the amount of fluorescence emission before irradiation was measured using the fluorescence emission amount measuring device of FIG. 3, and the ratio of the fluorescence emission amount was calculated by the following formula (1).

Equation (1) Fluorescence emission equivalent after 10 years outdoor exposure ratio (%) = (Fluorescence emission equivalent after 10 years outdoor exposure) ÷ (Fluorescence emission amount before exposure) × 100
The amount of fluorescence emitted after 10 years of outdoor exposure is based on the xenon light irradiation test using a xenon arc lamp (JIS K7350-2: 2008 plastic laboratory light source exposure test method, but water spraying was carried out. It was done in an accelerated test. Specifically, in the xenon light irradiation test, irradiation was performed at a BPT of 65 ° C. and a humidity of 50% RH for 6905 hours at an illuminance of 60 W / m ² .

As the fluorescence emission amount measuring device, the fluorescence emission amount measuring device 10 shown in FIG. 3 was used. The fluorescence emission amount measuring device 10 includes an ultraviolet light source unit 13 that mainly irradiates the fluorescent agent 12 coated on the resin 11 with ultraviolet rays, and a camera unit 14 that measures the amount of light emitted by the fluorescence emission.

As an ultraviolet light source, VL-6 manufactured by VILBER. LC was used. The distance from the irradiation surface of the light source to the fluorescent agent-coated surface of the target component was 5 cm, and irradiation was performed at an angle of 45 °.

The amount of fluorescence emitted was measured with a Nikon camera D850, using AF-S NIKKOR 35mm f / 1.4G as the lens, the distance from the front of the lens to the surface coated with the fluorescent agent was 10 cm, and the angle was 90 ° (directly above). ). The shooting conditions on the camera side were fixed, and the shot image was processed by image processing software to calculate the amount of fluorescence emission.

A commercially available polycarbonate resin plate is used as the resin, and the fluorescent agent is applied using a square having a coating range of 1 cm x 1 cm, a coating amount of 0.002 g per 1 cm ² , and a coating method using an inkjet method. It was.

The table below shows the ratio (%) of the amount of fluorescent light emitted after the xenon light irradiation test, which corresponds to outdoor exposure for 10 years using a xenon arc light source, to the amount of fluorescent light emitted before irradiation of the two measured fluorescent agents. Shown in I.

<Manufacturing of products including resin parts>
<Example 1>
A copying machine containing the following resin parts is assembled into a product, and the fluorescent agent A selected above is applied to the exterior surface exposed to ambient light from the upper surface (directly above: 0 °) to the side surface (directly beside: 90) when the product is used. A coating amount of 0.001 g / cm ² was applied to an area of 1 cm × 1 cm by an inkjet printing method on the exterior surface (corner surface) having an angle of up to °) of 60 °.

The product uses polycarbonate (PC) (product name 301-10; Sumitomo Polycarbonate Co., Ltd., weight average molecular weight 44000) as a resin component.

The following measurement method was used for the weight average molecular weight.

<Weight average molecular weight>
The resin to be measured is dissolved in tetrahydrofuran (THF) to a concentration of 1 mg / mL, then filtered using a membrane filter having a pore size of 0.2 μm, and the obtained solution is used as a sample for GPC measurement. There was. As the GPC measurement conditions, the GPC analysis conditions shown below were adopted, and the weight average molecular weight of the resin contained in the sample was measured.

(GPC measurement conditions)
"HLC-8320GPC / UV-8320 (manufactured by Tosoh Corporation)" is used as the GPC apparatus, two "TSKgel, Supermultipore HZ-H (manufactured by Tosoh Corporation, 4.6 mm ID x 15 cm)" are used as the column, and tetrahydrofuran is used as the eluent. (THF) was used. The analysis was performed using a flow rate of 0.35 mL / min, a sample injection volume of 20 μL, a measurement temperature of 40 ° C., and an RI detector. The calibration curve is "polystylene standard sample TSK standard" manufactured by Tosoh Corporation: "A-500", "F-1", "F-10", "F-80", "F-380", "A-2500". , "F-4", "F-40", "F-128", "F-700" were prepared from 10 samples. The data collection interval in the sample analysis was set to 300 ms.

As a deterioration acceleration test for the resin piece coated with the fluorescent agent and the fluorescent agent, a xenon light irradiation test using a xenon arc lamp (JIS K7350-2: 2008 conforms to the exposure test method using a plastic laboratory light source, but water spraying. Was not carried out), and the characteristics of the resin and the degree of deterioration of the light emission amount of the fluorescent agent were measured as shown in FIGS. 4 (a) and 4 (b), respectively. In the xenon light irradiation test, irradiation was performed at a BPT of 65 ° C. and a humidity of 50% RH for 6905 hours at an illuminance of 60 W / m ² .

As for the characteristics of the resin, the fluctuation of the weight average molecular weight by the above-mentioned measurement method was monitored.

The fluctuation of the fluorescence emission amount of the fluorescent agent was monitored by the fluorescence emission amount measuring device shown in FIG. 3, and the fluorescence emission amount ratio (%) after the xenon test irradiation was determined by the following formula (2).

Equation (2) Fluorescence emission amount ratio after xenon light irradiation test (%) = (Fluorescence emission amount after xenon light irradiation test) ÷ (Fluorescence emission amount before xenon light irradiation test) × 100
In addition, the rate of decrease in the amount of fluorescence emission was calculated by the following formula (3).

The "decrease rate" is the following defined value.

When the amount of fluorescence emitted before the xenon light irradiation test is 100%,
Fluorescence emission amount of the fluorescent agent used after 10 years of outdoor exposure: L ₁₀ (%)
Measurement result (fluorescence emission amount of recovered parts): L _m (%)
Then, the deterioration rate is expressed by the following formula, and represents how much the fluorescence intensity of the recovered component is reduced with respect to the corresponding decrease in fluorescence intensity after 10 years of exposure.

Equation (3) Decrease rate of fluorescence emission (%) = (100-L _m (%)) ÷ (100-L ₁₀ (%)) × 100
From the above measurement data, the degree of deterioration 1 (weight average molecular weight) of the resin characteristics estimated from the light emission amount of the fluorescent agent by the graph on the right side of FIG. 4 (c) (correlation graph between the resin characteristics and the light emission amount of the fluorescent agent). The degree of deterioration 2 of the resin whose weight average molecular weight was actually measured was compared. The degree of deterioration of the resin was determined by the following formula (4).

Equation (4) Deterioration of resin (%) = 100- (Variation rate (%) of resin characteristics before and after xenon light irradiation test)
At this time, the evaluation accuracy is particularly good (⊚) when the dissociation of the deterioration degrees 1 and 2 is less than 3%, and good (◯) when the dissociation is 3% or more and less than 5%, and 5% or more and less than 10%. A certain case was regarded as slightly good (Δ), and a case of 10% or more was regarded as defective (x).

<Examples 2 to 6>
In the production of the product of Example 1, the products of Examples 2 to 6 are made in the same manner except that the coating position, the coating amount, the coating area, and the coating form of the fluorescent agent are changed as shown in Table II. Was produced. In Example 6, the fluorescent agent was applied to the lower corner surface (120 °) of the product as the exterior surface to which the ambient light irradiation was weak.

<Comparative example 1>
In the production of the product of Example 1, the product of Comparative Example 1 shown in Table III was produced in the same manner except that the fluorescent agent B was used.

<Comparative example 2>
In the production of the product of Example 1, the product of Comparative Example 2 was produced in the same manner except that the fluorescent agent was similarly applied to the non-exterior surface of the resin part shown in FIG.

<Comparative Example 3 and Comparative Example 4>
In Comparative Example 3, in the production of the product of Example 1, resin parts used for the exterior surface similar to the fluorescent agent-coated portion are collected and evaluated for destruction by a hammer (presence or absence of destruction due to deterioration of the resin is determined). Was done.

In Comparative Example 4, in the production of the product of Example 1, resin parts used for the exterior surface similar to the fluorescent agent-coated portion were collected, and the weight average molecular weight was measured by the above method.

In each evaluation, the time required for measurement was monitored.

As described above, the configurations and evaluation results of Examples 1 to 6 and Comparative Examples 1 to 4 are shown in Table II and Table III.

From Table II and Table III, it was found that the degree of deterioration of the resin can be estimated in a short time by measuring the amount of fluorescent light emitted by the fluorescent agent applied on the resin. From the comparison with the actual deterioration degree of the resin, it is possible to accurately estimate the actual deterioration degree of the resin by using a fluorescent agent in which the fluorescence emission amount ratio after 10 years of outdoor exposure is in the range of 10 to 80%. It was found that it was possible (comparison between Example 1 and Comparative Example 1).

Looking at the evaluation results in detail, as compared with Example 1,
In the second embodiment, since the evaluation is performed at a plurality of locations, the evaluation accuracy is high.

In Example 3, the coating amount is small and the detection accuracy of the fluorescence emission amount is slightly low.

In Example 4, the coating range is small, and the detection accuracy of the fluorescence emission amount is slightly low.

In Example 5, since the fluorescent agent was applied in a bar code shape, the substantially application range was small and the application was mottled, so that the detection accuracy of the amount of fluorescence was slightly low.

In Example 6, since the coating is applied to a portion that is not easily exposed to ambient light, the error between the evaluation result of the degree of deterioration and the actual degree of deterioration is slightly large.

In Comparative Example 1, the decrease in the amount of light emitted by the fluorescent agent is small, and it is not possible to evaluate how much the product receives ultraviolet rays during use.

In Comparative Example 2, since the fluorescent agent was applied to the non-exterior surface, it was not possible to evaluate how much the product received ultraviolet rays during use.

In Comparative Example 3, the repeatability (reproducibility) is low in the fracture evaluation using a hammer. In addition, the operation / judgment criteria differ depending on the shape of the part and the type of resin, and the part is damaged and cannot be reused.

In Comparative Example 4, although the accuracy is high, the molecular weight measurement and evaluation takes too much time and cost, and is not practical.
[Example B]
Using the following polycarbonate resin and metal stabilizer, the effect of sorting (step (4)), removal (step (5)) and mixing by determining the compounding ratio (step (7)) in an actual recycling system, fluorescent agent / The effects of removing impurities (step (6)) and adding the following metal stabilizer (step (8)) were verified.

Polycarbonate (PC): Product name 301-10; Sumitomo Polycarbonate Co., Ltd., Weight average molecular weight 44000
Metal stabilizer: Product name 3- (N-salicyloyl) amino-1,2,4-triazole, ADEKA STAB CDA-1; ADEKA Corporation, 0.1% by mass added to resin.

"Production" of Example A In the same manner as in Example 1, a fluorescent agent A is applied to a molded product of virgin polycarbonate (PC) resin, a copying machine using the molded product is assembled, and 5 on the market. A plurality of types of copiers used for a year were randomly collected, and the amount of light emitted by the fluorescent agent applied to the polycarbonate resin was monitored by the fluorescence emission measuring device shown in FIG.

The degree of deterioration of the resin estimated from the amount of fluorescence emitted was determined for each recovered part.

The classification based on the degree of deterioration of the resin (step (4)) was divided into four stages of 0% or more and less than 5%, 5% or more and less than 10%, 10% or more and less than 15%, and 15% or more.

Based on the result, the compounding ratio of the separated resins was determined and mixed at the ratios described in each of Examples 7 to 11 shown in Table IV (step (7)). The resin was mixed in a tumbler (mixer) for 10 minutes and dried in an oven at 100 ° C. for 4 hours. At that time, in Examples 8 to 11, no resin having a deterioration degree of 15% or more was blended.

Next, with respect to the mixture of Examples 7 to 11, the presence / absence of a step of removing the fluorescent agent / impurity by washing with water (step (6)) and the presence / absence of addition of a metal stabilizer during the repelletization step (step (8)). In addition to the above operations, a test piece for impact test was molded with an injection molding machine JSW-110AD manufactured by Japan Steel Works, Ltd. under the conditions of a molding temperature of 280 ° C., an injection speed of 30 mm / min, and an injection molding thickness of 4 mm.

For the above washing, a horizontally long water washing tank is prepared, a Bransonic ultrasonic cleaner DHA-1000-6J (manufactured by Branson) is placed in the water washing tank, and ultrasonic waves are oscillated in a pure water bath at 30 ° C. The resin was continuously transported in this pure water bath for 10 minutes to perform a cleaning treatment.

The impact strength of the obtained test piece was evaluated under the following conditions.

(Impact strength)
The measurement was carried out using an impact tester under the test conditions of JIS K7110 (1999) after leaving the test piece at a temperature of 23 ° C. and a humidity of 50% RH for 16 hours. The impact tester used was Yasuda Seiki 258, and the test was carried out under the conditions of a temperature of 23 ° C. and a humidity of 55% RH.

Table V shows the above experimental contents and evaluation results.

From Table V, the following effects of the present invention are clear.

From the comparison between Example 7 and Example 8, by removing the resin having a deterioration degree of 15% or more from the recycling system of the present invention, the impact strength of the recycled product is 13.2 kJ / m ² to 48.8 kJ / m ^2. It improves remarkably.

From the comparison between Example 8 and Example 9, when the compounding ratio is determined and mixed (step (7)), the impact strength value can be improved by increasing the ratio of the resin having a low degree of deterioration. Therefore, it is possible to design the quality of recycled resin for each part used by changing the compounding ratio.

From Examples 9 to 11, the impact strength values can be improved by removing the fluorescent agent / impurities (step (6)) and adding the metal stabilizer during the repelletization step (step (8)). Is.

1 Resin parts 2 Environmental light 10 Fluorescent emission measuring device 11 Resin 12 Fluorescent agent 13 Ultraviolet light source unit 14 Camera unit

Claims (12)

A product containing resin parts that are collected and reused after use.
A fluorescent agent is applied to the resin parts constituting the exterior surface of the product.
A product containing a resin component, characterized in that the fluorescent agent emits light when irradiated with light of a specific wavelength, and the amount of light emitted decreases with time due to exposure to ultraviolet rays. The fluorescent agent is applied to any of the resin parts constituting the upper surface, the corner surface, and the exterior surface within the range of the side surface of the product, which is irradiated with ambient light when the product is used. A product comprising the resin component according to claim 1, which is characteristic. The fluorescent agent is applied to all of the resin parts constituting the upper surface, the corner surface, and the exterior surface within the range of the side surface of the product, which is irradiated with ambient light when the product is used. A product containing the resin parts according to claim 1 or 2. The fluorescent agent is applied to all a plurality of places of the resin parts constituting the upper surface, the corner surface and the exterior surface within the range of the side surface of the product which is irradiated with ambient light when the product is used. A product containing the resin part according to any one of claims 1 to 3, wherein the product comprises the same. The amount of fluorescence emitted by the fluorescent agent after a light irradiation test corresponding to outdoor exposure for 10 years using a xenon arc light source is within the range of 10 to 80% as compared with the amount of fluorescence emitted before light irradiation. A product containing the resin parts according to any one of claims 1 to 4, wherein the product comprises the same. A product containing the resin component according to any one of claims 1 to 5, wherein the coating amount of the fluorescent agent is 0.0005 g or more per 1 cm ² . A product containing the resin component according to any one of claims 1 to 6, wherein the application range of the fluorescent agent is 0.5 cm × 0.5 cm or more. A product containing the resin component according to any one of claims 1 to 7, wherein the fluorescent agent is transparent under visible light. A product containing the resin component according to any one of claims 1 to 8, wherein the fluorescent agent emits visible light when irradiated with ultraviolet rays. A recycling system for a product containing a resin part, which recycles the product containing the resin part according to any one of claims 1 to 9.
A product containing a resin part, which comprises a step of evaluating the degree of deterioration of the resin part by irradiating the fluorescent agent applied to the resin part with ultraviolet rays and measuring the amount of fluorescence emission. Recycling system. The method for recycling a product containing a resin component according to claim 10, further comprising a step of removing the fluorescent agent and other impurities from the resin in the next step of the deterioration degree evaluation step. When the resin parts are coated with fluorescent agents at a plurality of places and the evaluation results of the respective deterioration degrees are different, the resin parts are characterized by having a step of determining the evaluation results having a large degree of deterioration as the deterioration degree of the parts. The method for recycling a product containing the resin component according to claim 10.

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