Method for producing regenerated resin

Abstract

Provided is a method for producing a regenerated resin having excellent recycling efficiency of molded waste products. This method for producing a regenerated resin comprises a step in which a molded waste containing a thermoplastic resin is irradiated with a laser, the type of thermoplastic resin in the molded waste is identified on the basis of Raman scattered light scattered by the molded waste, and the molded waste is classified and collected. And a step for obtaining a regenerated resin from the molding waste product that has been classified and collected. The thermoplastic resin contains at least one selected from the group consisting of a structural unit (A) derived from a monomer represented by general formula (1), a structural unit (B) derived from a monomer represented by general formula (2), a structural unit (C) derived from a monomer represented by general formula (3), a structural unit (D) derived from a monomer represented by general formula (4), and a structural unit (E) derived from a monomer represented by general formula (5).

Description

Technical Field

[0001] This invention relates to a method for manufacturing recycled resin, etc. Background Technology

[0002] In recent years, as concerns about environmental degradation and increased waste emissions have deepened, the trend of recycling plastic products with the goal of achieving a circular society has intensified.

[0003] Injection molding is a representative manufacturing method for plastic products. Specifically, by injecting molten resin into a mold and allowing it to cool, a plastic product (molded body) of a specified shape can be manufactured. In this case, injection molding may generate molding waste originating from the molten resin channels within the mold, along with the plastic product itself. For example, during the process of obtaining the molded body, residual portions known as flash (found at the ends of the runner, sprue, film, or sheet), and non-standard products may be generated. The amount of these molding wastes generated during the industrial manufacturing of plastic products can sometimes be very large, therefore, the recycling of molding waste has been a subject of ongoing research.

[0004] For example, Patent Document 1 discloses an invention concerning a method for manufacturing recycled thermoplastic resin molded articles. In this method, a mixture is formed by crushing runners (molding waste) and / or defective molded articles generated during the molding process of thermoplastic resin molded articles and mixing them with new thermoplastic resin, and then injection molding the mixture again to form a thermoplastic resin molded article. The invention is characterized by the fact that even if the melt flow characteristics of the mixture change, molding can still be performed under the same conditions as when molding with new thermoplastic resin, using a gas-assisted method. Patent Document 1 also describes that, according to the invention, dimensionally stable recycled resin molded articles with high commercial value can be obtained without defects such as shrinkage marks, deformation, or warping.

[0005] Existing technical documents Patent documents Patent Document 1: Japanese Patent Application Publication No. 2006-256339 Summary of the Invention

[0006] Recycling thermoplastic resin molding waste involves recycling the waste composition obtained from recovering the generated molding waste. While it's desirable to recycle molding waste according to resin type, the waste composition often contains a mixture of multiple resins. As a result, directly using the waste composition for recycling often leads to reduced recycling efficiency and lower quality of the recycled resin.

[0007] Therefore, the present invention provides a technical solution to improve the recycling efficiency and / or the quality of the obtained recycled resin in a method for manufacturing recycled resin from molding waste.

[0008] The present invention is described below, for example.

[0009] [1] A method for manufacturing a recycled resin, comprising: A process of irradiating molded waste containing thermoplastic resin with a laser, identifying the type of thermoplastic resin in the molded waste based on Raman scattering light scattered by the molded waste, and then sorting and recycling it; and The process of obtaining recycled resin from the above-mentioned molded waste products after sorting and recycling. The thermoplastic resin described above comprises at least one structural unit (A) derived from a monomer represented by the following general formula (1), a structural unit (B) derived from a monomer represented by the following general formula (2), a structural unit (C) derived from a monomer represented by the following general formula (3), a structural unit (D) derived from a monomer represented by the following general formula (4), and a structural unit (E) derived from a monomer represented by the following general formula (5). In equation (1), R a and R b The elements are independently selected from hydrogen atoms, halogen atoms, alkyl groups having 1 to 20 carbon atoms that may have substituents, alkoxy groups having 1 to 20 carbon atoms that may have substituents, cycloalkyl groups having 5 to 20 carbon atoms that may have substituents, cycloalkoxy groups having 5 to 20 carbon atoms that may have substituents, aryl groups having 6 to 20 carbon atoms that may have substituents, heteroaryl groups containing one or more heterocyclic atoms selected from O, N, and S and having 3 to 20 carbon atoms that may have substituents, aryloxy groups having 6 to 20 carbon atoms that may have substituents, and -C≡C-R. h , R h This indicates an aryl group having 6 to 20 carbon atoms that may have substituents, or a heteroaryl group containing one or more heterocyclic atoms selected from O, N, and S and having 3 to 20 carbon atoms that may have substituents. X represents a single bond or a fluorene group that may have substituents. A and B independently represent alkylene groups with 1 to 5 carbon atoms that can have substituents. m and n independently represent integers from 0 to 6. a and b represent integers from 0 to 10 independently; In equation (2), R c and R dThe groups are independently selected from hydrogen atoms, halogen atoms, alkyl groups having 1 to 20 carbon atoms that may have substituents, alkoxy groups having 1 to 20 carbon atoms that may have substituents, cycloalkyl groups having 5 to 20 carbon atoms that may have substituents, cycloalkoxy groups having 5 to 20 carbon atoms that may have substituents, and aryl groups having 6 to 20 carbon atoms that may have substituents. Y is selected from single bonds, fluorene groups that may have substituents, and -CR groups. 21 R 22 -, -S-, -S(=O)-, -(CH2) r ―、-O-、―(CH2) r ―(SiR 23 R 24 -O) s -SiR 23 R 24 ―(CH2) r —and —CR 25 R 26 -Ph-CR 25 R 26 -, R 21 R 22 R 23 R 24 R 25 and R 26 Each can independently represent a hydrogen atom, a halogen atom, an alkyl group with 1 to 20 carbon atoms that may have substituents, or an aryl group with 6 to 30 carbon atoms that may have substituents, or R 61 and R 62 Or R 71 and R 72 The carbon rings or heterocycles formed by mutual bonding can have 1 to 20 carbon atoms and can have substituents. Ph represents phenyl. r and s independently represent integers from 0 to 5000. A and B independently represent alkylene groups with 1 to 5 carbon atoms that can have substituents. p and q represent integers from 0 to 4 independently. a and b represent integers from 0 to 10 independently; In equation (3), R a and R bThe elements are independently selected from hydrogen atoms, halogen atoms, alkyl groups having 1 to 20 carbon atoms that may have substituents, alkoxy groups having 1 to 20 carbon atoms that may have substituents, cycloalkyl groups having 5 to 20 carbon atoms that may have substituents, cycloalkoxy groups having 5 to 20 carbon atoms that may have substituents, aryl groups having 6 to 20 carbon atoms that may have substituents, heteroaryl groups containing one or more heterocyclic atoms selected from O, N, and S and having 3 to 20 carbon atoms that may have substituents, aryloxy groups having 6 to 20 carbon atoms that may have substituents, and -C≡C-R. h , R h This indicates an aryl group having 6 to 20 carbon atoms that may have substituents, or a heteroaryl group containing one or more heterocyclic atoms selected from O, N, and S and having 3 to 20 carbon atoms that may have substituents. X represents a single bond or a fluorene group that may have substituents. A and B independently represent alkylene groups with 1 to 5 carbon atoms that can have substituents. m and n independently represent integers from 0 to 6. a and b independently represent integers from 0 to 10. R' and R" are independently selected from hydroxyl, halogen atom, alkoxy group with 1 to 20 carbon atoms that can have substituents, and aryloxy group with 6 to 20 carbon atoms that can have substituents, respectively; In equation (4), R g Each can be independently represented by an alkyl group having 1 to 3 hydrogen atoms or carbon atoms. In formula (5), G1 and G2 independently represent alkylene groups with 1 to 8 carbon atoms that can have substituents. K1 and K2 independently represent hydroxyl, alkoxy, or halogen atoms, respectively. R p1 and R p2 Each of the following can be independently represented: a halogen atom, a cyano group, and an alkyl group with 1 to 8 carbon atoms that may have substituents. Ar1 and Ar2 independently represent phenyl or naphthyl groups that can have substituents. r1 and r2 independently represent integers from 0 to 2. r3 and r4 represent integers from 0 to 1 independently.

[0010] [2] According to the manufacturing method described in [1], the thermoplastic resin comprises at least one structural unit (A) derived from a monomer represented by the above general formula (1), a structural unit (B) derived from a monomer represented by the above general formula (2), a structural unit (C) derived from a monomer represented by the above general formula (3), and a structural unit (D) derived from a monomer represented by the above general formula (4).

[0011] [3] According to the manufacturing method described in [2], the thermoplastic resin is selected from the resin composed of the above-mentioned structural unit (A) and the above-mentioned structural unit (B), the resin composed of the above-mentioned structural unit (B) and the above-mentioned structural unit (C), the resin composed of the above-mentioned structural unit (B) and the above-mentioned structural unit (D), the resin composed of the above-mentioned structural unit (A), the resin composed of the above-mentioned structural unit (B), the resin composed of the above-mentioned structural unit (C), and the resin composed of the above-mentioned structural unit (D).

[0012] [4] According to the manufacturing method described in [2], the thermoplastic resin is represented by any one of the following formulas (I-1), (I-2), (I-3), (II-1), (II-2), (II-3), (II-4), (II-5) or (II-6). In the formula, x, y, and z represent the number of repeating units.

[0013] [5] According to the manufacturing method described in [1], wherein the above-mentioned thermoplastic resin is selected from the following resins: (III-1) A resin comprising the structural unit represented by formula (iii-a1), the structural unit represented by formula (iii-a2), the structural unit represented by formula (iii-a3), and the structural unit represented by formula (iii-a4); (III-2) A resin comprising the structural unit represented by formula (iii-a1), the structural unit represented by formula (iii-a2), the structural unit represented by formula (iii-a4), and the structural unit represented by formula (iii-a5); and (III-3) A resin comprising the structural unit represented by formula (iii-a1), the structural unit represented by formula (iii-a4), and the structural unit represented by formula (iii-a6). [6] The manufacturing method according to any one of [1] to [5], wherein the above-mentioned molded waste product has a gating section and / or a runner section from which the optical material is discharged after molding.

[0014] [7] The manufacturing method according to any one of [1] to [6], wherein the sorting and recycling process is carried out continuously on the conveying device, and the supply speed of the molded waste products to the conveying device is 0.5 to 5 pieces / second.

[0015] [8] The manufacturing method according to any one of [1] to [7], wherein the above-mentioned sorting and recycling process collects molded waste belonging to the recycling object by compressed air spray and / or removes molded waste not belonging to the recycling object by compressed air spray.

[0016] [9] The manufacturing method according to any one of [1] to [8] includes, prior to the sorting and recycling step described above, a step of supplying a waste composition containing the molded waste to a vibrating conveyor bed and vibrating the waste composition.

[0017]

[10] The manufacturing method according to [9] includes, in the above-mentioned sorting and recycling process, a process of feeding the molded waste to the conveying device at equal intervals.

[0018]

[11] According to the manufacturing method described in

[10] , the molded waste product has an axial gating section and two or more runner sections that extend equally in the circumferential direction from below the axial section, and the front ends of the axial gating sections of the molded waste product are all facing upwards.

[0019]

[12] A method for sorting and recycling molded waste products, comprising: A process involving irradiating molded waste containing thermoplastic resin with a laser, identifying the type of thermoplastic resin in the molded waste based on Raman scattering light from the molded waste, and then sorting and recycling it. The thermoplastic resin described above comprises at least one structural unit (A) derived from a monomer represented by the following general formula (1), a structural unit (B) derived from a monomer represented by the following general formula (2), a structural unit (C) derived from a monomer represented by the following general formula (3), a structural unit (D) derived from a monomer represented by the following general formula (4), and a structural unit (E) derived from a monomer represented by the following general formula (5). In equation (1), R a and R bThe elements are independently selected from hydrogen atoms, halogen atoms, alkyl groups having 1 to 20 carbon atoms that may have substituents, alkoxy groups having 1 to 20 carbon atoms that may have substituents, cycloalkyl groups having 5 to 20 carbon atoms that may have substituents, cycloalkoxy groups having 5 to 20 carbon atoms that may have substituents, aryl groups having 6 to 20 carbon atoms that may have substituents, heteroaryl groups containing one or more heterocyclic atoms selected from O, N, and S and having 3 to 20 carbon atoms that may have substituents, aryloxy groups having 6 to 20 carbon atoms that may have substituents, and -C≡C-R. h , R h This indicates an aryl group having 6 to 20 carbon atoms that may have substituents, or a heteroaryl group containing one or more heterocyclic atoms selected from O, N, and S and having 3 to 20 carbon atoms that may have substituents. X represents a single bond or a fluorene group that may have substituents. A and B independently represent alkylene groups with 1 to 5 carbon atoms that can have substituents. m and n independently represent integers from 0 to 6. a and b represent integers from 0 to 10 independently; In equation (2), R c and R d The groups are independently selected from hydrogen atoms, halogen atoms, alkyl groups having 1 to 20 carbon atoms that may have substituents, alkoxy groups having 1 to 20 carbon atoms that may have substituents, cycloalkyl groups having 5 to 20 carbon atoms that may have substituents, cycloalkoxy groups having 5 to 20 carbon atoms that may have substituents, and aryl groups having 6 to 20 carbon atoms that may have substituents. Y is selected from single bonds, fluorene groups that may have substituents, and -CR groups. 21 R 22 -, -S-, -S(=O)-, -(CH2) r ―、-O-、―(CH2) r ―(SiR 23 R 24 -O) s -SiR 23 R 24 ―(CH2) r —and —CR 25 R 26 -Ph-CR 25 R 26 -, R 21 R 22 R 23 R 24 R 25 and R26 Each can independently represent a hydrogen atom, a halogen atom, an alkyl group with 1 to 20 carbon atoms that may have substituents, or an aryl group with 6 to 30 carbon atoms that may have substituents, or R 61 and R 62 Or R 71 and R 72 The carbon rings or heterocycles formed by mutual bonding can have 1 to 20 carbon atoms and can have substituents. Ph represents phenyl. r and s independently represent integers from 0 to 5000. A and B independently represent alkylene groups with 1 to 5 carbon atoms that can have substituents. p and q represent integers from 0 to 4 independently. a and b represent integers from 0 to 10 independently; In equation (3), R a and R b The elements are independently selected from hydrogen atoms, halogen atoms, alkyl groups having 1 to 20 carbon atoms that may have substituents, alkoxy groups having 1 to 20 carbon atoms that may have substituents, cycloalkyl groups having 5 to 20 carbon atoms that may have substituents, cycloalkoxy groups having 5 to 20 carbon atoms that may have substituents, aryl groups having 6 to 20 carbon atoms that may have substituents, heteroaryl groups containing one or more heterocyclic atoms selected from O, N, and S and having 3 to 20 carbon atoms that may have substituents, aryloxy groups having 6 to 20 carbon atoms that may have substituents, and -C≡C-R. h , R h This indicates an aryl group having 6 to 20 carbon atoms that may have substituents, or a heteroaryl group containing one or more heterocyclic atoms selected from O, N, and S and having 3 to 20 carbon atoms that may have substituents. X represents a single bond or a fluorene group that may have substituents. A and B independently represent alkylene groups with 1 to 5 carbon atoms that can have substituents. m and n independently represent integers from 0 to 6. a and b independently represent integers from 0 to 10. R' and R" are independently selected from hydrogen atom, hydroxyl group, alkoxy group with 1 to 20 carbon atoms that can have substituents, and aryloxy group with 6 to 20 carbon atoms that can have substituents, respectively; In equation (4), R g Each can be independently represented by an alkyl group having 1 to 3 hydrogen atoms or carbon atoms. In formula (5), G1 and G2 independently represent alkylene groups with 1 to 8 carbon atoms that can have substituents. K1 and K2 independently represent hydroxyl, alkoxy, or halogen atoms, respectively. R p1 and R p2 Each of the following can be independently represented: a halogen atom, a cyano group, and an alkyl group with 1 to 8 carbon atoms that may have substituents. Ar1 and Ar2 independently represent phenyl or naphthyl groups that can have substituents. r1 and r2 independently represent integers from 0 to 2. r3 and r4 represent integers from 0 to 1 independently.

[0020] According to the present invention, recycled resin can be manufactured from molding waste with excellent recycling efficiency and / or high quality. Attached Figure Description

[0021] Figure 1 A diagram illustrating one embodiment of the mold.

[0022] Figure 2 This diagram is intended to schematically illustrate one embodiment of injection molding.

[0023] Figure 3 This is a schematic diagram of a single piece of plastic product and molding waste obtained after injection molding.

[0024] Figure 4 This diagram illustrates a method for sorting and recycling molded waste products in one embodiment of a sorting and recycling process.

[0025] Figure 5 The diagram is intended to schematically illustrate a method for sorting and recycling molded waste products in a sorting and recycling process according to another embodiment.

[0026] Figure 6 A is a schematic diagram showing a molded defect with an axial gating section 7 and a runner section 8 arranged in a state where the orientation of the axial section (gating section) is inconsistent. Figure 6 B is a schematic diagram showing the shape of molded waste products with sprue section 7 and runner section 8 arranged in a consistent manner with the shaft section (sprue section 7) extending upwards. Detailed Implementation

[0027] The following explains the meaning of the terms used in this specification and provides a detailed description of the invention.

[0028] In this specification, "halogen atom" refers to fluorine (F), chlorine (Cl), bromine (Br) and iodine (I).

[0029] Examples of alkyl groups having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecylalkyl, dodecylalkyl, eicosylalkyl, etc.

[0030] Examples of alkyl groups having 1 to 10 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, and pentyl. Examples of alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, and hexyl.

[0031] Examples of alkoxy groups with 1 to 20 carbon atoms include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentoxy, hexoxy, heptoxy, octoxy, nonoxy, decoxy, undecylalkoxy, dodecylalkoxy, and eicosylalkoxy.

[0032] Examples of alkoxy groups with 1 to 10 carbon atoms include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, and pentoxy.

[0033] Examples of cycloalkyl groups with 5 to 20 carbon atoms include cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl, cyclotridecyl, cyclotetradecyl, cyclopentadecanyl, cyclooctadecyl, bicyclo[2.2.1]heptyl, bicyclo[2.2.2]octyl, etc.

[0034] Examples of cycloalkyl groups with 5 to 10 carbon atoms include cyclopentyl, cyclohexyl, cycloheptyl, bicyclo[2.2.1]heptyl, and bicyclo[2.2.2]octyl.

[0035] Examples of cycloalkoxy groups with 5 to 20 carbon atoms include cyclopentoxy, cyclohexoxy, cycloheptoxy, cyclooctoxy, cyclododecoxy, cyclotridecoxy, cyclotetradecoxy, cyclopentadecanoxy, cyclopentadecanoxy, cyclooctadecoxy, bicyclo[2.2.1]heptoxy, and bicyclo[2.2.2]octoxy.

[0036] Examples of cycloalkoxy groups with 5 to 10 carbon atoms include cyclopentoxy, cyclohexoxy, cycloheptoxy, bicyclo[2.2.1]heptoxy, and bicyclo[2.2.2]octoxy.

[0037] Examples of aryl groups with 6 to 20 carbon atoms include phenyl, tolyl, xylyl, trimethylphenyl, tetramethylphenyl, ethylphenyl, ethylmethylphenyl, diethylphenyl, propylphenyl, isopropylphenyl, isopropylmethylphenyl, benzyl, phenethyl, phenylpropyl, naphthyl, anthracene, phenanthrene, tetraphenyl, phenylyl, pyrene, biphenyl, triphenyl, and tetraphenyl.

[0038] Examples of heteroaryl groups containing 3 to 20 carbon atoms, including one or more heterocyclic atoms selected from O, N, and S, include furanyl, benzofuranyl, isobenzofuranyl, pyrroloyl, imidazolyl, pyrazolyl, triazolyl, pyridinyl, pyrimidyl, pyridazinyl, pyrrolidinyl, indolyl, isoindolyl, indolyl, quinolinyl, isoquinolinyl, naphridinyl, quinoxolinyl, quinazolyl, pteridinyl, phenanthinyl, acridineyl, pyrimidinyl, phenazinyl, thiophenyl, thiaranyl, benzothiopheneyl, benzothiaranyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, furazolyl, oxadiazolyl, dithiazolyl, benzoxazolyl, benzoisoxazolyl, benzothiazolyl, and benzoisothiazolyl.

[0039] Examples of aryloxy groups with 6 to 20 carbon atoms include phenoxy, toluoxy, xyleneoxy, trimethylphenoxy, tetramethylphenoxy, ethylphenoxy, ethyl methylphenoxy, diethylphenoxy, propylphenoxy, isopropylphenoxy, isopropyl methylphenoxy, naphthoxy, anthraceneoxy, phenanthreneoxy, phenoxy, phenoxy, phenoxy, phenoxy, biphenoxy, triphenoxy, and tetraphenoxy.

[0040] Examples of alkyloxycarbonyl groups with 2 to 10 carbon atoms include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, and tert-butoxycarbonyl.

[0041] Examples of cycloalkyloxycarbonyl groups with 5 to 10 carbon atoms include cyclopentyloxycarbonyl, cyclohexyloxycarbonyl, bicyclo[2.2.1]heptyloxycarbonyl, and bicyclo[2.2.2]octyloxycarbonyl.

[0042] Examples of aryloxycarbonyl groups with 7 to 15 carbon atoms include phenoxycarbonyl, tolueneoxycarbonyl, xyleneoxycarbonyl, trimethylphenoxycarbonyl, tetramethylphenoxycarbonyl, ethylphenoxycarbonyl, ethylmethylphenoxycarbonyl, diethylphenoxycarbonyl, naphthoxycarbonyl, etc.

[0043] Examples of alkyl carbonyloxy groups with 2 to 10 carbon atoms include methyl carbonyloxy, ethyl carbonyloxy, propyl carbonyloxy, isopropyl carbonyloxy, and butyl carbonyloxy.

[0044] Examples of cycloalkyl carbonyl groups with 5 to 10 carbon atoms include cyclopentyl carbonyl group, cyclohexyl carbonyl group, bicyclo[2.2.1]heptyl carbonyl group, and bicyclo[2.2.2]octyl carbonyl group.

[0045] Examples of aryl carbonyloxy groups with 7 to 15 carbon atoms include phenyl carbonyloxy, tolyl carbonyloxy, xylyl carbonyloxy, trimethylphenyl carbonyloxy, tetramethylphenyl carbonyloxy, ethylphenyl carbonyloxy, ethylmethylphenyl carbonyloxy, diethylphenyl carbonyloxy, and naphthyl carbonyloxy.

[0046] Examples of hydroxyalkyl carbonyl groups with 2 to 10 carbon atoms include hydroxymethyl carbonyl, hydroxyethyl carbonyl, and hydroxypropyl carbonyl.

[0047] Examples of amide groups with 1 to 10 carbon atoms include methylaminocarbonyl, ethylaminocarbonyl, dimethylaminocarbonyl, and acetylamino.

[0048] <Method for manufacturing regenerated resin> One aspect of the present invention relates to a method for manufacturing a recycled resin. The manufacturing method includes a step of irradiating a molded waste containing thermoplastic resin with a laser, identifying the type of thermoplastic resin in the molded waste based on Raman scattering light scattered by the molded waste, and sorting and recycling it (hereinafter also referred to as the "sorting and recycling step"); and a step of obtaining recycled resin from the molded waste that has been sorted and recycled (hereinafter also referred to as the "recycled resin manufacturing step").

[0049] The manufacturing method described above may, as needed, include, before the sorting and recycling process described above, a process of supplying a waste composition containing the molded waste to a vibrating conveyor bed and vibratingly conveying the waste composition (hereinafter also referred to as the "vibrating conveying process").

[0050] In the above manufacturing method, the thermoplastic resin comprises at least one structural unit (A) derived from a monomer represented by the following general formula (1), a structural unit (B) derived from a monomer represented by the following general formula (2), a structural unit (C) derived from a monomer represented by the following general formula (3), a structural unit (D) derived from a monomer represented by the following general formula (4), and a structural unit (E) derived from a monomer represented by the following general formula (5).

[0051] In some embodiments, in the above manufacturing method, the thermoplastic resin includes at least one structural unit (A) derived from a monomer represented by the following general formula (1), a structural unit (B) derived from a monomer represented by the following general formula (2), a structural unit (C) derived from a monomer represented by the following general formula (3), and a structural unit (D) derived from a monomer represented by the following general formula (4). The present invention will now be described with reference to the accompanying drawings. It should be noted that, for illustrative purposes, the drawings contain exaggerated descriptions and may differ from the actual dimensions.

[0052] Figure 1 This diagram schematically illustrates one embodiment of the mold. The mold 1 has a sprue 2, a runner 3, a gate 4, a mold cavity core 5, and cold slug wells 6 and 6'.

[0053] Molten resin is injected from the sprue 2 into the mold 1. The inner diameter of the sprue 2 is circular, increasing as it moves into the mold 1. Therefore, the sprue 2 has a roughly frustum-shaped (truncated cone) shape. Furthermore, the length of the sprue 2 typically depends on its distance to the runner 3, i.e., the thickness of the mold.

[0054] Molten resin injected from gating 2 flows through two-way runners 3. The length and inner diameter of runners 3 are determined after considering the shape of the molded part and the properties of the molten resin. Runners 3 are typically roughly cylindrical in shape. It should be noted that, although Figure 1 The flow channel 3 is divided into two paths, but it can also be without branching and have only one flow channel, or it can be divided into three or more paths. In the case of small molded products, from the perspective of manufacturing efficiency, it is preferable that the flow channel 3 is divided into three or more paths, more preferably into 3 to 30 paths, further preferably into 3 to 25 paths, particularly preferably into 3 to 20 paths, extremely preferably into 3 to 10 paths, and most preferably into 4 to 8 paths.

[0055] The molten resin flowing through runner 3 passes through gate 4. Gate 4 controls the injection speed of the molten resin into the mold core 5. The inner diameter of gate 4 is usually set smaller than the inner diameter of runner 3, thereby accelerating the injection speed of the molten resin. It should be noted that, although Figure 1 The gate 4 is formed in a direction perpendicular to the runner 3, but it can also be formed in a direction parallel to the runner 3.

[0056] Molten resin passing through gate 4 is injected into mold core 5. Mold core 5 comprises a concave mold cavity and a convex core. Molten resin is injected into the mold cavity (concave portion) of mold core 5, and the cavity created by the mold cavity (concave portion) and the core (convex portion) during molding can be molded into the desired shape of a plastic product (molded body). It should be noted that mold core 5 can be made into a so-called "nested structure," meaning that the mold 1 is pre-processed with a pocket, and a separately manufactured mold cavity and core are assembled within this pocket processing.

[0057] The mold 1 forms a cold slug well 6 at the end of the sprue 2 and a cold slug well 6' at the end of the runner. The cold slug wells 6 and 6' have the function of preventing poor molding of plastic products by sealing in impurities, decomposition gases, etc. that may be contained in the leading edge of the molten resin.

[0058] After the molten resin is injected, the mold is cooled to solidify the molten resin present in the sprue 2, runner 3, gate 4, mold cavity core 5, and cold slug wells 6 and 6' (cold runner method). Figure 2 This diagram schematically illustrates one embodiment after injection molding. Figure 2 In this process, the plastic product 11 is cut off and removed from the molded waste. It should be noted that the plastic product 11 and the molded waste can also be removed as a single unit, and then the plastic product 11 is cut off.

[0059] like Figure 2 As shown, the portion of the solidified molten resin molded body excluding the plastic product 11 is considered a molding waste. Figure 2 In the manner shown, the molded waste includes the gating section 7 originating from the gating system, the runner section 8 originating from the runner, the gating section 9 originating from the gate, and the cold slug well sections 10 and 10' originating from the cold slug well.

[0060] Figure 3 This is a schematic diagram of an integral piece consisting of a plastic product obtained after injection molding and a molding waste. The molding waste is formed by cutting off the remaining portion of the plastic product 11 from the integral piece, and has a gating section 7, eight runner sections 8 with a branching structure, a gate section 9, and a cold slug well section 10 at the end of the gating section. In the integral piece of this embodiment, the gate section 9 is formed at the end of the runner section 9, and the plastic product 11 is formed at the front end of the gate section 9. Figure 3 The molded waste shown has an axial sprue section 7, eight leg-shaped (branched structure) runner sections 8 extending evenly in the circumferential direction from below the sprue section, a gate section 9 at the front end of the runner section 8, and a cold slug well section 10 at the end of the sprue section 7.

[0061] (Molded waste) Molding waste refers to the molded body generated during the thermoplastic resin molding process that contains any defects other than the finished product (e.g., ...). Figure 2 and Figure 3 The part other than the plastic product 11 shown. Therefore, the molded waste is composed of thermoplastic resin. The molded waste can be composed of one thermoplastic resin or two or more thermoplastic resins. The types and combinations of thermoplastic resins constituting the molded waste can be set according to the physical properties of the desired plastic product (molded body).

[0062] In some embodiments, molding waste is the portion of optical material that is to be discharged after molding. In some embodiments, molding waste is the portion of optical lenses that is to be discharged after molding.

[0063] The molded waste has at least one of the following: gating section, runner section, gate section, and cold slug well section. It should be noted that at least one of the gating section, runner section, gate section, and cold slug well section may be detached from the molded waste due to mechanical impacts such as damage caused by the recycling, conveying, or mixing of the molded waste.

[0064] In some embodiments, the molded waste has one, two, three, or four of the following: a gating section, a runner section, a gate section, and a cold slug well section. In one embodiment, the molded waste has a gating section and / or a runner section. In one embodiment, the molded waste has a gating section and / or a runner section. In one embodiment, the molded waste has a gating section, a runner section, and a gate section. In one embodiment, the molded waste has a gating section, a runner section, a gate section, and a cold slug well section. In these embodiments, the molded waste is the portion of the optical material (preferably an optical lens) that is discharged after molding.

[0065] It should be noted that the molded waste composition may contain molded waste of different shapes. It should also be noted that in this specification, "having" means allowing for other structures and is synonymous with, for example, "comprising".

[0066] In this specification, "sprue section" refers to the portion having the shape of a sprue (flow path of molten resin) originating from within the mold. In this specification, "molten resin" refers to resin in a molten state.

[0067] The shape of the gating section is preferably, but not particularly limited to, a frustum conical shape.

[0068] While the inner diameter of the sprue will vary depending on the properties of the molten resin used and the shape of the desired plastic article (molded article), it is preferably 0.1 to 10 mm, more preferably 1 to 8 mm, and even more preferably 1 to 6 mm. It should be noted that, in this specification, "inner diameter" refers to the maximum distance between two points on the outline of a vertical cross-section relative to the length direction of the object. For example, when the shape of the sprue is a frustum conical, its maximum inner diameter is equivalent to the "inner diameter".

[0069] The length of the runner (equivalent to the height of the truncated cone when it is truncated cone-shaped) is preferably 0.1 to 200 mm, more preferably 1 to 100 mm, and even more preferably 1 to 50 mm.

[0070] In this specification, "runner section" refers to a portion having the shape of a runner (the flow path of molten resin) originating within the mold. Molding defects with runner sections are prone to tangling together.

[0071] The flow channel is preferably cylindrical. Alternatively, the flow channel may have a shape in which it branches off in two or more directions, preferably in two or three directions.

[0072] The runner section is preferably formed in a direction perpendicular to the length of the gating section. This helps prevent molding defects. However, because the runner section is formed in a direction perpendicular to the length of the gating section, it can easily cause molded defective parts to become entangled.

[0073] Furthermore, as described above, the mold can have a structure that allows molten resin injected from the gating system to flow in two or more directions via branched runners. Therefore, the molded product may have two or more runner sections. In one embodiment, the molded product preferably has three or more runner sections, more preferably three to 30 runner sections, further preferably three to 25 runner sections, particularly preferably three to 20 runner sections, extremely preferably three to 10 runner sections, and most preferably four to eight runner sections.

[0074] The inner diameter of the flow channel may vary depending on the properties of the molten resin used and the shape of the desired plastic product (molded article), but is preferably 0.1 to 5 mm, more preferably 0.1 to 4 mm, and even more preferably 1 to 4 mm.

[0075] The length of the flow channel (equivalent to the height of a cylinder when it is cylindrical) is preferably 0.1 to 200 mm, more preferably 1 to 100 mm, and even more preferably 1 to 50 mm.

[0076] In this specification, "gate section" refers to the part that has the shape of a gate (the flow path of molten resin) originating from inside the mold.

[0077] There are no particular restrictions on the shape of the gate; it can be appropriately set according to the physical properties of the molten resin used and the shape of the required plastic product (molded part).

[0078] The inner diameter of the gate portion may vary depending on the properties of the molten resin used and the shape of the desired plastic product (molded article), but is preferably 0.1 to 5 mm, more preferably 0.1 to 3 mm, and even more preferably 0.1 to 2 mm. The inner diameter of the gate portion is preferably smaller than the inner diameter of the runner portion.

[0079] There are no particular restrictions on the length of the gate section; it can be set appropriately according to the physical properties of the molten resin used and the shape of the required plastic product (molded part).

[0080] In this specification, "cold slug well section" refers to a section having the shape of a cold slug well (a section containing molten resin containing impurities, decomposition gases, etc.) originating from within the mold.

[0081] The shape of the cold material well is preferably, but not particularly limited to, a test tube shape, a frustum conical shape, or a cylinder shape.

[0082] Although the inner diameter of the cold slug well may vary depending on the properties of the molten resin used and the shape of the required plastic product (molded article), when the gate is formed at the end of the runner section, it is preferably 0.1 to 10 mm, more preferably 1 to 8 mm.

[0083] Furthermore, when the gate portion is formed at the end of the runner portion, the inner diameter of the cold slug well portion is preferably 0.1 to 5 mm, more preferably 1 to 4 mm.

[0084] The length of the cold material well section is preferably, but not particularly limited to, 0.1 to 20 mm, and more preferably 0.1 to 10 mm.

[0085] Molded waste may include resins other than thermoplastic resins, additives, and decomposition products of these substances, in addition to thermoplastic resins. It should be noted that in this specification, "resin" refers to a substance with a weight-average molecular weight of 1000 or higher.

[0086] The content of thermoplastic resin in the molded waste relative to the total weight of the molded waste is usually 80% by weight or more, preferably 85% by weight or more, more preferably 90% by weight or more, further preferably 95% by weight or more, even more preferably 98% by weight or more, and particularly preferably 100% by weight.

[0087] (Waste composition) In this specification, the waste composition includes two or more types of molded waste. The waste composition includes molded waste generated during the manufacturing process of the molded body. In addition, it may also include molded articles that are recycled after being used in the market as part of a product, defective articles generated during the molding process, defective articles that appear in the productization process, and unused molded articles that are no longer needed.

[0088] The content of molded waste in the waste composition is preferably 30% by mass or more, more preferably 40% by mass or more, further preferably 50% by mass or more, and particularly preferably 50 to 100% by mass, relative to the total mass of the waste composition.

[0089] The waste composition can be made from recycled materials from the same batch of molded waste products, or it can be made from recycled materials from different batches of molded waste products and then combined for use.

[0090] (Thermoplastic resin) The thermoplastic resin constituting the molded waste can be, but is not particularly limited to, polyester resin, polycarbonate resin, polyester carbonate resin, epoxy resin, polyurethane resin, polyacrylate resin, polymethyl methacrylate resin, etc., preferably polyester carbonate resin or polyester resin, more preferably polycarbonate resin.

[0091] In this invention, the thermoplastic resin constituting the molded waste product comprises at least one structural unit selected from a monomer derived from a monomer represented by general formula (1), a structural unit selected from a monomer derived from a monomer represented by general formula (2), a structural unit selected from a monomer derived from a monomer represented by general formula (3), a structural unit selected from a monomer derived from a monomer represented by general formula (4), and a structural unit selected from a monomer derived from general formula (5). In some embodiments, the thermoplastic resin constituting the molded waste product comprises at least one structural unit selected from a monomer derived from a monomer represented by general formula (1), a structural unit selected from a monomer derived from a monomer represented by general formula (2), a structural unit selected from a monomer derived from a monomer represented by general formula (3), and a structural unit selected from a monomer derived from a monomer represented by general formula (4).

[0092] For example, when the thermoplastic resin is a polycarbonate resin, it contains at least one selected from the above-described structural unit (A), structural unit (B), and structural unit (D).

[0093] For example, when the thermoplastic resin is a polyester resin or a polyester carbonate resin, it includes at least one selected from the above-described structural unit (A), structural unit (B), structural unit (C), structural unit (D), and structural unit (E). Or, when the thermoplastic resin is a polyester resin or a polyester carbonate resin, it includes at least one selected from the above-described structural unit (A), structural unit (B), structural unit (C), and structural unit (D).

[0094] In some embodiments, when the thermoplastic resin is a resin having a structural unit (C) derived from a monomer represented by formula (3) above and / or a structural unit (E) derived from a monomer represented by formula (5) above, it is a resin containing the aforementioned structural unit (E) and generally also containing a structural unit derived from a dihydroxy compound (diol) (e.g., polyester resin). Examples of the aforementioned dihydroxy compound (diol) include structural units (A), structural units (B), structural units (D) derived from dihydroxy compounds (diols) represented by formulas (1), (2) and / or (4) above and / or structural units derived from dihydroxy compounds (diols) from which other structural units are derived later.

[0095] (1) Structural unit (A) In some embodiments, the thermoplastic resin comprises a structural unit (A) derived from a monomer represented by the following general formula (1). The structural unit (A) may comprise one type or two or more types in combination. In equation (1), R a and R b The elements are independently selected from hydrogen atoms, halogen atoms, alkyl groups having 1 to 20 carbon atoms that may have substituents, alkoxy groups having 1 to 20 carbon atoms that may have substituents, cycloalkyl groups having 5 to 20 carbon atoms that may have substituents, cycloalkoxy groups having 5 to 20 carbon atoms that may have substituents, aryl groups having 6 to 20 carbon atoms that may have substituents, heteroaryl groups containing one or more heterocyclic atoms selected from O, N, and S and having 3 to 20 carbon atoms that may have substituents, aryloxy groups having 6 to 20 carbon atoms that may have substituents, and -C≡C-R. h .

[0096] R h It indicates an aryl group having 6 to 20 carbon atoms that may have substituents, or a heteroaryl group containing one or more heterocyclic atoms selected from O, N, and S and having 3 to 20 carbon atoms that may have substituents.

[0097] R a and R b Preferably, it is a hydrogen atom, an aryl group having 6 to 20 carbon atoms that may have substituents, or a heteroaryl group having 3 to 20 carbon atoms that includes one or more heterocyclic atoms selected from O, N, and S and may have substituents. More preferably, it is a hydrogen atom, an aryl group having 6 to 20 carbon atoms that may have substituents. Even more preferably, it is a hydrogen atom, an aryl group having 6 to 12 carbon atoms that may have substituents.

[0098] In formula (1), X represents a single bond or a fluorene group that may have substituents. X is preferably a single bond or a fluorene group that may have substituents with a total number of carbon atoms of 12 to 20.

[0099] In formula (1), A and B independently represent alkylene groups having 1 to 5 carbon atoms that may have substituents, preferably alkylene groups having 2 or 3 carbon atoms.

[0100] In equation (1), m and n independently represent integers from 0 to 6, preferably integers from 0 to 3, and more preferably 0 or 1.

[0101] In equation (1), a and b independently represent integers from 0 to 10, preferably integers from 1 to 3, and more preferably 1 or 2.

[0102] In the above formula (1), the substituents that can "have substituents" can be, but are not particularly limited to, halogen atoms, alkyl groups with 1 to 10 carbon atoms, cycloalkyl groups with 5 to 10 carbon atoms, alkoxy groups with 1 to 10 carbon atoms, cycloalkoxy groups with 5 to 10 carbon atoms, alkyloxycarbonyl groups with 2 to 10 carbon atoms, cycloalkyloxycarbonyl groups with 5 to 10 carbon atoms, aryloxycarbonyl groups with 7 to 15 carbon atoms, alkylcarbonyloxy groups with 2 to 10 carbon atoms, cycloalkylcarbonyloxy groups with 5 to 10 carbon atoms, arylcarbonyloxy groups with 7 to 15 carbon atoms, hydroxyalkylcarbonyl groups with 2 to 10 carbon atoms, glycidyloxycarbonyl groups, hydroxyl groups, carboxyl groups, cyano groups, amide groups with 1 to 10 carbon atoms, etc.

[0103] As specific examples of structural unit (A), structural units derived from 2,2'-bis(1-hydroxymethoxy)-1,1'-binaphthyl, 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl (also known as "BNE"), 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthyl (also known as "DP"), 9,9-bis[6-(2-hydroxyethoxy)naphthyl-2-yl]fluorene (also known as "BNEF"), 2,2'-bis(3-hydroxypropoxy)-1,1'-binaphthyl, 2,2'-bis(4-hydroxybutoxy)-1,1'-binaphthyl, etc.

[0104] In one implementation, structural unit (A) includes at least one of structural units derived from BNE, DP, and BNEF. (2) Structural Unit (B) In some embodiments, the thermoplastic resin comprises structural units (B) derived from monomers represented by the following general formula (2). The structural unit (B) may comprise one type or a combination of two or more types. In equation (2), R c and R d The substituents are independently selected from halogen atoms, alkyl groups having 1 to 20 carbon atoms that may have substituents, alkoxy groups having 1 to 20 carbon atoms that may have substituents, cycloalkyl groups having 5 to 20 carbon atoms that may have substituents, cycloalkoxy groups having 5 to 20 carbon atoms that may have substituents, and aryl groups having 6 to 20 carbon atoms that may have substituents.

[0105] R c and R dPreferably, it is a hydrogen atom, an aryl group having 6 to 20 carbon atoms that may have substituents, or a heteroaryl group having 3 to 20 carbon atoms that includes one or more heterocyclic atoms selected from O, N, and S and may have substituents. More preferably, it is a hydrogen atom, an aryl group having 6 to 20 carbon atoms that may have substituents. Even more preferably, it is a hydrogen atom, an aryl group having 6 to 12 carbon atoms that may have substituents.

[0106] In equation (2), Y is selected from single bonds, fluorene groups that may have substituents, and -CR groups. 21 R 22 -, -S-, -S(=O)-, -(CH2) r ―、-O-、―(CH2) r ―(SiR 23 R 24 -O) s -SiR 23 R 24 ―(CH2) r —and —CR 25 R 26 -Ph-CR 25 R 26 -, Y is preferably a single bond or -CR 21 R 22 -.

[0107] R 21 R 22 R 23 R 24 R 25 and R 26 Each can independently represent a hydrogen atom, a halogen atom, an alkyl group with 1 to 20 carbon atoms that may have substituents, or an aryl group with 6 to 30 carbon atoms that may have substituents, or R 61 and R 62 Or R 71 and R 72 The carbon rings or heterocycles formed by mutual bonding can have 1 to 20 carbon atoms and can have substituents.

[0108] Ph represents phenyl.

[0109] r and s represent integers from 0 to 5000 independently.

[0110] In formula (2), A and B independently represent alkylene groups having 1 to 5 carbon atoms that may have substituents. A and B are alkylene groups having 1 to 5 carbon atoms that may have substituents, preferably alkylene groups having 2 or 3 carbon atoms.

[0111] In equation (2), p and q independently represent integers from 0 to 4, preferably 0 or 1.

[0112] In equation (2), a and b independently represent integers from 0 to 10, preferably integers from 0 to 5, more preferably integers from 0 to 2, for example, 0 or 1.

[0113] In the above formula (2), the substituents that can "have substituents" can be, but are not particularly limited to, halogen atoms, alkyl groups with 1 to 10 carbon atoms, cycloalkyl groups with 5 to 10 carbon atoms, alkoxy groups with 1 to 10 carbon atoms, cycloalkoxy groups with 5 to 10 carbon atoms, alkyloxycarbonyl groups with 2 to 10 carbon atoms, cycloalkyloxycarbonyl groups with 5 to 10 carbon atoms, aryloxycarbonyl groups with 7 to 15 carbon atoms, alkylcarbonyloxy groups with 2 to 10 carbon atoms, cycloalkylcarbonyloxy groups with 5 to 10 carbon atoms, arylcarbonyloxy groups with 7 to 15 carbon atoms, hydroxyalkylcarbonyl groups with 2 to 10 carbon atoms, glycidyloxycarbonyl groups, hydroxyl groups, carboxyl groups, cyano groups, amide groups with 1 to 10 carbon atoms, etc.

[0114] Specific examples of structural unit (B) include those derived from 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (also known as "BCFL"), 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (also known as "BPEF"), 9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl]fluorene (also known as "BPPEF"), 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-methylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-tert-butylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-isopropylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-cyclohexylphenyl]fluorene, bisphenol A (also known as "BPA"), bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bis(4-hydroxyphenyl)-2,2-dichloroethylene, bisphenol E, bisphenol F, bisphenol G, bisphenol M (also known as "BPM") Bisphenol S, Bisphenol P, Bisphenol PH, Bisphenol TMC, Bisphenol P-AP (4,4'-(1-phenylethionide)bisphenol), Bisphenol P-CDE (4,4'-cyclododecylene bisphenol), Bisphenol P-HTG (4,4'-(3,3,5-trimethylcyclohexylene)bisphenol), Bisphenol P-MIBK (4,4'-(1,3-dimethylbutyrylene)bisphenol), Bisphenol PEO-FL (bisphenoxyethanolfluorene), Bisphenol P-3MZ (4-[1-(4-hydroxyphenyl)- The structural units of bisphenol, OC-FL (4,4'-[1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethoxy]bisphenol), bisphenol Z, BP-2EO (2,2'-[[1,1'-biphenyl]-4,4'-dimethylbis(oxo)diethanol), S-BOC (4,4'-(1-methylethoxy)bis(2-methylphenol)), TrisP-HAP (4,4',4''-ethoxytriol), etc.

[0115] In one implementation, structural unit (B) includes at least one of structural units derived from BPEF, BPPEF, BPA, BPM, and BCFL. (3) Structural unit (C) In some embodiments, the thermoplastic resin comprises structural units (C) derived from monomers represented by the following general formula (3). The structural unit (C) may comprise one type or a combination of two or more types. In equation (3), R a and R b The elements are independently selected from hydrogen atoms, halogen atoms, alkyl groups having 1 to 20 carbon atoms that may have substituents, alkoxy groups having 1 to 20 carbon atoms that may have substituents, cycloalkyl groups having 5 to 20 carbon atoms that may have substituents, cycloalkoxy groups having 5 to 20 carbon atoms that may have substituents, aryl groups having 6 to 20 carbon atoms that may have substituents, heteroaryl groups containing one or more heterocyclic atoms selected from O, N, and S and having 3 to 20 carbon atoms that may have substituents, aryloxy groups having 6 to 20 carbon atoms that may have substituents, and -C≡C-R. h , R h This indicates an aryl group having 6 to 20 carbon atoms that may have substituents, or a heteroaryl group containing one or more heterocyclic atoms selected from O, N, and S and having 3 to 20 carbon atoms that may have substituents. R a and R b Preferably, it is a hydrogen atom, an aryl group having 6 to 20 carbon atoms that may have substituents, or a heteroaryl group having 3 to 20 carbon atoms that includes one or more heterocyclic atoms selected from O, N, and S and may have substituents. More preferably, it is a hydrogen atom, an aryl group having 6 to 20 carbon atoms that may have substituents. Even more preferably, it is a hydrogen atom, an aryl group having 6 to 12 carbon atoms that may have substituents.

[0116] In formula (3), X represents a single bond or a fluorenyl group that may have substituents, and X is preferably a single bond or a fluorenyl group that may have a total number of carbon atoms of 12 to 20.

[0117] In formula (3), A and B independently represent alkylene groups having 1 to 5 carbon atoms that may have substituents, preferably alkylene groups having 2 or 3 carbon atoms.

[0118] In equation (3), m and n independently represent integers from 0 to 6, preferably integers from 0 to 3, and more preferably 0 or 1.

[0119] In equation (3), a and b independently represent integers from 0 to 10, preferably integers from 1 to 3, and more preferably 1 or 2.

[0120] In formula (3), R' and R" are independently selected from hydroxyl, halogen atom, alkoxy group with 1 to 20 carbon atoms that may have substituents, and aryloxy group with 6 to 20 carbon atoms that may have substituents. R' and R" are preferably hydroxyl, straight-chain alkoxy group with 1 to 5 carbon atoms, or aryloxy group with 6 to 10 carbon atoms, and are more preferably hydroxyl, methoxy, ethoxy, or phenoxy.

[0121] In the above formula (3), the substituents that can "have substituents" can be, but are not particularly limited to, halogen atoms, alkyl groups with 1 to 10 carbon atoms, cycloalkyl groups with 5 to 10 carbon atoms, alkoxy groups with 1 to 10 carbon atoms, cycloalkoxy groups with 5 to 10 carbon atoms, alkyloxycarbonyl groups with 2 to 10 carbon atoms, cycloalkyloxycarbonyl groups with 5 to 10 carbon atoms, aryloxycarbonyl groups with 7 to 15 carbon atoms, alkylcarbonyloxy groups with 2 to 10 carbon atoms, cycloalkylcarbonyloxy groups with 5 to 10 carbon atoms, arylcarbonyloxy groups with 7 to 15 carbon atoms, hydroxyalkylcarbonyl groups with 2 to 10 carbon atoms, glycidyloxycarbonyl groups, hydroxyl groups, carboxyl groups, cyano groups, amide groups with 1 to 10 carbon atoms, etc.

[0122] As a specific example of structural unit (C), one can cite structural units derived from 2,2'-([1,1'-binaphthyl]-2,2'-dimethylbis(oxo))acetoacetic acid (BINOL-DC) and its methyl, ethyl, and phenyl esters.

[0123] In one embodiment, the structural unit (C) comprises at least one of the structural units derived from BINOL-DC and its methyl, ethyl and phenyl esters.

[0124] (BINOL-DC) (Methyl ester of BINOL-DC) (Phenyl ester of BINOL-DC) (4) Structural unit (D) In some embodiments, the thermoplastic resin comprises structural units (D) derived from monomers represented by the following general formula (4). The structural unit (D) may comprise only one type or in combination of two or more types. In equation (4), R g Each can be independently represented by a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Examples of alkyl groups having 1 to 3 carbon atoms include methyl, ethyl, propyl, and isopropyl. Wherein, R...g Ideally, each atom should be a hydrogen atom.

[0125] As a specific example of the structural unit (D), structural units derived from decahydro-1,4:5,8-dimethylbridged naphthalenediol (also known as "D-NDM") can be cited. For example, structural units derived from (decahydro-1,4:5,8-dimethylbridged naphthalene-2,6-diyl)diethanol, (decahydro-1,4:5,8-dimethylbridged naphthalene-2,7-diyl)diethanol, (2-methyldecahydro-1,4:5,8-dimethylbridged naphthalene-2,6-diyl)diethanol, (2-methyldecahydro-1,4:5,8-dimethylbridged naphthalene-2,7-diyl)diethanol, (2-ethyldecahydro-1,4:5,8-dimethylbridged naphthalene-2,6-diyl)diethanol, (2-ethyldecahydro-1,4:5,8-dimethylbridged naphthalene-2,7-diyl)diethanol, etc.

[0126] In one embodiment, the structural unit (D) includes at least one structural unit derived from D-NDM. (5) Structural unit (E) In some embodiments, the thermoplastic resin comprises structural units (E) derived from monomers represented by the following general formula (5). The structural unit (E) may comprise only one type or in combination of two or more types. In formula (5), G1 and G2 independently represent alkylene groups having 1 to 8 carbon atoms that may have substituents. Examples of alkylene groups having 1 to 8 carbon atoms include methylene, ethylene, propylene, isopropylene, butylene, isobutylene, sec-butylene, tert-butylene, and pentylene. Among these, G1 and G2 are preferably methylene, ethylene, propylene, butylene, isobutylene, and sec-butylene, more preferably methylene, ethylene, and propylene, further preferably methylene and ethylene, and particularly preferably ethylene.

[0127] In formula (5), K1 and K2 independently represent hydroxyl, alkoxy, or halogen atoms, respectively. When K1 and K2 are alkoxy groups, their carbon number is, for example, but not specifically limited to, alkoxy groups with 1 to 20 carbon atoms.

[0128] In equation (5), R p1 and R p2 Each of the following can be independently represented: halogen atom, cyano group, and alkyl group with 1 to 8 carbon atoms that may have substituents.

[0129] In formula (5), Ar1 and Ar2 independently represent phenyl or naphthyl groups that may have substituents.

[0130] In equation (5), r1 and r2 independently represent integers from 0 to 2, preferably from 0 to 1.

[0131] In equation (5), r3 and r4 independently represent integers from 0 to 1.

[0132] In the above formula (5), the substituents that can "have substituents" can be, but are not specifically limited to, halogen atoms, hydroxyl groups, carboxyl groups, cyano groups, etc. These substituents can exist alone or in combination of two or more.

[0133] In some embodiments, the thermoplastic resin preferably contains a resin having at least one structural unit selected from the following general formulas (5-1) to (5-3). General formula (5-1) is a 9,9-bis(carboxylalkyl)fluorene, which is a structural unit derived from monomers in formula (5) where r3 and r4 are 0. General formula (5-2) is a 9,9-bis(carboxylalkyl)-diarylfluorene, which is a structural unit derived from monomers where r3 and r4 are 1 and Ar1 and Ar2 are phenyl. General formula (5-3) is a 9,9-bis(carboxylalkyl)-dinaphthylfluorene, which is a structural unit derived from monomers where r3 and r4 are 1 and Ar1 and Ar2 are naphthyl. In equations (5-1), (5-2), and (5-3) above, G1 and G2, R p1 and R p2 r1 and r2 are defined in the same way as in equation (5).

[0134] As a specific example of a monomer that derives the structural unit represented by formula (5-1), 9,9-bis(carboxyl C) can be cited. 2-6 Alkyl)fluorenes, preferably 9,9-bis(carboxyl C) 2-4 Alkyl)fluorene, more preferably 9,9-bis(carboxyl C) 2-3 Alkyl fluorenes and their alkyl esters and acyl halides. Examples include 9,9-bis(2-carboxyethyl)fluorene, 9,9-bis(2-carboxypropyl)fluorene and their alkyl esters and acyl halides, with 9,9-bis(2-carboxyethyl)fluorene and their alkyl esters and acyl halides being preferred. In the case of alkyl esters, the alkyl group is, for example, but not particularly limited to, an alkyl group having 1 to 20 carbon atoms.

[0135] As a specific example of a monomer that derives the structural unit represented by formula (5-2), 9,9-bis(carboxyl C) can be cited. 2-6 Alkyl)-diphenylfluorene, preferably 9,9-bis(carboxyl)-C 2-4 Alkyl)-diphenylfluorene, more preferably 9,9-bis(carboxyl C) 2-3Alkyl)-diphenylfluorenes and their alkyl esters and acyl halides. Examples include 9,9-bis(2-carboxyethyl)-1,8-diphenylfluorene, 9,9-bis(2-carboxyethyl)-2,7-diphenylfluorene, 9,9-bis(2-carboxyethyl)-3,6-diphenylfluorene, 9,9-bis(2-carboxyethyl)-4,5-diphenylfluorene, 9,9-bis(2-carboxypropyl)-2,7-diphenylfluorene and their alkyl esters and acyl halides. In the case of alkyl esters, the alkyl group is, for example, but not particularly limited to, alkyl groups having 1 to 20 carbon atoms.

[0136] As a specific example of a monomer derived from the structural unit represented by formula (5-3), one can cite the monomer derived from 9,9-bis(carboxyl C). 2-6 The structural unit is an alkyl group (-dinaphthylfluorene). In this case, the compound derived from the above structural unit can be an alkyl ester, an acyl halide, or an anhydride. Examples include structural units derived from compounds selected from 9,9-bis(2-carboxyethyl)-1,8-bis(2-naphthyl)fluorene, 9,9-bis(2-carboxyethyl)-2,7-bis(2-naphthyl)fluorene, 9,9-bis(2-carboxyethyl)-3,6-bis(2-naphthyl)fluorene, 9,9-bis(2-carboxyethyl)-4,5-bis(2-naphthyl)fluorene, 9,9-bis(2-carboxypropyl)-2,7-bis(2-naphthyl)fluorene, 9,9-bis(2-carboxyethyl)-2,7-bis(1-naphthyl)fluorene, and their alkyl esters and acyl halides. In the case of alkyl esters, the alkyl group is, for example, but not particularly limited to, an alkyl group having 1 to 20 carbon atoms.

[0137] In some embodiments, the structural unit (E) comprises structural units derived from 9,9-bis(2-carboxyethyl)fluorene and its alkyl esters and acyl halides having 1 to 20 carbon atoms (preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms).

[0138] In a particular embodiment, the structural unit (E) comprises a structural unit derived from 9,9-bis(2-carboxyethyl)fluorene. The above-mentioned structural units (A), (B), (C), (D), and (E) can be contained in the resin individually or in combination of two or more.

[0139] (6) Other structural units In addition to the above-mentioned structural units, the resin may also contain structural units of other polycarbonate resins, and may further contain structural units of other resins (polyester resin, polyester carbonate resin, polyolefin resin, etc.).

[0140] For example, structural units of other polycarbonate resins can be derived from dihydroxy compounds (diols) such as 2,2'-[1,4-phenylenebis(methyleneoxy[1,1'-binaphthyl]-2',2-diyloxo)]bis(ethane-1-ol) (DBHBNABHP), spirodiol (3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, SPG), bisphenol TMC, bisphenol A, ethylene glycol, propylene glycol, butanediol, pentanediol, neopentanediol, octanediol, and other alkylene glycols. In addition, as structural units of polyester resins or polyester carbonate resins, examples can be found that are dicarboxylic acids or their ester derivatives derived from terephthalic acid, naphthalenedicarboxylic acid, 9H-fluorene-9,9-dipropionic acid or their monoalkyl (methyl, ethyl, propyl, isopropyl, butyl) ester derivatives or dialkyl ester derivatives (e.g., 9,9-di(2-methoxycarbonylethyl)fluorene, 9,9-bis(2-carboxyethyl)fluorene), 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl, 2,2'-bis(carboxyethoxy)-1,1'-binaphthyl, 2,2'-bis(carboxyphenoxy)-1,1'-binaphthyl, compounds represented by the following formulas, etc. In addition, as structural units derived from dihydroxy compounds (diols) constituting polyester resins or polyester carbonate resins, examples include structural units derived from dihydroxy compounds (diols) such as 2,2'-[1,4-phenylenebis(methyleneoxy[1,1'-binaphthyl]-2',2-diyloxo)]bis(ethane-1-ol) (DBHBNABHP), spirodiol (3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, SPG), bisphenol TMC, bisphenol A, ethylene glycol, propylene glycol, butanediol, pentanediol, neopentanediol, octanediol, and other alkylene glycols.

[0141] In some embodiments, it is preferable to have as little content as possible in these other structural units, for example, preferably 50% by weight or less, more preferably 30% by weight or less, and even more preferably 10% by weight or less, relative to the total weight of the thermoplastic resin constituting the molded waste.

[0142] In some embodiments, the content of the thermoplastic resin comprising at least one selected from the above-described structural unit (A), structural unit (B), structural unit (C), structural unit (D), and structural unit (E) relative to the total mass of the waste composition is preferably 80% by mass or more, more preferably 80 to 99% by mass. When the resin content is 80% by mass or more, the recycling efficiency is improved, and therefore it is preferred.

[0143] In some embodiments, the content of the thermoplastic resin comprising at least one selected from the above structural unit (A), the above structural unit (B), the above structural unit (C), and the above structural unit (D) relative to the total mass of the waste composition is preferably 80% by mass or more, more preferably 80 to 99% by mass. When the content of the above resin is 80% by mass or more, the recycling efficiency becomes particularly high, and is therefore preferred.

[0144] In some embodiments, the thermoplastic resin constituting the molded waste preferably includes at least one selected from the following: a resin composed of the above-described structural unit (A) and structural unit (B); a resin composed of the above-described structural unit (B) and structural unit (C); a resin composed of the above-described structural unit (B) and structural unit (D); a resin composed of the above-described structural unit (A); a resin composed of the above-described structural unit (B); a resin composed of the above-described structural unit (C); and a resin composed of the above-described structural unit (D). Such resins exhibit excellent optical properties, such as refractive index.

[0145] In some embodiments, the thermoplastic resin constituting the molded waste is represented by any one of the following formulas: (I-1), (I-2), (I-3), (II-1), (II-2), (II-3), (II-4), (II-5), or (II-6). Such resins exhibit excellent optical properties, such as refractive index. In the formula, x, y, and z represent the number of repeating units. There are no particular restrictions on x, y, and z, as long as they are determined according to the required molecular weight and monomer ratio. x, y, and z are each independently integers from, for example, 1 to 100, preferably integers from 1 to 10.

[0146] The weight-average molecular weight (Mw) of the thermoplastic resin comprising at least one of the above-described structural units (A), (B), (C), and (D) is preferably, but not particularly limited, to 10,000 to 70,000, more preferably 15,000 to 50,000. When the weight-average molecular weight (Mw) is 10,000 or higher, it is preferable to maintain, for example, adequate strength of the molded body as a resin for optical lenses. On the other hand, when the weight-average molecular weight (Mw) is 70,000 or lower, appropriate flowability and improved moldability can be ensured during resin molding, which is also preferable. It should be noted that, in this specification, "weight-average molecular weight (Mw)" refers to the weight-average molecular weight converted from polystyrene obtained using gel permeation chromatography (GPC).

[0147] In some embodiments, the thermoplastic resin constituting the molded waste is a resin (e.g., a polyester resin) comprising a structural unit (E) derived from a monomer represented by formula (5) above (e.g., at least one structural unit selected from formulas (5-1), (5-2), and (5-3) above) and a structural unit derived from a dihydroxy compound (diol). Examples of the dihydroxy compound (diol) above include structural units (A), structural units (B), structural units (D) derived from dihydroxy compounds (diols) represented by formulas (1), (2), and / or (4) above, and / or structural units derived from dihydroxy compounds (diols) from which other structural units are derived later.

[0148] In addition, the thermoplastic resin may contain structural units (E) derived from the monomer represented by the above formula (5) (for example, at least one structural unit selected from the above formulas (5-1), (5-2) and (5-3)) and structural units derived from the above dihydroxy compound (diol), as well as structural units of other resins (polyester resin, polyester carbonate resin, polyolefin resin) etc.

[0149] In some embodiments, the thermoplastic resin constituting the molded waste comprises structural units derived from 9,9-bis(2-carboxyethyl)fluorene (or its esters and acyl halides).

[0150] For example, the thermoplastic resin constituting the molded waste may be a resin containing at least one structural unit selected from formulas (iii-a1) to (iii-a5). In the structural units represented by formulas (iii-a1) to (iii-a6) above, formulas (iii-a1) and (iii-a2) are structural units derived from dicarboxylic acids (or their esters or acyl halides), formulas (iii-a3), (iii-a4), (iii-a5) and (iii-a6) are structural units derived from dihydroxy compounds (diols), and the structural unit represented by formula (iii-a1) is a structural unit derived from 9,9-bis(2-carboxyethyl)fluorene (or its esters and acyl halides).

[0151] For example, thermoplastic resins are selected from (III-1), (III-2), and (III-3). These resins exhibit excellent optical properties such as refractive index.

[0152] (III-1) A resin comprising the structural unit represented by formula (iii-a1), the structural unit represented by formula (iii-a2), the structural unit represented by formula (iii-a3), and the structural unit represented by formula (iii-a4). In some embodiments, the thermoplastic resin is a polyester resin in which ester bonds are formed between the structural units represented by formulas (iii-a1) and (iii-a2), and between the structural units represented by formulas (iii-a3) and (iii-a4). The proportions of each structural unit are not particularly limited. Alternatively, other structural units may be included.

[0153] In one embodiment, the thermoplastic resin is a copolyester resin obtained from naphthalene dicarboxylic acid, BPEF, fluorene dipropionate, and ethylene glycol.

[0154] (III-2) A resin comprising the structural unit represented by formula (iii-a1), the structural unit represented by formula (iii-a2), the structural unit represented by formula (iii-a4), and the structural unit represented by formula (iii-a5). In some embodiments, the thermoplastic resin is a polyester resin in which ester bonds are formed between the structural units represented by formulas (iii-a1) and (iii-a2), and between the structural units represented by formulas (iii-a4) and (iii-a5). The proportions of each structural unit are not particularly limited. Alternatively, other structural units may be included.

[0155] In one embodiment, the thermoplastic resin is a copolyester resin obtained from naphthalene dicarboxylic acid, BPPEF, fluorene dipropionate, and ethylene glycol.

[0156] (III-3) Resins containing structural units represented by formula (iii-a1), formula (iii-a4), and formula (iii-a6). In some embodiments, the thermoplastic resin is a polyester resin in which ester bonds are formed between the structural units represented by formula (iii-a1) and the structural units represented by formulas (iii-a4) and (iii-a6). The proportions of each structural unit are not particularly limited. Alternatively, other structural units may be included.

[0157] In one embodiment, the thermoplastic resin is a copolyester resin obtained from BNEF, fluorene dipropionate, and ethylene glycol.

[0158] In another embodiment, the thermoplastic resin is a copolyester resin obtained from BNEF, BPEF, fluorene dipropionate, and ethylene glycol.

[0159] It should be noted that the weight-average molecular weight (Mw) of the resins (III-1) to (III-3) described above is preferably, but not particularly limited to, 10,000 to 70,000, and more preferably 15,000 to 50,000. When the weight-average molecular weight (Mw) is 10,000 or higher, it is preferable to maintain, for example, adequate strength of the molded body as a resin for optical lenses. On the other hand, when the weight-average molecular weight (Mw) is 70,000 or lower, it is preferable to ensure appropriate flowability and improve moldability during resin molding.

[0160] (Additives / Decomposition Products) There are no particular restrictions on the use of additives that constitute molded waste products; any known additives may be used.

[0161] In addition, as decomposition products constituting molded waste, examples include monomers, dimers, copolymers, oligomers, aromatic alcohols such as phenol, carbonate diesters such as diphenyl carbonate, monomer modifiers such as those with at least one structural unit (A) to (E) selected from general formulas (1) to (5), and resin modifiers having partial structures represented by formulas (B-1) and (B-2). The following is a detailed explanation of each process.

[0162] In some embodiments, the method for manufacturing recycled resin includes, as optional steps, a vibration conveying process, a sorting and recycling process, and a recycled resin manufacturing process.

[0163] 1. Vibrating conveyor process The vibratory conveying process is a process of feeding a waste composition containing shaped waste into a vibratory conveying bed and vibrating the waste composition.

[0164] When molded waste has a structure that is prone to entanglement, such as a flow channel, it is easy for the molded waste to become entangled with each other. If a waste composition containing entangled molded waste is attempted to be fed into a shredder, it may obstruct the feeding into the shredder, resulting in a decrease in recycling efficiency. In this case, by passing the molded waste through a vibrating conveyor process before the sorting and recycling process, the entanglement of the molded waste can be eliminated or reduced, resulting in the production of recycled resin from the molded waste with excellent recycling efficiency.

[0165] The vibration conveying process is an arbitrary process that can be implemented as needed. When there is little or no entanglement between the molded waste products, the vibration conveying process can be omitted. When the molded waste products have flow channels, it is preferable to perform the vibration conveying process before the sorting and recycling process.

[0166] (Vibrating conveyor bed) There are no particular limitations on the vibrating conveyor bed, as long as it can eliminate or reduce the entanglement of the molded waste products contained in the waste composition by vibrating and conveying the waste composition. Specifically, the vibrating conveyor bed can be a plate-shaped member, a conveyor belt, a turntable, or other shapes, preferably a plate-shaped member or a conveyor belt, and more preferably a conveyor belt. In this case, the size of the vibrating conveyor bed can be appropriately set. In addition, the vibrating conveyor bed can be set parallel to the horizontal plane or at an inclination.

[0167] When the vibrating conveyor bed is a plate-shaped component or a conveyor belt, the width of the vibrating conveyor bed is preferably 5cm to 5m, more preferably 10cm to 3m, and even more preferably 20cm to 1m.

[0168] In addition, the length of the vibrating conveyor bed is preferably 50cm to 30m, more preferably 1 to 10m, and even more preferably 1 to 5m.

[0169] Vibrating conveyor beds are usually equipped with a vibration mechanism (such as an induction motor, resonator, vibrating motor, etc.).

[0170] In addition, the vibrating conveyor bed may also be equipped with a feeder for supplying the waste composition to the vibrating conveyor bed, a vibration control mechanism (full-time drive, intermittent drive, variable speed drive, etc.) for controlling the vibration mechanism, and a discharge mechanism for removing the waste composition after removing it from the vibrating conveyor bed.

[0171] (Vibration conveyor) By vibrating and conveying the waste composition on a vibrating conveyor bed, the entanglement of the molded waste components contained in the waste composition can be eliminated or reduced.

[0172] The vibration frequency of the vibrating conveyor bed is preferably 1-1000Hz, more preferably 5-500Hz, further preferably 10-100Hz, and even more preferably 30-80Hz. When the vibration frequency of the vibrating conveyor bed is within the above range, entanglement is easily eliminated, energy consumption is suppressed, and operating efficiency is high, making it a preferred option.

[0173] The feed amount of the waste composition relative to the width of the vibrating conveyor bed is preferably 100-5000 g / m, more preferably 100-2000 g / m, and from the perspective of effectively eliminating or reducing entanglement, it is more preferably 100-1500 g / m, particularly preferably 100-1000 g / m, and from the perspective of high manufacturing efficiency, it is most preferably 500-1000 g / m.

[0174] The feeding speed of the waste composition to the vibrating conveyor bed is preferably 5 to 100 g / s, more preferably 5 to 60 g / s, more preferably 5 to 40 g / s from the perspective of effectively eliminating or reducing entanglement, and more preferably 15 to 40 g / s from the perspective of manufacturing efficiency.

[0175] In one embodiment, the amount of waste composition supplied relative to the width of the vibrating conveyor bed is preferably 100 to 2000 g / m, and the supply speed of the waste composition supplied to the vibrating conveyor bed is preferably 5 to 40 g / s, more preferably the above-mentioned supply amount is 100 to 1500 g / m and the above-mentioned supply speed is 5 to 40 g / s, and even more preferably the above-mentioned supply amount is 500 to 1000 g / m and the above-mentioned supply speed is 15 to 40 g / s.

[0176] The specific gravity of the molded waste is preferably 0.9 to 1.5, more preferably 0.9 to 1.4, further preferably 1.0 to 1.4, even more preferably 1.0 to 1.3, and particularly preferably 1.1 to 1.3. When the specific gravity of the molded waste is within the above range, it is preferable because it is easy to eliminate or reduce the entanglement of the molded waste by using vibration conveying.

[0177] 2. Sorting and recycling process The sorting and recycling process involves irradiating molded waste containing thermoplastic resin with a laser, and then identifying the type of thermoplastic resin in the molded waste based on the Raman scattered light scattered by the molded waste, thereby sorting and recycling the molded waste.

[0178] When recycling molding waste from thermoplastic resins, the generated molding waste is collected and the resulting waste composition is recycled. Although molding waste needs to be sorted and recycled according to resin type, the waste composition may contain a mixture of multiple resins. As a result, directly using the waste composition for recycling often leads to a decrease in recycling efficiency and the quality of the recycled resin. According to the sorting and recycling process of this embodiment, before recycling, molding waste can be sorted and recycled according to the type and grade of thermoplastic resin using a simple laser method. As a result, excellent recycling efficiency and / or the production of high-quality recycled resin can be achieved.

[0179] Therefore, another embodiment of the present invention also relates to a method for sorting and recycling molded waste containing thermoplastic resin, including the sorting and recycling step. Specifically, one embodiment of the present invention provides a sorting and recycling method for molded waste comprising the following steps: irradiating the molded waste containing thermoplastic resin with a laser, identifying the type of thermoplastic resin in the molded waste based on Raman scattering light scattered by the molded waste, and sorting and recycling it, wherein the thermoplastic resin comprises at least one structural unit (A) derived from a monomer represented by the above general formula (1), a structural unit (B) derived from a monomer represented by the above general formula (2), a structural unit (C) derived from a monomer represented by the above general formula (3), a structural unit (D) derived from a monomer represented by the above general formula (4), and a structural unit (E) derived from a monomer represented by the above general formula (5). The sorting and recycling method of this embodiment can perform the above-mentioned vibration conveying step before the sorting and recycling step.

[0180] Figure 4 The diagram illustrates a method for classifying and recycling molded waste products in a classification and recycling process according to one embodiment of the present invention.

[0181] like Figure 4 As shown, the classification and recycling of molded waste products involves identifying the types of thermoplastic resins that constitute the molded waste product 12, and then classifying and recycling the molded waste product 12 according to the types of thermoplastic resins based on the identification results.

[0182] The sorting and recycling process is preferably carried out continuously on a conveyor system. For example, such as Figure 4 As shown, molded waste 12 containing thermoplastic resin is supplied to a conveying device such as a conveyor belt 16 and continuously fed on the conveyor belt 16.

[0183] There are no particular limitations on the conveying device, as long as it can transport the formed waste 12. In addition to conveyor belts, belt loaders and the like can also be used.

[0184] Preferably, the molded waste 12 is fed to the conveying device at equal intervals. By feeding at equal intervals, the accuracy of identification and sorting recycling of thermoplastic resins can be improved.

[0185] Preferably, the molded waste products 12 are fed onto the conveying device one by one in a state where they are untangled. If the molded waste products 12 become entangled, it is preferable to perform a sorting and recycling process in a state where the entanglement of the molded waste products has been untangled by performing the above-described vibration conveying process. For example, after the above-described vibration conveying process, the process can be carried out by a system (e.g., an arm robot, a picking robot) that places the untangled molded waste products at equal intervals on the conveying device.

[0186] Preferably, the shaped waste products 12 are fed onto the conveyor with a consistent shape orientation. By configuring them with consistent shapes, identification errors can be reduced and prevented. For example, as... Figure 3 As shown, the molded product 12 has an axial gating section 7 and two or more runner sections 8 extending circumferentially from below the axis of the gating section 7. When viewed from the side, the molded product 12 with this axial gating section 7 and bifurcated runner sections 8 has a roughly T-shaped appearance. Figure 6 As shown in B, the roughly T-shaped molded waste 12 is preferably arranged in an inverted T-shape on the conveyor with the shapes facing the same direction.

[0187] Specifically, it is preferable to arrange the molded waste products 12 on the conveyor with their front ends of the axial sprue section 7 all facing upwards in a uniform orientation. By arranging them with uniform orientation, the focus of laser irradiation can be focused, improving the recognition rate and resulting in a form with a recognition rate close to 100%. On the other hand, if the orientations are inconsistent and they are arranged haphazardly, the focus may not be able to be focused, and the recognition accuracy may be reduced.

[0188] In addition, such as Figure 6 As shown in B, it is preferable to arrange the molded waste product 12 in contact with the conveying device by its bifurcated runner section 8, which extends evenly in the circumferential direction. This arrangement allows the molded waste product 12 to be stably positioned on the conveying device, preventing it from rolling or moving during transport and improving identification accuracy. On the other hand, when the approximately T-shaped molded waste product 12 is arranged in a sideways tilted state, i.e., with the front end of the axial runner section 7 in contact with the conveyor belt, it may roll or move during transport on the conveyor belt, resulting in reduced identification accuracy.

[0189] When sorting and recycling molded waste products of various shapes, it is preferable to arrange them on the conveyor with the convex and acute-angled parts facing upwards.

[0190] In some embodiments, when the above-mentioned vibration conveying process is present, the molded waste products are arranged on the conveying device with the same orientation after the vibration conveying process.

[0191] This alignment of orientation on the conveyor is achieved by, for example, an arm robot, a pickup robot, etc.

[0192] From the perspective of preventing identification errors, the spacing between the molded waste products on the conveying device in the direction of travel of the conveying device is preferably 1 to 30 cm, more preferably 1 to 20 cm, and even more preferably 1 to 10 cm.

[0193] From the perspective of reducing and preventing identification errors, the spacing between the molded waste products on the conveying device in the width direction of the conveying device (the direction perpendicular to the direction of travel of the conveying device) is preferably 1 to 30 cm, more preferably 1 to 20 cm, and even more preferably 1 to 10 cm.

[0194] There is no particular limitation on the supply speed of the aforementioned molded waste products to the conveying device. From the perspective of reducing and preventing identification errors, it is preferably 0.5 to 5 pieces / second, more preferably 0.5 to 4 pieces / second, and even more preferably 1 to 3 pieces / second.

[0195] The speed of the conveying device is preferably, but not particularly limited to, 10 to 100 m / s, more preferably 20 to 80 m / s, and even more preferably 30 to 50 m / s.

[0196] The sorting and recycling speed of molded waste products is preferably, but not particularly limited to, 0.2 to 3.0 pieces / second, more preferably 0.3 to 2.0 pieces / second. It should be noted that "sorting and recycling speed" refers to the processing speed from the time the laser irradiates the molded waste products until the type of thermoplastic resin in the molded waste products is identified and sorted for recycling.

[0197] It should be noted that, without a doubt, the sorting and recycling process can be implemented discontinuously.

[0198] (Identification) In an embodiment of the present invention, during the sorting and recycling process, the thermoplastic resin constituting the molded waste is identified using Raman scattering spectroscopy. This is achieved by irradiating the molded waste with a laser, and the types of thermoplastic resin constituting the waste are identified based on the Raman scattered light. By using Raman scattering light to identify the resin, resins with different structural units constituting the molded waste can be distinguished from each other. By employing this Raman scattering-based identification method, different types of thermoplastic resins can be sorted and recycled with high accuracy, thereby improving recycling efficiency and / or the quality of the recycled resin.

[0199] For example, the identification of resin types using Raman scattering light, such as... Figure 4 As shown, this can be implemented using a Raman scattering identification device 13. Using the Raman scattering identification device 13, a laser (not shown) is irradiated onto the molded waste 12, and the type of thermoplastic resin in the molded waste is identified based on the Raman scattered light scattered by the molded waste.

[0200] A typical Raman scattering identification device includes a unit that irradiates a laser, measures the Raman scattering spectrum, and acquires Raman scattering information; and an identification unit that analyzes the measured Raman scattering information and known Raman scattering information (the Raman scattering information of a reference resin) to identify the type of resin constituting the molded waste product. For example, the Raman scattering information of a known resin (the Raman scattering information of a reference resin) is first obtained beforehand. Then, a laser is irradiated onto the molded waste product, which is the resin to be identified, to measure the Raman scattering spectrum and obtain the Raman scattering information of each resin. The type of resin is then identified by comparing the Raman scattering information of the reference resin with the measured Raman scattering information of the resin to be identified.

[0201] Figure 4 This is a top-down view of the Raman scattering identification device 13. Figure 4 As shown, the Raman scattering identification device 13 includes a laser irradiation unit (not shown) located above the conveyor belt 16 and a sensor 17 located above the conveyor belt 16. A laser is irradiated from the laser irradiation unit onto the molded waste products (12a, 12b) on the conveyor belt 16. The sensor 17 captures the reflected Raman light to measure the Raman scattering spectrum and obtain Raman scattering information. The Raman scattering information is processed by the Raman scattering information analysis unit (not shown) of the Raman scattering identification device 13 to identify the type of resin.

[0202] Such Raman scattering identification devices are described in, for example, Japanese Patent No. 4203916, Japanese Unexamined Patent No. 2009-092458, Japanese Unexamined Patent No. 2011-214917, and Japanese Unexamined Patent No. 2012-42248, and these devices can also be well used in the manufacturing method of the present invention.

[0203] In the manufacturing method of the present invention, as described above, the thermoplastic resin includes at least one structural unit (A) derived from a monomer represented by general formula (1), a structural unit (B) derived from a monomer represented by general formula (2), a structural unit (C) derived from a monomer represented by general formula (3), a structural unit (D) derived from a monomer represented by general formula (4), and a structural unit (E) derived from a monomer represented by general formula (5). By employing a Raman scattering-based identification method to identify and distinguish differences in the intensity and pattern of scattered light, it is possible to quickly and accurately identify resins containing at least one of the above-mentioned structural units (A), (B), (C), (D), and (E), as well as resins containing multiple structural units, and other differences in their structural unit types and proportions.

[0204] (Classified recycling) After identifying the type of thermoplastic resin in the molded waste as described above, the molded waste is classified and recycled according to the type of thermoplastic resin constituting it based on the identification results. If the type of thermoplastic resin in the molded waste matches the resin to be recycled, it is collected as molded waste intended for recycling. Conversely, if the type of thermoplastic resin in the molded waste does not match the resin to be recycled, it is excluded from the list of molded waste intended for recycling and collected as molded waste not intended for recycling, as needed. In some embodiments, the classification and recycling process includes a step of collecting molded waste intended for recycling by compressed air spraying and / or a step of removing molded waste not intended for recycling by compressed air spraying.

[0205] For example, such as Figure 4 As shown, the Raman scattering identification device has a mechanism (unit) for injecting compressed air 14 based on the identification results based on Raman scattering light. For sorting and recycling, if the type of thermoplastic resin constituting the molded waste matches the resin to be recycled, the molded waste 12a to be recycled is collected into a recycling container 15 located outside the Raman scattering identification device 13 by injecting compressed air 14.

[0206] Although not illustrated, various types of molded waste can be recycled based on the identification results based on Raman scattering light. For example, based on the identification results based on Raman scattering light, compressed air 14 can be injected to sequentially collect the first type of molded waste 12a (identified product) belonging to the recycling target into the recycling container 15. Then, on the downstream side of the conveyor belt, the second type of molded waste 12a (identified product) belonging to the recycling target is collected into the recycling container 15. Further downstream, the third and subsequent types of molded waste 12a (identified product) belonging to the recycling target are collected into the recycling container 15.

[0207] Figure 5 The diagram is intended to schematically illustrate a method for sorting and recycling molded waste products in a sorting and recycling process according to another embodiment.

[0208] exist Figure 5 In the embodiment shown, if the type of thermoplastic resin constituting the molded waste is inconsistent with the resin of the recycling target, the molded waste is discharged outside the conveyor belt 16 (outside the Raman scattering identification device 13) by spraying compressed air 14, and the molded waste 12a (identified product) that belongs to the recycling target is collected downstream of the conveyor belt 16.

[0209] You can also Figure 4 The recycling mechanism shown is Figure 5The recycling facility shown is used to classify and collect molded waste 12a that belongs to the recycling target and molded waste 12b (non-identified product) that does not belong to the recycling target.

[0210] exist Figure 4 and Figure 5 In the process of collecting molded waste 12a that belongs to the recycling target and molded waste 12b (non-identification product) that does not belong to the recycling target, compressed air 14 is used. However, it is also possible to separate and collect molded waste 12a that belongs to the recycling target and molded waste 12b (non-identification product) that does not belong to the recycling target by spraying inert gas instead of compressed air 14.

[0211] 3. Recycled resin manufacturing process The recycled resin manufacturing process is a process of obtaining recycled resin from the aforementioned molded waste through the sorting and recycling process. Since the molded waste is obtained from the sorting and recycling process, it contains the same type of thermoplastic resin. Therefore, in the recycled resin manufacturing process, high-quality recycled resin can be produced from the molded waste with high recycling efficiency.

[0212] There are no particular limitations on the recycled resin manufacturing process; any suitable known method can be used, as long as recycled resin can be obtained from the sorted and recycled molding waste. In a preferred embodiment, the recycled resin manufacturing process includes a process of crushing the molding waste (crushing process), a process of removing impurities contained in the molding waste (impurity removal process), and a process of manufacturing recycled resin (resin manufacturing process).

[0213] (Grinding process) The crushing process is the process of crushing shaped waste products.

[0214] Molded waste can be pulverized into shapes suitable for recycling.

[0215] The crushing method can be any method, but is not particularly limited to compression, impact, shearing, or friction.

[0216] Examples of usable crushers include coarse grinding mills such as jaw crushers, gyratory crushers, impact crushers, single-shaft crushers, and twin-shaft crushers; medium-sized grinding mills such as roller crushers, edge runners, mill mills, SAG (Semi-Autogenous Grinding) mills, crushing rollers, hammer mills, and roller mills; and fine grinding mills such as bead mills, ball mills, vibrating ball mills, rod mills, jet mills, and planetary mills. Coarse grinding mills are preferred, and single-shaft crushers and twin-shaft crushers are even more preferred. Specific examples of crushers include high-powered crushers 35-560, 35-720, 55-770, and 55-1050 (manufactured by Tanaka Co., Ltd.), and low-speed crushers KGA-250 and KGA-350 (manufactured by Kawada Co., Ltd.). It should be noted that the above crushers can be used individually or in combination.

[0217] (Impurity removal process) The impurity removal process is the process of removing impurities contained in the molded waste. Molded waste sometimes contains two or more types of resin. Furthermore, it may also contain additives, resin decomposition products, and additive decomposition products. From the perspective of producing recycled resin with excellent physical properties, it is preferable to remove impurities from the molded waste.

[0218] Methods for removing impurities contained in molded waste products may include, but are not specifically limited to, methods that utilize the differences in physical properties between the target resin and the impurities, or methods that utilize the differences in chemical properties between the target resin and the impurities.

[0219] Methods that utilize the difference in physical properties between the target resin and impurities include using magnetic force, wind force, sieving, specific gravity, and buoyancy.

[0220] For example, when the impurity is metallic, it can be removed using magnetic force. Specifically, metals that may be present in the molded waste can be removed by using magnets or metal detectors.

[0221] In addition, it can also be applied to impurity removal methods that utilize the difference in buoyancy by using brine, impurity removal methods that utilize the difference in adsorption by using activated carbon, and impurity removal methods that utilize the difference in specific gravity by using hydrocyclone treatment.

[0222] One method that utilizes the difference in chemical properties between the target resin and impurities is to depolymerize the target resin.

[0223] For example, a resin having at least one structural unit selected from the above structural unit (A), the above structural unit (B), the above structural unit (C), the above structural unit (D) and the above structural unit (E) can be treated with an alkaline aqueous solution and depolymerized to obtain at least one monomer compound (depolymerized monomer) selected from the above general formulas (1) to (5).

[0224] In cases where molded waste contains thermoplastic resin having at least one structural unit selected from structural units (A) to (E) above, as well as other resins that are not depolymerized (e.g., impurity resins such as cyclic polyolefins), treatment with an alkaline aqueous solution results in only the resin having at least one structural unit selected from structural units (A) to (E) being depolymerized. Since the resulting monomer compound (depolymerized monomer) differs significantly in physical properties from the other resins that are not depolymerized (impurity resins), the other resins that are not depolymerized (impurity resins) can be removed.

[0225] It should be noted that the above-described alkali treatment is not particularly limited and can be carried out by known methods. For example, the above-described alkali treatment can be carried out by adding the waste composition and an alkaline aqueous solution to the reaction solvent to allow them to react.

[0226] Examples of solvents used in the above reactions include, but are not specifically limited to, aliphatic hydrocarbon solvents and aromatic hydrocarbon solvents.

[0227] Examples of aliphatic hydrocarbon solvents mentioned above include, but are not specifically limited to, pentane, hexane, heptane, octane, nonane, decane, cyclohexane, and cyclodecane.

[0228] Examples of aromatic hydrocarbon solvents mentioned above include, but are not specifically limited to, toluene, xylene, and mesitylene.

[0229] The reaction solvent is preferably an aromatic hydrocarbon solvent, more preferably toluene or xylene. It should be noted that the above-mentioned reaction solvents can be used alone or in combination of two or more.

[0230] The amount of reaction solvent used can be, but is not particularly limited to, 30 to 2000 parts by mass relative to 100 parts by mass of the waste composition, more preferably 40 to 1500 parts by mass, and even more preferably 100 to 1000 parts by mass. When the amount of reaction solvent used is 30 parts by mass or more, the organic components of the waste composition can be fully dissolved in the reaction solvent, which improves the reaction efficiency and is therefore preferred. On the other hand, when the amount of reaction solvent used is 2000 parts by mass or less, the reaction time is shortened and is therefore preferred.

[0231] In some embodiments, the above-mentioned alkaline aqueous solution comprises a metal hydroxide and water.

[0232] Examples of the aforementioned metal hydroxides include, but are not specifically limited to, hydroxides of alkali metals such as sodium hydroxide, potassium hydroxide, and rubidium hydroxide; and hydroxides of alkaline earth metals such as calcium hydroxide and barium hydroxide. Among these, alkali metal hydroxides are preferred, sodium hydroxide and potassium hydroxide are more preferred, and potassium hydroxide is even more preferred. It should be noted that these metal hydroxides can be used alone or in combination of two or more.

[0233] The amount of the aforementioned metal hydroxide is preferably, but not particularly limited to, 1.5 to 10 moles, more preferably 2 to 8 moles, and even more preferably 2 to 4 moles, relative to 1 mole of the carbonate bond in the polycarbonate resin. When the amount of metal hydroxide used is 1.5 moles or more, sufficient depolymerization is preferred. On the other hand, when the amount of metal hydroxide used is 10 moles or less, manufacturing costs are reduced, which is preferred.

[0234] The concentration of the metal hydroxide in the alkaline aqueous solution relative to the total mass of the alkaline aqueous solution is preferably 10-60% by mass, more preferably 15-55% by mass, and even more preferably 20-50% by mass. When the concentration of the metal hydroxide is 10% by mass or more, the depolymerization reaction rate is increased, which is preferred. On the other hand, when the concentration of the metal hydroxide is 60% by mass or less, the alkaline aqueous solution does not form a slurry, making the reaction easier to proceed, which is also preferred.

[0235] The processing temperature (depolymerization reaction temperature) is preferably, but not particularly limited to, 120°C or below, more preferably 100°C or below, and even more preferably 30 to 90°C. When the processing temperature is below 120°C, side reactions can be prevented, which is preferable.

[0236] (Resin manufacturing process).

[0237] The resin manufacturing process is the process of producing recycled resin.

[0238] In the above-mentioned impurity removal process, if the impurities are removed by utilizing the difference in physical properties between the target resin and the impurities, the resin obtained after removing the impurities becomes a regenerated resin since the composition of the target resin remains unchanged.

[0239] On the other hand, if impurities are removed by utilizing the difference in chemical properties between the target resin and the impurities, recycled resin can be produced by polymerizing the depolymerized monomers of the target resin. In this case, the produced recycled resin can be the same type of resin as the target resin contained in the molding waste, or it can be a different type of resin.

[0240] There are no particular limitations on the method of polymerizing the depolymerized monomers of the target resin to produce regenerated resin, and it can be produced by known methods.

[0241] For example, when the depolymerization monomer is at least one monomer compound selected from the above general formulas (1) to (4), the dihydroxy compound (diol) and carbonate diester represented by the above formulas (1), (2) and / or (4) can be used to produce polycarbonate resin as a recycled resin by solution polycondensation in the presence of an alkaline compound catalyst and / or an ester exchange catalyst, or in the absence of a catalyst.

[0242] In addition, the dihydroxy compounds (diols) represented by formulas (1), (2) and / or (4), the monomer compounds represented by formula (3), and the diesters can be subjected to solution polycondensation in the presence of an alkaline compound catalyst and / or an ester exchange catalyst, or in the absence of a catalyst, to produce polyester carbonate resins as recycled resins.

[0243] In addition, the dihydroxy compounds (diols) represented by formulas (1), (2) and / or (4) and dicarboxylic acid (ester) compounds can be reacted with basic compound catalysts and / or transesterification catalysts to produce polyester resins as recycled resins.

[0244] In addition, the dihydroxy compound and the dicarboxylic acid (ester) compound represented by formula (3) can be reacted to produce a polyester resin as a recycled resin in the presence of an alkaline compound catalyst and / or an ester exchange catalyst.

[0245] In addition, the dihydroxy compound and the dicarboxylic acid (ester) compound represented by formula (5) can be reacted to produce a polyester resin as a recycled resin in the presence of an alkaline compound catalyst and / or an ester exchange catalyst.

[0246] In the above case, compounds that derive structural units represented by general formulas (1) to (5) and diesters may also be used, along with compounds that derive structural units of other polycarbonate resins and compounds that derive structural units of other resins (polyester resin, polyester carbonate resin, polyolefin resin), etc.

[0247] Examples of the aforementioned dicarbonate include, but are not particularly limited to, diphenyl carbonate, dimethyl carbonate, bis(chlorophenyl) carbonate, m-toluene carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, and dicyclohexyl carbonate. Among these, diphenyl carbonate is preferred.

[0248] The amount of the dicarbonate compound used relative to 1 mole of the dihydroxy compound is preferably 0.97 to 1.20 moles, more preferably 0.98 to 1.10 moles, and even more preferably 1.00 to 1.10 moles.

[0249] Examples of basic compound catalysts include, but are not specifically limited to, alkali metal compounds, alkaline earth metal compounds, and nitrogen-containing compounds.

[0250] Examples of alkali metal compounds include, but are not specifically limited to, organic acid salts, inorganic salts, oxides, hydroxides, hydrides, and alkoxides of alkali metals. Specific examples include sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium bicarbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, cesium acetate, lithium acetate, sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium borohydride, sodium phenylborate, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium phenyl phosphate, disodium salts of bisphenol A (sodium, dipotassium, dicesium, or dilithium), and sodium, potassium, cesium, or lithium salts of phenol.

[0251] Examples of alkaline earth metal compounds include, but are not specifically limited to, organic acid salts, inorganic salts, oxides, hydroxides, hydrides, or alkoxides. Specific examples include magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium bicarbonate, calcium bicarbonate, strontium bicarbonate, barium bicarbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, magnesium stearate, calcium stearate, calcium benzoate, and magnesium phenyl phosphate.

[0252] Examples of nitrogen-containing compounds mentioned above include, but are not specifically limited to, quaternary ammonium hydroxides and their salts, amines, etc. Specifically, examples include quaternary ammonium hydroxides containing alkyl or aryl groups, such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and trimethylbenzylammonium hydroxide; tertiary amines such as triethylamine, dimethylbenzylamine, and triphenylamine; secondary amines such as diethylamine and dibutylamine; primary amines such as propylamine and butylamine; imidazoles such as 2-methylimidazole, 2-phenylimidazole, and benzimidazole; and ammonia, tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutylammonium tetraphenylborate, and tetraphenylammonium tetraphenylborate.

[0253] Salts of zinc, tin, zirconium, and lead can be used as transesterification catalysts. Specific examples include zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, tin(II) chloride, tin(IV) chloride, tin(II) acetate, tin(IV) acetate, dibutyltin dilaurate, dibutyltin oxide, dibutyldimethoxytin, zirconium acetylacetonate, zirconium oxoacetate, tetrabutoxyzirconium, lead(II) acetate, and lead(IV) acetate.

[0254] The aforementioned alkaline compound catalysts and transesterification catalysts can be used alone or in combination of two or more.

[0255] The preferred amount of basic compound catalyst and transesterification catalyst (total amount when used in combination) relative to 1 mole of dihydroxy compound is 1 × 10⁻⁶. ﹣9 ~1×10 ﹣3 moles, more preferably 1×10﹣7 ~1×10 ﹣4 Moore.

[0256] The melt polycondensation method preferably involves melting a dihydroxy compound, a dicarboxylic acid (ester) compound, and a carbonate diester in a reaction vessel, and then reacting the mixture while preserving the resulting monohydroxy compound. To preserve the monohydroxy compound, the reaction apparatus can be sealed or subjected to pressure control, such as depressurization or pressurization.

[0257] Example The present invention is illustrated below with specific examples, but the invention is not limited thereto. It should be noted that, unless otherwise stated, "%" refers to weight.

[0258] As a Raman scattering device, a device manufactured by Saimu Corporation was used.

[0259] The weight-average molecular weight (Mw) was determined by gel permeation chromatography (GPC) with tetrahydrofuran as the developing solvent. A calibration curve was plotted using standard polystyrene with a known molecular weight (molecular weight distribution = 1), and the weight-average molecular weight (Mw) was calculated from the retention time of GPC based on the calibration curve.

[0260] The molded bodies PC1, PC2, PC3, PC4, PC5, PC6 and PC7 used as molded waste are shown below.

[0261] BNEF: 9,9-bis[6-(2-hydroxyethoxy)naphthyl-2-yl]fluorene BNE: 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthylene BPEF: 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene BPPEF: 9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl]fluorene BPA: Bisphenol A D-NDM: Decahydro-1,4:5,8-dimethyl-bridged naphthalenediol (1) PC1: BNEF / BNE / BPPEF BNEF / BNE / BPPEF=x / y / x=27.0 / 52.0 / 21.0(mol%) Mw = 33000 Synthesized according to the method described in International Publication No. WO2018 / 016516.

[0262] (2) PC2: BNE / BPPEF BNE / BPPEF=x / y=45.0 / 55.0(mol%) Mw = 47000 Synthesized according to the method described in International Publication No. WO2014 / 073496.

[0263] (3) PC3: BNE / BPEF BNE / BPEF=x / y=42.1 / 57.9(mol%) Mw = 35000 Synthesized according to the method described in International Publication No. WO2014 / 073496.

[0264] (4) PC4: BPEF-HOMO Mw = 29000 Synthesized according to the method described in Synthesis Example 2 of International Publication No. WO2015 / 166951.

[0265] (5) PC5: BPEF / BPA BPEF / BPA=x / y=65.8 / 34.2(mol%) Mw = 30000 Synthesized according to the method described in International Publication No. WO2007 / 142149.

[0266] (6) PC6: BPEF / BPA BPEF / BPA=x / y=13.6 / 86.4(mol%) Mw = 31000 Synthesized according to the method described in International Publication No. WO2007 / 142149.

[0267] (7) PC7: D-NDM / BPEF D-NDM / BPEF=x / y=66 / 34(mol%) Mw = 28000 Synthesized according to the method described in International Publication No. WO2016 / 052370.

[0268] [Example 1-1] (1) Vibration conveying process As molding waste, recycled molding waste from optical material manufacturing plants was used. Specifically, molding waste with partial gating and runner sections was used after optical lenses were molded from PC1, PC2, PC3, PC4, PC5, PC6, and PC7 resins. Each molding waste was recycled from... Figure 3 The product shown is the product after the plastic product 11 has been removed from the integral product. Each molded product has the shape of a shaft-shaped sprue 7 (inner diameter: 4.3 mm, length: 48.1 mm), eight leg-shaped (branched structure) runners 8 (inner diameter: 2.5 mm, length to the branched structure: 12 mm, length of each branched structure: 9.6 mm) extending evenly in the circumferential direction from below the shaft, a gate 9 (inner diameter: 1.0 mm), and a cold slug well 10 (inner diameter: 4.3 mm, length: 6.3 mm) at the end of the sprue.

[0269] Molded waste products were fed into one end of a conveyor system (vibrating conveyor bed, width: 30cm, length: 1.5m) vibrating at 50Hz. In this case, 500g of molded waste products were fed in over 10 seconds. After the molded waste products reached the other end of the vibrating conveyor bed, they were collected. Through the above process, entanglement between molded waste products can be eliminated, and the untangled molded waste products can be efficiently arranged one by one on the conveyor system of the Raman scattering light device for subsequent sorting and recycling processes.

[0270] (2) Sorting and recycling process use Figure 4 The Raman scattering device shown is configured such that the resin species to be identified (set for identification) is PC1, and air is blown onto the identified resin species. The conveyor belt speed of the device is set to 20 m / min.

[0271] Ten pieces of each type of defective product are randomly placed on the aforementioned conveyor belt at equal intervals at a speed of 1 piece / second. When placing these products onto the conveyor belt, as follows... Figure 6 As shown in B, the eight leg-shaped runners 8, which extend upward from the shaft of the gating section 7 and extend evenly in the circumferential direction from below the shaft, contact the conveyor belt, so that the orientation of each molded waste product is consistent and arranged in an inverted T shape.

[0272] As a result, 100% of the molded parts were sorted. The operating conditions and results are shown in Table 1.

[0273] [Examples 1-2 to 1-7] Except for changing the operating conditions of the device as shown in Table 1, the same procedure as in Example 1-1 is followed.

[0274] As a result, 100% of the molded parts were sorted. The operating conditions and results are shown in Table 1.

[0275] [Examples 1-8] Except for placing 5 out of 10 molded defective products onto the conveyor belt with the front end of the gating section 7 in contact with the conveyor belt, the process was the same as in Example 1-1. The operating conditions and results are shown in Table 1.

[0276] The success rate of identification was 50%. The operating conditions and results are shown in Table 1.

[0277] [Examples 2-1 to 6-1] Except that the types of resins to be identified are set as shown in Table 2, the process is the same as in Examples 1-1.

[0278] The operating conditions and results are shown in Table 2.

[0279] [Example 7-1] use Figure 5 The Raman scattering device shown uses PC1 as the resin type to be identified and blows air towards the resin species other than those to be identified. The conveyor belt speed of the device is set to 20 m / min. The molded body utilizes the gating and runner sections discharged after optical lenses are molded from PC1, PC2, PC3, PC4, PC5, PC6, and PC7 resins. Similar to Examples 1-1, each molded defect uses... Figure 3 The product shown is the structure of the integral product after the plastic product 11 has been removed. Each molded waste product has the shape of an axial sprue section 7 (inner diameter: 4.3 mm, length: 48.1 mm), eight leg-shaped (branched structure) runner sections 8 (inner diameter: 2.5 mm, length to the branched structure: 12 mm, length of each branched structure section: 9.6 mm) extending evenly in the circumferential direction from below the sprue, a gate section 9 (inner diameter: 1.0 mm), and a cold slug well section 10 (inner diameter: 4.3 mm, length: 6.3 mm) at the end of the sprue section. Before the sorting and recycling process using the Raman scattering light device, a vibration conveying process was performed as in Example 1-1 to de-entangle the molded waste products from each other.

[0280] Ten pieces of each type of defective product are randomly placed on a conveyor belt at equal intervals at a speed of 1 piece / second. When placing these products onto the conveyor belt, if... Figure 6 As shown in Figure B, the eight leg-shaped runner sections 8, extending upwards from the shaft of the gating section 7 and equally extending circumferentially from below the shaft, contact the conveyor belt, thus aligning all molded defective products in an inverted T-shape. As a result, 100% of the molded parts are sorted. Operating conditions and results are shown in Table 3.

[0281] [Examples 7-2 to 7-6] Except for changing the operating conditions of the device as shown in Table 3, the process was the same as in Example 7-1. As a result, 100% of the molded parts were sorted. The operating conditions and results are shown in Table 3.

[0282] [Examples 8-1 to 12-1] Except that the types of resins to be identified were set as shown in Table 4, the process was the same as in Example 7-1. As a result, 100% of the molded articles were sorted. The operating conditions and results are shown in Table 4.

[0283] [Example 13] Using the PC-4 (a polycarbonate resin containing structural units derived from 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (BPEF) recovered in Examples 1-1), after pulverization, a regenerated resin was manufactured according to the same method as in Synthesis Example 2 of WO2015 / 166951. Specifically, the regenerated resin was manufactured according to the following steps.

[0284] 100 parts by weight of pulverized PC4, 88 parts by weight of 48% sodium hydroxide aqueous solution, and 734 parts by weight of toluene were added to a reactor equipped with a stirrer and cooling pipe, and the reaction was carried out under reflux for 3 hours. The liquid temperature was then cooled to 80–85°C, and 178 parts by weight of ion-exchanged water were added. After stirring and settling, the aqueous phase was separated, and the organic phase was washed with ion-exchanged water. Part of the toluene was distilled off from the organic phase, filtered, and 23 parts by weight of ion-exchanged water were added. The mixture was cooled to room temperature with stirring. The precipitated crystals were filtered and dried to obtain 85 parts by weight of white crystals of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (BPEF).

[0285] Then, 19.5 kg (44.5 mol) of the above-obtained 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (BPEF), 9.81 kg (45.8 mol) of diphenyl carbonate, and 2.2 × 10⁻⁶ sodium bicarbonate were added. -2 g (2.7×10 -4(Moles) were added to a 50-liter reactor equipped with a stirrer and distillation apparatus, and heated to 215°C with stirring under a nitrogen atmosphere of 760 mmHg for 1 hour. Then, the pressure was adjusted to 150 mmHg over 15 minutes, and the transesterification reaction was carried out at 215°C and 15 mmHg for 20 minutes. The temperature was then increased to 240°C at a rate of 37.5°C / hr and held at 240°C and 150 mmHg for 10 minutes. It was then adjusted to 120 mmHg over 10 minutes and held at 240°C and 120 mmHg for 70 minutes. Afterward, it was adjusted to 100 mmHg over 10 minutes and held at 240°C and 100 mmHg for 10 minutes. Finally, it was adjusted to below 1 mmHg over 40 minutes and polymerized under stirred conditions at 240°C and below 1 mmHg for 10 minutes. After the reaction was completed, nitrogen gas was introduced into the reactor to pressurize it, and the generated polycarbonate resin was extracted while being granulated. The Mw of the obtained polycarbonate resin was 28000.

[0286] As described above, BPEF obtained from recycled resin was reacted with diester carbonate via solution polycondensation to produce a recycled resin containing BPEF structural units.

[0287] [Table 1] [Table 2] [Table 3] [Table 4] The results in Tables 1 to 4 confirm that by using Raman scattering light, it is possible to identify the types of thermoplastic resins in molded waste and achieve efficient sorting and recycling.

[0288] It was confirmed that when the axial runners are arranged with their front ends facing upwards in a uniform orientation, the identification rate of thermoplastic resin types is higher (100%) compared to Examples 1-8, where the front ends of the axial runners are arranged to contact the conveyor belt, thus improving the accuracy of sorting and recycling.

[0289] The results showed that the recycled resin made from the separated and recovered molding waste had a sufficient molecular weight to produce high-quality resin (Example 13).

[0290] Symbol Explanation 1: Mold 2: Sprue 3: Flow channel 4: Gate 5: Mold cavity core 6, 6': Cold material well 7: Gating section 8: Flow channel section 9: Gate section 10, 10': Cold material well section 11: Plastic products 12: Molded waste 12a: Molded waste products that are subject to recycling 12b: Molded waste that is not eligible for recycling 13: Raman scattering identification device 14: Compressed air 15: Recycling Containers 16: Conveyor Belt 17: Sensors.

Claims

1. A method for manufacturing recycled resin, characterized in that, include: A process of irradiating molded waste containing thermoplastic resin with a laser, identifying the type of thermoplastic resin in the molded waste based on the Raman scattered light scattered by the molded waste, and then sorting and recycling it. and The process of obtaining recycled resin from the molded waste that has undergone the sorting and recycling process. The thermoplastic resin comprises at least one structural unit selected from the monomers represented by the following general formula (1), the structural unit B derived from the monomers represented by the following general formula (2), the structural unit C derived from the monomers represented by the following general formula (3), the structural unit D derived from the monomers represented by the following general formula (4), and the structural unit E derived from the monomers represented by the following general formula (5). In equation (1), R a and R b The elements are independently selected from hydrogen atoms, halogen atoms, alkyl groups having 1 to 20 carbon atoms that may have substituents, alkoxy groups having 1 to 20 carbon atoms that may have substituents, cycloalkyl groups having 5 to 20 carbon atoms that may have substituents, cycloalkoxy groups having 5 to 20 carbon atoms that may have substituents, aryl groups having 6 to 20 carbon atoms that may have substituents, heteroaryl groups containing one or more heterocyclic atoms selected from O, N, and S and having 3 to 20 carbon atoms that may have substituents, aryloxy groups having 6 to 20 carbon atoms that may have substituents, and -C≡C-R. h , R h This indicates an aryl group having 6 to 20 carbon atoms that may have substituents, or a heteroaryl group containing one or more heterocyclic atoms selected from O, N, and S and having 3 to 20 carbon atoms that may have substituents. X represents a single bond or a fluorene group that may have substituents. A and B independently represent alkylene groups with 1 to 5 carbon atoms that can have substituents. m and n independently represent integers from 0 to 6. a and b represent integers from 0 to 10 independently; In equation (2), R c and R d The groups are independently selected from hydrogen atoms, halogen atoms, alkyl groups having 1 to 20 carbon atoms that may have substituents, alkoxy groups having 1 to 20 carbon atoms that may have substituents, cycloalkyl groups having 5 to 20 carbon atoms that may have substituents, cycloalkoxy groups having 5 to 20 carbon atoms that may have substituents, and aryl groups having 6 to 20 carbon atoms that may have substituents. Y is selected from single bonds, fluorene groups that may have substituents, and -CR groups. 21 R 22 -, -S-, -S(=O)-, -(CH2) r ―、-O-、―(CH2) r ―(SiR 23 R 24 -O) s -SiR 23 R 24 ―(CH2) r —and —CR 25 R 26 -Ph-CR 25 R 26 -, R 21 R 22 R 23 R 24 R 25 and R 26 Each can independently represent a hydrogen atom, a halogen atom, an alkyl group with 1 to 20 carbon atoms that may have substituents, or an aryl group with 6 to 30 carbon atoms that may have substituents, or R 61 and R 62 or R 71 and R 72 The carbon rings or heterocycles formed by mutual bonding can have 1 to 20 carbon atoms and can have substituents. Ph represents phenyl. r and s independently represent integers from 0 to 5000. A and B independently represent alkylene groups with 1 to 5 carbon atoms that can have substituents. p and q represent integers from 0 to 4 independently. a and b represent integers from 0 to 10 independently; In equation (3), R a and R b The elements are independently selected from hydrogen atoms, halogen atoms, alkyl groups having 1 to 20 carbon atoms that may have substituents, alkoxy groups having 1 to 20 carbon atoms that may have substituents, cycloalkyl groups having 5 to 20 carbon atoms that may have substituents, cycloalkoxy groups having 5 to 20 carbon atoms that may have substituents, aryl groups having 6 to 20 carbon atoms that may have substituents, heteroaryl groups containing one or more heterocyclic atoms selected from O, N, and S and having 3 to 20 carbon atoms that may have substituents, aryloxy groups having 6 to 20 carbon atoms that may have substituents, and -C≡C-R. h , R h This indicates an aryl group having 6 to 20 carbon atoms that may have substituents, or a heteroaryl group containing one or more heterocyclic atoms selected from O, N, and S and having 3 to 20 carbon atoms that may have substituents. X represents a single bond or a fluorene group that may have substituents. A and B independently represent alkylene groups with 1 to 5 carbon atoms that can have substituents. m and n independently represent integers from 0 to 6. a and b independently represent integers from 0 to 10. R' and R" are independently selected from hydroxyl, halogen atom, alkoxy group with 1 to 20 carbon atoms that can have substituents, and aryloxy group with 6 to 20 carbon atoms that can have substituents, respectively; In equation (4), R g Each can be independently represented by an alkyl group having 1 to 3 hydrogen atoms or carbon atoms. In formula (5), G1 and G2 independently represent alkylene groups with 1 to 8 carbon atoms that can have substituents. K1 and K2 independently represent hydroxyl, alkoxy, or halogen atoms, respectively. R p1 and R p2 Each of the following can be independently represented: a halogen atom, a cyano group, and an alkyl group with 1 to 8 carbon atoms that may have substituents. Ar1 and Ar2 independently represent phenyl or naphthyl groups that can have substituents. r1 and r2 independently represent integers from 0 to 2. r3 and r4 represent integers from 0 to 1 independently.

2. The manufacturing method according to claim 1, characterized in that: The thermoplastic resin comprises at least one structural unit selected from the monomers represented by the general formula (1), the structural unit B represented by the monomers represented by the general formula (2), the structural unit C represented by the monomers represented by the general formula (3), and the structural unit D represented by the monomers represented by the general formula (4).

3. The manufacturing method according to claim 2, characterized in that: The thermoplastic resin is selected from the resin composed of structural unit A and structural unit B, the resin composed of structural unit B and structural unit C, the resin composed of structural unit B and structural unit D, the resin composed of structural unit A, the resin composed of structural unit B, the resin composed of structural unit C, and the resin composed of structural unit D.

4. The manufacturing method according to claim 2, characterized in that: The thermoplastic resin is represented by any one of the following formulas: (I-1), (I-2), (I-3), (II-1), (II-2), (II-3), (II-4), (II-5), or (II-6). In the formula, x, y, and z represent the number of repeating units.

5. The manufacturing method according to claim 1, characterized in that: The thermoplastic resin is selected from the following resins: (III-1) A resin comprising the structural unit represented by formula (iii-a1), the structural unit represented by formula (iii-a2), the structural unit represented by formula (iii-a3), and the structural unit represented by formula (iii-a4); (III-2) A resin comprising the structural unit represented by formula (iii-a1), the structural unit represented by formula (iii-a2), the structural unit represented by formula (iii-a4), and the structural unit represented by formula (iii-a5); (III-3) A resin comprising the structural unit represented by formula (iii-a1), the structural unit represented by formula (iii-a4), and the structural unit represented by formula (iii-a6). 。 6. The manufacturing method according to any one of claims 1 to 5, characterized in that: The molded waste has a gating section and / or a runner section from which the optical material is discharged after molding.

7. The manufacturing method according to any one of claims 1 to 6, characterized in that: The sorting and recycling process is carried out continuously on the conveying device, and the supply speed of the formed waste products to the conveying device is 0.5 to 5 pieces / second.

8. The manufacturing method according to any one of claims 1 to 7, characterized in that: The sorting and recycling process involves collecting molded waste that belongs to the recycling target by compressed air spraying and / or removing molded waste that does not belong to the recycling target by compressed air spraying.

9. The manufacturing method according to any one of claims 1 to 8, characterized in that: Prior to the sorting and recycling process, there is a process of feeding a waste composition containing the molded waste into a vibrating conveyor bed and vibrating the waste composition for conveying.

10. The manufacturing method according to claim 9, characterized in that: The sorting and recycling process includes a step of feeding shaped waste products onto a conveying device at equal intervals.

11. The manufacturing method according to claim 10, characterized in that: The molded waste has an axial gating section and two or more runner sections that extend equally in the circumferential direction from below the axial section, wherein the front ends of the axial gating sections of the molded waste are all aligned upwards.

12. A method for classifying and recycling molded waste products, characterized in that, include: A process involving irradiating molded waste containing thermoplastic resin with a laser, identifying the type of thermoplastic resin in the molded waste based on Raman scattering light from the molded waste, and then sorting and recycling it. The thermoplastic resin comprises at least one structural unit selected from the monomers represented by the following general formula (1), the structural unit B derived from the monomers represented by the following general formula (2), the structural unit C derived from the monomers represented by the following general formula (3), the structural unit D derived from the monomers represented by the following general formula (4), and the structural unit E derived from the monomers represented by the following general formula (5). In equation (1), R a and R b The elements are independently selected from hydrogen atoms, halogen atoms, alkyl groups having 1 to 20 carbon atoms that may have substituents, alkoxy groups having 1 to 20 carbon atoms that may have substituents, cycloalkyl groups having 5 to 20 carbon atoms that may have substituents, cycloalkoxy groups having 5 to 20 carbon atoms that may have substituents, aryl groups having 6 to 20 carbon atoms that may have substituents, heteroaryl groups containing one or more heterocyclic atoms selected from O, N, and S and having 3 to 20 carbon atoms that may have substituents, aryloxy groups having 6 to 20 carbon atoms that may have substituents, and -C≡C-R. h , R h This indicates an aryl group having 6 to 20 carbon atoms that may have substituents, or a heteroaryl group containing one or more heterocyclic atoms selected from O, N, and S and having 3 to 20 carbon atoms that may have substituents. X represents a single bond or a fluorene group that may have substituents. A and B independently represent alkylene groups with 1 to 5 carbon atoms that can have substituents. m and n independently represent integers from 0 to 6. a and b represent integers from 0 to 10 independently; In equation (2), R c and R d The groups are independently selected from hydrogen atoms, halogen atoms, alkyl groups having 1 to 20 carbon atoms that may have substituents, alkoxy groups having 1 to 20 carbon atoms that may have substituents, cycloalkyl groups having 5 to 20 carbon atoms that may have substituents, cycloalkoxy groups having 5 to 20 carbon atoms that may have substituents, and aryl groups having 6 to 20 carbon atoms that may have substituents. Y is selected from single bonds, fluorene groups that may have substituents, and -CR groups. 21 R 22 -, -S-, -S(=O)-, -(CH2) r ―、-O-、―(CH2) r ―(SiR 23 R 24 -O) s -SiR 23 R 24 ―(CH2) r —and —CR 25 R 26 -Ph-CR 25 R 26 -, R 21 R 22 R 23 R 24 R 25 and R 26 Each can independently represent a hydrogen atom, a halogen atom, an alkyl group with 1 to 20 carbon atoms that may have substituents, or an aryl group with 6 to 30 carbon atoms that may have substituents, or R 61 and R 62 or R 71 and R 72 The carbon rings or heterocycles formed by mutual bonding can have 1 to 20 carbon atoms and can have substituents. Ph represents phenyl. r and s independently represent integers from 0 to 5000. A and B independently represent alkylene groups with 1 to 5 carbon atoms that can have substituents. p and q represent integers from 0 to 4 independently. a and b represent integers from 0 to 10 independently; In equation (3), R a and R b The elements are independently selected from hydrogen atoms, halogen atoms, alkyl groups having 1 to 20 carbon atoms that may have substituents, alkoxy groups having 1 to 20 carbon atoms that may have substituents, cycloalkyl groups having 5 to 20 carbon atoms that may have substituents, cycloalkoxy groups having 5 to 20 carbon atoms that may have substituents, aryl groups having 6 to 20 carbon atoms that may have substituents, heteroaryl groups containing one or more heterocyclic atoms selected from O, N, and S and having 3 to 20 carbon atoms that may have substituents, aryloxy groups having 6 to 20 carbon atoms that may have substituents, and -C≡C-R. h , R h This indicates an aryl group having 6 to 20 carbon atoms that may have substituents, or a heteroaryl group containing one or more heterocyclic atoms selected from O, N, and S and having 3 to 20 carbon atoms that may have substituents. X represents a single bond or a fluorene group that may have substituents. A and B independently represent alkylene groups with 1 to 5 carbon atoms that can have substituents. m and n independently represent integers from 0 to 6. a and b independently represent integers from 0 to 10. R' and R" are independently selected from hydroxyl, halogen atom, alkoxy group with 1 to 20 carbon atoms that can have substituents, and aryloxy group with 6 to 20 carbon atoms that can have substituents, respectively; In equation (4), R g Each can be independently represented by an alkyl group having 1 to 3 hydrogen atoms or carbon atoms. In formula (5), G1 and G2 independently represent alkylene groups with 1 to 8 carbon atoms that can have substituents. K1 and K2 independently represent hydroxyl, alkoxy, or halogen atoms, respectively. R p1 and R p2 Each of the following can be independently represented: a halogen atom, a cyano group, and an alkyl group with 1 to 8 carbon atoms that may have substituents. Ar1 and Ar2 independently represent phenyl or naphthyl groups that can have substituents. r1 and r2 independently represent integers from 0 to 2. r3 and r4 represent integers from 0 to 1 independently.

13. The sorting and recycling method according to claim 12, characterized in that: The thermoplastic resin comprises at least one structural unit selected from the monomers represented by the general formula (1), the structural unit B represented by the monomers represented by the general formula (2), the structural unit C represented by the monomers represented by the general formula (3), and the structural unit D represented by the monomers represented by the general formula (4).

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