Method for manufacturing recycled plastics, method for manufacturing non-porous thin films, method for manufacturing microporous thin films, and method for manufacturing composite knitted fabrics

Abstract

To provide a recycled plastic material that enables production of a thin film and a composite woven fabric having waterproof and moisture-permeable capabilities.SOLUTION: The present invention provides a recycled plastic material, wherein a resin raw material comprises a plastic depolymerized product including a first monomer having a structure represented by HO-Rx-OOC-Ph-COO-R'x-OH and a second monomer having a structure represented by HO-Rx-OOC-HN-R-NH-COO-R'x-OH, a polyether polyol, a polyisocyanate, and a solvent. Ph represents a benzene ring. Rx and R'x are each independently selected from -CH2CH2-, -CH2CH2OCH2CH2-, -(CH2CH2O)n- and -(CH2CH2O)nCH2CH2-. n is 6 to 23. R is selected from diphenylmethanediyl, toluenediyl, or a specific cyclic compound.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to recycled plastics, and more particularly to recycled plastics obtained by polymerizing a resin raw material containing a plastic depolymerization product, a polyether polyol, and a polyfunctional isocyanate, as well as a method for producing the same and a product thereof. [Background technology]

[0002] In the current process of producing regenerated fiber from discarded clothing and fabrics, the regenerated fiber is produced by using, in principle, a single-component (100%) fiber material or at least 97% polyester fiber material as the main material, and processing it using methods such as physical recovery (for example, a method of mechanically cutting or crushing followed by injection granulation, or the method mentioned in the background art of Patent Document 1) and chemical recovery (for example, a method of decolorizing and alcohol decomposition followed by repolymerization, or the method mentioned in the background art of Patent Document 1).

[0003] Furthermore, while thin films can be manufactured using the aforementioned recycled fibers, such films typically do not meet the demand for waterproof and breathable knitted fabrics. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Taiwan Patent Application Publication No. 202423648 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] In view of the above, an object of the present invention is to provide a recycled plastic capable of alleviating at least one drawback of the prior art, a method for manufacturing the recycled plastic, and a porous thin film, a microporous thin film, and a composite woven fabric made of the recycled plastic.

Means for Solving the Problems

[0006] The present invention is a recycled plastic obtained by polymerizing a resin raw material, wherein the resin raw material includes a plastic depolymerized product, a polyether polyol, a multi-functional isocyanate, and a solvent, and the plastic depolymerized product includes a first monomer having a structure represented by HO-R x -OOC-Ph-COO-R’ x -OH and a second monomer having a structure represented by HO-R x -OOC-HN-R-NH-COO-R’ x -OH. In the above structures, Ph represents a benzene ring, and R x and R’ x are each independently selected from the group consisting of -CH2CH2-, -CH2CH2OCH2CH2-, -(CH2CH2O) n -, and -(CH2CH2O) n CH2CH2-, n is an integer within the range of 6 to 23, and R is selected from the group consisting of diphenylmethane diyl, toluene diyl, the following general formula (1), the following general formula (2), and -CH2CH2CH2CH2CH2CH2-. A recycled plastic is provided, which is characterized by the above.

[0007]

Chemical Formula

[0008]

Chemical Formula

[0009] The present invention includes the steps of: mixing waste plastics mainly containing polyester terephthalate and polyurethane with a depolymerizing agent, and depolymerizing the waste plastics at a first temperature to obtain a plastic depolymerizate (step a); mixing the plastic depolymerizate with a first polyether polyol to obtain a first mixture, and subjecting the first mixture to a polymerization reaction at a second temperature to obtain a polymeric diol mixture (step b); mixing the polymeric diol mixture with a second polyether polyol, a polyfunctional isocyanate, and a solvent to obtain a second mixture, and subjecting the second mixture to a reaction at a third temperature to obtain a recycled plastic having a carbamate group (step c). In step a, the plastic depolymerizate has a first monomer represented by the structure of HO-R x -OOC-Ph-COO-R’ x -OH and a second monomer represented by the structure of HO-R x -OOC-HN-R-NH-COO-R’ x -OH. In the above structures, Ph represents a benzene ring, and R x and R’ x are each independently selected from the group consisting of -CH2CH2-, -CH2CH2OCH2CH2-, -(CH2CH2O) n n-, and -(CH2CH2O) n CH2CH2-. n is an integer within the range of 6 to 23, and R is selected from the group consisting of diphenylmethane diyl, toluene diyl, the following general formula (1), the following general formula (2), and -CH2CH2CH2CH2CH2CH2-. A method for producing a recycled plastic is provided, which is characterized by the above.

[0010]

Chemical formula

[0011]

Chemical formula

[0012] The present invention relates to a non-porous thin film coated and heated with the above-mentioned recycled plastic, having a thickness in the range of 10 μm to 30 μm and a basis weight of 10 g / m². 2 ~30g / m 2 It falls within the specified range, and the water resistance measured in accordance with JIS L1092B exceeds 10,000 mmH2O, while the moisture permeability measured in accordance with JIS L1099B1 is 120,000 g / m². 2 The invention provides a non-porous thin film characterized by a duration exceeding 24 hours.

[0013] The present invention relates to a microporous thin film obtained by coating, solidifying, washing with water, and heating the above-mentioned recycled plastic, having a thickness in the range of 30 μm to 90 μm, and a basis weight of 10 g / m². 2 ~30g / m 2 It falls within the specified range, and the water resistance measured in accordance with JIS L1092B exceeds 10,000 mmH2O, and the moisture permeability measured in accordance with JIS L1099A1 is 3,000 g / m². 2 The present invention provides a microporous thin film characterized by a duration exceeding 24 hours.

[0014] The present invention provides a composite knitted fabric comprising a base fabric and a thin film attached to the base fabric, wherein the thin film is a non-porous thin film or a microporous thin film as described above. [Effects of the Invention]

[0015] The recycled plastic of the present invention is obtained by polymerizing a resin raw material containing plastic depolymers, and can be used to produce thin films and composite knitted fabrics having waterproof and breathable functions. [Modes for carrying out the invention]

[0016] Where prior art publications are referenced herein, such references should be understood not to constitute an acknowledgment that such publications form part of the general knowledge in the art in Taiwan or any other country.

[0017] For the purposes of this specification, it will be clearly understood that the word “includes” means “includes, but is not limited to,” and the word “includes” has a corresponding meaning.

[0018] Unless otherwise defined, all technical and scientific terms used herein have the meanings generally understood by those skilled in the art to which this invention belongs. Those skilled in the art will recognize many methods and materials similar or equivalent to those described herein that may be used in carrying out this invention. In fact, this invention is not limited to the methods and materials described herein.

[0019] Furthermore, in the description of this invention, terms such as "first," "second," etc., are used solely for the purpose of distinction and do not imply or suggest relative importance.

[0020] The present invention will be described in detail below.

[0021] The recycled plastic of the present invention is obtained by polymerizing a resin raw material; that is, the recycled plastic of the present invention is a polymer of the resin raw material.

[0022] The resin raw material comprises a plastic depolymer, a polyether polyol, a polyfunctional isocyanate, and a solvent.

[0023] The plastic depolymer is HO-R x -OOC-Ph-COO-R' x A first monomer having a structure represented by -OH, and HO-R x -OOC-HN-R-NH-COO-R' x It comprises a second monomer having a structure represented by -OH.

[0024] In the above structure, Ph represents a benzene ring, and R x and R' xThese are, independently, -CH2CH2-, -CH2CH2OCH2CH2-, and -(CH2CH2O) n -, and -(CH2CH2O) n n is an integer in the range of 6 to 23, selected from the group consisting of CH2CH2-, and R is selected from the group consisting of diphenylmethanediyl, toluenediyl, the following general formula (1), the following general formula (2), and -CH2CH2CH2CH2CH2CH2-.

[0025] [ka]

[0026] [ka]

[0027] In some embodiments, the resin raw material further comprises a small molecule polyol.

[0028] In some embodiments, the small molecule polyol is selected from the group consisting of ethylene glycol (EG), 1,3-propanediol (PDO), propylene glycol (PG), 1,4-butanediol (BDO), and 1,6-hexanediol (HDO).

[0029] In some embodiments, the polyether polyol is selected from the group consisting of polyethylene glycol (PEG), poly(tetramethylene ether) glycol (PTMEG), and polypropylene glycol (PPG).

[0030] In some embodiments, the polyfunctional isocyanate is selected from the group consisting of methylene diphenyl diisocyanate (MDI), toluene diisocyanate (TDI), m-xylylene diisocyanate (XDI), isophorone diisocyanate (IPDI), and hexamethylene diisocyanate (HDI).

[0031] The present invention's method for producing recycled plastic comprises the following steps a to c.

[0032] Step a: Mix waste plastic mainly containing polyester terephthalate and polyurethane (containing these as the main components) with a depolymerizing agent, and depolymerize the waste plastic at a first temperature to obtain the above-mentioned depolymerized plastic.

[0033] Step b: Mix the plastic depolymer with a first polyether polyol to obtain a first mixture, and then polymerize the first mixture at a second temperature to obtain a polymer diol mixture.

[0034] Step c: Mix the polymer diol mixture with a second polyether polyol, a polyfunctional isocyanate, and a solvent to obtain a second mixture, and then react the second mixture at a third temperature to obtain a recycled plastic having carbamate groups.

[0035] In some embodiments, the first temperature is higher than the second temperature, and the second temperature is higher than the third temperature.

[0036] In some embodiments, in step c, the polyfunctional isocyanate is mixed with the polymer diol mixture in two steps.

[0037] In some embodiments, the depolymerizer is selected from the group consisting of ethylene glycol, propylene glycol, diethylene glycol (DEG), polyethylene glycol, and combinations thereof.

[0038] In some embodiments, the first polyether polyol and the second polyether polyol are each independently selected from the group consisting of polyethylene glycol, polytetramethylene ether glycol, and polypropylene glycol.

[0039] In some embodiments, in step c, the second mixture further comprises a small molecule polyol.

[0040] The non-porous thin film of the present invention is obtained by coating and heating the above-mentioned recycled plastic. In this embodiment, the non-porous thin film of the present invention is obtained by coating the above-mentioned recycled plastic in a thin layer and then heating the thin layer.

[0041] The non-porous thin film has a thickness in the range of 10 μm to 30 μm and a basis weight of 10 g / m². 2 ~30g / m 2 It falls within the specified range, and the water resistance measured in accordance with JIS L1092B exceeds 10,000 mmH2O, while the moisture permeability measured in accordance with JIS L1099B1 is 120,000 g / m². 2 • More than 24 hours.

[0042] The microporous thin film of the present invention is obtained by coating, solidifying, washing with water, and heating the above-mentioned recycled plastic. In this embodiment, the microporous thin film of the present invention is obtained by coating the above-mentioned recycled plastic in a thin layer, solidifying the thin layer, washing with water, and heating it.

[0043] The microporous thin film has a thickness in the range of 30 μm to 90 μm and a basis weight of 10 g / m². 2 ~30g / m 2It falls within the specified range, has a water resistance exceeding 10,000 mmH2O as measured in accordance with JIS L1092B, and a moisture permeability of 3,000 g / m² as measured in accordance with JIS L1099A1. 2 • More than 24 hours.

[0044] The composite knitted fabric of the present invention comprises a base fabric and a thin film attached to the base fabric, wherein the thin film is selected from the above-mentioned non-porous thin film or the above-mentioned microporous thin film.

[0045] The following describes embodiments of the present invention. It should be understood that these embodiments are illustrative and descriptive, and should not be construed as limiting the present invention.

[0046] <Example 1> The method for producing recycled plastic in Example 1 includes the following steps (a) to (c).

[0047] (a) 1000 g of a first waste cloth made of composite fiber (polyester terephthalate fiber coated with polyurethane, with a total composite fiber content of 100 wt%, polyurethane content of 20 wt%, and polyester terephthalate content of 80 wt%) was mixed with 2760 g of diethylene glycol (DEG, as a depolymerizing agent), 0.5 g of zinc acetate (as a catalyst), and 0.6 g of Irganox® 1010 (as an antioxidant). The mixture was stirred for 2 to 3 hours in a nitrogen atmosphere and at a first temperature of 240°C to depolymerize the first waste cloth, and the temperature was lowered to 150°C to obtain a first mixture. The mixture was then filtered using a stainless steel filter mesh coated with diatomaceous earth (pore size of 10 μm) to obtain a depolymerized plastic product.

[0048] (b) 3762.1 g of the plastic depolymer obtained in step a above, 640 g of polyethylene glycol (PEG2000, as the first polyether polyol), and 0.1 g of titanium isopropoxide (as a catalyst) were mixed and heated to a second temperature in the range of 160°C to 200°C to carry out a polymerization reaction. During the polymerization reaction, a vacuum was created (absolute pressure was controlled to 10 torr or less) to remove excess DEG and by-products in the plastic depolymer (e.g., ethylene glycol) to obtain a polymeric diol mixture [hydroxyl value of 20.6 mg KOH / g, number average molecular weight of 5446, and polydispersity index (PDI) of 5.51].

[0049] (c) 171.96 g of the polymeric diol mixture obtained in step b above, 22.73 g of polyethylene glycol (PEG2000, as a second polyether polyol), 23.25 g of 1,4-butanediol (BDO, as a small molecule polyol), 0.1 g of stannous octoate (CAS No.: 301-10-0, T9, as a catalyst), 0.1 g of Irganox® 1010 (as an antioxidant), and 698.34 g of N,N-diethylformamide (DEF, as a solvent) were mixed and stirred at 60°C for 30 minutes to obtain an intermediate mixture. Thereafter, 48.8 g of 4,4'-methylenediphenyl diisocyanate (4,4'-MDI, as a polyfunctional isocyanate) was gradually added to the intermediate mixture (to induce an exothermic reaction) to obtain a second mixture. After the exothermic reaction was completed, the second mixture was stirred for 2 hours while maintaining a third temperature of 80°C using an external temperature control means. Then, 32.552 g of 4,4'-MDI was gradually added, and the reaction was carried out at the third temperature (80°C) for 3 to 4 hours to obtain the recycled plastic having carbamate groups of Example 1 (with a solid content of approximately 30% and a viscosity of approximately 56270 cP).

[0050] <Example 2> The method for producing recycled plastic in Example 2 is similar to that in Example 1, the difference between Example 2 and Example 1 is that in step a, instead of 1000g of first waste cloth, 1000g of second waste cloth made of artificial composite fiber (polyester terephthalate fiber coated with polyurethane, with the total amount of artificial composite fiber being 100wt%, the polyurethane content being 45wt% and the polyester terephthalate content being 55wt%) is used, and in step b, 640g of PEG2000 (first In this example, 640 g of polytetramethylene ether glycol (PTMEG1000) was used instead of the polyether polyol (as the first polyether polyol), and in step c, 22.73 g of another polytetramethylene ether glycol (PTMEG2000) was used instead of 22.73 g of PEG2000 (as the second polyether polyol), and finally, the recycled plastic having carbamate groups of Example 2 (with a solids content of approximately 25% and a viscosity of approximately 20,000 cP to 40,000 cP) was obtained.

[0051] <Manufacturing and property measurement of non-porous thin films> The recycled plastic having carbamate groups obtained in Example 1 above was applied to release paper in a thin layer [area approximately 62 inches (approximately 157.48 cm)], and the release paper with the thin layer applied was heated by passing it through an oven at a speed of 15 m / min [oven length 28 m, temperature gradient sequentially 60°C (0 m to 4 m), 80°C (4 m to 8 m), 110°C (8 m to 12 m), 130°C (12 m to 16 m), 150°C (16 m to 20 m), 150°C (20 m to 24 m), 150°C (24 m to 28 m)] to form a non-porous thin film on the release paper, and the non-porous thin film was separated from the release paper to form the non-porous thin film of Example 1 (thickness of the thin film is approximately 19 μm to 20 μm, basis weight of the thin film is approximately 16.7 g / m²). 2 ~17.0g / m 2 They manufactured (which is...).

[0052] The water resistance (n=3) of the non-porous thin film of Example 1, measured in accordance with JIS L1092B, exceeds 15,000 mmH2O. The water permeability (n=3) of the non-porous thin film of Example 1, measured in accordance with JIS L1099B1, is 125,776 g / m² on average. 2 It is 24 hours.

[0053] <Manufacturing and property measurement of microporous thin films> The recycled plastic having carbamate groups obtained in Example 2 above was applied to a polyethylene terephthalate (PET) woven fabric (40D × 40D) coated with a mold release agent to form a thin layer [approximately 60 inches (approximately 152.4 cm)]. The woven fabric with this thin layer was then passed at a speed of 18 m / min through a solidification tank (18 m in length) containing an aqueous solution of 15% DMF, a five-stage washing tank (containing pure water at 45°C, each stage 2 m in length), and an oven to heat it [the oven was 15 m long, with a temperature gradient of 120°C (stages 0-3), 130°C (stages 3-6), 140°C (stages 6-9), 150°C (stages 9-12), and 150°C (stages 12-15)] to obtain an intermediate thin film coated on the PET woven fabric. Then, using a substrate peeling machine (purchased from HWAI YUH MACHINERY CO., LTD., Taiwan, model number: HYK-1126-4), the intermediate thin film and the PET woven fabric were separated by winding. This resulted in the microporous thin film of Example 2 (the thickness of the thin film is approximately 56 μm, and the basis weight of the thin film is approximately 22.1 g / m²). 2 The result was a pore size of approximately 2 μm or less.

[0054] The water resistance (n=3) of the microporous thin film of Example 2, measured in accordance with JIS L1092B, is approximately 10500 mmH2O. The moisture permeability (n=3) of the microporous thin film of Example 2, measured in accordance with JIS L1099A1, is approximately 3400 g / m². 2 It is 24 hours.

[0055] <Manufacturing and property measurement of composite knitted fabrics> A reactive hot melt polyurethane adhesive (purchased from DIC Corporation, model number: TYFORCE NH-321), preheated to 100°C, was applied to one surface of the non-porous thin film obtained in Example 1 and one surface of the microporous thin film obtained in Example 2. The non-porous thin film obtained in Example 1 and the microporous thin film obtained in Example 2 were then attached to a PET woven fabric (30D x 30D as the base fabric) using the reactive hot melt polyurethane adhesive to obtain the composite knitted fabric of Example 1 and the composite knitted fabric of Example 2.

[0056] The water resistance of the composite knitted fabric of Example 1, measured in accordance with JIS L1092B, exceeds 20,000 mmH2O. The moisture permeability of the composite knitted fabric of Example 1, measured in accordance with JIS L1099 B1, is 30,000 g / m². 2 • Exceeds 24 hours. The water resistance of the composite knitted fabric of Example 2, measured in accordance with JIS L1092B, exceeds 10,000 mmH2O. The moisture permeability of the composite knitted fabric of Example 2, measured in accordance with JIS L1099A1, is 2,000 g / m². 2 • More than 24 hours.

[0057] According to the above, the recycled plastic of the present invention is obtained by polymerizing a resin raw material containing a depolymerized plastic, and can be used to produce thin films with waterproof and moisture-permeable functions (for example, the non-porous thin film obtained in Example 1 and the microporous thin film obtained in Example 2) and composite knitted fabrics (for example, the composite knitted fabrics obtained in Example 1 and Example 2).

[0058] Therefore, the objectives of the present invention can be reliably achieved.

[0059] The above embodiments are illustrative in illustrating the principles and effects of the present invention and do not limit it. A person skilled in the art can make some modifications and alterations to the above embodiments, provided that they do not deviate from the spirit and scope of the invention. Therefore, all modifications and alterations made by a person skilled in the art, provided that they do not deviate from the spirit of the invention, should also be considered to fall within the scope of protection of the present invention. [Industrial applicability]

[0060] The recycled plastic of the present invention is suitable for producing thin films and composite knitted fabrics having waterproof and breathable properties.

Claims

1. Step a involves mixing waste plastic mainly containing polyester terephthalate and polyurethane with a depolymerizing agent, and depolymerizing the waste plastic at a first temperature to obtain a depolymerized plastic product. Step b involves mixing the plastic depolymer with a first polyether polyol to obtain a first mixture, and then polymerizing the first mixture at a second temperature to obtain a polymer diol mixture. The process includes step c, which involves mixing the polymer diol mixture with a second polyether polyol, a polyfunctional isocyanate, and a solvent to obtain a second mixture, and then reacting the second mixture at a third temperature to obtain a recycled plastic having carbamate groups. In the step a, the plastic depolymerization product is HO-R ｘ -OOC-Ph-COO-R' ｘ -OH, a first monomer having a structure represented by HO-R ｘ -OOC-HN-R-NH-COO-R' ｘ -OH, a second monomer having a structure represented by HO-R ｘ and R' ｘ are each independently -CH ２ CH ２ -, -CH ２ CH ２ OCH ２ CH ２ -, -(CH ２ CH ２ O) ｎ -, and -(CH ２ CH ２ O) ｎ CH ２ CH ２ - and are selected from the group consisting of, n is an integer within the range of 6 to 23, and R is diphenylmethanediyl, toluenediyl, the following general formula (1), the following general formula (2), and -CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ -, a method for producing recycled plastic, characterized in that. 【Chemistry 1】 【Chemistry 2】

2. The method for producing recycled plastic according to claim 1, characterized in that the first temperature is higher than the second temperature, and the second temperature is higher than the third temperature.

3. The method for producing recycled plastic according to claim 1, characterized in that, in step c, the polyfunctional isocyanate is mixed with the polymer diol mixture in two stages.

4. The method for producing recycled plastic according to claim 1, characterized in that the polyfunctional isocyanate is selected from the group consisting of methylenediphenyl diisocyanate, toluene diisocyanate, m-xylylene diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate.

5. The method for producing recycled plastic according to claim 1, characterized in that the depolymerizing agent is selected from the group consisting of ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, and combinations thereof.

6. The method for producing recycled plastic according to claim 1, characterized in that the first polyether polyol and the second polyether polyol are each independently selected from the group consisting of polyethylene glycol, polytetramethylene ether glycol, and polypropylene glycol.

7. The method for producing recycled plastic according to claim 1, characterized in that, in step c, the second mixture further comprises a small molecule polyol.

8. The method for producing recycled plastic according to claim 7, characterized in that the small molecule polyol is selected from the group consisting of ethylene glycol, 1,3-propanediol, propylene glycol, 1,4-butanediol, and 1,6-hexanediol.

9. Step a, which involves mixing waste plastic mainly containing polyester terephthalate and polyurethane with a depolymerizing agent and depolymerizing the waste plastic at a first temperature to obtain a depolymerized plastic product, Step b involves mixing the plastic depolymer with a first polyether polyol to obtain a first mixture, and then polymerizing the first mixture at a second temperature to obtain a polymer diol mixture. Step c is to mix the polymer diol mixture with a second polyether polyol, a polyfunctional isocyanate, and a solvent to obtain a second mixture, and then react the second mixture at a third temperature to obtain a recycled plastic having carbamate groups. Step d includes obtaining a non-porous thin film in which the recycled plastic having the carbamate group is coated and heated, In step a, the plastic depolymer comprises a first monomer having a structure represented by HO-R x-OOC-Ph-COO-R' x-OH and a second monomer having a structure represented by HO-R x-OOC-HN-R-NH-COO-R' x-OH, wherein in the above structure, Ph represents a benzene ring, R x and R' x are each independently selected from the group consisting of -CH2CH2-, -CH2CH2OCH2CH2-, -(CH2CH2O)n-, and -(CH2CH2O)nCH2CH2-, where n is an integer in the range of 6 to 23, and R is diphenylmethanediyl, toluenediyl, the following general formula (1), the following general formula (2), and -CH2CH2 Selected from the group consisting of CH2 CH2 CH2 CH2 - The non-porous thin film has a thickness in the range of 10 μm to 30 μm and a basis weight of 10 g / m². ２ ~30g / m ２ It is within the range, and the water resistance measured in accordance with JIS L1092B is 10,000 mmH ２ The moisture permeability, measured in accordance with JIS L1099B1, exceeds 0 and is 120,000 g / m². ２ A method for producing a non-porous thin film, characterized by a process exceeding 24 hours. 【Transformation 3】 【Chemistry 4】

10. Step a, which involves mixing waste plastic mainly containing polyester terephthalate and polyurethane with a depolymerizing agent and depolymerizing the waste plastic at a first temperature to obtain a depolymerized plastic product, Step b involves mixing the plastic depolymer with a first polyether polyol to obtain a first mixture, and then polymerizing the first mixture at a second temperature to obtain a polymer diol mixture. Step c is to mix the polymer diol mixture with a second polyether polyol, a polyfunctional isocyanate, and a solvent to obtain a second mixture, and then react the second mixture at a third temperature to obtain a recycled plastic having carbamate groups. The process includes step d, which involves applying, solidifying, washing with water and heating the recycled plastic having the carbamate group to obtain a microporous thin film. In step a, the plastic depolymer comprises a first monomer having a structure represented by HO-R x-OOC-Ph-COO-R' x-OH and a second monomer having a structure represented by HO-R x-OOC-HN-R-NH-COO-R' x-OH, wherein in the above structure, Ph represents a benzene ring, R x and R' x are each independently selected from the group consisting of -CH2CH2-, -CH2CH2OCH2CH2-, -(CH2CH2O)n-, and -(CH2CH2O)nCH2CH2-, where n is an integer in the range of 6 to 23, and R is diphenylmethanediyl, toluenediyl, the following general formula (1), the following general formula (2), and -CH2CH2 Selected from the group consisting of CH2 CH2 CH2 CH2 - The aforementioned microporous thin film has a thickness in the range of 30 μm to 90 μm and a basis weight of 10 g / m². ２ ~30g / m ２ It is within the range, and the water resistance measured in accordance with JIS L1092B is 10,000 mmH ２ The moisture permeability, measured in accordance with JIS L1099A1, exceeds 0 and is 3000 g / m². ２ A method for producing a microporous thin film, characterized by a process exceeding 24 hours. 【Transformation 5】 【Transformation 6】

11. Step a, which involves mixing waste plastic mainly containing polyester terephthalate and polyurethane with a depolymerizing agent and depolymerizing the waste plastic at a first temperature to obtain a depolymerized plastic product, Step b involves mixing the plastic depolymer with a first polyether polyol to obtain a first mixture, and then polymerizing the first mixture at a second temperature to obtain a polymer diol mixture. Step c is to mix the polymer diol mixture with a second polyether polyol, a polyfunctional isocyanate, and a solvent to obtain a second mixture, and then react the second mixture at a third temperature to obtain a recycled plastic having carbamate groups. Step d is to obtain a non-porous thin film in which the recycled plastic having the carbamate group is coated and heated, The step includes attaching the non-porous thin film to a base fabric to obtain a composite knitted fabric, In step a, the plastic depolymer comprises a first monomer having a structure represented by HO-R x-OOC-Ph-COO-R' x-OH and a second monomer having a structure represented by HO-R x-OOC-HN-R-NH-COO-R' x-OH, wherein in the above structure, Ph represents a benzene ring, R x and R' x are each independently selected from the group consisting of -CH2CH2-, -CH2CH2OCH2CH2-, -(CH2CH2O)n-, and -(CH2CH2O)nCH2CH2-, where n is an integer in the range of 6 to 23, and R is diphenylmethanediyl, toluenediyl, the following general formula (1), the following general formula (2), and -CH2CH2 Selected from the group consisting of CH2 CH2 CH2 CH2 - The non-porous thin film has a thickness in the range of 10 μm to 30 μm and a basis weight of 10 g / m². ２ ~30g / m ２ It is within the range, and the water resistance measured in accordance with JIS L1092B is 10,000 mmH ２ The moisture permeability, measured in accordance with JIS L1099B1, exceeds 0 and is 120,000 g / m². ２ A method for manufacturing a composite knitted fabric, characterized by a process exceeding 24 hours. 【Transformation 7】 【Transformation 8】

12. Step a, which involves mixing waste plastic mainly containing polyester terephthalate and polyurethane with a depolymerizing agent and depolymerizing the waste plastic at a first temperature to obtain a depolymerized plastic product, Step b involves mixing the plastic depolymer with a first polyether polyol to obtain a first mixture, and then polymerizing the first mixture at a second temperature to obtain a polymer diol mixture. Step c is to mix the polymer diol mixture with a second polyether polyol, a polyfunctional isocyanate, and a solvent to obtain a second mixture, and then react the second mixture at a third temperature to obtain a recycled plastic having carbamate groups. Step d is to obtain a microporous thin film by coating, solidifying, washing with water and heating the recycled plastic having the carbamate group, The step includes step e, which involves attaching the microporous thin film to a base fabric to obtain a composite knitted fabric, In step a, the plastic depolymer comprises a first monomer having a structure represented by HO-R x-OOC-Ph-COO-R' x-OH and a second monomer having a structure represented by HO-R x-OOC-HN-R-NH-COO-R' x-OH, wherein in the above structure, Ph represents a benzene ring, R x and R' x are each independently selected from the group consisting of -CH2CH2-, -CH2CH2OCH2CH2-, -(CH2CH2O)n-, and -(CH2CH2O)nCH2CH2-, where n is an integer in the range of 6 to 23, and R is diphenylmethanediyl, toluenediyl, the following general formula (1), the following general formula (2), and -CH2CH2 Selected from the group consisting of CH2 CH2 CH2 CH2 - A method for manufacturing a composite knitted fabric, characterized in that the microporous thin film has a thickness in the range of 30 μm to 90 μm, a basis weight in the range of 10 g / m² to 30 g / m², a water resistance measured in accordance with JIS L1092B exceeding 10,000 mmH₂O, and a moisture permeability measured in accordance with JIS L1099A1 exceeding 3,000 g / m²・24 hours. 【Chemistry 9】 【Chemistry 10】

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