Recycled plastic, and preparation process and use thereof

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 particularly to recycled plastics obtained by polymerizing a resin raw material containing a plastic depolymerization product, a polyether polyol, and a polyfunctional isocyanate, a method for producing the same, and products thereof.

Background Art

[0002] In the process of manufacturing regenerated fibers from currently discarded clothes and discarded fabrics, in principle, a single-component (100%) fiber material or at least 97% or more of a polyester fiber material is used as the main material, and physical recovery treatment (for example, a method of cutting and pulverizing with a machine and then performing injection granulation, or the method mentioned in the background art of Patent Document 1) and chemical recovery treatment (for example, a method of decolorizing and performing alcoholysis and then polymerizing again, or the method mentioned in the background art of Patent Document 1) and other methods are used for treatment to produce regenerated fibers.

[0003] In addition, a thin film may be manufactured from the above-mentioned regenerated fibers, but such a thin film usually has difficulty meeting the demand as a waterproof and moisture-permeable woven fabric.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[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, and the resin raw material includes a plastic depolymerized product, a polyether polyol, a multi-functional isocyanate, and a solvent. 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 in 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, 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 performing depolymerization of the waste plastics at a first temperature to obtain a plastic depolymerized product (step a); mixing the plastic depolymerized product with a first polyether polyol to obtain a first mixture, and performing a polymerization reaction on the first mixture 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 performing a reaction on the second mixture at a third temperature to obtain a recycled plastic having a carbamate group (step c). In step a, the plastic depolymerized product is HO-R x -OOC-Ph-COO-R’ x -OH having a structure represented by a first monomer, and HO-R x -OOC-HN-R-NH-COO-R’ x -OH having a structure represented by a second monomer. 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 in 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 porous thin film coated and heated with the above recycled plastic, having a thickness in the range of 10 μm to 30 μm, a basis weight in the range of 10 g / m 2 ~30 g / m 2 and having a water resistance measured in accordance with JIS L1092B exceeding 10000 mmH2O and a moisture permeability measured in accordance with JIS L1099B1 exceeding 120000 g / m 2 ·24 hours, and provides a porous thin film characterized by this.

[0013] The present invention relates to a microporous thin film coated, coagulated, washed with water and heated with the above recycled plastic, having a thickness in the range of 30 μm to 90 μm, a basis weight in the range of 10 g / m 2 ~30 g / m 2 and having a water resistance measured in accordance with JIS L1092B exceeding 10000 mmH2O and a moisture permeability measured in accordance with JIS L1099A1 exceeding 3000 g / m 2 ·24 hours, and provides a microporous thin film characterized by this.

[0014] The present invention provides a composite woven fabric including a base fabric and a thin film attached to the base fabric, wherein the thin film is the above porous thin film or microporous thin film.

Effects of the Invention

[0015] The recycled plastic of the present invention is obtained by polymerizing a resin raw material containing a plastic depolymerized product, and can produce a thin film and a composite woven fabric having a waterproof and moisture-permeable function.

Modes for Carrying Out the Invention

[0016] It should be understood that when a prior art publication is referred to in this specification, such reference does not admit that the publication forms part of the common general knowledge in the art in Taiwan or other countries.

[0017] For the purposes of this specification, it should be clearly understood that the term "comprising" means "including but not limited to", and the term "comprises" has a corresponding meaning.

[0018] Unless otherwise defined, all technical and scientific terms used in this specification have the meaning commonly understood by those skilled in the art to which this invention pertains. Those skilled in the art will recognize many methods and materials similar or equivalent to those described herein that can be used in the practice of the present invention. Indeed, the present invention is not limited to the methods and materials described herein.

[0019] Also, in the description of the present invention, terms such as "first", "second", etc. are used for the sole purpose of distinction and do not teach or imply 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 includes a plastic depolymerization product, a polyether polyol, a polyfunctional isocyanate, and a solvent.

[0023] The plastic depolymerization 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.

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

[0025]

Chemical formula

[0026]

Chemical formula

[0027] In some embodiments, the resin raw material further includes 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 method for producing the recycled plastic of the present invention includes the following steps a to c.

[0032] Step a: Mixing waste plastic mainly containing polyethylene terephthalate and polyurethane (containing as a main component) with a depolymerizing agent, and depolymerizing the waste plastic at a first temperature to obtain the above plastic depolymerized product.

[0033] Step b: Mixing the plastic depolymerized product 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 high molecular weight diol mixture.

[0034] Step c: Mixing the high molecular weight diol mixture, a second polyether polyol, a polyfunctional isocyanate, and a solvent to obtain a second mixture, and reacting the second mixture at a third temperature to obtain a recycled plastic having a carbamate group.

[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 high molecular weight diol mixture in two steps.

[0037] In some embodiments, the depolymerizing agent 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 porous thin film of the present invention is obtained by applying and heating the above-mentioned recycled plastic. In this embodiment, the porous thin film of the present invention is obtained by applying the above-mentioned recycled plastic to form a thin layer and then heating the thin layer.

[0041] The porous thin film has a thickness in the range of 10 μm to 30 μm, a basis weight in the range of 10 g / m 2 ~30 g / m 2 , a water resistance measured in accordance with JIS L1092B exceeding 10000 mmH2O, and a moisture permeability measured in accordance with JIS L1099B1 exceeding 120000 g / m 2 ·24 h.

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

[0043] 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 / m 2 ~30 g / m 2within the range, the water resistance measured in accordance with JIS L1092B exceeds 10,000 mmH2O, and the moisture permeability measured in accordance with JIS L1099A1 exceeds 3000 g / m 2 ·24 hours.

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

[0045] Hereinafter, examples of the present invention will be described. It should be understood that these examples are illustrative and explanatory and should not be construed as limiting the present invention.

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

[0047] (a) 1000 g of a first waste cloth made of a man-made composite fiber (composite fiber, polyester terephthalate fiber coated with polyurethane, with the total amount of the man-made composite fiber being 100 wt%, the polyurethane content being 20 wt%, and the polyester terephthalate content being 80 wt%), 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 (registered trademark) 1010 (as an antioxidant) are mixed and stirred at a first temperature of 240 °C in a nitrogen atmosphere for 2 to 3 hours to depolymerize the first waste cloth, and then cooled to 150 °C to obtain a first mixture. Thereafter, filtration is performed using a stainless steel filter mesh coated with diatomaceous earth (pore diameter: 10 μm) to obtain a plastic depolymerized product.

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

[0049] (c) 171.96 g of the high molecular weight diol mixture obtained in the above step b, 22.73 g of polyethylene glycol (PEG2000, as the second polyether polyol), 23.25 g of 1,4 - butanediol (BDO, as a small molecule polyol), 0.1 g of stannous octoate (CAS number: 301 - 10 - 0, T9, as a catalyst), 0.1 g of Irganox (registered trademark) 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. Then, 48.8 g of 4,4’ - methylenediphenyl diisocyanate (4,4’ - MDI, as a polyfunctional isocyanate) was gradually added to the intermediate mixture (causing an exothermic reaction) to obtain a second mixture. After the exothermic reaction ended, the second mixture was stirred for 2 hours while maintaining it at a third temperature of 80°C using an external temperature control means, and then 32.552 g of 4,4’ - MDI was gradually added and reacted at the third temperature (80°C) for 3 to 4 hours to obtain the recycled plastic having a carbamate group of Example 1 (with a solid content of about 30% and a viscosity of about 56270 cP).

[0050] <Example 2> The manufacturing method of the recycled plastic in Example 2 is similar to that in Example 1. The differences between Example 2 and Example 1 are as follows: in step a, instead of 1000 g of the first waste cloth, 1000 g of a second waste cloth made of artificial composite fibers (polyester terephthalate fibers coated with polyurethane, with the total amount of artificial composite fibers being 100 wt%, the polyurethane content being 45 wt%, and the polyester terephthalate content being 55 wt%) is used; in step b, instead of 640 g of PEG2000 (as the first polyether polyol), 640 g of polytetramethylene ether glycol (PTMEG1000) is used; in step c, instead of 22.73 g of PEG2000 (as the second polyether polyol), 22.73 g of another polytetramethylene ether glycol (PTMEG2000) is used; and finally, a recycled plastic having a carbamate group in Example 2 (with a solid content of about 25% and a viscosity of about 20000 cP to 40000 cP) is obtained.

[0051] <Manufacture and Property Measurement of Porous Thin Film> The recycled plastic having a carbamate group obtained in Example 1 above was applied to release paper in a thin layer [with an area of about 62 inches (about 157.48 cm)], and the release paper coated with the thin layer was passed through an oven at a speed of 15 m / min for heating [the length of the oven was 28 m, and the temperature gradient was successively 60 °C (from 0 m to 4 m), 80 °C (from 4 m to 8 m), 110 °C (from 8 m to 12 m), 130 °C (from 12 m to 16 m), 150 °C (from 16 m to 20 m), 150 °C (from 20 m to 24 m), 150 °C (from 24 m to 28 m)] to form a porous thin film on the release paper, and then the porous thin film was separated from the release paper to manufacture the porous thin film of Example 1 (the thickness of the thin film was about 19 μm to 20 μm, and the basis weight of the thin film was about 16.7 g / m 2 ~17.0 g / m 2 and that's it).

[0052] The water resistance (n = 3) of the non-porous thin film of Example 1 measured in accordance with JIS L1092B exceeds 15000 mmH2O. The moisture permeability (n = 3) of the non-porous thin film of Example 1 measured in accordance with JIS L1099B1 is on average 125776 g / m 2 ·24 hours.

[0053] <Manufacture and Property Measurement of Microporous Thin Films> The regenerated plastic having a carbamate group obtained in Example 2 above was applied to a woven fabric (40D × 40D) of polyethylene terephthalate (PET) coated with a release agent to form a thin layer [width of about 60 inches (about 152.4 cm)]. The woven fabric coated with the thin layer was passed through a coagulation bath (length 18 m) containing an aqueous solution of 15% DMF, a five-stage water washing bath (containing pure water at 45°C, each stage having a length of 2 m), and an oven at a speed of 18 m / min and heated [the length of the oven is 15 m, and the temperature gradient is 120°C (0 m to 3 m), 130°C (3 m to 6 m), 140°C (6 m to 9 m), 150°C (9 m to 12 m), 150°C (12 m to 15 m) in sequence] to obtain an intermediate thin film coated on the PET woven fabric. Then, it was wound using a substrate peeling machine (purchased from Taiwan HWAI YUH MACHINERY CO., LTD., model number: HYK-1126-4) to separate the intermediate thin film and the PET woven fabric, and a microporous thin film of Example 2 (the thickness of the thin film is about 56 μm, the basis weight of the thin film is about 22.1 g / m 2 and the pore diameter is about 2 μm or less) was obtained.

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

[0055] <Manufacture and Property Measurement of Composite Woven Fabrics> On one side of the non-porous thin film obtained in Example 1 above and on one side of the microporous thin film obtained in Example 2 above, a reactive hot melt polyurethane adhesive (purchased from DIC Corporation, model number: TYFORCE NH-321) pre-heated to 100°C was applied, and each of the non-porous thin film obtained in Example 1 and the microporous thin film obtained in Example 2 above was attached to a PET woven fabric (30D×30D as the base fabric) with the reactive hot melt polyurethane adhesive to obtain the composite woven fabric of Example 1 and the composite woven fabric of Example 2.

[0056] The water resistance of the composite woven fabric of Example 1 measured in accordance with JIS L1092B exceeds 20,000 mmH2O. The moisture permeability of the composite woven fabric of Example 1 measured in accordance with JIS L1099 B1 exceeds 30,000 g / m 2 ·24 hours. The water resistance of the composite woven fabric of Example 2 measured in accordance with JIS L1092B exceeds 10,000 mmH2O. The moisture permeability of the composite woven fabric of Example 2 measured in accordance with JIS L1099A1 exceeds 2,000 g / m 2 ·24 hours.

[0057] According to the above content, the recycled plastic of the present invention is obtained by polymerizing a resin raw material containing a plastic depolymerized product, and can produce a thin film having a waterproof and moisture-permeable function (for example, the non-porous thin film obtained in Example 1 and the microporous thin film obtained in Example 2) and a composite woven fabric (for example, the composite woven fabrics obtained in Example 1 and Example 2).

[0058] Therefore, the object of the present invention can be surely achieved.

[0059] The above embodiments are illustrative of the principles and effects of the present invention and do not limit the present invention. Those skilled in the art can make some changes and modifications to the above embodiments on the premise of not departing from the spirit and scope of the present invention. Therefore, all changes and modifications made on the premise that those skilled in the art do not depart from the gist of the present invention should also be included in the protection scope of the present invention.

Industrial Applicability

[0060] The recycled plastic of the present invention is suitable for manufacturing thin films and composite woven fabrics having a waterproof and moisture-permeable function.

Claims

1. Recycled plastic obtained by polymerizing a resin raw material, wherein the resin raw material includes a plastic depolymerized product, a polyether polyol, a polyfunctional isocyanate, and a solvent. The plastic depolymerization 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, and In the above structure, Ph represents a benzene ring. 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, and n is an integer in the range of 6 to 23, R is selected from the group consisting of 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 -, and is characterized by recycled plastic. 【Chemical 1】 [Chemical Formula 2]

2. The resin raw material further includes a small molecule polyol. The recycled plastic according to claim 1, characterized in that.

3. The polyether polyol is selected from the group consisting of polyethylene glycol, polytetramethylene ether glycol, and polypropylene glycol. The recycled plastic according to claim 1, characterized in that.

4. The polyfunctional isocyanate is selected from the group consisting of methylene diphenyl diisocyanate, toluene diisocyanate, m-xylene diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate. The recycled plastic according to claim 1, characterized in that.

5. 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. The recycled plastic according to claim 2, characterized in that.

6. 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 plastic depolymerized product, step a; Mixing the plastic depolymerized product and 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 high molecular diol mixture, step b; Mixing the high molecular diol mixture, a second polyether polyol, a polyfunctional isocyanate, and a solvent to obtain a second mixture, and reacting the second mixture at a third temperature to obtain a recycled plastic having a carbamate group, step c. 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 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 -CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ -, and a method for producing a recycled plastic, characterized in that. [Chemical Formula 3] 【Chemical Formula 4】

7. The first temperature is higher than the second temperature, and the second temperature is higher than the third temperature. The method for manufacturing a recycled plastic according to claim 6, characterized in that.

8. In step c, the polyfunctional isocyanate is mixed with the high molecular diol mixture in two steps. The method for manufacturing a recycled plastic according to claim 6, characterized in that.

9. The polyfunctional isocyanate is selected from the group consisting of methylene diphenyl diisocyanate, toluene diisocyanate, m-xylylene diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate. The method for producing recycled plastic according to claim 6 is characterized by this.

10. The depolymerizing agent is selected from the group consisting of ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, and combinations thereof. The method for producing recycled plastic according to claim 6 is characterized by this.

11. 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. The method for producing recycled plastic according to claim 6 is characterized by this.

12. In step c, the second mixture further contains a small molecule polyol. The method for producing recycled plastic according to claim 6 is characterized by this.

13. 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. The method for producing recycled plastic according to claim 12 is characterized by this.

14. A non-porous thin film coated and heated with recycled plastic according to any one of claims 1 to 5, having a thickness in the range of 10 μm to 30 μm and a basis weight in the range of 10 g / m ２ to 30 g / m ２ , having a water resistance of more than 10,000 mmH ２ O measured in accordance with JIS L1092B and a moisture permeability of more than 120,000 g / m ２ ·24 hours, characterized by a non-porous thin film.

15. A microporous thin film obtained by applying, solidifying, washing with water and heating the recycled plastic according to any one of claims 1 to 5, the thickness of which is within the range of 30 μm to 90 μm and the basis weight of which is 10 g / m ２ ~30g / m ２ The water resistance measured in accordance with JIS L1092B is within the range of 10,000 mmH ２ O, and the moisture permeability measured in accordance with JIS L1099A1 is 3000 g / m ２ A microporous thin film characterized by being more than 24 hours.

16. A composite woven fabric comprising a base fabric and a thin film attached to the base fabric, wherein the thin film is the porous thin film according to claim 14.

17. A composite woven fabric comprising a base fabric and a thin film attached to the base fabric, wherein the thin film is the microporous thin film according to claim 15.

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