Hot melt adhesive film having no urethane group, and composite laminate having no urethane group

Abstract

A hot melt adhesive film having no urethane group [-NH-C (O)-O-] comprises a polyester base material layer having a moisture permeability of 5000 g / m < 2 > * 24 hr or less and a hot melt adhesive layer provided on the polyester base material layer. The hot melt adhesive layer comprises regenerated copolyester. The regenerated copolyester has a melting point of from 80 DEG C to 130 DEG C, a glass transition temperature of from-60 DEG C to 10 DEG C, and a heat enthalpy of from 5 J / g to 30 J / g. The regenerated copolyester is obtained by processing a polyester recovery regenerated material component, and the regenerated copolyester comprises 50 to 100 mol% of a first carboxylic ester chain segment represented by a formula (I), 0 to 35 mol% of a second carboxylic ester chain segment represented by a formula (II), and 0 to 15 mol% of a third carboxylic ester chain segment represented by a formula (III) based on the regenerated copolyester. The regenerated copolyester has more than 20 wt% of a recycled component derived from a polyester recycled material component. The invention also provides a composite laminated body without the carbamate group, which comprises the hot melt adhesive film without the carbamate group. The definitions of R11, R21, R31 and R32 refer to the description and the claims.

Description

Technical Field

[0001] This invention relates to a recycled polyester product produced by reusing depolymerization products. The depolymerization products are formed by depolymerizing recycled aromatic polyesters, and the recycled polyester product is produced without an esterification step and is polymerized from the depolymerization products. In particular, it relates to a hot-melt film and composite laminate containing the recycled copolyester of this invention and lacking urethane groups.

[0002] The hot melt film of the present invention, which does not contain urethane groups, is a thermoplastic polyester copolymer and includes a recycled copolyester formed by alcoholysis of recycled materials (e.g., recycled polyethylene terephthalate) to obtain depolymerization products. At the same time, the hot melt film, which does not contain urethane groups, is made of a single all-polyester material, so that it can be easily recycled and reused. Background Technology

[0003] In everyday items such as snowsuits, windbreakers, waterproof casual jackets, hiking boots, waterproof casual shoes, medical protective clothing, and tents, heat-fused films are often used to prevent water from entering the interior of the item through the joints (such as gaps or seams) between the components (such as waterproof and breathable membranes).

[0004] Chinese Patent Publications CN101760163A, CN107163892B, and CN101434821B all disclose a method for preparing a water-resistant polyester hot melt adhesive using polyethylene terephthalate (PET) waste. This method includes a depolymerization step, an esterification step, and a recombination step. Experiments have shown that the polyester hot melt adhesive formed by the method including the esterification step has a high enthalpy, causing the adhesive to fail to adhere firmly to the substrate after washing, thus failing to meet consumer requirements.

[0005] Taiwan Patent Publication No. TWI499612B discloses a method for preparing a copolyester ether. This method includes performing an alcoholysis reaction between recycled aromatic polyester and a diol to obtain a first intermediate product; then, subjecting the first intermediate product to an ester exchange reaction to obtain a second intermediate product; and finally, subjecting the second intermediate product (polydiol) to a recombination reaction. The copolyester ether has an aromatic dicarboxylic acid ethylene glycol ester block structure and an aromatic dicarboxylic acid butylene glycol ester block structure. The copolyester film has a melting point of 150°C to 200°C and a glass transition temperature of -20°C to -40°C. Experiments have shown that when this copolyester ether is used as a hot melt adhesive, its high melting point causes the copolyester ether to fail to adhere firmly to the substrate after washing, thus failing to meet consumer requirements.

[0006] Taiwan Patent Publication No. TWI822243B discloses a breathable and waterproof membrane made of thermoplastic polyester elastomer. The preparation method of this thermoplastic polyester elastomer includes alcoholysis of recycled polyethylene terephthalate and an aliphatic diol to form diethyl terephthalate, followed by polymerization of the diethyl terephthalate with a long-chain polyalkyl diol. The manufacturing process of this thermoplastic polyester elastomer differs from that of this patent. The melting point of this thermoplastic polyester elastomer is above 200°C. When this thermoplastic polyester elastomer is used as a hot melt adhesive, its high melting point causes the elastomer to fail to adhere firmly to the substrate after washing, thus failing to meet consumer requirements.

[0007] Taiwan Patent Publication No. TWI747380B discloses a heat-sealable polyester film made from recycled polyester material. The heat-sealable polyester film comprises a base layer and a heat-sealable layer, the heat-sealable layer being formed from a first polyester composition. The first polyester composition comprises 50 wt% to 95 wt% of physically recycled polyester resin and 1 wt% to 40 wt% of chemically recycled polyester resin. The physically recycled polyester resin is formed from physically recycled polyester masterbatch, which includes physically recycled conventional polyester masterbatch and physically recycled modified polyester masterbatch. The physically recycled modified polyester masterbatch includes recycled polyethylene terephthalate and 0 wt% to 30 wt% of polybutylene terephthalate. This patent application requires both chemically recycled polyester resin and physically recycled polyester resin for the heat-sealable layer, resulting in a more complex composition. Furthermore, it does not disclose the washability of the product after the heat-sealable layer is bonded to a polyester waterproof and breathable membrane.

[0008] Taiwanese Patent Publication No. TW202302729A discloses a thermoplastic film composed of a single layer of hot melt adhesive film. This single layer of hot melt adhesive film has a melting point of 50°C to 160°C and a hardness of 40A to 80A. The material of this single layer of hot melt adhesive film is a thermoplastic polyurethane with urethane groups. This thermoplastic film can be used to bond garments such as shoe uppers or clothing, thereby reducing the amount of stitching. However, the peel strength between the hot melt adhesive film and the garment before and after washing is only 63-76%, significantly reduced. Therefore, the garment containing the hot melt adhesive film has poor wash resistance, which does not meet the needs of manufacturers. Furthermore, since most clothing and shoe uppers are made of polyester, when thermoplastic polyurethane with urethane groups is used as a hot melt adhesive film, it will be impossible to recycle due to the presence of foreign materials. Moreover, after the hot melt adhesive film is heated and bonded, it is difficult to remove from clothing or shoe uppers, thus failing to achieve the sustainable environmental goal of waste reduction.

[0009] Taiwan Patent Publication No. TWI473716B discloses a waterproof strip comprising a polyester waterproof membrane and a polyester hot melt adhesive. However, this patent does not disclose the wash resistance of the product after the waterproof strip and the polyester waterproof and breathable membrane are bonded together, and the polyester hot melt adhesive is not made from recycled materials (e.g., recycled polyethylene terephthalate). The polyester hot melt adhesive has a relatively regular structure, and experiments have shown that products bonded to polyester waterproof and breathable membranes using polyester hot melt adhesive made from non-recycled materials fail the wash resistance test (washing at 45°C followed by drying at 60°C). Furthermore, the use of polyester hot melt adhesive not made from recycled materials fails to achieve the effect of waste reduction and plastic reduction.

[0010] In addition to the aforementioned patents, Chinese Patent Publication No. CN87107206A, Chinese Patent Announcement No. CN1015371B, Chinese Patent Publication No. CN110997318A, Chinese Patent Announcement No. CN112585199A, Chinese Patent Publication No. CN115160939A, Taiwan Patent Publication No. TW200403146A, and Japanese Patent Publication No. JP2007296798A do not use polyester hot melt adhesives made from recycled materials (such as recycled polyethylene terephthalate), and do not disclose the water resistance of the product after the polyester hot melt adhesive is bonded to a polyester waterproof and breathable membrane.

[0011] Japanese Patent Publication No. JP3942367B2 discloses a water-resistant sealing tape comprising an adhesive layer and a substrate layer. Neither the adhesive layer nor the substrate layer is made from recycled materials (e.g., recycled polyethylene terephthalate). Furthermore, the polyether ester elastomer in the adhesive layer is formed by transesterification and polycondensation of aromatic dicarboxylic acid esters and polyether alcohols, and is dissolved in a solvent before being formed into a film, raising concerns about solvent residue. Additionally, the polyether ester elastomer has a more regular structure, unlike the more random structure of the recycled copolyester of this invention. The regular structure also has a higher enthalpy, requiring higher temperature conditions for bonding. Summary of the Invention

[0012] The first objective of this invention is to provide a hot melt film made from recycled materials that does not contain urethane groups.

[0013] The hot melt adhesive film of the present invention, which does not contain urethane groups [-NH-C(O)-O-], comprises 5000 g / m 2A polyester substrate layer with a moisture permeability of less than 24 hours and a hot-melt adhesive layer disposed on the polyester substrate layer. The hot-melt adhesive layer comprises a recycled copolyester. The recycled copolyester is formed by a recombination reaction of reactive components containing raw materials, and the raw materials contain depolymerization components. The depolymerization component includes depolymers selected from (A) depolymers with a terephthalic acid ester group in the main chain, (B) depolymers with both terephthalic acid ester and isophthalic acid ester groups in the main chain, (C) depolymers with a terephthalic acid ester group in the main chain and a dicarboxylic acid ester group of C1 to C4 linear alkyl groups, (D) depolymers with terephthalic acid ester, isophthalic acid ester, and dicarboxylic acid ester groups of C1 to C4 linear alkyl groups in the main chain, (E) depolymers with an isophthalic acid ester group in the main chain, (F) depolymers with a dicarboxylic acid ester group of C1 to C4 linear alkyl groups in the main chain, (G) depolymers with an isophthalic acid ester group in the main chain and a dicarboxylic acid ester group of C1 to C4 linear alkyl groups, or any combination thereof. The depolymerization component is obtained by depolymerizing the recycled material component in the presence of a depolymerizing agent. The depolymerizing agent comprises a polyol component and a polycarboxylic acid component. The recycled material component comprises recycled polyester, which is selected from (i) recycled polyester with a terephthalic acid ester group in the main chain, (ii) recycled polyester with a terephthalic acid ester group and an isophthalic acid ester group in the main chain, or (iii) recycled polyester with a terephthalic acid ester group and a dicarboxylic acid ester group of a C1 to C4 straight-chain extended alkyl group in the main chain. The amount of the polycarboxylic acid component is 0 mol% or more and less than 10 mol%, based on a total amount of 100 mol% of the polycarboxylic acid component and the recycled polyester. The recycled copolyester has 20 wt% or more of the recycled components derived from the recycled material component. The recycled copolyester has a melting point of 80°C to 130°C, a glass transition temperature of -60°C to 10°C, and an enthalpy of 5 J / g to 30 J / g. Based on the recycled copolyester, the recycled copolyester comprises 50 mol% to 100 mol% of a first carboxylic acid ester segment of formula (I), 0 mol% to 35 mol% of a second carboxylic acid ester segment of formula (II), and 0 mol% to 15 mol% of a third carboxylic acid ester segment of formula (III).

[0014]

[0015]

[0016] In equation (I), R 11 This refers to C2 to C6 alkyl groups or alkyl ether groups with a number average molecular weight of 450 to 1000 g / mol.

[0017] In equation (II), R 21This refers to C2 to C6 alkyl groups or alkyl ether groups with a number average molecular weight of 450 to 1000 g / mol.

[0018] In equation (III), R 31 R represents a straight-chain extended alkyl group from C1 to C4. 32 It refers to C2 to C6 alkyl groups or alkyl ether groups with an average molecular weight of 450 to 1000 g / mol.

[0019] The hot melt adhesive film of the present invention does not have a urethane group, and the polyol component is a biomass polyol component.

[0020] The hot melt adhesive film of the present invention does not have a urethane group, and the polyester substrate layer has a content of 1600 g / m². 2 • Moisture permeability for less than 24 hours.

[0021] The hot melt adhesive film of the present invention does not have a urethane group, wherein the polyol component comprises two or more polyols, and the polyols are selected from C2 to C6 diol compounds or polyether polyols with an average molecular weight of 450 g / mol to 1000 g / mol.

[0022] The hot melt adhesive film of the present invention does not have a urethane group, and the raw material further comprises polyether polyols with an average molecular weight of 450 g / mol to 1000 g / mol.

[0023] The hot melt adhesive film of the present invention does not have a urethane group, wherein the C2 to C6 diol compound is selected from ethylene glycol, propylene glycol, butanediol, pentanediol, 3-methyl-1,5-pentanediol, hexanediol, or neopentanediol.

[0024] The hot melt adhesive film of the present invention does not have a urethane group, wherein the polyether polyol is selected from copolymers of ethylene oxide and propylene oxide, copolymers of ethylene oxide and tetrahydrofuran, polyethylene glycol, polypropylene glycol, poly(tetramethyl ether) glycol, polyhexane glycol, poly(trimethyl ether) glycol, or decaethylene glycol.

[0025] The hot melt adhesive film of the present invention does not have a urethane group, wherein one of the polyols in the polyol component is hexanediol.

[0026] The hot melt adhesive film of the present invention, which does not have urethane groups, uses 0 wt% to 44 wt% of the polyether polyol, based on a total amount of 100 wt% of the C2 to C6 diol compound and the polyether polyol.

[0027] The second objective of this invention is to provide a composite laminate that does not have urethane groups.

[0028] The composite laminate of the present invention, which does not contain urethane groups [-NH-C(O)-O-], comprises the aforementioned urethane-free hot-melt film and a urethane-free polyester component. The urethane-free polyester component has a content of 5000 g / m³. 2 • A moisture permeability of less than 24 hours, and it is provided in the hot-melt adhesive layer of the hot-melt film without urethane groups. According to the water pressure method of JIS L1092 (2012 edition), the composite laminate has a water pressure resistance of 4000 mmH2O to 8000 mmH2O. The peel strength retention rate between the hot-melt adhesive layer in the composite laminate without urethane groups and the polyester component without urethane groups is more than 80%, and the peel strength retention rate is {1-[(peel strength before washing - peel strength after washing) / peel strength before washing]}×100%.

[0029] The present invention relates to a composite laminate without urethane groups, wherein the polyester substrate layer of the heat-melt film without urethane groups comprises a polyether ester elastomer.

[0030] The composite laminate of the present invention, which does not have urethane groups, further includes a polyester textile layer disposed on a polyester substrate layer of the hot melt adhesive film that does not have urethane groups.

[0031] The composite laminate of the present invention, which does not have urethane groups, further includes a polyester textile layer disposed on the polyester component that does not have urethane groups.

[0032] The beneficial effects of this invention are as follows: By rationally combining the melting point, glass transition temperature, and enthalpy of the recycled copolyester, when the urethane-free hot melt adhesive film is applied to multiple items (e.g., waterproof and breathable membranes) in products such as films, fabrics, or footwear, the hot melt adhesive layer in the urethane-free hot melt adhesive film remains firmly fixed to the item even after at least one wash, thus giving the product water resistance. Furthermore, since the urethane-free hot melt adhesive film is primarily made of polyester, the hot melt adhesive film can be easily removed from products such as fabrics or footwear during recycling, effectively separating the product. Simultaneously, the use of recycled copolyester in the hot melt adhesive layer ensures that the urethane-free hot melt adhesive film meets the sustainable environmental goals of carbon reduction and waste reduction. Furthermore, through the design of this recycled copolyester, when preparing the composite laminate without urethane groups, the hot melt adhesive layer of the hot melt film without urethane groups can melt rapidly, so that the hot melt adhesive layer can be quickly attached to the polyester component without urethane groups. Detailed Implementation

[0033] The present invention will now be described in detail.

[0034] <Hot melt film without urethane groups [-NH-C(O)-O-]>

[0035] The polyester substrate layer has a strength of 5000 g / m³. 2 • Moisture permeability of less than 24 hours. In some embodiments of the invention, the polyester substrate layer comprises a polyether ester elastomer. This polyester substrate layer, for example, but not limited to, the exemplary model manufactured by Far East New Century Company, is... Commercially available polyester waterproof and breathable membrane TE1351SR (permeability 1061g / m²) 2 • 24hrs; Melting point: 174℃; Composition: polyether ester elastomer; Model: TE1331SR polyester waterproof and breathable membrane (permeability 1550g / m²) 2 • 24hrs; Melting point: 172℃; Water pressure resistance: 13000mmH2O; Composition: Polyether ester elastomer; Model: TE1223R polyester waterproof and breathable membrane (permeability 1649g / m²) 2 • 24hrs; Melting point: 186℃; Water pressure resistance: 13000mmH2O; Composition: Polyether ester elastomer) or model number: TE1142SR polyester waterproof and breathable membrane (permeability 4624 g / m²) 2 • 24hrs; melting point 163℃; water pressure resistance 13000mmH2O; composition: polyether ester elastomer, etc. In some embodiments of the present invention, the polyester substrate layer has a content of 1600g / m². 2 • Moisture permeability for less than 24 hours.

[0036] The hot-melt adhesive layer is disposed on the polyester substrate layer and comprises recycled copolyester. The recycled copolyester has a melting point of 80°C to 130°C, a glass transition temperature of -60°C to 10°C, and an enthalpy of 5 J / g to 30 J / g. In some embodiments of the invention, the recycled copolyester has a melting point of 85°C to 125°C, a glass transition temperature of -60°C to 7°C, and an enthalpy of 12 J / g to 30 J / g.

[0037] Based on the experience of this invention, when the melting point of the recycled copolyester is greater than 130°C, the hot melt film needs to be bonded to the polyester component (e.g., a polyester waterproof and breathable membrane) under higher temperature conditions, which may cause the polyester component to crack and result in water leakage. When the melting point of the recycled copolyester is lower than 80°C, it may become difficult to cool and wrap around the cutter during the granulation process, resulting in inconsistent granulation quality and affecting subsequent processing.

[0038] Based on the experience of this invention, when the glass transition temperature of the recycled copolyester is greater than 10°C, the molecular chains of the recycled copolyester have poor mobility, which means that when the hot melt film is heated and bonded to the polyester component (e.g., a polyester waterproof and breathable membrane), the hot melt adhesive layer of the hot melt film cannot adhere well to the polyester component. When the glass transition temperature of the recycled copolyester is less than -60°C, when the composite laminate is washed with water, the hot melt adhesive layer of the hot melt film is easily swollen by water and thus separates from the polyester component.

[0039] Based on the experience of this invention, when the enthalpy of the recycled copolyester is higher than 30 J / g, the crystallinity of the recycled copolyester is too high, making it difficult to melt. Even if the temperature is increased, the polyester component (e.g., a polyester waterproof and breathable membrane) may crack during the melt bonding process. When the enthalpy of the recycled copolyester is less than 5 J / g, the crystallinity of the recycled copolyester is insufficient, causing water to easily penetrate into the molecular chain of the recycled copolyester in the hot melt adhesive layer when the composite laminate is washed, causing the hot melt adhesive layer to swell and then separate from the polyester component.

[0040] The melting point, glass transition temperature, and enthalpy of the recycled copolyester can be obtained by rationally combining the types and proportions of the raw materials of the recycled copolyester and controlling parameters such as process temperature and time.

[0041] The recycled copolyester comprises 50 mol% to 100 mol% of a first carboxylic acid ester segment of formula (I), 0 mol% to 35 mol% of a second carboxylic acid ester segment of formula (II), and 0 mol% to 15 mol% of a third carboxylic acid ester segment of formula (III).

[0042]

[0043] In equation (I), R 11 This refers to C2 to C6 alkyl groups or alkyl ether groups with a number average molecular weight of 450 to 1000 g / mol.

[0044] In equation (II), R 21 This refers to C2 to C6 alkyl groups or alkyl ether groups with a number average molecular weight of 450 to 1000 g / mol.

[0045] In equation (III), R 31 R represents a straight-chain extended alkyl group from C1 to C4. 32 It refers to C2 to C6 alkyl groups or alkyl ether groups with an average molecular weight of 450 to 1000 g / mol.

[0046] The alkyl group can be a straight-chain alkyl group or a branched alkyl group. Examples of straight-chain alkyl groups include ethyl alkyl (-CH2-CH2-), propyl alkyl (-CH2-CH2-CH2-), butyl alkyl, pentyl alkyl, or hexyl alkyl. Examples of branched alkyl groups include -CH2-CH2-CH(CH3)-CH2-CH2- or -CH2-C(CH3)2-CH2-.

[0047] The alkyl ether group is, for example, but not limited to, -(X). n -O-, X independently represents alkyl, and n independently represents 2 or more. In some embodiments of the present invention, the number of alkyl ether groups in formula (I) has an average molecular weight of 960 g / mol to 1000 g / mol. In some embodiments of the present invention, the number of alkyl ether groups in formula (II) has an average molecular weight of 960 g / mol to 1000 g / mol. In some embodiments of the present invention, the number of alkyl ether groups in formula (III) has an average molecular weight of 960 g / mol to 1000 g / mol.

[0048] In some embodiments of the present invention, the first carboxylic acid ester segment of formula (I), the second carboxylic acid ester segment of formula (II), and the third carboxylic acid ester segment of formula (III) of the recycled copolyester are arranged randomly. In some embodiments of the present invention, the recycled copolyester is formed by recombination reaction of reactive components containing raw materials, and the raw materials contain depolymerization components. The depolymerization component includes depolymers selected from (A) depolymers with a terephthalic acid ester group in the main chain, (B) depolymers with both terephthalic acid ester and isophthalic acid ester groups in the main chain, (C) depolymers with a terephthalic acid ester group in the main chain and a dicarboxylic acid ester group of C1 to C4 linear alkyl groups, (D) depolymers with terephthalic acid ester, isophthalic acid ester, and dicarboxylic acid ester groups of C1 to C4 linear alkyl groups in the main chain, (E) depolymers with an isophthalic acid ester group in the main chain, (F) depolymers with a dicarboxylic acid ester group of C1 to C4 linear alkyl groups in the main chain, (G) depolymers with an isophthalic acid ester group in the main chain and a dicarboxylic acid ester group of C1 to C4 linear alkyl groups, or any combination thereof. The depolymerization component is obtained by depolymerizing the recycled material component in the presence of a depolymerizing agent. The depolymerizing agent comprises a polyol component and a polycarboxylic acid component. The recycled material component comprises recycled polyester, and the recycled polyester is selected from (i) recycled polyester with a terephthalic acid ester group structure in the main chain, (ii) recycled polyester with a terephthalic acid ester group structure and an isophthalic acid ester group structure in the main chain, or (iii) recycled polyester with a terephthalic acid ester group structure and a dicarboxylic acid ester group structure of a straight-chain extended alkyl group of C1 to C4 in the main chain. The amount of the polycarboxylic acid component is 0 mol% or more and less than 10 mol%, based on a total amount of 100 mol% of the polycarboxylic acid component and the recycled polyester. In some embodiments of the present invention, the polyol component comprises two or more polyols, and the polyols are selected from C2 to C6 diol compounds or polyether polyols with a number average molecular weight of 450 g / mol to 1000 g / mol. In some embodiments of the present invention, the polyol component comprises two or more polyols, and the polyols are selected from C2 to C6 diol compounds or polyether polyols with a number average molecular weight of 960 g / mol to 1000 g / mol. In some embodiments of the present invention, one of the polyols in the polyol component is hexanediol.

[0049] The recycled polyester includes, but is not limited to, waste polymer materials, waste PET bottles, waste fabrics, waste clothing, or waste fishing nets.

[0050] Since the components in the recycled material are recycled and the recycled copolyester is prepared using the recycled material, the hot melt film of the present invention, which does not have a urethane group, gives the recycled material to be reusable, and in this case, the recycled material will reduce environmental pollution.

[0051] In some embodiments of the present invention, the polyol component is a biomass polyol component, and the biomass polyol component can be produced by biological organisms [e.g., plants (e.g., corn)]. In some embodiments of the present invention, the polyol component can be produced by the conversion treatment of waste gas (e.g., carbon dioxide). In some embodiments of the present invention, the C2 to C6 diol compound is, for example, but not limited to, ethylene glycol, propylene glycol, butanediol, pentanediol, 3-methyl-1,5-pentanediol, hexanediol, or neopentanediol. In some embodiments of the present invention, the polyether polyol has a weight average molecular weight of 500 g / mol to 4000 g / mol. In some embodiments of the present invention, the polyether polyol is, for example, but not limited to, copolymers of ethylene oxide and propylene oxide, copolymers of ethylene oxide and tetrahydrofuran, polyethylene glycol, polypropylene glycol, poly(trimethylene ether) glycol, polyethylene glycol, poly(tetrahydrofuran) glycol, or decaethylene glycol, etc. The copolymer of ethylene oxide and tetrahydrofuran is, for example, a commercially available product manufactured by Donglian Chemical and designated as CT183, with a weight average molecular weight of 1000 g / mol to 3000 g / mol.

[0052] In some embodiments of the present invention, the raw material further comprises a polyether polyol with a quantity average molecular weight of 450 g / mol to 1000 g / mol. In some embodiments of the present invention, the polyether polyol has a quantity average molecular weight of 960 g / mol to 1000 g / mol. The polyether polyol of the reaction component is, for example, the polyether polyol of the polyol component, and therefore will not be described further.

[0053] In some embodiments of the present invention, the amount of the polyether polyol is 0 wt% to 44 wt%, based on a total amount of 100 wt% of the C2 to C6 diol compound and the polyether polyol.

[0054] In some embodiments of the present invention, the recycled copolyester has 50 wt% to 80 wt% recycled components.

[0055] To impart suitable elasticity to the recycled copolyester, in some embodiments of the present invention, the polycarboxylic acid component includes at least one linear alkyl dicarboxylic acid material with a total carbon number of 6 to 12. This linear alkyl dicarboxylic acid material with a total carbon number of 6 to 12 is, for example, but not limited to, adipic acid, heptanoic acid, octanoic acid, azelaic acid, or sebacic acid. In some embodiments of the present invention, the depolymerizing agent also includes at least one dialkyl phthalate. This dimethyl phthalate is, for example, but not limited to, dimethyl terephthalate or dimethyl isophthalate.

[0056] <Composite laminates without urethane groups>

[0057] The composite laminate of the present invention, which does not contain urethane groups, comprises the aforementioned hot-melt film without urethane groups and a polyester component without urethane groups. The polyester component without urethane groups has a content of 5000 g / m³. 2 • It has a moisture permeability of less than 24 hours and is applied to the hot-melt adhesive layer of the non-urethane-based hot-melt film. According to the hydrostatic test method of JIS L1092 (2012 edition), the non-urethane-based composite laminate has a water pressure resistance of 4000 mmH2O to 8000 mmH2O. The peel strength retention rate between the hot-melt adhesive layer in the non-urethane-based composite laminate and the non-urethane-based polyester component is above 80%, and this peel strength retention rate is {1 - [(peel strength before washing - peel strength after washing) / peel strength before washing]} × 100%.

[0058] In some embodiments of the present invention, the peel strength retention rate between the hot-melt adhesive layer in the composite laminate without urethane groups and the polyester component without urethane groups is 85% or more. In some embodiments of the present invention, the peel strength retention rate between the hot-melt adhesive layer in the composite laminate without urethane groups and the polyester component without urethane groups is 90% or more.

[0059] In some embodiments of the present invention, the urethane-free polyester component comprises a thermoplastic elastomer. This urethane-free polyester component is, for example, but not limited to, a product manufactured by Far East New Century Corporation and model number [model number missing]. Commercially available polyester waterproof and breathable membrane TE1142SR (permeability 4624 g / m²) 2 • 24hrs, melting point 163℃, and water pressure resistance 13000mmH2O; composition: polyether ester elastomer) or model number TE1223R polyester waterproof and breathable membrane (permeability 1649g / m²) 2• 24hrs, melting point 186℃, water pressure resistance 13000mmH2O; composition: polyether ester elastomer), model: TE1331 SR polyester waterproof and breathable membrane (permeability 1550g / m²) 2 • 24hrs; Melting point: 172℃; Water pressure resistance: 13000mmH2O; Composition: Polyether ester elastomer) or model number: TE1351 SR is a commercially available polyester waterproof and breathable membrane (with a moisture permeability of 1061 g / m²). 2 • 24hrs; melting point is 174℃; water pressure resistance is 13000mmH2O; composition: polyether ester elastomer, etc.

[0060] In some embodiments of the present invention, the composite laminate further includes a polyester textile layer disposed on the polyester substrate layer of the heat-melt film without urethane groups. In some embodiments of the present invention, the composite laminate further includes a polyester textile layer disposed on the polyester component without urethane groups. This polyester textile layer is, for example, part of clothing or footwear; specifically, it may be a fabric element of clothing or a material element of footwear.

[0061] The method for preparing the composite laminate without urethane groups is to heat the hot melt adhesive layer of the hot melt film without urethane groups to make the hot melt adhesive layer melted, and then bond it together with the polyester component without urethane groups. The heating method includes, for example, hot pressing, hot air roller pressing, microwave, or high frequency welding.

[0062] The composite laminate without urethane groups can be used as part of clothing or footwear. For example, the polyester component without urethane groups can be a fabric element of clothing or a fabric element of footwear.

[0063] The present invention will be further described with reference to the following embodiments, but it should be understood that the embodiments are for illustrative purposes only and should not be construed as limiting the implementation of the present invention.

[0064] Example 1

[0065] 192 grams (1 mole) of recycled polyethylene terephthalate (PET) resin granules (source: Far East New Century Company; the main chain contains PET and isophthalate segments, and the isophthalate segment accounts for 3 mole% of the PET resin granules); were produced from raw materials including recycled PET bottles, waste cloth, and waste clothing. The polyethylene terephthalate (PET) resin was prepared through sorting, crushing, washing, decomposition, polymerization, viscosity enhancement, and granulation. 89 g (0.99 mol) of 1,4-butanediol, 24 g (0.2 mol) of 1,6-hexanediol, and 0.37 g of titanium isopropoxide (as a depolymerization catalyst) were subjected to a depolymerization reaction at 240°C until no residual PET particles remained, indicating complete depolymerization. The depolymerized component contained depolymers with terephthalate and isophthalate group structures in the main chain. Then, to this depolymerized component, 74 g (0.074 mole) of polyethylene glycol (weight average molecular weight 1000 g / mol), 0.63 g of titanium isopropoxide (as a recombination catalyst), and 0.32 g of N,N'-(hexane-1,6-diyl)bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanamide] (as an antioxidant) were added; Source: BASF; Model: 1098) and 0.48 g of bis(2,4-dicumylphenyl)pentaerythritol diphosphite (as an antioxidant; model: 608) was subjected to a recombination reaction at a temperature of 250°C and a pressure of 1 torr for 4 hours to obtain a recycled copolyester.

[0066] The recycled copolyester was sandwiched between two release papers and hot-pressed at a temperature of 200°C and a pressure of 50 kgf to obtain a 50 μm thick hot-melt adhesive layer formed from the recycled copolyester. Then, the hot-melt adhesive layer was placed on one surface of a 50 μm thick polyester substrate layer (source: Far East New Century Company; model: TE1331 SR; composition: polyether ester elastomer). Next, it was placed in a hot press and hot-pressed at a temperature of 140°C and a pressure of 2 kgf to laminate a 50 μm thick hot-melt adhesive layer onto the surface of the polyester substrate layer, thus obtaining a hot-melt film containing the hot-melt adhesive layer.

[0067] The hot-melt adhesive layer of the hot-melt film was stacked with a polyester component without urethane groups and placed in a hot press. Then, it was hot-pressed at 150°C and 2 kgf to obtain a composite laminate. The polyester component without urethane groups was a waterproof and breathable membrane manufactured by Far East New Century Co., Ltd., and its model number was [model number missing]. TE1142SR and commercially available products with a thickness of 40μm, model number TE1223R and commercially available products with a thickness of 20μm and model number One of the commercially available products with a thickness of 50μm, TE1331 SR.

[0068] Examples 2 to 7 and Comparative Examples 2 to 3

[0069] The preparation of Examples 2 to 7 and Comparative Examples 2 to 3 was generally similar to that of Example 1, except that the types and amounts of components were changed, as shown in Tables 1 and 2. In the examples and comparative examples, the 1,3-propanediol and poly(trimethylol)diol were generated using biomass materials (e.g., corn) and were biomass monomers. In Example 6, the polyethylene terephthalate (PET) recycled granules were sourced from Far East New Century Company, and the main chain contained PET segments but not PET segments. Therefore, the PET segments accounted for 0 mole% of the PET recycled granules. The PET recycled granules were made from raw materials containing recycled PET bottles, waste cloth, and waste clothing through sorting, crushing, washing, decomposition, polymerization, viscosity enhancement, and granulation.

[0070] Comparative Example 1

[0071] 188 g (0.97 mol) of dimethyl terephthalate, 4 g (0.03 mol) of dimethyl isophthalate, 89 g (0.99 mol) of 1,4-butanediol, 24 g (0.2 mol) of 1,6-hexanediol, and 0.37 g of titanium isopropoxide (as esterification catalyst) were mixed and esterified at 240 °C for 4 hours until no methanol distilled off. Then, 74 g (0.074 mol) of polyethylene glycol (weight average molecular weight) was added. The product contained 1000 g / mol of titanium isopropoxide (as a recombination catalyst), 0.63 g of N,N'-(hexane-1,6-diyl)bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanamide] (as an antioxidant); Source: BASF; Model: 1098) and 0.48 g of bis(2,4-dicumylphenyl)pentaerythritol diphosphite (as an antioxidant; model: 608) was subjected to a recombination reaction at a temperature of 250°C and a pressure of 1 torr for 4 hours to obtain a copolyester.

[0072] Comparative Example 4

[0073] 15 g (0.1 mol) of adipic acid, 45 g (0.72 mol) of ethylene glycol, 50 g (0.42 mol) of 1,6-hexanediol, 6 g (0.06 mol) of neopentyl glycol, and 0.27 g of titanium isopropoxide (as a depolymerization catalyst) were mixed and subjected to an esterification reaction at 240°C for 1 hour until no more water was distilled off. Then, 173 g (0.9 mol) of polyethylene terephthalate-based recycled resin particles (source: Far East New Century Company; main chain containing polyethylene terephthalate segments and isophthalic acid) were added. The polyethylene terephthalate (PET) resin granules contain PET segments, and the PET segments comprise 3 mole% of the PET recycled resin granules. The PET segments are obtained from raw materials including recycled PET bottles, waste cloth, and waste clothing through sorting, crushing, washing, decomposition, polymerization, viscosity enhancement, and granulation. The PET segments are then subjected to a depolymerization reaction at 240°C for 4 hours until the PET recycled resin granules are completely depolymerized without any residue, yielding a depolymerized component. This depolymerized component comprises depolymers with terephthalate and isophthalate group structures in their main chains. Then, to the depolymerized component, 0.46 g of titanium isopropoxide (as a recombination catalyst) and 0.23 g of N,N'-(hexane-1,6-diyl)bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanamide] were added; Source: BASF; Model: 1098) and 0.35 g of bis(2,4-dicumylphenyl)pentaerythritol diphosphite (as an antioxidant; model: 608) was subjected to a recombination reaction at a temperature of 250°C and a pressure of 1 torr for 4 hours to obtain a recycled copolyester.

[0074] The recycled copolyester was sandwiched between two release papers and hot-pressed at a temperature of 200°C and a pressure of 50 kgf to obtain a 50 μm thick hot-melt adhesive layer formed from the recycled copolyester. Then, the hot-melt adhesive layer was placed on one surface of a 50 μm thick polyester substrate layer (source: Far East New Century Company; model: TE1331 SR; composition: polyether ester elastomer). Next, it was placed in a hot press and hot-pressed at a temperature of 140°C and a pressure of 2 kgf to laminate a 50 μm thick hot-melt adhesive layer onto the surface of the polyester substrate layer, thus obtaining a hot-melt film containing the hot-melt adhesive layer.

[0075] The hot-melt adhesive layer of the hot-melt film was stacked with a polyester component without urethane groups and placed in a hot press. Then, it was hot-pressed at 150°C and 2 kgf to obtain a composite laminate. The non-urethane-group-free polyester hydrophilic component is a waterproof and breathable membrane manufactured by Far East New Century Co., Ltd., and its model number is [model number missing]. TE1142SR and commercially available products with a thickness of 40μm, model number TE1223R and commercially available products with a thickness of 20μm and model number One of the commercially available products with a thickness of 50μm, TE1331 SR.

[0076] Comparative Example 5

[0077] 173 grams (0.9 moles) of recycled polyethylene terephthalate (PET) resin granules (source: Far East New Century Company; the main chain contains PET and isophthalate segments, and the isophthalate segment accounts for 3 moles of the PET recycled resin granules); were obtained from raw materials including recycled PET bottles, waste cloth, and waste clothing, after sorting and crushing. The mixture, consisting of 45 g (0.72 mol) of ethylene glycol, 50 g (0.42 mol) of 1,6-hexanediol, 6 g (0.06 mol) of neopentyl glycol, and 0.27 g of titanium isopropoxide (as a depolymerization catalyst), was subjected to a depolymerization reaction at 240°C for 4 hours until no residual recycled polyethylene terephthalate resin particles remained, indicating complete depolymerization. This depolymerized component comprises depolymers with terephthalate and isophthalate group structures in the main chain. Then, 15 g (0.1 mole) of adipic acid was added to the depolymerized component, and an esterification reaction was carried out at 240°C for 1 hour until no water distilled off. Next, 0.46 g of titanium isopropoxide (as a recombination catalyst) and 0.23 g of N,N'-(hexane-1,6-diyl)bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanamide] were added (as an antioxidant). Source: BASF; Model: 1098) and 0.35 g of bis(2,4-dicumylphenyl)pentaerythritol diphosphite (as an antioxidant; model: 608) was subjected to a recombination reaction at a temperature of 250°C and a pressure of 1 torr for 4 hours to obtain a recycled copolyester.

[0078] The recycled copolyester was sandwiched between two release papers and hot-pressed at a temperature of 200°C and a pressure of 50 kgf to obtain a 50 μm thick hot-melt adhesive layer formed from the recycled copolyester. Then, the hot-melt adhesive layer was placed on one surface of a 50 μm thick polyester substrate layer (source: Far East New Century Company; model: TE1331SR; composition: polyether ester elastomer). Next, it was placed in a hot press and hot-pressed at a temperature of 140°C and a pressure of 2 kgf to laminate a 50 μm thick hot-melt adhesive layer onto the surface of the polyester substrate layer, thus obtaining a hot-melt film containing the hot-melt adhesive layer.

[0079] The hot-melt adhesive layer of the hot-melt film was stacked with a polyester component without urethane groups and placed in a hot press. Then, it was hot-pressed at 150°C and 2 kgf to obtain a composite laminate. The polyester component without urethane groups was a waterproof and breathable membrane manufactured by Far East New Century Co., Ltd., and its model number was [model number missing]. TE1142SR and commercially available products with a thickness of 40μm, model number TE1223R and commercially available products with a thickness of 20μm and model number One of the commercially available products, TE1331SR and 50μm thick.

[0080] Comparative Example 6

[0081] 192 grams (1 mole) of recycled polyethylene terephthalate (PET) resin granules (source: Far East New Century Company; the main chain contains PET and isophthalate segments, and the isophthalate segment accounts for 3 mole% of the PET resin granules); were obtained from raw materials including recycled PET bottles, waste cloth, and waste clothing after sorting. The polyethylene terephthalate (PET) resin was prepared through a process involving selection, crushing, washing, decomposition, polymerization, thickening, and granulation. 43 g (0.48 mol) of 1,4-butanediol, 85 g (0.72 mol) of 1,6-hexanediol, and 0.47 g of titanium isopropoxide (as a depolymerization catalyst) were subjected to a depolymerization reaction at 240°C for 4 hours until no residual PET particles remained, indicating complete depolymerization. The depolymerized component contained depolymers with terephthalate and isophthalate group structures in the main chain. Then, to the depolymerized component, 75 g (0.075 mole) of polyethylene glycol (weight average molecular weight 1000 g / mol), 75 g (0.078 mole) of a copolymer of ethylene oxide and propylene oxide, 0.81 g of titanium isopropoxide (as a recombination catalyst), and 0.41 g of N,N'-(hexane-1,6-diyl)bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanamide] (as an antioxidant); Source: BASF; Model: 1098) and 0.61 g of bis(2,4-dicumylphenyl)pentaerythritol diphosphite (as an antioxidant; model: 608) and under the conditions of 250℃ and 1 torr, a recombination reaction was carried out for 4 hours to obtain recycled copolyester.

[0082] The recycled copolyester was sandwiched between two release papers and hot-pressed at a temperature of 200°C and a pressure of 50 kgf to obtain a 50 μm thick hot-melt adhesive layer formed from the recycled copolyester. Then, the hot-melt adhesive layer was placed on one surface of a 50 μm thick polyester substrate layer (source: Far East New Century Company; model: TE1331SR; composition: polyether ester elastomer). Next, it was placed in a hot press and hot-pressed at a temperature of 140°C and a pressure of 2 kgf to laminate a 50 μm thick hot-melt adhesive layer onto the surface of the polyester substrate layer, thus obtaining a hot-melt film containing the hot-melt adhesive layer.

[0083] The hot-melt adhesive layer of the hot-melt film was stacked with a polyester component without urethane groups and placed in a hot press. Then, it was hot-pressed at 150°C and 2 kgf to obtain a composite laminate. The polyester component without urethane groups was a waterproof and breathable membrane manufactured by Far East New Century Co., Ltd., and its model number was [model number missing]. TE1142SR and commercially available products with a thickness of 40μm, model number TE1223R and commercially available products with a thickness of 20μm and model number One of the commercially available products, TE1331SR and 50μm thick.

[0084] Evaluation Project

[0085] Measurement of melting point (unit: °C), enthalpy (unit: J / g), and glass transition temperature (unit: °C): The recycled copolyesters of Examples 1 to 7, the copolyester of Comparative Example 1, the recycled copolyesters of Comparative Examples 2 to 3, and the recycled copolyesters of Comparative Examples 4 to 6 were measured using a differential scanning calorimeter (source: TA Instruments; model: Q2000), with the parameters being that the temperature was increased from -100 °C to 250 °C at a heating rate of 10 °C / min.

[0086] The percentage of recycled components in the copolyester is: {[weight of recycled polyethylene terephthalate resin particles x (molecular weight of terephthalic acid / molecular weight of repeating unit of polyethylene terephthalate)] / yield of copolyester)} x 100%. The repeating unit of the polyethylene terephthalate system refers to -[C(O)-phenyl-C(O)-O-CH2-CH2-O]-, and its molecular weight is 192 g / mol.

[0087] Peel strength measurement before washing: The peel strength between the hot melt adhesive and the non-urethane polyester component in the composite laminates of Examples 1 to 7 and Comparative Examples 1 to 6 was measured according to the standard test method for adhesive peel resistance in ASTM D1876 (2015 edition).

[0088] Peel strength measurement after washing: Following the shrinkage test method of AATCC 135 (2018 edition), the composite laminates of Examples 1 to 7 and Comparative Examples 1 to 6 were immersed in water at 45°C for washing. They were then removed from the water and dried in an oven at 60°C for 30 minutes. This washing and drying process was repeated 10 times. Then, according to the standard test method for adhesive peel resistance of ASTM D1876 (2015 edition), the peel strength between the hot-melt film and the non-urethane-based polyester component in the composite laminate was measured, and the peel strength retention rate before and after washing was calculated. Peel strength retention rate before and after washing = {1 - [(peel strength before washing - peel strength after washing) / peel strength before washing]} x 100%.

[0089] Measurement of water pressure resistance: The polyester component was cut into two pieces, and then the pieces were sewn together to obtain a sewn piece. Next, the hot-melt adhesive layer of the hot-melt film from Examples 1 to 7 and Comparative Examples 1 to 6 was applied to the sewn joint of the sewn piece. Then, a hot-pressing treatment was performed at a temperature of 150°C and a pressure of 2 kgf to cover the sewn joint with the hot-melt film, forming a test sample. Referring to the shrinkage test method of AATCC 135 (2018 edition), the test sample was washed in water at 45°C. Then, it was removed from the water and dried in an oven at 60°C for 30 minutes. This washing and drying process was repeated 10 times to obtain a treated test sample. Next, the water pressure resistance of the treated test sample was measured according to the water resistance test method of JIS L1092 (2012 edition).

[0090] Table 1

[0091]

[0092]

[0093]

[0094] Table 2

[0095]

[0096]

[0097]

[0098] Table 3

[0099]

[0100]

[0101]

[0102]

[0103] Referring to Tables 1 and 2, the experimental data from Examples 1 to 7 show that the recycled copolyester of the present invention forms the hot melt adhesive layer of the hot melt film, which can be firmly bonded to the polyester component, thus having good peel strength. At the same time, after the composite laminate is washed with water at 45°C and dried at 60°C for 30 minutes, and the above-mentioned cycle is repeated 10 times, the peel strength retention rate before and after washing can be maintained at more than 80%, and the composite laminate has excellent water pressure resistance.

[0104] Referring to Table 3, the experimental data of Comparative Example 1 show that the copolyester of Comparative Example 1 was formed using petroleum-derived monomers, rather than using monomers formed from recycled polyester materials through a depolymerization reaction. In this case, the chain segments of the copolyester of Comparative Example 1 have a nearly regular arrangement structure, resulting in a significant increase in the melting point and enthalpy of the copolyester compared to the recycled copolyester of Example 1. Furthermore, the melting point of the copolyester is greater than 130°C, which leads to poor adhesion between the hot melt adhesive layer containing the copolyester and the polyester component. Consequently, the peel strength between the hot melt adhesive layer of the composite laminate and the polyester component decreases significantly after washing.

[0105] Referring to Table 3, the experimental data from Comparative Example 2 show that when the enthalpy of the recycled copolyester is less than 5 J / g, the crystallinity of the recycled copolyester is too low, resulting in poor mechanical strength. This leads to poor adhesion between the hot melt adhesive layer containing the recycled copolyester and the polyester component. Furthermore, after washing, the peel strength between the hot melt adhesive layer of the composite laminate and the polyester component decreases, resulting in poor water pressure resistance of the composite laminate. Furthermore, experimental data from Comparative Examples 4 and 5 show that when the process of the recycled copolyester includes an esterification reaction, the segments of the recycled copolyester are arranged in a nearly regular pattern, both before and after the depolymerization reaction. Therefore, compared to the melting point and enthalpy of the recycled copolyester in Example 5, the melting point and enthalpy of the recycled copolyester in Comparative Examples 4 and 5 increase significantly. This results in poor hot-melt effect of the recycled copolyester when the hot-melt film is bonded to the polyester component. Moreover, after the composite laminate is washed and dried, the peel strength between the hot-melt adhesive layer of the hot-melt film and the polyester component, as well as the water pressure resistance of the composite laminate, are both poor.

[0106] Referring to Table 3, the experimental data from Comparative Example 3 shows that when the glass transfer temperature of the recycled copolyester is greater than 10°C, the molecular chain mobility of the recycled copolyester is poor. Therefore, the hot-melt adhesive layer containing the recycled copolyester cannot adhere well to the polyester component, resulting in poor peel strength between the hot-melt adhesive layer and the polyester component. Furthermore, after washing, both the peel strength between the hot-melt adhesive layer and the polyester component and the water pressure resistance of the composite laminate are poor. Additionally, the experimental data from Comparative Example 6 shows that when the glass transfer temperature of the recycled copolyester is less than -60°C, the molecular chain mobility of the recycled copolyester is too high. During washing of the composite laminate, the hot-melt adhesive layer is easily swelled by water, resulting in poor peel strength between the hot-melt adhesive layer and the polyester component and poor water pressure resistance of the composite laminate after washing at 45°C and drying at 60°C.

[0107] In summary, through the rational design of the melting point, glass transition temperature, and enthalpy of this recycled copolyester, when the non-urethane-based hot-melt film is applied to the joints between multiple components (e.g., waterproof and breathable membranes) in products such as films, fabrics, or footwear, the hot-melt adhesive layer in the non-urethane-based hot-melt film remains firmly fixed to the components even after at least one wash, thus giving the product water resistance. Furthermore, it retains good adhesion after washing with 45°C warm water and drying at 60°C, maintaining the waterproof function of seams in fabrics or footwear. Moreover, since the non-urethane-based hot-melt film is primarily made of polyester, the hot-melt film can be easily removed from products formed by applying this non-urethane-based hot-melt film to fabrics or footwear during recycling, effectively separating the product. Meanwhile, the hot-melt adhesive layer uses recycled copolyester, thus the urethane-free hot-melt film can meet the sustainable environmental goals of carbon reduction and waste reduction. Furthermore, by rationally designing the reactive monomers of the recycled copolyester and matching their melting point, glass transition temperature, and enthalpy, the hot-melt adhesive layer of the urethane-free hot-melt film can melt rapidly during the preparation of the composite laminate, allowing it to quickly adhere to the urethane-free polyester component. Therefore, the objective of this invention is indeed achieved.

Claims

1. A hot-melt adhesive film not having a urethane group, characterized by, The hot-melt adhesive layer includes a renewable copolyester, a polyester base layer having a 5000 g / m 2 • a moisture permeability of 24 hr or less; and The hot-melt adhesive layer includes a renewable copolyester, The renewable copolyester is formed by a polymerization reaction of a raw material including a reaction component, and the raw material includes a depolymerizer component, The depolymerizer component includes a depolymerizer, and the depolymerizer is selected from (A) a depolymerizer having a terephthalate structure in a main chain, (B) a depolymerizer having a terephthalate structure and an isophthalate structure in a main chain, (C) a depolymerizer having a terephthalate structure and a C1 to C4 linear alkyldicarboxylate structure in a main chain, (D) a depolymerizer having a terephthalate structure, an isophthalate structure, and a C1 to C4 linear alkyldicarboxylate structure in a main chain, (E) a depolymerizer having an isophthalate structure in a main chain, (F) a depolymerizer having a C1 to C4 linear alkyldicarboxylate structure in a main chain, (G) a depolymerizer having an isophthalate structure and a C1 to C4 linear alkyldicarboxylate structure in a main chain, or a combination thereof, The depolymerizer component is obtained by subjecting a recovered material component to a depolymerization reaction in the presence of a depolymerization agent, the depolymerization agent includes a polyol component and a polycarboxylic acid component, the recovered material component includes a recovered polyester, and the recovered polyester is selected from (i) a recovered polyester having a terephthalate structure in a main chain, (ii) a recovered polyester having a terephthalate structure and an isophthalate structure in a main chain, or (iii) a recovered polyester having a terephthalate structure and a C1 to C4 linear alkyldicarboxylate structure in a main chain, the amount of the polycarboxylic acid component is 0 mol% or more and less than 10 mol% based on 100 mol% of the total amount of the polycarboxylic acid component and the recovered polyester, The renewable copolyester has a recovery content of 20 wt% or more derived from the recovered material component, The renewable copolyester has a melting point of 80°C to 130°C, a glass transition temperature of -60°C to 10°C, and a heat of fusion of 5 J / g to 30 J / g, The renewable copolyester includes 50 mol% to 100 mol% of a first carboxylate segment represented by Formula (I), 0 mol% to 35 mol% of a second carboxylate segment represented by Formula (II), and 0 mol% to 15 mol% of a third carboxylate segment represented by Formula (III), based on the renewable copolyester, In formula (I), R 11 represents a C2 to C6 alkylene group or an alkyl ether group having a number average molecular weight of 450 to 1000 g / mol, In formula (II), R 21 represents a C2 to C6 alkylene group or an alkyl ether group having a number average molecular weight of 450 to 1000 g / mol, In formula (III), R 31 represents a linear alkylen group of C1 to C4, R 32 represents a linear alkylen group of C2 to C6 or an alkyl ether group having a number average molecular weight of 450 to 1000 g / mol.

2. The hot melt adhesive film according to claim 1, wherein: The polyol component is a bio-based polyol component.

3. The hot melt adhesive film according to claim 1, wherein: The polyester base layer has a 1600 g / m 2 • a moisture permeability of 24 hr or less.

4. The hot melt adhesive film according to claim 1, wherein: The polyol component includes two or more polyols selected from a C2 to C6 diol compound or a polyether polyol having a number average molecular weight of 450 g / mol to 1000 g / mol.

5. The hot melt adhesive film according to claim 1, wherein: The raw material further includes a polyether polyol having a number average molecular weight of 450 g / mol to 1000 g / mol.

6. The hot melt adhesive film according to claim 4, wherein: The C2 to C6 diol compound is selected from ethylene glycol, propylene glycol, butylene glycol, pentanediol, 3-methyl-1,5-pentanediol, hexanediol, or neopentyl glycol.

7. The hot-melt adhesive film without urethane group according to claim 4 or 5, characterized by: The polyether polyol is selected from a copolymer of ethylene oxide and propylene oxide, a copolymer of ethylene oxide and tetrahydrofuran, polyethylene glycol, polypropylene glycol, poly(tetramethylene ether) glycol, poly(hexamethylene ether) glycol, poly(trimethylene ether) glycol, or decaglycol.

8. The hot melt adhesive film according to claim 4, wherein: One of the polyols of the polyol component is hexanediol.

9. The hot-melt adhesive film without urethane group according to claim 4 or 5, characterized by: The polyether polyol is used in an amount of 0 wt% to 44 wt% based on 100 wt% of the total amount of the C2 to C6 diol compound and the polyether polyol.

10. A composite laminate body not having a urethane group, characterized by, The urethane group-free composite laminate includes: the urethane group-free hot melt adhesive film according to claim 1; and a urethane group-free polyester member disposed on the hot melt adhesive layer of the urethane group-free hot melt adhesive film and having a thickness of 5000 g / m 2 • a moisture permeability of 24 hr or less measured according to the water pressure method of JIS L1092 (2012); the urethane group-free composite laminate has a water pressure resistance of 4000 to 8000 mmH2O, a peeling strength retention rate between the hot melt adhesive layer and the urethane group-free polyester member in the urethane group-free composite laminate is 80% or more, and the peeling strength retention rate is {1 - [(peeling strength before water washing - peeling strength after water washing) / peeling strength before water washing]} x 100%.

11. The composite laminate not having urethane groups according to claim 10, characterized in that: The polyester base layer of the hot-melt adhesive film without urethane groups comprises a polyether ester elastomer.

12. The composite laminate not having urethane groups according to claim 10, characterized in that: The composite laminate without urethane groups further comprises a polyester textile layer disposed on the polyester base layer of the hot-melt adhesive film without urethane groups.

13. The composite laminate not having urethane groups according to claim 10, characterized in that: The composite laminate without urethane groups further comprises a polyester textile layer disposed on the polyester base layer of the hot-melt adhesive film without urethane groups. The composite laminate without urethane groups further comprises a polyester textile layer disposed on the polyester base layer of the hot-melt adhesive film without urethane groups.

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