Crystallizable shrinkable films, as well as thermoformable films and sheets, made from reactor-grade resins having recycled materials

Abstract

This disclosure relates to crystallizable shrinkable films and thermoformable films or sheets comprising amorphous polyester compositions containing residues of terephthalic acid, neopentyl glycol (NPG), 1,4-cyclohexanedimethanol (CHDM), ethylene glycol (EG), and diethylene glycol (DEG) in specific compositional ranges with particular advantages and improved properties. This disclosure further relates to crystallizable shrinkable films and thermoformable films and / or sheets containing residues of recycled terephthalic acid, recycled neopentyl glycol (NPG), recycled 1,4-cyclohexanedimethanol (CHDM), recycled ethylene glycol (EG), and recycled diethylene glycol (DEG) in specific compositional ranges with particular advantages and improved properties.

Description

Field of the Invention

[0001]

[0001] This disclosure relates to a crystallizable shrinkable film and a thermoformable film and / or sheet comprising a polyester composition containing residues of terephthalic acid, neopentyl glycol (NPG), 1,4-cyclohexanedimethanol (CHDM), ethylene glycol (EG), and diethylene glycol (DEG) within a specific composition range having specific advantages and improved properties. This disclosure further relates to a crystallizable shrinkable film and a thermoformable film and / or sheet comprising a polyester composition containing residues of recycled terephthalic acid, recycled neopentyl glycol (NPG), recycled 1,4-cyclohexanedimethanol (CHDM), recycled ethylene glycol (EG), and recycled diethylene glycol (DEG) within a specific composition range having specific advantages and improved properties.

Background Art

[0002]

[0002] There is a commercial demand for shrink films having the following desirable shrink film properties, namely (1) a low shrink start temperature, (2) a shrinkage rate that increases gradually and in a controlled manner with increasing temperature over the temperature range in which shrinkage occurs, (3) a low shrink force sufficient to prevent crushing of the underlying container, (4) a high maximum shrinkage rate (shrinkage rate at the highest temperature), e.g., a shrinkage rate of 60% or more in the major shrink direction at 95°C, (5) a low shrinkage rate in the direction orthogonal to the shrink direction, (6) high toughness of the film to prevent unwanted cracking, breaking, tearing, splitting, foaming, or wrinkling of the film during manufacture and before and after shrinkage, (7) recyclability, and (8) at least one of recycled materials.

[0003]

[0003] There is a commercial demand for thermoformable films or sheets having excellent film or sheet properties and recyclability and / or recycled materials. Summary of the Invention

[0004]

[0004] It has been found that a film having excellent shrink film performance can be produced by a specific combination of glycol monomers in the shrink film resin composition, and further that crystallization is possible so as not to affect the recycling of PET flakes during recycling. These crystallizable shrink film resins can be processed together with PET bottles and become a component of recyclable PET flakes after the recycling process. The selection of a specific combination of glycol monomers and their amounts have been found to be important for producing a film having excellent shrink film properties and for producing a crystallizable film. The optimized polyester resin composition of the present disclosure is amorphous but crystallizable. Thus, these compositions exhibit excellent properties in film applications including shrink films, and since these strain-induced crystals have a high melting point, they provide compatibility with the recycling process. The labels of the shrink films of the present disclosure do not need to be removed during the recycling process and do not affect this recycling process.

[0005]

[0005] Thermally shrinkable films need to meet various compatibilities with respect to usage criteria in order to be implemented in this application. This film needs to be strong, shrink in a controlled manner, and provide sufficient shrink force to hold itself on the bottle surface without crushing the contents. Further, when these labels are attached to polyester containers, the polyester shrink film labels must not interfere with the recycling process of the bottles. The shrink films of the present disclosure are advantageous because the labels can be recycled together with the bottles or containers. Thus, the entire bottle including the label can be recycled and converted into a new product without additional operating requirements or the occurrence of new environmental problems. Thermally shrinkable films are made from various raw materials to meet a certain range of material demands. The present disclosure describes an unprecedented and unexpected effect of dealing with a specific combination of monomers for the shrink film resin composition.

[0006] [

[0006] ]Polyester shrink film compositions have been commercially used as shrink film labels for foods, beverages, personal care products, household products, etc. In many cases, these shrink films are used in combination with transparent polyethylene terephthalate (PET) bottles or containers. After use, the entire product (bottle and label) enters the recycling process. At typical recycling sites, due to similar composition and density, PET and the shrink film material often end up mixed at the end of the process. Drying of PET flakes is necessary for the removal of residual water adhering to the PET during the recycling process. Typically, PET is dried at temperatures above 200 °C. At these temperatures, common polyester shrink film resins soften and become sticky, and the PET flakes often form agglomerates. These agglomerates need to be removed before subsequent processing. These agglomerates reduce the yield of PET flakes from this process and require additional processing steps.

[0007] [

[0007] ]Furthermore, it has been found that certain combinations of glycol monomers in a film or sheet resin composition can produce films or sheets with excellent performance characteristics, and these combinations are also capable of crystallizing so that the film or sheet does not affect the recycling of PET flakes. These crystallizable film or sheet resins can be processed with the PET to be recycled and ultimately become a component of the recyclable PET flakes after the end of the recycling process. The selection and amount of a particular combination of glycol monomers have been found to be important for producing a film or sheet with excellent performance characteristics and for producing a crystallizable film or sheet. The optimized polyester resin compositions of the present disclosure are amorphous but crystallizable. Thus, these compositions exhibit excellent properties in film or sheet applications such as formed, thermoformed, or molded parts and / or articles, etc., and since they have a high melting point of strain-induced crystals, they can be recycled with PET. The films or sheets of the present disclosure do not need to be removed during the recycling process and do not affect the recycling process.

[0008]

[0008] One embodiment of the present disclosure is a crystallizable film comprising an amorphous polyester composition comprising at least one polyester comprising (a) a dicarboxylic acid component and (b) a diol component, wherein the (a) dicarboxylic acid component comprises (i) about 70 to about 100 mol% terephthalic acid residues and (ii) about 0 to about 30 mol% aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, and the (b) diol component comprises at least about 75 mol% ethylene glycol residues and (i) less than about 0 to about 24 mol% neopentyl glycol residues, (ii) less than about 0 to about 24 mol% 1,4-cyclohexanedimethanol residues, and (iii) less than about 1 to about 10 mol% of one or more of the total diethylene glycol residues in the final polyester composition, wherein the total mol% of the dicarboxylic acid component is 100 mol% and the total mol% of the diol component is 100 mol%; or the (b) diol component comprises at least about 75 mol% ethylene glycol residues and (i) about 0.1 to less than about 24 mol% neopentyl glycol residues, (ii) about 0.1 to less than about 24 mol% 1,4-cyclohexanedimethanol residues, and (iii) less than about 1 to about 10 mol% of one or more of the total diethylene glycol residues in the final polyester composition, wherein the total mol% of the dicarboxylic acid component is 100 mol% and the total mol% of the diol component is 100 mol%.

[0009]

[0009] One embodiment of the present disclosure is a crystallizable film comprising an amorphous polyester composition comprising at least one polyester comprising (a) a dicarboxylic acid component and (b) a diol component, wherein the (a) dicarboxylic acid component comprises (i) from about 70 to about 100 mol% terephthalic acid residues and (ii) from about 0 to about 30 mol% aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, and the (b) diol component comprises at least about 75 mol% ethylene glycol residues and (i) less than about 15 mol% neopentyl glycol residues, (ii) less than about 5 mol% 1,4-cyclohexanedimethanol residues, and (iii) up to about 25 mol% other glycols comprising one or more of the total diethylene glycol residues in the final polyester composition, wherein the total mol% of the dicarboxylic acid component is 100 mol% and the total mol% of the diol component is 100 mol%.

[0010]

[0010] One embodiment of the present disclosure is a crystallizable film comprising an amorphous polyester composition comprising at least one polyester comprising (a) a dicarboxylic acid component and (b) a diol component, wherein the (a) dicarboxylic acid component comprises (i) from about 70 to about 100 mol% terephthalic acid residues and (ii) from about 0 to about 30 mol% aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, and the (b) diol component comprises at least about 80 mol% ethylene glycol residues and (i) from about 5 to less than about 17 mol% neopentyl glycol residues, (ii) from about 2 to less than about 10 mol% 1,4-cyclohexanedimethanol residues, and (iii) up to about 20 mol% other glycols comprising one of the total diethylene glycol residues in the final polyester composition, wherein the total mol% of the dicarboxylic acid component is 100 mol% and the total mol% of the diol component is 100 mol%.

[0011] [

[0011] ]One embodiment of the present disclosure is a crystallizable film comprising an amorphous polyester composition comprising at least one polyester comprising (a) a dicarboxylic acid component and (b) a diol component, wherein the (a) dicarboxylic acid component comprises (i) from about 70 to about 100 mol% terephthalic acid residues, and (ii) from about 0 to about 30 mol% aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, and the (b) diol component comprises at least about 76 mol% ethylene glycol residues, and an amorphous component of up to about 24 mol% comprising one or more of (i) neopentyl glycol residues, (ii) cyclohexanedimethanol residues, and (iii) total diethylene glycol residues in the final polyester composition, where the total mol% of the dicarboxylic acid component is 100 mol% and the total mol% of the diol component is 100 mol%.

[0012] [

[0012] ]One embodiment of the present disclosure is a crystallizable film comprising an amorphous polyester composition comprising at least one polyester comprising (a) a dicarboxylic acid component and (b) a diol component, wherein the (a) dicarboxylic acid component comprises (i) from about 70 to about 100 mol% terephthalic acid residues, and (ii) from about 0 to about 30 mol% aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, and the (b) diol component comprises at least about 75 mol% ethylene glycol residues, and other glycols of up to about 25 mol% comprising one or more of (i) less than about 10 to about 15 mol% neopentyl glycol residues, (ii) less than about 1 to about 5 mol% 1,4-cyclohexanedimethanol residues, and (iii) less than about 1 to about 5 mol% total diethylene glycol residues in the final polyester composition, where the total mol% of the dicarboxylic acid component is 100 mol% and the total mol% of the diol component is 100 mol%.

[0013]

[0013] One embodiment of the present disclosure is a crystallizable film comprising a polyester composition comprising at least one polyester comprising (a) a dicarboxylic acid component and (b) a diol component, wherein the (a) dicarboxylic acid component comprises (i) from about 70 to about 100 mol% terephthalic acid residues, and (ii) from about 0 to about 30 mol% aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, and the (b) diol component comprises (i) from about 0 to about 30 mol% neopentyl glycol residues, (ii) less than about 0 to about 30 mol% 1,4-cyclohexanedimethanol residues, and (iii) diethylene glycol residues, whether formed in situ or not, and the balance of the glycol component comprises (iv) ethylene glycol residues and (v) optionally from 0 to 10 mol% or 0 to 5 mol% of at least one modified glycol residue, wherein the total mol% of the dicarboxylic acid component is 100 mol% and the total mol% of the diol component is 100 mol%.

[0014]

[0014] One embodiment of the present disclosure is a crystallizable film of any of the foregoing embodiments, the film being stretched in at least one direction, the stretched film having a melting point of strain-induced crystals of 190 °C or higher or 200 °C or higher.

[0015]

[0015] One embodiment of the present disclosure is an extruded film or a rolled film comprising a crystallizable film of any of the foregoing embodiments.

[0016] One embodiment of the present disclosure is a thermoformed film or sheet comprising a polyester composition comprising at least one polyester comprising (a) a dicarboxylic acid component and (b) a diol component, wherein the (a) dicarboxylic acid component comprises (i) from about 70 to about 100 mol% terephthalic acid residues, and (ii) from about 0 to about 30 mol% aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, and the (b) diol component comprises at least about 75 mol% ethylene glycol residues, and (i) from about 0 to less than about 24 mol% neopentyl glycol residues, (ii) from about 0 to less than about 24 mol% 1,4-cyclohexanedimethanol residues, and (iii) from about 1 to less than about 10 mol% of one or more of the total diethylene glycol residues in the final polyester composition, and wherein the total mol% of the dicarboxylic acid component is 100 mol% and the total mol% of the diol component is 100 mol%, or the (b) diol component comprises at least about 75 mol% ethylene glycol residues, and (i) from about 0.1 to less than about 24 mol% neopentyl glycol residues, (ii) from about 0.1 to less than about 24 mol% 1,4-cyclohexanedimethanol residues, and (iii) from about 1 to less than about 10 mol% of one or more of the total diethylene glycol residues in the final polyester composition, and wherein the total mol% of the dicarboxylic acid component is 100 mol% and the total mol% of the diol component is 100 mol%.

[0016]

[0017] One embodiment of the present disclosure is a thermoformed film or sheet comprising a polyester composition comprising at least one polyester comprising (a) a dicarboxylic acid component and (b) a diol component, wherein the (a) dicarboxylic acid component comprises (i) from about 70 to about 100 mol% terephthalic acid residues and (ii) from about 0 to about 30 mol% aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, and the (b) diol component comprises at least about 75 mol% ethylene glycol residues and (i) up to about 15 mol% neopentyl glycol residues, (ii) up to about 5 mol% 1,4-cyclohexanedimethanol residues, and (iii) up to about 25 mol% of other glycols comprising one or more of the total diethylene glycol residues in the final polyester composition, wherein the total mol% of the dicarboxylic acid component is 100 mol% and the total mol% of the diol component is 100 mol%.

[0017]

[0018] One embodiment of the present disclosure is a thermoformed film or sheet comprising a polyester composition comprising at least one polyester comprising (a) a dicarboxylic acid component and (b) a diol component, wherein the (a) dicarboxylic acid component comprises (i) from about 70 to about 100 mol% terephthalic acid residues and (ii) from about 0 to about 30 mol% aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, and the (b) diol component comprises at least about 80 mol% ethylene glycol residues and (i) less than from about 5 to about 17 mol% neopentyl glycol residues, (ii) less than from about 2 to about 10 mol% 1,4-cyclohexanedimethanol residues, and (iii) less than from about 1 to about 5 mol% of other glycols comprising one or more of the total diethylene glycol residues in the final polyester composition, wherein the total mol% of the dicarboxylic acid component is 100 mol% and the total mol% of the diol component is 100 mol%.

[0018]

[0019] One embodiment of the present disclosure is a thermoformed film or sheet comprising a polyester composition comprising at least one polyester comprising (a) a dicarboxylic acid component and (b) a diol component, wherein (a) the dicarboxylic acid component comprises (i) from about 70 to about 100 mol% terephthalic acid residues, and (ii) from about 0 to about 30 mol% aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, and (b) the diol component comprises at least about 76 mol% ethylene glycol residues and up to about 24 mol% amorphous components including one or more of (i) neopentyl glycol residues, (ii) cyclohexanedimethanol residues, and (iii) diethylene glycol residues in the final polyester composition, where the total mol% of the dicarboxylic acid component is 100 mol% and the total mol% of the diol component is 100 mol%.

[0019]

[0020] One embodiment of the present disclosure is a thermoformed film or sheet comprising a polyester composition comprising at least one polyester comprising (a) a dicarboxylic acid component and (b) a diol component, wherein (a) the dicarboxylic acid component comprises (i) from about 70 to about 100 mol% terephthalic acid residues, and (ii) from about 0 to about 30 mol% aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, and (b) the diol component comprises at least about 75 mol% ethylene glycol residues and up to about 25 mol% other glycols including one or more of (i) less than about 10 to about 15 mol% neopentyl glycol residues, (ii) less than about 1 to about 5 mol% 1,4-cyclohexanedimethanol residues, and (iii) less than about 1 to about 5 mol% of the total diethylene glycol residues in the final polyester composition, where the total mol% of the dicarboxylic acid component is 100 mol% and the total mol% of the diol component is 100 mol%.

[0020]

[0021] One embodiment of the present disclosure is a thermoformed film or sheet comprising a polyester composition comprising at least one polyester comprising (a) a dicarboxylic acid component and (b) a diol component, wherein the (a) dicarboxylic acid component comprises (i) from about 70 to about 100 mol% terephthalic acid residues, and (ii) from about 0 to about 30 mol% aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, and the (b) diol component comprises, whether formed in situ or not, (i) from about 0 to about 30 mol% neopentyl glycol residues, (ii) less than about 0 to about 30 mol% 1,4-cyclohexanedimethanol residues, and (iii) diethylene glycol residues, and the balance of the glycol component comprises (iv) ethylene glycol residues and (v) optionally from 0 to 10 mol% or 0 to 5 mol% of at least one modified glycol residue, wherein the total mol% of the dicarboxylic acid component is 100 mol% and the total mol% of the diol component is 100 mol%.

[0021]

[0022] One embodiment of the present disclosure is a formed, thermoformed, or molded article comprising a film or sheet of any of the preceding embodiments.

[0023] One embodiment of the present disclosure is a medical device, a medical-related packaging product, a health management product, a commercial food supply product, a tray, a container, a food dish, a tumbler, a storage box, a bottle, a cooking utensil, a blender and a mixing bowl, a household product, a water bottle, a vegetable bin tray, a washing machine part, a refrigerator part, a vacuum cleaner part, an ophthalmic lens, and a framework material or a toy comprising a film or sheet of any of the preceding embodiments.

[0022]

[0024] One embodiment of the present disclosure is a manufactured article comprising a thermoformed film or sheet according to any of the preceding claims.

[0025] One embodiment of the present disclosure is a method for producing a thermoformed film or sheet of any of the foregoing embodiments, the method comprising: A) heating a polyester film or sheet; B) applying pneumatic pressure, vacuum, and / or physical pressure to the film or sheet softened by heat; C) conforming the sheet to a mold shape by vacuum or pressurization; and D) removing the thermoformed part or article from the mold.

[0023]

[0026] One aspect of the present disclosure is a process for preparing the polyester of the present invention from recycled polyester. One aspect of the present disclosure is a process for preparing a copolyester from recycled polyester and / or recycled copolyester.

[0024]

[0027] On one side, the present disclosure provides a process for preparing a linear and high molecular weight copolymer polyester from any of the following: (A) a recycled polyester and / or a recycled copolyester in which the acid component consists of at least 70 mol% terephthalic acid and the diol component consists of at least 70 mol% ethylene glycol; (B) a recycled copolyester in which the acid component consists of at least 70 mol% terephthalic acid and at least 70 mol% of the diol component consists of a mixture of ethylene glycol, 1,4-cyclohexanedimethanol, and diethylene glycol in a molar ratio of 96:3:1 to 20:68:12; (C) a recycled copolyester in which the acid component consists of at least 70 mol% terephthalic acid and at least 70 mol% of the diol component consists of a mixture of two or more glycols including ethylene glycol (EG), diethylene glycol (DEG), 1,4-cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), or 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD), butanediol, and isosorbide; or (D) a recycled copolyester in which the acid component consists of at least 70 mol% terephthalic acid and at least 70 mol% of the diol component consists of a mixture of ethylene glycol and 1,4-cyclohexanedimethanol in a molar ratio of 3.5:96.5 to 100:0.

[0025]

[0028] This process provides a high polymerization rate, and the polymers thus produced can be used in the manufacture of plastics, fibers, films, shrink films, sheets, molded articles, and other molded bodies having excellent physical properties. On one side, the disclosed process describes a method for converting waste products from factories and consumers into high-quality copolyester resins that can be used to produce new plastics with a high concentration of recycled components. On another side, the disclosed process describes a method for converting waste products from factories and consumers into resins that can be used to produce high-quality shrink films.

[0026]

[0029] One aspect of the present disclosure is a process for producing a copolyester from a recycled copolyester, the process comprising: (a) introducing recycled PET, recycled PETG, recycled PCT, recycled PCTG, recycled PCTA, recycled PCTM, and / or recycled PETM, terephthalic acid (TPA), and ethylene glycol (EG) into a paste tank, stirring and heating at a temperature of up to 150 °C to produce a slurry; (b) delivering the slurry from the paste tank to a first reaction zone; (c) introducing at least one additional glycol including 1,4-cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), or 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) into the first reaction zone, and optionally additional recycled PET, recycled PETG, recycled PCTM, and / or recycled PETM, and adding terephthalic acid (TPA) and ethylene glycol (EG) with a molar ratio of EG:TPA of 1:1 to 4:1, and optionally adding a catalyst; (d) reacting TPA with EG and at least one additional glycol (such as CHDM) in the first reaction zone at a melting temperature of at least 200 °C and a pressure of up to 40 psi to produce a first esterification product comprising oligomers and unreacted TPA, EG, and additional glycol (such as CHDM); (e) delivering the first esterification product to a second reaction zone; (f) esterifying unreacted TPA, EG, and additional glycol (such as CHDM) in the first esterification product in the second reaction zone at a melting temperature of at least 200 °C and a pressure of up to 20 psi to produce a second esterification product comprising a copolyester oligomer; (g) delivering the second esterification product to a third reaction zone; (h) polycondensing the second esterification product in the third reaction zone in the presence of a polycondensation catalyst as needed to produce a prepolymerization product comprising a copolyester; and (i) It includes the step of delivering the prepolymerization product to one or more finishing zones.

[0027]

[0030] One aspect of the present disclosure is a process for producing a copolyester from a recycled copolyester, and this process (a) Introducing recycled PET, recycled PETG, recycled PCT, recycled PCTG, or recycled PCTA, and terephthalic acid (TPA) and ethylene glycol (EG) into a paste tank, stirring and heating at a temperature of up to 150 °C to produce a slurry; (b) Delivering the slurry in the paste tank to a first reaction zone; (c) Introducing at least one additional glycol including 1,4 - cyclohexanedimethanol (CHDM), DEG, or neopentyl glycol (NPG) into the first reaction zone, and optionally additional recycled PET, recycled PETG, recycled PCT, recycled PCTG, or recycled PCTA, and terephthalic acid (TPA) and ethylene glycol (EG) with a molar ratio of EG:TPA of 1:1 to 4:1, and adding in the presence of an esterification catalyst as required; (d) Reacting TPA with EG and at least one additional glycol (such as CHDM) in the first reaction zone at a melting temperature of at least 200 °C and a maximum pressure of 40 psi to produce a first esterification product containing oligomers and unreacted TPA, EG, and additional glycol (such as CHDM and / or NPG and / or DEG); (e) Delivering the first esterification product to a second reaction zone; (f) Esterifying the unreacted TPA, EG, and additional glycol (such as CHDM) in the first esterification product in the second reaction zone at a melting temperature of at least 200 °C and a maximum pressure of 20 psi to produce a second esterification product containing a copolyester oligomer; (g) Delivering the second esterification product to a third reaction zone; (h) In the third reaction zone, polycondensing the second esterification product in the presence of a polycondensation catalyst as needed to produce a prepolymerization product containing a copolyester; and (i) delivering the prepolymerization product to one or more finishing zones.

[0028]

[0031] One aspect of the present disclosure is a process of any one of the foregoing aspects, which further includes the step of adding a catalyst or an additive by adding a recycled polyester, and the catalyst or additive is a component in the recycled polyester such as Sb, Ti, Co, Mn, Li, Al, P.

[0029]

[0032] One aspect of the present disclosure is a method of introducing or forming a recycled content in a polyester produced by the process of the foregoing aspect, and the method includes (a) obtaining an allocation or limit of the recycled monomer for at least one recycled monomer including TPA, EG, DMT, CHDM, NPG, or DEG; (b) converting the recycled monomer during the synthesis process to produce a polyester; (c) designating at least a portion of the polyester as corresponding to at least a portion of the recycled monomer allocation or limit; and (d) optionally, marketing or selling the polyester as including or obtained using the content of the recycled monomer corresponding to the designation.

Brief Description of the Drawings

[0030]

Figure 1

[0033] FIG. 1 is a temperature recording diagram of a differential scanning calorimeter showing the melting point of the first heat distortion-induced crystal of Embrace LV.

Figure 2

[0034] FIG. 2 shows the shrinkage characteristics of the production film using Embrace LV (residence time of 10 seconds).

Figure 3

[0035] FIG. 3 shows the shrinkage performance.

Figure 4

[0036] Figure 4 is a temperature recording diagram of DSC of the film N stretched by the first heating at 80°C.

Figure 5

[0037] Figure 5 is a temperature recording diagram of DSC of the film N stretched by the second heating at 80°C.

Figure 6

[0038] Figure 6 is a flowchart of various processes according to the present disclosure.

Figure 7

[0039] Figure 7 shows the concentration of Sb catalyst in the final material as a function of the filling concentration of the starting material of rPET (recycled PET).

Mode for Carrying Out the Invention

[0031]

[0040] With reference to the following detailed description of specific embodiments and examples of the present disclosure, the present disclosure can be more easily understood. In accordance with the objectives of the present disclosure, specific embodiments of the present disclosure are described in the gist of the invention and are further described herein as follows. In addition, other embodiments of the present disclosure are described herein.

[0032]

[0041] The heat-shrinkable plastic film is used as a coating material for holding a plurality of objects together and as an outer packaging material for bottles, cans, and other types of containers. For example, this film is used for coating the lid, neck, shoulder, body, or the entire bottle of a product for the purpose of product labeling, protection, packaging, or value improvement, and other reasons. Further, this film can be used as a coating material for packaging objects such as boxes, bottles, plates, rods, or notes as a group, and this film can also be closely adhered as a packaging material. In the above uses, the shrinkability and internal shrinkage stress of the film are utilized.

[0033]

[0042] Historically, polyvinyl chloride (PVC) films have been the mainstream in the shrink film market. However, polyester films have become significant alternatives because they do not have the environmental problems associated with PVC films. Polyester shrink films ideally have very similar properties to PVC films, so polyester films can function as "drop-in" replacement films and can be processed with existing heat shrink tunnel equipment. The properties of PVC films desired for replicas are: (1) a relatively low shrink start temperature, (2) a total shrinkage rate that increases gradually and in a controlled manner with increasing temperature, (3) a low shrink force to prevent crushing of the underlying container, (4) a high total shrinkage rate (e.g., 50% or more), (5) inherent film toughness to prevent undue tearing and splitting of the film before and after shrinkage, and (6) a high melting point of strain-induced crystals.

[0034]

[0043] Heat shrinkable films need to fully meet various compatibilities with usage criteria in order to be implemented in this application. The film needs to be strong, shrink in a controlled manner, and provide sufficient shrink force to hold itself on the bottle surface without crushing the contents. Further, when these labels are applied to polyester containers, these labels must not impede the recycling process of PET bottles. In fact, it would be advantageous if the labels were also recyclable and the entire bottle could be recycled and converted into new products without additional processing requirements or the generation of new environmental problems. Heat shrinkable films are manufactured from various raw materials to meet the demand for a range of materials. This disclosure describes an unprecedented and unexpected effect addressed by a combination with specific monomers that improve the recyclability of labels made of polyester shrink films.

[0035]

[0044] The shrink film composition is commercially used as a shrink film label for foods, beverages, personal care products, household products, etc. In many cases, these shrink films are used in combination with transparent polyethylene terephthalate (PET) bottles or containers. Subsequently, the entire product (bottle and label) enters the recycling process. At typical recycling sites, due to similar composition and density, PET and the shrink film material are often mixed together at the end of the process. Drying of the PET flakes is necessary to remove residual water adhering to the PET during the recycling process. Typically, PET is dried at temperatures above 200 °C. At these temperatures, typical polyester shrink film resins soften and become sticky, often forming agglomerates with the PET flakes. These agglomerates need to be removed before subsequent processing. These agglomerates reduce the yield of PET flakes from this process and require additional processing steps.

[0036]

[0045] It has been found that a specific combination of glycol monomers in the shrink film resin composition can produce a film with excellent shrink film properties and can be crystallized so as not to affect the recycling of PET flakes during the recycling process. These crystallizable shrink film resins can be processed with PET bottles and become a component of recyclable PET flakes after the end of the recycling process. The selection of the specific combination of glycol monomers and their amount have been found to be important for producing a film with excellent shrink film properties and a crystallizable film.

[0037]

[0046] As used herein, the term "polyester" is intended to include "copolyester" and means a synthetic polymer prepared by reacting one or more difunctional carboxylic acids and / or polyfunctional carboxylic acids with one or more difunctional hydroxyl compounds and / or polyfunctional hydroxyl compounds, such as branching agents. Typically, the difunctional carboxylic acid may be a dicarboxylic acid, and the difunctional hydroxyl compound may be a dihydric alcohol, such as a glycol and a diol. As used herein, the term "glycol" includes, but is not limited to, diols, glycols, and / or polyfunctional hydroxyl compounds, such as branching agents. Alternatively, the difunctional carboxylic acid may be a hydroxycarboxylic acid, such as p-hydroxybenzoic acid, and the difunctional hydroxyl compound may have an aromatic nucleus bearing two hydroxyl substituents, such as hydroquinone. As used herein, the term "residue" means any organic structure incorporated into the polymer by polycondensation and / or esterification reactions from the corresponding monomer. As used herein, the term "repeat unit" means an organic structure having a dicarboxylic acid residue and a diol residue linked via an ester group. Thus, for example, the dicarboxylic acid residue may be derived from a dicarboxylic acid monomer or its related acid halide, ester, salt, anhydride, and / or mixtures thereof. Further, as used herein, the term "diacid" includes polyfunctional acids, such as branching agents. Thus, as used herein, the term "dicarboxylic acid" is intended to include dicarboxylic acids useful for reacting with diols to obtain polyesters, as well as any dicarboxylic acid derivatives such as related acid halides, esters, half-esters, salts, half-salts, anhydrides, mixed anhydrides, and / or mixtures thereof. As used herein, the term "terephthalic acid" is intended to include terephthalic acid itself and its residues useful for reacting with diols to obtain polyesters, as well as any terephthalic acid derivatives such as related acid halides, esters, half-esters, salts, half-salts, anhydrides, mixed anhydrides, and / or mixtures or residues thereof.

[0038]

[0047] The polyesters used in the present disclosure can typically be prepared from dicarboxylic acids and diols that react in substantially equal proportions and are incorporated into the polyester polymer as their corresponding residues. Thus, the polyesters of the present disclosure may contain acid residues (100 mol%) and diol (and / or polyfunctional hydroxyl compound) residues (100 mol%) in a substantially equimolar ratio such that the total moles of repeating units equals 100 mol%. Accordingly, the mole percentages shown in the present disclosure may be based on the total moles of acid residues, the total moles of diol residues, or the total moles of repeating units. For example, a polyester containing 10 mol% isophthalic acid based on total acid residues means that the polyester contains 10 mol% isophthalic acid residues out of a total of 100 mol% of acid residues. That is, there are 10 moles of isophthalic acid residues per 100 moles of acid residues. In another example, a polyester containing 25 mol% 1,4-cyclohexanedimethanol based on total diol residues means that the polyester contains 25 mol% 1,4-cyclohexanedimethanol residues out of a total of 100 mol% of diol residues. That is, there are 25 moles of 1,4-cyclohexanedimethanol residues per 100 moles of diol residues.

[0039]

[0048] In certain embodiments, terephthalic acid or its esters, such as dimethyl terephthalate or a mixture of terephthalic acid residues and their esters, may constitute some or all of the dicarboxylic acid component used to produce the polyesters useful in this disclosure. In certain embodiments, the terephthalic acid residues may constitute some or all of the dicarboxylic acid component used to form the polyesters useful in this disclosure. For the purposes of this disclosure, the terms "terephthalic acid" and "dimethyl terephthalate" are used interchangeably herein. In one embodiment, dimethyl terephthalate is some or all of the dicarboxylic acid component used to make the polyesters useful in this disclosure. In some embodiments, 70 - 100 mol%; or 80 - 100 mol%; or 90 - 100 mol%; or 99 - 100 mol%; or 100 mol% of terephthalic acid and / or dimethyl terephthalate and / or mixtures thereof may be used.

[0040]

[0049] In addition to terephthalic acid, the dicarboxylic acid component of the polyesters useful in this disclosure may include up to 30 mol%, up to 20 mol%, up to 10 mol%, up to 5 mol%, or up to 1 mol% of one or more modified aromatic dicarboxylic acids. Yet another embodiment includes 0 mol% of the modified aromatic dicarboxylic acids. Thus, when present, the amount of one or more modified aromatic dicarboxylic acids may vary within any of the above-described endpoint values, for example, 0.01 - 10 mol%, 0.01 - 5 mol%, 0.01 - 1 mol%. In one embodiment, the modified aromatic dicarboxylic acids that may be used in this disclosure include, but are not limited to, those having up to 20 carbon atoms and that can be chain-like, para-oriented, or symmetric. Examples of modified aromatic dicarboxylic acids that may be used in this disclosure include, but are not limited to, isophthalic acid, 4,4'-biphenyldicarboxylic acid, 1,4-, 1,5-, 2,6-, 2,7-naphthalenedicarboxylic acid, and trans-4,4'-stilbenedicarboxylic acid, and their esters. In one embodiment, the modified aromatic dicarboxylic acid is isophthalic acid.

[0041]

[0050] The carboxylic acid component of the polyester useful in the present disclosure may further be modified with up to 10 mol%, such as up to 5 mol% or up to 1 mol%, of one or more aliphatic dicarboxylic acids containing 2 to 16 carbon atoms, such as cyclohexanedicarboxylic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and / or dodecanedioic acid. Also in certain embodiments, 0.01 to 10 mol%, such as 0.1 to 10 mol%, 1 or 10 mol%, 5 to 10 mol%, etc., of one or more modified aliphatic dicarboxylic acids may be included. Yet another embodiment includes 0 mol% of modified aliphatic dicarboxylic acids. The total mol% of the dicarboxylic acid component is 100 mol%. In one embodiment, adipic acid and / or glutaric acid are provided in the modified aliphatic dicarboxylic acid component of the polyester and are useful in the present disclosure.

[0042]

[0051] Esters of terephthalic acid and other modified dicarboxylic acids or their corresponding esters and / or salts may be used instead of the dicarboxylic acids. Suitable examples of dicarboxylic acid esters include, but are not limited to, dimethyl, diethyl, dipropyl, diisopropyl, dibutyl, and diphenyl esters. In one embodiment, the ester is selected from at least one of methyl, ethyl, propyl, isopropyl, and phenyl esters.

[0043]

[0052] In one embodiment, the diol component of the polyester composition and polyester blend composition useful in the present disclosure may include 1,4-cyclohexanedimethanol. In another embodiment, the diol component of the polyester composition and polyester blend composition useful in the present disclosure includes 1,4-cyclohexanedimethanol and 1,3-cyclohexanedimethanol. The molar ratio of cis / trans 1,4-cyclohexanedimethanol may vary within the range of 50 / 50 to 0 / 100, such as 40 / 60 to 20 / 80.

[0044]

[0053] The diol components of the polyester composition and polyester blend composition useful in the present disclosure include, but are not limited to, the total of 1,4-cyclohexanedimethanol residues and neopentyl glycol residues in the final polyester composition being 0 to 30 mol%, 1 to 30 mol%, or 1 to 25 mol%, or 1 to 20 mol%, or 1 to 15 mol%, or 1 to 10 mol%, or 2 to 30 mol%, or 2 to 25 mol%, or 2 to 20 mol%, or 2 to 15 mol%, or 2 to 10 mol%, or 3 to 30 mol%, or 3 to 25 mol%, or 3 to 20 mol%, or 3 to 15 mol%, or 3 to 10 mol%, 4 to 30 mol%, or 4 to 25 mol%, 4 to 20 mol%, or 4 to 15 mol%, or 4 to 10 mol%, 5 to 30 mol%, or 5 to 25 mol%, 5 to 20 mol%, or 5 to 15 mol%, or 5 to 10 mol%, or 6 to 30 mol%, or 6 to 25 mol%, or 6 to 20 mol%, or 6 to 15 mol%, or 6 to 10 mol%, or 7 to 30 mol%, or 7 to 25 mol%, 7 to 20 mol%, or 7 to 15 mol%, or 7 to 10 mol%, or 8 to 30 mol%, or 8 to 25 mol%, or 8 to 20 mol%, or 8 to 15 mol%, or 8 to 10 mol%, or 9 to 30 mol%, or 9 to 25 mol%, or 9 to 20 mol%, or 9 to 15 mol%, or 9 to 10 mol%, or 10 to 30 mol%, or 10 to 25 mol%, or 10 to 20 mol%, or 10 to 15 mol%, or 11 to 30 mol%, or 11 to 30 mol%, or 11 to 25 mol%, or 11 to 20 mol%, or 11 to 15 mol%, or 12 to 30 mol%, or 12 to 25 mol%, or 12 to 20 mol%, or 12 to 15 mol%, or 13 to 30 mol%, or 13 to 25 mol%, or 13 to 20 mol%, or 13 to 15 mol%, or 14 to 30 mol%, or 14 to 25 mol%, or 14 to 20 mol%, or 14 to 15 mol%, or 15 to 30 mol%, or 15 to 25 mol%, or 15 to 20 mol%, or 16 to 20 mol%, or 18 to 20 mol%, or 10 to 18 mol%, or 16 to 18 mol%, or 12 to 16 mol%, or 16 to 20 mol%, or 14 to 18 mol%, or 11 to 30 mol%, or 13 to 30 mol%, or 14 to 30 mol%,It may contain a composition that is 10 to 29 mol%, or 11 to 29 mol%, or 12 to 29 mol%, or 13 to 29 mol%, or 14 to 29 mol%, or 15 to 29 mol%, or 10 to 28 mol%, or 11 to 28 mol%, or 12 to 28 mol%, or 13 to 28 mol%, or 14 to 28 mol%, or 15 to 28 mol%. In one embodiment, the total of the 1,4-cyclohexanedimethanol residues and neopentyl glycol residues in the final polyester composition is 4 to 15 mol%, or 2 to 21 mol%, or less than 2 to 20 mol%, or 4 to 20 mol%, or 5 to 18 mol%, or 10 to 21 mol%, or 12 to 21 mol%, where the total mol% of the diol component is 100 mol%.

[0045]

[0054] In one embodiment, the diol component of the polyester composition and the polyester blend composition useful in the present disclosure may contain 0 to 30 mol% of neopentyl glycol based on the total mol% of the diol component which is 100 mol%. In one embodiment, the diol component of the polyester composition and the polyester blend composition useful in the present disclosure may contain 0 to 25 mol% of neopentyl glycol based on the total mol% of the diol component which is 100 mol%. In one embodiment, the diol component of the polyester composition useful in the present disclosure may contain 0 to 17 mol% of neopentyl glycol based on the total mol% of the diol component which is 100 mol%. In one embodiment, the diol component of the polyester composition and the polyester blend composition useful in the present disclosure may contain 5 to 20 mol% of neopentyl glycol based on the total mol% of the diol component which is 100 mol%. In one embodiment, the diol component of the polyester composition and the polyester blend composition useful in the present disclosure may contain 10 to 20 mol% of neopentyl glycol based on the total mol% of the diol component which is 100 mol%. In one embodiment, the diol component of the polyester composition and the polyester blend composition useful in the present disclosure may contain 10 to 15 mol% of neopentyl glycol based on the total mol% of the diol component which is 100 mol%. In one embodiment, the diol component of the polyester composition and the polyester blend composition useful in the present disclosure may contain 15 to 25 mol% of neopentyl glycol based on the total mol% of the diol component which is 100 mol%.

[0046]

[0055] In one embodiment, the diol component of the polyester composition and the polyester blend composition useful in the present disclosure may contain 1,4-cyclohexanedimethanol residues in an amount of 0 to 30 mol%, 0.01 to 30 mol%, or 0 to 20 mol%, or 0.1 to 20 mol%, or 2 to 20 mol%, or 0.01 to 15 mol%, or 0.01 to 14 mol%, or 0.01 to 13 mol%, or 0.01 to 12 mol%, or 0.01 to 11 mol%, or 0.01 to 10 mol%, or 0.01 to 9 mol%, or 0.01 to 8 mol%, or 0.01 to 7 mol%, or 0.01 to 6 mol%, or 0.01 to 5 mol%, or 3 to 15 mol%, or 3 to 14 mol%, or 3 to 13 mol%, or 3 to 12 mol%, or 3 to 11 mol%, or 3 to 10 mol%, or 3 to 9 mol%, or 3 to 8 mol%, or 3 to 7 mol%, or 2 to 10 mol%, or 2 to 9 mol%, or 2 to 8 mol%, or 2 to 7 mol%, or 2 to 5 mol%, or 1 to 7 mol%, or 1 to 5 mol%, or 1 to 3 mol%, based on the total mol% of the diol component which is 100 mol%.

[0047]

[0056] In one embodiment, the diol component of the polyester composition useful in the present disclosure may contain 0.01 to 15 mol% of 1,4-cyclohexanedimethanol based on the total mol% of the diol component which is 100 mol%. In one embodiment, the diol component of the polyester composition useful in the present disclosure may contain 0 or more and less than 15 mol% of 1,4-cyclohexanedimethanol based on the total mol% of the diol component which is 100 mol%. In one embodiment, the diol component of the polyester composition useful in the present disclosure may contain 0.01 to 10 mol% of 1,4-cyclohexanedimethanol based on the total mol% of the diol component which is 100 mol%. In one embodiment, the diol component of the polyester composition useful in the present disclosure may contain 0 or more and less than 10 mol% of 1,4-cyclohexanedimethanol based on the total mol% of the diol component which is 100 mol%. In one embodiment, the diol component of the polyester composition useful in the present disclosure may contain 0.01 to 5 mol% of 1,4-cyclohexanedimethanol based on the total mol% of the diol component which is 100 mol%. In one embodiment, the diol component of the polyester composition useful in the present disclosure may contain 0 or more and less than 5 mol% of 1,4-cyclohexanedimethanol based on the total mol% of the diol component which is 100 mol%.

[0048]

[0057] Some other diol residues may, of course, be generated in situ during processing. The total amount of diethylene glycol residues may be present in any amount, whether generated in situ during processing, intentionally added, or both, for example, 1 to 15 mol%, or 2 to 12 mol%, or 2 to 11 mol%, or 2 to 10 mol%, or 2 to 9 mol%, or 3 to 12 mol%, or 3 to 11 mol%, or 3 to 10 mol%, or 3 to 9 mol%, or 4 to 12 mol%, or 4 to 11 mol%, or 4 to 10 mol%, or 4 to 9 mol%, or 5 to 12 mol%, or 5 to 11 mol%, or 5 to 10 mol%, or 5 to 9 mol% of diethylene glycol residues based on the total mol% of the diol component which is 100 mol%.

[0049]

[0058] In one embodiment, the total amount of diethylene glycol residues that may be present in the polyester useful in the present disclosure is 4 mol% or less, or 3.5 mol% or less, or 3.0 mol% or less, or 2.5 mol% or less, or 2.0 mol% or less, or 1.5 mol% or less, or 1.0 mol% or less, or 1 to 4 mol%, or 1 to 3 mol%, or 1 to 2 mol%, or 2 to 8 mol%, or 2 to 7 mol%, or 2 to 6 mol%, or 2 to 5 mol%, or 3 to 8 mol%, or 3 to 7 mol%, or 3 to 6 mol%, or 3 to 5 mol% based on the total mol% of the diol component which is 100 mol%, regardless of whether it is generated in situ during processing, intentionally added, or both. Alternatively, in some embodiments, there are no intentionally added diethylene glycol residues. In certain embodiments, no modified diol is added to the polyester composition.

[0050]

[0059] In all embodiments, the remainder of the diol component may contain ethylene glycol residues in any amount based on the total mol% of the diol component which is 100 mol%. In one embodiment, the polyester portion of the polyester composition useful in the present disclosure may contain 50 mol% or more, or 55 mol% or more, or 60 mol% or more, or 65 mol% or more, or 70 mol% or more, or 75 mol% or more, or 80 mol% or more, or 85 mol% or more, or 90 mol% or more, or 95 mol% or more, or 50 to 80 mol%, or 55 to 80 mol%, or 60 to 80 mol%, or 50 to 75 mol%, or 55 to 75 mol%, or 60 to 75 mol%, or 65 to 75 mol% of ethylene glycol residues based on the total mol% of the diol component which is 100 mol%.

[0051]

[0060] In one embodiment, the diol component of the polyester composition useful in the present disclosure may contain up to 20 mol%, or up to 19 mol%, or up to 18 mol%, or up to 17 mol%, or up to 16 mol%, or up to 15 mol%, or up to 14 mol%, or up to 13 mol%, or up to 12 mol%, or up to 11 mol%, or up to 10 mol%, or up to 9 mol%, or up to 8 mol%, or up to 7 mol%, or up to 6 mol%, or up to 5 mol%, or up to 4 mol%, or up to 3 mol%, or up to 2 mol%, or up to 1 mol% of one or more modified diols (this modified diol is defined as a diol other than ethylene glycol, diethylene glycol, neopentyl glycol, or 1,4-cyclohexanedimethanol). In certain embodiments, the polyester useful in the present disclosure may contain up to 10 mol% of one or more modified diols. In certain embodiments, the polyester useful in the present disclosure may contain up to 5 mol% of one or more modified diols. In certain embodiments, the polyester useful in the present disclosure may contain up to 3 mol% of one or more modified diols. In another embodiment, the polyester useful in the present disclosure may contain 0 mol% of modified diol. However, since some other diol residues may be generated in situ, the amount of residues generated in situ may also be considered an embodiment of the present disclosure.

[0052]

[0061] In some embodiments, the modified diol used within the polyesters as defined herein, when used, contains from 2 to 16 carbon atoms. Examples of modified diols include, but are not limited to, 1,2-propanediol, 1,3-propanediol, isosorbide, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, p-xylene glycol, polytetramethylene glycol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD), and mixtures thereof. In one embodiment, isosorbide is the modified diol. In another embodiment, the modified diol includes, but is not limited to, at least one of 1,3-propanediol and 1,4-butanediol. In one embodiment, 1,3-propanediol and / or 1,4-butanediol may be excluded. When 1,4- or 1,3-butanediol is used, in one embodiment, more than 4 mol% or more than 5 mol% may be provided. In one embodiment, at least one modified diol is 1,4-butanediol present in an amount of 5 to 25 mol%.

[0053]

[0062] In one embodiment, a shrink film is provided that includes a polyester composition further including the following configuration: based on the total mol% of the diol component being 100 mol%, 1,4-cyclohexanedimethanol residues are present in an amount of 0.01 to about 10 mol%; diethylene glycol residues are present in an amount of 2 to 9 mol%; neopentyl glycol residues are present in an amount of 5 to 30 mol%; and ethylene glycol residues are present in an amount of 60 mol% or more.

[0054]

[0063] In some embodiments, the polyesters according to the present disclosure may include one or more branched monomer residues, also referred to herein as branching agents, each having 3 or more carboxyl substituents, hydroxyl substituents, or combinations thereof, in an amount of 0 to 10 mol%, such as 0.01 to 5 mol%, 0.01 to 1 mol%, 0.05 to 5 mol%, 0.05 to 1 mol%, or 0.1 to 0.7 mol%, based on the total mol% of either diol or diacid residues. In certain embodiments, the branching monomer or branching agent may be added before and / or during and / or after the polymerization of the polyester. Thus, in some embodiments, the polyesters useful in the present disclosure may be linear or branched.

[0055]

[0064] Examples of branching monomers include, but are not limited to, polyfunctional acids or polyfunctional alcohols such as trimellitic acid, trimellitic anhydride, pyromellitic dianhydride, trimethylolpropane, glycerin, pentaerythritol, citric acid, tartaric acid, 3-hydroxyglutaric acid. In one embodiment, the branched monomer residue may include one or more residues selected from at least one of trimellitic anhydride, pyromellitic dianhydride, glycerin, sorbitol, 1,2,6-hexanetriol, pentaerythritol, trimethylolethane, and / or trimesic acid in an amount of 0.1 to 0.7 mol%. The branching monomer may be added to the polyester reaction mixture or may be mixed with the polyester in the form of a concentrate, as described, for example, in U.S. Pat. Nos. 5,654,347 and 5,696,176, and this disclosure regarding the branching monomer is incorporated herein by reference.

[0056]

[0065] The polyesters useful in the present disclosure may contain at least one chain extender. Suitable chain extenders include, but are not limited to, polyfunctional isocyanates (such as bifunctional ones), polyfunctional epoxides such as epoxidized novolac, and phenoxy resins. In certain embodiments, the chain extender may be added at the end of the polymerization process or after the polymerization process. When added after the polymerization process, the chain extender may be blended or added and incorporated during a conversion process such as injection molding or extrusion molding.

[0057]

[0066] The amount of the chain extender used may vary depending on the specific monomer composition used and the desired physical properties, but generally it is 0.1 wt% to 10 wt%, for example 0.1 wt% to 5 wt%, based on the total weight of the polyester.

[0058]

[0067] The polyester compositions useful in the present disclosure are considered to optionally have at least one of the intrinsic viscosity ranges described herein and at least one of the monomer ranges of the polyester compositions described herein, unless otherwise specified. The polyester compositions useful herein are also considered to optionally have at least one of the Tg ranges described herein and at least one of the monomer ranges of the polyester compositions described herein, unless otherwise specified. The polyester compositions useful in the present disclosure are also considered to optionally have at least one of the intrinsic viscosity ranges described herein, at least one of the Tg ranges described herein, and at least one of the monomer ranges of the polyester compositions described herein, unless otherwise specified.

[0059]

[0068] In embodiments of the present disclosure, the polyesters useful in the present disclosure may exhibit at least one of the following intrinsic viscosity values measured in 60 / 40 (weight / weight) phenol / tetrachloroethane at 25 °C and a concentration of 0.25 g / 50 mL: 0.50 to 1.2 dL / g; 0.50 to 1.0 dL / g; 0.50 to 0.90 dL / g; 0.50 to 0.80 dL / g; 0.55 to 0.80 dL / g; 0.60 to 0.80 dL / g; 0.65 to 0.80 dL / g; 0.70 to 0.80 dL / g; 0.50 to 0.75 dL / g; 0.55 to 0.75 dL / g; or 0.60 to 0.75 dL / g.

[0060]

[0069] The glass transition temperature (Tg) of the polyester is measured using a TA DSC 2920 manufactured by Thermal Analyst Instrument at a scanning rate of 20 °C / min.

[0070] In certain embodiments, the oriented film or shrink film of the present disclosure comprises a polyester / polyester composition having a Tg of the polyester of 60 to 80 °C, 70 to 80 °C, 65 to 80 °C, or 65 to 75 °C. In certain embodiments, these Tg ranges can be met regardless of the presence or absence of at least one plasticizer added during polymerization.

[0061]

[0071] In embodiments of the present disclosure, certain oriented films and / or shrink films comprising polyesters and / or polyester compositions useful in the present disclosure have all of the following properties: namely, excellent stretchability, controlled shrinkage properties, specific toughness, specific intrinsic viscosity, specific glass transition temperature (Tg), specific melting point of strain-induced crystals, specific flexural modulus, specific density, specific tensile modulus, specific surface tension, excellent melt viscosity, excellent transparency, and excellent color tone.

[0062]

[0072] In one embodiment, a particular polyester composition useful in the present disclosure may be visually transparent. As used herein, the term "visually transparent" is defined as being clearly free of haze, cloudiness, and / or turbidity when visually inspected.

[0063]

[0073] The polyester portion of the polyester composition useful in the present disclosure may be prepared by known methods from the literature, for example, methods in homogeneous solution, methods by transesterification in the melt, and methods by two-phase interface. Suitable methods include, but are not limited to, reacting one or more dicarboxylic acids with one or more diols at a temperature of 100°C to 315°C and a pressure of 0.1 to 760 mmHg for a time sufficient to produce a polyester. For the method of manufacturing polyester, refer to U.S. Patent No. 3,772,405, and the disclosure regarding the method is incorporated herein by reference.

[0064]

[0074] Polyesters can generally be prepared by gradually raising the temperature to about 225°C to 310°C during the condensation process in an inert atmosphere and condensing a dicarboxylic acid or dicarboxylic acid ester with a diol in the presence of a catalyst. Also, as described in more detail in U.S. Patent No. 2,720,507, which is incorporated herein by reference, the latter part of the condensation can be prepared by condensation at low pressure.

[0065]

[0075] In some embodiments, during the manufacturing process of the polyester useful in the present disclosure, a specific chemical substance for coloring the polymer may be added to the melt containing the toner or dye. In one embodiment, a blue-toning agent is added to the melt to reduce the b * of the melt-phase product of the resulting polyester polymer. Such blue-toning agents include blue inorganic and organic toners and / or dyes. Also, the color tone of a * may be adjusted using a red toner and / or dye. Organic toners such as those described in U.S. Patent Nos. 5,372,864 and 5,384,377, which are incorporated herein by reference in their entirety, for example, blue and red organic toners, may be used. The organic toner may be supplied as a premixed composition. The premixed composition may be a neat blend of red and blue compounds, or the composition may be pre-dissolved or slurried in one of the raw materials of the polyester, such as ethylene glycol.

[0066]

[0076] The total amount of toner components added depends on the amount of inherent yellow in the base polyester and the effectiveness of the toner. In one embodiment, the mixed organic toner components may be used at a maximum concentration of about 15 ppm and a minimum concentration of about 0.5 ppm. In one embodiment, the total amount of the blueing additive may range from 0.5 to 10 ppm. In one embodiment, the toner may be added to the esterification reaction zone or the polycondensation reaction zone. Preferably, the toner is added to the esterification reaction zone or at an initial stage of the polycondensation zone, such as a prepolymerization reactor.

[0067]

[0077] The present disclosure further relates to a polymer mixture. In one embodiment, this polymer mixture comprises (a) 5 to 95 wt% of the polyester composition of the present disclosure described herein; and (b) 5 to 95 wt% of at least one polymer component.

[0068]

[0078] Suitable examples of the polymer component include, but are not limited to, nylon; polyesters different from the polyesters described herein; polyamides such as ZYTEL® manufactured by DuPont; polystyrene; polystyrene copolymers; styrene acrylonitrile copolymers; acrylonitrile butadiene styrene copolymers; polymethyl methacrylate; acrylic copolymers; polyetherimides such as ULTEM® (polyetherimide manufactured by General Electric); polyphenylene oxides such as poly(2,6-dimethylphenylene oxide) or NORYL 1000® (a mixture of poly(2,6-dimethylphenylene oxide) and polystyrene resin manufactured by General Electric); polyphenylene sulfides; polyphenylene sulfide / sulfone; polyester carbonate; polycarbonates such as LEXAN® (polycarbonate manufactured by General Electric); polysulfones; polysulfone ethers; and polyether ketones of aromatic dihydroxy compounds; or any mixture of the aforementioned polymers. In one embodiment, aliphatic-aromatic polyesters may be excluded from the polyester compositions useful in the present disclosure. The following polyesters that can be mixed to produce the polyester compositions of the present disclosure may be excluded as polymer components for additional mixing if the mixture exceeds the composition ranges of the present disclosure: polyethylene terephthalate (PET), glycol-modified PET (PETG), glycol-modified polycyclohexylene dimethylene terephthalate (PCTG), polycyclohexylene dimethylene terephthalate (PCT), acid-modified polycyclohexylene dimethylene terephthalate (PCTA), polybutylene terephthalate, and / or diethylene glycol-modified PET (EASTOBOND TM copolyester).

[0069]

[0079] This mixture may be prepared by conventional processing techniques known in the art such as melt mixing or solution mixing.

[0080] In some embodiments, the polyester composition and the polymer blend composition may also contain colorants, toners, dyes, release agents, flame retardants, plasticizers, glass bubbles, nucleating agents, stabilizers such as, but not limited to, UV stabilizers and heat stabilizers, and / or reaction products thereof, fillers, and common additives such as impact modifiers, in an amount of 0.01 to 25% by weight of the total composition. Examples of commercially available impact modifiers include, but are not limited to, ethylene / propylene terpolymers, functionalized polyolefins such as methyl acrylate and / or glycidyl methacrylate, each impact modifier of styrenic block copolymers, and various acrylic core / shell type impact modifiers. Residues of those additives are also considered to be part of the polyester composition.

[0070]

[0081] Reinforcing materials may be added to the compositions useful in the present disclosure. Reinforcing materials may include, but are not limited to, carbon fibers, silicates, mica, clay, talc, titanium dioxide, wollastonite, glass flakes, glass beads and glass fibers, as well as polymer fibers, and combinations thereof. In one embodiment, the reinforcing materials include glass such as fibrous glass, mixtures of glass and talc, glass and mica, and glass and polymer fibers.

[0071]

[0082] In one embodiment, the films and shrink films according to the present disclosure may contain 0.01 to 10% by weight of a polyester plasticizer. In one embodiment, the shrink film may contain 0.1 to 5% by weight of a polyester plasticizer. Generally, the shrink film may contain 90 to 99.99% by weight of a copolyester. In certain embodiments, the shrink film may contain 95 to 99.9% by weight of a copolyester.

[0072]

[0083] In one aspect, the present disclosure relates to the shrink films and molded articles of the present disclosure that include polyester compositions and / or polymer mixtures useful in the present disclosure. Methods of forming polyester compositions and / or mixtures into films and / or sheets are well known in the art. Examples of films and / or sheets useful in the present disclosure include, but are not limited to, extruded films and / or sheets, compression molded films, rolled films and / or sheets, solution cast films and / or sheets. In one aspect, methods of making films and / or sheets useful for manufacturing the shrink films of the present disclosure include, but are not limited to, extrusion, compression molding, rolling, and solution casting.

[0073]

[0084] In one embodiment, the polyester compositions useful in the present disclosure are produced into films using any method known in the art for producing films from polyesters, such as solution casting, extrusion, compression molding, or rolling.

[0074]

[0085] In one embodiment, the as-formed film is subsequently oriented in one or more directions (e.g., as a uniaxially and / or biaxially oriented film). This orientation of the film can be carried out by any method known in the art using standard orientation conditions. For example, the oriented films of the present disclosure may be produced from films having a thickness of about 100 to 400 μm, such as extruded, cast, or rolled films, and this oriented film may be oriented at a ratio of 5:1 to 3:1 at a temperature of Tg to Tg + 55°C, or 70°C to 125°C, for example, at a ratio of 5:1 or 3:1 at a temperature of 100°C to 114°C, and this film may also be oriented to a thickness of 20 to 80 μm. In one embodiment, the orientation of the initially pre-shrunk film may be carried out on a tenter frame according to these orientation conditions.

[0075]

[0086] The shrink films of the present disclosure may have a shrink start temperature of about 55 to about 80°C, or about 55 to about 75°C, or about 55 to about 70°C. The shrink start temperature is the temperature at which the start of shrinkage occurs.

[0076]

[0087] In certain embodiments, the polyester compositions useful in the present disclosure may have a density of 1.6 g / cc or less, or 1.5 g / cc or less, or 1.4 g / cc or less, or from 1.1 g / cc to 1.5 g / cc, or from 1.2 g / cc to 1.4 g / cc, or from 1.2 g / cc to 1.35 g / cc.

[0077]

[0088] In one embodiment, many small pores or holes are introduced into the film or molded article to reduce the density of the film. This process is called "voiding" and may also be called "cavitating" or "microvoiding". These pores are obtained by incorporating about 1 to about 50 wt% of small organic particles or inorganic particles (including glass microspheres), i.e., "inclusions" (referred to in the art as "voiding" agents or "cavitating" agents) into the base polymer and stretching the polymer at least in one direction to orient it. During stretching, small cavities or voids are formed around the voiding agent. When voids are introduced into the polymer film, the resulting voided film not only has a lower density than the void-free film but also becomes opaque and exhibits a paper-like surface. This surface also has the advantage of improving printability, i.e., the surface can accept more ink in a substantially larger volume than the void-free film. Typical examples of voided films are described in U.S. Patent Nos. 3,426,754; 3,944,699; 4,138,459; 4,582,752; 4,632,869; 4,770,931; 5,176,954; 5,435,955; 5,843,578; 6,004,664; 6,287,680; 6,500,533; 6,720,085; U.S. Patent Application Publication Nos. 2001 / 0036545; 2003 / 0068453; 2003 / 0165671; 2003 / 0170427; Japanese Patent Application Publication Nos. 61-037827; 63-193822; 2004-181863; European Patent No. 0 581 970 B1; European Patent Application Publication No. 0 214 859 A2.

[0078]

[0089] In certain embodiments, the as-extruded film is oriented during stretching. The oriented or shrinkable films of the present disclosure can be made from films having any thickness depending on the desired end use. In one embodiment, desirable conditions are that the oriented and / or shrinkable films can be printed with ink for applications such as photographic films that can adhere to substrates such as labels, paper, etc., and / or for other applications where such films are useful. It may be desirable to co-extrude the polyesters useful in the present disclosure with another polymer such as PET to make the film usable as the oriented and / or shrink film of the present disclosure. One advantage of performing the latter co-extrusion is that in some embodiments, a tie layer may not be required.

[0079]

[0090] In one embodiment, the uniaxially and biaxially oriented films of the present disclosure may be made from films having a thickness of about 100 - 400 μm, such as extruded, cast, or rolled films, which may be stretched at a ratio of 6.5:1 to 3:1 at a temperature of Tg to Tg + 55 °C of the film and may be stretched to a thickness of 20 - 80 μm. In one embodiment, the orientation of the initial as-extruded film may be carried out on a tenter frame according to these orientation conditions. The shrink films of the present disclosure can be made from the oriented films of the present disclosure.

[0080]

[0091] In certain embodiments, the shrink films of the present disclosure shrink gently so that there are few or no wrinkles. In certain embodiments, the shrink films of the present disclosure have a shrinkage rate of 40% or less in the transverse direction for every 5 °C increase in temperature.

[0081]

[0092] In certain embodiments of the present disclosure, when the shrink film of the present disclosure is immersed in water at 65°C for 10 seconds, it has a shrinkage rate of 10% or less, or 5% or less, or 3% or less, or 2% or less in the machine direction, or does not shrink. In certain embodiments of the present disclosure, when the shrink film of the present disclosure is immersed in water at 65°C for 10 seconds, it has a shrinkage rate of -10% to 10%, -5% to 5%, or -5% to 3%, or -5% to 2%, or -4% to 4%, or -3% to 4%, or -2% to 4%, or -2% to 2.5%, or -2% to 2%, or 0 to 2% in the machine direction, or does not shrink. Here, a negative shrinkage rate in the machine direction indicates expansion in the machine direction. A positive shrinkage rate in the machine direction indicates shrinkage in the machine direction.

[0082]

[0093] In certain embodiments of the present disclosure, when the shrink film of the present disclosure is immersed in water at 95°C for 10 seconds, it has a shrinkage rate of 50% or more, or 60% or more, or 70% or more in the main shrinkage direction.

[0083]

[0094] In certain embodiments of the present disclosure, when the shrink film of the present disclosure is immersed in water at 95°C for 10 seconds, it has a shrinkage rate of 50 to 90% in the main shrinkage direction and a shrinkage rate of 10% or less or -10% to 10% in the machine direction.

[0084]

[0095] In one embodiment, the polyesters useful in the present disclosure are formed into films using any method known in the art for manufacturing films from polyesters, such as solution casting, extrusion, compression molding, or rolling. Next, the as-extruded (or as-formed) film is oriented in one or more directions (e.g., uniaxially and / or biaxially oriented film). This orientation of the film may be carried out by any method known in the art using standard orientation conditions. For example, the uniaxially oriented film of the present disclosure may be made from a film having a thickness of about 100 to 400 μm, such as an extruded, cast, or rolled film, and this film may be stretched at a ratio of 6.5:1 to 3:1 at a temperature of Tg to Tg + 55 °C of the film, and may also be stretched to a thickness of 20 to 80 μm. In one embodiment, the orientation of the initial as-extruded film may be carried out on a tenter frame according to these orientation conditions.

[0085]

[0096] In certain embodiments, the shrink film of the present disclosure has a shrinkage rate of 40% or less in the transverse direction for every 5 °C increase in temperature.

[0097] In certain embodiments of the present disclosure, the shrink film of the present disclosure may have a shrink start temperature of about 55 to about 80 °C, or about 55 to about 75 °C, or about 55 to about 70 °C. The shrink start temperature is the temperature at which the start of shrinkage occurs.

[0086]

[0098] In certain embodiments of the present disclosure, the shrink film of the present disclosure may have a shrink start temperature of about 55 to about 70 °C.

[0099] In certain embodiments of the present disclosure, the shrink film of the present disclosure may have an elongation at break rate exceeding 200% at a stretching rate of 500 mm / min in a direction perpendicular to the main shrinkage direction according to ASTM method D882.

[0087]

[0100] In certain embodiments of the present disclosure, the shrink film of the present disclosure may have an elongation at break rate exceeding 300% at a stretching rate of 500 mm / min in a direction perpendicular to the main shrinkage direction according to ASTM method D882.

[0088]

[0101] In certain embodiments of the present disclosure, the shrink film of the present disclosure may have a tensile stress at break (breaking stress) of 20 to 400 MPa, or 40 to 260 MPa, or 42 to 260 MPa as measured according to ASTM method D882.

[0089]

[0102] In certain embodiments of the present disclosure, the shrink film of the present disclosure may have a shrinkage force of 4 to 18 MPa, or 4 to 15 MPa as measured according to ISO method 14616, depending on the stretching conditions and the desired end use. For example, when measured by ISO method 14616 using a shrinkage force tester manufactured by LabThink at 80 °C, a specific label made for a plastic bottle may have a shrinkage force of 4 to 8 MPa, and a specific label made for a glass bottle may have a shrinkage force of 10 to 14 MPa.

[0090]

[0103] In one embodiment of the present disclosure, the polyester composition may be produced by reacting monomers by a known method for producing a polyester typically called a reactor grade composition.

[0091]

[0104] In one embodiment of the present disclosure, the polyester composition of the present disclosure is a polyester such as polyethylene terephthalate (PET), glycol-modified PET (PETG), glycol-modified polycyclohexylene dimethylene terephthalate (PCTG), polycyclohexylene dimethylene terephthalate (PCT), acid-modified polycyclohexylene dimethylene terephthalate (PCTA), polybutylene terephthalate, and / or diethylene glycol-modified PET (EASTOBOND TM copolyester), etc., may be produced by mixing to achieve the monomer ranges of these compositions.

[0092]

[0105] In certain embodiments, the polyester composition and the polymer blend composition may contain, based on the total weight of the composition, from 0.01 to 25 weight percent of common additives such as colorants, toners, dyes, mold release agents, flame retardants, plasticizers, glass bubbles, nucleating agents, stabilizers including but not limited to UV stabilizers and heat stabilizers, and / or reaction products thereof, fillers, and impact modifiers. Examples of commercially available impact modifiers include, but are not limited to, ethylene / propylene terpolymers, functionalized polyolefins such as olefins containing methyl acrylate and / or glycidyl methacrylate, each impact modifier of styrenic block copolymers, and various acrylic core / shell type impact modifiers. Residues of those additives are also considered to be part of the polyester composition.

[0093]

[0106] Reinforcing materials may be added to the polyester compositions useful in the present disclosure. Reinforcing materials may include, but are not limited to, carbon fibers, silicates, mica, clay, talc, titanium dioxide, wollastonite, glass flakes, glass beads and glass fibers, as well as polymer fibers, and combinations thereof. In one embodiment, the reinforcing material includes glass such as fibrous glass, mixtures of glass and talc, glass and mica, and glass and polymer fibers.

[0094]

[0107] Molded articles made of shrink films, or molded articles that do not consist of shrink films but include such films, can also be manufactured from any of the polyester compositions disclosed herein and are within the scope of the present disclosure.

[0095]

[0108] Generally, the shrink films according to the present disclosure may contain from 0.01 to 10 weight percent of a polyester plasticizer. In one embodiment, the shrink film may contain from 0.1 to 5 weight percent of a polyester plasticizer. Generally, the shrink film may contain from 90 to 99.99 weight percent of a copolyester. Generally, the shrink film may contain from 95 to 99.9 weight percent of a copolyester.

[0096]

[0109] In one embodiment, when having a pre-oriented thickness of about 100 to 400 μm and subsequently being oriented by a width expanding machine to a thickness of about 20 to about 80 μm at a temperature of Tg to Tg + 55°C and a ratio of 6.5:1 to 3:1, the shrink film of the present disclosure has the following characteristics: (1) When immersed in water at 95°C for 10 seconds, it shrinks by an amount exceeding 60% (or exceeding 70%) in the main shrinkage direction or the transverse direction, and shrinks by an amount of 10% or less (or -5% to 4%) in the machine direction; (2) A shrink start temperature of about 55°C to about 70°C; (3) According to ASTM method D882, a breaking elongation rate exceeding 200%, or 200 to 600%, or 200 to 500%, or 226 to 449%, or 250 to 455% in the transverse direction, the machine direction, or both directions at a stretching rate of 500 mm / min; (4) Shrinking by 40% or less for each 5°C increase in temperature; and / or (5) A melting point of strain-induced crystals exceeding 200°C, and may have one or more of these characteristics. Any combination of these characteristics, or all of these characteristics, may be present in the shrink film of the present disclosure. The shrink film of the present disclosure may have a combination of two or more of the above-described shrink film characteristics. The shrink film of the present disclosure may have a combination of three or more of the above-described shrink film characteristics. The shrink film of the present disclosure may have a combination of four or more of the above-described shrink film characteristics. In a specific embodiment, the characteristics of (1) to (2) are present. In a specific embodiment, the characteristics of (1) to (5) are present. In a specific embodiment, the characteristics of (1) to (3), etc. are present.

[0097]

[0110] The shrinkage rate in this specification is based on an initially produced as-is film having a thickness of about 20 to 80 μm, which is oriented by a width expanding machine at a ratio of 6.5:1 to 3:1 at a temperature of Tg to Tg + 55°C, for example, at a ratio of 5:1 at a temperature of 70°C to 85°C. In one embodiment, there was no variation in the shrinkage characteristics of the oriented film used to produce the shrink film of the present disclosure when the film was heat-treated at a temperature higher than the temperature at which the film was oriented.

[0098]

[0111] The shape of the film useful for producing the alignment film or shrink film of the present disclosure is not restricted at all. For example, the shape may be a flat film or a film formed into a tube. To produce a shrink film useful in the present disclosure, the polyester is first formed into a flat film and then "uniaxially stretched", which means orienting the polyester film in one direction. The film may also be "biaxially oriented", which means orienting the polyester film in two different directions. For example, the film is stretched in both directions in a direction different from the machine direction and the machine direction. Typically, the two directions are substantially perpendicular, but not always. For example, in one embodiment, the two directions are the longitudinal or machine direction ("MD") of the film (the direction in which the film is manufactured by a film manufacturing machine) and the transverse direction ("TD") of the film (the direction perpendicular to the MD of the film). The biaxially oriented film may be continuously oriented, simultaneously oriented, or oriented by any combination of simultaneous and continuous stretching.

[0099]

[0112] The film may be oriented by any conventional method such as a roll stretching method, a long-gap stretching method, a width stretching method, and a tubular stretching method. Using any of these methods, continuous biaxial stretching, simultaneous biaxial stretching, uniaxial stretching, or a combination thereof may be performed. Using the biaxial stretching described above, stretching in the machine direction and the transverse direction may be performed simultaneously. Also, stretching may be performed first in one direction and then in the other direction to efficiently result in biaxial stretching. In one embodiment, the stretching of the film is performed by preliminarily heating the film 5°C to 80°C higher than their glass transition temperature (Tg). In one embodiment, the film may be preliminarily heated at a temperature 10°C to 30°C higher than their Tg. In one embodiment, the stretching speed is 5 to 20 inches (12.7 to 50.8 cm) per second. Next, the film may be oriented, for example, in either the machine direction, the transverse direction, or both directions, to 2 to 6 times the original dimensions. The film may be oriented as a single film layer or coextruded with another polyester such as PET (polyethylene terephthalate) as a multilayer film and then oriented.

[0100]

[0113] In one embodiment, the present disclosure includes a manufactured or molded article that includes a shrink film of any of the embodiments of the shrink film of the present disclosure. In another embodiment, the present disclosure includes a manufactured or molded article that includes an oriented film of any of the embodiments of the oriented film of the present disclosure.

[0101]

[0114] In certain embodiments, the present disclosure includes, but is not limited to, containers, plastic bottles, glass bottles, packaged goods, batteries, hot-fill containers, and / or shrink films applicable to industrial products or other uses. In one embodiment, the present disclosure includes, but is not limited to, containers, packaged goods, plastic bottles, glass bottles, photographic substrates such as paper, batteries, hot-fill containers, and / or oriented films applicable to industrial products or other uses.

[0102]

[0115] In certain embodiments of the present disclosure, the shrink film of the present disclosure may be formed into a label or a sleeve. The label or sleeve may then be affixed to a manufactured article such as a container wall, a battery, or onto a sheet or film.

[0103]

[0116] The oriented film or shrink film of the present disclosure can be affixed to molded articles such as sheets, films, tubes, or bottles and is commonly used for various packaging applications. For example, films and sheets made from polymers such as polyolefins, polystyrene, polyvinyl chloride, polyesters, polylactic acid (PLA), etc. are frequently used in the manufacture of shrink labels for plastic beverage containers or food containers. For example, the shrink film of the present disclosure can be used in many packaging applications, in which the shrink film affixed to the molded article exhibits properties such as excellent printability, high opacity, high shrink force, excellent texture, and high rigidity.

[0104]

[0117] A combination of improved shrinkage properties and enhanced toughness should be able to provide new commercial options, including, but not limited to, containers, plastic bottles, glass bottles, packaged goods, batteries, hot-fill containers, and / or shrink films applied to industrial products or other applications.

[0105]

[0118] In one aspect of the present disclosure, the disclosed polyester compositions are useful as thermoformed films or sheets, and / or thermoformable films or sheets. The present disclosure also encompasses manufactured articles incorporating the thermoformed films and / or sheets of the present disclosure. In one embodiment, the polyester compositions of the present disclosure are useful as films and sheets that can be readily formed into molded or shaped articles. In one embodiment, the films and / or sheets of the present disclosure can be processed into molded articles or parts by thermoforming. The polyester compositions of the present disclosure can be used in a variety of molding and extrusion applications.

[0106]

[0119] In yet another embodiment, the polyester compositions and polyester blends useful in the thermoformed sheets of the present disclosure may also contain common additives such as colorants, release agents, flame retardants, plasticizers, nucleating agents, stabilizers including, but not limited to, UV stabilizers and heat stabilizers, fillers, and impact modifiers, in an amount of 0.1 to 25 wt% of the total composition.

[0107]

[0120] In one embodiment, a reinforcing material may be included in the thermoformed film or sheet comprising the polyester composition of the present disclosure. For example, suitable reinforcing materials may include carbon fibers, silicates, mica, clay, talc, titanium dioxide, wollastonite, glass flakes, glass beads and fibers, polymer fibers, and combinations thereof.

[0108]

[0121] In one embodiment, the thermoformed film or sheet of the present disclosure is a multilayer film or sheet. In one embodiment, at least one layer of the multilayer film or sheet is a foam layer, or a foamed polymer or polyester layer.

[0109]

[0122] One aspect of the present disclosure is a method of manufacturing formed parts and articles or molded parts and articles using thermoforming. Any thermoforming technique or process known to those skilled in the art can be used to manufacture the formed or molded articles of the present disclosure.

[0110]

[0123] In one embodiment, the thermoforming process can be carried out in several ways, for example, as taught in "Technology of Thermoforming" (Throne, James; Hanser Publishers; 1996; pp. 16 - 29), which is incorporated herein by reference. Depending on the embodiment, the process is a male mold thermoforming process in which gas pressure or air pressure is applied to a softened sheet, then the sheet is stretched and drawn out like a bubble, and the male mold is inserted into the bubble from the inside. Next, a vacuum is applied to further draw out the part and conform it to the surface of the male mold. In this thermoforming process, when gas pressure or air pressure is applied to the softened sheet, biaxial stretching / orientation is mainly carried out in one step. Next, the forming step is completed by fixing the orientation in the sheet using a vacuum and the male mold to achieve a good balance between physical and appearance properties. In other embodiments, the process is a female mold thermoforming process in which a vacuum or a physical plug is applied to a heat - softened sheet, the sheet is stretched and drawn out to approximately the final part dimensions, then the sheet is drawn out by positive air pressure from the inside or further external vacuuming from the outside and conformed to the outer female mold, and the orientation is fixed in the polymer to form the sheet into an article.

[0111]

[0124] Depending on the embodiment, the generation of the bubble may further be formed using a plug assist, followed by covering and molding the rising male mold with the sheet, and then drawing in corners and shelf ledges etc. into the mold by applying a vacuum. Depending on the embodiment, after removing from the mold, the formed part or article may be trimmed, drilled, and the corners may be cut off as required.

[0112]

[0125] In other embodiments, thermoforming is a process in which a film or sheet of the polyester composition of the present disclosure is heated to a temperature sufficient for it to be deformable, and then the heated film or sheet is conformed to the contour of a mold by means such as vacuum assistance, pneumatic assistance, and matched mold assistance. In another embodiment, the heated film or sheet is placed within a mold and forced to conform to the contour of the mold, for example, by applying air pressure, using a vacuum plug assist, or using a matched mold. Depending on the embodiment, thin-walled articles are manufactured by thermoforming.

[0113]

[0126] In one embodiment, the thermoforming process shapes the film or sheet into the desired shape by pressing a male mold into the heated film or sheet. In this embodiment, thermoforming includes having a male mold of the article supported between a vacuumed surface or table. In this embodiment, heat from an external heat source such as a hot air blower, a heat lamp, or other radiant heat source is directed towards the film or sheet. In this embodiment, the film or sheet is heated to its softening point. In this embodiment, the table, under the table, and around the mold are then vacuumed to draw the heat-softened film or sheet towards the table and position it to contact the mold surface. In this embodiment, the vacuum causes the softened film or sheet to closely contact and conform to the contour of the mold surface. Thereby, the film or sheet takes the shape of the mold. In these embodiments, after the film or sheet has cooled, the sheet hardens and the resulting article or part can be removed from the mold.

[0114]

[0127] In one embodiment, the thermoforming process includes the steps of forming a film or sheet from the polyester composition of the present disclosure; heating the film or sheet until it softens and placing the sheet over a mold; drawing the preheated film or sheet against the heated mold surface; cooling the film or sheet; then removing the formed article or part from the mold cavity, or alternatively, heating and fixing the formed film or sheet by continuing to contact the film or sheet against the heated mold for a time sufficient to partially crystallize the film or sheet.

[0115]

[0128] In one embodiment, the thermoforming process includes the steps of forming a sheet from the polyester composition of the present disclosure; heating the film or sheet to a temperature above the Tg of the polyester; applying gas pressure, vacuum, and / or physical pressure to the heat-softened film or sheet to stretch the film or sheet to substantially final part dimensions; conforming the film or sheet to the shape of the mold by vacuum or pressure; cooling the film or sheet to a temperature below the Tg of the polyester; then removing the thermoformed article or part from the mold.

[0116]

[0129] The film or sheet used in the thermoforming process may be made by any conventional method known to those skilled in the art. In one embodiment, the film or sheet is formed by extrusion. In one embodiment, the film or sheet is formed by rolling. In one embodiment, during the thermoforming process, the film or sheet is heated to a temperature above the Tg of the polyester. In one embodiment, this temperature is about 10 °C to about 60 °C higher than the Tg of the polyester. In one embodiment, in order to achieve a shorter forming time, it is necessary to heat the film or sheet before placing it on the thermoforming mold. In one embodiment, it is necessary to heat the sheet above its Tg and lower than the temperature at which the sheet sags excessively while being placed over the depression of the mold. In one embodiment, before removing the formed film or sheet from the mold, it is cooled to a temperature below the Tg of the polyester. In one embodiment, the thermoforming method may include a vacuum assist, an air assist, a mechanical plug assist, or a matched mold. In some embodiments, the mold is heated to a temperature above the Tg of the film or sheet. The selection of the optimal mold temperature depends on the mold of the thermoforming apparatus, the structure and thickness of the article to be formed, and other factors.

[0117]

[0130] In some embodiments, the heated film or sheet is stretched by generating and introducing a vacuum.

[0131] In one embodiment, heat setting is a process that thermally induces partial crystallization of the polyester film or sheet without the presence of a recognizable orientation. In one embodiment, heat setting is achieved by maintaining the contact between the film or sheet and the heated mold surface for a time sufficient to achieve a level of crystallinity that imparts appropriate physical properties to the finished part. In one embodiment, the level of crystallinity should be from about 10% to about 30%.

[0118]

[0132] In one embodiment, the heat-fixed part may be removed from the recess of the mold by known means for removal. For example, in one embodiment, blowback is used, which involves introducing compressed air to break the vacuum established between the mold and the formed film or sheet. In some embodiments, the excess portion of the formed article or part is then cut off, and the waste is pulverized for recycling.

[0119]

[0133] In some embodiments, the addition of a nucleating agent provides faster crystallization during thermoforming, and thus faster forming. In one embodiment, a nucleating agent such as an inorganic or organic material with a particulate size may be used. For example, in one embodiment, suitable nucleating agents include talc, titanium dioxide, calcium carbonate, and immiscible or cross-linked polymers. In one embodiment, the nucleating agent may be used in an amount that varies from about 0.01% to about 20% based on the weight of the article. In one embodiment, other conventional additives such as pigments, dyes, plasticizers, anti-cracking agents, and stabilizers may be used as needed for thermoforming. In some embodiments, the anti-cracking agent improves impact strength, and the nucleating agent provides faster crystallization. In some embodiments, crystallization is necessary to achieve high-temperature stability.

[0120]

[0134] In one embodiment, the foamed polyester film or sheet is produced by foaming the polyester composition of the present disclosure with a chemical and / or physical foaming agent, extruding the foamed polyester into a sheet or film, and thermoforming the foamed polyester film or sheet. Additives for improving the properties of the foamed polyester film may be added to the polyester before foaming. Examples of such additives include lubricants, anti-adhesion agents, plasticizers, fluorescent brighteners, and ultraviolet inhibitors. In one embodiment, the foamed polyester film may be an extruded or laminated product coated on one or both sides using conventional techniques to improve its properties. In one embodiment, the coating material is preferably the printing surface that provides product labeling rather than the foamed film itself.

[0121]

[0135] The compositions of the present disclosure are useful as formed or molded plastic parts or as solid plastic articles. The compositions of the present disclosure are useful as thermoformed parts or articles. The compositions are suitable for use in any application where a transparent and rigid plastic is required. Examples of such parts include disposable knives, forks, spoons, plates, cups, straws, as well as eyeglass frames, toothbrush handles, toys, automotive equipment, tool handles, camera parts, electronic device parts, razor parts, ink pen shafts, disposable syringes, bottles, and the like. In one embodiment, the compositions of the present disclosure are useful as plastics, films, fibers, and sheets. In one embodiment, the compositions are useful as plastics for manufacturing bottles, bottle caps, eyeglass frames, cutting tools, disposable cutting tools, handles of cutting tools, shelves, shelf dividers, housings of electronic devices, electronic device cases, computer monitors, printers, keyboards, tubes, automotive parts, automotive interior parts, automotive equipment, signs, thermoformed letters, wall panels, toys, thermally conductive plastics, ophthalmic lenses, tools, tool handles, and household goods.In another embodiment, the compositions of the present disclosure are suitable for use as films, sheets, fibers, formed articles, molded articles, formed parts, molded parts, medical devices, dental trays, dental instruments, containers, food containers, shipping containers, packages, bottles, bottle caps, eyeglass frames, cutting tools, disposable cutting tools, handles of cutting tools, shelves, shelf dividers, furniture parts, electronic device housings, electronic device cases, computer monitors, printers, keyboards, tubes, handles of toothbrushes, automotive parts, automotive interior parts, automotive accessories, signs, outdoor signs, skylights, multiwall layer films, multilayer films, insulation parts, insulation articles, insulated containers, thermoformed letters, wall panels, toys, toy parts, trays, food trays, dental trays, thermally conductive plastics, ophthalmic lenses and frame materials, tools, handles of tools, and household goods, health management products, commercially available food supply products, boxes, films for graphic arts, plastic films for plastic-glass laminates, point-of-purchase displays, skylights, smoke vents, laminated cards, fenestration, glazing, dividers, ceiling tiles, lighting, machine guards, graphic arts, lenses, extruded laminated sheets or films, decorative laminates, office furniture, face shields, medical packaging materials, sign holders for display shelves, and price holders for shelves.

[0122]

[0136] The thermoformed composition or thermoformable composition of the present disclosure is useful for forming films, formed articles, formed parts, molded articles, molded parts, and sheets. The method of manufacturing the thermoformed composition or thermoformable composition into films, formed articles, formed parts, molded articles, molded parts, and sheets may follow any method known in the art. Examples of formed articles include, but are not limited to, medical devices, medical packages, health management products, trays, containers, food dishes, tumblers, storage boxes, bottles, commercially available food supply products such as food processors, mixing bowls, household goods, water bottles, vegetable crisper trays, washing machine parts, refrigerator parts, vacuum cleaner parts, ophthalmic lenses and frames, and toys.

[0123]

[0137] The present disclosure further relates to a manufactured article comprising a film and / or a sheet comprising the polyester composition described herein. In some embodiments, the film and / or sheet of the present disclosure may be of any thickness required for the intended use.

[0124]

[0138] The present disclosure further relates to a film and / or a sheet as described herein. Methods of forming the polyester composition into a film and / or a sheet include any method known in the art. Examples of the film and / or sheet of the present disclosure include, but are not limited to, extruded film and / or sheet, rolled film and / or sheet, compression molded film and / or sheet, and solution cast film and / or sheet. Methods of making the film and / or sheet include, but are not limited to, extrusion, rolling, compression molding, wet block processing, dry block processing, and solution casting.

[0125]

[0139] The present disclosure further relates to a formed article or a molded article as described herein. Methods of molding the polyester composition into a formed article or a molded article include any method known in the art. Examples of the formed article or the molded article of the present disclosure include, but are not limited to, a thermoformed article or a thermoformable article, an injection molded article, an extrusion molded article, an injection blow molded article, an injection stretch blow molded article, and an extrusion blow molded article. Methods of manufacturing the formed article include, but are not limited to, thermoforming, injection molding, extrusion, injection blow molding, injection stretch blow molding, and extrusion blow molding. The process of the present disclosure may include any thermoforming process known in the art. The process of the present disclosure may include any blow molding process known in the art, including, but not limited to, extrusion blow molding, extrusion stretch blow molding, injection blow molding, and injection stretch blow molding.

[0126]

[0140] This disclosure includes any injection blow molding manufacturing process known in the art. By way of non-limiting example, a typical description of an injection blow molding (IBM) manufacturing process includes: 1) melting a composition in a reciprocating screw extruder; 2) injecting the molten composition into an injection mold to form a partially cooled tube (i.e., a preform) with one end closed; 3) moving the preform into a blow mold having a desired final shape around the preform and closing the blow mold around the preform; 4) blowing air into the preform to stretch and expand the preform to fill the mold; 5) cooling the molded article; and 6) removing the article from the mold.

[0127]

[0141] This disclosure includes any injection stretch blow molding manufacturing process known in the art. By way of non-limiting example, a typical description of an injection stretch blow molding (ISBM) manufacturing process includes: 1) melting a composition in a reciprocating screw extruder; 2) injecting the molten composition into an injection mold to form a partially cooled tube (i.e., a preform) with one end closed; 3) moving the preform into a blow mold having a desired final shape around the preform and closing the blow mold around the preform; 4) stretching the preform using an internal stretching rod, blowing air into the preform, and stretching and expanding the preform to fill the mold; 5) cooling the molded article; and 6) removing the article from the mold.

[0128]

[0142] This disclosure includes any extrusion blow molding manufacturing process known in the art. By way of non-limiting example, a typical description of an extrusion blow molding manufacturing process includes: 1) melting a composition in an extruder; 2) extruding the molten composition through a die to form a tube of molten polymer (i.e., a parison); 3) securing a mold having a desired final shape around the parison; 4) blowing air into the parison to stretch and expand the extrudate to fill the mold; 5) cooling the molded article; 6) removing the article from the mold; and 7) removing excess plastic (commonly referred to as flash) from the article.

[0129]

[0143] In another aspect of the present disclosure, it has been found that it is possible to produce the polyester resin of the present disclosure from recycled copolyester and / or recycled polyester.

[0130]

[0144] One embodiment of the present disclosure is a process for producing a polyester composition from recycled polyester, the process comprising: (a) introducing a recycled polyester comprising terephthalic acid (TPA), ethylene glycol (EG), and at least one of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG into a paste tank, stirring and heating at a temperature of up to 150 °C to produce a slurry; (b) delivering the slurry from the paste tank to a first reaction zone; (c) introducing at least one additional glycol comprising 1,4-cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), or diethylene glycol (DEG) into the first reaction zone, and optionally adding additional terephthalic acid (TPA) and ethylene glycol (EG) such that the molar ratio of total glycol:TPA is from 1:1 to 4:1, optionally in the presence of an esterification catalyst and / or a stabilizer; (d) reacting TPA and EG with at least one additional glycol at a melting temperature of at least 200 °C in the first reaction zone to produce a first esterification product comprising oligomers and unreacted TPA, EG, and additional glycol; (e) delivering the first esterification product to a second reaction zone; (f) further reacting the first esterification product and optionally additional glycol added thereto at a melting temperature of at least 200 °C in the second reaction zone, optionally in the presence of an esterification catalyst and / or a stabilizer, to produce a second esterification product comprising polyester oligomers; (g) delivering the second esterification product to a third reaction zone; and (h) In a third reaction zone, polycondensing the second esterification product in the presence of a polycondensation catalyst and / or a stabilizer as necessary to produce a polymerization product containing polyester.

[0131]

[0145] One embodiment of the present disclosure is a process for producing a polyester composition from a recycled polyester, the process comprising: (a) Introducing a recycled polyester containing terephthalic acid (TPA) or its ester, ethylene glycol (EG), and one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG into a paste tank, stirring and heating at a temperature of up to 150°C to produce a slurry; (b) Delivering the slurry in the paste tank to a first reaction zone; (c) Introducing at least one additional glycol containing 1,4 - cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), or diethylene glycol (DEG) into the first reaction zone, adding an additional recycled polyester containing one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG as necessary, and adding additional terephthalic acid (TPA) and ethylene glycol (EG) as necessary such that the molar ratio of total glycol:TPA is 1:1 to 4:1, in the presence of an esterification catalyst and / or a stabilizer as necessary; (d) Reacting TPA and EG with at least one additional glycol at a melting temperature of at least 200°C in the first reaction zone to produce a first esterification product containing oligomers and unreacted TPA, EG, and additional glycol; (e) Delivering the first esterification product to a second reaction zone; (f) In the second reaction zone, additional glycols including one or more of CHDM, NPG, or DEG as needed and / or additional recycled polyesters including one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG are added, and the first esterification product is further reacted at a melting temperature of at least 200 °C in the presence of an esterification catalyst and / or a stabilizer as needed to produce a second esterification product containing a polyester oligomer; (g) Delivering the second esterification product to a third reaction zone; and (h) In the third reaction zone, polycondensing the second esterification product in the presence of a polycondensation catalyst and / or a stabilizer as needed to produce a polymerization product containing a polyester.

[0132]

[0146] One embodiment of the present disclosure is a process for producing a polyester composition from recycled polyesters, the process comprising: (a) Introducing terephthalic acid (TPA), ethylene glycol (EG), and a recycled polyester including one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG into a paste tank, stirring and heating at a temperature of up to 150 °C to produce a slurry; (b) Delivering the slurry in the paste tank to a first reaction zone; (c) Introducing at least one additional glycol including 1,4 - cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), or diethylene glycol (DEG) into the first reaction zone, adding additional recycled polyester including one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG as needed, and adding additional terephthalic acid (TPA) and ethylene glycol (EG) as needed such that the molar ratio of total glycol:TPA is from 1:1 to 4:1, and adding in the presence of an esterification catalyst and / or a stabilizer as needed; (d)In the first reaction zone, reacting TPA and EG with at least one additional glycol at a melting temperature of at least 200 °C to produce a first esterification product comprising oligomers and unreacted TPA, EG, and the additional glycol; (e)Delivering the first esterification product to a second reaction zone; (f)In the second reaction zone, adding an additional glycol optionally containing one or more of CHDM, NPG, or DEG and / or an additional recycled polyester optionally containing one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG, and further reacting the first esterification product at a melting temperature of at least 200 °C in the presence of an esterification catalyst and / or stabilizer as needed to produce a second esterification product comprising polyester oligomers; (g)Delivering the second esterification product to a third reaction zone; and (h)In the third reaction zone, adding an additional recycled polyester optionally containing one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG, and polycondensing the second esterification product in the presence of a polycondensation catalyst and / or stabilizer as needed to produce a polymerization product comprising polyester.

[0133]

[0147] One embodiment of the present disclosure is a process for producing a polyester composition from a recycled polyester, the process comprising: (a)Introducing terephthalic acid (TPA) and ethylene glycol (EG) into a paste tank, stirring and heating at a temperature of up to 150 °C to produce a slurry; (b)Delivering the slurry from the paste tank to a first reaction zone; (c) Introduce at least one additional glycol including 1,4 - cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), or diethylene glycol (DEG) into the first reaction zone, add a recycled polyester including one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG, and optionally add additional terephthalic acid (TPA) and ethylene glycol (EG) such that the molar ratio of total glycol:TPA is from 1:1 to 4:1, and add in the presence of an esterification catalyst and / or stabilizer as required; (d) React TPA and EG with at least one additional glycol at a melting temperature of at least 175 °C in the first reaction zone to produce a first esterification product including oligomers and unreacted TPA, EG, and additional glycol; (e) Deliver the first esterification product to a second reaction zone; (f) In the second reaction zone, add additional glycol including one or more of CHDM, NPG, or DEG and / or additional recycled polyester including one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG, and further react the first esterification product at a melting temperature of at least 200 °C in the presence of an esterification catalyst and / or stabilizer as required to produce a second esterification product including polyester oligomers; (g) Deliver the second esterification product to a third reaction zone; and (h) In the third reaction zone, add additional recycled polyester including one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG as required, and polycondense the second esterification product in the presence of a polycondensation catalyst and / or stabilizer as required to produce a polymerization product including polyester.

[0134]

[0148] One embodiment of the present disclosure is a process for producing a polyester composition from recycled polyester, the process comprising: (a) introducing a recycled polyester containing terephthalic acid (TPA), ethylene glycol (EG), and at least one of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG into a paste tank, stirring and heating at a temperature of up to 150 °C to form a slurry; (b) delivering the slurry from the paste tank to a first reaction zone; (c) introducing at least one additional glycol containing 1,4 - cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), or diethylene glycol (DEG) into the first reaction zone, adding a recycled polyester containing at least one of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG, and, if necessary, adding additional terephthalic acid (TPA) and ethylene glycol (EG) such that the molar ratio of total glycol:TPA is from 1:1 to 4:1, in the presence of an esterification catalyst and / or stabilizer as necessary; (d) reacting TPA and EG with at least one additional glycol at a melting temperature of at least 200 °C in the first reaction zone to form a first esterification product containing oligomers and unreacted TPA, EG, and additional glycol; (e) delivering the first esterification product to a second reaction zone; (f) adding an additional glycol containing at least one of CHDM, NPG, or DEG and / or an additional recycled polyester containing at least one of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG to the second reaction zone and further reacting the first esterification product at a melting temperature of at least 200 °C in the presence of an esterification catalyst and / or stabilizer as necessary to form a second esterification product containing polyester oligomers; (g) delivering the second esterification product to a third reaction zone; and (h) In the third reaction zone, add one or more additional recycled polyesters including recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG as needed, and polycondense the second esterification product in the presence of a polycondensation catalyst and / or stabilizer as needed to produce a polymerization product containing polyester.

[0135]

[0149] One embodiment of the present disclosure is a process for producing a polyester composition from recycled polyester, the process comprising (a) Introducing terephthalic acid (TPA), ethylene glycol (EG), and a recycled polyester containing one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG into a paste tank, stirring and heating at a temperature of up to 150 °C to produce a slurry; (b) Delivering the slurry in the paste tank to a first reaction zone; (c) Introducing at least one additional glycol including 1,4 - cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), or diethylene glycol (DEG) into the first reaction zone, adding additional recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG as needed, and adding terephthalic acid (TPA) and ethylene glycol (EG) as needed such that the molar ratio of total glycol:TPA is from 1:1 to 4:1, in the presence of an esterification catalyst and / or stabilizer as needed; (d) Reacting TPA and EG with at least one additional glycol at a melting temperature of at least 200 °C in the first reaction zone to produce a first esterification product containing oligomers and unreacted TPA, EG, and additional glycol; (e) Delivering the first esterification product to a second reaction zone; (f) In the second reaction zone, additional glycols including one or more of CHDM, NPG, or DEG as needed and / or additional recycled polyesters including one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG are added, and the first esterification product is further reacted at a melting temperature of at least 200 °C in the presence of an esterification catalyst and / or a stabilizer as needed to produce a second esterification product containing a polyester oligomer; (g) Delivering the second esterification product to a third reaction zone; and (h) In the third reaction zone, additional recycled polyesters including one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG are added, and the second esterification product is polycondensed in the presence of a polycondensation catalyst and / or a stabilizer as needed to produce a polymerization product containing a polyester.

[0136]

[0150] One embodiment of the present disclosure is a process for producing a polyester composition from recycled polyesters, the process comprising: (a) Introducing terephthalic acid (TPA), ethylene glycol (EG), and a recycled polyester including one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG into a paste tank, stirring and heating at a temperature of up to 150 °C to produce a slurry; (b) Delivering the slurry of the paste tank to a first reaction zone; (c) Introducing at least one additional glycol including 1,4 - cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), or diethylene glycol (DEG) into the first reaction zone, adding additional recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG, and adding terephthalic acid (TPA) and ethylene glycol (EG) as necessary such that the molar ratio of total glycol:TPA is from 1:1 to 4:1, in the presence of an esterification catalyst and / or stabilizer as necessary; (d) Reacting TPA and EG with at least one additional glycol at a melting temperature of at least 200°C in the first reaction zone to produce a first esterification product containing oligomers and unreacted TPA, EG, and the additional glycol; (e) Delivering the first esterification product to a second reaction zone; (f) Adding an additional glycol containing one or more of CHDM, NPG, or DEG and / or an additional recycled polyester containing one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG as necessary in the second reaction zone, and further reacting the first esterification product at a melting temperature of at least 200°C in the presence of an esterification catalyst and / or stabilizer as necessary to produce a second esterification product containing polyester oligomers; (g) Delivering the second esterification product to a third reaction zone; and (h) Adding an additional recycled polyester containing one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG in the third reaction zone, and polycondensing the second esterification product in the presence of a polycondensation catalyst and / or stabilizer as necessary to produce a polymerization product containing polyester.

[0137]

[0151] In one embodiment, the recycled polyester and / or copolyester may be recovered as manufacturing scraps or industrial waste or post-consumer recycled (PCR) waste. Typically, PCR or recycled waste is an article made from used and discarded polyester or copolyester. Currently, PET is recycled by mechanical methods and incorporated as a mixture with virgin materials into new PET bottles and other PET articles.

[0138]

[0152] Copolyesters having a recycled content and copolyesters made from a recycled content contain dicarboxylic acid monomer residues, diol or glycol monomer residues, and repeating units. Thus, as used herein, the term "monomer residue" means each residue of a dicarboxylic acid, diol or glycol, or hydroxycarboxylic acid. As used herein, "repeating unit" means an organic structure having two monomer residues bonded through a carbonyloxy group. The copolyesters of the present disclosure contain acid residues (100 mol%) and glycol residues (100 mol%) that react in substantially equal proportions such that the total number of moles of repeating units is equal to 100 mol%. Thus, the mol% shown in the present disclosure may be based on the total number of moles of acid residues, the total number of moles of glycol residues, or the total number of moles of repeating units. For example, a copolyester containing 30 mol% monomers that can be dicarboxylic acids, glycols, or hydroxycarboxylic acids based on the total repeating units means that the copolyester contains 30 mol% monomers out of 100 mol% total repeating units. Thus, there will be 30 mol of monomer residues per 100 mol of repeating units. Similarly, a copolyester containing 30 mol% dicarboxylic acid monomers based on the total acid residues means that the polyester contains 30 mol% dicarboxylic acid monomers out of 100 mol% total acid residues. Thus, in this latter case, there will be 30 mol of dicarboxylic acid monomer residues per 100 mol of acid residues.

[0139]

[0153] As used herein, the term "polyester" encompasses both "homopolymers" and "homopolyesters" as well as "copolyester", and means a synthetic polymer prepared by polycondensation of at least one diacid component containing one or more difunctional carboxylic acids and at least one glycol component containing one or more difunctional hydroxyl compounds. The term "copolyester" as used herein is intended to mean a polyester formed from the polycondensation of at least three different monomers, for example, the polycondensation of a dicarboxylic acid and two or more glycols, or in another example, the polycondensation of a diol and two or more different dicarboxylic acids. Typically, the difunctional carboxylic acid is a dicarboxylic acid and the difunctional hydroxyl compound is a dihydric alcohol such as, for example, glycol and diol. Alternatively, the difunctional carboxylic acid may be a hydroxycarboxylic acid such as, for example, p-hydroxybenzoic acid, and the difunctional hydroxyl compound may be an aromatic nucleus having two hydroxy substituents such as, for example, hydroquinone. The term "residue" as used herein means any organic structure incorporated into the polymer by a polycondensation reaction involving the corresponding monomer. The dicarboxylic acid residue may be derived from a dicarboxylic acid monomer, or its related acid halide, ester, salt, anhydride, or a mixture thereof. For example, in one embodiment, in the copolyesters of the present disclosure, the diacid component is supplied as terephthalic acid or isophthalic acid.

[0140]

[0154] The recycled polyester and / or copolyester may be repolymerized into a copolyester using any polycondensation reaction conditions known in the art. These may be produced by each of the continuous, semi - continuous, and batch operating modes and may utilize various types of reactors. Examples of suitable reactor types include, but are not limited to, stirred tank, continuous stirred tank, slurry type, tubular type, wiped film type, falling film type, or extrusion type reactors. As used herein, the term "continuous" means a process in which reactants are introduced and products are simultaneously withdrawn in a manner that is not interrupted. This process is beneficially operated as a continuous process for economic reasons and is operated to produce a polymer with an excellent color tone because staying in the reactor at a high temperature for too long a period may cause deterioration of the appearance of the copolyester.

[0141]

[0155] The copolyester of the present disclosure is prepared by procedures known to those skilled in the art. The reaction of the diol component and the dicarboxylic acid component may be carried out using conventional copolyester polymerization conditions. For example, when preparing a copolyester by transesterification from the ester form of the dicarboxylic acid component, the reaction process may include two steps. In the first step, the diol component and a dicarboxylic acid component such as terephthalic acid are reacted at a high temperature of about 150 °C to about 250 °C for about 0.5 to about 8 hours at a pressure in the range of about 0.0 kPa gauge to about 414 kPa gauge (60 pounds per square inch, "psig") based on atmospheric pressure. The temperature of the transesterification reaction is in the range of about 180 °C to about 230 °C for about 1 hour to about 4 hours, and the pressure is in the range of about 103 kPa gauge (15 psig) to about 276 kPa gauge (40 psig). Thereafter, the reaction product is heated at a higher temperature and under reduced pressure to remove the diol to produce a copolyester, and at this time, the diol easily volatilizes and is removed from the system under these conditions.

[0142]

[0156] This second step, i.e., the polycondensation step, is carried out under a higher vacuum and generally at a temperature in the range of about 230°C to about 350°C, or about 250°C to about 310°C, or about 260°C to about 290°C, for about 0.1 to about 6 hours, or about 0.2 to about 2 hours, until a polymer having a desired degree of polymerization determined by the intrinsic viscosity is obtained. The polycondensation step may be carried out under a reduced pressure in the range of about 53 kPa (400 torr) to about 0.013 kPa (0.1 torr). Stirring conditions or appropriate conditions are used in both stages to ensure sufficient heat transfer of the reaction mixture and regeneration of the surface, and to promote the reaction and polymerization by ensuring the elimination of water, excess glycol, or alcohol. The reaction rate in both stages is increased by appropriate catalysts such as alkoxytitanium compounds, alkali metal hydroxides, and alcoholates, organic carboxylates, alkyltin compounds, metal oxides, etc. In particular, when using a mixed monomer raw material of an acid and an ester, a three-step manufacturing procedure similar to the manufacturing procedure described in U.S. Patent No. 5,290,631 may be further used.

[0143]

[0157] To ensure the completion of the reaction between the diol component and the dicarboxylic acid component by transesterification, it may be desirable to use about 1.05 to about 2.5 moles of the diol component per mole of the dicarboxylic acid component and remove the excess glycol in a subsequent step. However, those skilled in the art know that the ratio of the diol component to the dicarboxylic acid component is generally determined by the design of the reactor in which the reaction process occurs.

[0144]

[0158] For example, in the preparation of a copolyester by direct esterification from the acid form of a dicarboxylic acid component, the copolyester is produced by reacting a dicarboxylic acid or a mixture of dicarboxylic acids with a glycol component or a mixture of glycol components. This reaction is carried out at a pressure of about 7 kPa gauge (1 psig) to about 1379 kPa gauge (200 psig), or less than 689 kPa (100 psig), to produce a low molecular weight, linear or branched copolyester product having an average degree of polymerization of about 1.4 to about 10. The temperature used during the direct esterification reaction is about 180 °C to about 280 °C, or about 220 °C to about 270 °C. This low molecular weight polymer may be further polymerized by a polycondensation reaction.

[0145]

[0159] In some embodiments, suitable glycols include, but are not limited to, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, p-xylene glycol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethylcyclobutane-1,3-diol, polytetramethylene glycol, isosorbide, or mixtures thereof.

[0146]

[0160] In some embodiments, copolyesters containing the following diacids are suitable for use in a repolymerization process or a polymerization process for producing a novel copolyester having a recycled content: terephthalic acid, isophthalic acid, trimellitic anhydride (or trimellitic acid), naphthalenedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid.

[0147]

[0161] According to some embodiments, the copolymerized polyester suitable for use in the polymerization process or in the polymerization process for producing a novel copolymerized polyester having a recycling content is a copolymerized polyester containing the following glycols: ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, p-xylene glycol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethylcyclobutane-1,3-diol, polytetramethylene glycol, isosorbide, or a mixture thereof.

[0148]

[0162] In one embodiment, a recycled waste material containing terephthalic acid polyester and / or copolyester may be used in the repolymerization step. In one embodiment, a terephthalate polyester or copolyester prepared by any conventional method may be used in the repolymerization step. In one embodiment, suitable terephthalic acid polyesters and / or copolyesters include polyethylene terephthalate (PET), glycol-modified polyethylene terephthalate (PETG), glycol-modified polycyclohexylene dimethylene terephthalate (PCTG), acid-modified polycyclohexylene dimethylene terephthalate (PCTA), polybutylene terephthalate (PBT), polypropylene terephthalate (PPT), polytrimethylene terephthalate (PTT), polycyclohexanedimethanol terephthalate (PCT), polyethylene naphthalate (PEN), TMCD-modified polyethylene terephthalate (PETM), TMCD-modified polycyclohexylene dimethylene terephthalate (PCTM), and mixtures thereof. In one embodiment, the terephthalic acid polyester is polyethylene terephthalate (PET). In one embodiment, the copolyester is PETG. In one embodiment, the copolyester is PCT. In one embodiment, the copolyester is PCTG. In one embodiment, the copolyester is PCTA. In one embodiment, the copolyester is PCTM. In one embodiment, the copolyester is PETM.

[0149]

[0163] In one embodiment, a mixture of terephthalate polyester and copolymerized polyester is combined and repolymerized together. In one embodiment, PET and PETG are combined and repolymerized together. In one embodiment, PET and PETM are combined and repolymerized together. In one embodiment, PET and PCT are combined and repolymerized together. In one embodiment, PET and PCTA are combined and repolymerized together. In one embodiment, PET and PCTG are combined and repolymerized together. In one embodiment, PET and PCTM are combined and repolymerized together. In one embodiment, PET, PETG, and PETM are combined and repolymerized together. In one embodiment, PET, PETG, and PCTM are combined and repolymerized together. In one embodiment, PET, PETG, PCTM, and PETM are combined and repolymerized together.

[0150]

[0164] In one embodiment, the copolymerized polyester suitable for use in the present disclosure is prepared from monomers such as dimethyl terephthalate (DMT), terephthalic acid (TPA), isophthalic acid (IPA), 1,4 - cyclohexanedicarboxylic acid (CHDA), ethylene glycol (EG), diethylene glycol (DEG), neopentyl glycol (NPG), 1,4 - cyclohexanedimethanol (CHDM), and 2,2,4,4 - tetramethyl - 1,3 - cyclobutanediol (TMCD).

[0151]

[0165] One embodiment of the present disclosure relates to a process for preparing a copolymerized polyester having a high concentration of recycled content, which is obtained by repolymerizing waste or post - consumer polyester containing terephthalic acid - containing polyester (e.g., PET) and / or copolymerized polyester (e.g., PETG) with water or alcohol or glycol and using recycled monomers to prepare a copolymerized polyester containing a high molar% of recycled monomer residues.

[0152]

[0166] In one aspect of the present disclosure, it is a high molecular weight copolyester containing a glycol component and a diacid component. The glycol component includes ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol, 1,2 - propanediol, 1,3 - propanediol, neopentyl glycol, 1,4 - butanediol, 1,5 - pentanediol, dimethyl 1,4 - cyclohexanedicarboxylate, dimethyl trans - 1,4 - cyclohexanedicarboxylate, 1,6 - hexanediol, p - xylene glycol, 1,4 - cyclohexanedimethanol, 2,2,4,4 - tetramethylcyclobutane - 1,3 - diol, polytetramethylene glycol, adipic acid, isosorbide, and mixtures thereof. The diacid component includes dimethyl terephthalate, terephthalic acid, isophthalic acid (IPA), trimellitic anhydride (or trimellitic acid), salts of 5 - sulfoisophthalic acid (SIPA), naphthalenedicarboxylic acid, 1,4 - cyclohexanedicarboxylic acid, and mixtures thereof. When a depolymerization aid or solvent such as water, alcohol, or excess glycol is introduced under conditions where a reversible transesterification reaction can occur, depolymerization by hydrolysis, alcoholysis, or glycolysis occurs, and the chain length (molecular weight) of the polymer decreases. When a sufficient amount of solvent is used, the reaction proceeds until the mixture consists mainly of monomers, glycols, and diesters of acid components. In one aspect, the glycol of the mixture includes ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol, 1,2 - propanediol, 1,3 - propanediol, neopentyl glycol, 1,4 - butanediol, 1,5 - pentanediol, dimethyl 1,4 - cyclohexanedicarboxylate, dimethyl trans - 1,4 - cyclohexanedicarboxylate, 1,6 - hexanediol, p - xylene glycol, 1,4 - cyclohexanedimethanol, 2,2,4,4 - tetramethylcyclobutane - 1,3 - diol, polytetramethylene glycol, adipic acid, isosorbide, and mixtures thereof.In one embodiment, the glycol of the mixture includes ethylene glycol, 1,2-propanediol, 1,3-propanediol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethylcyclobutane-1,3-diol, and mixtures thereof. In one embodiment, the glycol of the mixture includes ethylene glycol, neopentyl glycol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethylcyclobutane-1,3-diol, and mixtures thereof. These recycled monomers can then be used to prepare a copolyester containing a high mole % of recycled monomer residues.

[0153]

[0167] The present invention relates to a process for utilizing recycled polyethylene terephthalate (PET) and recycled glycol-modified polyethylene terephthalate copolymer polyester (PETG), particularly post-consumer waste, in the production of linear high molecular weight copolymer polyesters. There is an increasing demand to use a large amount of recycled materials in plastic articles. This demand for recycled content has created a need to develop new methods and processes for capturing existing plastic waste streams and converting them into new plastic products. In particular, there is growing interest in the recycling of PETG waste. In recent years, attempts have been made to legalize the separation of recycled glycol-modified PET (PETG) waste from recycled polyethylene terephthalate (PET) waste having resin identification code (RIC) 1 because problems have arisen in the treatment of these composite wastes. Furthermore, there is a large amount of PETG that has not been recycled today, but this has the potential to be recovered and converted into new plastic products. In particular, shrink films made of PETG contain inks and other contaminants that need to be removed in the recycling stream in order to produce high-quality transparent recycled PET (rPET). In addition, medical packaging materials are manufactured from a high proportion of PETG, and this material is not currently part of the recycling stream. The present invention provides a process for utilizing recycled PETG and recycled PETG combined with recycled PET as reaction intermediates in the production of copolymer polyesters useful in the manufacture of shrink films, fibers, durable consumer goods, and other extruded and injection molded articles such as molded products and moldings.

[0154]

[0168] Today, there is a very well-defined and large-scale mechanical recycling process in which polyethylene terephthalate (PET) articles are recycled and converted into semi-crystalline recycled PET (rPET), which is then incorporated into new plastic articles. Glycol-modifying PET with other glycols such as 1,4-cyclohexanediol, diethylene glycol, butanediol, or neopentyl glycol is a very common way to increase transparency, improve toughness, and lower the crystallinity of PET. These glycol-modified materials are generally called glycol-modified PET or PETG. Although the chemical composition of these materials is very similar to that of PET, modifying with glycols other than ethylene glycol produces materials that are difficult to recycle in the PET recycling process. To recycle and reuse these PETG materials, new methods need to be developed.

[0155]

[0169] In the process described in this disclosure, recycled PETG is used as a feedstock to produce various new copolyester resins. In this process, recycled PETG (rPETG) is introduced as a paste together with ethylene glycol and terephthalic acid and fed into a transesterification reactor at the beginning of the manufacturing process to produce a new copolyester. During this process, the added glycol decomposes rPETG into its original acid residue and glycol residue starting materials, new glycol and acid are added, and then the mixture is esterified and polymerized to produce a new copolyester. This process has the advantage that there is no need to further purify the acids and glycols produced, and recycled PETG can be used as a raw material. Furthermore, this process is valuable because it does not currently ride on the mechanical recycling stream and thus provides a way to use rPETG, which otherwise would have to be landfilled at a waste disposal site.

[0156]

[0170] Furthermore, rPETG (or rPCTG, or rPCTM, or rPETM, or rPCTA, or rPCTG, or rPCT) contains di- or higher-valent expensive monomers such as CHDM, TMCD, DEG, and NPG that are not present in rPET. PETG products manufactured from this process have the same performance as unused PETG and can be used for exactly the same applications without sacrificing any performance due to the addition of recycled materials. Conventionally, rPETG has been physically mixed with unused materials to produce a mixture. These mixtures often lose performance with respect to mechanical properties or color tone and appearance and often cannot be used for the same applications as unused materials.

[0157]

[0171] In the synthesis of new PET for manufacturing bottles for water and carbonated beverages, it has become commercially desirable to use PET that has been used in the past, particularly post-consumer PET. Several chemical treatment techniques are known for facilitating the recycling and reclamation of polyester materials that have been used in the past. Such techniques are used to depolymerize the recycled polyester material, thereby reducing the polyester material to monomeric components and / or oligomeric components. The monomeric components and / or oligomeric components can then be repolymerized to produce a recycled polyester material.

[0158]

[0172] As one known depolymerization technique, recycled PET is subjected to methanolysis. According to the methanolysis method, rPET is reacted with methanol to produce dimethyl terephthalate (DMT) and ethylene glycol (EG). DMT and EG can be easily purified and then used in the production of PET including recycled polyester materials. However, most of the conventional commercial PET manufacturing facilities worldwide are designed to use any terephthalic acid (TPA), and although there are small-scale facilities that use DMT, most facilities are not designed to use both TPA and DMT as monomer raw materials. Therefore, generally, additional processing is required to convert DMT to TPA, which is necessary as a raw material for many such facilities, and in any case, further purification of glycol and DMT / TPA is required.

[0159]

[0173] Another known depolymerization technique is hydrolysis, by which recycled PET is reacted with water to depolymerize rPET into TPA and EG. However, it is generally known that removing certain contaminants present in recycled PET from TPA is very difficult and expensive. Furthermore, in facilities designed to use DMT as a raw material, it is necessary to convert TPA to DMT, and further purification of glycol and DMT / TPA is required.

[0160]

[0174] Glycolysis may also be used for the depolymerization of recycled PET. Glycolysis occurs when rPET reacts with EG, thereby producing bis-(2-hydroxyethyl) terephthalate (BHET) and / or its oligomers. Glycolysis has a greater advantage than either methanolysis or hydrolysis, mainly because BHET can be used as a raw material in the production process of either DMT-based PET or TPA-based PET without major changes to the manufacturing facility or further purification. Another important advantage provided by the glycolysis technique is that there is no need to remove glycol from the depolymerization solvent.

[0161]

[0175] Known glycolysis processes have included the independent complete glycolysis of post-consumer rPET and the subsequent addition of the glycolysis products to a polycondensation process. This glycolysis process is described in U.S. Patent No. 5,223,544. This process requires high pressure and a large excess of ethylene glycol. These requirements result in a decrease in reactor efficiency due to a decrease in the potential production capacity of the reactor.

[0162]

[0176] Typically, these glycolysis processes have been found to require high temperatures and a large excess of EG to solubilize the polyester molecules so that they can be broken down into their components such as BHET and its oligomers. This high temperature and excess EG result in a large amount of diethylene glycol as a byproduct. The diethylene glycol thus produced cannot be easily removed from BHET, and thus when producing recycled PET using BHET, the resulting PET product will have an excessive diethylene glycol content and will be a polymer that is unacceptable for many commercial applications.

[0163]

[0177] Other known processes involving glycolysis require retaining the ends of BHET oligomers having a degree of polymerization greater than 10 in the reactor in order to solubilize post-consumer rPET, which is mostly insoluble in most solvents. These procedures are described in U.S. Patent No. 4,609,680. Thus, in the production of new packaging-grade PET, there clearly remains a need in the art for a glycolysis process that can efficiently process post-consumer rPET that has been used in the past.

[0164]

[0178] The present disclosure provides a solution to the problems considered above. In particular, the process of the present disclosure utilizes recycled polyester and / or recycled copolyester containing recycled PET, recycled PETG, recycled PETM, and recycled PCTM, or mixtures of these materials to provide an efficient and economical procedure for manufacturing packaging-grade polyester products.

[0165]

[0179] In one embodiment, the viscosity of the materials in the kneading zone and the viscosity of the materials occurring in the kneading zone are significantly reduced by rPETG (and its mixture with rPCTM or rPET) as compared to rPET alone. In one embodiment, TPA dissolves faster in rPET than in EG alone. In one embodiment, TPA can dissolve even faster in rPETG, rPETM, or rPCTM.

[0166]

[0180] In one embodiment, TPA is completely replaced with recycled polyester or copolyester.

[0181] In one embodiment, the composition control of the final polyester product is performed by the combination of the recycled feedstock and the components added to the first reaction zone.

[0167]

[0182] In one embodiment of the present disclosure, the copolyester is manufactured in two main stages. In the first stage, the starting materials are reacted to produce monomers and / or oligomers. When the starting materials entering the first stage contain acid end groups such as TPA or isophthalic acid, the first stage is called esterification. The esterification stage may be a single step or may be divided into multiple steps. In the second stage, the monomers and / or oligomers are further reacted to produce the final copolyester product. The second stage is generally called the polycondensation stage. The polycondensation stage may be a single step or may be divided into a prepolycondensation (or prepolymerization) step and a final (or finishing) polycondensation step.

[0168]

[0183] Figure 6 is a flow diagram of a process for manufacturing a copolymer polyester such as polyester or PETG according to various embodiments of the present disclosure. This flow diagram (Figure 6) shows the reaction zones as separate vessels, typically continuous stirred tank reactors (CSTRs), although these vessels may be an integrated unit having multiple esterification zones with appropriate partitions and controls. Similarly, the reaction zones are typically shown as separate vessels that are wiped film or thin film CSTRs, although these vessels may be combined into one or more integrated units having multiple polycondensation zones with appropriate partitions and controls. Various other types of esterification reactors and polycondensation reactors as well as reactor configurations are known in the art and may be adapted for use in accordance with the present disclosure.

[0169]

[0184] Referring to Figure 6, in one embodiment, a paste comprising EG and TPA in a 2:1 molar ratio and constituting the recycled copolymer polyester and / or polyester is fed to a location designated as the paste tank. Additional EG is fed to the first reaction zone or reactor 1, and other glycols such as CHDM, TMCD, NPG, and DEG may also be fed to the first reaction zone based on the target final composition of the copolymer polyester, and additional recycled materials may also be added as needed. In one embodiment, these raw materials may be added separately and / or directly into the first reaction zone. Depending on the embodiment, the recycled copolymer polyester and / or polyester is fed to at least one location among the paste tank, zone #1, zone #2, or the finishing zone. Depending on the embodiment, the recycled copolymer polyester and / or polyester is fed to one or more locations among the paste tank, zone #1, zone #2, or the finishing zone.

[0170]

[0185] The reaction mixture in the first reaction zone is heated via a recycle loop that includes a heat exchanger. Esterification occurs in the first reaction zone, producing a first esterification product that includes monomers, oligomers, or both of the copolyester, and unreacted TPA, EG, and other glycols such as CHDM, TMCD, NPG, or DEG. The reaction product of the first reaction zone is then delivered to the second reaction zone. Further esterification occurs in the second reaction zone, forming a second esterification product that includes additional monomers, oligomers, or both of the copolyester.

[0171]

[0186] In some embodiments, the average chain length of the monomers and / or oligomers at the end of the esterification stage may be less than 25, 1 to 20, or 5 to 15.

[0187] In one embodiment, the second reaction zone is optional. In some embodiments, the product is delivered from the first reaction zone to the third reaction zone.

[0172]

[0188] The reaction product of the second reaction zone is then delivered to the third reaction zone. In some embodiments, polycondensation occurs in the third reaction zone, optionally in the presence of a polycondensation catalyst, producing a prepolymerization product that includes copolyester oligomers. In some embodiments, polycondensation occurs in the third reaction zone without the need for a polycondensation catalyst, producing a prepolymerization product that includes copolyester oligomers. In some embodiments, the recycled copolyester and the catalyst residues remaining in the polyester are sufficient to act as a polycondensation catalyst. In some embodiments, in the third reaction zone, monomers from the esterification stage are converted to oligomers having an average chain length in the range of 2 to 40, 5 to 35, or 10 to 30.

[0173]

[0189] Next, the prepolymerization product is delivered to one or more reaction zones or finishing zones. Further polycondensation occurs in the finishing zone in the presence of a polycondensation catalyst as needed, producing a copolymer polyester having the desired average chain length or IV. The copolymer polyester is then recovered from the finishing zone and subjected to subsequent processing such as forming into pellets via an extruder connected to a underwater pelletizer.

[0174]

[0190] In one embodiment, the temperature in the kneading tank is 120 - 180 °C.

[0191] In one embodiment, the temperature in the glycolysis and transesterification zone is 200 - 300 °C.

[0175]

[0192] In one embodiment, the reaction step is carried out at a melting temperature of at least 253 °C, at least 255 °C, or at least 257 °C. In one embodiment, further or alternatively, the reaction step is carried out at a melting temperature of 290 °C or less, 285 °C or less, 280 °C or less, 275 °C or less, 270 °C or less, or 265 °C or less. In various embodiments, the reaction step is carried out at a melting temperature of 250 - 270 °C, or 257 - 265 °C.

[0176]

[0193] In one embodiment, the reaction step is carried out at a pressure of 25 - 40 psi, or 30 - 40 psig.

[0194] In one embodiment, the esterification step is carried out at a melting temperature of at least 253 °C, at least 255 °C, or at least 257 °C. In one embodiment, further or alternatively, the esterification step is carried out at a melting temperature of 290 °C or less, 285 °C or less, 280 °C or less, 275 °C or less, 270 °C or less, or 265 °C or less. In various embodiments, the esterification step is carried out at a melting temperature of 250 - 270 °C, or 257 - 265 °C.

[0177]

[0195] In one embodiment, the esterification step (d) is carried out at a pressure of 8 - 20 psig.

[0196] In one embodiment, the average residence time of the reactants in the reaction step is 2 hours or less, 1.75 hours or less, 1.5 hours or less, 1.25 hours or less, 1 hour or less, or 0.75 hours or less. In various embodiments, the average residence time of the reactants in the reaction step is 30 minutes to 40 minutes.

[0178]

[0197] In one embodiment, the average residence time of the reactants in the esterification step is 2 hours or less, 1.75 hours or less, 1.5 hours or less, 1.25 hours or less, 1 hour or less, or 0.75 hours or less. In various embodiments, the average residence time of the reactants in the esterification step (d) is 30 to 40 minutes.

[0179]

[0198] In various embodiments, the overall molar ratio of EG:TPA introduced into the process ranges from 2.3:1 to 3.0:1.

[0199] In various embodiments, the overall molar ratio of EG:TPA introduced into the process ranges from 2.3:1 to 2.71:1.

[0180]

[0200] The temperature, pressure, and average residence time of the reaction step in the first reaction zone are as described above.

[0201] In various embodiments, the reaction step in the first reaction zone is carried out at a melting temperature of 250 - 270 °C and a pressure of 25 - 40 psi.

[0181]

[0202] In various embodiments, the reaction step in the first reaction zone is carried out at a melting temperature of 257 - 265 °C and a pressure of 30 - 40 psi.

[0203] The temperature, pressure, and average residence time of the esterification step in the second reaction zone may be as described above.

[0182]

[0204] In various embodiments, the esterification step in the second reaction zone is carried out at a melting temperature of 250 - 270 °C and a pressure of 8 - 20 psi.

[0205] In various embodiments, the esterification step in the second reaction zone is carried out at a melting temperature of 257-265 °C and a pressure of 8-20 psi.

[0183]

[0206] The polycondensation catalysts useful in the processes of the present disclosure are not particularly limited. Examples of such catalysts include titanium-based compounds, antimony-based compounds, and germanium-based compounds. Titanium catalysts are very efficient and provide a fast polycondensation rate at low catalyst concentrations. The polycondensation catalyst may be added either during the esterification stage or during the polycondensation stage. In one embodiment, these catalysts are added to the first reaction zone together with the feed materials. In one embodiment, the catalyst is added in the range of 1-500 ppm based on the weight of the copolyester. In the case of titanium in one embodiment, the catalyst may be added in the range of 1-50 ppm based on the weight of the copolyester.

[0184]

[0207] In one embodiment, the choice of catalyst is influenced by the catalyst derived from the recycled raw materials. The advantages of a particular catalyst are achieved by the combination of the catalyst from the raw materials and the catalysts added to the first and second reaction zones. Catalysts that are likely to be obtained from rPET include Sb and Li / Al. Catalysts that may be obtained from rPETG are Ti, Co, Ge, and Sb. Catalysts obtained from rPETM and rPCTM contain Co.

[0185]

[0208] In some embodiments, in order to improve thermal stability, a phosphorus compound is often added together with the catalyst. Phosphorus compounds useful as heat stabilizers include phosphoric acid, phosphorous acid, phosphonic acid, phosphinic acid, phosphonous acid, and various esters and salts thereof. The ester may be alkyl, branched alkyl, substituted alkyl, difunctional alkyl, alkyl ether, aryl, and substituted aryl. In some embodiments, a suitable heat stabilizer includes Merpol A which is triphenyl phosphate. In one embodiment, phosphorus is added in the range of 10-100 ppm based on the weight of the copolyester.

[0186]

[0209] In various embodiments, one or more other additives may be added to the starting materials, the copolyester, and / or the copolyester monomer / oligomer at one or more positions within the process. In various embodiments, suitable additives include, for example, trifunctional or tetrafunctional comonomers such as trimellitic anhydride, trimethylolpropane, pyromellitic dianhydride, pentaerythritol, or other polyacids or polyols; crosslinking agents or other branching agents; colorants; toners; pigments; carbon black; glass fibers; fillers; impact modifiers; antioxidants; ultraviolet light absorbing compounds; deoxygenating compounds, and the like.

[0187]

[0210] The processes according to the present disclosure are particularly suitable for use on an industrial scale. For example, in one embodiment, those processes may be carried out in a commercial production line capable of operating at a rate of 500 to 30,000 pounds per hour of polymer.

[0188]

[0211] In another aspect, the present disclosure relates to a copolyester produced from the processes of the present disclosure.

[0212] Furthermore, according to the aforementioned process, the new polyester product may contain ethylene glycol, diethylene glycol, and 1,4-cyclohexanedimethanol diol units, and this 1,4-cyclohexanedimethanol unit may account for up to about 25 mol% of all the diol units, and this diethylene glycol may account for up to about 15 mol% of all the diol units. In this case, the 1,4-cyclohexanedimethanol unit and the diethylene glycol unit may be directly added to a part of the ethylene glycol component in the first reaction mixture, or may be derived from a part of the flake material of polyethylene terephthalate or glycol-modified polyethylene terephthalate after consumption.

[0189]

[0213] In various embodiments, the copolyester (a) a diacid component containing 60 to 100 mol% of terephthalic acid residues, isophthalic acid residues, or a mixture residue thereof; and (b) It contains a diol component comprising 0 to 96.5 mol% of ethylene glycol residues and 3.5 to 100 mol% of 1,4-cyclohexanedimethanol residues, wherein the diacid component is based on 100 mol% of all diacid residues in the copolyester, and the diol component is based on 100 mol% of all diol residues in the copolyester.

[0190]

[0214] In various embodiments, the copolyester (a) a diacid component containing 90 to 100 mol% of terephthalic acid residues; and (b) a diol component containing 50 to 96.5 mol% of ethylene glycol residues and 3.5 to 50 mol% of 1,4-cyclohexanedimethanol residues, wherein the diacid component is based on 100 mol% of all diacid residues in the copolyester, and the diol component is based on 100 mol% of all diol residues in the copolyester.

[0191]

[0215] In various embodiments, the copolyester (a) a diacid component containing 90 to 100 mol% of terephthalic acid residues; and (b) a diol component containing 0 to 50 mol% of ethylene glycol residues and 50 to 100 mol% of 1,4-cyclohexanedimethanol residues, wherein the diacid component is based on 100 mol% of all diacid residues in the copolyester, and the diol component is based on 100 mol% of all diol residues in the copolyester.

[0192]

[0216] In various embodiments, the copolyester (a) a diacid component containing 60 to 100 mol% of terephthalic acid residues; and (b) a diol component containing 65 to 85 mol% of ethylene glycol residues and 25 to 35 mol% of 1,4-cyclohexanedimethanol residues, Here, the diacid component is based on 100 mol% of all diacid residues in the copolyester, and the diol component is based on 100 mol% of all diol residues in the copolyester.

[0193]

[0217] In various embodiments, the intrinsic viscosity of the copolyester is 0.4 to 1.5 dL / g or 0.5 to 1.2 dL / g or 0.6 to 0.9 dL / g.

[0218] In various other embodiments, the copolyester (a) a diacid component containing 100 mol% of terephthalic acid residues, isophthalic acid residues, or a mixture residue thereof; and (b) a diol component containing 0 to 96.5 mol% of ethylene glycol residues, 3.5 to 100 mol% of 1,4-cyclohexanedimethanol residues, and 0 to 0.4 mol% of trimellitic anhydride residues, wherein the intrinsic viscosity (IV) of the copolyester is 0.4 to 1.5 dL / g, all weight percentages are based on the total weight of the copolyester, and the diacid component is based on 100 mol% of all diacid residues in the copolyester, and the diol component is based on 100 mol% of all diol residues in the copolyester.

[0194]

[0219] In one embodiment, the present disclosure includes a manufactured article or a molded article including a shrink film of any of the embodiments of the shrink film of the present disclosure. In another embodiment, the present disclosure includes a manufactured article or a molded article including an oriented film of any of the embodiments of the oriented film of the present disclosure.

[0195]

[0220] In certain embodiments, the present disclosure includes, but is not limited to, containers, plastic bottles, glass bottles, packaged goods, batteries, high-temperature filling containers, and / or shrink films suitable for industrial products or other applications. In one embodiment, the present disclosure includes, but is not limited to, containers, packaged goods, plastic bottles, glass bottles, photographic substrates such as paper, batteries, high-temperature filling containers, and / or oriented films suitable for industrial products or other applications.

[0196]

[0221] In certain embodiments of the present disclosure, the shrink film of the present disclosure may be formed into a label or a sleeve. The label or sleeve may then be applied to the wall of a container, a manufactured article such as a battery, or onto a sheet or film.

[0197]

[0222] The oriented film or shrink film of the present disclosure can be applied to molded articles such as sheets, films, tubes, bottles, etc., and is commonly used in various packaging applications. For example, films and sheets made from polymers such as polyolefin, polystyrene, polyvinyl chloride, polyester, polylactic acid (PLA), etc. are frequently used in the manufacture of shrink labels for plastic beverage containers or food containers. For example, the shrink film of the present disclosure can be used in many packaging applications, in which the shrink film applied to the molded article exhibits properties such as excellent printability, high opacity, excellent shrink force, excellent texture, and high rigidity.

[0198]

[0223] The combination of improved shrinkage characteristics and improved toughness should provide new commercial options, including shrink films that are suitable for, but not limited to, containers, plastic bottles, glass bottles, packaging products, batteries, hot-fill containers, and / or industrial products or other applications.

[0199]

[0224] Furthermore, the materials of the present disclosure may be extruded into a sheet, which may be further thermoformed into a three-dimensional article. The materials of the present disclosure may be converted into molded articles, films, shrinkable films, oriented films, blow-molded articles, and blow-film articles.

[0200]

[0225] The present disclosure includes any and all combinations of the embodiments, features, characteristics, parameters, and / or ranges described herein, and those combinations are explicitly contemplated and disclosed. That is, the subject matter of the present disclosure can be defined by any combination of the embodiments, features, characteristics, parameters, and / or ranges described herein.

[0201]

[0226] Any process / method, apparatus, compound, composition, embodiment, or component of the present disclosure may be modified by a transitional phrase that is "comprising," "consisting essentially of," or "consisting of," or variations of those terms.

[0202]

[0227] As used herein, the indefinite articles "a" and "an" mean one or more unless clearly indicated otherwise in context. Similarly, the singular form of a noun includes its plural form and vice versa unless clearly indicated otherwise in context.

[0203]

[0228] Although attempts have been made to be precise, the numerical values and ranges described herein should be considered approximations unless otherwise specifically indicated in context. These numerical values and ranges may vary from the recited values due to the desired characteristics to be obtained by the present disclosure, as well as variations resulting from the standard deviation found in measurement techniques. Further, the ranges described herein are intended and specifically contemplated to include all sub-ranges and numerical values within the recited range. For example, the range of 50 to 100 is intended to include all numerical values within the range that includes sub-ranges such as 60 to 90, 70 to 80, etc.

[0204]

[0229] Any two numerical values of the same characteristic or parameter reported in the examples may define a range. Those numerical values may be rounded to the nearest thousandth, hundredth, tenth, integer, ten, hundred, or thousand for the purpose of defining the range.

[0205]

[0230] The contents of all documents cited herein, including patent documents and non-patent documents, are hereby incorporated by reference in their entirety. If any incorporated subject matter conflicts with any disclosure herein, the disclosure herein shall prevail over the incorporated content.

[0206]

[0231] The present disclosure can be further illustrated by the following examples. Of course, these examples are included for illustrative purposes only and are not intended to limit the scope of the present disclosure. Unless otherwise indicated, parts are by weight, temperature is in °C (Celsius) or at room temperature, and pressure is atmospheric or near atmospheric.

Example

[0207]

[0232] The present disclosure is further illustrated by the following examples of its embodiments. Needless to say, these examples are included for illustrative purposes only and are not intended to limit the scope of the present disclosure, unless otherwise indicated.

[0208] Comparative Example 1

[0233] Table 1 shows the shrink film properties of a standard polyester shrink film resin (sample SPR) (this standard resin is commercially available from Eastman Chemical). The shrink film made using this standard shrink film resin is designated as Comparative Example #1.

[0209]

[0234] The shrinkage properties are shown in Figure 2. The shrinkage rate is measured in the temperature range of 60 - 95 °C in the main shrinkage direction (TD direction) and the direction perpendicular to the main shrinkage direction (MD direction). The melting point of the strain-induced crystals is measured using a differential scanning calorimeter (DSC) for the stretched film (Figure 1). Also, the crystallinity of the sample can be evaluated by crystallizing the pellet sample in an oven at 170 °C for 2 hours. The melting point of the strain-induced crystals is measured by the first heating at a heating rate of 20 °C / min. However, the resins described in the present disclosure typically do not have a melting point of crystals that can be measured by the second heating in the DSC procedure at a heating rate of 20 °C / min.

[0210]

Table 1

[0211]

[0235] The Association of Plastic Recyclers (APR) constructed a test to measure whether materials are compatible with the current recycling process (PET-CG-03). Using this test method, labels (minimum weight: 3% by weight) and bottles were shredded to flake dimensions of 1 / 4 to 1 / 2 inch. The bottle flakes were then mixed 50:50 with reference bottle flakes without labels. Next, the sample was wet classified under conditions that permit up to 1.2% PET to be carried over with labels. The flakes were washed at 88 °C for 15 minutes with 0.3% Triton X-100 and 1.0% caustic alkali. Subsequently, the flakes were washed with water after removing all suspended matter, then filtered to remove excess water. The flakes were wet classified again as before. Subsequently, 2 pounds of washed flakes were placed in a Teflon®-coated baking dish for each washed sample, and the flakes were added until a layer thickness of 1.5 inches was reached. The dish containing the flakes was placed in a circulating oven at 208 °C for one and a half hours. The flakes were cooled and then passed through a sieve with an opening of 0.0625 inch. If the material passes through the sieve, the material is not aggregated, i.e., not overly coarsened so as not to pass through the sieve. Following this test, each step of extrusion / pelletization and molding was performed to confirm the quality of the flakes.

[0212]

[0236] The film samples described in Table 1 produce more than 1% by weight of lumpy PET flakes when using this APR test, so their use in PET recycling will be approved. Therefore, labels made of this type of resin need to be removed prior to the PET recycling process to eliminate lumping of the processed PET flakes. However, the crystallizable films in the present disclosure are more compatible with the recycling process and can be recycled together with PET flakes, so this crystallizable film composition will provide benefits in the recycling process.

[0213]

[0237] The crystallizable compositions described in this disclosure are designed to be compatible with the recycling process. To make them compatible with the recycling process, the crystallizable film is designed not to become "sticky" during the drying process at 208 °C, as described in the APR test. However, this film also needs to meet the performance criteria typically required for shrink films (such as high maximum shrinkage rate, low to negative MD shrinkage rate, etc.). To meet both of these requirements, i.e., recyclability and excellent shrinkage properties, the polyester composition needs to be amorphous, i.e., the composition should not contain crystallinity when measured using the second heating at a heating rate of 20 °C per minute in DSC. However, after stretching, the film made from the optimized polyester resin composition needs to contain a melting peak of strain-induced crystals above 200 °C measured during the first heating when using a DSC operating at a heating rate of 20 °C per minute. This level of strain-induced crystallinity can prevent stickiness during the drying process associated with recycled PET flakes. Therefore, the optimized polyester resin composition of this disclosure can be described as amorphous but crystallizable.

[0214]

[0238] The following examples further illustrate how the polyesters of this disclosure can be made and evaluated, and these examples are intended to be purely illustrative and not to limit the scope thereof. Unless otherwise indicated, parts are by weight, temperature is in °C (Celsius) or at room temperature, and pressure is atmospheric or near atmospheric.

[0215]

[0239] This disclosure can be further illustrated by the following examples of its preferred embodiments, which of course are included for illustrative purposes only and are not intended to limit the scope of this disclosure unless otherwise indicated.

[0216] Example 1

[0240] To more clearly understand these performance goals, a series of copolyester with various CHDM and DEG contents were produced using procedures well-known to those skilled in the art of manufacturing polyester. After synthesis, these resins were ground into powders and compressed into 10-mil film samples using a hot press. The compressed films were then stretched using a film stretcher manufactured by Bruckner so that the properties of the shrink film could be measured. The ground samples were crystallized at 170 °C for 2 hours in a forced-air circulation oven so that the crystal melting point could be measured. This crystallized sample was used as a proxy for the melting peak of the strain-induced crystals present after stretching. The details of the experiment are summarized in Table 2. Comparative Example 1 (Film #L-1 / Resin Sample SPR) was also prepared and evaluated as a control.

[0217]

Table 2

[0218]

[0241] The data in Table 2 show that resin samples with an amorphous monomer content (in this case DEG + CHDM) of less than 24 have a melting peak of crystals above 200 °C after heat treatment. The composition of Film #L-5 was then scaled up in a larger reactor to produce shrink films using a commercially available film extruder. The shrinkage properties of this film are shown in Figure 3 together with the sample of Comparative Example 1 (Resin SPR). The composition of Film A was the same as that of Film #L-5.

[0219]

Table 3

[0220]

[0242] Table 3 summarizes the comparison between Sample SPR and Film Sample A. From this data, it can be seen that the Film A composition does not shrink in a form similar to Comparative Example #1. The maximum shrinkage rate (shrinkage rate in the main shrinkage direction, i.e., TD, at 95 °C) is 17% lower than that of Comparative Example #1. Furthermore, the shrinkage rate in the direction orthogonal to the main shrinkage direction (MD shrinkage rate) is actually positive (7%) in Sample A compared to Comparative Example #1. A positive MD shrinkage rate is not desirable.

[0221] Example 2

[0243] Neopentyl glycol (NPG) is another glycol monomer that can produce an amorphous copolyester composition. It was thought that by adding NPG instead of CHDM, it was possible to reduce the MD shrinkage rate. To examine this effect in more detail, another resin sample with a similar composition containing NPG instead of CHDM was prepared. This new resin sample was mixed with the resin used in the production of L-5 to examine the effect of monomer substitution. These resins were extruded into 10-mil films and then drawn on a film drawing machine manufactured by Bruckner. Tests of these films gave the following results: When the CHDM content is less than 8 mol%, the MD shrinkage rate at 75 °C is 0%; when the CHDM content is further reduced, the MD shrinkage rate becomes negative and shows expansion instead of shrinkage. Further, the effect of the amorphous monomer content was confirmed. All the samples shown in Table 4 have an amorphous monomer content exceeding 23. Subsequently, the melting point of the strain-induced crystals of these compositions was less than 200 °C. This melting point of the strain-induced crystals less than 200 °C is too low to pass the APR test. Typically, for the APR test to be passed, the melting point of the strain-induced crystals needs to exceed 200 °C. From this examination, it was determined that it is necessary to further reduce the amorphous monomer to ensure a melting point of the strain-induced crystals exceeding 200 °C. Also, in some cases, it is necessary to make the CHDM content less than 10 mol% to ensure the production of a film having the minimum shrinkage rate in the direction orthogonal to the main shrinkage direction (MD direction).

[0222]

Table 4

[0223] Example 3

[0244] Next, a series of resins were produced, extruded into 10-mil films using a 2.5-inch Davis and Standard extruder, stretched, and then their shrink film properties were evaluated to compare shrinkage characteristics and crystallinity. The details of these resin compositions and the performance of the shrink films made from these resin compositions are shown in Table 5. From this analysis, an optimal resin composition was designed that gives a low MD shrinkage rate at 75 °C and a melting point of strain-induced crystals above 200 °C. This optimized resin composition contains 10 mol% NPG, 5 mol% CHDM, and 5 mol% DEG. Also in this case, resins containing less than 24 mol% amorphous monomer content were judged to have a melting point of strain-induced crystals above 200 °C. Also, when the content of the CHDM monomer is less than 10 mol%, the MD shrinkage rate is minimized.

[0224]

Table 5

[0225]

Table 6

[0226] Example 4

[0245] Next, some of these resins were tested in an aggregation test that mimics the APR protocol to evaluate the effect of the melting point (Tm) on aggregation. The parameters of the aggregation test are as follows. · Approximately 135 g of PET flakes per sample; and approximately 3.4 g of shrink film in its shrunk state (2.5% film with the flakes). · The PET flakes and film were placed in an aluminum dish to a depth of 1.5 inches. · The dish containing the flakes was placed in a forced-air circulation oven at an oven temperature of 208 °C for 1.5 hours.

[0227]

[0246] The results of these tests are illustrated in Table 7.

[0228]

Table 7

[0229] Comparative Example 2

[0247] Films made from these compositions with an amorphous monomer content of less than 20 (and thus a DEG content of less than 12) were also extremely tough. The toughness of these films was measured using ASTM method D882. Films having an elongation at break of more than 300% at a tensile speed of 300 mm / min and further at a tensile speed of 500 mm / min are considered tough.

[0230]

[0248] Using other film structures, these crystallizable polyester shrink film resins can be manufactured. For example, a multilayer film may be formed in which the core of the film is made of one type of amorphous shrink film resin (e.g., Comparative Example #1) and the skin is made of the crystallizable shrink film resin of the present disclosure. In this structure, the properties of the shrink film are similar to those of the core layer, but the skin exhibits a degree of crystallinity such that the amount of lumping can be reduced during recycling. Further, mixtures of various commercially available resin compositions may be prepared to replicate the resin composition of the reactor-grade resin. In any case, it is necessary to evaluate the performance of the resulting shrink film for effectiveness in shrink film applications. The configurations of these shrink films are shown in Table 12. These films were manufactured using a commercially available film extruder and evaluated for their performance in these shrink film applications.

[0231]

[0249] Standard sample E21, sample E12, sample SP, and sample SPR were evaluated. All standard samples evaluated are commercially available from Eastman Chemical. Samples E226, E213, and E2616 were manufactured in the laboratory using procedures well known to those skilled in the art of manufacturing copolyester.

[0232]

Table 12

[0233]

Table 13

[0234]

Table 14

[0235]

[0250] As can be seen in the examples of these mixtures, many of the properties of the resulting shrink films meet the desired properties of the compositions of the present disclosure. However, two of the film examples have a large MD shrinkage rate at 75 °C. In these examples, however, the melting point of the strain-induced crystals is higher (235 - 240 °C). This higher melting point of the strain-induced crystals can be advantageous in applications where a higher melting point is required, but these high melting points result in a higher MD shrinkage rate, so it is necessary to achieve a good balance of properties. Details of the tests

[0251] The resin samples were dried in a dehumidifying dryer at 60 °C and then mixed and extruded into films using two different processes. In the laboratory-scale extruder process, a 2.5-inch Davis and Standard extruder was used to extrude a film with a thickness of 10 mils (250 μm). After extrusion, the film was cut and drawn to a final thickness of 50 μm at a draw ratio of approximately 5:1 at a temperature 10 - 15 °C higher than the Tg using a Bruckner Karo 4-width draw machine. In the commercial process, the film was produced in a commercial width draw process where the extruded film was drawn immediately after extrusion. These films were drawn to a thickness of 50 μm at a draw ratio of approximately 5:1 under conditions almost identical to those of the films produced in the laboratory-scale process.

[0236]

[0252] In the experimental-scale compression film process, the resin is dried in vacuo overnight (about 12 hours) in an oven set at a temperature slightly below the Tg of the material. After drying, 8.00 g of the resin is weighed and placed between two metal plates according to the resin-Capton film-plate configuration surrounded by a plate-Capton film-10-mil square spacer. Before inserting this assembly into the press, the press platens are heated to a temperature about 100 °C higher than the Tm of the resin. The assembly is then inserted between the press platens and sufficient force is applied to the plates such that the resin is completely melted. After melting the resin for 3 minutes, the pressure is increased to 12,000 psi over 1.5 minutes. Next, the "bubble bump" procedure is performed. That is, release of pressure from 12,000 psi to 0 psi and increase to 13,000 psi; immediately release of pressure to 0 psi again and increase to 14,000 psi; repetition of 1000 psi increments until 16,000 psi is achieved and holding of the pressure at 16,000 psi for 1.5 minutes. Thereafter, the resin / plate assembly is removed from the press and withdrawn from the spacer using a razor blade. As a result, a 6×6 square 10-mil film suitable for stretching on a Bruckner width stretcher is obtained.

[0237]

[0253] The glycol content of the extruded film composition was measured by NMR. All NMR spectra were recorded on a JEOL Eclipse Plus 600 MHz nuclear magnetic resonance spectrometer using either chloroform-trifluoroacetic acid (70-30 volume / volume) for polymers or 60 / 40 (weight / weight) phenol / tetrachloroethane for oligomer samples, together with deuterated chloroform added for locking. The acid component of the mixed polymers used in the examples herein was 100 mol% terephthalic acid. The total mol% of the glycol component was equal to 100 mol%, and the total mol% of the acid component was equal to 100 mol%.

[0238]

[0254] In this specification, the intrinsic viscosity of the polyester was measured in 60 / 40 (weight / weight) phenol / tetrachloroethane at a concentration of 0.5 g / 100 mL at 25 °C. The viscosity is expressed in dL / g.

[0239]

[0255] In this specification, the shrinkage rate is measured by placing a 100 mm × 100 mm square film sample in water at 65°C to 95°C for 10 seconds without restricting shrinkage in any direction. At that time, the shrinkage rate is calculated by the following formula.

[0240] Shrinkage rate (%) = [(100 mm - length after shrinkage) / 100 mm] × 100%.

[0256] The shrinkage rate was measured in the direction perpendicular to the main shrinkage direction (machine direction: MD) and also in the main shrinkage direction (transverse direction: TD).

[0241]

[0257] In the examples of this specification, the shrinkage force was measured in MPa using an FST-02 thermal shrinkage tester manufactured by LabThink.

[0258] The tensile film properties were measured for the examples of this specification using the ASTM method D882. The films were evaluated using multiple film draw speeds (300 mm / min and 500 mm / min).

[0242]

[0259] The glass transition temperature and the melting point of strain-induced crystals (Tg and Tm, respectively) of the polyester are measured using a TA DSC 2920 manufactured by Thermal Analyst Instrument at a scanning rate of 20°C / min. Tm is measured in the first heating of the drawn sample, and Tg is measured during the second heating step. Furthermore, the sample can be crystallized in a forced air circulation oven at 170°C for 2 hours and then analyzed by DSC. For all samples, during the second heating of the DSC scan at a heating rate of 20°C / min, the melting point of the crystals typically does not exist.

[0243]

[0260] Although the present disclosure has been described in detail with particular reference to its preferred embodiments, it is understood that various changes and modifications can be made within the spirit and scope of the present disclosure. Results of the experimental scale process

[0261] General procedure: 53.16 g of TPA, A mixture of 62.21 g of EG, 2.97 g of DEG, 11.52 g of CHDM, and 18.86 g of rPET was placed in a 500 mL flask equipped with an inlet for nitrogen, a metal stirrer, and a short distillation column. Further, 0.14 mL of a Ti catalyst solution (targeting 16 ppm of Ti) and 1 mL of an Mn solution (targeting 45 ppm of Mn) were added to the flask. The flask was placed in a Wood's metal bath preheated to 200 °C. The stirring speed at the start of the experiment was set to 200 rpm. The contents of the flask were heated at 200 °C for 60 minutes, and then the temperature was gradually raised to 250 °C over 300 minutes. Next, the stirrer was decelerated to 100 rpm, and the reaction mixture was heated to 270 °C in 20 minutes while gradually increasing the vacuum to 0.4 torr. Then the temperature was raised to 278 °C in 20 minutes, the stirring was decelerated to 60 rpm, and the mixture was held at this condition for 120 minutes. After this holding, the mixture was returned to atmospheric pressure and cooled. Then the polymer was taken out of the flask for analysis. In Example 1, it was prepared by substituting TPA with rPET 100%. In Example 2, it was prepared by substituting 20% of TPA with rPET.

[0244]

[0262] In one aspect of the present disclosure, under conditions where a moderately constant amount of rPET is supplied, the amounts of Sb and other residual catalysts and additives can be predicted as shown in FIG. 7. Depending on the embodiment, FIG. 7 shows the amount of antimony that needs to be added to the system in a balanced manner based on the amount of rPET supplied into the process. For example, when putting 100 ppm of Sb in the final product, 60% of rPET can be supplied to the process, or when supplying 20% of rPET, 60 ppm of Sb is added to the system.

[0245]

Table 15

[0246]

[0263] The resins produced in both examples were similar with respect to all important performance criteria. Both materials had similar color tones, IV, and compositions regardless of the amount of rPET added. Results of the pilot plant process

[0264] To a reactor containing 45.7 wt% ethylene glycol, 0.7 wt% diethylene glycol, 9.8 wt% 1,4-cyclohexanedimethanol, and 36.4 wt% terephthalic acid, 7.3 wt% recycled PET was added to produce resin samples (A1 and A2). A Ti catalyst was added at 30 ppm. The glycol-to-acid ratio was 3.3, and ethylene glycol and 1,4-cyclohexanedimethanol were used in excess. This reaction mixture was held at 250 - 255 °C and 25 - 30 psig for 3 - 3.5 hours. Phosphorus was added at 21 ppm, and then the reaction mixture was heated to 270 °C and stirred under vacuum until the target melt viscosity was reached.

[0247]

[0265] A control resin sample (B) was produced using the same process except that 50 ppm of Ti catalyst was used without adding rPET or DEG to the reaction mixture. 44.1 wt% ethylene glycol, 10.5 wt% 1,4-cyclohexanedimethanol, and 45.5 wt% terephthalic acid were charged into the reactor. The glycol-to-acid ratio was 2.9, and ethylene glycol and 1,4-cyclohexanedimethanol were used in excess. The excess of CHDM was the same as that of the above samples, but the excess of EG was decreased.

[0248]

[0266] The properties of these resins are described in the following table.

[0249]

Table 16

[0250]

[0267] Resin Examples A1 and A2 were mixed to obtain Resin A. Resin A and B were dried in a dryer at 60 °C for 4 to 6 hours. Subsequently, a film having a thickness of 10 mils (250 μm) was extruded using a 2.5-inch extruder manufactured by Davis and Standard. After extrusion, the film was cut and stretched to a final thickness of 50 μm using a Karo 4-width stretcher manufactured by Bruckner. This film was stretched at a ratio of 5:1, a stretching speed of 100% / second, and a stretching temperature 5 to 15 °C higher than the Tg of the extruded film. The property evaluation of the shrinkable film produced by this process is described in the following table.

[0251]

Table 17

[0252]

[0268] Resins A and B were very similar in composition, IV, and color tone. Also, the shrinkable films produced from these resins showed very similar performance. These results demonstrate that incorporating rPET into the resin manufacturing process does not affect the final performance of the resin or the articles manufactured from the resin. Commercial-scale process

[0269] Resin samples were also produced using commercial manufacturing equipment to demonstrate the usefulness of the present invention.

[0253]

[0270] In the commercial-scale process, 5% recycled PET was added along with terephthalic acid and ethylene glycol. The slurry storage tank was stirred for 30 minutes or more to allow for sufficient mixing. The slurry was then added to reaction zone 1 along with a catalyst, additional ethylene glycol, diethylene glycol, and cyclohexanediol. The mixture was reacted under a pressure of 35 + psig and at a temperature above 235°C for at least 1 hour, simultaneously depolymerizing the PET and reacting the monomers. Subsequently, the monomers and oligomers from reaction zone 1 were delivered to reaction zone 2, where further reaction was carried out while maintaining the reaction temperature and removing additional glycol. This material was delivered into reaction zone 3, where finishing treatment was performed under higher temperature and higher vacuum conditions. The properties of the final product, Example C, are shown in the following table compared to Example D, another copolyester resin of the same composition produced in a commercial process without adding rPET.

[0254]

Table 18

[0255]

[0271] Resins C and D were dried in a dryer at 60°C for 4 - 6 hours. Then, a film with a thickness of 10 mils (250 μm) was extruded using a 2.5-inch extruder from Davis and Standard. After extrusion, the film was cut and stretched to a final thickness of 50 μm using a Karo 4-width stretcher from Bruckner. The film was stretched at a ratio of 5:1 with a stretching speed of 100% / second and a stretching temperature 5 - 15°C higher than the Tg of the extruded film. The property evaluation of the shrinkable film produced by this process is described in the following table.

[0256]

Table 19

[0257]

[0272] Resins C and D were very similar in composition, IV, and color tone. The shrink films made from these resins also retained very similar properties. These results demonstrate that incorporating rPET into the resin manufacturing process does not affect the final properties of the resin or the articles manufactured from the resin.

[0258]

[0273] Although the present disclosure has been described in detail with particular reference to its specific embodiments, it is understood that variations and modifications may be made within the spirit and scope of the present disclosure. Embodiments are described below. Embodiment 1 A process for producing a polyester composition from recycled polyester, comprising: (a) introducing a recycled polyester containing terephthalic acid (TPA), ethylene glycol (EG), and one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG into a paste tank, stirring and heating at a temperature of up to 150 °C to produce a slurry; (b) delivering the slurry from the paste tank to a first reaction zone; (c) introducing at least one additional glycol containing 1,4 - cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), or diethylene glycol (DEG) into the first reaction zone, optionally adding additional recycled polyester containing one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG, and optionally adding additional terephthalic acid (TPA) and ethylene glycol (EG) such that the molar ratio of total glycol:TPA is from 1:1 to 4:1, optionally in the presence of an esterification catalyst and / or a stabilizer; (d) reacting the TPA, EG, and recycled polyester in the first reaction zone with the at least one additional glycol at a melting temperature of at least 200 °C to produce an esterification product containing oligomers and unreacted TPA, EG, and the additional glycol; (e) optionally delivering the esterification product to a second reaction zone; (f) further reacting the esterification product, optionally adding additional glycol containing at least one of CHDM, NPG, or DEG and / or additional recycled polyester containing one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG, and further reacting the esterification product at a melting temperature of at least 200 °C in the second reaction zone, optionally in the presence of an esterification catalyst and / or a stabilizer, to produce an esterification product resulting in a polyester oligomer. (g) The step of delivering the resulting esterification product from one or more reaction zones to a third reaction zone; and (h) In the third reaction zone, adding one or more additional recycled polyesters including at least one of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG as needed, and polycondensing the resulting esterification product in the presence of a polycondensation catalyst and / or a stabilizer as needed to produce a polymerization product containing polyester. A process comprising the steps. Aspect 2 A process for producing a polyester composition from recycled polyester, comprising: (a) Introducing terephthalic acid (TPA) and ethylene glycol (EG) into a paste tank, stirring and heating at a temperature of up to 150 °C to produce a slurry; (b) The step of delivering the slurry in the paste tank to a first reaction zone; (c) Introducing at least one additional glycol including 1,4-cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), or diethylene glycol (DEG) into the first reaction zone, adding a recycled polyester including one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG, and adding additional terephthalic acid (TPA) and ethylene glycol (EG) as needed so that the molar ratio of total glycol:TPA is 1:1 to 4:1, and adding in the presence of an esterification catalyst and / or a stabilizer as needed; (d) In the first reaction zone, reacting the TPA, EG, and recycled polyester with the at least one additional glycol at a melting temperature of at least 175 °C to produce an esterification product containing oligomers and unreacted TPA, EG, and the additional glycol. (e) The step of delivering the esterification product to a second reaction zone as needed; (f) Optionally, delivering the esterification product from the second reaction zone to a third reaction zone; (f) Further react the esterification product, and optionally add additional glycols containing one or more of CHDM, NPG, or DEG and / or additional recycled polyesters containing one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG, optionally within the second reaction zone; further react the esterification product at a melting temperature of at least 200 °C, optionally in the presence of an esterification catalyst and / or a stabilizer, to produce an esterification product resulting in a polyester oligomer; (g) Delivering the resulting esterification product to a third reaction zone; and (h) In the third reaction zone, optionally adding additional recycled polyesters containing one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, recycled PCTG, recycled PCTM, or recycled PETM, and polycondensing the resulting esterification product, optionally in the presence of a polycondensation catalyst and / or a stabilizer, to produce a polymerization product containing a polyester. A process comprising the steps. Aspect 3 A polyester composition comprising at least one polyester produced from a recycled polyester by the process according to Aspect 1 or 2, wherein the at least one polyester comprises (a) A dicarboxylic acid component comprising: (i) From about 70 to about 100 mol% of terephthalic acid residues, and (ii) From about 0 to about 30 mol% of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; and (b) A diol component comprising: At least about 75 mol% of ethylene glycol residues, and (i) From about 0 to less than about 24 mol% of neopentyl glycol residues, (ii) From about 0 to less than about 24 mol% of 1,4-cyclohexanedimethanol residues, and (iii) Up to about 25 mol% of other glycols containing one or more of up to about 1 to less than about 10 mol% of the total diethylene glycol residues in the final polyester composition comprising, The total mol% of the dicarboxylic acid component is 100 mol%, and the total mol% of the diol component is 100 mol%; or (b) A diol component comprising: At least about 75 mol% of ethylene glycol residues, and (i) From about 0.1 to less than about 24 mol% of neopentyl glycol residues, (ii) from about 0.1 to less than about 24 mol% of 1,4 - cyclohexanedimethanol residues, and (iii) from about 1 to less than about 10 mol% of other glycols, including one or more of the total diethylene glycol residues in the final polyester composition, wherein the total mol% of the dicarboxylic acid component is 100 mol% and the total mol% of the diol component is 100 mol%, a polyester composition. Aspect 4 A crystallizable film, thermoformed film or sheet comprising a polyester composition comprising at least one polyester produced from a recycled polyester by the process according to Aspect 1 or 2, wherein the at least one polyester (a) a dicarboxylic acid component comprising: (i) from about 70 to about 100 mol% of terephthalic acid residues, and (ii) from about 0 to about 30 mol% of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms and (b) a diol component comprising: at least about 75 mol% of ethylene glycol residues, and (i) from about 0 to less than about 24 mol% of neopentyl glycol residues, (ii) from about 0 to less than about 24 mol% of 1,4 - cyclohexanedimethanol residues, and (iii) from about 1 to less than about 10 mol% of other glycols, including one or more of the total diethylene glycol residues in the final polyester composition, wherein the total mol% of the dicarboxylic acid component is 100 mol% and the total mol% of the diol component is 100 mol%; or (b) a diol component comprising: at least about 75 mol% of ethylene glycol residues, and (i) from about 0.1 to less than about 24 mol% of neopentyl glycol residues, (ii) from about 0.1 to less than about 24 mol% of 1,4 - cyclohexanedimethanol residues, and (iii) from about 1 to less than about 10 mol% of other glycols, including one or more of the total diethylene glycol residues in the final polyester composition, wherein the total mol% of the dicarboxylic acid component is 100 mol% and the total mol% of the diol component is 100 mol%, a crystallizable film, thermoformed film or sheet. Aspect 5 ​ ​ A crystallizable film, thermoformed film or sheet comprising a polyester composition comprising at least one polyester produced from a recycled polyester by the process according to embodiment 1 or 2, wherein said at least one polyester comprises: (a) A dicarboxylic acid component comprising: (i) From about 70 to about 100 mol% terephthalic acid residues, and (ii) From about 0 to about 30 mol% aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; and (b) A diol component comprising: At least about 75 mol% ethylene glycol residues, and (i) Up to about 15 mol% neopentyl glycol residues, (ii) Up to about 5 mol% 1,4-cyclohexanedimethanol residues, and (iii) Up to about 25 mol% of other glycols, including one or more of the total diethylene glycol residues in the final polyester composition, wherein the total mol% of the dicarboxylic acid component is 100 mol% and the total mol% of the diol component is 100 mol%, a crystallizable film or thermoformed film or sheet. Embodiment 6 A crystallizable film, thermoformed film or sheet comprising a polyester composition comprising at least one polyester produced from a recycled polyester by the process according to embodiment 1 or 2, wherein said at least one polyester comprises: (a) A dicarboxylic acid component comprising: (i) From about 70 to about 100 mol% terephthalic acid residues, and (ii) From about 0 to about 30 mol% aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; and (b) A diol component comprising: At least about 80 mol% ethylene glycol residues, and (i) Less than about 5 to about 17 mol% neopentyl glycol residues, (ii) Less than about 2 to about 10 mol% 1,4-cyclohexanedimethanol residues, and (iii) Less than about 1 to about 5 mol% of other glycols, including one or more of the total diethylene glycol residues in the final polyester composition, wherein the total mol% of the dicarboxylic acid component is 100 mol% and the total mol% of the diol component is 100 mol%, a crystallizable film or thermoformed film or sheet. Embodiment 7 ​ A crystallizable film, thermoformed film or sheet comprising a polyester composition comprising at least one polyester produced from a recycled polyester by the process according to embodiment 1 or 2, wherein said at least one polyester comprises (a) a dicarboxylic acid component comprising: (i) from about 70 to about 100 mol% terephthalic acid residues, and (ii) from about 0 to about 30 mol% aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; and (b) a diol component comprising: at least about 76 mol% ethylene glycol residues, and (i) neopentyl glycol residues, (ii) cyclohexanedimethanol residues, and (iii) an amorphous content of up to about 24 mol% comprising one or more of the diethylene glycol residues in the final polyester composition, wherein the total mol% of said dicarboxylic acid component is 100 mol% and the total mol% of said diol component is 100 mol%, a crystallizable film, thermoformed film or sheet. Embodiment 8 A crystallizable film, thermoformed film or sheet comprising a polyester composition comprising at least one polyester produced from a recycled polyester by the process according to embodiment 1 or 2, wherein said at least one polyester comprises (a) a dicarboxylic acid component comprising: (i) from about 70 to about 100 mol% terephthalic acid residues, and (ii) from about 0 to about 30 mol% aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; and (b) a diol component comprising: at least about 75 mol% ethylene glycol residues, and (i) less than about 10 to about 15 mol% neopentyl glycol residues, (ii) less than about 1 to about 5 mol% 1,4-cyclohexanedimethanol residues, and (iii) less than about 1 to about 5 mol% other glycols comprising one or more of the total diethylene glycol residues in the final polyester composition, wherein the total mol% of said dicarboxylic acid component is 100 mol% and the total mol% of said diol component is 100 mol%, a crystallizable film, thermoformed film or sheet. Embodiment 9 A crystallizable film, thermoformed film or sheet comprising a polyester composition comprising at least one polyester produced from a recycled polyester by the process according to embodiment 1 or 2, wherein the at least one polyester comprises (a) a dicarboxylic acid component comprising: (i) from about 70 to about 100 mol% terephthalic acid residues, and (ii) from about 0 to about 30 mol% aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; and (b) a diol component comprising: (i) from about 0 to about 30 mol% neopentyl glycol residues, (ii) less than about 0 to about 30 mol% 1,4-cyclohexanedimethanol residues, and (iii) whether formed in situ or not, comprising diethylene glycol residues, the balance of the glycol component being (iv) ethylene glycol residues, and (v) optionally, from 0 to 10 mol% or from 0 to 5 mol% of at least one modified glycol, wherein the total mol% of the dicarboxylic acid component is 100 mol% and the total mol% of the diol component is 100 mol%, a crystallizable film, thermoformed film or sheet. Embodiment 10 The intrinsic viscosity of the polyester is from 0.50 to 0.80 dL / g when measured at 25 °C and a concentration of 0.25 g / 50 mL in 60 / 40 (weight / weight) phenol / tetrachloroethane, a crystallizable film, thermoformed film or sheet according to any one of embodiments 1 to 9. Embodiment 11 The polyester has a Tg of from 65 °C to 80 °C when measured at a scanning rate of 20 °C / min using a TA DSC 2920 from Thermal Analyst Instrument, a crystallizable film, thermoformed film or sheet according to any one of embodiments 1 to 10. Embodiment 12 The total diol content of one or more diol monomer components capable of producing an amorphous component in the final polyester is from 5 to 25 mol% based on the total diol content which is 100 mol%; or The total diol content of one or more diol monomer components capable of producing an amorphous component in the final polyester is from 10 to 20 mol% based on the total diol content which is 100 mol%; or The total diol content of one or more diol monomer components capable of forming an amorphous component in the final polyester is 15 to 20 mol% based on the total diol content of 100 mol%; or The total diol content of one or more diol monomer components capable of forming an amorphous component in the final polyester is 15 to 25 mol% based on the total diol content of 100 mol%, the crystallizable film or thermoformed film or sheet according to any one of Aspects 1 to 11. Aspect 13 The total diol content of the 1,4 - cyclohexanedimethanol residue and the neopentyl glycol residue in the final polyester is 5 to 25 mol%, 5 to 15 mol%, 10 to 15 mol%, 10 to 20 mol%, or 5 to 20 mol%, or more than 5 mol% to less than 20 mol% based on the total diol content of 100 mol%; or The 1,4 - cyclohexanedimethanol residue is present in an amount of 0 to about 10 mol%, the diethylene glycol residue is present in an amount of 2 to 10 mol%, the neopentyl glycol residue is present in an amount of 5 to 20 mol%, and the ethylene glycol residue is present in an amount of 75 mol% or more; or The 1,4 - cyclohexanedimethanol residue is present in an amount of 2 to 5 mol%, the diethylene glycol residue is present in an amount of 5 mol% or less, the neopentyl glycol residue is present in an amount of 10 to 15 mol%, and the ethylene glycol residue is present in an amount of more than 75 mol%, the crystallizable film or thermoformed film or sheet according to any one of Aspects 1 to 11. Aspect 14 The total of the 1,4 - cyclohexanedimethanol residue and the neopentyl glycol residue in the final polyester in terms of the diol content of the crystallizable polyester component is 4 to 15 mol%, 1 to 25 mol%, 2 to 20 mol%, or more than 2 mol% to less than 20 mol% based on the total diol content of 100 mol%, the crystallizable film or thermoformed film or sheet according to any one of Aspects 1 to 11. Aspect 15 The film or sheet is stretched in at least one direction and the stretched film or sheet has a melting point of strain-induced crystals of 170 °C or higher, or the film or sheet is stretched in at least one direction and the stretched film or sheet has a melting point of strain-induced crystals of 200 °C or higher, the crystallizable film or thermoformable film or sheet according to any one of Aspects 1 to 11. Aspect 16 A method of introducing or forming a recycled content in a polyester produced by the process according to Aspect 1, comprising: (a) obtaining an allocation or limit of the recycled monomer with respect to at least one recycled monomer including TPA, EG, DMT, CHDM, NPG, or DEG; (b) converting the recycled monomer in a synthesis process to produce a polyester; (c) designating at least a part of the polyester as corresponding to at least a part of the allocation or limit of the recycled monomer; and (d) optionally, selling or marketing the polyester as including the content of the recycled monomer corresponding to the designation, or obtained using the content. Aspect 17 The amount of the recycled polyester added to the process is 5 to 100% based on the amount of TPA required, the process according to Aspect 1 or 2. Aspect 18 The esterification catalyst includes one or more of Mn, Ti, Zn, Co, Ge, or Al, the process according to Aspect 1 or 2. Aspect 19 The polycondensation catalyst includes one or more of Sn, Sb, Ti, Li / Al, Al, Ge, Pb, Zn, Co, Bi, Cd, Ca, or Ni, the process according to Aspect 1 or 2. Aspect 20 The process further includes adding a catalyst or an additive by adding a recycled polyester, and the catalyst or the additive is a component of the recycled polyester such as Sb, Ti, Co, Mn, Li, Al, P, etc., the process according to Aspect 1 or 2.

Claims

1. A process for producing a polyester composition from recycled polyester, comprising: (a) introducing a recycled polyester containing terephthalic acid (TPA), ethylene glycol (EG), and one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG into a paste tank, and stirring and heating at a temperature of up to 150°C to produce a slurry; (b) delivering the slurry from the paste tank to a first reaction zone; (c) introducing at least one additional glycol containing 1,4-cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), or diethylene glycol (DEG) into the first reaction zone, optionally adding additional recycled polyester containing one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG, and optionally adding additional terephthalic acid (TPA) and ethylene glycol (EG) such that the molar ratio of total glycol:TPA is from 1:1 to 4:1, optionally in the presence of an esterification catalyst and / or a stabilizer; (d) reacting the TPA, EG, and recycled polyester in the first reaction zone with the at least one additional glycol at a melt temperature of at least 200°C to produce an esterification product containing oligomers and unreacted TPA, EG, and the additional glycol; (e) optionally delivering the esterification product to a second reaction zone; (f) further reacting the esterification product, optionally adding additional glycol containing at least one of CHDM, NPG, or DEG and / or additional recycled polyester containing one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG, and further reacting the esterification product at a melt temperature of at least 200°C in the second reaction zone, optionally in the presence of an esterification catalyst and / or a stabilizer, to produce an esterification product resulting in a polyester oligomer; (g) delivering the resulting esterification product from one or more reaction zones to a third reaction zone; and (h) In the third reaction zone, adding one or more additional recycled polyesters including recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG as needed, and polycondensing the resulting esterification product in the presence of a polycondensation catalyst and / or a stabilizer as needed to produce a polymerization product containing polyester.

2. A process for producing a polyester composition from recycled polyester, (a) introducing terephthalic acid (TPA) and ethylene glycol (EG) into a paste tank, stirring and heating at a temperature of up to 150°C to produce a slurry; (b) delivering the slurry from the paste tank to a first reaction zone; (c) introducing at least one additional glycol including 1,4-cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), or diethylene glycol (DEG) into the first reaction zone, adding a recycled polyester including one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG, and adding additional terephthalic acid (TPA) and ethylene glycol (EG) as needed so that the molar ratio of total glycol:TPA is 1:1 to 4:1, adding in the presence of an esterification catalyst and / or a stabilizer as needed; (d) reacting the TPA, EG, and recycled polyester with the at least one additional glycol at a melting temperature of at least 175°C in the first reaction zone to produce an esterification product containing oligomers and unreacted TPA, EG, and the additional glycol; (e) delivering the esterification product to a second reaction zone as needed; (f) Further reacting the esterification product, and optionally adding an additional glycol containing one or more of CHDM, NPG, or DEG and / or an additional recycled polyester containing one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, or recycled PCTG, and optionally within the second reaction zone; further reacting the esterification product at a melt temperature of at least 200° C., optionally in the presence of an esterification catalyst and / or a stabilizer, to produce an esterification product resulting in a polyester oligomer; (g) Delivering the resulting esterification product to a third reaction zone; and (h) In the third reaction zone, optionally adding an additional recycled polyester containing one or more of recycled PET, recycled PETG, recycled PCT, recycled PCTA, recycled PCTG, recycled PCTM, or recycled PETM, and polycondensing the resulting esterification product, optionally in the presence of a polycondensation catalyst and / or a stabilizer, to produce a polymerization product containing a polyester. A process comprising: [

3. ] A polyester composition comprising at least one polyester produced from a recycled polyester by the process of claim 1 or 2, wherein the at least one polyester comprises: (a) A dicarboxylic acid component comprising: (i) From about 70 to about 100 mol % terephthalic acid residues, and (ii) From about 0 to about 30 mol % aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; and (b) A diol component comprising: At least about 75 mol % ethylene glycol residues, and (i) From about 0 to less than about 24 mol % neopentyl glycol residues, (ii) From about 0 to less than about 24 mol % 1,4-cyclohexanedimethanol residues, and (iii) Up to about 25 mol % of other glycols containing one or more of the total diethylene glycol residues in the final polyester composition of from about 1 to less than about 10 mol % wherein the total mol % of the dicarboxylic acid component is 100 mol % and the total mol % of the diol component is 100 mol %; or (b) A diol component comprising: At least about 75 mol % ethylene glycol residues, and (i) From about 0.1 to less than about 24 mol % neopentyl glycol residues, (ii) from about 0.1 to less than about 24 mol% of 1,4 - cyclohexanedimethanol residues, and (iii) up to about 25 mol% of other glycols containing one or more of the total diethylene glycol residues in the final polyester composition of from about 1 to less than about 10 mol% comprising wherein the total mol% of the dicarboxylic acid component is 100 mol% and the total mol% of the diol component is 100 mol%, a polyester composition.

4. A crystallizable film, thermoformed film or sheet comprising a polyester composition comprising at least one polyester produced from a recycled polyester by the process according to claim 1 or 2, wherein the at least one polyester is (a) a dicarboxylic acid component comprising: (i) from about 70 to about 100 mol% of terephthalic acid residues, and (ii) from about 0 to about 30 mol% of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms and (b) a diol component comprising: at least about 75 mol% of ethylene glycol residues, and (i) from about 0 to less than about 24 mol% of neopentyl glycol residues, (ii) from about 0 to less than about 24 mol% of 1,4 - cyclohexanedimethanol residues, and (iii) up to about 25 mol% of other glycols containing one or more of the total diethylene glycol residues in the final polyester composition of from about 1 to less than about 10 mol% wherein the total mol% of the dicarboxylic acid component is 100 mol% and the total mol% of the diol component is 100 mol%; or (b) a diol component comprising: at least about 75 mol% of ethylene glycol residues, and (i) from about 0.1 to less than about 24 mol% of neopentyl glycol residues, (ii) from about 0.1 to less than about 24 mol% of 1,4 - cyclohexanedimethanol residues, and (iii) up to about 25 mol% of other glycols containing one or more of the total diethylene glycol residues in the final polyester composition of from about 1 to less than about 10 mol% comprising wherein the total mol% of the dicarboxylic acid component is 100 mol% and the total mol% of the diol component is 100 mol%, a crystallizable film, thermoformed film or sheet.

5. A crystallizable film, thermoformed film or sheet comprising a polyester composition comprising at least one polyester produced from a recycled polyester by the process according to claim 1 or 2, wherein said at least one polyester is (a) A dicarboxylic acid component comprising: (i) From about 70 to about 100 mol% terephthalic acid residues, and (ii) From about 0 to about 30 mol% aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; and (b) A diol component comprising: At least about 75 mol% ethylene glycol residues, and (i) Up to about 15 mol% neopentyl glycol residues, (ii) Up to about 5 mol% 1,4-cyclohexanedimethanol residues, and (iii) Up to about 25 mol% of other glycols comprising one or more of the total diethylene glycol residues in the final polyester composition, wherein the total mol% of said dicarboxylic acid component is 100 mol% and the total mol% of said diol component is 100 mol%, a crystallizable film, thermoformed film or sheet. **Claim 6** A crystallizable film, thermoformed film or sheet comprising a polyester composition comprising at least one polyester produced from a recycled polyester by the process according to claim 1 or 2, wherein said at least one polyester is (a) A dicarboxylic acid component comprising: (i) From about 70 to about 100 mol% terephthalic acid residues, and (ii) From about 0 to about 30 mol% aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; and (b) A diol component comprising: At least about 80 mol% ethylene glycol residues, and (i) Less than about 5 to about 17 mol% neopentyl glycol residues, (ii) Less than about 2 to about 10 mol% 1,4-cyclohexanedimethanol residues, and (iii) Up to about 20 mol% of other glycols comprising one or more of the total diethylene glycol residues in the final polyester composition, wherein the total mol% of said dicarboxylic acid component is 100 mol% and the total mol% of said diol component is 100 mol%, a crystallizable film, thermoformed film or sheet. **Claim 7** A crystallizable film, thermoformed film or sheet comprising a polyester composition comprising at least one polyester produced from a recycled polyester by the process according to claim 1 or 2, wherein the at least one polyester comprises (a) a dicarboxylic acid component comprising: (i) from about 70 to about 100 mol% terephthalic acid residues, and (ii) from about 0 to about 30 mol% aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; and (b) a diol component comprising: at least about 76 mol% ethylene glycol residues, and (i) neopentyl glycol residues, (ii) cyclohexanedimethanol residues, and (iii) having an amorphous content of up to about 24 mol% comprising one or more of the diethylene glycol residues in the final polyester composition, wherein the total mol% of the dicarboxylic acid component is 100 mol% and the total mol% of the diol component is 100 mol%, a crystallizable film, thermoformed film or sheet.

8. A crystallizable film, thermoformed film or sheet comprising a polyester composition comprising at least one polyester produced from a recycled polyester by the process according to claim 1 or 2, wherein the at least one polyester comprises (a) a dicarboxylic acid component comprising: (i) from about 70 to about 100 mol% terephthalic acid residues, and (ii) from about 0 to about 30 mol% aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; and (b) a diol component comprising: at least about 75 mol% ethylene glycol residues, and (i) less than about 10 to about 15 mol% neopentyl glycol residues, (ii) less than about 1 to about 5 mol% 1,4-cyclohexanedimethanol residues, and (iii) less than about 1 to about 5 mol% of other glycols comprising one or more of the total diethylene glycol residues in the final polyester composition, having an amorphous content of up to about 25 mol%, wherein the total mol% of the dicarboxylic acid component is 100 mol% and the total mol% of the diol component is 100 mol%, a crystallizable film, thermoformed film or sheet.

9. A crystallizable film, thermoformed film or sheet comprising a polyester composition comprising at least one polyester produced from a recycled polyester by the process according to claim 1 or 2, wherein the at least one polyester comprises (a) A dicarboxylic acid component comprising: (i) From about 70 to about 100 mol% of terephthalic acid residues, and (ii) From about 0 to about 30 mol% of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; and (b) A diol component comprising: (i) From about 0 to about 30 mol% of neopentyl glycol residues, (ii) Less than about 0 to about 30 mol% of 1,4-cyclohexanedimethanol residues, and (iii) Whether formed in situ or not, comprising diethylene glycol residues, The balance of the diol component is (iv) Ethylene glycol residues, and (v) Optionally, from 0 to 10 mol% or from 0 to 5 mol% of at least one modified glycol, A crystallizable film, thermoformed film or sheet, wherein the total mol% of the dicarboxylic acid component is 100 mol% and the total mol% of the diol component is 100 mol%.

10. The intrinsic viscosity of the polyester is from 0.50 to 0.80 dL / g when measured at 25 °C and a concentration of 0.25 g / 50 mL in 60 / 40 (weight / weight) phenol / tetrachloroethane. A crystallizable film, thermoformed film or sheet according to any one of claims 4 to 9.

11. The polyester has a Tg of 65 °C to 80 °C when measured at a scanning rate of 20 °C / min using a TA DSC 2920 manufactured by Thermal Analyst Instrument. A crystallizable film, thermoformed film or sheet according to any one of claims 4 to 10.

12. In a polyester composition comprising at least one polyester produced from a recycled polyester by the process, The total diol content of one or more diol monomer components capable of forming an amorphous component is from 5 to 25 mol% based on the total diol content of 100 mol%; or The total diol content of one or more diol monomer components capable of forming an amorphous component is from 10 to 20 mol% based on the total diol content of 100 mol%; or The total diol content of one or more diol monomer components capable of forming an amorphous component is 15 to 20 mol% based on the total diol content of 100 mol%; or The total diol content of one or more diol monomer components capable of forming an amorphous component is 15 to 25 mol% based on the total diol content of 100 mol%, the crystallizable film or thermoformable film or sheet according to any one of claims 4 to 11.

13. In a polyester composition containing at least one polyester produced from a recycled polyester by the process The total diol content of the 1,4 - cyclohexanedimethanol residue and the neopentyl glycol residue is 5 to 25 mol%, 5 to 15 mol%, 10 to 15 mol%, 10 to 20 mol%, or 5 to 20 mol%, or more than 5 mol% to less than 20 mol% based on the total diol content of 100 mol%; or The 1,4 - cyclohexanedimethanol residue is present in an amount of 0 to about 10 mol%, the diethylene glycol residue is present in an amount of 2 to 10 mol%, the neopentyl glycol residue is present in an amount of 5 to 20 mol%, and the ethylene glycol residue is present in an amount of 75 mol% or more; or The 1,4 - cyclohexanedimethanol residue is present in an amount of 2 to 5 mol%, the diethylene glycol residue is present in an amount of 5 mol% or less, the neopentyl glycol residue is present in an amount of 10 to 15 mol%, and the ethylene glycol residue is present in an amount of more than 75 mol%, the crystallizable film or thermoformable film or sheet according to any one of claims 4 to 11.

14. The total diol content of the 1,4 - cyclohexanedimethanol residue and the neopentyl glycol residue in a polyester composition containing at least one polyester produced from a recycled polyester by the process is 4 to 15 mol%, 1 to 25 mol%, 2 to 20 mol%, or more than 2 mol% to less than 20 mol% based on the total diol content of 100 mol%, the crystallizable film or thermoformable film or sheet according to any one of claims 4 to 11.

15. The film or sheet is stretched in at least one direction and the stretched film or sheet has a melting point of strain-induced crystals of 170 °C or higher, or the film or sheet is stretched in at least one direction and the stretched film or sheet has a melting point of strain-induced crystals of 200 °C or higher. The crystallizable film or thermoformable film or sheet according to any one of claims 4 to 11.

16. A method for introducing or forming a recycled content in a polyester produced by the process according to claim 1, comprising: (a) obtaining an allocation or limit of the recycled monomer with respect to at least one recycled monomer containing TPA, EG, DMT, CHDM, NPG, or DEG; (b) converting the recycled monomer in the synthesis process to produce a polyester; (c) designating at least a part of the polyester as corresponding to at least a part of the allocation or limit of the recycled monomer; and (d) optionally, selling or marketing the polyester as containing the content of the recycled monomer corresponding to the designation, or as obtained using the content.

17. The amount of the recycled polyester added to the process is 5 to 100% based on the amount of TPA required. The process according to claim 1 or 2.

18. The esterification catalyst contains one or more of Mn, Ti, Zn, Co, Ge, or Al. The process according to claim 1 or 2.

19. The polycondensation catalyst contains one or more of Sn, Sb, Ti, an alloy of Li and Al, Al, Ge, Pb, Zn, Co, Bi, Cd, Ca, or Ni. The process according to claim 1 or 2.

20. The process further includes adding a catalyst or an additive by adding a recycled polyester. The catalyst or additive is a component of the recycled polyester such as Sb, Ti, Co, Mn, Li, Al, P. The process according to claim 1 or 2.

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