Crystallizable shrinkable films and thermoformable sheets made from reactor-grade resins

Abstract

The present disclosure relates to crystallizable shrinkable films and thermoformable 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 composition ranges that have certain advantages, including recyclability, and improved properties.

Description

FIELD OF THE INVENTION

[0001]

[0001] This disclosure relates to crystallizable shrinkable films and thermoformable sheets comprising polyester compositions containing residues of terephthalic acid, neopentyl glycol (NPG), 1,4-cyclohexanedimethanol (CHDM), ethylene glycol (EG), and diethylene glycol (DEG) in specific composition ranges that have particular advantages and improve properties. [Background technology]

[0002]

[0002] There is a commercial need for shrink films that have at least one of the following desirable properties: (1) a low shrink onset temperature; (2) a shrink rate that increases gradually and in a controlled manner with increasing temperature over the temperature range over which shrinkage occurs; (3) a shrink force that is low enough to prevent crushing of the underlying container; (4) a high maximum shrink rate (shrink rate at the highest temperature), e.g., a shrink rate of 60% or more in the main shrink direction at 95°C; (5) a low shrink rate in the direction perpendicular to the high shrink rate; (6) high film toughness to prevent undesirable crushing, breaking, tearing, splitting, bubbling, or wrinkling of the film during manufacturing and before and after shrinking; and (7) recyclability.

[0003]

[0003] There is a commercial need for thermoformable polyester sheeting with excellent properties and recyclability.

[0004] It has been discovered that a specific combination of glycol monomers in a shrink film resin composition can produce a film with excellent shrink film properties and can be crystallized without affecting the recycling of the PET flakes that are generated simultaneously during recycling. These crystallizable shrink film resins can be processed with PET bottles and become a component of the recyclable PET flakes after the recycling process is completed. The selection of a specific combination of glycol monomers and their amounts has been found to be important for producing a film with excellent shrink film properties and for producing a crystallizable film. The optimized polyester resin compositions of the present disclosure are amorphous but crystallizable. Thus, these compositions exhibit excellent properties in film applications, including shrink film, and the high melting points of these strain-induced crystals make them compatible with the recycling process. The shrink film labels of the present disclosure do not need to be removed during the recycling process and do not affect the recycling process.

[0005] To be used in the present disclosure, heat-shrinkable films must meet various standards for use. The film must be strong, shrink in a controlled manner, and provide sufficient shrinkage force to hold itself against the bottle surface without crushing the contents. Furthermore, when these labels are applied to polyester containers or bottles, these polyester shrink film labels must not interfere with the recycling process of the polyester containers or bottles. The shrink films of the present disclosure are advantageous because the labels can be recycled along with the bottles or containers. Thus, the entire container or bottle, including the label, can be recycled and converted into a new product without requiring additional handling requirements or creating new environmental problems. Heat-shrinkable films are made from a variety of raw materials to meet a range of material needs. This disclosure describes the unique and unexpected effects of specific monomer combinations on shrink film resin compositions.

[0006] Polyester shrink film compositions have been used commercially as shrink film labels for food, beverages, personal care products, and household goods. Often, these shrink films are combined with clear polyethylene terephthalate (PET) bottles or containers. After use, the entire product (bottle and label) is recycled. At typical recycling sites, due to their similar compositions and densities, PET and shrink film materials can end up commingled at the end of the process. Drying of PET flakes is necessary to remove residual water from the PET during the recycling process. PET is typically dried at temperatures exceeding 200°C. At these temperatures, typical polyester shrink film resins soften and become sticky, often causing the PET flakes to form clumps. These clumps must be removed before further processing. These clumps reduce the yield of PET flakes from the process, necessitating additional handling steps.

[0007]

[0007] In the present disclosure, it has been discovered that film or sheet resin compositions having specific combinations of glycol monomers can produce films or sheets with excellent performance properties, and that these compositions are also crystallizable so as not to affect the recyclability of PET flakes. These crystallizable film or sheet resins can be processed with recycled PET and become a component of the recyclable PET flakes after the recycling process is complete. It has been discovered that the selection of specific combinations of glycol monomers and their amounts are important for producing films or sheets with excellent performance properties and for producing crystallizable films or sheets. That is, although the polyester compositions of the present disclosure are amorphous, they are "crystallizable" in the sense that they have a high strain-induced crystalline melting point. Thus, these compositions exhibit excellent properties in film or sheet applications, such as in shrink film applications and in formed, thermoformed, or molded parts and / or articles, but also have a high strain-induced crystalline melting point, allowing them to be recycled with PET. This is because when recycled PET flakes are subjected to high temperature drying conditions, the crystallizable polyesters of the present invention do not form agglomerates that interfere with the normal mechanical operations of grinding, drying, and feeding the flakes into an extruder for subsequent processing into (recycled) polyester pellets. Similarly, the sheets of the present disclosure do not need to be removed during the recycling process and therefore do not adversely affect the recycling process (e.g., https: / / www.thebalancesmb.com / recycling-polyethylene-terephthalate-pet-2877869 (See

[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 % of terephthalic acid residues, and (ii) about 0 to about 30 mol % of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, and the (b) diol component comprises about 75 mol % or more of ethylene glycol residues and about 25 mol % or less of other glycols including one or more of (i)-(iii), wherein (i) about 0.1 to less than about 24 mol % of neopentyl glycol residues, (ii) 0 to less than about 24 mol % of 1,4-cyclohexanedimethanol residues, and (iii) about 1 to less than about 10 mol % of 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 %.

[0008]

[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) about 70 to about 100 mol % of terephthalic acid residues, and (ii) about 0 to about 30 mol % of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, and the (b) diol component comprises about 80 mol % or more of ethylene glycol residues and about 20 mol % or less of other glycols including one or more of (i)-(iii), wherein (i) about 5 to less than about 17 mol % of neopentyl glycol residues, (ii) about 2 to less than about 10 mol % of 1,4-cyclohexanedimethanol residues, and (iii) about 1 to less than about 5 mol % of 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]

[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) about 70 to about 100 mol % of terephthalic acid residues, and (ii) about 0 to about 30 mol % of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, and the (b) diol component comprises about 76 mol % or more of ethylene glycol residues, and about 24 mol % or less of amorphous components selected from (i)-(iii), wherein (i) neopentyl glycol residues, (ii) cyclohexanedimethanol residues, and (iii) 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 %.

[0010]

[0011] 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) about 70 to about 100 mole % of terephthalic acid residues, and (ii) about 0 to about 30 mole % of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, and the (b) diol component comprises (i) about 1 to about 30 mole % of neopentyl glycol residues, (ii) about 1 to less than about 30 mole % of 1,4-cyclohexanedimethanol residues, and (iii) about 1.5 to 6 mole % of diethylene glycol residues, with the remainder of the glycol component comprising (iv) ethylene glycol residues and (v) 0 to 20 mole % of at least one modified glycol residue, wherein the total mole % of the dicarboxylic acid component is 100 mole % and the total mole % of the glycol component is 100 mole %.

[0011]

[0012] One embodiment of the present disclosure is a crystallizable film of any of the above-described embodiments, wherein the film is stretched in at least one direction, and the stretched film has a melting point of strain-induced crystals of 190° C. or higher. One embodiment of the present disclosure is a crystallizable film of any of the above-described embodiments, wherein the film is stretched in at least one direction, and the stretched film has a melting point of strain-induced crystals of about 190° C. to about 215° C.

[0012]

[0013] One embodiment of the present disclosure is an extruded or calendered film comprising the crystallizable film of any of the previous embodiments.

[0014] One embodiment of the present disclosure is a thermoformed sheet having a thickness of about 0.25 mm to about 6.4 mm, the sheet comprising a polyester composition including at least one polyester comprising (a) a dicarboxylic acid component and (b) a diol component, the (a) dicarboxylic acid component comprising (i) about 70 to about 100 mole % of terephthalic acid residues, and (ii) about 0 to about 30 mole % of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, and the (b) diol component comprising about 75 mole % or more of ethylenediamine diol. and up to about 25 mol % of other glycols, including ethylene glycol residues, and one or more of (i)-(iii), where (i) from about 0.1 to less than about 24 mol % neopentyl glycol residues, (ii) from 0 to less than about 24 mol % 1,4-cyclohexanedimethanol residues, and (iii) from about 1 to less than about 10 mol % total diethylene glycol residues in the final polyester composition, where the total mol % of the dicarboxylic acid components is 100 mol % and the total mol % of the diol components is 100 mol %.

[0013]

[0015] One embodiment of the present disclosure is a thermoformed sheet having a thickness of about 0.25 mm to about 6.4 mm, the sheet comprising a polyester composition including at least one polyester comprising (a) a dicarboxylic acid component and (b) a diol component, the (a) dicarboxylic acid component comprising (i) about 70 to about 100 mole % of terephthalic acid residues, and (ii) about 0 to about 30 mole % of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, and the (b) diol component comprising about 80 mole % or more of terephthalic acid residues. ethylene glycol residues, and up to about 20 mol % of other glycols including one or more of (i)-(iii), wherein (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) from about 1 to less than about 5 mol % total diethylene glycol residues in the final polyester composition, wherein the total mol % of the dicarboxylic acid components is 100 mol % and the total mol % of the diol components is 100 mol %.

[0014]

[0016] One embodiment of the present disclosure is a thermoformed sheet having a thickness of about 0.25 mm to about 6.4 mm, the sheet comprising a polyester composition including 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 % of terephthalic acid residues, and (ii) about 0 to about 30 mol % of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, and the (b) diol component comprises about 76 mol % or more of ethylene glycol residues, and about 24 mol % or less of an amorphous component selected from (i)-(iii), wherein (i) neopentyl glycol residues, (ii) cyclohexanedimethanol residues, and (iii) 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 %.

[0015]

[0017] One embodiment of the present disclosure is a thermoformed sheet having a thickness of about 0.25 mm to about 6.4 mm, the sheet comprising a polyester composition including 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 mole % of terephthalic acid residues, and (ii) about 0 to about 30 mole % of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, and the (b) diol component comprises (i) about 1 to about 30 mole % of neopentyl glycol residues, (ii) about 1 to less than about 30 mole % of 1,4-cyclohexanedimethanol residues, and (iii) about 1.5 to 6 mole % of diethylene glycol residues, with the remainder of the glycol component comprising (iv) ethylene glycol residues, and (v) 0 to 20 mole % of at least one modified glycol residue, wherein the total mole % of the dicarboxylic acid component is 100 mole % and the total mole % of the diol component is 100 mole %.

[0016]

[0018] One embodiment of the present disclosure is a formed, thermoformed, or molded article prepared from or including a sheet of any of the preceding embodiments.

[0019] In one embodiment of the present disclosure, the thermoformed sheet has a crystalline melting point of about 190°C to about 225°C.

[0017]

[0020] One embodiment of the present disclosure is an article selected from medical device packaging, medical related packaging, healthcare product packaging, commercial food supply packaging, trays, containers, food plates, tumblers, storage bins, bottles, cookware, mixing bowls, household items, water bottles, crisper trays, dishwasher parts, refrigerator parts, vacuum cleaner parts, ophthalmic lenses, and frames or toys prepared from or comprising the sheet of any of the preceding embodiments.

[0018]

[0021] One embodiment of the present disclosure is a method of making a formed or thermoformed article or part from a sheet of any of the previous embodiments, the method comprising: A) heating a sheet comprising a polyester composition of the present disclosure; B) applying air pressure, vacuum, and / or physical pressure to the heat-softened sheet; C) conforming the sheet to the shape of a mold with vacuum or pressure; D) cooling the sheet to a temperature below its Tg; and E) removing the formed or thermoformed part or article from the mold.

[0019]

[0022] One embodiment of the present disclosure is a polyester recycling process stream comprising recycled polyethylene terephthalate flakes mixed together with at least about 0.1% by weight of the crystallizable recycled shrink film or thermoformed sheet of the present disclosure.

[0020]

[0023] As a result, the crystallizable composition of the present disclosure provides an effective component of a PET recycling process stream, to the extent that the composition can accompany PET in the recycling process stream without the need for an additional separation step. Accordingly, in one embodiment of the present disclosure, a polyester recycling process stream is provided that includes recycled polyethylene terephthalate flakes having at least about 0.1% by weight of a crystallizable composition of the present disclosure mixed therewith. In another embodiment, the process stream has passed the "Critical Guidance Protocol for Clear PET Articles with Labels and Closures," Document No. PET-CG-02, dated April 11, 2019. [Brief explanation of the drawings]

[0021] [Figure 1]

[0024] Figure 1 shows PET agglomeration (%) versus relative crystallinity. Triangular dots indicate PET agglomeration greater than 1%. Circle dots indicate PET agglomeration less than 1%, thus passing Document No. PET-CG-02, "Important Instructions for Transparent PET Articles with Labels and Seals," dated April 11, 2019. Detailed Description of the Invention

[0022]

[0025] The present disclosure will be more readily understood with reference to the following detailed description of certain embodiments and examples of the present disclosure. In accordance with the purposes of this disclosure, certain embodiments of the present disclosure are described in the Summary of the Invention and further described herein below. Other embodiments of the present disclosure are also described herein.

[0023]

[0026] Heat-shrinkable plastic films are used as coverings to hold multiple objects together and as outer packaging materials for bottles, cans, and other types of containers. For example, the films are used to cover the lid, neck, shoulder, body, or entire bottle for product labeling, protection, packaging, or value enhancement, and for other reasons. Furthermore, the films can be used as coverings to package a group of objects, such as boxes, bottles, boards, sticks, or notebooks, and the films can also be tightly adhered as packaging materials. The above uses take advantage of the film's shrinkability and internal shrinkage stress.

[0024]

[0027] Historically, polyvinyl chloride (PVC) film dominated the shrink film market. However, polyester film has become a viable alternative because it does not have the environmental issues associated with PVC film. Ideally, polyester shrink film would have properties very similar to PVC film, allowing it to function as a "drop-in" replacement and be processed in existing heat shrink tunnel equipment. Desired PVC film properties for replication include: (1) a relatively low shrink initiation temperature; (2) a total shrink rate that increases gradually and in a controlled manner with increasing temperature; (3) a low shrink force to prevent collapse of the underlying container; (4) a high total shrink rate (e.g., greater than 50%); and (5) inherent film toughness to prevent undue tearing and splitting of the film before and after shrinking.

[0025]

[0028] To be used in this application, heat-shrinkable films must meet various standards. The film must be strong, shrink in a controlled manner, and provide sufficient shrinkage force to hold itself against the bottle surface without crushing the contents. Furthermore, when these labels are applied to polyester containers, they must not interfere with the recycling process of PET bottles. In fact, it would be advantageous if the label were also recyclable, allowing the entire bottle to be recycled and converted into a new product without creating additional handling requirements or new environmental problems. Heat-shrinkable films are manufactured from a variety of raw materials to meet a range of material needs. This disclosure describes the unique and unexpected effects of combining specific monomers to improve the recyclability of polyester shrink film labels.

[0026]

[0029] Polyester shrink film compositions are commercially used as shrink film labels for food, beverages, personal care products, and household goods. These shrink films are often combined with clear polyethylene terephthalate (PET) bottles or containers. The entire product (bottle and label) is then sent to a recycling process. At typical recycling sites, PET and shrink film materials are often mixed together at the end of the process due to their similar compositions and densities. Drying of the PET flakes is necessary to remove residual water from the PET during the recycling process. During the recycling process, PET is typically dried at temperatures exceeding 200°C. At these temperatures, typical polyester shrink film resins soften and become sticky, often forming agglomerates with the PET flakes. These agglomerates must be removed before further processing. These agglomerates reduce the yield of PET flakes from the process, necessitating additional handling steps.

[0027]

[0030] In the present disclosure, it has been discovered that specific combinations of glycol monomers in shrink film resin compositions can produce shrink films that have excellent performance properties and are also crystallizable so as not to affect the recyclability of PET flakes during the recycling process. These crystallizable shrink film resins can be processed with PET bottles and become a component of the recyclable PET flakes after the recycling process is complete. The selection of the specific combination of glycol monomers and their amounts have been found to be important in producing films with excellent shrink film properties and that are crystallizable.

[0028]

[0031] The term "polyester" as used herein is intended to encompass "copolyester" and is understood to mean 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. Generally, the difunctional carboxylic acid may be a dicarboxylic acid, and the difunctional hydroxyl compound may be a dihydric alcohol, such as glycols and diols. The term "glycol" as used herein 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. The term "residue" as used herein refers to any organic structure incorporated into a polymer by polycondensation and / or esterification reactions from the corresponding monomers. The term "repeating unit" as used herein refers to an organic structure having dicarboxylic acid residues and diol residues linked via ester groups. Thus, for example, the dicarboxylic acid residues may be derived from a dicarboxylic acid monomer or its associated acid halides, esters, salts, anhydrides, and / or mixtures thereof. Additionally, the term "diacid" as used herein includes polyfunctional acids, such as branching agents. Thus, the term "dicarboxylic acid" as used herein is intended to encompass any dicarboxylic acid derivative useful for reacting with a diol to yield a polyester, such as a dicarboxylic acid and its associated acid halides, esters, half-esters, salts, half-salts, anhydrides, mixed anhydrides, and / or mixtures thereof. The term "terephthalic acid" as used herein is intended to encompass terephthalic acid itself and its residues, as well as any terephthalic acid derivative useful for reacting with a diol to yield a polyester, such as its associated acid halides, esters, half-esters, salts, half-salts, anhydrides, mixed anhydrides, and / or mixtures thereof.

[0029]

[0032] 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 the corresponding residues. Thus, the polyesters of the present disclosure may contain substantially equal molar ratios of acid residues (100 mol%) and diol (and / or polyfunctional hydroxyl compound) residues (100 mol%), such that the total moles of repeat units equal 100 mol%. Thus, the mole percentages presented 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 repeat units. For example, a polyester containing 10 mol% isophthalic acid, based on the total acid residues, means that the polyester contains 10 mol% isophthalic acid residues out of a total of 100 mol% acid residues. That is, there are 10 moles of isophthalic acid residues for every 100 moles of acid residues. As another example, a polyester containing 25 mole percent 1,4-cyclohexanedimethanol, based on total diol residues, means that the polyester contains 25 mole percent 1,4-cyclohexanedimethanol residues out of a total of 100 mole percent diol residues, i.e., there are 25 moles of 1,4-cyclohexanedimethanol residues in every 100 moles of diol residues.

[0030]

[0033] In certain embodiments, terephthalic acid or its esters, such as dimethyl terephthalate or mixtures of terephthalic acid residues and their esters, can comprise part or all of the dicarboxylic acid component used to form polyesters useful in the present disclosure. In certain embodiments, terephthalic acid residues can comprise part or all of the dicarboxylic acid component used to form polyesters useful in the present disclosure. For purposes of this disclosure, the terms "terephthalic acid" and "dimethyl terephthalate" are used interchangeably herein. In one embodiment, dimethyl terephthalate is part or all of the dicarboxylic acid component used to make polyesters useful in the present disclosure. In some embodiments, 70 to 100 mol %; or 80 to 100 mol %; or 90 to 100 mol %; or 99 to 100 mol %; or 100 mol % terephthalic acid and / or dimethyl terephthalate and / or mixtures thereof may be used.

[0031]

[0034] In addition to terephthalic acid, the dicarboxylic acid component of the polyesters useful in the present disclosure may comprise 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% modified aromatic dicarboxylic acids. Therefore, it is contemplated that the amount of one or more modified aromatic dicarboxylic acids, if present, may vary within any of these endpoints, e.g., 0.01 to 10 mol%, 0.01 to 5 mol%, or 0.01 to 1 mol%. In one embodiment, modified aromatic dicarboxylic acids that may be used in the present disclosure include, but are not limited to, those having up to 20 carbon atoms and which can be linear, para-oriented, or symmetrical. Examples of modified aromatic dicarboxylic acids that may be used in the present 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'-stilbene dicarboxylic acid, and esters thereof. In one embodiment, the modifying aromatic dicarboxylic acid is isophthalic acid.

[0032]

[0035] The carboxylic acid component of the polyesters useful in the present disclosure can be further modified with up to 10 mol%, e.g., 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. Certain embodiments may also include 0.01 to 10 mol%, e.g., 0.1 to 10 mol%, 1 or 10 mol%, or 5 to 10 mol%, of one or more modified aliphatic dicarboxylic acids. Yet another embodiment includes 0 mol% 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 polyesters useful in the present disclosure.

[0033]

[0036] Esters of terephthalic acid and other modified dicarboxylic acids or their corresponding esters and / or salts may be used in place 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.

[0034]

[0037] In one embodiment, the diol component of the polyester compositions and polyester blend compositions useful in this disclosure may comprise 1,4-cyclohexanedimethanol. In another embodiment, the diol component of the polyester compositions useful in this disclosure comprises 1,4-cyclohexanedimethanol and 1,3-cyclohexanedimethanol. The molar ratio of cis / trans 1,4-cyclohexanedimethanol may vary from 50 / 50 to 0 / 100, for example, from 40 / 60 to 20 / 80.

[0035]

[0038] The diol component of the polyester compositions useful in the present disclosure may include, but is not limited to, 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%, or 4 to 20 mol%, or 4 to 15 mol%, or 4 to 10 mol%, or 5 to 30 mol%, or 5 to 25 mol%, or 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%, or 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 is 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%, or 10 to 29 mol%, or 11 to 29 mol%,Alternatively, the total mol% of 1,4-cyclohexanedimethanol residues and neopentyl glycol residues in the final polyester composition may be 1 to 16 mol%, 2 to 14 mol%, 4 to 15 mol%, 2 to 21 mol%, 2 to less than 20 mol%, 4 to 20 mol%, 5 to 18 mol%, 10 to 21 mol%, or 12 to 21 mol%, where the total mol% of the diol component is 100 mol%.

[0036]

[0039] In one embodiment, the diol component of a polyester composition useful in the present disclosure may comprise 1 to 30 mol % neopentyl glycol, based on the total mole percent of the diol component being 100 mol %. In one embodiment, the diol component of a polyester composition useful in the present disclosure may comprise 1 to 25 mol % neopentyl glycol, based on the total mole percent of the diol component being 100 mol %. In one embodiment, the diol component of a polyester composition useful in the present disclosure may comprise 1 to 17 mol % neopentyl glycol, based on the total mole percent of the diol component being 100 mol %. In one embodiment, the diol component of a polyester composition useful in the present disclosure may comprise 5 to 20 mol % neopentyl glycol, based on the total mole percent of the diol component being 100 mol %. In one embodiment, the diol component of a polyester composition useful in the present disclosure may comprise 10 to 20 mol % neopentyl glycol, based on the total mole percent of the diol component being 100 mol %. In one embodiment, the diol component of the polyester compositions useful in the present disclosure may comprise 10 to 15 mole percent neopentyl glycol, based on the total mole percent of the diol component being 100 mole percent. In one embodiment, the diol component of the polyester compositions useful in the present disclosure may comprise 15 to 25 mole percent neopentyl glycol residues, based on the total mole percent of the diol component being 100 mole percent.

[0037]

[0040] In one embodiment, the diol component of the polyester compositions useful in the present disclosure comprises from 0.01 to 30 mol%, or from 0.1 to 20 mol%, or from 2 to 20 mol%, or from 0.01 to 15 mol%, or from 0.01 to 14 mol%, or from 0.01 to 13 mol%, or from 0.01 to 12 mol%, or from 0.01 to 11 mol%, or from 0.01 to 10 mol%, or from 0.01 to 9 mol%, or from 0.01 to 8 mol%, or from 0.01 to 7 mol%, or from 0.01 to 18 mol%, based on the total mol% of the diol components being 100 mol%. It may contain 1 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% of 1,4-cyclohexanedimethanol residues.

[0038]

[0041] In one embodiment, the diol component of a polyester composition useful in the present disclosure may comprise 0.01 to 15 mol % of 1,4-cyclohexanedimethanol residues, based on the total mole percent of the diol component, which is 100 mol %. In one embodiment, the diol component of a polyester composition useful in the present disclosure may comprise 0 to less than 15 mol % of 1,4-cyclohexanedimethanol residues, based on the total mole percent of the diol component, which is 100 mol %. In one embodiment, the diol component of a polyester composition useful in the present disclosure may comprise 0.01 to 10 mol % of 1,4-cyclohexanedimethanol residues, based on the total mole percent of the diol component, which is 100 mol %. In one embodiment, the diol component of a polyester composition useful in the present disclosure may comprise 0 to less than 10 mol % of 1,4-cyclohexanedimethanol residues, based on the total mole percent of the diol component, which is 100 mol %. In one embodiment, the diol component of the polyester compositions useful in the present disclosure may comprise 0.01 to 5 mole percent of 1,4-cyclohexanedimethanol residues, based on the total mole percent of the diol component being 100 mole percent. In one embodiment, the diol component of the polyester compositions useful in the present disclosure may comprise 0 to less than 5 mole percent of 1,4-cyclohexanedimethanol residues, based on the total mole percent of the diol component being 100 mole percent.

[0039]

[0042] Some other diol residues may, of course, be generated in situ during processing. In one embodiment, the diol component of the polyester compositions described herein may contain any amount of diethylene glycol residues, either generated in situ during processing or intentionally added, or both. For example, in one embodiment, a polyester composition useful in the present disclosure may contain 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%.

[0040]

[0043] In one embodiment, the total amount of diethylene glycol residues present in the polyester compositions useful in the present disclosure, whether generated in situ during processing, intentionally added, or both, based on the total mole percent of the diol component being 100 mole%, can be 4 mole percent or less, or 3.5 mole percent or less, or 3.0 mole percent or less, or 2.5 mole percent or less, or 2.0 mole percent or less, or 1.5 mole percent or less, or 1.0 mole percent or less, or from 1 to 4 mole percent, or from 1 to 3 mole percent, or from 1 to 2 mole percent, or from 2 to 8 mole percent, or from 2 to 7 mole percent, or from 2 to 6 mole percent, or from 2 to 5 mole percent, or from 3 to 8 mole percent, or from 3 to 7 mole percent, or from 3 to 6 mole percent, or from 3 to 5 mole percent, or in some embodiments, no intentionally added diethylene glycol residues.

[0041]

[0044] In all embodiments, the remainder of the diol component may comprise any amount of ethylene glycol residues, based on the total mole percent of the diol component being 100 mole percent. In one embodiment, the polyester portion of the polyester composition useful in the present disclosure may comprise 50 mole percent or more, or 55 mole percent or more, or 60 mole percent or more, or 65 mole percent or more, or 70 mole percent or more, or 75 mole percent or more, or 80 mole percent or more, or 85 mole percent or more, or 90 mole percent or more, or 95 mole percent or more, or 50-85 mole percent, or 50-80 mole percent, or 55-80 mole percent, or 60-80 mole percent, or 50-75 mole percent, or 55-75 mole percent, or 60-75 mole percent, or 65-75 mole percent, or 70-80 mole percent, or 75-85 mole percent, based on the total mole percent of the diol component being 100 mole percent.

[0042]

[0045] In one embodiment, the diol component of the polyester compositions useful in the present disclosure may comprise 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 (a modified diol is defined as a diol that is not ethylene glycol, diethylene glycol, neopentyl glycol, or 1,4-cyclohexanedimethanol). In certain embodiments, the polyester compositions useful in the present disclosure may comprise up to 10 mol% of one or more modified diols. In certain embodiments, the polyesters useful in the present disclosure may comprise up to 5 mol% of one or more modified diols. In certain embodiments, polyesters useful in the present disclosure may contain 3 mole percent or less of one or more modified diols. In other embodiments, polyesters useful in the present disclosure may contain 0 mole percent of modified diols. However, because some other diol residues may be generated in situ, amounts of residues generated in situ may also be considered embodiments of the present disclosure.

[0043]

[0046] In some embodiments, the modifying diols used in the polyesters defined herein, if used, contain 2 to 16 carbon atoms. Examples of modifying 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 modifying diol. In another embodiment, the modifying 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, it may provide more than 4 mol % or more than 5 mol %. In one embodiment, the at least one modifying diol is 1,4-butanediol present in an amount of 5 to 25 mole %. In certain embodiments, no modifying diol is added to the polyester composition.

[0044]

[0047] In one embodiment, there is provided a shrink film comprising a polyester composition further comprising: 1,4-cyclohexanedimethanol residues present in an amount of 0.01 to about 10 mole %, diethylene glycol residues present in an amount of 2-9 mole %, neopentyl glycol residues present in an amount of 5-30 mole %, and ethylene glycol residues present in an amount of 60 mole % or greater, based on the total mole % of the diol component being 100 mole %.

[0045]

[0048] In one embodiment, the polyesters useful in the present disclosure may include at least one chain extender. Suitable chain extenders include, but are not limited to, multifunctional (including, but not limited to, difunctional) isocyanates, multifunctional epoxides such as epoxidized novolacs, and phenoxy resins. In certain embodiments, the chain extender may be added at the end of the polymerization process or after the polymerization process. If added after the polymerization process, the chain extender may be incorporated by compounding or by addition during a conversion process such as injection molding or extrusion.

[0046]

[0049] In certain embodiments, the amount of chain extender used may vary depending on the particular monomer composition used and the physical properties desired, but is generally from 0.1% to 10% by weight, for example, from 0.1% to 5% by weight, based on the total weight of the polyester.

[0047]

[0050] It is believed that the polyester compositions useful in the present disclosure may have at least one of the intrinsic viscosity ranges described herein and at least one of the monomer ranges for the polyester compositions described herein, unless otherwise specified. It is also believed that the polyester compositions useful in the present disclosure may have at least one of the Tg ranges described herein and at least one of the monomer ranges for the polyester compositions described herein, unless otherwise specified. It is also believed that the polyester compositions useful in the present disclosure may 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 for the polyester compositions described herein, unless otherwise specified.

[0048]

[0051] In embodiments of the present disclosure, polyester compositions useful in the present disclosure may exhibit at least one of the following intrinsic viscosity values ​​measured in 60 / 40 (wt / wt) phenol / tetrachloroethane at 25° C. and a concentration of 0.5 g / dL: 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.

[0049]

[0052] The glass transition temperature and strain-induced crystalline melting point (Tg and Tm, respectively) of polyesters are measured using a Thermal Analyst Instrument TA DSC 2920 at a scan rate of 20°C / min. Tm was measured during the first heat of the stretched sample, and Tg was measured during the second heat step. Additionally, samples can be crystallized in a forced air oven at 170°C for 2 hours and then analyzed by DSC. For all samples, the crystalline melting point is typically absent during the second heat of the DSC scan at a heating rate of 20°C / min.

[0050]

[0053] In certain embodiments, the oriented film, shrink film, or thermoformed sheet of the present disclosure comprises a polyester / polyester composition in which the polyester has a Tg of 60-80° C., 70-80° C., 65-80° C., 72-77° C., or 65-75° C. In certain embodiments, the polyester has an intrinsic viscosity of 0.68-0.75 dL / g measured in 60 / 40 (wt / wt) phenol / tetrachloroethane at 25° C. and a concentration of 0.5 g / dL, and a Tg of 72-77° C. measured using a Thermal Analyst Instrument TA DSC 2920 at a scan rate of 20° C. / min.

[0051]

[0054] In certain embodiments, these Tg ranges can be met with or without at least one plasticizer added during polymerization or extrusion or compounding.

[0055] In embodiments of the present disclosure, a particular oriented film and / or shrinkable film comprising a polyester and / or polyester composition useful in the present disclosure may have a unique combination of all of the following properties: excellent stretchability, controlled shrinkage properties, a particular toughness, a particular intrinsic viscosity, a particular glass transition temperature (Tg), a particular strain-induced crystalline melting point, a particular flexural modulus, a particular density, a particular tensile modulus, a particular surface tension, excellent melt viscosity, excellent clarity, and excellent color.

[0052]

[0056] In one embodiment, certain polyester compositions useful in the present disclosure may be visually clear, the term "visually clear" being defined herein as the apparent absence of haze, mist, and / or cloudiness upon visual inspection.

[0053]

[0057] The polyester portion of the polyester composition useful in the present disclosure may be prepared by methods known in the literature, such as in homogeneous solution, by transesterification in the melt, and by two-phase interfacial methods. Suitable methods include, but are not limited to, reacting one or more dicarboxylic acids with one or more diols at temperatures between 100°C and 315°C and pressures between 0.1 and 760 mmHg for a time sufficient to produce the polyester. For methods of preparing polyesters, see U.S. Pat. No. 3,772,405, the disclosure of which is incorporated herein by reference.

[0054]

[0058] In certain embodiments, the polyesters may be prepared by condensing a dicarboxylic acid or dicarboxylic acid ester with a diol in the presence of a catalyst in an inert atmosphere at gradually increasing temperatures during the condensation, or by condensing the latter part of the condensation at low pressures, as described in more detail in U.S. Pat. No. 2,720,507, incorporated herein by reference.

[0055]

[0059] In some embodiments, during the manufacturing process of the polyesters useful in this disclosure, certain chemicals that color the polymer may be added to the melt containing the toner or pigment. In one embodiment, the resulting melt phase product of the polyester polymer is * Bluing toners are added to the melt to reduce the bluing effect. Such bluing agents include blue inorganic and organic toners and / or pigments. Red toners and / or pigments are also used to reduce the bluing effect. * The color tone of the polyester may be adjusted. 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 entireties, may be used, for example, blue and red organic toners. The organic toner may be supplied as a premixed composition. The premixed composition may be a neat mixture of the red and blue compounds, or the composition may be pre-dissolved or pre-slurried in one of the raw materials for the polyester, such as ethylene glycol.

[0056]

[0060] The total amount of toner components added depends on the amount of inherent yellow color in the base polyester and the efficacy of the toner. In one embodiment, 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 bluing 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 early stage of the polycondensation zone, for example, in a prepolymerization reactor.

[0057]

[0061] In some embodiments, the polyester composition may also contain common additives, such as lubricants, antiblocking agents, mold release agents, flame retardants, plasticizers, glass bubbles, nucleating agents, stabilizers such as, but not limited to, UV stabilizers and thermal stabilizers, and / or their reaction products, fillers, and impact modifiers, in amounts of 0.01 to 25 weight percent 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, styrenic block copolymer impact modifiers, and various acrylic core / shell impact modifiers. Residues of these additives are also contemplated as part of the polyester composition.

[0058]

[0062] In one embodiment, films and shrink films according to the present disclosure may contain 0.01 to 10 weight percent of a polyester plasticizer, such as those described in U.S. Patent No. 10,329,393, incorporated herein by reference. In one embodiment, shrink films may contain 0.01 to 10 weight percent of a polyester plasticizer incorporated into a copolyester of the present invention.

[0059]

[0063] In one aspect, the present disclosure relates to shrink films, extruded sheets, thermoformed articles, and molded articles comprising the polyester compositions of the present disclosure. Methods for forming polyester compositions into films and / or sheets are well known in the art. Examples of sheets useful in the present disclosure include, but are not limited to, extruded sheets, compression molded films, calendered films and / or sheets, and solution-cast films and / or sheets. In one aspect, methods for producing films and / or sheets useful for producing the shrink films of the present disclosure include, but are not limited to, extrusion, compression molding, calendering, and solution casting.

[0060]

[0064] In one embodiment, the polyester compositions useful in the present disclosure are made into films using any method known in the art for making films from polyesters, such as solution casting, extrusion, compression molding, or calendaring. See, for example, U.S. Patent Nos. 6,846,440; 6,551,699; 6,551,688; and 6,068,910, which are incorporated herein by reference.

[0061]

[0065] 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, 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 calendered films, and the oriented films may be oriented at temperatures from Tg to Tg+55°C or from 70°C to 125°C to a ratio of 5:1 to 3:1, e.g., a 5:1 or 3:1 ratio at temperatures from 70°C to 100°C, and the films may be oriented to a thickness of 20 to 80 μm. In one embodiment, orientation of the initial pre-shrunk film may be carried out in a tenter frame according to these orientation conditions.

[0062]

[0066] Shrink films of the present disclosure may have a shrink initiation temperature of from about 55 to about 80° C., or from about 55 to about 75° C., or from about 55 to about 70° C. The shrink initiation temperature is the temperature at which the initiation of shrinkage occurs.

[0063]

[0067] In certain embodiments, 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.

[0064]

[0068] In one embodiment, many small voids or holes are introduced into a film or molded article to reduce the film's density. This process is called "voiding," sometimes referred to as "cavitating" or "microvoiding." These voids are created by incorporating about 1 to about 50% by weight of small organic or inorganic particles (including glass microspheres) or "inclusions" (known in the art as "void-forming" or "cavitating" agents) into a matrix polymer and then stretching the polymer in at least one direction to orient it. During stretching, small cavities or voids are formed around the void-forming agents. When voids are introduced into a polymer film, the resulting voided film is not only less dense than a non-voided film, but also opaque and exhibits a paper-like surface. This surface also has the advantage of improving printability; i.e., the surface can accept more ink at a substantially greater volume than a non-voided film. Typical examples of apertured films are 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; 6,287,68 0; 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 Application Publication No. 0 581 970 B1; and European Patent Application Publication No. 0 214 859 A2.

[0065]

[0069] 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 of any thickness depending on the desired end use. In one embodiment, a desirable condition is that the oriented and / or shrinkable film can be printed with ink for applications such as labels, photographic films that can be adhered to substrates such as paper, and / or other applications where the films are useful for bottles or containers and can be shrunk to surround the outside. It may be desirable to coextrude the polyesters useful in the present disclosure with another polymer, such as PET, to enable the film to be used as the oriented and / or shrinkable films of the present disclosure. One advantage of the latter coextrusion technique is that, in some embodiments, a tie layer may not be required.

[0066]

[0070] In one embodiment, uniaxially and biaxially oriented films of the present disclosure may be made from films, such as extruded, cast, or calendered films, having a thickness of about 100-400 μm, which may be stretched at a ratio of 6.5:1 to 3:1 at a temperature from the Tg of the film to Tg+55°C and stretched to a thickness of 20-80 μm. In one embodiment, orientation of the initial as-extruded film may be performed in a tenter frame according to these orientation conditions. Shrink films of the present disclosure can be made from the oriented films of the present disclosure.

[0067]

[0071] In certain embodiments, the shrink films of the present disclosure shrink slowly with little or no wrinkling. In certain embodiments, the shrink films of the present disclosure have a shrinkage rate in the transverse direction of 40% or less per 5° C. increment of temperature increase.

[0068]

[0072] In certain embodiments of the present disclosure, shrink films of the present disclosure have a machine direction shrinkage of 10% or less, or 5% or less, or 3% or less, or 2% or less, or no shrinkage, when immersed in water at 65°C for 10 seconds. In certain embodiments of the present disclosure, shrink films of the present disclosure have a machine direction shrinkage 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%, or no shrinkage, when immersed in water at 65°C for 10 seconds. A negative machine direction shrinkage indicates expansion in the machine direction. A positive machine direction shrinkage indicates shrinkage in the machine direction.

[0069]

[0073] In certain embodiments of the present disclosure, the shrink films of the present disclosure have a shrink percentage in the main shrink direction of 50% or more, or 60% or more, or 70% or more when immersed in water at 95°C for 10 seconds.

[0070]

[0074] In certain embodiments of the present disclosure, the shrink film of the present disclosure has a shrinkage percentage of 50 to 90% in the main shrink direction and a shrinkage percentage of 10% or less, or -10% to 10%, in the machine direction when immersed in water at 95°C for 10 seconds.

[0071]

[0075] In one embodiment, polyesters useful in the present disclosure are formed into films using any method known in the art for producing films from polyesters, such as solution casting, extrusion, compression molding, or calendering. The as-extruded (or as-formed) film is then 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, uniaxially oriented films of the present disclosure may be made from films, e.g., extruded, cast, or calendered, having a thickness of about 100 to 400 μm, which may be stretched at a ratio of 6.5:1 to 3:1 from the Tg of the film to Tg+55°C and stretched to a thickness of 20 to 80 μm. In one embodiment, orientation of the initial as-extruded film may be carried out in a tenter frame according to these orientation conditions.

[0072]

[0076] In certain embodiments of the present disclosure, the shrink films of the present disclosure may have a breaking strain of greater than 200% at a stretch rate of 500 mm / min in the direction perpendicular to the main shrink direction according to ASTM method D882.

[0073]

[0077] In certain embodiments of the present disclosure, the shrink films of the present disclosure may have a breaking strain of greater than 300% at a stretch rate of 500 mm / min in the direction perpendicular to the main shrink direction according to ASTM method D882.

[0074]

[0078] In certain embodiments of the present disclosure, the shrink films of the present disclosure may have a tensile stress at break (stress at break) of 20 to 400 MPa, or 40 to 260 MPa, or 42 to 260 MPa, measured according to ASTM method D882.

[0075]

[0079] In certain embodiments of the present disclosure, the shrink films of the present disclosure may have a shrink force of 4 to 18 MPa, or 4 to 15 MPa, depending on the stretching conditions and desired end use, as measured by ISO Method 14616. For example, certain labels made for plastic bottles may have a shrink force of 4 to 8 MPa, and certain labels made for glass bottles may have a shrink force of 10 to 14 MPa, as measured by ISO Method 14616 using a LabThink FST-02 Heat Shrinkage Tester and reported in units of MPa.

[0076]

[0080] In one embodiment of the present disclosure, the polyester composition may be produced by reacting monomers by known methods for producing polyesters, typically referred to as reactor grade compositions.

[0077]

[0081] Molded articles can be made from any of the polyester compositions disclosed herein, which may consist of or include shrink film, and are included within the scope of this disclosure.

[0078]

[0082] In one embodiment, when having a pre-oriented thickness of about 100 to 400 μm and subsequently oriented in a tenter frame at a temperature from Tg to Tg+55°C and a ratio of 6.5:1 to 3:1 to a thickness of about 20 to about 80 μm, the shrink film of the present disclosure exhibits the following properties: (1) upon immersion in 95°C water for 10 seconds, it shrinks by an amount greater than 60% (or greater than 70%) in the main shrinkage or transverse direction, and 10% or less (or -5% to 4%) in the machine direction. (2) a shrink onset temperature of about 55°C to about 70°C; (3) a strain at break of greater than 200%, or 200-600%, or 200-500%, or 226-449%, or 250-455%, in accordance with ASTM Method D882, at a stretching rate of 500 mm / min in the transverse direction, machine direction, or both; (4) a shrinkage of 40% or less per 5°C temperature increase increment; and / or (5) a melting point of strain-induced crystallinity of 200°C or greater. Any combination of these properties, or all of these properties, may be present in a shrink film of the present disclosure. A shrink film of the present disclosure may have a combination of two or more of the above-mentioned shrink film properties. A shrink film of the present disclosure may have a combination of three or more of the above-mentioned shrink film properties. A shrink film of the present disclosure may have a combination of four or more of the above-mentioned shrink film properties. In certain embodiments, properties (1) and (2) are present. In certain embodiments, characteristics (1) to (5) are present. In certain embodiments, characteristics (1) to (3), etc. are present.

[0079]

[0083] The shrinkage percentages herein are based on initial, as-produced films having a thickness of about 20-80 μm that have been oriented in a tenter frame at a ratio of 6.5:1 to 3:1 at temperatures from Tg to Tg+55° C., e.g., a ratio of 5:1 at temperatures from 70° C. to 85° C. In one embodiment, the shrink properties of oriented films used to make the shrink films of the present disclosure were unchanged when the films were annealed at temperatures higher than the temperature at which they were oriented.

[0080]

[0084] The shape of a film useful for making the oriented or shrink films of the present disclosure is not limited in any way. For example, the shape can be a flat film or a film formed into a tube. A film formed into a tube can have its edges bonded or held together during shrinking using a stitching solvent or stitching adhesive. To produce a shrink film useful in the present disclosure, the polyester is first formed into a flat film and then "uniaxially oriented," meaning that the polyester film is oriented in one direction. The film may also be "biaxially oriented," meaning that the polyester film is oriented in two different directions; for example, the film is stretched in both the machine direction and a direction different from the machine direction. Typically, the two directions are substantially perpendicular, but this is not always the case. For example, in one embodiment, the two directions are the longitudinal direction or machine direction ("MD") of the film (the direction in which the film is produced on the film-making machine) and the transverse direction ("TD") of the film (the direction perpendicular to the MD of the film). Biaxially oriented films may be sequentially oriented, simultaneously oriented, or oriented by some combination of simultaneous and sequential stretching.

[0081]

[0085] Films may be oriented by any conventional method, such as roll stretching, long-gap stretching, tenter frame stretching, and tubular stretching. Any of these methods may be used to achieve sequential biaxial stretching, simultaneous biaxial stretching, uniaxial stretching, or a combination thereof. The biaxial stretching described above may achieve simultaneous stretching in the machine and transverse directions. Stretching may also be performed first in one direction and then in the other, effectively resulting in biaxial orientation. In one embodiment, film stretching is performed by preheating the film to 5°C to 80°C above its glass transition temperature (Tg). In one embodiment, the film may be preheated to 5°C to 30°C above its Tg. In one embodiment, the stretching rate is 0.5 to 20 inches (1.27 to 50.8 cm) per second. The film may then be oriented, for example, to 2 to 6 times its original dimensions in either the machine direction, the transverse direction, or both. The film may be oriented as a single film layer or may be coextruded with another polyester, such as PET (polyethylene terephthalate), as a multilayer film and then oriented.

[0082]

[0086] In one embodiment, the present disclosure includes an article of manufacture or a molded article comprising a shrink film of any of the shrink film embodiments of the present disclosure. In another embodiment, the present disclosure includes an article of manufacture or a molded article comprising an oriented film of any of the oriented film embodiments of the present disclosure.

[0083]

[0087] In certain embodiments, the present disclosure includes, but is not limited to, shrink films applied to containers, plastic bottles, glass bottles, packaging, batteries, hot-fill containers, and / or industrial products or other uses. In one embodiment, the present disclosure includes, but is not limited to, oriented films applied to containers, packaging, plastic bottles, glass bottles, photographic substrates such as paper, batteries, hot-fill containers, and / or industrial products or other uses.

[0084]

[0088] In certain embodiments of the present disclosure, the shrink films of the present disclosure may be formed into labels or sleeves which may then be applied to the wall of a container, an article of manufacture such as a battery, or onto a sheet or film.

[0085]

[0089] The oriented or shrink films of the present disclosure can be applied to molded articles such as tubes or bottles and are commonly used in a variety of packaging applications. For example, films and sheets made from polymers such as polyolefins, polystyrene, polyvinyl chloride, polyester, and polylactic acid (PLA) are frequently used to manufacture shrink labels for plastic beverage or food containers. For example, the shrink films of the present disclosure can be used in many packaging applications, where the shrink films applied to molded articles exhibit properties such as excellent printability, excellent shrink force, excellent texture, high shrink ratio, controlled shrink rate, high stiffness, and recyclability.

[0086]

[0090] The improved shrink properties and recyclability should provide new commercial options such as, but not limited to, shrink films applied to containers, plastic bottles, glass bottles, packaging, batteries, hot fill containers, and / or industrial products or other uses.

[0087]

[0091] In one aspect of the present disclosure, the disclosed polyester compositions are useful as thermoformed and / or thermoformable sheets. The present disclosure is also directed to articles of manufacture incorporating the thermoformed sheets of the present disclosure. In one embodiment, the polyester compositions of the present disclosure are useful as sheets that are easily formed into molded or shaped articles or parts. 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.

[0088]

[0092] Additionally, in one embodiment, the polyester compositions useful in the thermoformed sheets of the present disclosure may also contain common additives such as colorants, antiblocking agents, lubricants, mold release agents, flame retardants, plasticizers, nucleating agents, stabilizers such as, but not limited to, UV stabilizers, heat stabilizers, fillers, and impact modifiers, in amounts of 0.1 to 25% by weight of the total composition.

[0089]

[0093] In one embodiment, reinforcing materials may be included in thermoformed sheets comprising the polyester compositions 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, polymeric fibers, and combinations thereof.

[0090]

[0094] In one embodiment, the thermoformed sheet of the present disclosure is a multi-layer sheet, hi one embodiment, at least one layer of the multi-layer sheet is a foam layer or an expanded polymer or polyester layer.

[0091]

[0095] One aspect of the present disclosure is a method of producing formed or molded parts and articles using thermoforming. Any thermoforming technique or process known to one of ordinary skill in the art can be used to produce the formed or molded articles and parts of the present disclosure.

[0092]

[0096] In one embodiment, the thermoforming process can be carried out in several ways, as taught, for example, in "Technology of Thermoforming" (Throne, James; Hanser Publishers; 1996; pp. 16-29), which is incorporated herein by reference. In some embodiments, the process is a male thermoforming process in which gas or air pressure is applied to a softened sheet, which is then stretched and drawn like a bubble, with a male mold placed inside the bubble. A vacuum is then applied to further draw the part and conform it to the surface of the male mold. In this thermoforming process, biaxial stretching / orientation is primarily accomplished in one step as gas or air pressure is applied to the softened sheet. The forming process is then completed by cooling below the Tg of the sheet and using a vacuum and a male mold to lock in the orientation in the sheet for a good balance of physical and cosmetic properties. In another embodiment, the process is a female mold process in which a vacuum or physical plug is applied to the heat-softened sheet to stretch and draw it to approximately the final part dimensions, then internal positive air pressure or an additional external vacuum is used to draw the sheet and conform it to an external female mold, which is cooled below the Tg of the sheet to lock in the orientation and form the sheet into an article.

[0093]

[0097] In some embodiments, the bubble formation may be further formed using a plug assist, followed by covering and molding the rising male mold with a sheet, and then applying a vacuum to pull the corners, sleeve guides, etc. into the mold. In some embodiments, after removal from the mold, the formed part or article may be cut, punched, cornered, etc., as needed.

[0094]

[0098] In another embodiment, thermoforming is a process in which a sheet of the polyester composition of the present disclosure is heated to a temperature sufficient to allow it to deform, and then the heated sheet is forced to conform to the contours of a mold by means such as vacuum assistance, air pressure assistance, and mating mold assistance. In another embodiment, the heated sheet is placed in a mold and forced to conform to the contours of the mold, for example, by applying air pressure, using a vacuum plug assist, or using a mating mold. In some embodiments, thin-walled articles are produced by thermoforming. In some embodiments, thick-walled articles are produced by thermoforming.

[0095]

[0099] In one embodiment, the thermoforming process involves forcing a male mold into a heated sheet, thereby forming the sheet into a desired shape. In certain embodiments, thermoforming involves having the male mold of the article supported between a vacuumed surface or table. In these embodiments, heat from an external heat source, such as a hot air blower, heat lamp, or other radiant heat source, is directed at the sheet. In these embodiments, the sheet is heated to its softening point. In these embodiments, a vacuum is then applied to the table, under the table, and around the mold, drawing the heat-softened sheet toward the table, placing the softened sheet in contact with the mold surface. In these embodiments, the vacuum draws the softened sheet into intimate contact with and conforms to the contours of the mold surface, thereby forming the sheet into the shape of the mold. In these embodiments, after the sheet cools, it solidifies and the resulting article or part can be removed from the mold.

[0096]

[0100] In one embodiment, the thermoforming process includes forming a sheet from the polyester composition of the present disclosure; heating the sheet until it softens and placing the sheet over a mold; drawing the preheated sheet over the heated mold surface; cooling the sheet; and then removing the formed article or part from the mold cavity, or, as the case may be, heat-setting the formed sheet by maintaining the sheet in contact with the heated mold for a time sufficient to partially crystallize the sheet.

[0097]

[0101] In one embodiment, the thermoforming process includes forming a sheet from the polyester composition of the present disclosure; heating the sheet to a temperature at or above the Tg of the polyester; applying gas pressure, vacuum, and / or physical pressure to the heat-softened sheet to stretch the sheet to approximately the final part dimensions; conforming the sheet to the shape of a mold with the vacuum or pressure; cooling the sheet to a temperature below the Tg of the polyester; and then removing the thermoformed article or part from the mold.

[0098]

[0102] Sheets used in thermoforming processes may be made by any conventional method known to those skilled in the art. In one embodiment, the sheet is formed by extrusion. In one embodiment, the sheet is formed by calendaring. In one embodiment, during the thermoforming process, the sheet is heated to a temperature equal to or greater than 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, to achieve shorter forming times, it is necessary to heat the sheet before placing it on the thermoforming mold. In one embodiment, the sheet must be heated above its Tg but below a temperature at which the sheet sags excessively while being placed over the mold cavity. In one embodiment, the formed sheet is cooled to a temperature below the Tg of the polyester before being removed from the mold. In one embodiment, the thermoforming method may include vacuum assistance, air assistance, mechanical plug assistance, or mating molds. In some embodiments, the mold is heated to a temperature equal to or greater than the Tg of the sheet. Selection of the optimal mold temperature depends on the mold of the thermoforming device, the configuration and wall thickness of the article being formed, and other factors.

[0099]

[0103] In some embodiments, the heated sheet is stretched by generating and applying a vacuum.

[0104] In one embodiment, heat setting is a process that thermally induces partial crystallization of a polyester sheet without appreciable orientation. In one embodiment, heat setting is achieved by maintaining contact of the sheet with a heated mold surface for a time sufficient to achieve a level of crystallinity that imparts suitable physical properties to the finished part. In certain embodiments, the level of crystallinity (relative crystallinity) should be greater than 8 cal / g.

[0100]

[0105] In one embodiment, the heat-set part may be removed from the mold cavity by known means for removal. For example, in one embodiment, a blowback is used, which involves introducing compressed air to break the vacuum established between the mold and the formed sheet. In some embodiments, excess material from the formed article or part is then trimmed, and the waste material is crushed and recycled.

[0101]

[0106] In some embodiments, the addition of a nucleating agent provides faster crystallization during thermoforming, and therefore faster molding. In one embodiment, a nucleating agent such as a fine particle-sized inorganic or organic material may be used. For example, in one embodiment, suitable nucleating agents include talc, titanium dioxide, calcium carbonate, and immiscible or crosslinked polymers. In one embodiment, the nucleating agent may be used in an amount ranging 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, crack inhibitors, and stabilizers, may be used as needed for thermoforming. In some embodiments, the crack inhibitor improves impact strength, and the nucleating agent provides faster crystallization. In some embodiments, crystallization is necessary to achieve high temperature stability.

[0102]

[0107] In one embodiment, a foamed polyester sheet is prepared by foaming a polyester composition of the present disclosure with a chemical and / or physical foaming agent, extruding the foamed polyester into a sheet, and thermoforming the foamed polyester sheet. Additives to improve the properties of the foamed polyester sheet may be added to the polyester before foaming. Examples of such additives include lubricants, antiblocking agents, plasticizers, optical brighteners, and UV inhibitors. In one embodiment, the foamed polyester sheet may be an extrusion or laminate coated on one or both sides using conventional techniques to improve its properties. In one embodiment, the coating material may be a printing surface that provides product labeling, rather than the foam sheet itself.

[0103]

[0108] In certain embodiments, the compositions of the present disclosure are useful as formed or molded plastic parts or solid plastic articles. In some embodiments, the compositions of the present disclosure are useful as thermoformed parts or articles. In some embodiments, the compositions of the present disclosure are suitable for use in any application where a clear, rigid plastic is required. In some embodiments, for example, the compositions of the present disclosure are suitable for use as parts for disposable knives, forks, spoons, plates, cups, straws, eyeglass frames, toothbrush handles, toys, automotive accessories, tool handles, camera parts, electronic device parts, razor parts, ink pen barrels, disposable syringes, bottles, and the like. In one embodiment, the compositions of the present disclosure are useful as plastics, films, fibers, and sheets.

[0104]

[0109] In one embodiment, the compositions are useful as plastics for manufacturing bottles, bottle caps, eyeglass frames, cutlery, disposable cutlery, cutlery handles, shelves, shelf dividers, electronic device housings, electronic device cases, computer monitors, printers, keyboards, tubing, automotive parts, automotive interior parts, automotive trim, signage, thermoformed letters, siding, toys, thermally conductive plastics, ophthalmic lenses, tools, tool handles, and household items. In another embodiment, the compositions of the present disclosure are formed into films, sheets, fibers, formed articles, molded articles, formed parts, molded parts, medical devices, dental trays, dental instruments, containers, food containers, shipping containers, packaging, bottles, bottle caps, eyeglass frames, cutlery, disposable cutlery, cutlery handles, shelves, shelf dividers, furniture parts, electronics enclosures, electronics cases, computer monitors, printers, keyboards, tubing, toothbrush handles, automotive parts, automotive interior parts, automotive trim, signs, outdoor signs, skylights, multi-walled layer films, multi-layer films, insulation parts, insulation articles, insulated containers, thermoformed letters, wallboard, toys, toy parts, trays, food trays, teeth Suitable for use as medical trays, thermally conductive plastics, ophthalmic lenses and frames, tools, tool handles, and household items, healthcare products, commercial food supply products, boxes, graphic arts film, plastic film for plastic glazing laminates, point of purchase signs, skylights, smoke vents, laminated cards, fenestration, glazing, dividers, ceiling tiles, lighting, machine guards, graphic arts, lenses, extruded laminate sheet or film, decorative laminates, office furniture, face shields, medical packaging, shelf sign holders, and shelf price holders.

[0105]

[0110] The thermoformed or thermoformable sheet is useful for forming films, formed articles, formed parts, molded articles, molded parts, and sheets. The thermoformed or thermoformable composition can be manufactured into films, formed articles, formed parts, molded articles, molded parts, and sheets by any method known in the art. Examples of formed articles include, but are not limited to, medical devices, medical packaging, healthcare products, commercial food service products such as trays, containers, food plates, tumblers, storage boxes, bottles, food processors, mixing bowls, household products, water bottles, crisper trays, washing machine parts, refrigerator parts, vacuum cleaner parts, ophthalmic lenses and frames, and toys.

[0106]

[0111] The present disclosure further relates to articles of manufacture comprising sheets comprising the polyester compositions described herein. In some embodiments, the sheets of the present disclosure may be of any thickness required for the intended use.

[0107]

[0112] The present disclosure further relates to the sheets described herein. Methods for forming the polyester composition into a sheet include any method known in the art. Examples of sheets of the present disclosure include, but are not limited to, extruded sheets, calendered sheets, compression molded sheets, and solution-cast sheets. Methods for making sheets of the present disclosure include, but are not limited to, extrusion, calendering, compression molding, wet-blocking, dry-blocking, and solution-casting.

[0108]

[0113] The present disclosure further relates to the formed or molded articles described herein. Methods for forming the polyester composition into a formed or molded article include any method known in the art. Examples of formed or molded articles of the present disclosure include, but are not limited to, thermoformed or thermoformable articles, injection molded articles, extrusion molded articles, injection blow molded articles, injection stretch blow molded articles, and extrusion blow molded articles. Methods for producing formed articles 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.

[0109]

[0114] This disclosure includes any injection blow molding manufacturing process known in the art. A typical, but non-limiting, 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) closed at one end, 3) transferring the preform into a blow mold having the desired final shape around the preform and closing the blow mold around the preform, 4) blowing air into the preform to stretch and expand it to fill the mold, 5) cooling the molded article, and 6) removing the article from the mold.

[0110]

[0115] This disclosure includes any injection stretch blow molding manufacturing process known in the art. A typical, but not limited to, 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) closed at one end; 3) transferring the preform to a blow mold having the desired final shape around the preform and closing the blow mold around the preform; 4) stretching the preform using an internal stretch rod and blowing air into the preform to stretch and expand it to fill the mold; 5) cooling the molded article; and 6) removing the article from the mold.

[0111]

[0116] This disclosure includes any extrusion blow molding manufacturing process known in the art. A typical, but non-limiting, 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 molten preform), 3) clamping a mold having the desired final shape around the molten preform, 4) blowing air into the molten preform 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.

[0112]

[0117] The following examples further illustrate how the polyesters of the present disclosure can be made and evaluated, and are intended to be purely illustrative and not limiting in scope. Unless otherwise indicated, parts are parts by weight, temperature is in ° C (Celsius) or is at room temperature, and pressure is at or near atmospheric. [Example]

[0113]

[0118] Copolyester resin samples were prepared using the procedures described herein. In all cases, the resin samples were dried before extrusion.

[0119] Test film samples were prepared by extruding the resin samples into 10 mil (250 μm) films using a 2.5 inch Davis and Standard single screw extruder. These 10 mil films were cut and stretched to a final thickness of 50 μm in a Bruckner Karo 4 tenter frame at a temperature 5-15°C above the glass transition temperature (Tg) of the extruded film and a stretch ratio of approximately 5:1.

[0114]

[0120] Tenterframe film samples were prepared by extruding resin samples and stretching them in a commercially available tenterframe (located at Marshall and Williams, a division of Parkinson Technologies). Here, the film was extruded using three layers from an ABC die, with the B layer extruded through a 2.5-inch single-screw extruder and the A and C layers extruded through separate 1.25-inch single-screw satellite extruders. The film was cast at approximately 10 mils (250 μm) thick and then stretched to 50 μm using a 5:1 stretch ratio. Typically, the cast thickness was 250 μm, with a final film thickness of 50 μm. The line speed was 45 fpm.

[0115]

[0121] The glycol content of the extruded film compositions was measured by NMR. All NMR spectra were recorded on a JEOL Eclipse Plus 600 MHz nuclear magnetic resonance spectrometer using chloroform-trifluoroacetic acid (70-30:vol / vol) for all polymers 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%.

[0116]

[0122] The intrinsic viscosity of the polyesters herein was measured in 60 / 40 (wt / wt) phenol / tetrachloroethane at 25° C. and a concentration of 0.5 g / dL, and the values ​​are reported in dL / g.

[0117]

[0123] Shrinkage is measured herein by placing a 50 mm x 50 mm square film sample in water at temperatures between 65°C and 95°C in 5°C increments. The film is immersed in water for 10 seconds without restricting shrinkage in either direction, and the shrinkage (or expansion) of the film sample is measured. Shrinkage is calculated using the following formula: Shrinkage rate (%) = [(50 mm - length after shrinkage) / 50 mm] x 100%

[0124] Shrinkage was measured in the direction perpendicular to the main shrinkage direction (machine direction: MD) and also in the main shrinkage direction (transverse direction: TD).

[0118]

[0125] Shrinkage force was measured in MPa using a LabThink FST-02 heat shrinkage tester at the same temperatures used to stretch the films for the examples herein.

[0126] Tensile film properties were measured for the examples herein using ASTM method D882. Multiple film stretching speeds (300 mm / min and 500 mm / min) were used to evaluate film toughness.

[0119]

[0127] The glass transition temperature and strain-induced crystalline melting point (Tg and Tm, respectively) of the polyester were measured using a Thermal Analyst Instrument TA DSC 2920 at a scan rate of 20°C / min. Tm was measured on the first heat of the stretched sample, and Tg was measured on the second heat step. Additionally, samples can be crystallized at 165°C for 30 minutes in a forced air oven and then analyzed by DSC. For all samples, the crystalline melting point was generally absent during the second heat of the DSC scan at a heating rate of 20°C / min.

[0120]

[0128] The suitability of materials for recycling processes is governed by procedures published by the Association for Plastic Recyclers (APR). In the case of PETG resins, PET clumping is the primary issue addressed by this invention. A laboratory process was developed to mimic this industry standard. The experimental clumping test parameters were as follows: Combine 582g of PET flakes with 18g of shrinkable film (3% film relative to the PET flakes) in its shrunk state (the film was immersed in 85°C water for 10 seconds to shrink it before combining). The PET flakes + film were placed in an aluminum dish to a depth of 1.5 inches. The dish containing the slices was placed in a forced air oven at 208°C for 1.5 hours. The flakes were then carefully poured through a 0.5 inch sieve and the amount of flakes that remained in the dish or failed to pass through the sieve was measured and the percent agglomeration was calculated as a percentage of the starting weight.

[0121]

[0129] The Association of Plastic Recyclers (APR) has established a test to determine whether materials comply with current recycling processes (Important Instructions for Clear PET Articles with Labels and Seals, revised or established on April 11, 2019; PET-CG-02). This method references the method for measuring PET cohesion (PET Flake Cohesion Assessment, revised on November 16, 2018; PET-S-08). Details of this test are as follows: Labeled bottle flakes are prepared by crushing the label (minimum weight: 3% by weight, pre-shrunk at 85°C for 10 seconds) and bottle into flakes measuring 1 / 4 to 1 / 2 inch. · Mix labeled bottle slices 50:50 with unlabeled reference bottle slices. · The samples were then wet classified under conditions that allowed no more than 1.2% of the PET to be carried over with the label. The slices are then washed in 0.3% Triton X-100 and 1.0% caustic at 88°C for 15 minutes. The flakes are then washed with water after removing all suspended solids and then filtered to remove excess water. · Wet classify the flakes again as before. · Place 2 pounds of cleaned flakes (including labels) into a Teflon-coated baking dish for each cleaned sample, adding the flakes to a layer thickness of 1.5 inches. Place the dish containing the slices in a circulating oven at 208°C for 1.5 hours. Cool the flakes and pass them through a sieve with 0.0625 inch openings. If the material passes through the sieve, it is not agglomerated, i.e., it is not too large to pass through the sieve. This test was followed by an extrusion / pelletization and molding process to confirm the quality of the flakes.

[0122]

[0130] Modulated differential scanning calorimetry (MDSC) is a technique that measures the difference in heat flow between a sample and an inert reference sample as a function of time and temperature. Furthermore, it uses a heat flux cell design identical to that used in conventional DSC. However, in MDSC, a different heating regime (temperature regime) is applied to the sample and reference sample. Specifically, a sinusoidal modulation (amplitude) is superimposed on a conventional linear heating or cooling ramp, producing a regime in which the average sample temperature varies continuously, but not linearly, with time. The net effect of applying this more complex heating regime to a sample is as if two tests were performed simultaneously on the material: one with a conventional linear (average) heating rate and one with a sinusoidal (instantaneous) heating rate. The actual rate of these two simultaneous tests depends on three operator-selectable variables: Base heating rate (3°C / min) Modulation period (60 seconds) Temperature amplitude of modulation (±1℃)

[0131] Reversing heat flow was used to analyze the glass transition temperature and the area of ​​the melting peak. The heat of fusion (Hf) upon heating was measured as the integrated reversing heat flow signal. The heat of crystallization (Hc) upon heating was integrated from the total heat flow signal. The relative crystallinity (C) of the sample was determined by subtracting the heat of fusion (Hf) from the heat of crystallization (Hc) upon heating. Examples 1 to 4

[0132] Copolyester resins with different glycol compositions were made and converted into shrinkable films using an experimental film process, and the corresponding shrinkable film properties were measured. Film samples were also tested for clumping with PET flakes using an experimental clumping test. Key performance properties are listed below. Films made with resin examples 1 and 2 had PET flake clumping rates of less than 1%. Films made with resin examples 1, 3, and 4 had excellent shrinkable film properties. Only the film made with resin example 1 had excellent shrinkable film properties and a clumping rate of less than 1%.

[0123] [Table 1]

[0124] Examples 5 to 7

[0133] Resin Examples 5-7 were made, converted into shrinkable films on a commercial tenter frame, and tested for suitability for PET recycling using the APR test procedure.

[0125] [Table 2]

[0126] Examples 8 to 11

[0134] Resins based on Examples 8-11 were converted into shrinkable film samples and tested for shrinkable film properties and for cohesion with PET flakes using an experimental cohesion test.

[0127] [Table 3]

[0128] Examples 12 to 16

[0135] Multilayer films were made using a commercial tenterframe process and tested for cohesion with PET flakes using an experimental cohesion test. These films were made with Example 4 as the core layer and Example 1 as the cap layer.

[0129] [Table 4]

[0130] Example of thermoforming sheet

[0136] Examples A, B, and C were extruded into 30 mil (750 μm) thick sheet material in a 2.5-inch Davis and Standard extruder. The sheet samples were then thermoformed into the basic tray shape (dimensions: 169 mm × 136 mm × 44 mm) using an aluminum female die designed to allow vacuum to be drawn throughout the shape. This molded body was mounted in a Hydrotrim laboratory thermoforming machine. The oven and mold temperatures were kept constant at 260°C and 42°C, respectively. The sheet samples were placed in the oven for different residence times, removed from the oven, immediately formed into trays, and cooled before being removed from the mold. The temperature of the sheet was measured using an infrared temperature sensor that was part of the thermoforming machine and confirmed with a handheld infrared thermometer.

[0131]

[0137] The dwell time was varied, starting at 15 seconds and increasing by 2 seconds each time, to identify a range of thermoforming conditions that would produce high-quality parts. The dwell time was varied so that the samples were heated to different temperatures before forming. The test was stopped after a dwell time of 29 seconds was reached because Example C became too hazy to be considered a production-ready tray. The haze of each sample was measured as an indicator of part quality and crystallization.

[0132]

[0138] The tray made from Example C began to exhibit slight haze at a residence time of 23 seconds. This indicates a smaller thermoforming range for Example C compared to Examples A and B, as Examples A and B did not exhibit an increase in haze over this range of residence times. The quality of the thermoformed parts is indicated by a "+" indicating acceptable quality or a "-" indicating poor quality. These quality ratings are based on a combination of post-thermoforming haze and part precision.

[0133]

[0139] Samples of extruded sheet and thermoformed parts were evaluated for suitability for PET recycling using an experimental agglomeration procedure. In addition, a pre-crystallization step was used as described in the APR screening test for PET agglomeration. The results of this agglomeration test are presented below.

[0134]

[0140] Example B exhibits desirable and differentiated properties, namely, a wider range of thermoforming conditions making it easier to process, and compatibility with PET recycling processes, allowing for crystallization during the recycling process.

[0135] [Table 5]

[0136] [Table 6]

[0137] [Table 7]

[0138] Injection Molded Samples

[0141] Samples A, B, C, and Examples 1 and 3 were injection molded and tested for their mechanical properties using conventional injection molding procedures known to those skilled in the art. Test parts were tested according to ASTM Method D638, ASTM Method D3763, ASTM Method D256, ASTM Method D4812, and ASTM Method D64. The mechanical properties of injection molded parts made with these reactor-grade resins are shown in Table 8.

[0139] [Table 8]

[0140]

[0142] Although the present disclosure has been described in detail with particular reference to preferred embodiments thereof, it will be understood that numerous changes and modifications can be effected within the spirit and scope of the disclosure. The following describes embodiments of the present invention. Aspect 1 1. A crystallizable film comprising a polyester composition comprising at least one polyester, said at least one polyester comprising: (a) a dicarboxylic acid component comprising: (i) about 70 to about 100 mole percent terephthalic acid residues, and (ii) from about 0 to about 30 mole % of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; and (b) a diol component comprising: greater than or equal to about 75 mole percent ethylene glycol residues, and (i) from about 0.1 to less than about 24 mole percent neopentyl glycol residues; (ii) 0 to less than about 24 mole percent 1,4-cyclohexanedimethanol residues, and (iii) about 1 to less than about 10 mole percent total diethylene glycol residues in the final polyester composition, and A crystallizable film wherein the total mole % of said dicarboxylic acid components is 100 mole % and the total mole % of said diol components is 100 mole %. Aspect 2 1. A crystallizable film comprising a polyester composition comprising at least one polyester, said at least one polyester comprising: (a) a dicarboxylic acid component comprising: (i) about 70 to about 100 mole percent terephthalic acid residues, and (ii) from about 0 to about 30 mole % of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; and (b) a diol component comprising: greater than or equal to about 80 mole percent ethylene glycol residues, and (i) from about 5 to less than about 17 mole percent neopentyl glycol residues; (ii) from about 2 to less than about 10 mole percent 1,4-cyclohexanedimethanol residues, and (iii) about 1 to less than about 5 mole percent total diethylene glycol residues in the final polyester composition, and A crystallizable film wherein the total mole % of said dicarboxylic acid components is 100 mole % and the total mole % of said diol components is 100 mole %. Aspect 3 1. A crystallizable film comprising a polyester composition comprising at least one polyester, said at least one polyester comprising: (a) a dicarboxylic acid component comprising: (i) about 70 to about 100 mole percent terephthalic acid residues, and (ii) from about 0 to about 30 mole % of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; and (b) a diol component comprising: greater than or equal to about 76 mole percent ethylene glycol residues, and (i) a neopentyl glycol residue, (ii) a cyclohexanedimethanol residue, and (iii) comprising about 24 mole % or less of an amorphous component selected from the total diethylene glycol residues in the final polyester composition; A crystallizable film wherein the total mole % of said dicarboxylic acid components is 100 mole % and the total mole % of said diol components is 100 mole %. Aspect 4 1. A crystallizable film comprising a polyester composition comprising at least one polyester, said at least one polyester comprising: (a) a dicarboxylic acid component comprising: (i) about 70 to about 100 mole percent terephthalic acid residues, and (ii) from about 0 to about 30 mole % of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; and (b) a diol component comprising: (i) about 1 to about 30 mole % neopentyl glycol residues; (ii) from about 1 to less than about 30 mole percent 1,4-cyclohexanedimethanol residues, and (iii) about 1.5 to 6 mole percent diethylene glycol residues, provided that the remainder of the glycol component is (iv) ethylene glycol residues, and (v) 0 to 20 mol % of at least one modifying glycol residue; A crystallizable film wherein the total mole % of said dicarboxylic acid components is 100 mole % and the total mole % of said diol components is 100 mole %. Aspect 5 5. The crystallizable film of any one of embodiments 1-4, wherein the polyester has an intrinsic viscosity of 0.68-0.75 dL / g as measured in a 60 / 40 (wt / wt) phenol / tetrachloroethane solution at a concentration of 0.5 g / dL at 25°C, and a Tg of 72°C-77°C as measured using a Thermal Analyst Instrument TA DSC 2920 at a scan rate of 20°C / min. Aspect 6 4. The crystallizable film of claim 3, wherein the sum of the diol content of the one or more diol monomer components capable of forming an amorphous component in the final polyester is 5 to 24 mol %, and the total diol content is 100 mol %. Aspect 7 4. The crystallizable film of claim 3, wherein the sum of the diol content of one or more diol monomer components capable of forming an amorphous component in the final polyester is 10-20 mol %, and the total diol content is 100 mol %. Aspect 8 4. The crystallizable film of claim 3, wherein the sum of the diol content of the one or more diol monomer components capable of forming an amorphous component in the final polyester is 15-20 mol %, and the total diol content is 100 mol %. Aspect 9 5. The crystallizable film of any one of embodiments 1, 3, or 4, wherein the 1,4-cyclohexanedimethanol residues are present in an amount from 2 to 5 mol %, the diethylene glycol residues are present in an amount less than or equal to 5 mol %, the neopentyl glycol residues are present in an amount from 10 to 15 mol %, and the ethylene glycol residues are present in an amount greater than 75 mol %. Aspect 10 10. The crystallizable film of any one of embodiments 1 to 9, wherein the film is stretched in at least one direction. Aspect 11 10. The crystallizable film of any one of embodiments 1 to 9, wherein the film is stretched and oriented in at least one direction. Aspect 12 10. The crystallizable film of any one of embodiments 1 to 9, wherein the film is annealed. Aspect 13 13. The crystallizable film of embodiment 12, wherein the film is annealed at a temperature of about 75°C to about 110°C. Aspect 14 14. The crystallizable film of any one of embodiments 1 to 13, wherein the film is stretched in at least one direction, and the stretched film has a melting point of strain-induced crystals of 200° C. or higher. Aspect 15 15. The crystallizable film of any one of aspects 1 to 14, wherein the film has a shrinkage of 60% or more in the main shrinkage direction when immersed in water at 85° C. for 10 seconds. Aspect 16 16. The crystallizable film of any one of embodiments 1 to 15, wherein the film has a shrinkage force of 5 MPa or greater. Aspect 17 17. The crystallizable film of any one of embodiments 1 to 16, further comprising at least one pore-forming agent. Aspect 18 18. The crystallizable film of any one of embodiments 1 to 17, wherein the crystallizable film is oriented in one or more directions. Aspect 19 19. The crystallizable film of any one of aspects 1 to 18, wherein the film has a shrinkage rate of 50 to 90% in the main shrinkage direction and a shrinkage rate of 10% or less in a direction perpendicular to the main shrinkage direction when immersed in water at 95°C for 10 seconds. Aspect 20 A flexible packaging film for lidding films, extrusion blow molded containers, extruded sheets, thermoformed sheets, stand-alone bags, comprising the crystallizable film of any one of embodiments 1-19. Aspect 21 An article of manufacture, a molded article, a container, a plastic bottle, a glass bottle, packaging, a battery, a hot fill container, or an industrial product having attached thereto a label or sleeve comprising the crystallizable film of any one of embodiments 1-20. Aspect 22 1. A thermoformed sheet having a thickness of about 0.25 mm to about 6.4 mm, comprising a polyester composition comprising at least one polyester, wherein the at least one polyester is (a) a dicarboxylic acid component comprising: (i) about 70 to about 100 mole percent terephthalic acid residues, and (ii) from about 0 to about 30 mole % of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; and (b) a diol component comprising: greater than or equal to about 75 mole percent ethylene glycol residues, and (i) from about 0.1 to less than about 24 mole percent neopentyl glycol residues; (ii) 0 to less than about 24 mole percent 1,4-cyclohexanedimethanol residues, and (iii) about 1 to less than about 10 mole percent total diethylene glycol residues in the final polyester composition, and A thermoformed sheet wherein the total mole % of said dicarboxylic acid components is 100 mole % and the total mole % of said diol components is 100 mole %. Aspect 23 1. A thermoformed sheet having a thickness of about 0.25 mm to about 6.4 mm, comprising a polyester composition comprising at least one polyester, wherein the at least one polyester is (a) a dicarboxylic acid component comprising: (i) about 70 to about 100 mole percent terephthalic acid residues, and (ii) from about 0 to about 30 mole % of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; and (b) a diol component comprising: greater than or equal to about 80 mole percent ethylene glycol residues, and (i) from about 5 to less than about 17 mole percent neopentyl glycol residues; (ii) from about 2 to less than about 10 mole percent 1,4-cyclohexanedimethanol residues, and (iii) about 1 to less than about 5 mole percent total diethylene glycol residues in the final polyester composition, and A thermoformed sheet wherein the total mole % of said dicarboxylic acid components is 100 mole % and the total mole % of said diol components is 100 mole %. Aspect 24 1. A thermoformed sheet having a thickness of about 0.25 mm to about 6.4 mm, comprising a polyester composition comprising at least one polyester, wherein the at least one polyester is (a) a dicarboxylic acid component comprising: (i) about 70 to about 100 mole percent terephthalic acid residues, and (ii) from about 0 to about 30 mole % of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; and (b) a diol component comprising: greater than or equal to about 76 mole percent ethylene glycol residues, and (i) a neopentyl glycol residue, (ii) a cyclohexanedimethanol residue, and (iii) comprising about 24 mole % or less of an amorphous component selected from diethylene glycol residues in the final polyester composition; A thermoformed sheet wherein the total mole % of said dicarboxylic acid components is 100 mole % and the total mole % of said diol components is 100 mole %. Aspect 25 1. A thermoformed sheet having a thickness of about 0.25 mm to about 6.4 mm, comprising a polyester composition comprising at least one polyester, wherein the at least one polyester is (a) a dicarboxylic acid component comprising: (i) about 70 to about 100 mole percent terephthalic acid residues, and (ii) from about 0 to about 30 mole % of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; and (b) a diol component comprising: (i) about 1 to about 30 mole % neopentyl glycol residues; (ii) from about 1 to less than about 30 mole percent 1,4-cyclohexanedimethanol residues, and (iii) about 1.5 to 6 mole percent diethylene glycol residues, with the remainder of the glycol component being (iv) ethylene glycol residues, and (v) 0 to 20 mol % of at least one modifying glycol residue; A thermoformed sheet wherein the total mole % of said dicarboxylic acid components is 100 mole % and the total mole % of said diol components is 100 mole %. Aspect 26 26. The thermoformable sheet of any one of aspects 22 to 25, wherein the polyester has a Tg of 65°C to 90°C, as measured using a Thermal Analyst Instrument TA DSC 2920 at a scanning rate of 20°C / min. Aspect 27 27. The thermoformed sheet of embodiment 26, wherein the sum of the diol content of the one or more diol monomer components capable of forming an amorphous component in the final polyester is 5 to 24 mol %, and the total diol content is 100 mol %. Aspect 28 28. The thermoformed sheet of embodiment 27, wherein the sum of the diol content of one or more diol monomer components capable of forming an amorphous component in the final polyester is 15-20 mol %, and the total diol content is 100 mol %. Aspect 29 28. The thermoformed sheet of claim 24, 26, or 27, wherein the 1,4-cyclohexanedimethanol residues are present in an amount from 2 to 5 mol %, the diethylene glycol residues are present in an amount less than or equal to 5 mol %, the neopentyl glycol residues are present in an amount from 10 to 15 mol %, and the ethylene glycol residues are present in an amount greater than 75 mol %. Aspect 30 A thermoformed sheet according to any one of aspects 22 to 29, wherein the sheet or thermoformed article has a crystalline melting point of from 190°C to 225°C. Aspect 31 A shaped or molded article prepared from the thermoformed sheet of any one of embodiments 22-30. Aspect 32 32. The article of claim 31, wherein the article is selected from medical device packaging, medical related packaging, healthcare product packaging, commercial food supply packaging, trays, containers, food plates, tumblers, storage bins, bottles, cookware, mixing bowls, household items, water bottles, vegetable trays, dishwasher parts, refrigerator parts, vacuum cleaner parts, ophthalmic lenses, and frames or toys. Aspect 33 A polyester recycling stream comprising recycled polyethylene terephthalate flakes mixed with at least about 0.1 wt. % of the recycled crystallizable film of any one of embodiments 1-19 and / or the recycled thermoformed sheet of any one of embodiments 22-25. Aspect 34 34. The polyester recycled stream of embodiment 33, comprising recycled polyethylene terephthalate flakes mixed with at least about 0.1 wt.% recycled crystallizable shrink film or thermoform sheet, wherein the stream passes Document No. PET-CG-02, “Important Instructions for Transparent PET Articles with Labels and Seals,” dated April 11, 2019.

Claims

1. 1. A crystallizable film comprising a polyester composition comprising at least one polyester, said at least one polyester comprising: (a) a dicarboxylic acid component comprising: (i) 70 to 100 mole percent terephthalic acid residues, and (ii) 0 to 30 mole % of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; and (b) a diol component comprising: 80 mole percent or more ethylene glycol residues, and (i) 10 to less than 17 mole percent neopentyl glycol residues; (ii) 2 to 5 mole percent of 1,4-cyclohexanedimethanol residues, and (iii) up to 20 mole % of other glycols, with 1 to less than 5 mole % total diethylene glycol residues in the final polyester composition; Including, A crystallizable film wherein the total mole percent of said dicarboxylic acid components is 100 mole percent and the total mole percent of said diol components is 100 mole percent.

2. 1. A crystallizable film comprising a polyester composition comprising at least one polyester, said at least one polyester comprising: (a) a dicarboxylic acid component comprising: (i) 70 to 100 mole percent terephthalic acid residues, and (ii) 0 to 30 mole % of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; and (b) a diol component comprising: (i) 10 to 30 mole % neopentyl glycol residues; (ii) 1 to 5 mole % of 1,4-cyclohexanedimethanol residues, and (iii) 1.5 to 6 mole percent diethylene glycol residues, with the remainder of the diol component being: (iv) ethylene glycol residues, and (v) 0 to 20 mole % of at least one modified diol residue; A modified diol is defined herein as a diol other than ethylene glycol, diethylene glycol, neopentyl glycol, and 1,4-cyclohexanedimethanol; the total mole percent of the dicarboxylic acid component is 100 mole percent, and the total mole percent of the diol component is 100 mole percent; Crystallizable film.

3. 3. The crystallizable film of claim 1, wherein the polyester has an intrinsic viscosity of 0.68 to 0.75 dL / g as measured in a 60 / 40 (wt / wt) phenol / tetrachloroethane solution at a concentration of 0.5 g / dL at 25°C, and a Tg of 72°C to 77°C as measured using a Thermal Analyst Instrument TA DSC 2920 at a scanning rate of 20°C / min.

4. 3. The crystallizable film of claim 2, wherein the 1,4-cyclohexanedimethanol residues are present in an amount of 2 to 5 mol %, the diethylene glycol residues are present in an amount of 5 mol % or less, the neopentyl glycol residues are present in an amount of 10 to 15 mol %, and the ethylene glycol residues are present in an amount greater than 75 mol %.

5. The film is stretched in at least one direction, or The film is stretched and oriented in at least one direction, or The film is annealed, preferably The film is annealed at a temperature of 75°C to 110°C. The crystallizable film according to any one of claims 1 to 4.

6. 6. The crystallizable film of any one of claims 1 to 5, wherein the film is stretched in at least one direction, and the stretched film has a melting point of strain-induced crystals of 200°C or higher.

7. 7. The crystallizable film of claim 1, wherein the film has a shrinkage of 60% or more in the main shrinkage direction when immersed in water at 85° C. for 10 seconds.

8. The crystallizable film of any one of claims 1 to 7, wherein the film has a shrinkage force of 5 MPa or more.

9. The crystallizable film of any one of claims 1 to 8, further comprising at least one pore-forming agent.

10. The crystallizable film of any one of claims 1 to 9, which is oriented in one or more directions.

11. 11. The crystallizable film according to claim 1, wherein the film has a shrinkage rate of 50 to 90% in the main shrinkage direction and a shrinkage rate of 10% or less in the direction perpendicular to the main shrinkage direction when immersed in water at 95°C for 10 seconds.

12. A flexible packaging film for lidding films, extrusion blow molded containers, extruded sheets, thermoformed sheets, stand-alone bags, comprising the crystallizable film of any one of claims 1 to 10; or 11. An article of manufacture, a molded article, a container, a plastic bottle, a glass bottle, packaging, a battery, a hot fill container, or an industrial product having attached thereto a label or sleeve comprising the crystallizable film of any one of claims 1 to 10.

13. A thermoformed sheet having a thickness of 0.25 mm to 6.4 mm, comprising a polyester composition comprising at least one polyester, The at least one polyester is (a) a dicarboxylic acid component comprising: (i) 70 to 100 mole percent terephthalic acid residues, and (ii) 0 to 30 mole % of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; and (b) a diol component comprising: (i) 10 to 30 mole % neopentyl glycol residues; (ii) 1 to 5 mole % of 1,4-cyclohexanedimethanol residues, and (iii) 1.5 to 6 mole percent diethylene glycol residues, with the remainder of the diol component being: (iv) ethylene glycol residues, and (v) 0 to 20 mole % of at least one modified diol residue; A modified diol is defined herein as a diol other than ethylene glycol, diethylene glycol, neopentyl glycol, and 1,4-cyclohexanedimethanol; the total mole percent of the dicarboxylic acid component is 100 mole percent, and the total mole percent of the diol component is 100 mole percent; Thermoforming sheet.

14. 14. The thermoformable sheet of claim 13, wherein the polyester has a Tg of 65°C to 90°C as measured using a Thermal Analyst Instrument TA DSC 2920 at a scan rate of 20°C / min.

15. 14. The thermoformed sheet of claim 13, wherein the 1,4-cyclohexanedimethanol residues are present in an amount of 2 to 5 mole %, the diethylene glycol residues are present in an amount of 5 mole % or less, the neopentyl glycol residues are present in an amount of 10 to 15 mole %, and the ethylene glycol residues are present in an amount greater than 75 mole %.

16. The thermoformable sheet according to any one of claims 13 to 15, wherein the thermoformable sheet has a crystalline melting point of 190°C to 225°C.

17. A formed or molded article prepared from the thermoformed sheet of any one of claims 13 to 16, preferably comprising: The article is a formed or molded article selected from medical device packaging, medical related packaging, healthcare product packaging, commercial food supply packaging, trays, containers, food plates, tumblers, storage bins, bottles, cookware, mixing bowls, household items, water bottles, vegetable trays, dishwasher parts, refrigerator parts, vacuum cleaner parts, ophthalmic lenses and frames, or toys.

18. A method for recycling polyester, comprising: at least 0.1% by weight of A recycled crystallizable film according to any one of claims 1 to 11, 13. A lidding film, an extrusion blow molded container, an extruded sheet, a thermoformed sheet, a flexible packaging film for a stand-up bag according to claim 12, or a recycled label or sleeve comprising the crystallizable film according to any one of claims 1 to 10, and / or preparing a polyester recycling stream comprising recycled polyethylene terephthalate flakes mixed with recycling of the thermoformed sheet of claim 13, preferably 12. A method for recycling polyester, wherein the stream comprises at least 0.1% by weight of recycled polyethylene terephthalate flakes mixed with recycled crystallizable film of claim 7, 8, or 11, or recycled thermoformed sheet material, and the stream has passed Document No. PET-CG-02, dated April 11, 2019, entitled "Important Instructions for Transparent PET Articles with Labels and Seals."

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