Heat-fillable articles made from multi-layer thermoformable films and sheets

Abstract

The present disclosure relates to heat-fillable articles made from multi-layer thermoformable films and sheets comprising polyester and copolyester compositions containing residues of terephthalic acid, 1,4-cyclohexanedimethanol (CHDM), 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD), ethylene glycol (EG), and diethylene glycol (DEG) in specific compositional ranges, having certain advantages and improved performance characteristics.

Description

Technical Field

[0001] The present disclosure relates to heat-fillable articles made from multilayer thermoformable films and sheets, comprising polyester and copolyester compositions containing residues of terephthalic acid, 1,4-cyclohexanedimethanol (CHDM), 2,2-dimethylpropane-1,3-diol (neopentyl glycol or NPG), 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD), ethylene glycol (EG) and diethylene glycol (DEG) in specific compositional ranges, having certain advantages and improved performance characteristics.

Background Art

[0002] Due to recyclability and environmental issues, PVC and styrene are avoided in heat-fillable containers. PET or mildly modified PET has become the material of choice for applications where recycling is important. However, for most heat-fill food packaging applications, PET is not suitable because it cannot withstand the required temperatures. There is a commercial need for recyclable thermoformed articles made from copolyester thermoplastic materials that are transparent, tough and heat-fillable.

[0003] The applicant has developed a multilayer article useful for heat-fillable applications. In one embodiment, the multilayer article has an A / B / A structure. Layer A is a high-temperature copolyester resin containing glycols such as CHDM and TMCD. In one embodiment, layer A contains different copolyester resins. In another embodiment, layer A contains the same copolyester. Layer B is PET or lightly modified PET. Layers A and B of this disclosure are co-extrudeable. The multilayer structure of this disclosure passes heat-filling requirements and necessary drop test parameters. The multilayer structure has a low haze value and is visually transparent. In one embodiment, the multilayer structure disclosed herein is a transparent, heat-fillable three-layer structure that also satisfies the RIC-1 requirements for recyclability into PET recycling flows. In several embodiments, the combination of layers A and B enables the recyclability of the structure and article in PET recycling flows. Furthermore, in one embodiment, during processing, edge trim and other scrap materials remaining from the thermoforming process can be recycled and reused in layer B without generating haze throughout the structure. Current regulations and consumer preferences are driving a shift in plastic packaging materials away from highly modified copolyesters towards materials that are considered to have a higher compatibility with PET recycling flows.

[0004] California defines resin identification code 1 (PETE) as a material that must have more than 90% PET and a crystalline melting point between 225°C and 255°C. Typically, highly modified copolyesters do not meet this requirement. Therefore, there is a need to develop RIC-1 compliant materials suitable for thermal filling applications. Materials that succeed in these applications must have sufficient toughness to withstand drop tests when filled with liquid. Often, drop impact strength is achieved by selecting specific glycols such as CHDM or TMCD. California's RIC-1 requirements significantly limit the amount of CHDM, TMCD, or other comonomers that can be used. Therefore, the polymers typically used in these applications are PET formulations with up to 10% modification. These materials meet California's RIC-1 requirements.

[0005] RIC-1 (Resin Identification Code 1 for PET-like materials) states that all RIC-1 permissible materials must be at least 90% by mass of PET. This includes the use of TPA or DMT together with EG. RIC-1 materials must also have a crystalline melting point of 225°C to 255°C. Pure PET has a melting point close to 255°C. Highly modified copolyesters typically do not meet the 90% PET requirement and do not have a crystalline melting point within the required range. Therefore, there is an unmet commercial need for a material that meets both RIC-1 requirements, can withstand thermal filling temperatures, and provides the toughness for good drop impact strength properties required for thermal filling applications. [Overview of the project]

[0006] The applicant has discovered a formulation suitable for RIC-1 applications and providing good melt strength and good drop impact resistance. This disclosure addresses this long-standing commercial need for thermoformed articles made from copolyester thermoplastic material that are transparent, tough, heat-fillable, and recyclable into the PET recycling stream.

[0007] There is a commercial need for recyclable thermoformable articles made from copolyester thermoplastic materials that are transparent, tough, heat-fillable, and recyclable.

[0008] For an item to be considered recyclable, it must be convertible into usable polymer material at the end of its working life. Currently, polyethylene (terephthalate) (PET) is the thermoplastic resin with the largest volume in existing, well-established mechanical recycling flows.

[0009] Recycling used PET is a complex process that involves separating opaque, colored, and transparent components from each other, as well as separating them from containers made of different materials (e.g., polyethylene, polypropylene, PVC, etc.). Proper separation is crucial because each of these materials can contaminate the PET flow and degrade the quality of the final sorted product. After separation, transparent PET bottles are crushed into flakes, washed, and dried at temperatures of 140°C to 180°C. The flakes can be used directly (e.g., in straps and fiber extrusions) or further processed into pellets for film, sheet, or bottle applications. In some applications, the pellets can be further crystallized before use and solid-phase polymerized at temperatures of 200°C to 220°C. Due to the established nature of this process, it is desirable that copolyester-based molded articles and containers be compatible with existing PET recycling flows.

[0010] This disclosure addresses the long-standing commercial need for durable molded articles made from copolyester thermoplastic materials that are not only transparent but also clear, tough, heat-fillable, and recyclable in PET flows.

[0011] One embodiment of the present invention is a thermoformable article comprising a multilayer film or sheet, wherein the multilayer film or sheet is The article comprises at least one layer (A1) comprising a copolyester composition containing TMCD-modified PET, at least one layer (B) comprising a polyester composition containing PET or slightly modified PET, and optionally at least one layer (A2) comprising a copolyester composition containing TMCD-modified PET, wherein the article is transparent, heat-fillable, and recyclable (RIC-1), and thermoformable.

[0012] In one embodiment of the present disclosure, the Tg of the layer (A1) and layer (A2) copolyester compositions is approximately 100°C or higher, and the Tg of the layer (B) polyester composition is approximately 73°C to approximately 83°C, as measured using a TA DSC 2920 from Thermal Analyst Instrument at a scan rate of 20°C / min.

[0013] In some embodiments, TMCD increases the Tg of the copolyester composition, enabling its use in heat-filling applications. In some embodiments, the level of TMCD provides the toughness and heat resistance necessary for heat-filling and drop-test performance. In one embodiment, the level of TMCD in the copolyester composition is in the range of 10 to 50 mol%.

[0014] One embodiment of the present disclosure is a thermoformable article comprising a multilayer film or sheet, the multilayer film or sheet comprising at least one layer (A1) comprising a high-Tg copolyester composition having a Tg greater than 100°C, at least one layer (B) comprising a low-Tg polyester composition having a Tg less than 100°C, and optionally at least one layer (A2) comprising a high-Tg copolyester composition having a Tg greater than 100°C, and the article is transparent and heat-fillable.

[0015] One embodiment of the present disclosure is a thermoformable article comprising a multilayer film or sheet, the multilayer film or sheet comprising at least one layer (A1) comprising a TMCD-modified copolyester composition, at least one layer (B) comprising a polyester composition comprising PET or slightly modified PET, and optionally at least one layer (A2) comprising a TMCD-modified copolyester composition, the article being transparent and heat-fillable.

[0016] In one embodiment of the present disclosure, a copolyester composition comprising TMCD-modified PET includes (a) (i) about 70 to about 100 mol% of terephthalic acid residues, (ii) about 0 to about 30 mol% of a dicarboxylic acid component comprising aromatic and / or aliphatic dicarboxylic acid residues having 20 or fewer carbon atoms, and (b) (i) about 0 to about 40 mol% of 2,2-dimethylpropane-1,3-diol (neopentyl glycol or NPG) residues, (ii) about 0 to about 100 mol% of 1,4-cyclohexanedimethanol (CHDM) residues, and (iii) about 0.01% to about The diol component comprises 50 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) residues, (iv) about 0 to about 10 mol% of diethylene glycol (DEG) residues (whether formed in situ or not), wherein the remainder of the glycol component comprises (v) ethylene glycol residues, and (vi) optionally about 0 to about 10 mol% of at least one other modified glycol residue, the total mol% of the dicarboxylic acid component being 100 mol%, and the total mol% of the glycol component being 100 mol%.

[0017] In one embodiment, a copolyester composition containing TMCD-modified PET comprises: (a) (i) about 70 to about 100 mol% of terephthalic acid residues; (ii) about 0 to about 30 mol% of a dicarboxylic acid component comprising aromatic and / or aliphatic dicarboxylic acid residues having 20 or fewer carbon atoms; and (b) (i) about 0 to about 100 mol% of ethylene glycol (EG) residues; (ii) about 0 to about 100 mol% of 1,4-cyclohexanedimethanol (CHDM) residues; and (iii) about 0.01% to about 50 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol. The diol component comprises (iv) a 2,2-dimethylpropane-1,3-diol (neopentyl glycol or NPG) residue, (v) a 2,2-dimethylpropane-1,3-diol (neopentyl glycol or NPG) residue, and (v) a diethylene glycol (DEG) residue, whether formed in situ or not, the remainder of the glycol component comprising (vi) optionally a 2,2-dimethylpropane-1,3-diol (neopentyl glycol or NPG) residue, the total mol% of the dicarboxylic acid component being 100 mol%, and the total mol% of the glycol component being 100 mol%.

[0018] In one embodiment, a copolyester composition comprising TMCD-modified PET comprises (a)(i) about 70 to about 100 mol% of terephthalic acid residues, (ii) about 0 to about 30 mol% of aromatic and / or aliphatic dicarboxylic acid residues having 20 or fewer carbon atoms, and a diol component comprising (a)(i) about 0 to about 100 mol% of ethylene glycol (EG) residues, (ii) about 0.01% to about 50 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) residues, and (iii) about 0 to about 10 mol% of diethylene glycol (DEG) residues (whether formed in situ or not), wherein the remainder of the glycol component optionally comprises (vi) about 0 to about 10 mol% of at least one other modified glycol residue, the total mol% of the dicarboxylic acid component being 100 mol%, and the total mol% of the glycol component being 100 mol%.

[0019] In one embodiment, a copolyester composition containing TMCD-modified PET comprises (a) (i) about 70 to about 100 mol% of terephthalic acid residues, (ii) about 0 to about 30 mol% of a dicarboxylic acid component including aromatic and / or aliphatic dicarboxylic acid residues having 20 or fewer carbon atoms, and (b) (i) about 0 to about 100 mol% of ethylene glycol (EG) residues, (ii) about 0 to about 100 mol% of 1,4-cyclohexanedimethanol (CHDM) residues, and (iii) about 0.01% to about 50 mol% The diol component comprises (iv) a 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) residue, (iv) about 0 to about 10 mol percent of diethylene glycol (DEG) residues (whether formed in situ or not), wherein the remainder of the glycol component optionally comprises (vi) about 0 to about 10 mol% of at least one other modified glycol residue, the total mol% of the dicarboxylic acid component being 100 mol%, and the total mol% of the glycol component being 100 mol%.

[0020] In one embodiment, a copolyester composition comprising TMCD-modified PET comprises (a) a dicarboxylic acid component comprising (i) about 70 to about 100 mol% of terephthalic acid residues, (ii) about 0 to about 30 mol% of aromatic and / or aliphatic dicarboxylic acid residues having 20 or fewer carbon atoms, and (b) a diol component comprising (i) about 0 to about 100 mol% of ethylene glycol (EG) residues, (ii) about 0 to about 50 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) residues, and (iii) about 0 to about 10 mol% of diethylene glycol (DEG) residues (whether formed in situ or not), wherein the remainder of the glycol component optionally comprises (vi) about 0 to about 10 mol% of at least one other modified glycol residue, the total mol% of the dicarboxylic acid component being 100 mol%, and the total mol% of the glycol component being 100 mol%.

[0021] In one embodiment, a polyester composition comprising PET or slightly modified PET includes (a) (i) about 90 to about 100 mol% of terephthalic acid residues, (ii) about 0 to about 10 mol% of a dicarboxylic acid component comprising aromatic and / or aliphatic dicarboxylic acid residues having 20 or fewer carbon atoms, and (b) (i) about 90 to about 100 mol% of ethylene glycol (EG) residues, (ii) about 0 to about 10 mol% of 1,4-cyclohexanedimethanol (CHDM) residues, and (ii) about 0% to about 10 mol The diol component comprises (iv) a 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) residue of (iv) about 0 to about 10 mol percent of diethylene glycol (DEG) residues (whether formed in situ or not), wherein the remainder of the glycol component optionally comprises (vi) about 0 to about 10 mol% of at least one other modified glycol residue, the total mol% of the dicarboxylic acid component being 100 mol%, and the total mol% of the glycol component being 100 mol%.

[0022] In one embodiment, based on the total mass of the article, layer A1 is about 3% to 15% of the article, layer B is about 70% to 94% of the article, and layer A2 is about 3% to 15% of the article; or, based on the total mass of the article, layer A1 is about 5% to 10% of the article, layer B is about 80% to 90% of the article, and layer A2 is about 5% to 10% of the article.

[0023] In one embodiment, the thermoformable article of the present disclosure is tough and has good drop test values.

[0024] In one embodiment, a high-temperature copolyester resin (or a copolyester resin with high temperature resistance) provides the thermal stability necessary to enable heat-filling applications. In some embodiments, the thermal deflection temperature (HDT) is an indicator of whether a copolyester composition produces an article that begins to creep or deform at high temperatures. The HDT is measured using ASTM D648.

[0025] In one embodiment, the copolyester composition in layer A1 or layer A2 has a low-pressure HDT of at least about 85 °C or at least about 90 °C, or the copolyester composition in layer A1 or layer A2 has a high-pressure HDT of at least 75 °C or 80 °C.

[0026] In one embodiment, layers A1 and A2 are 30% or less of the multilayer film or sheet, or layers A1 and A2 are 6% to 30% of the multilayer film or sheet.

[0027] In one embodiment, the multilayer film or sheet of the present disclosure is transparent and has a haze value of about 3% or less, or 2% or less, or 1% or less.

[0028] In one embodiment, the thermoformable article of the present disclosure can be heat-filled at any temperature required for the intended use. In one embodiment, the thermoformable article of the present disclosure can be heat-filled at a temperature of about 80 °C to 100 °C, or at a temperature of about 85 °C or less, or about 90 °C or less, or about 95 °C, or less, or about 100 °C or less.

[0029] In one embodiment, the thermoformable article of the present disclosure is recyclable in the PET RIC-1 stream.

[0030] In one embodiment, the thermoformable article of the present disclosure can be recycled or reused. In some embodiments, the multilayer edge trim generated during the thermoforming process can be melt processed back into the B layer without causing haze in the B layer.

[0031] In one embodiment, the thermoformable article of the present disclosure has a melt temperature of 225 °C to 255 °C. In one embodiment, the multilayer A / B / A film or sheet has a melt temperature of 225 °C to 255 °C. In some embodiments, the A / B / A structure when melted and mixed during the recycling process has a melt temperature of 225 °C to 255 °C.

[0032] In one embodiment, the multilayer film or sheet is manufactured by a co-extrusion, lamination, or blown film process. In some embodiments, the multilayer film or sheet has good adhesion. In some embodiments, good adhesion means that the multilayer structure does not peel off during or under the application processes of thermoforming, heat filling, and sealing.

[0033] One embodiment of the present disclosure is a thermoformed article comprising at least one layer (A1) comprising a copolyester composition comprising TMCD-modified PET, at least one layer (B) comprising a polyester composition comprising PET or slightly modified PET, and optionally at least one layer (A2) comprising a copolyester composition comprising TMCD-modified PET, wherein the article is transparent, heat-fillable, and recyclable (RIC-1).

[0034] In one embodiment, the thermoformed or thermoformable article has an A / B or B / A double-layer structure.

[0035] In one embodiment, the thermoformed or thermoformable article has an A / B / A three-layer structure.

[0036] In one embodiment, the thermoformed or thermoformable article has a B / A / B triple-layer structure.

[0037] In one embodiment, a thermoformed or thermoformable article has a five-layer A / B / A / B / A structure.

[0038] In one embodiment, a thermoformed or thermoformable article has any desired number of layers in any structural combination. For example, in one embodiment, a thermoformed or thermoformable article has a (A1) / (B) structure, a (B) / (A1) structure, a (A1) / (B) / (A1) structure, a (A1) / (B) / (A2) structure, a (B) / (A1) / (B) structure, a (A1) / (B) / (A1) / (B) / (A1) structure, a (A1) / (B) / (A1) / (B) / (A2) structure, or a (A1) / (B) / (A2) / (B) / (A1) structure.

[0039] One embodiment of the present disclosure is a molded, thermoformed, or fabricated article comprising a multilayer film or sheet of any of the embodiments described above.

[0040] One embodiment of the present disclosure is a medical packaging, foam-filled sealed packaging, reusable packaging, face shields, healthcare supplies, commercial food service products, household food service products, blenders, consumer electrical appliances, consumer electronics, automotive parts, cosmetic packaging, trays, containers, food pans, tumblers, cups, storage boxes, bottles, water bottles, washing machine parts, refrigerator parts, vacuum cleaner parts, or toys, including a thermoformed or thermoformable film or sheet of any of the embodiments described above.

[0041] One embodiment of the present disclosure is a manufactured article comprising a thermoformed or thermoformable film or sheet as described in any of the above claims.

[0042] One embodiment of the present disclosure is a method for manufacturing a thermoformed film or sheet of any of the embodiments described above, comprising: 1) heating a multilayer film or sheet; 2) applying air pressure, vacuum and / or physical pressure to the thermoformed film or sheet; 3) conforming the sheet to a mold shape by vacuum or pressure; and 4) removing the thermoformed part or article from the mold. [Modes for carrying out the invention]

[0043] This disclosure may be more readily understood by referring to the following detailed descriptions of specific embodiments of this disclosure. In accordance with the purpose of this disclosure, specific embodiments of this disclosure are described in the summary of the invention and are further described below in this specification. Other embodiments of this disclosure are also described herein.

[0044] This disclosure relates to a specific multilayer film or sheet capable of producing thermoformable articles having the following attributes, all of which are increasingly important to market demands: (1) the article is heat-fillable, (2) the article is transparent (low haze), (3) the multilayer article has a melting temperature (Tm) of 225-255°C and is therefore eligible as PET for recycling purposes and can be recycled at the end of its working life along with the current well-established PET recycling flow, and (4) the multilayer article may contain recycled or reused materials.

[0045] In one embodiment, the multilayer articles of the present disclosure relate to durable, environmentally friendly, and sustainable copolyester-based articles for consumer product applications, having two important attributes. First, the articles of the present disclosure enable the ability to form tough, heat-fillable, transparent articles. Second, the articles of the present disclosure are compatible with PET recycling flows, i.e., they can be processed under conditions used for homopolymer PET recycling.

[0046] In 2017, California Legislature Bill 906 – Beverage Containers: Polyethylene Terephthalate – was signed into law, defining "polyethylene terephthalate" (PET) as a plastic that meets certain conditions for the purpose of labeling with a resin code, including limitations on the polymer's chemical composition and its peak melting temperature within a specified range. AB-906 adds Section 18013 to the California Public Resources Act, which partially states: a. The reacted terephthalic acid or dimethyl terephthalate and monoethylene glycol constitute at least 90 percent of the mass of monomers that react to form polymers. b. The plastic exhibits a peak melting temperature of 225°C–255°C, as determined during the second thermal scan using procedure 10.1 specified in ASTM International (ASTM) D3418, with a sample heating rate of 10°C / min.

[0047] Therefore, the aforementioned copolyesters and blends that satisfy both of the conditions outlined in AB-906 are permitted to be called “PET,” and thus such materials may be compatible with the current PET recycling flow. The melting points of the multilayer articles in this disclosure make them acceptable as PET under this provision and thus compatible with the current PET recycling flow.

[0048] Accordingly, in one embodiment of this disclosure, “compatible with PET recycling streams” is defined as containing 10 wt% or less of glycols and / or acids other than EG, TPA, or DMT, while exhibiting a melting temperature of 225°C to 255°C in the first thermal DSC scan of the molded article. In this disclosure, it has been found that multilayer articles of certain combinations of PET polyester and TMCD-modified copolyesters can be used to produce thermoformed articles that are (1) low haze (transparent), (2) tough, (3) heat-fillable, and (4) recyclable in PET recycling streams.

[0049] In one embodiment of the present disclosure, the multilayer articles of the present disclosure have a melting temperature and mass% comonomer content loading that are consistent with the provisions of the assembly bill, and therefore, the multilayer articles of the present disclosure are expected to be processed in a standard PET recycling process.

[0050] These multilayer articles in this disclosure are also recyclable and can be processed with PET recycling streams, becoming components in recyclable PET flakes exiting the recycling process. The optimized PET polyester and copolyester multilayer articles of this disclosure have melting points that enable the recycling of thermoformed articles.

[0051] In one embodiment, the PET polyester composition may have minor modifications, such as containing 5 mol% or less of isophthalic acid and / or 5 mol% or less of CHDM or other diols.

[0052] During the recycling process, drying of the PET flakes is required to remove any residual water remaining in the PET throughout the recycling process. Typically, PET is dried at temperatures exceeding 200°C. At these temperatures, certain copolyester resins soften and become sticky, often forming clumps with the PET flakes. These clumps must be removed before further processing. These clumps reduce the yield of PET flakes from the process and create additional handling steps.

[0053] In some embodiments, the term polyester is intended to encompass copolyesters. In some embodiments, the term polyester is used to describe PET and slightly modified PET used in layer B of this disclosure. In some embodiments, the term copolyester describes glycol-containing modified high-temperature resins such as CHDM and TMCD used in layer A of this disclosure.

[0054] As used herein, the term “polyester” is intended to encompass “copolyester” and is understood to mean a synthetic polymer prepared by the reaction of one or more difunctional carboxylic acids and / or polyfunctional carboxylic acids with one or more difunctional hydroxyl compounds and / or polyfunctional hydroxyl compounds, such as branching agents. Typically, the difunctional carboxylic acid may be a dicarboxylic acid, and the difunctional hydroxyl compound may be a dihydric alcohol, such as glycols and diols. As used herein, the term “glycol” may include, 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 with two hydroxyl substituents, such as hydroquinone. As used herein, the term “residue” means any organic structure incorporated into the polymer by polycondensation and / or esterification reactions from the corresponding monomers. As used herein, the term “repeating unit” means an organic structure in which dicarboxylic acid residues and diol residues are linked via an ester group. Therefore, for example, dicarboxylic acid residues can be derived from dicarboxylic acid monomers or their associated acid halides, esters, salts, anhydrides and / or mixtures thereof. Furthermore, as used herein, the term “diacid” includes polyfunctional acids, such as branching agents. Therefore, as used herein, the term “dicarboxylic acid” is intended to include dicarboxylic acids and any derivatives thereof, such as their associated acid halides, esters, semi-esters, salts, semi-salts, anhydrides, mixed anhydrides and / or mixtures thereof, which are useful in reaction processes with diols for producing polyesters.As used herein, the term “terephthalic acid” is intended to include terephthalic acid itself and its residues, as well as any derivatives of terephthalic acid, such derivatives include its associated acid halides, esters, semi-esters, salts, semi-salts, anhydrides, mixed anhydrides and / or mixtures thereof, which are useful in reaction processes with diols for the production of polyesters.

[0055] The polyesters used in this disclosure can typically be prepared from dicarboxylic acids and diols that react in substantially equal proportions and are incorporated into the polyester polymer as their corresponding residues. Thus, the polyesters of this disclosure can contain substantially equal molar proportions of acid residues (100 mol%) and diol (and / or polyfunctional hydroxyl compound) residues (100 mol%) such that the total moles of repeating units are 100 mol%. Accordingly, the molar percentages provided in this disclosure can be based on the total number of moles of acid residues, the total number of moles of diol residues, or the total number of moles of repeating units. For example, a polyester containing 10 mol% isophthalic acid based on total acid residues means a polyester containing 10 mol% isophthalic acid residues out of a total of 100 mol% acid residues. Thus, there are 10 moles of isophthalic acid residues for every 100 moles of acid residues. In another example, a polyester containing 25 mol% 1,4-cyclohexanedimethanol based on total diol residues means a polyester containing 25 mol% 1,4-cyclohexanedimethanol residues out of a total of 100 mol% diol residues. Therefore, there are 25 moles of 1,4-cyclohexanedimethanol residues for every 100 moles of diol residues.

[0056] In certain embodiments, terephthalic acid or its esters, such as dimethyl terephthalate or a mixture of terephthalic acid residues and their esters, may constitute some or all of the dicarboxylic acid components used to form polyesters useful in this disclosure. In certain embodiments, terephthalic acid residues may constitute some or all of the dicarboxylic acid components used to form polyesters useful in this disclosure. For the purposes of this disclosure, the terms “terephthalic acid” and “dimethyl terephthalate” are used interchangeably herein. In one embodiment, dimethyl terephthalate is some or all of the dicarboxylic acid components used to produce polyesters useful in this disclosure. In embodiments, terephthalic acid and / or dimethyl terephthalate and / or mixtures thereof may be used in the range of 70-100 mol%, 80-100 mol%, 90-100 mol%, 99-100 mol%, or 100 mol%.

[0057] In addition to terephthalic acid, the polyester dicarboxylic acid components useful in this disclosure may include one or more modified aromatic dicarboxylic acids in amounts of 30 mol% or less, 20 mol% or less, 10 mol% or less, 5 mol% or less, or 1 mol% or less. Yet another embodiment includes 0 mol% of a modified aromatic dicarboxylic acid. Therefore, the amount of one or more modified aromatic dicarboxylic acids, if present, can be considered to be in a range from any of these above-mentioned endpoint values, including, for example, 0.01 to 10 mol%, 0.01 to 5 mol%, and 0.01 to 1 mol%. In one embodiment, modified aromatic dicarboxylic acids that can be used in this disclosure include, but are not limited to, those having 20 or fewer carbon atoms and being linear, para-oriented, or symmetric. Examples of modified aromatic dicarboxylic acids that can be used in this disclosure include, but are not limited to, isophthalic acid, 4,4'-biphenyldicarboxylic acid, 1,4-, 1,5-, 2,6-, 2,7-naphthalenedicarboxylic acid and trans-4,4'-stilbenidicarboxylic acid and their esters. In one embodiment, the modified aromatic dicarboxylic acid is isophthalic acid.

[0058] The carboxylic acid component of the polyester useful in this disclosure may be further modified with 10 mol% or less, for example 5 mol% or less or 1 mol% or less, 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 dodecanediic acid dicarboxylic acid. Certain embodiments may also include 0.01 to 10 mol%, for example 0.1 to 10 mol%, 1 or 10 mol%, or 5 to 10 mol%, one or more modified aliphatic dicarboxylic acids. Yet another embodiment includes 0 mol% of modified aliphatic dicarboxylic acid. The total mol% of the dicarboxylic acid component is 100 mol%. In one embodiment, adipic acid and / or glutaric acid are provided in the modified aliphatic dicarboxylic acid component of the polyester and are useful in this disclosure.

[0059] Instead of dicarboxylic acids, esters of terephthalic acid and other modified dicarboxylic acids or their corresponding esters and / or salts can be used. 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.

[0060] In one embodiment, the diol component of a copolyester composition useful in this disclosure may include 1,4-cyclohexanedimethanol. In another embodiment, the diol component of a copolyester composition useful in this disclosure may include 1,4-cyclohexanedimethanol and 1,3-cyclohexanedimethanol. The molar ratio of cis / trans 1,4-cyclohexanedimethanol may vary within the range of 50 / 50 to 0 / 100, for example, between 40 / 60 and 20 / 80.

[0061] In one embodiment, the glycol component of the copolyester useful in this disclosure may include 2,2,4,4-tetramethyl-1,3-cyclobutanediol. In another embodiment, the molar ratio of cis / trans 2,2,4,4-tetramethyl-1,3-cyclobutanediol may vary from their respective pure forms and mixtures thereof. In certain embodiments, the molar percentages of cis and / or trans 2,2,4,4-tetramethyl-1,3-cyclobutanediol are such that cis is greater than 50 mol% and trans is less than 50 mol%, or cis is greater than 55 mol% and trans is less than 45 mol%, or cis is between 50 and 70 mol% and trans is between 50 and 30 mol%, or cis is between 60 and 70 mol% and trans is between 30 and 40 mol%, or cis is greater than 70 mol% and trans is less than 30 mol%, where the total molar percentage of cis- and trans-2,2,4,4-tetramethyl-1,3-cyclobutanediol is equal to 100 mol%. In additional embodiments, the molar ratio of cis / trans 2,2,4,4-tetramethyl-1,3-cyclobutanediol is in the range of 50 / 50 to 0 / 100, and can vary, for example, from 40 / 60 to 20 / 80.

[0062] In one embodiment, the total comonomer content of the copolyester composition useful in this disclosure from glycols and acids other than ethylene glycol (EG), terephthalic acid (TPA), or dimethyl terephthalate (DMT) is 1-10 wt%, or 5-10 wt%, or 2-10 wt%, or 3-10 wt%, or 4-10 wt%, or 6-10 wt%, or 7-10 wt%, or 8-10 wt%, or 9-10 wt%.

[0063] In one embodiment, the glycol component of a copolyester composition useful in this disclosure may contain 0 to 50 mol% neopentyl glycol, with a total mol% of the glycol component being 100 mol%. In one embodiment, the glycol component of a copolyester composition useful in this disclosure may contain 0 to 25 mol% neopentyl glycol, with a total mol% of the glycol component being 100 mol%. In one embodiment, the glycol component of a copolyester composition useful in this disclosure may contain 0 to 50 mol% neopentyl glycol, with a total mol% of the glycol component being 100 mol%. In one embodiment, the glycol component of a copolyester composition useful in this disclosure may contain 5 to 50 mol% neopentyl glycol, with a total mol% of the glycol component being 100 mol%. In one embodiment, the glycol component of a copolyester composition useful in this disclosure may contain 10 to 30 mol% neopentyl glycol, with a total mol% of the glycol component being 100 mol%. In one embodiment, the glycol component of a copolyester composition useful in this disclosure may contain 10 to 15 mol% neopentyl glycol, with the total mol% of the glycol component being 100 mol%. In one embodiment, the glycol component of a copolyester composition useful in this disclosure may contain 15 to 45 mol% neopentyl glycol, with the total mol% of the glycol component being 100 mol%.

[0064] In one embodiment, the glycol component of a copolyester composition useful in this disclosure is 0 to 50 mol%, or 0 to 40 mol%, or 0 to 30 mol%, or 0 to 20 mol%, or 0 to 10 mol%, or 0.01 to 50 mol%, or 0.01 to 40 mol%, or 0.01 to 30 mol%, or 0.01 to 20 mol%, or 0.01 to 15 mol%, or 0.01 to 14 mol%, or 0.01 to 13 mol%, or 0.01 to 12 mol%, or 0.01 to 11 mol%, or 0.01 to 10 mol%, or 0.01 to 9 mol%, or 0.01 to 8 mol%, or 0.01 to 7 mol%, with the total mol% of the glycol component being 100 mol%. or 0.01-6 mol%, or 0.01-5 mol%, or 0.1-50 mol%, or 0.1-40 mol%, or 0.1-30 mol%, or 0.1-20 mol%, or 0.1-10 mol%, or 5-50 mol%, or 10-50 mol%, or 20-50 mol%, or 30-50 mol%, or 40-50 mol%, or 20-40 mol%, or 30-40 mol%, or 10-40 mol%, or 10-30 mol%, or 10-20 mol%, or 20-30 mol%, or 2-50 mol%, or 2-40 mol%, or 2-30 mol%, or 2-20 mol%, or 3-15 mol%, or 3-14 mol%, or 3-13 mol%, or 3-12 mol% It may contain, or 3-11 mol%, or 3-10 mol%, or 3-9 mol%, or 3-8 mol%, or 3-7 mol%, or 2-10 mol%, or 2-9 mol%, or 2-8 mol%, or 2-7 mol%, or 2-5 mol%, or 1-7 mol%, or 1-5 mol%, or 1-3 mol%, of neopentyl glycol residues.

[0065] In one embodiment, the glycol component of a copolyester composition useful in this disclosure may contain 0 to 100 mol% or 0 to 50 mol% of 1,4-cyclohexanedimethanol, with a total mol% of the glycol component being 100 mol%. In one embodiment, the glycol component of a copolyester composition useful in this disclosure may contain 0.01 to less than 50 mol% of 1,4-cyclohexanedimethanol, with a total mol% of the glycol component being 100 mol%. In one embodiment, the glycol component of a copolyester composition useful in this disclosure may contain 0 to 15 mol% of 1,4-cyclohexanedimethanol, with a total mol% of the glycol component being 100 mol%. In one embodiment, the glycol component of a copolyester composition useful in this disclosure may contain 0.01 to less than 15 mol% of 1,4-cyclohexanedimethanol, with a total mol% of the glycol component being 100 mol%. In one embodiment, the glycol component of a copolyester composition useful in this disclosure may contain 0.01 to 5 mol% of 1,4-cyclohexanedimethanol, with the total mol% of the glycol component being 100 mol%. In one embodiment, the glycol component of a copolyester composition useful in this disclosure may contain 0 to less than 5 mol% of 1,4-cyclohexanedimethanol, with the total mol% of the glycol component being 100 mol%.

[0066] In one embodiment, the glycol component of a copolyester composition useful in this disclosure is 0 to 100 mol%, or 0 to 50 mol%, or 0 to 40 mol%, or 0 to 30 mol%, or 0 to 20 mol%, or 0 to 10 mol%, or 0.01 to 50 mol%, or 0.01 to 40 mol%, or 0.01 to 30 mol%, or 0.01 to 20 mol%, or 0.01 to 15 mol%, or 0.01 to 14 mol%, or 0.01 to 13 mol%, or 0.01 to 12 mol%, or 0.01 to 11 mol%, or 0.01 to 10 mol%, or 0.01 to 9 mol%, with the total mol% of the glycol component being 100 mol%. , or 0.01-8 mol%, or 0.01-7 mol%, or 0.01-6 mol%, or 0.01-5 mol%, or 0.1-50 mol%, or 0.1-40 mol%, or 0.1-30 mol%, or 0.1-20 mol%, or 0.1-10 mol%, or 5-50 mol%, 10-50 mol%, or 20-50 mol%, or 30-50 mol%, or 40-50 mol%, or 20-40 mol%, or 30-40 mol%, or 10-40 mol%, 10-30 mol%, or 10-20 mol%, or 20-30 mol%, or It may contain 2-50 mol%, or 2-40 mol%, or 2-30 mol%, or 2-20 mol%, 3-15 mol%, or 3-14 mol%, or 3-13 mol%, or 3-12 mol%, or 3-11 mol%, or 3-10 mol%, or 3-9 mol%, or 3-8 mol%, or 3-7 mol%, or 2-10 mol%, or 2-9 mol%, or 2-8 mol%, or 2-7 mol%, or 2-5 mol%, or 1-7 mol%, or 1-5 mol%, or 1-3 mol% of 1,4-cyclohexanedimethanol residues.

[0067] In one embodiment, the glycol component of a copolyester composition useful in this disclosure is 0 to 50 mol%, or 0 to 45 mol%, or 0 to 40 mol%, or 0 to 35 mol%, or 0 to 30 mol%, or 0 to 25 mol%, or 0 to 20 mol%, or 0 to 10 mol%, or 0.01 to 50 mol%, or 0.01 to 45 mol%, or 0.01 to 40 mol%, or 0.01 to 35 mol%, or 0.01 to 30 mol%, with the total mol% of the glycol component being 100 mol%, or 0.01-25 mol%, or 0.01-20 mol%, or 0.01-15 mol%, or 0.01-14 mol%, or 0.01-13 mol%, or 0.01-12 mol%, or 0.01-11 mol%, or 0.01-10 mol%, or 0.01-9 mol%, or 0.01-8 mol%, or 0.01-7 mol%, or 0.01-6 mol%, or 0.01-5 mol%, or 0.1-35 mol%, or 0.1-30 mol%, or 0.1-25 mol%, or 0.1-20 mol%, or 0.1-10 mol%, or 10-50 mol%, or 10-45 mol%, or 10-40 mol%, or 20-50 mol%, or 20-45 mol%, or 20-40 mol%, or 25-50 mol%, or 25-45 mol%, or 25-40 mol%, or 5-35 mol%, 10-35 mol%, or 20-35 mol%, or 25-35 mol%, or 10-30 mol%, or 10-20 mol%, or 20-30 mol%, or 2-35 mol%, or 2-25 mol%, or 2-30 mol It may contain 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues in amounts of %, or 2-20 mol%, 3-15 mol%, 3-14 mol%, 3-13 mol%, 3-12 mol%, 3-11 mol%, 3-10 mol%, 3-9 mol%, 3-8 mol%, 3-7 mol%, 2-10 mol%, 2-9 mol%, 2-8 mol%, 2-7 mol%, 2-5 mol%, 1-7 mol%, 1-5 mol%, or 1-3 mol%.

[0068] In one embodiment, the glycol component of a copolyester composition useful in this disclosure may contain 0 to 45 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, with the total mol% of the glycol component being 100 mol%. In one embodiment, the glycol component of a copolyester composition useful in this disclosure may contain 0.01 to less than 45 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, with the total mol% of the glycol component being 100%. In one embodiment, the glycol component of a copolyester composition useful in this disclosure may contain 0 to 40 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, with the total mol% of the glycol component being 100%. In one embodiment, the glycol component of a copolyester composition useful in this disclosure may contain 0.01 to less than 40 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, with the total mol% of the glycol component being 100%. In one embodiment, the glycol component of a copolyester composition useful in this disclosure may contain 0 to 35 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, with the total mol% of the glycol component being 100%. In one embodiment, the glycol component of a copolyester composition useful in this disclosure may contain 0.01 to less than 35 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, with the total mol% of the glycol component being 100%. In one embodiment, the glycol component of a copolyester composition useful in this disclosure may contain 0 to 30 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, with the total mol% of the glycol component being 100%. In one embodiment, the glycol component of a copolyester composition useful in this disclosure may contain 0.01 to less than 30 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, with the total mol% of the glycol component being 100%.In one embodiment, the glycol component of a copolyester composition useful in this disclosure may contain 0.01 to 25 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, with the total mol% of the glycol component being 100%. In one embodiment, the glycol component of a copolyester composition useful in this disclosure may contain 0 to less than 25 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, with the total mol% of the glycol component being 100%. In one embodiment, the glycol component of a copolyester composition useful in this disclosure may contain 10 to 50 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, with the total mol% of the glycol component being 100%. In one embodiment, the glycol component of a copolyester composition useful in this disclosure may contain 10 to 45 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, with the total mol% of the glycol component being 100%. In one embodiment, the glycol component of a copolyester composition useful in this disclosure may contain 10 to 40 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, with the total mol% of the glycol component being 100%. In one embodiment, the glycol component of a copolyester composition useful in this disclosure may contain 20 to 50 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, with the total mol% of the glycol component being 100%. In one embodiment, the glycol component of a copolyester composition useful in this disclosure may contain 20 to 45 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, with the total mol% of the glycol component being 100%. In one embodiment, the glycol component of a copolyester composition useful in this disclosure may contain 20 to 40 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, with the total mol% of the glycol component being 100%.

[0069] It should be understood that several other glycol residues may be formed in situ during processing. For example, in one embodiment, the total amount of diethylene glycol residues can be any amount in the copolyester useful in this disclosure, whether formed in situ during processing, intentionally added, or both, and the amount may be, for example, 1 to 15 mol%, or 1 to 10 mol%, or 1 to 8 mol%, or 1 to 7 mol%, or 1 to 6 mol%, or 1 to 5 mol%, with the total mol% of the glycol component being 100%. It is a diethylene glycol residue in mol%, or 1-2 mol%, or 1-12 mol%, or 2-12 mol%, or 2-11 mol%, or 2-10 mol%, or 2-9 mol%, or 3-12 mol%, or 3-11 mol%, or 3-10 mol%, or 3-9 mol%, or 4-12 mol%, or 4-11 mol%, or 4-10 mol%, or 4-9 mol%, or 5-12 mol%, or 5-11 mol%, or 5-10 mol%, or 5-9 mol%.

[0070] In one embodiment, the total amount of diethylene glycol (DEG) residues present in the copolyester useful in this disclosure may be 5 mol% or less, or 4 mol% or less, or 3.5 mol% or less, or 3.0 mol% or less, or 2.5 mol% or less, or 2.0 mol% or less, or 1.5 mol% or less, or 1.0 mol% or less, or 1 to 4 mol%, or 1 to 3 mol%, or 1 to 2 mol%, of the total mol% of the glycol component, whether formed in situ during processing, or intentionally added, or both, or 2 to 8 mol%, or 2 to 7 mol%, or 2 to 6 mol%, or 2 to 5 mol%, or 3 to 8 mol%, or 3 to 7 mol%, or 3 to 6 mol%, or 3 to 5 mol%, or in some embodiments, there are no intentionally added diethylene glycol residues. In certain embodiments, the copolyester does not contain added modified glycol. In certain embodiments, the diethylene glycol residue in the copolyester can be 5 mol% or less. It should be noted that the low levels of DEG formed in situ are not included in the total comonomer content from glycols and acids other than EG, TPA, or DMT.

[0071] In all embodiments, the remainder of the glycol component may contain any amount of ethylene glycol residue, with the total mol% of the glycol component being 100 mol%. In one embodiment, a copolyester useful in this disclosure may contain 50 mol% or more, or 55 mol% or more, or 60 mol% or more, or 65 mol% or more, or 70 mol% or more, or 75 mol% or more, or 80 mol% or more, or 85 mol% or more, or 90 mol% or more, or 95 mol% or more, or 98 mol% or more, or 50-90 mol%, or 55-90 mol%, or 50-80 mol%, or 55-80 mol%, or 60-80 mol%, or 50-75 mol%, or 55-75 mol%, or 60-75 mol%, or 65-75 mol%, with the total mol% of the glycol component being 100 mol%.

[0072] In one embodiment, the glycol component of a copolyester composition useful in this disclosure may include one or more other modified glycols in amounts of 10 mol% or less, or 9 mol% or less, or 8 mol% or less, or 7 mol% or less, or 6 mol% or less, or 5 mol% or less, or 4 mol% or less, or 3 mol% or less, or 2 mol% or less, or 1 mol% or less (the other modified glycols are defined as glycols other than ethylene glycol, diethylene glycol, neopentyl glycol, 1,4-cyclohexanedimethanol, or 2,2,4,4-tetramethyl-1,3-cyclobutanediol). In a particular embodiment, a copolyester useful in this disclosure may include one or more other modified glycols in amounts of 35 mol% or less, one or more other modified glycols in amounts of 30 mol% or less, one or more other modified glycols in amounts of 25 mol% or less, one or more other modified glycols in amounts of 20 mol% or less, one or more other modified glycols in amounts of 15 mol% or less, or one or more other modified glycols in amounts of 10 mol% or less. In a particular embodiment, a copolyester useful in this disclosure may include one or more other modified glycols in amounts of 5 mol% or less. In certain embodiments, a copolyester useful in this disclosure may contain one or more other modified glycols in an amount of 3 mol% or less. In other embodiments, a copolyester useful in this disclosure may contain 0 mol% of other modified glycols. However, since several other glycol residues may be formed in situ, these in-situ residues may also be embodiments of this disclosure.

[0073] In embodiments, other modified glycols for use in copolyesters, if used, contain 2 to 16 carbon atoms as defined herein. Examples of other modified glycols 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, and mixtures thereof. In one embodiment, isosorbide is another modified glycol. In one embodiment, polytetramethylene glycol is another modified glycol. In another embodiment, other modified glycols include, but are 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. If 1,4- or 1,3-butanediol is used, in one embodiment, an amount greater than 4 mol% or greater than 5 mol% may be provided. In one embodiment, at least one other modified glycol is 1,4-butanediol, present in an amount of 5 to 35 mol%.

[0074] In some embodiments, the polyester and copolyester compositions according to this disclosure may contain 0 to 10 mol%, for example, 0.01 to 5 mol%, 0.01 to 1 mol%, 0.05 to 5 mol%, 0.05 to 1 mol%, or 0.1 to 0.7 mol%, of one or more branched monomer residues based on the total molar percentage of either diol residues or diacid residues, where the branched monomer, also referred herein as a branching agent, has three or more carboxyl substituents, hydroxyl substituents, or a combination thereof. In certain embodiments, the branched monomer or branching agent may be added before and / or during and / or after polymerization of the polyester or copolyester. Thus, in some embodiments, the polyesters and copolyesters useful in this disclosure may be linear or branched.

[0075] Examples of branched monomers include, but are not limited to, trimellitic acid, trimellitic anhydride, pyromellitic dianhydride, trimethylolpropane, glycerol, pentaerythritol, citric acid, tartaric acid, and polyfunctional acids or polyfunctional alcohols such as 3-hydroxyglutaric acid. In one embodiment, the branched monomer residue may contain 0.01 to 0.7 mol% of one or more residues selected from at least one of trimellitic anhydride, pyromellitic anhydride, glycerol, sorbitol, 1,2,6-hexanetriol, pentaerythritol, trimethylolethane, and / or trimesic acid. The branched monomer may be added to the polyester reaction mixture or blended with the polyester in the form of concentrates, as described, for example, in U.S. Patent Nos. 5,654,347 and 5,696,176, and disclosures relating to these branched monomers are incorporated herein by reference.

[0076] Polyesters and copolyesters useful in this disclosure may include at least one chain extender. Suitable chain extenders include, but are not limited to, polyfunctional (including, but not limited to, bifunctional) isocyanates, polyfunctional epoxides including, for example, 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 adding during a conversion process such as injection molding or extrusion.

[0077] The amount of chain extender used may vary depending on the specific monomer composition used and the desired physical properties, but is generally about 0.1% to 10% by weight, for example, about 0.1% to 5% by weight, based on the total mass of the polyester.

[0078] Unless otherwise stated, polyester and copolyester compositions useful in this disclosure may have at least one of the intrinsic viscosity ranges described herein and at least one of the monomer ranges of polyester compositions described herein. Furthermore, unless otherwise stated, polyester compositions useful in this disclosure may have at least one of the Tg ranges described herein and at least one of the monomer ranges of polyester compositions described herein. Furthermore, unless otherwise stated, polyester compositions useful in this 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 of polyester or copolyester compositions described herein.

[0079] In embodiments of the present disclosure, polyester and copolyester compositions useful in the present disclosure can be determined in 60 / 40 (wt / wt) phenol / tetrachloroethane at a concentration of 0.25 g / 50 ml at 25°C to exhibit at least one of the following intrinsic viscosities: 0.50-1.2 dL / g, 0.50-1.0 dL / g, 0.50-0.90 dL / g, 0.50-0.80 dL / g, 0.55-0.80 dL / g, 0.60-0.80 dL / g, 0.65-0.80 dL / g, 0.70-0.80 dL / g, 0.50-0.75 dL / g, 0.55-0.75 dL / g, or 0.60-0.75 dL / g.

[0080] The glass transition temperature (Tg) of polyester and copolyester compositions is determined using a TA DSC 2920 from Thermal Analyst Instrument at a scan rate of 20°C / min. The glass transition temperature value is measured during the second heating cycle.

[0081] In certain embodiments, the A layer film or sheet of the present disclosure comprises a copolyester composition in which the polyester has a Tg of at least 90°C or at least 100°C, 90-115°C, 100-120°C, or 90-100°C. In certain embodiments, these Tg ranges can be met with or without the addition of at least one plasticizer during polymerization.

[0082] In certain embodiments, the B layer film or sheet of the present disclosure comprises a polyester composition in which the polyester has a Tg of 65-85°C, 73-83°C, 70-80°C, or 75-85°C. In certain embodiments, these Tg ranges can be met with or without the addition of at least one plasticizer during polymerization.

[0083] In embodiments of the present disclosure, films and / or sheets comprising a copolyester composition useful in the present disclosure may have a unique combination of all of the following properties: specific toughness, specific intrinsic viscosity, specific glass transition temperature (Tg), specific thermal deflection temperature (HDT), specific melting point, specific melt viscosity, and good color.

[0084] In one embodiment, certain polyester and copolyester compositions useful in this disclosure may be visually transparent. The term "visually transparent" is defined herein as the absence of evaluable cloudiness, haze, and / or turbidity when visually inspected. In one embodiment, certain copolyester compositions useful in this disclosure may have good color or a low haze value.

[0085] Polyester and copolyester compositions useful in this disclosure can be produced by methods known from the literature, such as processes in homogeneous solution, transesterification processes in molten materials, and two-phase interface processes. Suitable methods, but not limited to, include reacting one or more dicarboxylic acids with one or more diols at a temperature of 100°C to 315°C and a pressure of 0.1 to 760 mmHg for a time sufficient to form a polyester. For methods of producing polyesters, see U.S. Patent No. 3,772,405. Disclosures of such methods are incorporated herein by reference.

[0086] Polyesters and copolyesters can generally be produced by condensing a dicarboxylic acid or dicarboxylic acid ester with a diol and a catalyst in an inert atmosphere at a high temperature, gradually increasing the temperature during the condensation process to about 225°C to 310°C, and by carrying out the condensation at low pressure during the latter part of the condensation process. This is described in more detail in U.S. Patent No. 2,720,507, which is incorporated herein by reference.

[0087] In some embodiments, during a method for producing specific polyester and copolyester compositions useful in this disclosure, a specific agent for coloring the polymer, including a toner or dye, may be added to the molten material. In one embodiment, the resulting polyester polymer molten phase product is b * To reduce the amount, a bluing toner is added to the molten material. Such bluing agents include blue inorganic and organic toners and / or dyes. Furthermore, red toner and / or dyes are also included. *It can be used to adjust the color. Organic toners, such as blue and red organic toners, such as those described in U.S. Patent Nos. 5,372,864 and 5,384,377, can be used and are incorporated herein by reference in their entirety. The organic toners can be supplied as a premix composition. The premix composition may be a neat blend of red and blue compounds, or the composition may be pre-dissolved or slurryed in one of the polyester raw materials, such as ethylene glycol.

[0088] The total amount of toner components added may depend on the inherent yellowness in the base polyester or copolyester and the effectiveness of the toner. In one embodiment, concentrations of combined organic toner components of about 15 ppm or less and a minimum concentration of about 0.5 ppm can be used. In one embodiment, the total amount of bluing additives may be in the range of 0.5 to 10 ppm. In one embodiment, the toner may be added to the esterification zone or the polycondensation zone. Preferably, the toner is added to the initial stage of the esterification zone or polycondensation zone, for example, in the prepolymerization reactor.

[0089] Unless otherwise stated, polyester and copolyester compositions useful in this disclosure may have at least one of the intrinsic viscosity ranges described herein and at least one of the monomer ranges for polyester or copolyester compositions described herein. Furthermore, unless otherwise stated, polyester and copolyester compositions useful in this disclosure may have at least one of the Tg ranges described herein and at least one of the monomer ranges for polyester and copolyester compositions described herein. Furthermore, unless otherwise stated, polyester and copolyester compositions useful in this 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 polyester and copolyester compositions described herein.

[0090] In embodiments of this disclosure, polyester and copolyester compositions useful in this disclosure can be determined in 60 / 40 (wt / wt) phenol / tetrachloroethane at a concentration of 0.25 g / 50 ml at 25°C to exhibit at least one of the following intrinsic viscosities: 0.50-1.2 dL / g, 0.50-1.0 dL / g, 0.50-0.90 dL / g, 0.50-0.80 dL / g, 0.55-1.2 dL / g, 0.55-1.0 dL / g, 0.55-0.90 dL / g, 0.55-0.80 dL / g, 0.58~1.2dL / g, 0.58~1.0dL / g, 0.58~0.90dL / g, 0.58~0.80dL / g, 0.60~0.90dL / g, 0.60~0.80dL / g, 0.65~0.90dL / g, 0.60~0.80dL / g, 0.70~0.80dL / g, 0.50~0.75dL / g, 0.55~0.75dL / g, 0.58~0.75dL / g, 0.60~0.75dL / g, 0.60~0.70dL / g, 0.58~0.70dL / g or 0.55~0.70dL / g.

[0091] In one embodiment, the compositions of the present disclosure are useful as plastics, films, fibers, and sheets. The compositions of the present disclosure are useful as thermoformed articles and parts, extruded blow-molded or molded articles, molded or molded parts, or as solid plastic objects. In one embodiment, the compositions of the present disclosure are useful as thermoformed articles and parts, extruded blow-molded parts, or molded articles. The compositions are suitable for use in any application where transparent, tough, or rigid plastics are required. Examples of such parts and articles include containers, jars, cosmetic packaging, lids, decorative lids, packaging for personal care products, ink pen barrels, disposable syringes, bottles, bottle caps, automotive interior parts, automotive trim, toys, toy parts, thermally conductive plastics, medical devices, dental instruments, food containers, transport containers, packaging, furniture parts, multilayer films, multilayer films, insulation parts, insulation articles, insulation containers, storage boxes, food processors, blender and mixer bowls, water bottles, washing machine parts, refrigerator parts, vacuum cleaner parts, thermally conductive plastics, healthcare supplies, commercial food service products, medical packaging boxes, and the like.

[0092] This disclosure further relates to articles comprising films and / or sheets containing the polyester and copolyester compositions described herein. In embodiments, the films and / or sheets of this disclosure may be of any thickness required for the intended application.

[0093] This disclosure further relates to films and / or sheets described herein. Any method known in the art is used to form polyester and copolyester compositions into films and / or sheets. Examples of films and / or sheets of this disclosure, but not limited to, include extruded films and / or sheets, calendered films and / or sheets, and compression-molded films and / or sheets. Methods for manufacturing films and / or sheets, but not limited to, include extrusion, calendering, and compression molding.

[0094] This disclosure further relates to molded or shaped articles described herein. Methods for molding polyester and copolyester compositions into molded or shaped articles include methods known in the art. Examples of molded or shaped articles of this disclosure include, but are not limited to, thermoformed or thermoformable articles, extruded articles, and extruded blow articles. Methods for manufacturing molded articles include, but are not limited to, thermoforming, extrusion, and extruded blow molding. Methods of this disclosure include any thermoforming process known in the art. Processes of this disclosure include, but are not limited to, any blow molding processes known in the art, including extruded blow molding and extruded stretch blow molding.

[0095] This disclosure includes, but is not limited to, any extrusion blow molding manufacturing process known in the art, a typical description of an extrusion blow molding manufacturing process includes: 1) melting a composition in an extruder; 2) extruding the molten composition through a die to form a tube of molten polymer (i.e., a parison); 3) clamping a mold having the desired finished shape around the parison; 4) blowing air into the parison to stretch and expand the extruded material and fill the mold; 5) cooling the molded article; 6) ejecting the molded article; and 7) removing excess plastic (commonly known as burrs) from the molded article.

[0096] In one embodiment, the molded articles and parts of the Disclosure may have any thickness required for the intended end use. In one embodiment, the thickness of the molded articles and parts of the Disclosure is greater than about 3 mils. In one embodiment, the thickness of the molded articles and parts of the Disclosure is greater than about 4 mils. In one embodiment, the thickness of the molded articles and parts of the Disclosure is greater than about 5 mils. In one embodiment, the thickness of the molded articles and parts of the Disclosure is greater than about 1 mil. In one embodiment, the thickness of the molded articles and parts is between about 3 mils and about 25 mils. In one embodiment, the thickness of the molded articles and parts is between about 5 mils and about 20 mils.

[0097] In embodiments, the polyester or copolyester composition includes 0.01 to 25% by mass of general additives of the total composition, such as colorants, toners, dyes, mold release agents, flame retardants, plasticizers, glass bubbles, nucleating agents, stabilizers (including, but not limited to, UV stabilizers, heat stabilizers and / or their reaction products), fillers, and impact modifiers. Examples of commercially available impact modifiers include, but not limited to, functionalized polyolefins such as those containing ethylene / propylene polymer, methyl acrylate and / or glycidyl methacrylate, styrene-based block copolymer impact modifiers, and various acrylic core / shell type impact modifiers. Residues of such additives may also be considered as part of the polyester composition.

[0098] In one embodiment, the Disclosure relates to films and sheets and thermoformed or molded articles of the Disclosure, including polyester and copolyester compositions useful in the Disclosure. Methods for processing polyester and copolyester compositions into films and / or sheets are well known in the Art. Examples of films and / or sheets useful in the Disclosure include, but are not limited to, extruded films and / or sheets, compression-molded films, calendered films and / or films, and solution-cast films and / or sheets. In one embodiment, methods for producing films and / or sheets useful for producing the films and sheets of the Disclosure include, but are not limited to, extrusion, compression molding, calendering, and solution casting.

[0099] In one embodiment, polyester and copolyester compositions useful in this disclosure are made into films using any method known in the art for producing films from polyester and copolyester, such as solution casting, extrusion, compression molding or calendering.

[0100] In one embodiment, the polyester useful in this disclosure is made into a film using any method known in the art for producing a film from polyester, such as solution casting, extrusion, compression molding or calendering.

[0101] In one embodiment of the present disclosure, polyester and copolyester compositions can be formed by reacting monomers by known methods for producing polyester and copolyester, typically referred to as reactor-grade compositions.

[0102] Thermoformed articles or molded articles may also be manufactured from any polyester or copolyester composition disclosed herein.

[0103] In certain embodiments, this disclosure includes, but is not limited to, thermoformed articles such as containers, plastic bottles, heat-filled containers and / or industrial products or other uses.

[0104] In one embodiment of this disclosure, the disclosed polyester and copolyester compositions are useful as thermoformed and / or thermoformable films or sheets. This disclosure also covers manufactured products incorporating the thermoformable films and / or sheets of this disclosure. In one embodiment, the polyester compositions of this disclosure are useful as films and sheets that can be easily processed into molded or shaped articles. In one embodiment, the films and / or sheets of this disclosure can be processed into molded articles or parts by thermoforming. The polyester and copolyester compositions of this disclosure can be used in a variety of molding and extrusion applications.

[0105] One aspect of the present disclosure is a method for manufacturing molded or shaped parts and articles using thermoforming. The molded or shaped articles of the present disclosure can be manufactured using any thermoforming technique or process known to those skilled in the art.

[0106] 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 are incorporated herein by reference. In some embodiments, a positive thermoforming process is performed in which gas or pneumatic pressure is applied to a softened sheet, and the sheet is then stretched and drawn out like a bubble, with a male mold brought into the bubble from the inside. Vacuum is then applied to further compress the molded product and conform it to the surface of the male mold. In this thermoforming process, when gas or pneumatic pressure is applied to the softened sheet, biaxial stretching / orientation occurs mainly in one step. Vacuum and a male mold are then used to complete the molding process, freezing the orientation to the sheet and resulting in a good balance of physical and appearance properties. In another embodiment, a vacuum or physical plug is applied to a thermosoftening sheet, stretching the sheet to approximately the size of the final part, and then positive air pressure from within or from an external vacuum is applied to pull the sheet against an external female mold, causing the orientation to freeze within the polymer and the sheet to form an article, in a negative thermoforming process.

[0107] In other embodiments, thermoforming is a process of heating a film or sheet of the polyester composition of the Disclosure to a temperature sufficient to allow its deformation, and then conforming the heated film or sheet to the contour of a mold by means of vacuum assist, pneumatic assist, or conforming mold assist. In yet another embodiment, the heated film or sheet is placed in a mold and forcibly conformed to the contour of the mold by, for example, the application of pneumatic pressure, vacuum, plug assist, or conforming mold. In some embodiments, thin-walled articles are manufactured by thermoforming.

[0108] In one embodiment, the thermoforming process shapes a film or sheet into a desired shape by pressing a positive mold onto a heated film or sheet. In this embodiment, thermoforming includes supporting a positive mold of an article between a surface or table equipped with a vacuum. In this embodiment, heat from an external heat source, such as a hot air blower, a heating lamp, or other radiant heat source, is directed onto the film or sheet. In this embodiment, the film or sheet is heated to a softening point. In this embodiment, a vacuum is then applied to or below the table and around the mold, and the thermo-softened film or sheet is pulled towards the table, thus bringing the softened film or sheet into contact with the mold surface. In this embodiment, the vacuum pulls the softened film or sheet, making it adhere to and conform to the contour of the mold surface. In this way, the film or sheet then takes the shape of the mold. In this embodiment, after the film or sheet has cooled, it hardens and the resulting article or part can be removed from the mold.

[0109] In one embodiment, the thermoforming process includes forming a film or sheet from the polyester composition of the Disclosure, heating the film or sheet until it softens, placing the preheated film or sheet onto a heated mold surface, cooling the film or sheet, and then removing the formed article or part from the mold cavity, or optionally heat-setting the formed film or sheet by keeping it in contact with a heated mold for a time sufficient to partially crystallize the film or sheet.

[0110] In one embodiment, the thermoforming process includes forming a film or sheet from the polyester composition of the Disclosure; heating the film or sheet to a temperature above the Tg of polyester; applying gas, vacuum and / or physical pressure to the thermosoftened film or sheet to stretch the film or sheet to substantially the size of the final part; conforming the sheet to a mold shape by vacuum or pressure; cooling the film or sheet to a temperature below the Tg of polyester; and then removing the thermoformed article or part from the mold.

[0111] Films and sheets used in thermoforming processes can be manufactured by any conventional method known to those skilled in the art. In one embodiment, the sheet or film is formed by extrusion. In one embodiment, the sheet or film is formed by calendering. In one embodiment, during the thermoforming process, the film or sheet is heated to a temperature above the Tg of polyester. In one embodiment, this temperature is about 10 to about 60°C higher than the Tg of polyester. In one embodiment, to shorten the molding time, it is necessary to heat the film or sheet before placing it on the thermoforming mold. In one embodiment, the sheet must be heated to a temperature above its Tg but below the point at which the sheet becomes excessively slack when placed on the mold cavity. In one embodiment, the molded film or sheet is cooled to a temperature below the Tg of polyester before being removed from the mold. In one embodiment, the thermoforming method may include vacuum assistance, air assistance, mechanical plug assistance, or a fitted mold. In some embodiments, the mold is heated to a temperature above the Tg of the film or sheet. The optimal mold temperature selection depends on the type of thermoforming equipment, the shape and thickness of the molded part, and other factors.

[0112] In one embodiment, the heat-set molded product can be removed from the mold cavity by known removal means. For example, in one embodiment, blowback is used, which involves breaking the vacuum established between the mold and the molded film or sheet by introducing compressed air. In some embodiments, the molded article or part is then trimmed, and the scrap is crushed and recycled.

[0113] In some embodiments, the addition of a nucleating agent accelerates crystallization during thermoforming, and therefore accelerates the molding process. In one embodiment, a nucleating agent such as a particulate inorganic or organic material can 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 is used in an amount that varies from about 0.01% to about 20% based on the mass of the article. In one embodiment, other conventional additives such as pigments, dyes, plasticizers, crack inhibitors, and stabilizers can be used as needed for thermoforming. In some embodiments, crack inhibitors improve impact strength, and nucleating agents provide faster crystallization. In some embodiments, crystallization is required to achieve high-temperature stability.

[0114] The compositions of this disclosure are useful as thermoformed articles or molded or shaped plastic parts, or as solid plastic objects. The compositions of this disclosure are useful as thermoformed parts or articles. These compositions are suitable for use in any application requiring a transparent and tough plastic.

[0115] The thermoformable or thermoformable compositions of the present invention are useful for forming films, molded articles, molded parts, shaped articles and sheetings. Methods for forming films, molded articles, molded parts, shaped articles, shaped parts and sheetings from the thermoformable or thermoformable compositions can follow any method known in the art. Examples of molded articles, but not limited to, face shields and masks, medical packaging, healthcare supplies, commercial food service products, such as trays, containers, food pans, tumblers, storage boxes, bottles, cookware, water bottles, washing machine parts, refrigerator parts, vacuum cleaner parts and toys.

[0116] This disclosure further relates to articles comprising films and / or sheets comprising the polyester compositions described herein. In embodiments, the films and / or sheets of this disclosure may be of any thickness required for the intended application.

[0117] This disclosure further relates to films and / or sheets as described herein. Any method known in the art is used to process a polyester composition into films and / or sheets. Examples of films and / or sheets of this disclosure, but not limited to, include extruded films and / or sheets, calendered films and / or sheets, compression-molded films and / or sheets, and solution-cast films and / or sheets. Methods for manufacturing films and / or sheets, but not limited to, include extrusion, calendering, compression molding, and solution casting.

[0118] This disclosure further relates to molded or shaped articles described herein. Methods for processing polyester compositions into molded or shaped articles include methods known in the art. Examples of molded or shaped articles of this disclosure include, but are not limited to, thermoformed or thermoformable articles, extruded articles and extruded blow-formed articles. Methods for manufacturing molded articles include, but are not limited to, thermoforming, extrusion and extruded blow molding. Methods of this disclosure include any thermoforming process known in the art. Methods of this disclosure include, but are not limited to, any blow molding process known in the art, including extruded blow molding and extruded stretch blow molding.

[0119] This disclosure includes, but is not limited to, any extrusion blow molding manufacturing process known in the art, a typical description of an extrusion blow molding manufacturing process includes: 1) melting a composition in an extruder; 2) extruding the molten composition through a die to form a tube of molten polymer (i.e., a parison); 3) clamping a mold having the desired finished shape around the parison; 4) blowing air into the parison to stretch and expand the extruded material and fill the mold; 5) cooling the molded article; 6) removing the molded article; and 7) removing excess plastic (commonly called burrs) from the molded article. The following are aspects of the present invention. (Aspect 1) A layer (A1) comprising a copolyester composition containing TMCD-modified PET, A layer (B) comprising a polyester composition containing PET or slightly modified PET, In some cases, at least one layer (A2) containing a copolyester composition including TMCD-modified PET, A thermoformable article including a multilayer film or sheet, The article is transparent, heat-fillable, and recyclable (RIC-1). (Aspect 2) A thermoformable article according to Embodiment 1, wherein the Tg of the copolyester compositions of layer (A1) and layer (A2) is approximately 100°C or higher, and the Tg of the polyester composition of layer (B) is approximately 73°C to approximately 83°C, as measured using a Thermal Analyst Instrument TA DSC 2920 at a scan rate of 20°C / min. (Aspect 3) A layer (A1) comprising a high-Tg copolyester composition having a Tg exceeding 100°C, A layer (B) comprising a low-Tg polyester composition having a Tg of less than 100℃, and In some cases, at least one layer (A2) containing a high-Tg copolyester composition having a Tg greater than 100°C, A thermoformed article including a multilayer film or sheet, The article is transparent, heat-fillable, and recyclable (RIC-1). (Aspect 4) A copolyester composition comprising at least one layer (A1), optionally at least one layer (A2), and at least one layer (B) is (a)(i) Approximately 70 to 100 mol% of terephthalic acid residues, (ii) Aromatic and / or aliphatic dicarboxylic acid residues having 20 or fewer carbon atoms, in an amount of approximately 0 to approximately 30 mol% A dicarboxylic acid component, and (b)(i) Approximately 0 to approximately 100 mol% of ethylene glycol (EG) residues, (ii) Approximately 0 to approximately 100 mol% of 1,4-cyclohexanedimethanol (CHDM) residues, (iii) Approximately 0 to approximately 50 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) residues, (iv) Approximately 0 to approximately 40 mol% of 2,2-dimethylpropane-1,3-diol (neopentyl glycol or NPG) residues, (v) Approximately 0 to approximately 10 mole percent of diethylene glycol (DEG) residues, whether formed in situ or not. Includes diol components, It contains, and the remainder of the glycol component is (vi) in which the residue may contain at least one other modified glycol residue in about 0 to about 10 mol%, A thermoformable article according to embodiment 1 or 3, wherein the total mol% of the dicarboxylic acid component is 100 mol%, and the total mol% of the glycol component is 100 mol%. (Appendix 5) A polyester composition comprising at least one layer (B) containing PET or slightly modified PET, (a)(i) Approximately 90 to 100 mol% of terephthalic acid residues, (ii) Aromatic and / or aliphatic dicarboxylic acid residues having 20 or fewer carbon atoms in an amount of approximately 0 to approximately 10 mol%, A dicarboxylic acid component, and (b)(i) Approximately 90 to 100 mol% of ethylene glycol (EG) residues, (ii) Approximately 0 to approximately 10 mol% of 1,4-cyclohexanedimethanol (CHDM) residues, (ii) Approximately 0 to approximately 10 mol% of 2,2-dimethylpropane-1,3-diol (neopentyl glycol or NPG) residues, (iii) Approximately 0 to approximately 10 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) residues, (iv) Approximately 0 to approximately 10 mole percent of diethylene glycol (DEG) residues, whether formed in situ or not. Includes diol components, It contains, and the remainder of the glycol component is (v) optionally containing at least one other modified glycol residue in about 0 to about 10 mol%, The article according to embodiment 1 or 3, wherein the total mol% of the dicarboxylic acid component is 100 mol%, and the total mol% of the glycol component is 100 mol%. (Aspect 6) A thermoformable article according to Embodiment 1 or Embodiment 3, wherein, based on the total mass of the article, layer (A1) is about 3% to 30% of the article, layer (B) is about 70% to 97% of the article, and optionally layer (A2) is about 0% to 15% of the article, or, based on the total mass of the article, layer (A1) is about 5% to 20% of the article, layer (B) is about 80% to 95% of the article, and optionally layer (A2) is about 0% to 10% of the article. (Aspect 7) The thermoformable article according to Embodiment 1 or Embodiment 3, wherein the multilayer film or sheet is transparent or has a haze value of about 3% or less, 2% or less, or 1% or less. (Pattern 8) The article is a thermoformable article according to Embodiment 1 or Embodiment 3, which can be heat-filled at a temperature of approximately 80°C to 100°C, or at a temperature of approximately 85°C or lower, or approximately 90°C or lower, or approximately 95°C or lower, or approximately 100°C or lower. (Aspect 9) The article is a thermoformable article according to Embodiment 1 or Embodiment 3, wherein the article has a melting temperature of 225°C to 255°C and is recyclable in a PET RIC-1 flow. (Aspect 10) The article is reusable, and is a thermoformable article according to embodiment 1 or embodiment 3. (Aspect 11) A thermoformable article according to Embodiment 1 or Embodiment 3, having a melting temperature of 225°C to 255°C. (Aspect 12) The thermoformable article according to embodiment 1 or embodiment 3, wherein the multilayer film or sheet has a thickness of more than 3 mils, more than 5 mils, or 3 mils to 25 mils, or 5 mils to 20 mils. (Aspect 13) The multilayer film or sheet is a thermoformable article according to embodiment 1 or embodiment 3, manufactured by a co-extrusion, lamination, or blown film process. (Aspect 14) A thermoformed article according to embodiment 1 or embodiment 3 having an (A1) / (B) structure, (B) / (A1) structure, (A1) / (B) / (A1) structure, (A1) / (B) / (A1) / (B) / (A1) structure, (A1) / (B) / (A1) / (B) / (A2) structure or (A1) / (B) / (A2) / (B) / (A1) structure. (Aspect 15) Medical packaging, foam-filled and sealed packaging, reusable packaging, face shields, healthcare supplies, commercial food service products, household food service products, blenders, consumer electrical appliances, consumer electronics, automotive parts, cosmetic packaging, trays, containers, food pans, tumblers, cups, storage boxes, bottles, water bottles, washing machine parts, refrigerator parts, vacuum cleaner parts, or toys, including multilayer thermoformed articles as described in Embodiment 1 or Embodiment 3. (Aspect 16) A method for manufacturing a multilayer thermoformed article according to Embodiment 1 or Embodiment 3, A method comprising: 1) heating the multilayer film or sheet; 2) applying gas, vacuum and / or physical pressure to the heat-softened multilayer film or sheet; 3) conforming the multilayer film or sheet to a mold shape by vacuum or pressure; and 4) removing the thermoformed part or article from the mold. (Aspect 17) The method according to embodiment 15, wherein the multilayer film or sheet is formed by co-extrusion or lamination. (Aspect 18) The multilayer film or sheet according to embodiment 15, wherein the intrinsic viscosity of the film or sheet is measured at 25°C in 60 / 40 (wt / wt) phenol / tetrachloroethane at a concentration of 0.25 g / 50 ml and is approximately 0.50 to approximately 1.20 dL / g.

Claims

1. A layer (A1) comprising a high-Tg copolyester composition containing TMCD-modified PET and having a Tg of 100°C or higher, A layer (B) comprising a low-Tg polyester composition having a Tg of less than 100°C and containing PET or modified PET, In some cases, at least one layer (A2) comprising a high-Tg copolyester composition having a Tg greater than 100°C and containing TMCD-modified PET, A thermoformable article including a multilayer film or sheet, The aforementioned article has a haze value of approximately 3% or less. The aforementioned TMCD-modified PET is (a) (i) Approximately 70 to 100 mol% of terephthalic acid residues, (ii) Aromatic and / or aliphatic dicarboxylic acid residues having 20 or fewer carbon atoms, in an amount of approximately 0 to approximately 30 mol% Dicarboxylic acid components, including, (b) (i) Approximately 0 to approximately 100 mol% of ethylene glycol (EG) residues, (ii) Approximately 0.01 to approximately 50 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) residues, (iii) Approximately 0 to approximately 10 mole percent of diethylene glycol (DEG) residues, whether formed in situ or not. Includes diol components, It contains, and the remainder of the glycol component is (iv) Depending on the case, comprising at least one other modified glycol residue in about 0 to about 10 mol%, The total comonomer content of the aforementioned copolyester composition from glycols and acids other than ethylene glycol (EG), terephthalic acid (TPA), or dimethyl terephthalate (DMT) is 1 to 10 wt%. The total mol% of the dicarboxylic acid component is 100 mol%, and the total mol% of the glycol component is 100 mol%. The polyester composition of at least one layer (B) containing the aforementioned PET or modified PET is: (a) (i) Approximately 90 to 100 mol% of terephthalic acid residues, (ii) Aromatic and / or aliphatic dicarboxylic acid residues having 20 or fewer carbon atoms in an amount of approximately 0 to approximately 10 mol%, A dicarboxylic acid component, and (b) (i) Approximately 90 to 100 mol% of ethylene glycol (EG) residues, (ii) Approximately 0 to approximately 10 mol% of 1,4-cyclohexanedimethanol (CHDM) residues, (iii) Approximately 0 to approximately 10 mol% of 2,2-dimethylpropane-1,3-diol (neopentyl glycol or NPG) residues, (iv) Approximately 0 to approximately 10 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) residues, (v) Approximately 0 to approximately 10 mole percent of diethylene glycol (DEG) residues, whether formed in situ or not. Includes diol components, It contains, and the remainder of the glycol component is (vi) optionally comprising about 0 to about 10 mol% of at least one other modified glycol residue, The total mol% of the dicarboxylic acid component is 100 mol%, and the total mol% of the glycol component is 100 mol%, and The article has a melting temperature of 225°C to 255°C. An article characterized by the following features.

2. The thermoformable article according to claim 1, wherein the Tg of the copolyester compositions of layer (A1) and layer (A2) is approximately 100°C or higher, and the Tg of the polyester composition of layer (B) is approximately 73°C to approximately 83°C, as measured using a Thermal Analyst Instrument TA DSC 2920 at a scan rate of 20°C / min.

3. A thermoformable article according to claim 1, wherein, based on the total mass of the article, layer (A1) is about 3% to 30% of the article, layer (B) is about 70% to 97% of the article, and optionally layer (A2) is about 0% to 15% of the article, or, based on the total mass of the article, layer (A1) is about 5% to 20% of the article, layer (B) is about 80% to 95% of the article, and optionally layer (A2) is about 0% to 10% of the article.

4. The thermoformable article according to claim 1, wherein the multilayer film or sheet has a haze value of 2% or less, or 1% or less.

5. The thermoformable article according to claim 1, wherein the article can be heat-filled at a temperature of approximately 80°C to 100°C.

6. The thermoformable article according to claim 1, wherein the article is reusable.

7. The thermoformable article according to claim 1, wherein the multilayer film or sheet has a thickness of more than 3 mils, more than 5 mils, or 3 mils to 25 mils, or 5 mils to 20 mils.

8. The thermoformable article according to claim 1, wherein the multilayer film or sheet is manufactured by a co-extrusion, lamination, or blown film process.

9. A thermoformable article according to claim 1, having an (A1) / (B) structure, a (B) / (A1) structure, an (A1) / (B) / (A1) structure, an (A1) / (B) / (A2) structure, a (B) / (A1) / (B) structure, an (A1) / (B) / (A1) / (B) / (A1) structure, an (A1) / (B) / (A1) / (B) / (A2) structure, or an (A1) / (B) / (A2) / (B) / (A1) structure.

10. Medical packaging, foam-filled and sealed packaging, reusable packaging, face shields, healthcare supplies, commercial food service products, household food service products, blenders, consumer electrical appliances, consumer electronics, automotive parts, cosmetic packaging, trays, containers, food pans, tumblers, cups, storage boxes, bottles, water bottles, washing machine parts, refrigerator parts, vacuum cleaner parts, or toys, including the multilayer thermoformable article described in claim 1.

11. A method for manufacturing a multilayer thermoformable article according to claim 1, A method comprising: 1) heating the multilayer film or sheet; 2) applying gas, vacuum and / or physical pressure to the heat-softened multilayer film or sheet; 3) conforming the multilayer film or sheet to a mold shape by vacuum or pressure; and 4) removing the thermoformed part or article from the mold.

12. The method according to claim 11, wherein the multilayer film or sheet is formed by co-extrusion or lamination.

13. The multilayer film or sheet according to claim 1, wherein the intrinsic viscosity of the film or sheet is measured at 25°C in 60 / 40 (wt / wt) phenol / tetrachloroethane at a concentration of 0.25 g / 50 ml and is approximately 0.50 to approximately 1.20 dL / g.