Crystallizable shrinkable films and thermoformable sheets made from resin mixtures

Abstract

To provide thermoformable sheets with good properties and recyclability.SOLUTION: The present disclosure provides crystallizable shrinkable films and thermoformable films or sheets comprising blends of polyester compositions which comprise respective residues of terephthalic acid, neopentyl glycol (NPG), 1,4-cyclohexanedimethanol (CHDM), ethylene glycol (EG) and diethylene glycol (DEG), in certain compositional ranges having certain advantages and improved properties.SELECTED DRAWING: None

Description

Field of the Invention

[0001]

[0001] This disclosure relates to a crystallizable shrinkable film and a thermoformable sheet comprising a mixture of polyester compositions containing residues of terephthalic acid, neopentyl glycol (NPG), 1,4 - cyclohexanedimethanol (CHDM), ethylene glycol (EG), and diethylene glycol (DEG) in certain compositional ranges having certain advantages and improved properties.

Background Art

[0002]

[0002] There is a commercial need for shrink films having at least one of the following desirable shrink film properties: (1) a low shrink start temperature, (2) a shrinkage rate that increases gradually and in a controlled manner with increasing temperature over the temperature range in which shrinkage occurs, (3) a low shrink force sufficient to prevent crushing of the underlying container, (4) a high maximum shrinkage rate (shrinkage rate at the highest temperature), e.g., 50% or more in the major shrink direction at 95 °C, (5) a low shrinkage rate in the direction orthogonal to the direction of high shrinkage rate, (6) high film toughness to prevent unwanted cracking, breaking, tearing, splitting, foaming, or wrinkling of the film during manufacture and before and after shrinkage, and (7) recyclability.

[0003]

[0003] There is a commercial need for thermoformable sheets having excellent properties and recyclability. Summary of the Invention

[0004]

[0004] It has been found that a mixture made of polyester containing a specific combination of glycol monomers in a shrinkable film resin composition can produce a film with excellent shrinkable film properties, and that it can be crystallized without affecting the recycling of PET flakes that are generated simultaneously during recycling. These crystallizable shrinkable film resin mixtures can be processed together with PET bottles and become a component of recyclable PET flakes after the recycling process is complete. It has been found that the selection of a specific combination of polyesters in the mixture containing the specific glycol monomers and their amounts are important for producing a film with excellent shrinkable film properties and a crystallizable film. The optimized polyester resin mixtures of this disclosure are amorphous but crystallizable. Thus, these compositions exhibit excellent properties in film applications including shrinkable films, and because these strain-induced crystals have a high melting point, they exhibit excellent performance in the recycling process. The labels on the shrinkable films of this disclosure do not need to be removed during the recycling process and do not affect this recycling process.

[0005]

[0005] For use in this application, the heat-shrinkable film must meet various requirements for use. The film must be strong, shrink in a controlled manner, and provide sufficient shrinkage force to hold itself on the bottle surface without crushing the contents. Furthermore, when these labels are applied to polyester containers, the polyester shrinkable film labels must not interfere with the bottle recycling process. It is advantageous if the labels can be recycled, that is, if the entire bottle, including the labels, can be recycled and converted into a new product without requiring additional operational requirements or creating new environmental problems. Heat-shrinkable films are made from a variety of raw materials to meet a certain range of material needs. This disclosure describes the unique and unexpected effects brought about by polyester mixtures made from specific monomer combinations for shrinkable film resin compositions.

[0006]

[0006] Polyester shrink film compositions have been commercially used as shrink film labels for food, beverages, personal care products, household goods, etc. In many cases, these shrink films are used in combination with bottles or containers made of transparent polyethylene terephthalate (PET). After use, the entire product (bottle and label) is put into a recycling process. In a typical recycling site, PET and shrink film materials can become mixed together at the end of the process due to their similar composition and density. Drying of PET flakes is necessary to remove any residual water on the PET during the recycling process. Typically, PET is dried at temperatures above 200°C. At these temperatures, common polyester shrink film resins soften and become sticky, and PET flakes often form agglomerates. These agglomerates need to be removed before further processing. These agglomerates reduce the yield of PET flakes from this process and necessitate additional handling steps.

[0007]

[0007] Furthermore, it has been found that by using specific combinations of glycol monomers in a film or sheet resin composition, films or sheets with excellent performance properties can be produced, and that these combinations are crystallizable without affecting the recycling of PET flakes. These crystallizable film or sheet resins can be processed together with recycled PET and become a component of recyclable PET flakes after the recycling process is complete. It has been found that the selection of specific combinations of glycol monomers and their amounts are important for producing films or sheets with excellent performance properties and that are crystallizable. That is, these polyester compositions are amorphous, but they are "crystallizable" in the sense that they have a high melting point for strain-induced crystals. Thus, these compositions exhibit excellent properties in film or sheet applications such as formed, thermoformed, or as-formed parts and / or articles, and they are also recyclable together with PET because they have a high melting point for strain-induced crystals. This is because, when recycled PET flakes are subjected to high-temperature drying conditions, the crystallizable polyester of the present invention does not form agglomerates that would interfere with the normal mechanical operations of crushing, drying, and supplying the flakes to the extruder for subsequent processes of processing them into (recyclable) polyester pellets. Similarly, since the sheets of the present disclosure do not adversely affect the recycling process, there is no need to remove them during the recycling process. (For example, https: / / www.thebalancesmb.com / recycling-polyethylene-terephthalate-pet-2877869 (See reference)

[0008] One embodiment of the present disclosure is a crystallizable film comprising a mixture of polyester compositions comprising (1) at least one crystallizable polyester containing residues of terephthalic acid, neopentyl glycol (NPG), 1,4-cyclohexanedimethanol (CHDM), ethylene glycol (EG), and diethylene glycol (DEG) within a specific composition range, and (2) at least one amorphous polyester containing residues of terephthalic acid, neopentyl glycol (NPG), 1,4-cyclohexanedimethanol (CHDM), ethylene glycol (EG), and diethylene glycol (DEG) within a specific composition range.

[0008]

[0009] One embodiment of the present disclosure relates to a crystallizable polyester mixed composition. In one embodiment, the crystallizable polyester mixed composition comprises (a) 5 to 95% by weight of a crystallizable polyester composition and (b) 5 to 95% by weight of at least one amorphous polyester composition.

[0009]

[0010] One embodiment of the present disclosure is a crystallizable composition comprising a mixture of polyester compositions, the mixture comprising (1) 5 to 80% of at least one crystallizable polyester, and (2) 20 to 95% of at least one amorphous polyester. (1) At least one crystallizable polyester comprises (a) a dicarboxylic acid component and a diol component selected from either (b) or (b'), (a) The dicarboxylic acid component is (i) Approximately 70 to 100 mol% of terephthalic acid residues, and (ii) comprising about 0 to about 30 mol% aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, (b) The diol component is Approximately 75 mol% or more of ethylene glycol residues, and (i) Neopentyl glycol residues of approximately 0 to less than 25 mol%, (ii) 1,4-cyclohexanedimethanol residues in amounts of approximately 0 to less than 25 mol%, and (iii) The final polyester composition contains one or more total diethylene glycol residues in the total diethylene glycol composition in an amount of about 0 to less than 10 mol%, comprising about 25 mol% or less of other glycols. The total mole% of the dicarboxylic acid component is 100 mol%, the total mole% of the diol component is 100 mol%, and (b') The diol component is, Approximately 75 mol% or more of ethylene glycol residues, and (i) Neopentyl glycol residues in amounts of approximately 0.1 to less than approximately 24 mol%, (ii) 1,4-cyclohexanedimethanol residues in amounts of approximately 0.1 to less than approximately 24 mol%, and (iii) The final polyester composition contains one or more total diethylene glycol residues in the total diethylene glycol composition in an amount of about 1 to less than 10 mol%, comprising about 25 mol% or less of other glycols. The total mole% of the dicarboxylic acid component is 100 mol%, and the total mole% of the diol component is 100 mol%, and (2) At least one amorphous polyester comprises (a) a dicarboxylic acid component and (b) a diol component, (a) The dicarboxylic acid component is (i) Approximately 70 to 100 mol% of terephthalic acid residues, and (ii) comprising about 0 to about 30 mol% aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, (b) The diol component is Approximately 60 mol% or more of ethylene glycol residue, and (i) Neopentyl glycol residues in amounts of approximately 0 to less than 40 mol%, (ii) Approximately 0 to less than 40 mol% of 1,4-cyclohexanedimethanol residues, and (iii) The final polyester composition contains one or more total diethylene glycol residues in an amount of about 0 to less than 15 mol% of total diethylene glycol, comprising about 40 mol% or less of other glycols. The total mole% of the dicarboxylic acid component is 100 mol%, the total mole% of the diol component is 100 mol%, and the polyesters of (1) and (2) are different.

[0010]

[0011] One embodiment of the present disclosure is a crystallizable composition comprising a mixture of polyester compositions, the mixture comprising (1) 5 to 80% of at least one crystallizable polyester and (2) 20 to 95% of at least one amorphous polyester. (1) At least one crystallizable polyester comprises (a) a dicarboxylic acid component and (b) a diol component, (a) The dicarboxylic acid component is (i) Approximately 70 to 100 mol% of terephthalic acid residues, and (ii) comprising about 0 to about 30 mol% aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, (b) The diol component is Approximately 80 mol% or more of ethylene glycol residues, and (i) Neopentyl glycol residues in amounts of approximately 0 to less than 20 mol%, (ii) 1,4-cyclohexanedimethanol residues in amounts of approximately 0 to less than 20 mol%, and (iii) The final polyester composition contains one or more total diethylene glycol residues in an amount of about 0 to less than 10 mol%, including about 20 mol% or less of other glycols, The total mole% of the dicarboxylic acid component is 100 mol%, and the total mole% of the diol component is 100 mol%, and (2) At least one amorphous polyester comprises (a) a dicarboxylic acid component and (b) a diol component, (a) The dicarboxylic acid component is (i) Approximately 70 to 100 mol% of terephthalic acid residues, and (ii) comprising about 0 to about 30 mol% aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, (b) The diol component is Approximately 70 mol% or more of ethylene glycol residues, and (i) Neopentyl glycol residues in amounts of approximately 0 to less than 30 mol%, (ii) 1,4-cyclohexanedimethanol residues in amounts of approximately 0 to less than 30 mol%, and (iii) The final polyester composition contains one or more total diethylene glycol residues in the total diethylene glycol composition in an amount of about 0 to less than 15 mol%, comprising about 30 mol% or less of other glycols. The total mole% of the dicarboxylic acid component is 100 mol%, the total mole% of the diol component is 100 mol%, and the polyesters of (1) and (2) are different.

[0011]

[0012] One embodiment of the present disclosure is a crystallizable composition comprising a mixture of polyester compositions, the mixture comprising (1) 5 to 80% of at least one crystallizable polyester and (2) 20 to 95% of at least one amorphous polyester, (1) The at least one crystallizable polyester comprises (a) a dicarboxylic acid component and (b) a diol component, (a) The dicarboxylic acid component is (i) from about 70 to about 100 mol% terephthalic acid residues, and (ii) from about 0 to about 30 mol% aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, (b) The diol component is at least about 85 mol% ethylene glycol residues, and (i) less than about 0 to about 15 mol% neopentyl glycol residues, (ii) less than about 0 to about 15 mol% 1,4 - cyclohexanedimethanol residues, and (iii) up to about 15 mol% of other glycols including one or more of up to about 0 to about 5 mol% total diethylene glycol residues in the final polyester composition, The total mol% of the dicarboxylic acid component is 100 mol% and the total mol% of the diol component is 100 mol%, and (2) The at least one amorphous polyester comprises (a) a dicarboxylic acid component and (b) a diol component, (a) The dicarboxylic acid component is (i) from about 70 to about 100 mol% terephthalic acid residues, and (ii) from about 0 to about 30 mol% aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, (b) The diol component is at least about 60 mol% ethylene glycol residues, and (i) neopentyl glycol residues, (ii) 1,4 - cyclohexanedimethanol residues, and (iii) About 40 mol% or less of other glycols containing one or more diethylene glycol residues in the final polyester composition, regardless of whether they are generated in situ or not. Including, The total mole% of the dicarboxylic acid component is 100 mol%, the total mole% of the diol component is 100 mol%, and the polyesters of (1) and (2) are different.

[0012]

[0013] One embodiment of the present disclosure is a crystallizable composition comprising a mixture of polyester compositions, the mixture comprising (1) 5 to 80% of at least one crystallizable polyester and (2) 20 to 95% of at least one amorphous polyester. (1) At least one crystallizable polyester comprises (a) a dicarboxylic acid component and (b) a diol component, (a) The dicarboxylic acid component is (i) Approximately 70 to 100 mol% of terephthalic acid residues, and (ii) comprising about 0 to about 30 mol% aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, (b) The diol component is (i) Approximately 0 to approximately 30 mol% of neopentyl glycol residues, (ii) 1,4-cyclohexanedimethanol residues in amounts of approximately 0 to less than 30 mol%, and (iii) Containing a diethylene glycol residue, The remaining glycol component is (iv) Ethylene glycol residues, and (v) Containing 0.1 to 20 mol% of at least one modified glycol residue, The total mole% of the dicarboxylic acid component is 100 mol%, and the total mole% of the glycol component is 100 mol%, and (2) At least one amorphous polyester comprises (a) a dicarboxylic acid component and (b) a diol component, (a) The dicarboxylic acid component is (i) Approximately 70 to 100 mol% of terephthalic acid residues, and (ii) comprising about 0 to about 30 mol% aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, (b) The diol component is (i) Approximately 0 to approximately 40 mol% of neopentyl glycol residues, (ii) Approximately 0 to less than 40 mol% of 1,4-cyclohexanedimethanol residues, and (iii) Whether generated in situ or not, containing diethylene glycol residues, The remaining glycol component is (iv) Ethylene glycol residues, and (v) Containing at least one modified glycol residue in an amount of 0-20 mol%, or 0-10 mol%, or 0-5 mol%, The total mol% of the dicarboxylic acid component is 100 mol%, the total mol% of the glycol component is 100 mol%, and the polyesters of (1) and (2) are different.

[0013]

[0014] In other embodiments of the present disclosure, the mixed composition has a crystalline melting point in the range of about 200 to about 255°C.

[0015] In other embodiments of the present disclosure, the above-described mixture has a crystalline melting point in the range of about 220°C to about 230°C, or in the range of about 245°C to about 255°C. In other embodiments, component (1) has a crystalline melting point of about 220°C to about 230°C.

[0014]

[0016] One embodiment of the present disclosure is a crystallizable film of the above-described embodiment, wherein the film is stretched in at least one direction, and the stretched film has a strain-induced crystal melting point of 200°C or higher.

[0015]

[0017] One embodiment of the present disclosure is a thermoformed or thermoformable film or sheet comprising a mixture of polyester compositions comprising (1) at least one crystalline polyester containing residues of terephthalic acid, neopentyl glycol (NPG), 1,4-cyclohexanedimethanol (CHDM), ethylene glycol (EG), and diethylene glycol (DEG) in a specific composition range, and (2) at least one amorphous polyester containing residues of terephthalic acid, neopentyl glycol (NPG), 1,4-cyclohexanedimethanol (CHDM), ethylene glycol (EG), 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD), and diethylene glycol (DEG) in a specific composition range.

[0016]

[0018] One embodiment of the present disclosure relates to a thermoformed or thermoformable film or sheet comprising a crystallizable polyester blend composition. In one embodiment, the thermoformed or thermoformable film or sheet comprises a crystallizable polyester blend composition comprising (a) 5 to 95% by weight of a crystallizable polyester composition and (b) 5 to 95% by weight of at least one amorphous polyester composition.

[0017]

[0019] One embodiment of the present disclosure is a thermoformable sheet having a thickness of about 0.25 mm to about 6.4 mm, comprising a crystallizable composition comprising a mixture of polyester compositions, wherein the mixture comprises (1) 5 to 80% of at least one crystallizable polyester and (2) 20 to 95% of at least one amorphous polyester. (1) At least one crystallizable polyester comprises (a) a dicarboxylic acid component and a diol component selected from either (b) or (b'), (a) The dicarboxylic acid component is (i) Approximately 70 to 100 mol% of terephthalic acid residues, and (ii) comprising about 0 to about 30 mol% aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, (b) The diol component is Approximately 75 mol% or more of ethylene glycol residues, and (i) Neopentyl glycol residues of approximately 0 to less than 25 mol%, (ii) 1,4-cyclohexanedimethanol residues in amounts of approximately 0 to less than 25 mol%, and (iii) The final polyester composition contains one or more total diethylene glycol residues in the total diethylene glycol composition in an amount of about 0 to less than 10 mol%, comprising about 25 mol% or less of other glycols. The total mole% of the dicarboxylic acid component is 100 mol%, the total mole% of the diol component is 100 mol%, and (b') The diol component is, Approximately 75 mol% or more of ethylene glycol residues, and (i) Neopentyl glycol residues in amounts of approximately 0.1 to less than approximately 24 mol%, (ii) 1,4-cyclohexanedimethanol residues in amounts of approximately 0.1 to less than approximately 24 mol%, and (iii) The final polyester composition contains one or more total diethylene glycol residues in the total diethylene glycol composition in an amount of about 1 to less than 10 mol%, comprising about 25 mol% or less of other glycols. The total mole% of the dicarboxylic acid component is 100 mol%, and the total mole% of the diol component is 100 mol%, and (2) At least one amorphous polyester comprises (a) a dicarboxylic acid component and (b) a diol component, (a) The dicarboxylic acid component is (i) Approximately 70 to 100 mol% of terephthalic acid residues, and (ii) comprising about 0 to about 30 mol% aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, (b) The diol component is Approximately 60 mol% or more of ethylene glycol residue, and (i) Neopentyl glycol residues in amounts of approximately 0 to less than 40 mol%, (ii) Approximately 0 to less than 40 mol% of 1,4-cyclohexanedimethanol residues, and (iii) The final polyester composition contains one or more total diethylene glycol residues in an amount of about 0 to less than 15 mol% of total diethylene glycol, comprising about 40 mol% or less of other glycols. The total mole% of the dicarboxylic acid component is 100 mol%, the total mole% of the diol component is 100 mol%, and the polyesters of (1) and (2) are different.

[0018]

[0020] One embodiment of the present disclosure is a thermoformable sheet having a thickness of about 0.25 mm to about 6.4 mm, comprising a crystallizable composition comprising a mixture of polyester compositions, wherein the mixture comprises (1) 5 to 80% of at least one crystallizable polyester and (2) 20 to 95% of at least one amorphous polyester. (1) At least one crystallizable polyester comprises (a) a dicarboxylic acid component and (b) a diol component, (a) The dicarboxylic acid component is (i) Approximately 70 to 100 mol% of terephthalic acid residues, and (ii) comprising about 0 to about 30 mol% aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, (b) The diol component is Approximately 80 mol% or more of ethylene glycol residues, and (i) Neopentyl glycol residues in amounts of approximately 0 to less than 20 mol%, (ii) 1,4-cyclohexanedimethanol residues in amounts of approximately 0 to less than 20 mol%, and (iii) About 20 mol% of the total diethylene glycol residues in the final polyester composition, whether generated in situ or not, including one or more of about 0 to less than about 10 mol% Contains the following other glycols: The total mole% of the dicarboxylic acid component is 100 mol%, and the total mole% of the diol component is 100 mol%, and (2) At least one amorphous polyester comprises (a) a dicarboxylic acid component and (b) a diol component, (a) The dicarboxylic acid component is (i) Approximately 70 to 100 mol% of terephthalic acid residues, and (ii) comprising about 0 to about 30 mol% aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, (b) The diol component is Approximately 70 mol% or more of ethylene glycol residues, and (i) Neopentyl glycol residues in amounts of approximately 0 to less than 30 mol%, (ii) 1,4-cyclohexanedimethanol residues in amounts of approximately 0 to less than 30 mol%, and (iii) The final polyester composition contains one or more total diethylene glycol residues in the total diethylene glycol composition in an amount of about 0 to less than 15 mol%, comprising about 30 mol% or less of other glycols. The total mole% of the dicarboxylic acid component is 100 mol%, the total mole% of the diol component is 100 mol%, and the polyesters of (1) and (2) are different.

[0019]

[0021] One embodiment of the present disclosure is a thermoformable sheet having a thickness of about 0.25 mm to about 6.4 mm, comprising a crystallizable composition comprising a mixture of polyester compositions, wherein the mixture comprises (1) 5 to 80% of at least one crystallizable polyester and (2) 20 to 95% of at least one amorphous polyester. (1) At least one crystallizable polyester comprises (a) a dicarboxylic acid component and (b) a diol component, (a) The dicarboxylic acid component is (i) Approximately 70 to 100 mol% of terephthalic acid residues, and (ii) comprising about 0 to about 30 mol% aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, (b) The diol component is Approximately 80 mol% or more of ethylene glycol residues, and (i) Neopentyl glycol residues in amounts of approximately 0 to less than 15 mol%, (ii) 1,4-cyclohexanedimethanol residues in amounts of approximately 0 to less than 15 mol%, and (iii) The final polyester composition contains one or more total diethylene glycol residues in the total diethylene glycol composition in an amount of about 0 to less than 5 mol%, comprising about 15 mol% or less of other glycols. The total mole% of the dicarboxylic acid component is 100 mol%, and the total mole% of the diol component is 100 mol%, and (2) At least one amorphous polyester comprises (a) a dicarboxylic acid component and (b) a diol component, (a) The dicarboxylic acid component is (i) Approximately 70 to 100 mol% of terephthalic acid residues, and (ii) comprising about 0 to about 30 mol% aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, (b) The diol component is Approximately 60 mol% or more of ethylene glycol residue, and (i) neopentyl glycol residue, (ii) 1,4-cyclohexanedimethanol residue, and (iii) One or more diethylene glycol residues in the final polyester composition It contains other glycols in an amount of approximately 40 mol% or less, The total mole% of the dicarboxylic acid component is 100 mol%, the total mole% of the diol component is 100 mol%, and the polyesters of (1) and (2) are different.

[0022] One embodiment of the present disclosure is a thermoformable sheet having a thickness of about 0.25 mm to about 6.4 mm, comprising a crystallizable composition comprising a mixture of polyester compositions, wherein the mixture comprises (1) 5 to 80% of at least one crystallizable polyester and (2) 20 to 95% of at least one amorphous polyester. (1) At least one crystallizable polyester comprises (a) a dicarboxylic acid component and (b) a diol component, (a) The dicarboxylic acid component is (i) Approximately 70 to 100 mol% of terephthalic acid residues, and (ii) comprising about 0 to about 30 mol% aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, (b) The diol component is (i) Approximately 0 to approximately 30 mol% of neopentyl glycol residues, (ii) 1,4-cyclohexanedimethanol residues in amounts of approximately 0 to less than 30 mol%, and (iii) Containing a diethylene glycol residue, The remaining glycol component is (iv) Ethylene glycol residues, and (v) In some cases, the product contains 0.1 to 10 mol% of at least one modified glycol residue, The total mole% of the dicarboxylic acid component is 100 mol%, and the total mole% of the diol component is 100 mol%, and (2) At least one amorphous polyester comprises (a) a dicarboxylic acid component and (b) a diol component, (a) The dicarboxylic acid component is (i) Approximately 70 to 100 mol% of terephthalic acid residues, and (ii) comprising about 0 to about 30 mol% aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, (b) The diol component is (i) Approximately 0 to approximately 40 mol% of neopentyl glycol residues, (ii) Approximately 0 to less than 40 mol% of 1,4-cyclohexanedimethanol residues, and (iii) Containing a diethylene glycol residue, The remaining glycol component is (iv) Ethylene glycol residues, and (v) In some cases, the product contains 0.1 to 10 mol% of at least one modified glycol residue, The total mole% of the dicarboxylic acid component is 100 mol%, the total mole% of the diol component is 100 mol%, and the polyesters of (1) and (2) are different.

[0020]

[0023] One embodiment of the present disclosure is an extruded or calendered film comprising a mixture of any of the crystallizable compositions of the embodiments described above.

[0024] One embodiment of the present disclosure is a molded, thermoformed, or shaped article comprising, or prepared from, any of the sheets of the above embodiments.

[0021]

[0025] One embodiment of the present disclosure includes, or is prepared from, a thermoformed or thermoformable sheet of any of the embodiments described above, packaging materials for medical devices, medical-related packaging materials, packaging materials for healthcare supplies, packaging materials for commercial food supplies, trays, containers, food dishes, tumblers, storage boxes, bottles, cooking utensils, mixing bowls, household goods, water bottles, vegetable trays, washing machine parts, refrigerator parts, vacuum cleaner parts, ophthalmic lenses, and framing materials or toys.

[0022]

[0026] One embodiment of the present disclosure is a manufactured article comprising, or prepared from, a thermoformed or thermoformable sheet of any of the preceding claims.

[0027] One embodiment of the present disclosure is a method for producing a thermoformed film or sheet of any of the embodiments described above, the method comprising: A) heating a polyester film or sheet; B) applying pneumatic, vacuum, and / or physical pressure to the heat-softened film or sheet; C) conforming the sheet to a mold shape by vacuum or pressurization; D) cooling the thermoformed part; and E) removing the thermoformed part or article from the mold.

[0023]

[0028] The Association for Plastic Recyclers (APR) determines whether the material is compatible with the current recycling process (PET-CG-02). A test was established to measure [the substance]. In this test, the label (minimum 3 wt%) and bottle are crushed into 1 / 4 to 1 / 2 inch flakes. The bottle flakes are then mixed 50:50 with an unlabeled control bottle flake. Subsequently, the samples are wet-classified under conditions that allow less than 1.2% of PET to be retained with the label. These flakes are washed with 0.3% Triton X-100 and 1.0% caustic alkali at 88°C for 15 minutes. Then all suspended matter is measured. After removing the impurities, the flakes are washed with water and then filtered to remove excess water. The flakes are wet-classified again in the same manner as before. Next, 2 pounds of washed flakes are placed in a Teflon-coated baking dish as each washed sample, and the flakes are added to a layer thickness of 1.5 inches. The dish containing the flakes is placed in a circulating oven at 208°C for 1.5 hours. The flakes are cooled and passed through a sieve with a 0.0625-inch opening. If the material passes through the sieve, it is not agglomerated, i.e., it is not too large to pass through the sieve. Following this test, the extrusion / pelletization and molding processes are carried out to ensure the quality of the flakes.

[0024]

[0029] As a result, the crystallizable mixture of the present disclosure provides an effective component of a PET recycling process to the extent that the composition can accompany PET in the recycling process without requiring an additional separation step. Accordingly, one embodiment of the present disclosure provides a polyester recycling process flow comprising recycled polyethylene terephthalate flakes mixed together with at least about 0.1% by weight of the crystallizable mixture of the present disclosure. In another embodiment, the process flow complies with document number PET-CG-02, “Critical Guidance Protocol for Clear PET Articles with Labels and Closures,” dated April 11, 2019. [Brief explanation of the drawing]

[0025] [Figure 1]

[0030] Figure 1 shows the PET aggregation rate (%) relative to the degree of crystallinity for mixtures prepared with resin number 1 and resin number 2. [Figure 2]

[0031] Figure 2 shows the PET aggregation rate (%) relative to the degree of crystallinity for mixtures prepared with resin number 2 and resin number 3. Detailed description of the invention

[0026]

[0032] This disclosure will be more readily understood by referring to the following detailed descriptions of specific embodiments and examples of this disclosure. In accordance with the purpose of this disclosure, specific embodiments of this disclosure are described in the gist of the invention and are further described herein as follows. Other embodiments of this disclosure are also described herein.

[0027]

[0033] Heat-shrinkable plastic films are used as coverings to hold multiple objects together and as outer packaging for bottles, cans, and other types of containers. For example, the film is used to cover bottle caps, necks, shoulders, bodies, or the entire bottle for purposes such as labeling, protection, packaging, or enhancing the value of a product. Furthermore, the film can be used as a covering to package objects such as boxes, bottles, boards, rods, or notebooks together as a group, and it can also adhere tightly as a packaging material. The shrinkability and internal shrinkage stress of the film are utilized in the uses described above.

[0028]

[0034] Historically, polyvinyl chloride (PVC) film has been the dominant force in the shrink film market. However, polyester film has become a significant alternative because it does not have the environmental problems associated with PVC film. Since polyester shrink film ideally possesses properties very similar to PVC film, polyester can function as an alternative to the "drop-in" film method and existing heat shrink tunnels. It can be processed using a machine. Desired characteristics of PVC film for reproductions include: (1) a relatively low shrinkage initiation temperature, (2) a total shrinkage rate that increases gradually and in a controlled manner as the temperature rises, (3) a low shrinkage force to prevent the underlying container from collapsing, (4) a high total shrinkage rate (e.g., 50% or more), and (5) inherent film toughness to prevent useless tearing and splitting of the film before and after shrinkage.

[0029]

[0035] For use in this application, heat-shrinkable films must meet various compliance requirements. The film must be strong, shrink in a controlled manner, and provide sufficient shrinkage force to hold itself to the bottle surface without crushing the contents. Furthermore, when these labels are applied to polyester containers, they must not hinder the recycling process of PET bottles. In fact, it is advantageous if the labels are also recyclable, allowing the entire bottle to be recycled and converted into a new product without creating additional operational requirements or new environmental problems. Heat-shrinkable films are manufactured from a variety of raw materials to meet a certain range of material demands. This disclosure describes the unique and unexpected effects brought about by polyester mixtures, including combinations with specific monomers that improve the recyclability of labels made of polyester shrinkable film.

[0030]

[0036] Shrink film compositions are commercially used as shrink film labels for food, beverages, personal care products, and household goods. Often, these shrink films are used in combination with clear polyethylene terephthalate (PET) bottles or containers. The entire product (bottle and label) is then put into a recycling process. In a typical recycling site, PET and shrink film materials may be mixed together at the end of the process due to their similar composition and density. Drying the PET flakes is necessary to remove any residual water present on the PET during the recycling process. Typically, PET is dried at temperatures above 200°C, at which temperatures the typical polyester shrink film resin often softens and becomes sticky, forming agglomerates with the PET flakes. These agglomerates must be removed before further processing. These agglomerates reduce the yield of PET flakes from this process, thus requiring additional handling steps.

[0031]

[0037] Polyesters containing a specific combination of glycol monomers in a polyester resin mixture for shrinkable film yield films with excellent shrinkage performance and are also found to be crystallizable without affecting the recycling of PET flakes during recycling. These crystallizable shrinkable film resin mixtures can be processed together with PET bottles and become a component of recyclable PET flakes after the recycling process is complete. The selection and amount of specific combinations of glycol monomers in each composition (amorphous and crystallizable) of the crystallizable polyester mixture were found to be important for producing films with excellent shrinkage properties and for producing crystallizable films.

[0032]

[0038] As used herein, the term “polyester” is intended to encompass “copolymerized polyester” 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 a glycol and a diol. As used herein, the term “glycol” includes, but is not limited to, diols, glycols, and / or polyfunctional hydroxyl compounds, such as branching agents. Alternatively, the difunctional carboxylic acid may be a hydroxycarboxylic acid, such as p-hydroxybenzoic acid, and the difunctional hydroxyl compound may have an aromatic nucleus holding two hydroxyl substituents, such as a hydroquinone. As used herein, the term “residue” means any organic structure incorporated into the polymer by polycondensation and / or esterification reactions from the corresponding monomer. As used herein, the term “repeating unit” means an organic structure having dicarboxylic acid residues and diol residues linked via ester groups. Therefore, for example, the dicarboxylic acid residue may be derived from a dicarboxylic acid monomer or its related acid halide, ester, salt, anhydride, and / or mixture thereof. Furthermore, in this specification The term "diacid" as used herein includes polyfunctional acids, such as branching agents. Accordingly, the term "dicarboxylic acid" as used herein is intended to encompass dicarboxylic acids and any dicarboxylic acid derivatives useful for reaction with diols to obtain polyesters, including related acid halides, esters, semi-esters, salts, semi-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 derivatives useful for reaction with diols to obtain polyesters, including related acid halides, esters, semi-esters, salts, semi-salts, anhydrides, mixed anhydrides, and / or mixtures thereof or residues thereof.

[0033]

[0039] 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 corresponding residues. Thus, the polyesters of this disclosure may contain substantially equimolar amounts of acid residues (100 mol%) and diol (and / or polyfunctional hydroxyl compound) residues (100 mol%) such that the total moles of repeating units are equal to 100 mol%. Accordingly, the molar percentages shown in this disclosure may be based on the total moles of acid residues, the total moles of diol residues, or the total moles of repeating units. For example, a polyester containing 10 mol% isophthalic acid based on total acid residues means that the polyester contains 10 mol% isophthalic acid residues out of a total of 100 mol% of acid residues. That is, there are 10 moles of isophthalic acid residues in each 100 moles of acid residues. In another example, a polyester containing 25 mol% 1,4-cyclohexanedimethanol based on total diol residues means that the polyester contains 25 mol% 1,4-cyclohexanedimethanol residues out of a total of 100 mol% diol residues. That is, there are 25 moles of 1,4-cyclohexanedimethanol residues in each 100 moles of diol residues.

[0034]

[0040] 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 some embodiments, 70 to 100 mol%; or 80 to 100 mol%; or 90 to 100 mol%; or 99 to 100 mol%; or 100 mol% of terephthalic acid and / or dimethyl terephthalate and / or mixtures thereof may be used.

[0035]

[0041] In addition to terephthalic acid, the dicarboxylic acid component of the polyester useful in this disclosure may include one or more modified aromatic dicarboxylic acids in amounts up to 30 mol%, up to 20 mol%, up to 10 mol%, up to 5 mol%, or up to 1 mol%. Yet another embodiment includes 0 mol% of modified aromatic dicarboxylic acids. Therefore, if present, the amount of one or more modified aromatic dicarboxylic acids may vary within any range of these above endpoint values, for example, 0.01 to 10 mol%, 0.01 to 5 mol%, or 0.01 to 1 mol%. In one embodiment, the modified aromatic dicarboxylic acids that may be used in this disclosure include, but are not limited to, those having up to 20 carbon atoms and being linear, para-oriented, or symmetric. Examples of modified aromatic dicarboxylic acids that may be used in this disclosure include, but are not limited to, isophthalic acid, 4,4'-biphenyldicarboxylic acid, 1,4-, 1,5-, 2,6-, 2,7-naphthalenedicarboxylic acid, and trans-4,4'-stilbenidicarboxylic acid, and their esters. In one embodiment, the modified aromatic dicarboxylic acid is isophthalic acid.

[0036]

[0042] The carboxylic acid components of polyesters useful in this disclosure can be further modified with up to 10 mol%, for example, 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 dodecanediic acid. In certain embodiments, one or more modified aliphatic dicarboxylic acids may also be included, for example, 0.01 to 10 mol%, for example, 0.1 to 10 mol%, 1 or 10 mol%, or 5 to 10 mol%. Yet another embodiment includes 0 mol% of modified aliphatic dicarboxylic acids. The total mol% of the dicarboxylic acid components is 100 mol%. In one embodiment, adipic acid and / or glutaric acid are provided in the modified aliphatic dicarboxylic acid components of the polyester and are useful in this disclosure.

[0037]

[0043] Terephthalic acid esters and other modified dicarboxylic acids or their corresponding esters and / or salts may be used instead of dicarboxylic acids. Preferred 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 the methyl, ethyl, propyl, isopropyl, and phenyl esters.

[0038]

[0044] In one embodiment, the diol component of the polyester composition and polyester blend composition useful in this disclosure may include 1,4-cyclohexanedimethanol. In another embodiment, the diol component of the polyester composition and polyester blend composition useful in this disclosure includes 1,4-cyclohexanedimethanol and 1,3-cyclohexanedimethanol. The molar ratio of cis / trans 1,4-cyclohexanedimethanol may vary within the range of 50 / 50 to 0 / 100, for example, 40 / 60 to 20 / 80.

[0039]

[0045] The diol components of the crystallizable polyester compositions and crystallizable polyester mixed compositions useful in this disclosure include, but are not limited to, those in which the total amount of 1,4-cyclohexanedimethanol residues and neopentyl glycol residues in the final polyester composition is 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 2 5 mol%, or 3-20 mol%, or 3-15 mol%, or 3-10 mol%, 4-30 mol%, or 4-25 mol%, 4-20 mol%, or 4-15 mol%, or 4-10 mol%, 5-30 mol%, or 5-25 mol%, 5-20 mol%, or 5-15 mol%, or 5-10 mol%, or 6-30 mol%, or 6-25 mol%, or 6-20 mol%, or 6-15 mol%, or 6-10 mol%, or 7-30 mol%, or 7-25 mol%, 7-20 mol%, or 7-15 mol%, or 7-10 mol%, or 8-30 mol%, or 8-25 mol%, or 8-20 mol%, or 8-15 mol%, or 8-10 mol%, or 9-30 mol%, or 9-25 mol%, or 9-20 mol%, or 9-15 mol%, or 9-10 mol%, or 10-30 mol%, or 10-25 mol%, or 10-20 mol%, or 10-15 mol%, or 11-30 mol%, or 11-30 mol%, or 11-25 mol%, or 11-20 mol%, or 11-15 mol%, or 12-30 mol%, or 12 ~25 mol%, or 12~20 mol%, or 12~15 mol%, or 13~30 mol%, or 13~25 mol%, or 13~20 mol%, or 13~15 mol%, or 14~30 mol%, or 14~25 mol%, or 14~20 mol%, or 14~15 mol%, or 15~30 mol%, or 15~25 mol%, or 15~20 mol%, or 16~20 mol%, or 18~20 mol%, or 10~18 mol%, or 16~18 mol%, or 12~16 mol%, or 16~20 mol%, or 1 The composition may include 4-18 mol%, or 11-30 mol%, or 13-30 mol%, or 14-30 mol%, or 10-29 mol%, or 11-29 mol%, or 12-29 mol%, or 13-29 mol%, or 14-29 mol%, or 15-29 mol%, or 10-28 mol%, or 11-28 mol%, or 12-28 mol%, or 13-28 mol%, or 14-28 mol%, or 15-28 mol%. In one embodiment, the total amount of 1,4-cyclohexanedimethanol residues and neopentyl glycol residues in the final polyester composition may be 4 to 15 mol%, or 2 to 21 mol%, or less than 2 to 20 mol%, or 4 to 20 mol%, or 5 to 18 mol%, or 10 to 21 mol%, or 12 to 21 mol%, where the total mol% of the diol component is 100 mol%.

[0040]

[0046] In one embodiment, the diol component of the crystallizable polyester composition and crystallizable polyester mixed composition useful in this disclosure may contain 0 to 30 mol% neopentyl glycol based on the total mol% of the diol component, which is 100 mol%. In one embodiment, the diol component of the polyester composition and polyester mixed composition useful in this disclosure may contain 0 to 25 mol% neopentyl glycol based on the total mol% of the diol component, which is 100 mol%. In one embodiment, the diol component of the polyester composition and polyester mixed composition useful in this disclosure may contain 0 to 17 mol% neopentyl glycol based on the total mol% of the diol component, which is 100 mol%. In one embodiment, the diol component of the polyester composition and polyester mixed composition useful in this disclosure may contain 5 to 20 mol% neopentyl glycol based on the total mol% of the diol component, which is 100 mol%. In one embodiment, the diol component of the polyester composition and polyester blend composition useful in this disclosure may contain 10 to 20 mol% neopentyl glycol based on the total mol% of the diol component, which is 100 mol%. In one embodiment, the diol component of the polyester composition and polyester blend composition useful in this disclosure may contain 10 to 15 mol% neopentyl glycol based on the total mol% of the diol component, which is 100 mol%. In one embodiment, the diol component of the polyester composition and polyester blend composition useful in this disclosure may contain 15 to 25 mol% neopentyl glycol based on the total mol% of the diol component, which is 100 mol%.

[0041]

[0047] In one embodiment, the diol component of the crystallizable polyester composition and crystallizable polyester mixed composition useful in this disclosure is 0-30 mol%, or 0.01-30 mol%, or 0-20 mol%, or 0.1-20 mol%, or 2-20 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- It may also contain 8 mol%, or 0.01-7 mol%, or 0.01-6 mol%, or 0.01-5 mol%, or 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.

[0042]

[0048] In one embodiment, the diol component of the crystallizable polyester composition and polyester mixed composition useful in this disclosure may contain 0 to 15 mol% of 1,4-cyclohexanedimethanol based on the total mol% of the diol component, which is 100 mol%. In one embodiment, the diol component of the polyester composition useful in this disclosure may contain 0.01 to less than 15 mol% of 1,4-cyclohexanedimethanol based on the total mol% of the diol component, which is 100 mol%. In one embodiment, this disclosure The diol component of the polyester composition useful in this disclosure may contain 0 to 10 mol% of 1,4-cyclohexanedimethanol based on the total molar percentage of the diol component, which is 100 mol%. In one embodiment, the diol component of the polyester composition useful in this disclosure may contain 0.01 to less than 10 mol% of 1,4-cyclohexanedimethanol based on the total molar percentage of the diol component, which is 100 mol%. In one embodiment, the diol component of the polyester composition useful in this disclosure may contain 0.01 to 5 mol% of 1,4-cyclohexanedimethanol based on the total molar percentage of the diol component, which is 100 mol%. In one embodiment, the diol component of the polyester composition useful in this disclosure may contain 0 to less than 5 mol% of 1,4-cyclohexanedimethanol based on the total molar percentage of the diol component, which is 100 mol%.

[0043]

[0049] Some other diol residues may, naturally, be generated in situ during processing. The total amount of diethylene glycol residues may be present in any amount in the crystallizable polyester mixed composition useful in this disclosure, whether generated in situ during processing, intentionally added, or both. For example, based on the total molar percentage of the diol component being 100 mol%, there may be 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.

[0044]

[0050] In one embodiment, the total amount of diethylene glycol residues that may be present in the polyester useful in this disclosure may be 5 mol% or less, 4 mol% or less, or 3.5 mol% or less, or 3.0 mol% or less, or 2.5 mol% or less, or 2.0 mol% or less, or 1.5 mol% or less, or 1.0 mol% or less, or 1 to 4 mol%, or 1 to 3 mol%, or 1 to 2 mol%, or 2 to 8 mol%, or 2 to 7 mol%, or 2 to 6 mol%, or 2 to 5 mol%, or 3 to 8 mol%, or 3 to 7 mol%, or 3 to 6 mol%, or 3 to 5 mol%, based on the total mol% of the diol component being 100 mol%, regardless of whether they are generated in situ during processing, intentionally added, or both, or in some embodiments, there may be no intentionally added diethylene glycol residues. In certain embodiments, no modified diol is added to the polyester. In certain embodiments, the diethylene glycol residues in the crystallizable polyester composition of the polyester mixed composition may be 5 mol% or less.

[0045]

[0051] In one embodiment, the diol component of a crystallizable polyester mixed composition useful in this disclosure may contain up to 20 mol%, or up to 19 mol%, or up to 18 mol%, or up to 17 mol%, or up to 16 mol%, or up to 15 mol%, or up to 14 mol%, or up to 13 mol%, or up to 12 mol%, or up to 11 mol%, or up to 10 mol%, or up to 9 mol%, or up to 8 mol%, or up to 7 mol%, or up to 6 mol%, or up to 5 mol%, or up to 4 mol%, or up to 3 mol%, or up to 2 mol%, or up to 1 mol%, of one or more modified diols (a modified diol is defined as a diol that is not ethylene glycol, diethylene glycol, neopentyl glycol, or 1,4-cyclohexanedimethanol). In a particular embodiment, the polyester useful in this disclosure may contain up to 10 mol% of one or more modified diols. In a particular embodiment, the polyester useful in this disclosure may contain up to 5 mol% of one or more modified diols. In certain embodiments, the polyester useful in this disclosure may contain one or more modified diols in an amount of 3 mol% or less. In other embodiments, the polyester useful in this disclosure may contain 0 mol% of modified diols. However, some other diol residues may be generated in situ, and the amount of residues generated in situ may also be. This may be considered an embodiment of the present disclosure.

[0046]

[0052] In some embodiments, the modified diols used in the crystallizable polyester mixed compositions as defined herein contain 2 to 16 carbon atoms, if used. Examples of modified diols, but not limited to, include 1,2-propanediol, 1,3-propanediol, isosorbide, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, p-xylene glycol, polytetramethylene glycol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD), and mixtures thereof. In one embodiment, isosorbide is the modified diol. In another embodiment, the modified diol may be at least one of 1,3-propanediol and 1,4-butanediol, but not limited to, 1,3-propanediol and / or 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, greater than 4 mol% or greater than 5 mol% may be provided. In one embodiment, at least one modified diol is 1,4-butanediol, present in an amount of 5 to 25 mol%.

[0053] In all embodiments, the remainder of the diol component may contain any amount of ethylene glycol residues based on the total molar percentage of the diol component, which is 100 mol%. In one embodiment, a crystallizable polyester mixed composition 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 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%, based on the total molar percentage of the diol component, which is 100 mol%.

[0047]

[0054] In one embodiment, a shrinkable film is provided comprising a crystallizable polyester mixed composition (i.e., components (1) and (2)) further comprising the following components: based on the total molar percentage of the diol component, which is 100 mol%, the composition contains 0.01 to about 10 mol% of 1,4-cyclohexanedimethanol residues, 2 to 9 mol% of diethylene glycol residues, 5 to 30 mol% of neopentyl glycol residues, and 60 mol% or more of ethylene glycol residues.

[0048]

[0055] In one embodiment, the crystallizable polyester mixed composition includes the following components: The invention provides a shrinkable film. Based on the total molar percentage of the diol component, which is 100 mol%, the film contains 0.01 to approximately 5 mol% of 1,4-cyclohexanedimethanol residues, 1 to 9 mol% of diethylene glycol residues, 5 to 25 mol% of neopentyl glycol residues, and 60 mol% or more of ethylene glycol residues.

[0049]

[0056] One embodiment provides a shrinkable film comprising a crystallizable polyester mixed composition having the following configuration: Based on the total molar percentage of the diol component, which is 100 mol%, the composition contains approximately 10 to 20 mol% of 1,4-cyclohexanedimethanol residues, 1 to 10 mol% of diethylene glycol residues, up to approximately 1 mol% of neopentyl glycol residues, and 60 mol% or more of ethylene glycol residues.

[0050]

[0057] One embodiment provides a shrinkable film comprising a crystallizable polyester mixed composition having the following configuration: Based on the total molar percentage of the diol component, which is 100 mol%, the composition contains 2 to 7 mol% of 1,4-cyclohexanedimethanol residues, less than 10 mol% of diethylene glycol residues, 5 to 20 mol% of neopentyl glycol residues, and more than 60 mol% of ethylene glycol residues.

[0051]

[0058] One embodiment provides a shrinkable film comprising a crystallizable polyester mixed composition having the following configuration: Based on the total molar percentage of the diol component, which is 100 mol%, the composition contains less than 10 mol% of 1,4-cyclohexanedimethanol residues, 1 to 10 mol% of diethylene glycol residues, more than 5 mol% of neopentyl glycol residues, and 60 mol% or more of ethylene glycol residues.

[0052]

[0059] In one embodiment, a shrinkable film is provided in which the total amount of one or more diol monomer components capable of forming an amorphous polyester composition in the polyester mixed composition is 20-45 mol%, or 22-45 mol%, or 20-40 mol%, or 24-40 mol%, or 30-45 mol%, or 25-45 mol%, or 25-40 mol%, or 25-35 mol%, where the total mol% of the diol component content is 100 mol%.

[0053]

[0060] In one embodiment, a shrinkable film is provided in which the total amount of 1,4-cyclohexanedimethanol residues and neopentyl glycol residues in the amorphous polyester composition of the polyester mixture is 12-35 mol%, or 15-40 mol%, or 15-35 mol%, or 20-40 mol%, or 25-40 mol%, or 20-45 mol%, or 25-35 mol%, where the total mol% of the diol components is 100 mol%.

[0054]

[0061] One embodiment of the present disclosure provides a crystallizable film comprising a mixture of polyester compositions including: (1) at least one crystallizable polyester comprising terephthalic acid residues and 0 to about 20 mol%, or 0 to about 17 mol%, or about 1 to about 20 mol%, or about 1 to about 17 mol%, or about 5 to about 20 mol%, of neopentyl glycol (NPG) residues and 0 to about 20 mol%, or 0 to about 17 mol%, or about 1 to about 20 mol%, or about 1 to about 17 mol%, or about 5 to about 20 mol%, of 1,4-cyclohexanedimethanol (CHDM) and less than about 5 mol% of diethylene glycol (DEG) residues, with the remainder being ethylene glycol (EG) residues; and (2) terephthalic acid residues and 0 to about 40 mol% A amorphous polyester comprising, or 0 to about 30 mol%, or about 1 to about 40 mol%, or about 10 to about 20 mol%, or about 10 to about 40 mol%, or about 5 to about 30 mol%, of neopentyl glycol (NPG), and 0 to about 40 mol%, or 0 to about 35 mol%, or about 1 to about 30 mol%, or about 10 to about 40 mol%, or about 20 to about 40 mol%, of 1,4-cyclohexanedimethanol (CHDM), and 1 to about 15 mol%, or 2 to about 10 mol%, or about 5 to about 15 mol%, or about 5 to about 10 mol%, of diethylene glycol (DEG), with the remainder being ethylene glycol (EG) residues.

[0055]

[0062] Depending on the embodiment, the polyester composition according to this disclosure may contain one or more branched monomer residues in amounts of 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%, based on the total mol% 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. Accordingly, depending on the embodiment, the polyester useful in this disclosure may be linear or branched.

[0056]

[0063] Examples of branched monomers, but not limited to them, include trimellitic acid, trimellitic anhydride, pyromellitic dianhydride, trimethylolpropane, glycerol, pentaerythritol, citric acid, tartaric acid, 3-hydroxyglutaric acid, and other polyfunctional acids or polyfunctional alcohols. In one embodiment, the branched monomer residues are trimellitic anhydride, pyromellitic dianhydride, glycerol, sorbitol, and 1,2,6-hexanetrio The mixture may contain one or more residues in an amount of 0.1 to 0.7 mol%, selected from at least one of 1,000,

[0057]

[0064] The polyesters useful in this disclosure may contain at least one chain extender. Suitable chain extenders include, but are not limited to, polyfunctional (but not limited to, bifunctional, etc.) isocyanates, polyfunctional 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 adding it during a conversion process such as injection molding or extrusion molding.

[0058]

[0065] The amount of chain extender used may be varied depending on the specific monomer composition used and the desired physical properties, but generally it is about 0.1% to 10% by weight, for example, about 0.1% to 5% by weight, based on the total weight of the polyester.

[0059]

[0066] A polyester blend composition useful in this disclosure may, unless otherwise specified, have at least one of the intrinsic viscosity ranges described herein and at least one of the monomer ranges of the polyester compositions described herein. A polyester blend composition useful in this disclosure may, unless otherwise specified, have at least one of the Tg ranges described herein and at least one of the monomer ranges of the polyester compositions described herein. A polyester blend composition useful in this disclosure may, unless otherwise specified, have at least one of the intrinsic viscosity ranges described herein, at least one of the Tg ranges described herein and at least one of the monomer ranges of the polyester compositions described herein.

[0060]

[0067] 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 at 25°C and a concentration of 0.5 g / dL in 60 / 40 (weight / weight) phenol / tetrachloroethane: 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.

[0061]

[0068] The glass transition temperature (Tg) of the polyester in the polyester blend composition is measured using a TA DSC 2920 from Thermal Analyst Instruments at a scanning speed of 20°C / min. The glass transition temperature is measured during the second heating process.

[0062]

[0069] In certain embodiments, the orientation or shrinkage film of the Disclosure comprises a polyester / polyester composition having a polyester Tg of 60-80°C, 70-80°C, 65-80°C, or 65-75°C. In certain embodiments, these Tg ranges can be met regardless of whether or not at least one plasticizer is added during polymerization.

[0063]

[0070] In embodiments of the present disclosure, certain oriented films and / or shrinkable films comprising polyesters and / or polyester compositions useful in the present disclosure possess all of the following properties: excellent stretchability, controlled shrinkage properties, specific toughness, specific intrinsic viscosity, specific glass transition temperature (Tg), specific strain-induced crystal melting point, specific flexural modulus, specific density, and It may have a specific combination of a constant tensile modulus, a specific surface tension, excellent melt viscosity, excellent transparency, and excellent color tone.

[0064]

[0071] In one embodiment, certain polyester blend compositions useful in this disclosure may be visually transparent. The term “visually transparent” is defined herein as being clearly free from cloudiness, haze, and / or turbidity upon visual inspection.

[0065]

[0072] The polyester portion (amorphous and crystallizable compositions) of the polyester mixed compositions useful in this disclosure may be prepared by known methods from the literature, such as methods in homogeneous solution, methods by transesterification in molten material, and methods by two-phase interface. Preferred methods, but are not limited, 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 period of time sufficient to produce polyester. For methods of producing polyester, see U.S. Patent No. 3,772,405, the disclosure of that method is incorporated herein by reference. Born.

[0066]

[0073] Generally, polyesters may be prepared by condensing a dicarboxylic acid or dicarboxylic acid ester with a diol in the presence of a catalyst at high temperatures, gradually increasing the temperature to about 225°C to 310°C during the condensation process in an inert atmosphere, and the latter part of the condensation is at low pressure, as further described in U.S. Patent No. 2,720,507 incorporated herein by reference. It may also be prepared by condensation.

[0067]

[0074] Depending on the embodiment, certain chemicals that color the polymer may be added to the molten material containing toner or dye during the manufacturing process of the polyester mixed composition useful in this disclosure. In one embodiment, the molten phase product of the resulting polyester polymer is b * To reduce the blue tint, a blue-tinted toner is added to the molten material. Examples of such blue-tinted agents include blue inorganic and organic toners and / or dyes. Alternatively, red toner and / or dyes can be used. * The color tone may be adjusted. Organic toners, such as blue and red organic toners, such as those described in U.S. Patents No. 5,372,864 and No. 5,384,377, which are incorporated herein by reference in their entirety, may be used. The organic toners may be supplied as a premixed composition. The premixed composition may be an undiluted mixture 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.

[0068]

[0075] The total amount of toner components added depends on the inherent yellowness in the base polyester and the potency of the toner. In one embodiment, the mixed organic toner components may be used at a maximum concentration of about 15 ppm and a minimum concentration of about 0.5 ppm. In one embodiment, the total amount of the blue-coloring additive may be in the range of 0.5 to 10 ppm. In one embodiment, the toner may be added to the esterification reaction area or the polycondensation reaction area. Preferably, the toner may be added to the esterification reaction area or to the initial stage of the polycondensation area, for example, in the prepolymerization reactor, or during the compounding process or during the post-polymerization extrusion process.

[0069]

[0076] The Disclosure further relates to polymers compounded with crystallizable polyester compositions as part of a polyester mixed composition. In one embodiment, the compounded composition comprises (a) 5 to 80% by weight of a crystallizable polyester composition as described herein, and (b) 20 to 95% by weight of at least one polymer component (i.e., a component other than the mixture of the Disclosure).

[0070]

[0077] Suitable examples of polymer components include, but are not limited to, nylon; polyesters other than those described herein; polyamides such as ZYTEL(R) from DuPont; and polystyrene. Polystyrene copolymer; styrene acrylonitrile copolymer; acrylonitrile butadiene styrene copolymer; polymethyl methacrylate; acrylic copolymer; polyetherimides such as ULTEM(R) (polyetherimides manufactured by SABIC); poly(2,6-dimethylphenyl Polyphenylene oxide (such as poly(2,6-dimethylphenylene oxide) or polyphenylene oxide / polystyrene mixtures such as NORYL 1000(R) (a mixture of poly(2,6-dimethylphenylene oxide) and polystyrene resin manufactured by SABIC); polyphenylene sulfide; polyphenylene sulfide / sulfone; polyester carbonate; LEXAN(R) (a polycarbonate manufactured by SABIC) Examples include polycarbonates such as poly(I))(I)(I)(I)(I)(I)(I)(I)(I)(I))(I)(I)(I)(I)(I)(I)(I)(I))(I)(I TM Copolymer polyester ).

[0071]

[0078] This mixture may be prepared by conventional processing techniques known in the art, such as melt mixing or solution mixing.

[0079] In some embodiments, the polyester composition and polymer mixture composition may also contain common additives such as colorants, toners, dyes, mold release agents, flame retardants, plasticizers, glass bubble nucleating agents, stabilizers such as UV stabilizers and heat stabilizers (but not limited to those), and / or their reaction products, fillers, and impact modifiers, in amounts of 0.01 to 25% by weight of the total composition. Examples of commercially available impact modifiers include, but are not limited to, impact modifiers for ethylene / propylene ternary copolymers, functionalized polyolefins such as methyl acrylate and / or glycidyl methacrylate, styrene block copolymers, and various acrylic core / shell type impact modifiers. Residues of these additives are also assumed to be part of the polyester composition.

[0072]

[0080] Reinforcements may be added to compositions useful for the present disclosure. Reinforcements may include, but are not limited to, carbon fibers, silicates, mica, clay, talc, titanium dioxide, wollastonite, glass flakes, glass beads and fibers, polymer fibers, and combinations thereof. In one embodiment, the reinforcement includes glass materials such as fibrous glass filaments, glass and talc, glass and mica, and glass and polymer fibers.

[0073]

[0081] In one embodiment, the film and shrink film according to the present disclosure may contain 0.01 to 10% by weight of a polyester plasticizer. In one embodiment, the shrink film may contain 0.1 to 5% by weight of a polyester plasticizer. Generally, the shrink film may contain 90 to 99.99% by weight of a copolymerized polyester. In a particular embodiment, the shrink film may contain 95 to 99.9% by weight of a copolymerized polyester.

[0074]

[0082] In one aspect, this disclosure relates to shrinkable films and molded articles of the present invention, comprising polyester compositions and / or polymer mixtures useful in this disclosure. Methods for forming such polyesters and / or mixtures into films and / or sheets are well known in the art. Examples of films and / or sheets useful in this disclosure, but not limited to, include extruded films and / or sheets, compression-molded films, calendered films and / or sheets, and solution-cast films and / or sheets. In one aspect, a method for manufacturing films and / or sheets useful for producing the shrinkable films of this disclosure. Examples of such processes include, but are not limited to, extrusion, compression molding, calendering, and casting.

[0075]

[0083] In one embodiment, the polyester compositions useful in this disclosure are produced into films using any method known in the art for producing films from polyester, such as solution casting, extrusion, compression molding, or calendering.

[0076]

[0084] In one embodiment, the as-formed film is subsequently oriented in one or more directions (e.g., as a uniaxial and / or biaxially oriented film). This orientation of the film can be carried out by any method known in the art using standard orientation conditions. For example, the oriented film of the Disclosure may be manufactured from a film having a thickness of about 100 to 400 μm, e.g., an extruded, cast, or calendered film, and this oriented film may be oriented in a ratio of 5:1 to 3:1 at temperatures from Tg to Tg+55°C, or in a ratio of 5:1 or 3:1 at temperatures of, for example, 70°C to 125°C, and the film may also be oriented to a thickness of 20 to 80 μm. In one embodiment, the initial orientation of the as-formed film may be carried out on a tenter frame according to these orientation conditions.

[0077]

[0085] The shrinkable film of this disclosure may have a shrinkage initiation temperature of approximately 55 to approximately 80°C, or approximately 55 to approximately 75°C, or approximately 55 to approximately 70°C. The shrinkage initiation temperature is the temperature at which shrinkage begins.

[0078]

[0086] In certain embodiments, the polyester compositions useful in this 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 1.1 g / cc to 1.5 g / cc, or 1.2 g / cc to 1.4 g / cc, or 1.2 g / cc to 1.35 g / cc.

[0079]

[0087] In one embodiment, the density of a film or molded article is reduced by introducing many small voids or holes into the film. This process is called "voiding." This process is sometimes called "cavitating" or "microvoiding." These pores are obtained by incorporating small organic particles or inorganic particles (including glass microspheres) or "inclusions" (referred to in the art as "cavitating" agents or "void-forming" agents) in a matrix polymer at a concentration of about 1 to 50% by weight, and then orienting the polymer by stretching it in at least one direction. During stretching, small cavities or pores are formed around the cavitating agents. Once the pores are introduced into the polymer film, the resulting porous film is not only less dense than a non-cavitating film, but also opaque, resulting in a paper-like surface. This surface also has the advantage of improved printability; that is, the surface can accept a substantially larger volume of ink than a non-cavitating film. Typical examples of perforated films include 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 It is described in Patent No. 0; 6,500,533; 6,720,085; US Patent Application Publication No. 2001 / 0036545; 2003 / 0068453; 2003 / 0165671; 2003 / 0170427; Japanese Patent Application Publication No. 61-037827; 63-193822; 2004-181863; European Patent No. 0581970B1; European Patent Application Publication No. 0214859A2.

[0080]

[0088] In certain embodiments, the as-formed or as-extruded film is oriented during stretching. The oriented or shrinkable films of this disclosure can be made from films of any thickness depending on the desired end application. In one embodiment, a desirable condition is that the oriented and / or shrinkable films 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 in which the films may be useful. Polyesters useful in this disclosure are P It may be desirable to co-extrude the film with another polymer, such as ET, to make it usable as an oriented film and / or shrink film of this disclosure. One advantage of performing the latter co-extrusion is that, depending on the embodiment, a tie layer is not required. That is a good thing.

[0081]

[0089] In one embodiment, the uniaxial and biaxially oriented films of the present disclosure may be made from a film with a thickness of about 100 to 400 μm, for example, an extruded, cast, or calendered film, which may be stretched in one or more directions at a temperature from the film's Tg to Tg+55°C in a ratio of 6.5:1 to 3:1, and to a thickness of 20 to 80 μm. It may be stretched to a certain extent. In one embodiment, the initial as-extruded film orientation may be performed on a tenter frame according to these orientation conditions. The shrink film of the present disclosure can be produced from the oriented film of the present disclosure.

[0082]

[0090] In certain embodiments, the shrinkable film of the Disclosure shrinks slowly with little to no wrinkles. In certain embodiments, the shrinkable film of the Disclosure has a shrinkage rate of 40% or less in the principal shrinkage direction for every 5°C temperature increase increment.

[0083]

[0091] In certain embodiments of the present disclosure, the shrinkable film of the present disclosure shrinks by 10% or less, 5% or less, 3% or less, or 2% or less in the mechanical direction (i.e., the direction perpendicular to the principal shrinkage direction) when immersed in water at 65°C for 10 seconds, or does not shrink at all. In certain embodiments of the present disclosure, the shrinkable film of the present disclosure shrinks by -5% to 10%, -5% to 5%, or -5% to 3%, or -5% to 2%, or -4% to 5%, or -3% to 5%, or -2% to 5%, or -2% to 3%, or -2% to 2%, or 0% to 2%, when immersed in water at 65°C for 10 seconds, or does not shrink at all. Here, a negative shrinkage rate in the mechanical direction indicates expansion in the mechanical direction. A positive shrinkage rate in the mechanical direction indicates contraction in the mechanical direction.

[0084]

[0092] In certain embodiments of the present disclosure, the shrinkable film of the present disclosure has a shrinkage rate of 50% or more, or 60% or more, or 70% or more in the principal shrinkage direction when immersed in water at 95°C for 10 seconds.

[0085]

[0093] In certain embodiments of the present disclosure, the shrinkable film of the present disclosure has a shrinkage rate of 50-90% in the principal shrinkage direction and a shrinkage rate of 10% or less or -10%-10% in the mechanical direction when immersed in water at 95°C for 10 seconds.

[0086]

[0094] 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, e.g., solution casting, extrusion, compression molding, or calendering. The as-extruded (or as-formed) film is then oriented in one or more directions (e.g., a uniaxial 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, a uniaxially oriented film in this disclosure may be made from a film with a thickness of about 100 to 400 μm, e.g., an extruded, cast, or calendered film, which may be stretched at a temperature from Tg to Tg+55°C in a ratio of 6.5:1 to 3:1 and to a thickness of 20 to 80 μm. In one embodiment, the initial orientation of the as-extruded film may be carried out on a tenter frame according to these orientation conditions.

[0087]

[0095] In certain embodiments of the present disclosure, the shrinkable film of the present disclosure may have a shrinkage initiation temperature of about 55 to about 80°C, or about 55 to about 75°C, or 55 to about 70°C. The shrinkage initiation temperature is the temperature at which shrinkage begins.

[0088]

[0096] In certain embodiments of the present disclosure, the shrinkable film of the present disclosure may have a shrinkage initiation temperature of 55°C to 70°C.

[0097] In certain embodiments of the present disclosure, the shrinkage film of the present disclosure may have a breaking strain of more than 200% at a stretching rate of 500 mm / min in a direction perpendicular to the principal shrinkage direction, according to ASTM Method D882.

[0089]

[0098] In certain embodiments of the present disclosure, the shrinkage film of the present disclosure may have a breaking strain of more than 300% at a stretching rate of 500 mm / min in a direction perpendicular to the principal shrinkage direction, according to ASTM Method D882.

[0090]

[0099] In certain embodiments of the present disclosure, the shrinkage film of the present disclosure may have a tensile stress at break (breaking stress) of 20 to 400 MPa, or 40 to 260 MPa, or 42 to 260 MPa, or 20 to 100 MPa, as measured according to ASTM method D882.

[0091]

[0100] In certain embodiments of this disclosure, the shrinkage film of this disclosure is stretched under desired conditions. Depending on the end use, the shrinkage force may be 4–18 MPa or 4–15 MPa, as measured by ISO method 14616. For example, when measured at 80°C according to ISO method 14616 using a shrinkage force tester manufactured by LabThink, a specific label made for plastic bottles may have a shrinkage force of 4–8 MPa, and a specific label made for glass bottles may have a shrinkage force of 10–14 MPa.

[0092]

[0101] In one embodiment of the present disclosure, the polyester composition is typically a reactor grade. It may be produced by reacting monomers by known methods for producing polyesters called a pedicle composition.

[0093]

[0102] In one embodiment of the present disclosure, the polyester composition of the present disclosure is made of polyethylene polyester. Phthalates (PET), glycol-modified PET (PETG), glycol-modified polycyclohexylenedimethylene terephthalate (PCTG), polycyclohexylenedimethylene terephthalate (PCT), acid-modified polycyclohexylenedimethylene terephthalate (PCTA), polybutylene terephthalate, and / or diethylene glycol-modified PET (EASTOBOND TM Polyesters such as copolymerized polyesters are used as monomers in these compositions. It may be mixed and formed until it reaches the surrounding area.

[0094]

[0103] In certain embodiments, the polyester composition and the polymer mixture composition are also attached The composition may contain common additives such as colorants, toners, dyes, mold release agents, flame retardants, plasticizers, glass bubbles, nucleating agents, stabilizers including UV stabilizers, heat stabilizers, and / or their reaction products, fillers, and impact modifiers, in amounts of 0.01 to 25% by weight. Examples of commercially available impact modifiers include, but are not limited to, impact modifiers for functionalized polyolefins such as ethylene / propylene ternary polymers, polyolefins containing methyl acrylate and / or glycidyl methacrylate, styrene-based block copolymers, and various acrylic core / shell type impact modifiers. Residues of such additives are also assumed to be part of the polyester composition.

[0095]

[0104] Reinforcements may be added to polyester compositions useful in this disclosure. The reinforcements include: The reinforcing materials may include, but are not limited to, carbon fibers, silicates, mica, clay, talc, titanium dioxide, wollastonite, glass flakes, glass beads and glass fibers, polymer fibers, and combinations thereof. In one embodiment, the reinforcing material may include glass materials such as fibrous glass filaments, glass and talc, glass and mica, and glass and polymer fibers.

[0096]

[0105] Molded articles can be manufactured from any of the polyester compositions disclosed herein, which may consist of or contain shrink films, and these are included within the scope of this disclosure.

[0097]

[0106] Generally, the shrinkable film according to this disclosure may contain 0.01 to 10% by weight of a polyester plasticizer. In one embodiment, the shrinkable film may contain 0.1 to 5% by weight of a polyester plasticizer. Generally, the shrinkable film may contain 90 to 99.99% by weight of a copolymerized polyester. In a particular embodiment, the shrinkable film may contain 95 to 99.9% by weight of a copolymerized polyester.

[0098]

[0107] In one embodiment, when a pre-oriented film has a thickness of approximately 100 to 400 μm and is then oriented on a tenter frame at temperatures from Tg to Tg+55°C and in a ratio of 6.5:1 to 3:1 to a thickness of approximately 20 to approximately 80 μm, the shrink film of the present disclosure has the following properties: (1) when immersed in water at 95°C for 10 seconds, it shrinks by more than 50% (or more than 60%) in the principal shrinkage direction or transverse direction, and by 10% or less (or -10% to 10%) in the mechanical direction; (2) when immersed in water at approximately 55°C to approximately The shrinkable film may have one or more of the following properties: (3) a shrinkage initiation temperature of 70°C, (4) a fracture strain of more than 200%, or 200-600%, or 200-500%, or 226-449%, or 250-455% in the transverse direction, mechanical direction, or both directions at a stretching rate of 500 mm / min, according to ASTM method D882, (5) a shrinkage of 40% or less for every 5°C temperature increase increment, and / or (6) a strain-induced crystal melting point above 190°C as measured by the first heating of the DSC scan according to ASTM. Any combination of these properties, or all of these properties, may be present in the shrinkable film of the Disclosure. The shrinkable film of the Disclosure may have two or more combinations of the above shrinkable film properties. The shrinkable film of the Disclosure may have three or more combinations of the above shrinkable film properties. The shrinkable film of the Disclosure may have four or more combinations of the above shrinkable film properties. In certain embodiments, properties (1) to (2) are present. In certain embodiments, characteristics (1) to (5) exist. In certain embodiments, characteristics such as (1) to (3) exist.

[0099]

[0108] The shrinkage rates described herein are based on an initial as-produced film with a thickness of approximately 20–80 μm, oriented in a tenter frame at a ratio of 6.5:1 to 3:1 at temperatures from Tg to Tg+55°C, and, for example, at a ratio of 5:1 at temperatures from 70°C to 85°C. In one embodiment, the shrinkage properties of the oriented film used to produce the shrinkage film of this disclosure remained unchanged even when the film was annealed at a temperature higher than the temperature at which it was oriented. In other embodiments, the shrinkage properties may be adjusted by heat treatment.

[0100]

[0109] The shape of the film useful for producing the oriented or shrinkable films of this disclosure is not limited in any way. For example, the shape may be a flat film or a film formed into a tubular shape. To produce a shrinkable film useful in this disclosure, polyester is first formed into a flat film and then “uniaxially stretched,” which means that the polyester film is oriented in one direction. The ends of the stretched film are then joined using a suture solvent or suture adhesive to form a shrinkable tube. The film may also be “biaxially oriented,” which means that the polyester film is oriented in two different directions, for example, the film is stretched in both the machine direction and a direction opposite to the machine direction. Typically the two directions are substantially perpendicular, but not always. For example, in one embodiment, the two directions are the longitudinal or machine direction ("MD") of the film (the direction in which the film is produced in the film manufacturing machine) and the transverse direction ("TD") of the film (the direction perpendicular to the MD of the film). The biaxially oriented film may be continuously oriented, simultaneously oriented, or any combination of simultaneous and continuous stretching. They may be oriented accordingly.

[0101]

[0110] The film is produced using roll stretching, long-gap stretching, and tenter stretching. The film may be oriented by any conventional method, such as frame stretching and tubular stretching. Continuous biaxial stretching, simultaneous biaxial stretching, uniaxial stretching, or a combination thereof may be performed using any of these methods. The biaxial stretching described above may allow for simultaneous stretching in the machine direction and transverse direction. Alternatively, stretching can be performed first in one direction and then in the other to efficiently achieve biaxial stretching. In one embodiment, the film is stretched by preheating it to a temperature 5°C to 80°C above its glass transition temperature (Tg). In another embodiment, the film may be preheated to a temperature 10°C to 30°C above its Tg. In another embodiment, the stretching speed is 5 to 20 inches per second (12.7 to 50.8 cm). The film may then be oriented to 2 to 6 times its original dimensions, for example, in the machine direction, transverse direction, or both directions. The film may be oriented as a single film layer, or it may be co-extruded as a multilayer film with another polymer material such as PET (polyethylene terephthalate) or polyester, and then oriented.

[0102]

[0111] In one embodiment, the present disclosure relates to any of the embodiments of the shrink film of the present disclosure. This includes manufactured or molded articles containing the shrink film. In another embodiment, the Disclosure includes manufactured or molded articles containing any of the orientation films of the Disclosure.

[0103]

[0112] In certain embodiments, the disclosure includes, but is not limited to, shrink films applied to containers, plastic bottles, glass bottles, packaging materials, batteries, high-temperature filling containers, and / or industrial products or other applications. In one embodiment, the disclosure includes, but is not limited to, orientation films applied to containers, packaging materials, plastic bottles, glass bottles, photographic substrates such as paper, batteries, high-temperature filling containers, and / or industrial products or other applications.

[0104]

[0113] In certain embodiments of the present disclosure, the shrink film of the present disclosure may be formed into a label or sleeve. The label or sleeve may then be affixed to a manufactured article such as a container wall or a battery, or onto a sheet or film.

[0105]

[0114] The orientation film or shrink film of this disclosure may be a sheet, film, tube, or bottle. These films and sheets can be applied to molded products 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 in the manufacture of shrinkable labels for plastic beverage or food containers. For example, the shrinkable films of this disclosure can be used in many packaging applications in which molded articles exhibit properties such as excellent printability, high opacity, excellent shrinkage strength, excellent texture, and high rigidity after the shrinkable film is applied.

[0106]

[0115] By combining improved shrinkage properties and increased toughness, containers (but not limited to) This should provide new commercial options such as shrink films applied to plastic bottles, glass bottles, packaging materials, batteries, high-temperature filled containers, and / or industrial products or other applications.

[0107]

[0116] In one aspect of this disclosure, the disclosed polyester blended composition is thermoformed, and / or useful as thermoformable films or sheets. The disclosure also covers manufactured articles incorporating the thermoformed films and / or sheets of the disclosure. In one embodiment, the polyester blend compositions of the disclosure are useful as films and sheets that are readily formed into molded or formed articles. In one embodiment, the films and / or sheets of the disclosure can be processed into molded articles or parts by thermoforming. Polyester compositions can be used in a variety of molding and extrusion applications.

[0108]

[0117] Furthermore, in one embodiment, a polyester composition useful in the thermoformable sheet of the present disclosure is provided. The polyester blended compositions may also contain, in an amount of 0.1 to 25% by weight of the total composition, common additives such as colorants, lubricants, anti-tacks, mold release agents, flame retardants, plasticizers, nucleating agents, stabilizers such as UV stabilizers and heat stabilizers, fillers, and impact modifiers, but are not limited to these.

[0109]

[0118] In one embodiment, the reinforcing material is a thermoformed material comprising the polyester composition of the present disclosure. They may be included in films or sheets. Suitable reinforcing materials may include, for example, carbon fibers, silicates, mica, clay, talc, titanium dioxide, wollastonite, glass flakes, glass beads and fibers, polymer fibers, and combinations thereof.

[0110]

[0119] In one embodiment, the thermoformed film or sheet of the present disclosure is a multilayer film. It is a film or a sheet. In one embodiment, at least one layer of the multilayer film or sheet is a foamed layer, or a foamed polymer or polyester layer.

[0111]

[0120] One aspect of this disclosure is the process of forming or molding parts and articles using thermoforming. This is a method of manufacture. The formed or molded articles of the Disclosure can be manufactured using any thermoforming technique or process known to those skilled in the art.

[0112]

[0121] 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-type thermoforming process in which gas or pneumatic pressure is applied to a softened sheet, the sheet is then stretched and drawn out like a bubble, and a male mold is inserted into the bubble from the inside. Vacuum is then applied to further draw out the part and conform it to the surface of the male mold. In this thermoforming process, biaxial stretching / orientation is mainly performed in a single step when gas or pneumatic pressure is applied to the softened sheet. The forming process is then completed using vacuum and a male mold to fix the orientation within the sheet after cooling to achieve a good balance between physical and cosmetic properties. In other embodiments, the process involves applying a vacuum or physical plug to a heat-softened sheet, stretching and drawing the sheet to near final part dimensions, then drawing the sheet out by positive air pressure from the inside or further external vacuum drawing, fitting it to an outer mold, and after cooling, fixing the orientation in the polymer to form the sheet into an article.

[0113]

[0122] Depending on the embodiment, the bubbles are further formed using a plugging aid. This may occur, followed by covering the rising male mold with a sheet and molding it, and then drawing the corners and sleeve guides into the mold by applying vacuum. Depending on the embodiment, after removal from the mold, the formed part or article can be cut, perforated, and the corners trimmed as needed.

[0114]

[0123] In other embodiments, thermoforming is performed on a film or of the polyester composition of the Disclosure. This is a process in which a sheet is heated to a temperature sufficient to deform, and then the heated sheet is conformed to the contour of a mold by means such as vacuum assistance, pneumatic assistance, and mold fitting assistance. In another embodiment, the heated film or sheet is placed in a mold and forced to conform to the contour of the mold by, for example, applying pneumatic pressure, using a vacuum plug aid, or using a mold fitting. In some embodiments, thin-walled articles are manufactured by thermoforming.

[0115]

[0124] In one embodiment, the thermoforming process involves heating a male mold to form a film or sheet. The film or sheet is molded into a desired shape by pressing it into a mold. In this embodiment, thermoforming includes having a male mold of the article supported between a vacuumed surface or table. In this embodiment, heat from an external heat source, such as a hot air blower, a heat lamp, or other radiant heat source, is directed onto the film or sheet. In this embodiment, the film or sheet is heated to its softening point. In this embodiment, the table, below the table, and around the mold are then vacuumed to pull the heat-softened film or sheet towards the table and position it so that it is in contact with the mold surface. In this embodiment, the vacuum pulls the softened film or sheet into tight contact with the contour of the mold surface and conforms to it. This causes the film or sheet to take the shape of the mold. In this embodiment, after the film or sheet has cooled, it has solidified and the resulting article or part can be removed from the mold.

[0116]

[0125] In one embodiment, the thermoforming process involves using the polyester blend composition of the Disclosure. The process includes forming a film or sheet; heating the film or sheet until it softens and placing the film or sheet on a mold; drawing the preheated film or sheet towards the heated mold surface; cooling the film or sheet; then removing the formed article or part from the mold cavity, or, optionally, heating and fixing the formed film or sheet by continuing to contact the film or sheet with the heated mold for a time sufficient to partially crystallize the film or sheet.

[0117]

[0126] In one embodiment, the thermoforming process involves using the polyester blend composition of the Disclosure. This process includes forming a film or sheet; heating the film or sheet to a temperature above the Tg of polyester; stretching the film or sheet to near final part dimensions by applying gas pressure, vacuum, and / or physical pressure to the heat-softened film or sheet; conforming the sheet to the shape of a mold 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.

[0118]

[0127] Films and sheets used in thermoforming processes are any conformation known to those skilled in the art. It may also be manufactured by conventional methods. 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°C to about 60°C higher than the Tg of polyester. In one embodiment, to achieve a shorter forming time, it is necessary to heat the film or sheet before placing it on the thermoforming mold. In one embodiment, the sheet needs to be heated to a temperature above its Tg, but below the temperature at which the sheet sags excessively while being placed on the mold cavity. In one embodiment, it is preferable to cool the formed film or sheet to a temperature below the Tg of polyester before removing it from the mold. In one embodiment, the thermoforming method may include a vacuum aid, an air aid, a mechanical plug aid, or a fitted mold. Depending on the embodiment, the mold is heated to a temperature above the Tg of the film or sheet. The selection of the optimal mold temperature depends on the mold of the thermoforming apparatus, the structure and thickness of the article to be formed, and other factors.

[0119]

[0128] Depending on the embodiment, a heated film or sheet is subjected to a vacuum, Furthermore, it will be introduced and extended.

[0129] In one embodiment, heat setting is performed on polyester without any apparent orientation. This is a process that thermally induces partial crystallization of a film or sheet. In one embodiment, heat setting is achieved by maintaining contact between the film or sheet and the heated mold surface for a sufficient time to achieve a level of crystallinity that imparts appropriate physical properties to the finished part. In one embodiment, the level of crystallinity should be about 10 to 30%.

[0120]

[0130] In one embodiment, the heat-fixed component is removed by known means for removal. The product may be removed from the mold cavity. For example, in one embodiment, a blowback is used, which involves introducing compressed air to break the vacuum established between the mold and the molded film or sheet. In some embodiments, any excess portion of the formed article or part is then cut off, and the waste is crushed and recycled.

[0131] Depending on the embodiment, the addition of a nucleating agent provides faster crystallization during thermoforming. Therefore, it provides faster molding. In one embodiment, a nucleating agent such as a particulate 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 that varies from about 0.01% to about 20% based on the weight of the article. In one embodiment, other conventional additives such as pigments, dyes, plasticizers, crack inhibitors, and stabilizers may 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 necessary to achieve high-temperature stability.

[0121]

[0132] In one embodiment, a foamed polyester film or sheet is produced by foaming the polyester composition of the Disclosure with a chemical and / or physical foaming agent, extruding the foamed polyester into a sheet or film, and thermoforming the foamed polyester film or sheet. Additives to improve the properties of the foamed polyester film may be added to the polyester before foaming. Examples of such additives include lubricants, anti-tacks, plasticizers, fluorescent whitening agents, and UV inhibitors. In one embodiment, the foamed polyester film may be an extruded or laminated product coated on one or both sides using conventional techniques to improve its properties. In one embodiment, the coating material may be applied to a printed surface that provides labeling for the product, rather than to the foamed film itself.

[0122]

[0133] The mixed compositions of this disclosure can be formed or molded as plastic parts, and The mixed compositions of this disclosure are useful as solid plastic articles. The mixed compositions of this disclosure are useful as thermoformed parts or articles. The mixed compositions of this disclosure are suitable for use in any application where a clear, rigid plastic is required. Examples of such parts include disposable knives, forks, spoons, plates, cups, straws, as well as eyeglass frames, toothbrush handles, toys, automotive parts, tool handles, camera parts, electronic equipment parts, razor parts, ink pen barrels, disposable syringes, bottles, and the like. In one embodiment, the mixed compositions of this disclosure are useful as plastics, films, fibers, and sheets. In one embodiment, the compositions are useful as plastics for manufacturing bottles, bottle caps, eyeglass frames, knives, disposable knives, knife handles, shelves, shelf dividers, electronic equipment housings, electronic equipment cases, computer monitors, printers, keyboards, tubes, automotive parts, automotive interior parts, automotive equipment, signs, thermoformed letters, siding, toys, thermally conductive plastics, ophthalmic lenses, tools, tool handles, and household goods. In another embodiment, the mixed composition of the present disclosure is used in films, sheets, fibers, formed articles, molded articles, formed parts, molded parts, medical devices, dental trays, dental instruments, containers, food containers, transport containers, packaging materials, bottles, bottle caps, eyeglass frames, knives, disposable knives, knife handles, shelves, shelf dividers, furniture parts, electronic equipment housings, electronic equipment cases, computer monitors, printers, keyboards, tubes, toothbrush handles, automotive parts, automotive interior parts, automotive equipment, signs, outdoor signs, skylights, multi-layer films, multi-layer films. Rooms, insulation components, insulation articles, insulation containers, thermoformed letters, wall panels, toys, toy parts, trays, food trays, dental trays, thermally conductive plastics, ophthalmic lenses and framing materials, tools, tool handles, and household goods, healthcare products, commercially available food supply products, boxes, graphic art films, plastic films for plastic glass laminates, purchase point displays, skylights, smoke vents, laminated cards, fenestration, glazing, partitions, ceiling tiles, lighting, machine protective panels, graphs Suitable for use in art, lenses, extruded laminates or films, decorative laminates, office furniture, face shields, medical packaging materials, sign holders for display shelves, and price holders for shelves.

[0123]

[0134] This thermoformed or thermoformable mixed composition, film, formed article, formed It is useful for forming parts, molded articles, molded parts, and sheets. Methods for producing thermoformed or thermoformable mixed compositions into films, molded articles, molded parts, molded articles, molded parts, and sheets may follow any method known in the art. Examples of molded articles include, but are not limited to, medical device packaging, medical packaging, healthcare product packaging, trays, containers, food dishes, tumblers, storage boxes, bottles, food processors, mixing bowls and other commercially available food supply products, household goods, water bottles, vegetable trays, washing machine parts, refrigerator parts, vacuum cleaner parts, ophthalmic lenses and frames, and toys.

[0124]

[0135] This disclosure further relates to films and films comprising the polyester compositions described herein. The present disclosure relates to manufactured articles including / or sheets. In embodiments, the films and / or sheets of the present disclosure may be of any thickness required for the intended use.

[0125]

[0136] This disclosure further relates to films and / or sheets as described herein. Methods for forming polyester mixed compositions into films and / or sheets include any method known in the art. Examples of films and / or sheets of the Disclosure include, but are not limited to, 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 producing films and / or sheets of the Disclosure include, but are not limited to, extrusion, calendering, compression molding, wet block processing, dry block processing, and solution casting.

[0126]

[0137] This disclosure further relates to the formed or molded articles described herein. Methods for forming a sterl composition into a formed or molded article include any method known in the art. Examples of formed or molded articles of the Disclosure include, but are not limited to, thermoformed or thermoformable articles, injection molded articles, extruded articles, injection blow molded articles, injection stretch blow molded articles, and extruded blow molded articles. Methods for manufacturing formed articles include, but are not limited to, thermoforming, injection molding, extrusion, injection blow molding, injection stretch blow molding, and extruded blow molding. The processes of the Disclosure may include any thermoforming process known in the art. The processes of the Disclosure may include, but are not limited to, any blow molding process known in the art, including extruded blow molding, extruded stretch blow molding, injection blow molding, and injection stretch blow molding.

[0127]

[0138] This disclosure includes any injection blow molding manufacturing process known in the art. While not defined, a typical description of the injection blow molding (IBM) manufacturing process includes: 1) melting the composition in a reciprocating screw extruder; 2) injecting the molten composition into an injection mold to form a partially cooled tube with one end closed (i.e., a preform); 3) moving the preform into a blow mold having the desired final shape around the preform to close the blow mold around the preform; 4) blowing air into the preform to stretch and expand it and fill the mold; 5) cooling the molded article; and 6) removing the article from the mold.

[0128]

[0139] This disclosure includes any injection stretch blow molding manufacturing process known in the art. A typical description of an injection stretch blow molding (ISBM) manufacturing process includes, but is not limited to, 1) melting the composition in a reciprocating screw extruder, and 2) injecting the molten composition into an injection mold to form a partially cooled tube with one end closed (i.e., a premolded product). 3) moving 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 stretching rod and blowing air into the preform to stretch and expand the preform and fill the mold; 5) cooling the molded article; and 6) removing the article from the mold.

[0129]

[0140] This disclosure includes any extrusion blow molding manufacturing process known in the art. While not strictly defined, a typical description of an extrusion blow molding manufacturing process includes: 1) melting the 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) fixing a mold having the desired final shape around the molten preform; 4) blowing air into the molten preform to stretch and expand the extruder and fill the mold; 5) cooling the molded article; 6) removing the article from the mold; and 7) removing excess plastic (commonly called burrs) from the article.

[0130]

[0141] The following examples illustrate how the polyester of this disclosure is manufactured and evaluated. This further illustrates the nature of these examples, which are intended to be purely illustrative and not to limit their scope. Unless otherwise specified, parts are by weight, temperature is in degrees Celsius (°C) or room temperature, and pressure is atmospheric pressure or near atmospheric pressure. [Examples]

[0131]

[0142] Copolymerized polyester resin samples are prepared using the procedures described in other parts of this specification. The resin sample was prepared. In all cases, the resin sample was dried before extrusion.

[0143] The test film sample was placed on a 2.5-inch Davis and Standard single-axis screen. The resin samples were extruded into 10 mil (250 μm) films using a 10 mil extruder. These 10 mil films were cut and stretched to a final thickness of 50 μm at a temperature 5 to 15°C higher than the glass transition temperature (Tg) of the extruded films and at a stretching ratio of approximately 5:1 using a Bruckner Karo 4 tenter frame.

[0132]

[0144] The film sample is extruded using a tenter frame, and the resin sample is also extruded using a commercially available tenter (located at Marshall and Williams, a division of Parkinson Technologies). The film was fabricated by stretching on a frame. Here, the film was extruded using three layers from A, B, and C die sets, with layer B extruded from a 2.5-inch single-screw extruder and layers A and C extruded from separate 1.25-inch single-screw satellite extruders. This film was cast to a thickness of approximately 10 mil (250 μm) and then stretched to a thickness of 50 μm at a stretch ratio of 5:1. Generally, the molded thickness is 250 μm, and the final film thickness is 50 μm. The line speed was 45 fpm.

[0133]

[0145] The glycol content of the extruded film composition was measured by NMR. All NMR spectra were recorded using a JEOL Eclipse Plus 600 MHz nuclear magnetic resonance spectrometer with chloroform-trifluoroacetic acid (70-30:vol / vol) on polymers doped with deuterated chloroform 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%.

[0134]

[0146] The intrinsic viscosity of polyester in this specification is defined as being at 25°C and a concentration of 0.5 g / dL. The measurement was performed in 60 / 40 (weight / weight) phenol / tetrachloroethane. The value is expressed in dL / g.

[0135]

[0147] In this specification, the shrinkage rate is defined as 65 for a 50mm x 50mm square film sample. Measurements are taken by placing the film in water at temperatures between ℃ and 95℃ in 5℃ increments. The film is immersed in water for 10 seconds without restricting shrinkage in any direction, and the shrinkage (or expansion) of the film sample is measured. The shrinkage rate is calculated using the following formula. Shrinkage rate (%) = [(50mm - length after shrinkage) / 50mm] × 100%

[0148] The contraction was measured in a direction perpendicular to the principal contraction direction (mechanical direction: MD), and the principal contraction Measurements were also taken in the transverse direction (TD).

[0136]

[0149] The shrinkage force was measured using a LabThink FST-02 thermal shrinkage tester in the examples described herein. Therefore, the measurement is performed in units of MPa at the same temperature used for stretching the film.

[0150] The tensile film properties were determined using ASTM method D882 for the examples described herein. The measurements were taken using multiple film stretching speeds (300 mm / min and 500 mm / min) to evaluate the films.

[0137]

[0151] Glass transition temperature of polyester and melting point of strain-induced crystal (Tg and Tm was measured using a Thermal Analyst Instruments TA DSC 2920 at a scanning rate of 20°C / min. Tm was measured during the first heating of the stretched sample, and Tg was measured during the second heating step. Alternatively, the sample can be crystallized in a forced-air circulation oven at 165°C for 30 minutes and then analyzed by DSC. For all samples, the crystal melting point is usually not present during the second heating step of DSC scanning at a heating rate of 20°C / min.

[0138]

[0152] The suitability of materials for the recycling process is determined by the Plastics Recycling Association (AP). The procedure is stipulated in the document published by the Association for Plastic Recyclers. In the case of PETG resin, PET aggregation is a major problem addressed by this invention. A laboratory process was developed to mimic this industry standard. The parameters for the experimental aggregation test are as follows: • 582g of PET flakes were combined with 18g of shrink film (3% of the PET flakes) in its shrunk state (the film was shrunk before combination by immersing it in 85°C water for 10 seconds). • The PET strips and film were placed in an aluminum dish to a depth of 1.5 inches. The dish containing the thin slices was placed in a forced-air circulating oven at 208°C for 1.5 hours. Next, the flakes were carefully poured out through a 0.5-inch sieve, and the amount of flakes remaining on the plate or that did not pass through the sieve was measured. The cohesiveness (%) was then calculated as a percentage of the starting weight.

[0139]

[0153] The Association of Plastics Recyclers (APR) states that materials are currently subject to the recycling process. A test has been established to determine compliance with the Key Guidelines for Transparent PET Articles with Labels and Sealings (PET-CG-02), revised or established on April 11, 2019. This method refers to the method for measuring PET aggregation (PET Section Aggregation Evaluation, revised on November 16, 2018; PET-S-08). Details of this test are as follows. The labels (minimum weight: 3% by weight, pre-shrunk at 85°C for 10 seconds) and bottles are crushed into 1 / 4 to 1 / 2 inch flakes to produce labeled bottle flakes. Mix labeled bottle flakes with unlabeled reference bottle flakes in a 50:50 ratio. Next, the samples were wet-classified under the condition that less than 1.2% of PET was allowed to be carried over with labels. Next, wash the flakes with 0.3% Triton X-100 and 1.0% caustic alkali at 88°C for 15 minutes. Next, the flakes are washed with water after removing all suspended particles, and then filtered to remove excess water. The thin sections are subjected to wet classification again, as in the previous attempt. Place 2 pounds (including labels) of washed flakes into a Teflon-coated baking dish, one flake per washed sample, and add the flakes until the layer is 1.5 inches thick. Place the dish containing the slices in a circulating oven at 208°C for 1.5 hours. • Cool the thin section and pass it through a sieve with a 0.0625-inch opening. If the material passes through the sieve, it is not agglomerated, meaning it is not too large to pass through the sieve. Following this test, extrusion / pelletization and molding processes were carried out to confirm the quality of the flakes.

[0140]

[0154] Modulated differential scanning calorimetry (MDSC) measures the sample temperature as a function of time and temperature. This technique measures the difference in heat flow between a sample and an inert reference sample. Furthermore, the same heat flux cell design used in conventional DSC is employed. However, MDSC applies different heating modes (temperature states) to the sample and the reference sample. Specifically, sinusoidal modulation (amplitude) is superimposed on the conventional linear heating or cooling gradient, creating a mode in which the average sample temperature changes continuously over time but not linearly. The net effect of adding this more complex heating mode to the sample is that it is as if two tests—one with a conventional linear (average) heating rate and another with a sinusoidal (instantaneous) heating rate—were performed simultaneously on the material. The actual speeds of these two simultaneous tests depend on three variables that can be selected by the operator. • Basic heating rate (3°C / min) • Modulation period (60 seconds) • Modulation temperature amplitude (±1°C)

[0155] Using reversed heat flow, the glass transition temperature and the area of ​​the melt peak were analyzed. The heat of fusion (Hf) during heating was measured as an integrated inverted heat flow signal. The heat of crystallization (Hc) during heating was integrated from the total heat flow signal. The relative crystallinity (C) of the sample was measured by subtracting the heat of fusion (Hf) from the heat of crystallization (Hc) during heating. Examples 1-12

[0156] Test film samples were prepared using a resin mixture and evaluated by experimental agglomeration tests. The details of the resin compositions and the film properties obtained from them are described in the following examples.

[0141]

[0157] The polymer mixture is used in common to change the properties of the resin. In these studies, By mixing a crystalline resin with an amorphous resin capable of forming a shrinkable film, we found that a novel resin can be provided that can be used as a shrinkable film with an unexpectedly high melting point for strain-induced crystals, which helps improve the suitability of the shrinkable film for recycling processes. Table 1 shows the results. The compositions of the three resins used to prepare these test mixtures are shown below. (Resin 1 or Resin 3) Shrinkable films produced solely from resin 1 possess acceptable shrinkage characteristics, but are not designed to minimize PET aggregation during the recycling process. Resin 2 is an example of a crystallizable copolymer polyester resin that can be used to improve the recyclability of resins 1 and 3. Transparent and compatible films were formed using an extruder from mixtures of resins 1 and 2, or resins 2 and 3.

[0142] [Table 1]

[0143]

[0158] Using laboratory-scale processes, mixtures 1, 2, and 3 were prepared as shown in Table 2. The films were prepared by mixing resin 1 and resin 2, and resin 2 and resin 3. Mixtures using these unmixed starting materials were converted into shrinkable films using a laboratory-scale process, and the properties of these films were measured. The results are summarized in Table 3. Films made from resin 1 or resin 3 alone were unsuitable for the PET recycling process and showed a PET aggregation rate of more than 1%. The properties of the shrinkable films made from these mixtures are shown in Tables 4 and 5.

[0144] [Table 2]

[0145] [Table 3]

[0146] [Table 4]

[0147] [Table 5]

[0148]

[0159] * As described herein, "crystallinity" is calculated by subtracting the heat of crystallization from the heat of fusion. The value is calculated, and if this value is greater than 8, this value corresponds to a composition that is sufficiently crystalline and recyclable in the context of this disclosure. Examples 13-16

[0160] Regarding the suitability of film samples obtained using a tenter frame for recycling processes... The materials were prepared using a commercially available tenter frame to form sufficient material for evaluation using the APR test procedure. In this commercially available tenter frame process, the resin was dried, mixed, extruded into a 10 mil film, and then stretched directly on the tenter frame. The resin compositions used to prepare these mixtures are shown in Table 6. The combinations of mixtures used to prepare these shrinkable films are shown in Table 7. The film properties of these mixtures are shown in Table 8.

[0149] [Table 6]

[0150] [Table 7]

[0151] [Table 8]

[0152]

[0161] Films made from these mixtures exhibit excellent shrinkage film properties and high These compositions possess a strain-induced crystallization melting point. The melting points of the strain-induced crystals in all of these compositions exceeded 200°C. Typically, a strain-induced crystallization melting point exceeding 200°C is necessary to withstand the drying temperature of PET and maintain free fluidity. The melting points of the strain-induced crystals in these resin mixtures are significantly higher than those expected for reactor-grade materials made from the same compositions. This high strain-induced crystallization melting point is likely to be advantageous in applications requiring a higher melting point. For example, when PET flakes were dried at a temperature higher than the APR test temperature (e.g., 420°F, or 210°C), the labels did not become tacky and could still be recycled along with the PET. The suitability of these films for recycling processes was tested (results are shown in Table 11). Films made from these compositions passed through both lower and higher drying temperatures and were therefore considered suitable for recycling processes (an aggregation rate of less than 1% is considered "suitable for recycling processes").

[0153]

[0162] Appearance 1 A crystallizable composition comprising a mixture of polyester compositions, wherein the mixture comprises (1) 5 to 80% of at least one crystallizable polyester and (2) 20 to 95% of at least one amorphous polyester. (1) At least one crystallizable polyester comprises (a) a dicarboxylic acid component and a diol component selected from either (b) or (b'), (a) The dicarboxylic acid component is (i) Approximately 70 to 100 mol% of terephthalic acid residues, and (ii) comprising about 0 to about 30 mol% aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, (b) The diol component is Approximately 75 mol% or more of ethylene glycol residues, and (i) Neopentyl glycol residues of approximately 0 to less than 25 mol%, (ii) 1,4-cyclohexanedimethanol residues in amounts of approximately 0 to less than 25 mol%, and (iii) The final polyester composition contains one or more total diethylene glycol residues in the total diethylene glycol composition in an amount of about 0 to less than 10 mol%, comprising about 25 mol% or less of other glycols. The total mole% of the dicarboxylic acid component is 100 mol%, the total mole% of the diol component is 100 mol%, and (b') The diol component is, Approximately 75 mol% or more of ethylene glycol residues, and (i) Neopentyl glycol residues in amounts of approximately 0.1 to less than approximately 24 mol%, (ii) 1,4-cyclohexanedimethanol residues in amounts of approximately 0.1 to less than approximately 24 mol%, and (iii) The final polyester composition contains one or more total diethylene glycol residues in the total diethylene glycol composition in an amount of about 1 to less than 10 mol%, comprising about 25 mol% or less of other glycols. The total mole% of the dicarboxylic acid component is 100 mol%, and the total mole% of the diol component is 100 mol%, and (2) At least one amorphous polyester comprises (a) a dicarboxylic acid component and (b) a diol component, (a) The dicarboxylic acid component is (i) Approximately 70 to 100 mol% of terephthalic acid residues, and (ii) comprising about 0 to about 30 mol% aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, (b) The diol component is Approximately 60 mol% or more of ethylene glycol residue, and (i) Neopentyl glycol residues in amounts of approximately 0 to less than 40 mol%, (ii) Approximately 0 to less than 40 mol% of 1,4-cyclohexanedimethanol residues, and (iii) The final polyester composition contains one or more total diethylene glycol residues in an amount of about 0 to less than 15 mol% of total diethylene glycol, comprising about 40 mol% or less of other glycols. A composition in which the total mol% of the dicarboxylic acid component is 100 mol%, the total mol% of the diol component is 100 mol%, and the polyesters of (1) and (2) are different. Appearance 2 A crystallizable composition comprising a mixture of polyester compositions, wherein the mixture comprises (1) 5 to 80% of at least one crystallizable polyester and (2) 20 to 95% of at least one amorphous polyester. (1) At least one crystallizable polyester comprises (a) a dicarboxylic acid component and (b) a diol component, (a) The dicarboxylic acid component is (i) Approximately 70 to 100 mol% of terephthalic acid residues, and (ii) comprising about 0 to about 30 mol% aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, (b) The diol component is Approximately 80 mol% or more of ethylene glycol residues, and (i) Neopentyl glycol residues in amounts of approximately 0 to less than 20 mol%, (ii) 1,4-cyclohexanedimethanol residues in amounts of approximately 0 to less than 20 mol%, and (iii) The final polyester composition contains one or more total diethylene glycol residues in an amount of about 0 to less than 10 mol%, including about 20 mol% or less of other glycols, The total mole% of the dicarboxylic acid component is 100 mol%, and the total mole% of the diol component is 100 mol%, and (2) At least one amorphous polyester comprises (a) a dicarboxylic acid component and (b) a diol component, (a) The dicarboxylic acid component is (i) Approximately 70 to 100 mol% of terephthalic acid residues, and (ii) comprising about 0 to about 30 mol% aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, (b) The diol component is Approximately 70 mol% or more of ethylene glycol residues, and (i) Neopentyl glycol residues in amounts of approximately 0 to less than 30 mol%, (ii) 1,4-cyclohexanedimethanol residues in amounts of approximately 0 to less than 30 mol%, and (iii) The final polyester composition contains one or more total diethylene glycol residues in the total diethylene glycol composition in an amount of about 0 to less than 15 mol%, comprising about 30 mol% or less of other glycols. A composition in which the total mol% of the dicarboxylic acid component is 100 mol%, the total mol% of the diol component is 100 mol%, and the polyesters of (1) and (2) are different. Appearance 3 A crystallizable composition comprising a mixture of polyester compositions, wherein the mixture comprises (1) 5 to 80% of at least one crystallizable polyester and (2) 20 to 95% of at least one amorphous polyester. (1) At least one crystallizable polyester comprises (a) a dicarboxylic acid component and (b) a diol component, (a) The dicarboxylic acid component is (i) Approximately 70 to 100 mol% of terephthalic acid residues, and (ii) comprising about 0 to about 30 mol% aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, (b) The diol component is Approximately 85 mol% or more of ethylene glycol residues, and (i) Neopentyl glycol residues in amounts of approximately 0 to less than 15 mol%, (ii) 1,4-cyclohexanedimethanol residues in amounts of approximately 0 to less than 15 mol%, and (iii) The final polyester composition contains one or more total diethylene glycol residues in the total diethylene glycol composition in an amount of about 0 to less than 5 mol%, comprising about 15 mol% or less of other glycols. The total mole% of the dicarboxylic acid component is 100 mol%, and the total mole% of the diol component is 100 mol%, and (2) At least one amorphous polyester contains (a) a dicarboxylic acid component and (b) a diol component, (a) The dicarboxylic acid component is (i) about 70 to about 100 mol% of terephthalic acid residues, and (ii) contains about 0 to about 30 mol% of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, (b) The diol component is about 60 mol% or more of ethylene glycol residues, and (i) neopentyl glycol residues, (ii) 1,4 - cyclohexanedimethanol residues, and (iii) contains about 40 mol% or less of other glycols including one or more of the diethylene glycol residues in the final polyester composition, The total mol% of the dicarboxylic acid component is 100 mol%, the total mol% of the diol component is 100 mol%, and the polyesters of (1) and (2) are different, composition. Aspect 4 A crystallizable composition containing a mixture of polyester compositions, wherein the mixture contains (1) 5 to 80% of at least one crystallizable polyester and (2) 20 to 95% of at least one amorphous polyester, (1) At least one crystallizable polyester contains (a) a dicarboxylic acid component and (b) a diol component, (a) The dicarboxylic acid component is (i) about 70 to about 100 mol% of terephthalic acid residues, and (ii) contains about 0 to about 30 mol% of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, (b) The diol component is (i) about 0 to about 30 mol% of neopentyl glycol residues, (ii) less than about 0 to about 30 mol% of 1,4 - cyclohexanedimethanol residues, and (iii) contains diethylene glycol residues, The remainder of the glycol component is (iv) ethylene glycol residues, and (v) optionally, containing from 0.1 to 10 mol% of at least one modified glycol residue, the total mol% of the dicarboxylic acid component is 100 mol%, the total mol% of the glycol component is 100 mol%, and (2) at least one amorphous polyester contains (a) a dicarboxylic acid component and (b) a diol component, (a) The dicarboxylic acid component is (i) from about 70 to about 100 mol% of terephthalic acid residues, and (ii) containing from about 0 to about 30 mol% of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, (b) The diol component is (i) from about 0 to about 40 mol% of neopentyl glycol residues, (ii) from about 0 to less than about 40 mol% of 1,4-cyclohexanedimethanol residues, and (iii) containing diethylene glycol residues, the remainder of the glycol component is (iv) ethylene glycol residues, and (v) optionally, containing from 0.1 to 10 mol% of at least one modified glycol residue, the total mol% of the dicarboxylic acid component is 100 mol%, the total mol% of the glycol component is 100 mol%, and the polyesters of (1) and (2) are different, compositions. Aspect 5 The mixture has a melting point of crystals of from about 200 to about 255 °C, the composition according to any one of Aspects 1 to 4. Aspect 6 The value obtained by subtracting the heat of crystallization from the heat of fusion of the mixture is greater than about 8.0, the composition according to any one of Aspects 1 to 4. Aspect 7 The composition according to any one of Aspects 1 to 6, which is in the form of a film capable of crystallization. Aspect 8 The crystallizable film according to embodiment 7, wherein the intrinsic viscosity of the film, as measured with a 60 / 40 (weight / weight) phenol / tetrachloroethane solution at a concentration of 0.5 g / dL at 25°C, is 0.50 to 0.80 dL / g. Appearance 9 The crystallizable film according to embodiment 7, wherein the Tg of the film, measured using a TA DSC 2920 manufactured by Thermal Analyst Instrument at a scanning speed of 20°C / min, is 65°C to 80°C. Appearance 10 The crystallizable film according to embodiment 7, wherein the total diol content of one or more diol monomer components capable of forming the amorphous polyester in the final polyester is 15 to 40 mol%, and the total diol content is 100 mol%. Appearance 11 The crystallizable film according to embodiment 7, wherein the total diol content of one or more diol monomer components capable of forming the amorphous polyester in the final polyester is 20 to 40 mol%, and the total diol content is 100 mol%. Appearance 12 The crystallizable film according to embodiment 7, wherein the total diol content of one or more diol monomer components capable of forming the amorphous polyester in the final polyester is 30 to 40 mol%, and the total diol content is 100 mol%. Appearance 13 The crystallizable film according to embodiment 7, wherein the film is stretched in at least one direction. Appearance 14 The crystallizable film according to embodiment 7, wherein the film is stretched and oriented in at least one direction. Appearance 15 The crystallizable film according to embodiment 7, wherein the film is annealed. Appearance 16 The crystallizable film according to embodiment 7, wherein the film is annealed at a temperature approximately 15°C higher than its Tg. Appearance 17 The crystallizable film according to embodiment 7, wherein the film is annealed at a temperature of approximately 75°C to approximately 110°C. Appearance 18 The crystallizable film according to embodiment 7, wherein the total diol content of 1,4-cyclohexanedimethanol residues and neopentyl glycol residues in the crystallizable polyester component is 4 to 15 mol%, and the total diol content is 100 mol%. Appearance 19 The crystallizable film according to embodiment 7, wherein the film is stretched in at least one direction, and the melting point of the strain-induced crystals of the stretched film is 200°C or higher. Appearance 20 The film is a crystallizable film according to embodiment 7, wherein the film has a shrinkage rate of 60% or more in the main shrinkage direction when immersed in water at 85°C for 10 seconds. Appearance 21 The film is a crystallizable film according to embodiment 7, wherein the film has a shrinkage rate of 50% or more in the main shrinkage direction when immersed in water at 85°C for 10 seconds. Appearance 22 The film is a crystallizable film according to embodiment 7, wherein the film has a shrinkage rate of 40% or more in the principal shrinkage direction when immersed in water at 85°C for 10 seconds. Appearance 23 The aforementioned film is a crystallizable film according to embodiment 7, having a shrinkage force of 5 MPa or more. Pattern 24 A crystallizable film according to embodiment 7, which is oriented in one or more directions. Appearance 25 A crystallizable film according to embodiment 7, having a pre-oriented thickness of approximately 50 to 400 μm, and oriented to a thickness of approximately 10 to approximately 80 μm on a tenter frame at temperatures from the Tg of the film to Tg + 55°C and in a ratio of 5:1 to 3:1. Appearance 26 The crystallizable film according to embodiment 7, wherein the film has a shrinkage rate of 50-90% in the principal shrinkage direction and a shrinkage rate of 10% or less in a direction perpendicular to the principal shrinkage direction when immersed in water at 95°C for 10 seconds. Appearance 27 A shrink film comprising a crystallizable film according to any one of Aspects 7 to 26. Aspect 28 A stretched film comprising a crystallizable film according to Aspect 7. Aspect 29 An oriented film comprising a crystallizable film according to Aspect 7. Aspect 30 A lid film, an extruded blow molded container, an extruded sheet, a thermoformed sheet, a flexible packaging film for a stand-up pouch, comprising a crystallizable film according to Aspect 7. Aspect 31 A label or sleeve comprising a crystallizable film according to Aspect 7, attached to a manufactured article, a molded article, a container, a plastic bottle, a glass bottle, a packaging material, a battery, a high-temperature filling container, or an industrial product. Aspect 32 An extruded or calendered film comprising a crystallizable film according to Aspect 7. Aspect 33 A thermoformed sheet having a thickness of about 0.25 mm to about 6.4 mm, comprising a crystallizable composition according to any one of Aspects 1 to 4. Aspect 34 The intrinsic viscosity of the film measured in a 60 / 40 (weight / weight) phenol / tetrachloroethane solution at a concentration of 0.5 g / dL at 25°C is 0.50 to 0.80 dL / g, the thermoformed sheet according to Aspect 33. Aspect 35 The Tg of the film measured at a scanning rate of 20°C / min using a TA DSC 2920 manufactured by Thermal Analyst Instrument is 65°C to 120°C, the thermoformed sheet according to Aspect 33. Aspect 36 The total diol content of one or more diol monomer components capable of forming the amorphous polyester in the final polyester is 15 to 90 mol%, and the total diol content is 100 mol%, the thermoformed sheet according to Aspect 33. Aspect 37 The sheet is stretched in at least one direction, the thermoformed sheet according to Aspect 33. Appearance 38 The thermoformable sheet according to embodiment 33, wherein the sheet is stretched and oriented in at least one direction. Appearance 39 The thermoformable sheet according to embodiment 33, wherein the sheet is annealed. Pattern 40 The thermoformable sheet according to embodiment 33, wherein the sheet is annealed at a temperature approximately 15°C higher than its Tg. Appearance 41 The thermoformable sheet according to embodiment 33, wherein the sheet is annealed at a temperature of approximately 75°C to approximately 110°C. Pattern 42 The thermoformable sheet according to embodiment 33, wherein the total diol content of 1,4-cyclohexanedimethanol residues and neopentyl glycol residues in the final polyester in the crystalline polyester component is 4 to 15 mol%, and the total diol content is 100 mol%. Appearance 43 A formed article or molded article comprising or prepared therefrom the thermoformable sheet described in embodiment 33. 44 A thermoformable sheet comprising any of the embodiments 33 to 43, or prepared therefrom, Medical device packaging materials, medical-related packaging materials, healthcare product packaging materials, commercial food supply packaging materials, trays, containers, food dishes, tumblers, storage boxes, bottles, cookware, mixing bowls, household goods, water bottles, vegetable trays, washing machine parts, refrigerator parts, vacuum cleaner parts, ophthalmic lenses, and framing materials or toys. Appearance 45 A polyester recycling flow comprising recycled polyethylene terephthalate flakes mixed with at least about 0.1% by weight of a recycled crystallizable film according to any one of embodiments 1 to 7.

[0154] Appearance 46 The aforementioned flow conforms to Document No. PET-CG-02, "Key Instructions for Transparent PET Articles with Labels and Sealings," dated April 11, 2019, and is a polyester recycling flow described in Embodiment 45. In addition to the embodiments described in the preceding paragraph, further embodiments are described below. [Aspect 1] A crystallizable composition comprising a mixture of polyester compositions, wherein the mixture comprises (1) 50 to 80% by weight of at least one crystallizable polyester, and (2) 20 to 50% by weight of at least one amorphous polyester. (1) At least one crystallizable polyester comprises (a) a dicarboxylic acid component and a diol component selected from either (b) or (b'), (a) The dicarboxylic acid component is (i) 70-100 mol% of terephthalic acid residues, and (ii) comprising 0 to 30 mol% aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, (b) The diol component is 75 mol% or more of ethylene glycol residues, and (i) Neopentyl glycol residues of less than 0-25 mol%, (ii) 1,4-cyclohexanedimethanol residues in less than 0-25 mol%, and (iii) The final polyester composition contains 25 mol% or less of other glycols, which include one or more of the total diethylene glycol residues of 0 to 10 mol% in the final polyester composition. The total mole% of the dicarboxylic acid component is 100 mol%, the total mole% of the diol component is 100 mol%, and (b') The diol component is, 75 mol% or more of ethylene glycol residues, and (i) Neopentyl glycol residues of less than 0.1 to 24 mol%, (ii) 0.1 to less than 24 mol% of 1,4-cyclohexanedimethanol residues, and (iii) The final polyester composition contains 25 mol% or less of other glycols, which include one or more of the total diethylene glycol residues of 1 to 10 mol% in the final polyester composition. The total mole% of the dicarboxylic acid component is 100 mol%, and the total mole% of the diol component is 100 mol%, and (2) At least one amorphous polyester comprises (a) a dicarboxylic acid component and (b) a diol component, (a) The dicarboxylic acid component is (i) 70-100 mol% of terephthalic acid residues, and (ii) comprising 0 to 30 mol% aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, (b) The diol component is 60 mol% or more of ethylene glycol residue, and (i) Neopentyl glycol residues in less than 0-40 mol%, (ii) 1,4-cyclohexanedimethanol residues in less than 0-40 mol%, and (iii) The final polyester composition contains 40 mol% or less of other glycols, which include one or more of the total diethylene glycol residues of 0 to 15 mol%. The total mole% of the dicarboxylic acid component is 100 mol%, and the total mole% of the diol component is 100 mol%, and the polyesters of (1) and (2) are different, The final polyester composition is a composition comprising a neopentyl glycol residue and a 1,4-cyclohexanedimethanol residue. [Aspect 2] A crystallizable composition comprising a mixture of polyester compositions, wherein the mixture comprises (1) 50 to 80% by weight of at least one crystallizable polyester, and (2) 20 to 50% by weight of at least one amorphous polyester. (1) At least one crystallizable polyester comprises (a) a dicarboxylic acid component and (b) a diol component, (a) The dicarboxylic acid component is (i) 70-100 mol% of terephthalic acid residues, and (ii) comprising 0 to 30 mol% aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, (b) The diol component is Ethylene glycol residues of 80 mol% or more, and (i) Neopentyl glycol residues in less than 0-20 mol%, (ii) 1,4-cyclohexanedimethanol residues in less than 0-20 mol%, and (iii) The final polyester composition contains 20 mol% or less of other glycols, which include one or more of the total diethylene glycol residues of 0 to 10 mol%. The total mole% of the dicarboxylic acid component is 100 mol%, and the total mole% of the diol component is 100 mol%, and (2) At least one amorphous polyester comprises (a) a dicarboxylic acid component and (b) a diol component, (a) The dicarboxylic acid component is (i) 70-100 mol% of terephthalic acid residues, and (ii) comprising 0 to 30 mol% aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, (b) The diol component is 70 mol% or more of ethylene glycol residues, and (i) Neopentyl glycol residues in less than 0-30 mol%, (ii) 1,4-cyclohexanedimethanol residues in less than 0-30 mol%, and (iii) The final polyester composition contains 30 mol% or less of other glycols, which include one or more of the total diethylene glycol residues of 0 to 15 mol%. The total mole% of the dicarboxylic acid component is 100 mol%, and the total mole% of the diol component is 100 mol%, and the polyesters of (1) and (2) are different, The final polyester composition is a composition comprising a neopentyl glycol residue and a 1,4-cyclohexanedimethanol residue. [Aspect 3] A crystallizable composition comprising a mixture of polyester compositions, wherein the mixture comprises (1) 50 to 80% by weight of at least one crystallizable polyester, and (2) 20 to 50% by weight of at least one amorphous polyester. (1) At least one crystallizable polyester comprises (a) a dicarboxylic acid component and (b) a diol component, (a) The dicarboxylic acid component is (i) 70-100 mol% of terephthalic acid residues, and (ii) comprising 0 to 30 mol% aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, (b) The diol component is Ethylene glycol residues of 85 mol% or more, and (i) Neopentyl glycol residues of less than 0-15 mol%, (ii) 1,4-cyclohexanedimethanol residues in less than 0-15 mol%, and (iii) The final polyester composition contains 15 mol% or less of other glycols, which include one or more of the total diethylene glycol residues of 0 to 5 mol%. The total mole% of the dicarboxylic acid component is 100 mol%, and the total mole% of the diol component is 100 mol%, and (2) At least one amorphous polyester comprises (a) a dicarboxylic acid component and (b) a diol component, (a) The dicarboxylic acid component is (i) 70-100 mol% of terephthalic acid residues, and (ii) comprising 0 to 30 mol% aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, (b) The diol component is 60 mol% or more of ethylene glycol residue, and (i) neopentyl glycol residue, (ii) 1,4-cyclohexanedimethanol residue, and (iii) The final polyester composition contains 40 mol% or less of other glycols, which include one or more diethylene glycol residues. The total mole% of the dicarboxylic acid component is 100 mol%, and the total mole% of the diol component is 100 mol%, and the polyesters of (1) and (2) are different, The final polyester composition is a composition comprising a neopentyl glycol residue and a 1,4-cyclohexanedimethanol residue. [Aspect 4] A crystallizable composition comprising a mixture of polyester compositions, wherein the mixture comprises (1) 50 to 80% by weight of at least one crystallizable polyester, and (2) 20 to 50% by weight of at least one amorphous polyester. (1) At least one crystallizable polyester comprises (a) a dicarboxylic acid component and (b) a diol component, (a) The dicarboxylic acid component is (i) 70-100 mol% of terephthalic acid residues, and (ii) comprising 0 to 30 mol% aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, (b) The diol component is (i) 0-30 mol% neopentyl glycol residues, (ii) 1,4-cyclohexanedimethanol residues in less than 0-30 mol%, and (iii) Containing a diethylene glycol residue, The remaining glycol component is (iv) Ethylene glycol residues, and (v) In some cases, the product contains 0.1 to 10 mol% of at least one modified glycol residue, The total mole% of the dicarboxylic acid component is 100 mol%, and the total mole% of the glycol component is 100 mol%, and (2) At least one amorphous polyester comprises (a) a dicarboxylic acid component and (b) a diol component, (a) The dicarboxylic acid component is (i) 70-100 mol% of terephthalic acid residues, and (ii) comprising 0 to 30 mol% aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, (b) The diol component is (i) 0-40 mol% neopentyl glycol residues, (ii) 1,4-cyclohexanedimethanol residues in less than 0-40 mol%, and (iii) Containing a diethylene glycol residue, The remaining glycol component is (iv) Ethylene glycol residues, and (v) In some cases, the product contains 0.1 to 10 mol% of at least one 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 polyesters of (1) and (2) are different, The final polyester composition is a composition comprising a neopentyl glycol residue and a 1,4-cyclohexanedimethanol residue. [Aspect 5] The mixture has a crystalline melting point of 200-255°C, or The value obtained by subtracting the heat of crystallization from the heat of fusion of the aforementioned mixture is greater than 8.0. The composition according to any one of embodiments 1 to 4. [Aspect 6] A composition according to any one of embodiments 1 to 5, in the form of a crystallizable film. [Aspect 7] A crystallizable film according to embodiment 6, The intrinsic viscosity of the film, measured at 25°C with a 0.5 g / dL concentration 60 / 40 (weight / weight) phenol / tetrachloroethane solution, is 0.50 to 0.80 dL / g, or The Tg of the film, measured using a Thermal Analyst Instruments TA DSC 2920 at a scanning speed of 20°C / min, is 65°C to 80°C, or The total diol content of one or more diol monomer components capable of forming the amorphous polyester in the final polyester composition is 15 to 40 mol%, and the total diol content is 100 mol%, or The total diol content of one or more diol monomer components capable of forming the amorphous polyester in the final polyester composition is 20 to 40 mol%, and the total diol content is 100 mol%, or The total diol content of one or more diol monomer components capable of forming the amorphous polyester in the final polyester composition is 30-40 mol%, and the total diol content is 100 mol%, or The film is stretched in at least one direction, or The film is stretched and oriented in at least one direction, or The aforementioned film is annealed, or The aforementioned film is annealed at a temperature 15°C higher than its Tg, or The film is annealed at a temperature of 75°C to 110°C, or The total diol content of 1,4-cyclohexanedimethanol residues and neopentyl glycol residues in the crystallizable polyester component of the final polyester is 4 to 15 mol%, and the total diol content is 100 mol%, or The film is stretched in at least one direction, and the melting point of the strain-induced crystals of the stretched film is 200°C or higher, or The aforementioned film has a shrinkage rate of 60% or more in the principal shrinkage direction when immersed in 85°C water for 10 seconds, or The aforementioned film has a shrinkage rate of 50% or more in the principal shrinkage direction when immersed in 85°C water for 10 seconds, or The aforementioned film has a shrinkage rate of 40% or more in the principal shrinkage direction when immersed in 85°C water for 10 seconds, or The aforementioned film has a shrinkage force of 5 MPa or more, or Oriented in one or more directions, Having a pre-oriented thickness of 50-400 μm, the film is oriented to a thickness of 10-80 μm on a tenter frame at a temperature from Tg to Tg+55°C and in a ratio of 5:1-3:1, or The film, when immersed in 95°C water for 10 seconds, has a shrinkage rate of 50-90% in the principal shrinkage direction and a shrinkage rate of 10% or less in the direction perpendicular to the principal shrinkage direction. A film that can be crystallized. [Aspect 8] A shrinkable film comprising a crystallizable film according to embodiment 6 or 7. [Aspect 9] A crystallizable film as described in embodiment 6, stretched film, Orientation film, Lid films, extruded blow-molded containers, extruded sheets, thermoformed sheets, flexible packaging films for self-standing bags, Labels or sleeves affixed to manufactured goods, molded articles, containers, plastic bottles, glass bottles, packaging materials, batteries, high-temperature filled containers, or industrial products, or Extruded or calendered film. [Aspect 10] A thermoformable sheet having a thickness of 0.25 mm to 6.4 mm, comprising a crystallizable composition according to any one of embodiments 1 to 4. [Aspect 11] A thermoformable sheet according to embodiment 10, The intrinsic viscosity of the sheet, measured at 25°C in a phenol / tetrachloroethane solution at a concentration of 0.5 g / dL and a ratio of 60 / 40 (weight / weight), is 0.50 to 0.80 dL / g, or The Tg of the sheet, measured using a Thermal Analyst Instruments TA DSC 2920 at a scanning speed of 20°C / min, is 65°C to 120°C, or The total diol content of one or more diol monomer components capable of forming the amorphous polyester in the final polyester composition is 15 to 90 mol%, and the total diol content is 100 mol%, or The sheet is stretched in at least one direction, or The sheet is stretched and oriented in at least one direction, or The aforementioned sheet is annealed, or The aforementioned sheet is annealed at a temperature 15°C higher than its Tg, or The aforementioned sheet is annealed at a temperature of 75°C to 110°C, or The total diol content of 1,4-cyclohexanedimethanol residues and neopentyl glycol residues in the crystallizable polyester component of the final polyester composition is 4 to 15 mol%, and the total diol content is 100 mol%. Thermoformable sheet. [Aspect 12] A formed article or molded article comprising or prepared therefrom the thermoformable sheet described in Embodiment 10. [Aspect 13] A thermoformable sheet as described in embodiment 10 or 11, or a sheet prepared therefrom, Medical device packaging materials, medical-related packaging materials, healthcare product packaging materials, commercial food supply packaging materials, trays, containers, food dishes, tumblers, storage boxes, bottles, cookware, mixing bowls, household goods, water bottles, vegetable trays, washing machine parts, refrigerator parts, vacuum cleaner parts, ophthalmic lenses, and framing materials or toys. [Aspect 14] A polyester recycling flow comprising recycled polyethylene terephthalate flakes mixed with at least 0.1% by weight of recycled material of a crystallizable composition according to any one of embodiments 1 to 6. [Aspect 15] The aforementioned flow conforms to Document No. PET-CG-02, "Key Instructions for Transparent PET Articles with Labels and Sealings," dated April 11, 2019, and is the polyester recycling flow described in Embodiment 14.

Claims

1. A crystallizable composition comprising a mixture of polyester compositions, wherein the mixture comprises (1) 20 to 40% by weight of at least one crystallizable polyester, and (2) 60 to 80% by weight of at least one amorphous polyester. (1) At least one crystallizable polyester comprises (a) a dicarboxylic acid component and a diol component selected from either (b) or (b'), (a) The dicarboxylic acid component is (i) 70–100 mol% of terephthalic acid residues, and (ii) comprising 0 to 30 mol% aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, (b) The diol component is 75 mol% or more of ethylene glycol residues, and (i) Neopentyl glycol residues of less than 0-25 mol%, (ii) 1,4-cyclohexanedimethanol residues in amounts less than 0-25 mol%, and (iii) The final polyester composition contains 25 mol% or less of other glycols, which include one or more of the total diethylene glycol residues of 0 to less than 10 mol%. The total mole% of the dicarboxylic acid component is 100 mol%, the total mole% of the diol component is 100 mol%, and (b') The diol component is, 75 mol% or more of ethylene glycol residues, and (i) Neopentyl glycol residues in amounts of less than 0.1 to 24 mol%, (ii) 0.1 to less than 24 mol% of 1,4-cyclohexanedimethanol residues, and (iii) The final polyester composition contains 25 mol% or less of other glycols, which include one or more of the total diethylene glycol residues of 1 to less than 10 mol%. The total mole% of the dicarboxylic acid component is 100 mol%, and the total mole% of the diol component is 100 mol%, and (2) At least one amorphous polyester is (a) a dicarboxylic acid component and (b) Contains diol components, (a) The dicarboxylic acid component is (i) 70–100 mol% of terephthalic acid residues, and (ii) comprising 0 to 30 mol% aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, (b) The diol component is 60 mol% or more of ethylene glycol residues, and (i) Neopentyl glycol residues in amounts of 0 to less than 40 mol%, (ii) 1,4-cyclohexanedimethanol residues in amounts of 0 to less than 40 mol%, and (iii) The final polyester composition contains 40 mol% or less of other glycols, which include one or more of the total diethylene glycol residues of 0 to less than 15 mol%. The total mol% of the dicarboxylic acid component is 100 mol%, and the total mol% of the diol component is 100 mol%, and the polyesters of (1) and (2) are different, The final polyester composition is a composition comprising a neopentyl glycol residue and a 1,4-cyclohexanedimethanol residue.

2. A crystallizable composition comprising a mixture of polyester compositions, wherein the mixture comprises (1) 20 to 40% by weight of at least one crystallizable polyester, and (2) 60 to 80% by weight of at least one amorphous polyester. (1) At least one crystallizable polyester comprises (a) a dicarboxylic acid component and (b) a diol component, (a) The dicarboxylic acid component is (i) 70–100 mol% of terephthalic acid residues, and (ii) comprising 0 to 30 mol% aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, (b) The diol component is Ethylene glycol residues of 80 mol% or more, and (i) Neopentyl glycol residues of less than 0-20 mol%, (ii) 1,4-cyclohexanedimethanol residues in amounts less than 0-20 mol%, and (iii) The final polyester composition contains 20 mol% or less of other glycols, which include one or more of the total diethylene glycol residues of 0 to less than 10 mol%. The total mole% of the dicarboxylic acid component is 100 mol%, and the total mole% of the diol component is 100 mol%, and (2) At least one amorphous polyester comprises (a) a dicarboxylic acid component and (b) a diol component, (a) The dicarboxylic acid component is (i) 70–100 mol% of terephthalic acid residues, and (ii) comprising 0 to 30 mol% aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, (b) The diol component is 70 mol% or more of ethylene glycol residues, and (i) Neopentyl glycol residues of less than 0-30 mol%, (ii) 1,4-cyclohexanedimethanol residues in amounts of 0 to less than 30 mol%, and (iii) The final polyester composition contains 30 mol% or less of other glycols, which include one or more of the total diethylene glycol residues of 0 to less than 15 mol%. The total mol% of the dicarboxylic acid component is 100 mol%, and the total mol% of the diol component is 100 mol%, and the polyesters of (1) and (2) are different, The final polyester composition is a composition comprising a neopentyl glycol residue and a 1,4-cyclohexanedimethanol residue.

3. A crystallizable composition comprising a mixture of polyester compositions, wherein the mixture comprises (1) 20 to 40% by weight of at least one crystallizable polyester, and (2) 60 to 80% by weight of at least one amorphous polyester. (1) At least one crystallizable polyester comprises (a) a dicarboxylic acid component and (b) a diol component, (a) The dicarboxylic acid component is (i) 70–100 mol% of terephthalic acid residues, and (ii) comprising 0 to 30 mol% aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, (b) The diol component is Ethylene glycol residues of 85 mol% or more, and (i) Neopentyl glycol residues of less than 0-15 mol%, (ii) 1,4-cyclohexanedimethanol residues in amounts less than 0 to 15 mol%, and (iii) The final polyester composition contains 15 mol% or less of other glycols, which include one or more of the total diethylene glycol residues of 0 to less than 5 mol%. The total mole% of the dicarboxylic acid component is 100 mol%, and the total mole% of the diol component is 100 mol%, and (2) At least one amorphous polyester comprises (a) a dicarboxylic acid component and (b) a diol component, (a) The dicarboxylic acid component is (i) 70–100 mol% of terephthalic acid residues, and (ii) comprising 0 to 30 mol% aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, (b) The diol component is 60 mol% or more of ethylene glycol residues, and (i) neopentyl glycol residue, (ii) 1,4-cyclohexanedimethanol residue, and (iii) One of the diethylene glycol residues in the final polyester composition Contains the above plus 40 mol% or less of other glycols, The total mol% of the dicarboxylic acid component is 100 mol%, and the total mol% of the diol component is 100 mol%, and the polyesters of (1) and (2) are different, The final polyester composition is a composition comprising a neopentyl glycol residue and a 1,4-cyclohexanedimethanol residue.

4. A crystallizable composition comprising a mixture of polyester compositions, wherein the mixture comprises (1) 20 to 40% by weight of at least one crystallizable polyester, and (2) 60 to 80% by weight of at least one amorphous polyester. (1) At least one crystallizable polyester comprises (a) a dicarboxylic acid component and (b) a diol component, (a) The dicarboxylic acid component is (i) 70–100 mol% of terephthalic acid residues, and (ii) comprising 0 to 30 mol% aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, (b) The diol component is (i) 0-30 mol% neopentyl glycol residues, (ii) 1,4-cyclohexanedimethanol residues in amounts of 0 to less than 30 mol%, and (iii) Contains a diethylene glycol residue, The remaining glycol component is (iv) Ethylene glycol residue, and (v) In some cases, 0.1 to 10 mol% of at least one modified glycol residue Includes, The total mol% of the dicarboxylic acid component is 100 mol%, and the total mol% of the glycol component is 100 mol%, and (2) At least one amorphous polyester comprises (a) a dicarboxylic acid component and (b) a diol component, (a) The dicarboxylic acid component is (i) 70–100 mol% of terephthalic acid residues, and (ii) comprising 0 to 30 mol% aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, (b) The diol component is (i) 0 to 40 mol% neopentyl glycol residues, (ii) 1,4-cyclohexanedimethanol residues in amounts of 0 to less than 40 mol%, and (iii) Contains a diethylene glycol residue, The remaining glycol component is (iv) Ethylene glycol residue, and (v) In some cases, the product contains 0.1 to 10 mol% of at least one 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 polyesters of (1) and (2) are different, The final polyester composition is a composition comprising a neopentyl glycol residue and a 1,4-cyclohexanedimethanol residue.

5. The mixture has a crystalline melting point of 200 to 255°C, or The value obtained by subtracting the heat of crystallization from the heat of fusion of the aforementioned mixture is greater than 8.

0. The composition according to any one of claims 1 to 4.

6. The composition according to any one of claims 1 to 5, in the form of a crystallizable film.

7. A crystallizable film according to claim 6, The intrinsic viscosity of the film, measured at 25°C with a 0.5 g / dL concentration 60 / 40 (weight / weight) phenol / tetrachloroethane solution, is 0.50 to 0.80 dL / g, or Measurements were taken using a Thermal Analyst Instruments TA DSC 2920 at a scanning speed of 20°C / min. The Tg of the aforementioned film is 65°C to 80°C, or The total diol content of one or more diol monomer components capable of forming the amorphous polyester in the final polyester composition is 15 to 40 mol%, and the total diol content is 100 mol%, or The total diol content of one or more diol monomer components capable of forming the amorphous polyester in the final polyester composition is 20 to 40 mol%, and the total diol content is 100 mol%, or The total diol content of one or more diol monomer components capable of forming the amorphous polyester in the final polyester composition is 30 to 40 mol%, and the total diol content is 100 mol%, or The film is stretched in at least one direction, or The film is stretched and oriented in at least one direction, or The aforementioned film is annealed, or The aforementioned film is annealed at a temperature from its Tg to 15°C higher than its Tg, or The film is annealed at a temperature of 75°C to 110°C, or In the crystallizable polyester component of the final polyester composition, 1,4-cyclo The total diol content of xane dimethanol residues and neopentyl glycol residues is 4-15 mol%, and the total diol content is 100 mol%, or The film is stretched in at least one direction, and the melting point of the strain-induced crystals of the stretched film is 200°C or higher, or The aforementioned film has a shrinkage rate of 60% or more in the principal shrinkage direction when immersed in 85°C water for 10 seconds, or The aforementioned film has a shrinkage rate of 50% or more in the principal shrinkage direction when immersed in 85°C water for 10 seconds, or The aforementioned film has a shrinkage rate of 40% or more in the principal shrinkage direction when immersed in 85°C water for 10 seconds, or The aforementioned film has a shrinkage force of 5 MPa or more, or Oriented in one or more directions, Having a pre-oriented thickness of 50 to 400 μm, the film is oriented to a thickness of 10 to 80 μm on a tenter frame at a temperature from Tg to Tg + 55°C and in a ratio of 5:1 to 3:1, or The film, when immersed in 95°C water for 10 seconds, has a shrinkage rate of 50-90% in the principal shrinkage direction and a shrinkage rate of 10% or less in the direction perpendicular to the principal shrinkage direction. A film that can be crystallized.

8. A shrinkable film comprising the crystallizable film according to claim 6 or 7.

9. A crystallizable film as described in claim 6, stretched film, Orientation film, Lid films, extruded blow-molded containers, extruded sheets, thermoformed sheets, flexible packaging films for self-standing bags, Labels or sleeves affixed to manufactured goods, molded articles, containers, plastic bottles, glass bottles, packaging materials, batteries, high-temperature filled containers, or industrial products, or Extruded or calendered film.

10. A thermoformable sheet having a thickness of 0.25 mm to 6.4 mm, comprising the crystallizable composition according to any one of claims 1 to 4.

11. A thermoformable sheet according to claim 10, The intrinsic viscosity of the sheet, measured at 25°C in a phenol / tetrachloroethane solution at a concentration of 0.5 g / dL and a ratio of 60 / 40 (weight / weight), is 0.50 to 0.80 dL / g, or Measurements were taken using a Thermal Analyst Instruments TA DSC 2920 at a scanning speed of 20°C / min. The Tg of the aforementioned sheet is 65°C to 120°C, or The total diol content of one or more diol monomer components capable of forming the amorphous polyester in the final polyester composition is 15 to 90 mol%, and the total diol content is 100 mol%, or The sheet is stretched in at least one direction, or The sheet is stretched and oriented in at least one direction, or The aforementioned sheet is annealed, or The sheet is annealed at a temperature 15°C higher than its Tg, or The sheet is annealed at a temperature of 75°C to 110°C, or The total diol content of 1,4-cyclohexanedimethanol residues and neopentyl glycol residues in the crystallizable polyester component of the final polyester composition is The content is 4-15 mol%, and the total diol content is 100 mol%. Thermoformable sheet.

12. A formed article or molded article comprising or prepared therefrom the thermoformable sheet described in claim 10.

13. Medical device packaging materials, medical-related packaging materials, healthcare product packaging materials, commercial food supply packaging materials, trays, containers, food dishes, tumblers, storage boxes, bottles, cooking utensils, mixing bowls, household goods, water bottles, vegetable trays, washing machine parts, refrigerator parts, vacuum cleaner parts, ophthalmic lenses, and framing materials or toys, comprising or prepared from the thermoformed sheet described in claim 10 or 11.

14. A polyester recycling flow comprising recycled polyethylene terephthalate flakes mixed with at least 0.1% by weight of recycled material of the crystallizable composition according to any one of claims 1 to 6.

15. The aforementioned flow conforms to document number PET-CG-02, "Key Instructions for Transparent PET Articles with Labels and Sealings," dated April 11, 2019, and is a polyester recycling flow according to claim 14.

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