Molded polyester article with improved aesthetic chemical resistance

Abstract

A shaped article configured to accommodate contact with a chemical composition intended for body contact and comprising one or more degradable chemicals wherein the article is formed from a copolyester composition having a high chemical resistance to the degradable chemicals and having a Tg of at least 95 DEG C, and a method for improving the aesthetic chemical resistance of high Tg and high impact resistance polyesters to degraded chemicals.

Description

Technical Field

[0001] The present invention belongs to the field of polymer-based resins that can be used to form articles or components of articles intended for contact with chemical compositions that may degrade the properties of the polymer. In one aspect, the articles / components are intended for contact with such chemical compositions intended for body contact. Also provided are plastic articles or components of such articles made using these resin compositions, such as wearable articles, packaging or dispensing equipment for personal care product cosmetics, medical articles for use with body contact materials, or high-contact articles that may come into contact with sunscreen or tanning products (e.g., sunscreens). Background Art

[0002] Based on the relative efficiency of molding parts and articles of various shapes and designs, plastics are the materials of choice for manufacturing articles / devices that are wearable, intended for high contact, contain chemical compositions intended for contact with the body (e.g., packaging or delivery devices for such chemical compositions), or otherwise may come into contact with chemicals that may cause polymer degradation. For example, wearable articles and food or beverage products that may come into contact with such chemical compositions (e.g., wearable electronics or other high-contact articles / devices) are typically manufactured by molding plastic parts that are formed into assemblies to produce the device or article. Similarly, devices (such as cans, tubes, bags) or dispensing devices for transporting / storing chemical compositions (such as compositions intended for body contact (e.g., skin contact)) are also manufactured by molding plastics into component parts of various shapes.

[0003] However, when plastics are used in applications where they come into contact with chemicals, they may be subject to degradation (e.g., cracking, crazing, softening, optical distortion, etc.) caused by the chemical environment. Some particularly corrosive chemical categories include ingredients found in products intended for body contact, such as sunscreens, tanning lotions, cosmetics, personal care products, and corrosive food ingredients. Corrosive chemicals (e.g., sunscreens) can cause optical distortion of plastic articles. For example, fingerprints can leave permanent deformations on plastic surfaces due to the presence of sunscreens. Therefore, there is a need for plastic materials that are resistant to such chemicals, can be easily formed into articles, and maintain acceptable physical properties.

[0004] It would be beneficial to be able to provide polymer-based resins that can be melt processed, and articles made from such compositions that do not suffer from such disadvantages. Summary of the Invention

[0005] Surprisingly, articles molded from certain copolyester plastics have been found to have excellent resistance to corrosive chemical compositions, such as chemicals intended for body contact (e.g., sunscreens), which can cause optical distortion in transparent / clear articles. In embodiments, such articles can be used as containers and / or other components in articles or devices that will come into significant contact with chemical compositions intended for body contact during use, or high-contact articles that may come into contact with corrosive chemicals. In one aspect, articles intended for body contact can be made from copolyester compositions that can be prepared to have excellent chemical resistance to such chemical compositions and have a glass transition temperature (Tg) exceeding 95°C, or 100°C, or 105°C.

[0006] It has been discovered that molded articles configured to receive (or configured to accommodate contact with) chemical compositions containing degradation chemicals (e.g., chemical compositions intended for body contact or chemical compositions for high-contact articles) can be prepared from copolyester plastic materials that are resistant to the chemical compositions and have physical properties similar to or better than those of molded articles produced from other typically used oil-based engineered thermoplastics. More specifically, these molded articles are produced from copolyester compositions that retain their physical properties and / or optical appearance better than other plastics after exposure to the chemical compositions.

[0007] In a first aspect of the present invention, a transparent article is provided that is adapted to be exposed to contact with a chemical composition that is intended for body contact and that comprises one or more degradation chemicals. In an embodiment, the transparent article is formed from a copolyester composition comprising at least one copolyester comprising:

[0008] (a) a dicarboxylic acid component comprising:

[0009] i) 70 to 100 mole percent of terephthalic acid residues;

[0010] (b) a diol component comprising:

[0011] i) greater than 15 mol% and up to 33 mol% of cyclic diol residues having a 2- to 5-membered ring structure or 5 mol% to 33 mol% of cyclic diol residues having a bicyclic structure wherein each individual ring of the bicyclic structure has 2 to 5 members; and

[0012] ii) 55 mol% to 95 mol% of 1,4-cyclohexanedimethanol residues,

[0013] wherein the total mole % of the dicarboxylic acid component is 100 mole %, and the total mole % of the diol component is 100 mole %; and wherein the intrinsic viscosity is 0.60 to 1.2 dL / g, as measured at 25°C in 60 / 40 (wt / wt) phenol / tetrachloroethane at a concentration of 0.5 g / 100 ml; and wherein the polyester has a Tg of 95°C to 120°C or 95°C to 115°C and has an average haze of less than 5 or less than 3 after exposure to a sunscreen (tested in accordance with the Examples). In an embodiment, the cyclic diol is 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD), and the diol component comprises greater than 15 mole % and up to 33 mole %, or up to 30 mole %, or up to 25 mole %, or up to 22 mole % of TMCD residues. In other embodiments, the cyclic diol is isosorbide and the diol component comprises 5 mol% to 33 mol%, or 5 mol% to 30 mol%, or 5 mol% to 25 mol%, or 5 mol% to 22 mol%, or 5 mol% to 18 mol%, or 5 mol% to 16 mol% of isosorbide residues. In embodiments, the polyester has a transmittance greater than 90% after exposure to a sunscreen (tested according to the Examples).

[0014] In embodiments, the copolyester composition has a Tg in the range of 100° C. to 115° C. In embodiments, the copolyester composition has an intrinsic viscosity of 0.70 to 1.0 dL / g or 0.75 to 0.95 dL / g.

[0015] In embodiments, the glycol component comprises:

[0016] i) greater than 15 mol % and up to 22 mol % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) residues; and

[0017] ii) 78 mol% and up to less than 85 mol% of 1,4-cyclohexanedimethanol (CHDM) residues.

[0018] In embodiments, the dicarboxylic acid component comprises:

[0019] i) 95 to 100 mole percent terephthalic acid residues; and

[0020] ii) 0 to 5 mole % of isophthalic acid residues.

[0021] In other embodiments, the dicarboxylic acid component comprises:

[0022] i) 98 to 100 mole percent terephthalic acid residues; and

[0023] ii) 0 to 2 mole % of isophthalic acid residues.

[0024] In other embodiments, the dicarboxylic acid component comprises 100 mole percent terephthalic acid residues.

[0025] In embodiments, the copolyester composition has a crystallization half-time of 30 seconds to 10 minutes, or 30 seconds to 5 minutes.

[0026] In an embodiment, the article is selected from a wearable article, a high-contact article, a food or beverage container or utensil (or a component thereof), or a packaging article. In an embodiment, the chemical composition intended for body contact is a sunscreen. In an embodiment, the at least one copolyester has a total transmittance of at least 90% and a haze of less than 1%, the total transmittance and haze being measured according to ASTM D1003.

[0027] In a second aspect of the present invention, there is provided a shaped article configured to receive (or adapted to be in contact with) a chemical composition comprising one or more degradation chemicals. In an embodiment, the shaped article comprises a copolyester composition, wherein the copolyester composition has a Tg of at least 95°C, or at least 100°C, or at least 105°C, and good resistance to optical distortion after exposure to a sunscreen, for example, having a sunscreen score of 2 or less, or 1.5 or less (measured using the sunscreen test described herein). In an embodiment, the shaped article has an average haze (measured herein) of less than 5 or less than 3 after exposure to a sunscreen and / or a transmittance (measured herein) of greater than 88 or greater than 90 after exposure to a sunscreen.

[0028] In certain embodiments, the copolyester composition further has at least one of the following properties selected from: a tensile modulus greater than 1400 MPa as measured according to ASTM D638 using a 3.2 mm thick bar that has been subjected to 50% relative humidity at 23°C for 40 hours; a notched Izod impact strength greater than 600, or 700, or 800, or 900, or 1000 J / m as measured according to ASTM D256 at 23°C using a 3.2 mm thick bar that has been subjected to 50% relative humidity at 23°C for 40 hours; a tensile stress at yield of at least 40 MPa as measured according to ASTM D638; a transmittance of at least 70 as measured according to ASTM D1003 using a 3.2 mm plaque after injection molding at a barrel set point of 249°C and a mold temperature of 80°C; or an L* color of at least 85 as measured according to ASTM E1348 using a 3.2 mm plaque after injection molding with a barrel temperature of 249°C and a mold temperature of 80°C. In embodiments, the copolyester composition has at least 2 or at least 3 of the listed properties.In embodiments, the chemical composition is intended for body contact or is a chemical composition for use on high-contact articles.

[0029] In an embodiment of the present invention, the shaped article or component thereof may be selected from an injection molded article, an extrusion molded article, a rotational molded article, a compression molded article, a blow molded article, an injection blow molded article, an injection stretch blow molded article, an extrusion blow molded article, a sheet or film extruded article, a profile extruded article, a gas-assisted molded article, a structural foam molded article, or a thermoformed article.

[0030] In embodiments of the present invention, the shaped article is selected from transparent articles, see-through articles, thin-walled articles, technical articles (e.g., articles with complex designs), articles with high design specifications, complex design articles, containers for holding chemical compositions intended for body contact, or other shaped articles configured to receive (or contact) chemical compositions intended for body contact (or chemical compositions used on high-contact articles). In certain embodiments, the shaped article is a transparent or see-through article configured to receive (or contact) chemical compositions intended for body contact (or chemical compositions used on high-contact articles).

[0031] In an embodiment, technical articles, articles with high design specifications and complex design articles may be selected from articles comprising electrical / electronic components, perfume or cosmetic containers, medical contact devices or containers or components thereof.

[0032] In one embodiment of the injection molded article, the copolyester composition further comprises at least one property selected from the group consisting of: a tensile modulus greater than 1400 MPa as measured according to ASTM D638 using a 3.2 mm thick bar that has been subjected to 50% relative humidity at 23°C for 40 hours; a notched Izod impact strength greater than 600, or 700, or 800, or 900, or 1000 J / m as measured according to ASTM D256 at 23°C using a 3.2 mm thick bar that has been subjected to 50% relative humidity at 23°C for 40 hours; a tensile stress at yield of at least 40 MPa as measured according to ASTM D638; a transmittance of at least 70 as measured according to ASTM D1003 using a 3.2 mm test plaque after injection molding at a barrel set point of 249°C and a mold temperature of 80°C; a ΔE value of less than 25 as measured using a 3.2 mm test plaque after injection molding with a barrel temperature of 249°C and a mold temperature of 80°C; or a tensile strength of at least 100 MPa as measured according to ASTM D1003 using a 3.2 mm test plaque after injection molding with a barrel temperature of 249°C and a mold temperature of 80°C. E1348 has an L* color of at least 85 measured using a 3.2 mm test plaque after injection molding with a barrel temperature of 249° C. and a mold temperature of 80° C. In embodiments, the polymer-based resin comprises at least 2 or at least 3 of the listed properties.

[0033] In embodiments according to various aspects of the invention disclosed herein, the copolyester composition comprises at least one copolyester comprising:

[0034] (a) a dicarboxylic acid component comprising:

[0035] i) 70 to 100 mole percent of terephthalic acid residues;

[0036] (b) a diol component comprising:

[0037] i) greater than 15 mol% and up to 33 mol% or up to 22 mol% of cyclic diol residues having a 2- to 5-membered ring structure or 5 mol% to 33 mol% or 8 mol% to 16 mol% of cyclic diol residues having a bicyclic structure wherein each individual ring of the bicyclic structure has 2 to 5 members; and

[0038] ii) 55 to 95 mole percent of 1,4-cyclohexanedimethanol residues, wherein the total mole percent of the dicarboxylic acid components is 100 mole percent and the total mole percent of the diol components is 100 mole percent; and wherein the intrinsic viscosity is from 0.55 to 1.2 dL / g, as measured at 25°C in 60 / 40 (wt / wt) phenol / tetrachloroethane at a concentration of 0.5 g / 100 ml; and wherein the polyester has a Tg of at least 95°C to 115°C.

[0039] In certain embodiments, the copolyester composition comprises a copolyester comprising a diol component selected from the group consisting of: (1) 5 to 20 mole percent of cyclic diol residues and 55 to 95 mole percent of 1,4-cyclohexanedimethanol residues; or (2) 8 to 20 mole percent of cyclic diol residues and 55 to 92 mole percent of 1,4-cyclohexanedimethanol residues; or (3) 10 to 20 mole percent of cyclic diol residues and 55 to 90 mole percent of 1,4-cyclohexanedimethanol residues.

[0040] In an embodiment, the copolyester composition comprises a copolyester comprising a diol component selected from the group consisting of: (1) 10 to 22 mole percent cyclic diol residues and 55 to 90 mole percent 1,4-cyclohexanedimethanol residues; or (2) 15 to 22 mole percent cyclic diol residues and 55 to 85 mole percent 1,4-cyclohexanedimethanol residues; or (3) greater than 15 and up to 22 mole percent cyclic diol residues and 55 to less than 85 mole percent 1,4-cyclohexanedimethanol residues.

[0041] In embodiments, the copolyester has an intrinsic viscosity of 0.55 to 1.0 dL / g, or 0.55 to 0.8 dL / g, or 0.55 to 0.7 dL / g, as measured in 60 / 40 (wt / wt) phenol / tetrachloroethane at a concentration of 0.5 g / 100 ml at 25°C.

[0042] In embodiments, the copolyester has a Tg of 95°C to 115°C, or 100°C to 115°C, or 105°C to 115°C.

[0043] In embodiments, the dicarboxylic acid component comprises:

[0044] i) 95 to 100 mole percent terephthalic acid (TPA) residues; and

[0045] ii) 0 to 5 mole % of isophthalic acid (IPA) residues.

[0046] In an embodiment, the dicarboxylic acid component comprises 100 mole percent terephthalic acid (TPA) residues.

[0047] In an embodiment, the cyclic diol can be an aliphatic cyclic diol or an aromatic cyclic diol. In an embodiment, the cyclic diol can be an alicyclic diol. In an embodiment, the cyclic diol is cyclobutanediol, isosorbide, or a combination thereof. In one embodiment, the cyclic diol is cyclobutanediol. In one embodiment, the cyclobutanediol is 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD). In one embodiment, the alicyclic diol is isosorbide.

[0048] In embodiments, the dicarboxylic acid component comprises residues of: greater than 95 mol % to 100 mol % TPA and 0 mol % to less than 5 mol % IPA; 96 mol % to 100 mol % TPA and 0 mol % to 4 mol % IPA; 96.5 mol % to 100 mol % TPA and 0 mol % to 3.5 mol % IPA; 97 mol % to 100 mol % TPA and 0 mol % to 3 mol % IPA; 98 mol % to 100 mol % TPA and 0 mol % to 2 mol % IPA; 98.5 mol % to 100 mol % TPA and 0 mol % to 1.5 mol % IPA; 95 mol % to 98.5 mol % TPA and 1.5 mol % to 5 mol % IPA; greater than 95 mol % to 98.5 mol % TPA and 1.5 mol % to less than 5 mol % IPA; 96 mol % to 9 8.5 mol% TPA and 1.5 mol% to 4 mol% IPA; 96.5 mol% to 98.5 mol% TPA and 1.5 mol% to 3.5 mol% IPA; 97 mol% to 98.5 mol% TPA and 1.5 mol% to 3 mol% IPA; 97.5 mol% to 98.5 mol% TPA and 1.5 mol% to 2.5 mol% IPA; 95 mol% to 98 mol% TPA and 2 mol% to 5 mol% IPA; greater than 95 mol% to 98 mol% TPA and 2 mol% to less than 5 mol% IPA; 96 mol% to 98 mol% TPA and 2 mol% to 4 mol% IPA; 96.5 mol% to 98 mol% TPA and 2 mol% to 3.5 mol% IPA; or 97 mol% to 98 mol% TPA and 2 mol% to 3 mol% IPA.

[0049] In embodiments, the glycol component comprises:

[0050] i) greater than 15 mol % and up to 22 mol % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) residues; and

[0051] ii) 78 mol% and up to less than 85 mol% of 1,4-cyclohexanedimethanol (CHDM) residues.

[0052] In embodiments, the diol component comprises the following residues: greater than 15 mol% and up to 21 mol% TMCD and 79 mol% and up to less than 85 mol% CHDM; greater than 15 mol% and up to 20 mol% TMCD and 80 mol% and up to less than 85 mol% CHDM; greater than 15 mol% and up to 19 mol% TMCD and 81 mol% and up to less than 85 mol% CHDM; greater than 15 mol% and up to 18 mol% TMCD and 82 mol% and up to less than 85 mol% CHDM. % to 85 mol% CHDM; 16 mol% to 22 mol% TMCD and 78 mol% to 84 mol% CHDM; 16 mol% to 21 mol% TMCD and 79 mol% to 84 mol% CHDM; 16 mol% to 20 mol% TMCD and 80 mol% to 84 mol% CHDM; 16 mol% to 19 mol% TMCD and 81 mol% to 84 mol% CHDM; 16 mol% to 18 mol% TMCD and 82 mol% to 84 mol% % to 83 mol% CHDM; 17 mol% to 22 mol% TMCD and 78 mol% to 83 mol% CHDM; 17 mol% to 21 mol% TMCD and 79 mol% to 83 mol% CHDM; 17 mol% to 20 mol% TMCD and 80 mol% to 83 mol% CHDM; 17 mol% to 19 mol% TMCD and 81 mol% to 83 mol% CHDM; 18 mol% to 22 mol% TMCD and 78 mol% to 82 mol% CHDM ; or 18 mol % to 21 mol % TMCD and 79 mol % to 82 mol % CHDM; or 18 mol % to 20 mol % TMCD and 80 mol % to 82 mol % CHDM; or 19 mol % to 22 mol % TMCD and 78 mol % to 81 mol % CHDM; or 19 mol % to 21 mol % TMCD and 79 mol % to 81 mol % CHDM; or 20 mol % to 22 mol % TMCD and 78 mol % to 80 mol % CHDM.

[0053] In embodiments, the copolyester composition comprises at least one copolyester comprising:

[0054] (a) a dicarboxylic acid component comprising:

[0055] i) greater than 98.5 mol% and up to 100 mol% or from 99 mol% to 100 mol% terephthalic acid residues; and

[0056] ii) 0 mol % and up to less than 1.5 mol % or 0 mol % to 1 mol % of isophthalic acid residues;

[0057] (b) a diol component comprising:

[0058] i) greater than 15 mol % and up to 21 mol % or greater than 15 mol % and up to 19 mol % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and

[0059] ii) 79 mol % and up to less than 85 mol % or 81 mol % and up to less than 85 mol % of 1,4-cyclohexanedimethanol residues,

[0060] wherein the total mole % of the dicarboxylic acid component is 100 mole % and the total mole % of the glycol component is 100 mole %; and wherein the intrinsic viscosity is 0.70 to 1.0 dL / g or 0.75 to 0.95 dL / g, as measured at 25° C. in 60 / 40 (wt / wt) phenol / tetrachloroethane at a concentration of 0.5 g / 100 ml; and wherein the polyester has a Tg of at least 100° C. to 115° C. In an embodiment, the at least one copolyester is a melt-blended copolyester having an IV of 0.70 to 0.90 dL / g, or 0.75 to 0.85 dL / g, or 0.79 to 0.82 dL / g. In an embodiment, the melt-blended copolyester is solid-stateized to increase the IV. In embodiments, the solidified copolyester has an IV of 0.80 to 1.0 dL / g, or 0.85 to 1.0 dL / g, or 0.87 to 0.97 dL / g, or 0.90 to 0.95 dL / g.In one embodiment, the dicarboxylic acid component is 100 mole % terephthalic acid residues.

[0061] In embodiments, the copolyester composition is amorphous. In other embodiments, the copolyester composition is semi-crystalline.

[0062] In embodiments, the at least one copolyester is a reactor-grade polyester prepared by a process comprising transesterification of a reaction mixture comprising all monomers for the intended (monomer) residues to be included in the copolyester. For example, a copolyester intended to include TPA, CHDM, and TMCD residues is prepared by transesterification of each of these monomers. In embodiments, the reactor-grade polyester is amorphous.

[0063] In an embodiment, the at least one copolyester is a melt-blended polyester prepared by a process comprising melt blending at least two different starting polyesters to provide a final copolyester comprising the monomer residues contained in the starting polyesters. For example, a PCTA copolyester containing TPA, IPA, and CHDM residues is melt blended with a PCTM copolyester containing TPA, CHDM, and TMCD residues to provide a final copolyester having TPA, IPA, CHDM, and TMCD residues. In another example, a PCT copolyester containing TPA and CHDM residues is melt blended with a PCTM copolyester containing TPA, CHDM, and TMCD residues to provide a final copolyester having TPA, CHDM, and TMCD residues (wherein the amount of TMCD is less than that of the starting PCTM copolyester). In an embodiment, the melt-blended copolyester has residues according to any of the (net) amounts of the copolyesters (as described herein).

[0064] In embodiments, the melt blended copolyester is subjected to solid stateization to increase the intrinsic viscosity (IV) of the copolyester. In embodiments, the solid stateized copolyester has an IV according to any of the embodiments of the copolyester (as described herein).

[0065] In a third aspect, there is provided a method for improving the aesthetic chemical resistance of a high Tg and high impact polyester (Polyester A) to degradation chemicals, the method comprising:

[0066] (1) Providing polyester A, which comprises:

[0067] (a) a dicarboxylic acid component comprising:

[0068] i) 70 to 100 mole percent of terephthalic acid residues;

[0069] (b) a diol component comprising:

[0070] i) greater than 15 mol% and up to 40 mol% of cyclic diol residues having a 2- to 5-membered ring structure or 5 mol% to 40 mol% of cyclic diol residues having a bicyclic structure wherein each individual ring of the bicyclic structure has 2 to 5 members; and

[0071] ii) 50 to 85 mole percent of 1,4-cyclohexanedimethanol residues, wherein the total mole percent of the dicarboxylic acid components is 100 mole percent and the total mole percent of the diol components is 100 mole percent; and wherein the intrinsic viscosity is from 0.55 to 1.2 dL / g, as measured at 25°C in 60 / 40 (wt / wt) phenol / tetrachloroethane at a concentration of 0.5 g / 100 ml; and wherein the polyester has a Tg of at least 95°C and a notched Izod impact strength greater than 500 J / m, as measured in accordance with ASTM D256 at 23°C using a 3.2 mm thick bar that has been subjected to 50% relative humidity at 23°C for 40 hours;

[0072] (2) combining polyester A with polyester B, wherein polyester B is included in an amount sufficient to improve the aesthetic chemical resistance of the combination of polyester A and polyester B to degradation chemicals as compared to polyester A, wherein polyester B comprises:

[0073] (a) a dicarboxylic acid component comprising:

[0074] i) 95 to 100 mole percent terephthalic acid residues; and

[0075] ii) 0 to 5 mole percent of isophthalic acid residues; and

[0076] (b) a diol component comprising:

[0077] i) 95 to 100 mole percent of 1,4-cyclohexanedimethanol residues, wherein the total mole percent of the dicarboxylic acid component is 100 mole percent and the total mole percent of the diol component is 100 mole percent;

[0078] (3) Blending polyester A with polyester B to provide a blended polyester composition.

[0079] In an embodiment of the third aspect, the blended polyester composition comprises:

[0080] (a) a dicarboxylic acid component comprising:

[0081] i) 70 to 100 net mole percent of terephthalic acid residues;

[0082] (b) a diol component comprising:

[0083] i) greater than 15 and up to 22 net mole % of cyclic diol residues having a 2- to 5-membered ring structure or 5 to 22 net mole % or 8 to 16 net mole % of cyclic diol residues having a bicyclic structure wherein each individual ring of the bicyclic structure has 2 to 5 members; and

[0084] ii) 55 to 95 net mole % of 1,4-cyclohexanedimethanol residues,

[0085] wherein the total neat mole % of the dicarboxylic acid component is 100 mole % and the total neat mole % of the glycol component is 100 mole %; and wherein the intrinsic viscosity is from 0.60 to 1.2 dL / g as measured at 25°C in 60 / 40 (wt / wt) phenol / tetrachloroethane at a concentration of 0.5 g / 100 ml; and wherein the polyester has a Tg of from 95°C to 115°C and has an average haze after exposure to a sunscreen of less than 5 or less than 3 and / or has a transmittance greater than 90 after exposure to a sunscreen (tested according to the Examples).

[0086] In an embodiment of the third aspect, polyester A comprises:

[0087] (a) a dicarboxylic acid component comprising:

[0088] i) 100 mole % of terephthalic acid residues;

[0089] (b) a diol component comprising:

[0090] i) 20 to 25 mol% or 30 to 40 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and

[0091] ii) 75 to 80 mol% or 60 to 70 mol% of 1,4-cyclohexanedimethanol residues.

[0092] In other embodiments of the third aspect, polyester A comprises:

[0093] (a) a dicarboxylic acid component comprising:

[0094] i) 100 mole % of terephthalic acid residues;

[0095] (b) a diol component comprising:

[0096] i) 10 mol% to 35 mol%, or 15 mol% to 35 mol%, or 15 mol% to 25 mol% of isosorbide;

[0097] ii) 40 mol% to 80 mol%, or 50 mol% to 75 mol%, or 60 mol% to 75 mol% of 1,4-cyclohexanedimethanol residues; and

[0098] iii) 5 mol% to 30 mol%, or 7 mol% to 25 mol%, or 8 mol% to 16 mol% of ethylene glycol residues.

[0099] In an embodiment of the third aspect, polyester B comprises:

[0100] (a) a dicarboxylic acid component comprising:

[0101] i) 100 mole percent terephthalic acid residues; and

[0102] (b) a diol component comprising:

[0103] i) 100 mol % of 1,4-cyclohexanedimethanol residues.

[0104] In an embodiment of the third aspect, polyester B is included in an amount to provide a polyester A:polyester B weight ratio in the range of 90:10 to 50:50, or 90:10 to 60:40, or 90:10 to 65:35, or 85:15 to 50:50, or 85:15 to 60:40, or 85:15 to 65:35, or 80:20 to 50:50, or 80:20 to 60:40, or 80:20 to 65:35, or 80:20 to 70:30.

[0105] In an embodiment of the third aspect, the blending step (3) comprises melt blending polyester A and polyester B. In an embodiment, the blended polyester composition has a higher % transmittance and lower % haze after exposure to a sunscreen (tested according to the Examples) than polyester A. In an embodiment, the blended polyester composition has a % haze after exposure to a sunscreen that is at least 50% lower than polyester A (tested according to the Examples).

[0106] In another aspect, there is provided a method for improving the aesthetic chemical resistance of a high Tg and high impact polyester (Polyester A) to degradation chemicals, the method comprising:

[0107] (1) Providing polyester A, which comprises:

[0108] (a) a dicarboxylic acid component comprising:

[0109] i) 70 to 100 mole percent of terephthalic acid residues;

[0110] (b) a diol component comprising:

[0111] i) 15 to 40 mole percent of cyclic diol residues, wherein the cyclic diol has a 2- to 5-membered ring structure, or a bicyclic structure wherein each individual ring of the bicyclic structure has 2 to 5 members; and

[0112] ii) 50 to 85 mole percent of 1,4-cyclohexanedimethanol residues, wherein the total mole percent of the dicarboxylic acid components is 100 mole percent and the total mole percent of the diol components is 100 mole percent; and wherein the intrinsic viscosity is from 0.55 to 1.2 dL / g, as measured at 25°C in 60 / 40 (wt / wt) phenol / tetrachloroethane at a concentration of 0.5 g / 100 ml; and wherein the polyester has a Tg of at least 100°C and a notched Izod impact strength greater than 500 J / m, as measured in accordance with ASTM D256 at 23°C using a 3.2 mm thick bar that has been subjected to 50% relative humidity at 23°C for 40 hours;

[0113] (2) combining polyester A with polyester B, wherein polyester B is included in an amount sufficient to improve the aesthetic chemical resistance of the combination to degradation chemicals as compared to polyester A, wherein polyester B comprises:

[0114] (a) a dicarboxylic acid component comprising:

[0115] i) 95 to 100 mole percent terephthalic acid residues; and

[0116] ii) 0 to 5 mole percent of isophthalic acid residues; and

[0117] (b) a diol component comprising:

[0118] i) 95 to 100 mole percent of 1,4-cyclohexanedimethanol residues, wherein the total mole percent of the dicarboxylic acid component is 100 mole percent and the total mole percent of the diol component is 100 mole percent;

[0119] (3) Blending polyester A with polyester B to provide a combined polyester composition.

[0120] In an embodiment, polyester A comprises:

[0121] (a) a dicarboxylic acid component comprising:

[0122] i) 100 mole % of terephthalic acid residues;

[0123] (b) a diol component comprising:

[0124] i) 20 to 25 mol% or 30 to 40 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and

[0125] ii) 75 to 80 mol% or 60 to 70 mol% of 1,4-cyclohexanedimethanol residues.

[0126] In an embodiment, polyester A comprises:

[0127] (a) a dicarboxylic acid component comprising:

[0128] i) 100 mole % of terephthalic acid residues;

[0129] (b) a diol component comprising:

[0130] i) 10 mol% to 25 mol% or 15 mol% to 25 mol% of isosorbide residues;

[0131] ii) 50 to 80 or 60 to 75 mole percent of 1,4-cyclohexanedimethanol residues; and

[0132] iii) 5 mol% to 25 mol% or 7 mol% to 17 mol% of ethylene glycol residues.

[0133] In an embodiment, polyester B comprises:

[0134] (a) a dicarboxylic acid component comprising:

[0135] i) 100 mole percent terephthalic acid residues; and

[0136] (b) a diol component comprising:

[0137] i) 100 mol % of 1,4-cyclohexanedimethanol residues.

[0138] In an embodiment, polyester B is included in an amount to provide a polyester A:polyester B weight ratio in the range of 90:10 to 50:50, or 90:10 to 60:40, or 90:10 to 65:35, or 85:15 to 50:50, or 85:15 to 60:40, or 85:15 to 65:35, or 80:20 to 50:50, or 80:20 to 60:40, or 80:20 to 65:35, or 80:20 to 70:30.

[0139] In embodiments, the blending step (3) comprises melt blending polyester A and polyester B.

[0140] In an embodiment, the shaped article configured to receive (or configured to accommodate contact with) a chemical composition comprising one or more degradation chemicals is a transparent or see-through article made from a polyester composition, and the chemical composition is intended for body contact.

[0141] In an embodiment, the chemical composition intended for body contact is in the form of a liquid, gel, lotion, paste, mousse, emulsion and / or dispersion. In an embodiment, the chemical composition intended for body contact may be in the form of a spray, e.g., an aerosol or pump spray, such as a spray tanning oil or sunscreen.

[0142] In an embodiment, the chemical composition intended for body contact comprises a degradation chemical present in an amount of at least 1 wt% or at least 5 wt% based on the total weight of the chemical composition intended for body contact. BRIEF DESCRIPTION OF THE DRAWINGS

[0143] Figure 1 is a photograph of a sunscreen fingerprint on a representative test panel;

[0144] Figure 2 are photographs of representative test panels corresponding to different fingerprint scores. DETAILED DESCRIPTION

[0145] In one aspect of the present invention, a shaped article is provided, the shaped article being configured to receive a chemical composition comprising one or more degradation chemicals, the article comprising a copolyester composition, wherein the copolyester composition has a Tg of at least 95°C, or at least 100°C, or at least 105°C, comprises a copolyester (as described herein), and has good resistance to optical distortion after exposure to a sunscreen, for example, having a sunscreen score of 2 or less, or 1.5 or less (measured using the sunscreen test described herein). In embodiments, the shaped article also has an average haze (measured herein) of less than 5 or less than 3 after exposure to a sunscreen and / or a transmittance (measured herein) of greater than 88, or 89, or 90 after exposure to a sunscreen.

[0146] In certain embodiments, the copolyester composition further has at least one of the following properties selected from: a tensile modulus greater than 1400 MPa as measured according to ASTM D638 using a 3.2 mm thick bar that has been subjected to 50% relative humidity at 23°C for 40 hours; a notched Izod impact strength greater than 700, or 800, or 900, or 1000 J / m as measured according to ASTM D256 at 23°C using a 3.2 mm thick bar that has been subjected to 50% relative humidity at 23°C for 40 hours; a tensile stress at yield of at least 40 MPa as measured according to ASTM D638; a transmittance of at least 88 as measured according to ASTM D1003 using a 3.2 mm test plaque after injection molding at a barrel set point of 249°C and a mold temperature of 80°C; a ΔE value of less than 25 as measured using a 3.2 mm test plaque after injection molding with a barrel temperature of 249°C and a mold temperature of 80°C; or a tensile strength of at least 100 MPa as measured according to ASTM D1003 using a 3.2 mm test plaque after injection molding with a barrel temperature of 249°C and a mold temperature of 80°C. E1348 has an L* color of at least 85 measured using a 3.2 mm test plaque after injection molding with a barrel temperature of 249° C. and a mold temperature of 80° C. In an embodiment, the polymer-based resin has at least 2 or at least 3 of the listed properties. In one embodiment, the chemical composition is intended for body contact.

[0147] In another aspect of the present invention, a molded article is provided that is configured to adapt to contact with a chemical composition intended for body contact (or a chemical composition used on a high-contact article) and comprises such a copolyester composition. Such articles may include wearable articles that may or inevitably come into contact with one or more chemical compositions intended for skin contact (e.g., sunscreens). Such articles may include, for example, watches, fitness trackers, wristbands or bracelets, sunglasses, earplugs, or various articles of clothing. Such articles may also include high-contact articles, such as drinkware and wineware, that may or inevitably come into contact with one or more corrosive chemical compositions (such as sunscreens).

[0148] As used herein, the term "polyester" is intended to include "copolyesters" 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 hydroxy compounds and / or polyfunctional hydroxy compounds. Typically, the difunctional carboxylic acid can be a dicarboxylic acid, and the difunctional hydroxy compound can be a dihydric alcohol (such as, for example, diols and glycols). The term "glycol" as used in this application includes but is not limited to glycols, diols and / or polyfunctional hydroxy compounds, such as branching agents. Alternatively, the difunctional carboxylic acid can be a hydroxycarboxylic acid (such as, for example, p-hydroxybenzoic acid), and the difunctional hydroxy compound can be an aromatic core (such as, for example, hydroquinone) with two hydroxy substituents. As used herein, the term "residue" means any organic structure introduced into a polymer from the corresponding monomer by polycondensation and / or esterification. As used herein, the term "repeat unit" means an organic structure having a dicarboxylic acid residue and a diol residue bonded by a carbonyloxy group. Thus, for example, a dicarboxylic acid residue can be derived from a dicarboxylic acid monomer or its associated acyl halide, ester, salt, anhydride, or mixtures thereof. Thus, as used herein, the term dicarboxylic acid is intended to include dicarboxylic acids and any derivatives of dicarboxylic acids, including their associated acyl halide, ester, half-ester, salt, half-salt, anhydride, mixed anhydride, or mixtures thereof, which can be used in reaction processes with diols to prepare polyesters. Additionally, as used herein, the term "diacid" includes polyfunctional acids, such as branching agents. As used herein, the term "terephthalic acid" is intended to include terephthalic acid itself and its residues and any derivatives of terephthalic acid, including its associated acyl halide, ester, half-ester, salt, half-salt, anhydride, mixed anhydride, or mixtures thereof, or residues thereof, which can be used in reaction processes with diols to prepare polyesters.

[0149] In one embodiment, terephthalic acid can be used as starting material. In another embodiment, dimethyl terephthalate can be used as starting material. In another embodiment, a mixture of terephthalic acid and dimethyl terephthalate can be used as starting material and / or as intermediate material. In an embodiment, at least a portion of the terephthalic acid or dimethyl terephthalate used as starting material has a recycled component derived directly or indirectly from recycled waste. In an embodiment, the recycled component can be obtained from waste plastics containing terephthalic acid residues, for example, recycled monomers obtained by solvent decomposition (for example, methanol decomposition) process. In an embodiment, the terephthalic acid residues present in the polyester (according to any one of the embodiments herein) contain at least 50 mole % or at least 75 mole % or 100 mole % recycled components. In an embodiment, the dicarboxylic acid component of the polyester comprises monomer residues having at least 50 mole % recycled components, or at least 75 mole % recycled components, or 100 mole % recycled components.

[0150] In an embodiment, the polyester includes a diol component comprising CHDM and / or TMCD and / or EG residues. In an embodiment, at least a portion of the CHDM and / or TMCD and / or EG used as starting materials has recycled content derived directly or indirectly from recycled waste. In an embodiment, the recycled content can be obtained from waste plastics containing CHDM and / or TMCD and / or EG residues, for example, recycled monomers obtained by a solvent decomposition (e.g., methanol decomposition) process. In an embodiment, the CHDM and / or TMCD and / or EG residues present in the polyester (according to any one of the embodiments herein) contain at least 50 mole %, or at least 75 mole %, or 100 mole % recycled content. In an embodiment, the diol component of the polyester comprises monomer residues having at least 50 mole % recycled content, or at least 75 mole % recycled content, or 100 mole % recycled content.

[0151] The polyesters (as described herein) may have (or include) recycled content provided by chemical recycling, wherein waste materials are broken down into small molecules and then used to make the polyester, for example, a waste stream (e.g., containing waste plastics) is gasified to produce syngas, which is then used in one or more reaction schemes to produce the polyester.

[0152] A mass balance approach can also be used to provide recycled content polyesters having (or comprising) recycled content. In the mass balance approach, a recycled content value is determined and then applied to the polyester or associated with the polyester. A "recycled content value" is a unit of measure representing the amount of material derived from recycled waste (e.g., recycled plastics). A specific recycled content value can be determined by a mass balance approach or a mass ratio or percentage or any other unit of measure, and can be determined according to any system for tracking, allocating, and / or crediting recycled content in various compositions. The recycled content value can be deducted from the recycled content inventory and applied to a product or composition (e.g., polyester) to attribute the recycled content to the product or composition (e.g., polyester). The recycled content value can come from waste materials (e.g., mixed waste plastics) and can be applied to the polyester based on a mass balance approach that takes into account the stoichiometry and efficiency of the process used to prepare the polyester.

[0153] The recycled content in the polyester can be derived at least in part from recycled polyester of the same type, thereby providing a circular recycling solution. The circular recycling solution can include determining a recycled content value (or credit) for the same type of waste polyester and applying at least a portion of that recycled value or credit to new polyester (e.g., through a mass balance approach), or can be a closed-loop process for providing recycled polyester, wherein at least a portion of the raw materials utilized in the process / reaction scheme for producing the polyester are obtained from the same polyester type. In one aspect, the closed-loop process is based on chemical recycling rather than mechanical recycling.

[0154] In certain aspects, the closed loop can include a scrap vapor delivery article that is used as a feedstock to provide recycled content to a regenerated vapor delivery article containing a recycled content polyester composition (as described herein). A closed loop process differs from an open loop process in that the recycled article produced in the open loop process is different from the scrap article that is recycled as a feedstock. The match between the recycled article produced in the closed loop system and the recycled material does not have to be identical in composition, for example, the recycled article can have a different polymer formulation but a similar polyester base with the same type of monomer residues. The process of providing recycled content can be operated as both a closed loop process and an open loop process.

[0155] In various aspects, the polyester composition used to prepare the article (as described herein) contains at least 10% by weight, or at least 15% by weight, or at least 20% by weight, or at least 25% by weight, or at least 30% by weight, or at least 40% by weight, or at least 50% by weight, or at least 55% by weight, or at least 60% by weight, or at least 65% by weight, or at least 70% by weight, or at least 75% by weight, or at least 80% by weight, or at least 85% by weight, or at least 90% by weight, or at least 95% by weight, or 100% by weight of recycled content by any one of the methods described herein for providing recycled content (or a combination of methods). In certain embodiments, the polyester composition can include ingredients derived from renewable sources (e.g., bio-based materials). In one embodiment, the bio-based material is isosorbide. In embodiments, the polyester contains both recycled content and bio-based (or other renewable source) ingredients. In one embodiment, the polyester has at least 5 wt%, or at least 10 wt%, or at least 15 wt%, or at least 20 wt% renewable source content, and optionally also has recycled content as described above.

[0156] The polyesters used in the present invention can typically be prepared from dicarboxylic acids and diols that react in substantially equal proportions and are introduced into the polyester polymer as their respective residues. Thus, the polyesters of the present invention can contain substantially equal molar proportions of acid residues (100 mole %) and diol (and / or polyfunctional hydroxy compound) residues (100 mole %) such that the total moles of repeating units are equal to 100 mole %. Thus, the mole % provided in this disclosure can 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 4 mole % of isophthalic acid, based on the total acid residues, means that the polyester contains 4 mole % of isophthalic acid residues out of a total of 100 mole % of acid residues. Thus, there are 4 moles of isophthalic acid residues per 100 moles of acid residues. In another example, a polyester containing 15 mole percent 2,2,4,4-tetramethyl-1,3-cyclobutanediol, based on total diol residues, means that the polyester contains 15 mole percent 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues out of a total of 100 mole percent diol residues. Thus, for every 100 moles of diol residues, there are 15 moles of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues.

[0157] In other aspects of the invention, the Tg of the polyesters useful in the present invention can be at least one of the following ranges: 95°C to 115°C; 95°C to 110°C; 95°C to 105°C; 95°C to 100°C; 100°C to 115°C; 100°C to 110°C; 100°C to 105°C; 105°C to 115°C; 105°C to 110°C; and 110°C to 115°C.

[0158] In embodiments, the copolyester composition comprises at least one copolyester comprising:

[0159] (a) a dicarboxylic acid component comprising:

[0160] i) 70 to 100 mole percent of terephthalic acid residues;

[0161] (b) a diol component comprising:

[0162] i) greater than 15 mol% and up to 33 mol% of cyclic diol residues having a 2- to 5-membered ring structure or 5 mol% to 33 mol% of cyclic diol residues having a bicyclic structure wherein each individual ring of the bicyclic structure has 2 to 5 members; and

[0163] ii) 55 to 95 mole percent of 1,4-cyclohexanedimethanol residues, wherein the total mole percent of the dicarboxylic acid components is 100 mole percent and the total mole percent of the diol components is 100 mole percent; and wherein the intrinsic viscosity is from 0.55 to 1.2 dL / g, as measured at 25°C in 60 / 40 (wt / wt) phenol / tetrachloroethane at a concentration of 0.5 g / 100 ml; and wherein the polyester has a Tg of at least 95°C to 115°C.

[0164] In an embodiment, the copolyester composition comprises a copolyester comprising a diol component selected from the group consisting of: (1) 5 to 20 mole percent cyclic diol residues and 55 to 95 mole percent 1,4-cyclohexanedimethanol residues; or (2) 8 to 20 mole percent cyclic diol residues and 55 to 92 mole percent 1,4-cyclohexanedimethanol residues; or (3) 10 to 20 mole percent cyclic diol residues and 55 to 90 mole percent 1,4-cyclohexanedimethanol residues.

[0165] In an embodiment, the copolyester composition comprises a copolyester comprising a diol component selected from the group consisting of: (1) 10 to 22 mol% of cyclic diol residues and 55 to 90 mol% of 1,4-cyclohexanedimethanol residues; or (2) 15 to 22 mol% of cyclic diol residues and 55 to 85 mol% of 1,4-cyclohexanedimethanol residues; or (3) greater than 15 to 22 mol% of cyclic diol residues and 55 to less than 85 mol% of 1,4-cyclohexanedimethanol residues. In an embodiment, the cyclic diol may be an aliphatic cyclic diol or an aromatic cyclic diol. In an embodiment, the cyclic diol may be an aliphatic cyclic diol. In an embodiment, the cyclic diol is cyclobutanediol, isosorbide, or a combination thereof. In one embodiment, the cyclic diol is cyclobutanediol. In one embodiment, the cyclobutanediol is 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD). In one embodiment, the cycloaliphatic diol is isosorbide.

[0166] In an embodiment, the diol component of the polyester useful in the present invention includes, but is not limited to, at least one of the following range combinations: 9 mol% to 16 mol% isosorbide and 70 mol% to 91 mol% 1,4-cyclohexanedimethanol; 9 mol% to 15 mol% isosorbide and 71 mol% to 91 mol% 1,4-cyclohexanedimethanol; 9 mol% to 14 mol% isosorbide and 72 mol% to 91 mol% 1,4-cyclohexanedimethanol; 9 mol% to 13 mol% isosorbide and 73 mol% to 91 mol% 1,4-cyclohexanedimethanol; 9 mol% to 12 mol% isosorbide and 74 mol% % to 91 mol % of 1,4-cyclohexanedimethanol; 9 mol % to 11 mol % of isosorbide and 75 mol % to 91 mol % of 1,4-cyclohexanedimethanol; 10 mol % to 16 mol % of isosorbide and 70 mol % to 90 mol % of 1,4-cyclohexanedimethanol; 10 mol % to 15 mol % of isosorbide and 71 mol % to 90 mol % of 1,4-cyclohexanedimethanol; 10 mol % to 14 mol % of isosorbide and 72 mol % to 90 mol % of 1,4-cyclohexanedimethanol; 10 mol % to 13 mol % of isosorbide and 73 mol % to 90 mol % of 1,4-cyclohexanedimethanol; 10 mol% to 12 mol% of isosorbide and 74 mol% to 90 mol% of 1,4-cyclohexanedimethanol; 11 mol% to 16 mol% of isosorbide and 70 mol% to 89 mol% of 1,4-cyclohexanedimethanol; 11 mol% to 15 mol% of isosorbide and 71 mol% to 89 mol% of 1,4-cyclohexanedimethanol; 11 mol% to 14 mol% of isosorbide and 72 mol% to 89 mol% of 1,4-cyclohexanedimethanol; 11 mol% to 13 mol% of isosorbide and 73 mol% to 89 mol% of 1,4-cyclohexanedimethanol; 12 mol% to 16 mol% of isosorbide and 70 mol% % to 88 mol % of 1,4-cyclohexanedimethanol; 12 mol % to 15 mol % of isosorbide and 71 mol % to 88 mol % of 1,4-cyclohexanedimethanol; 12 mol % to 14 mol % of isosorbide and 72 mol % to 88 mol % of 1,4-cyclohexanedimethanol; 13 mol % to 16 mol % of isosorbide and 70 mol % to 87 mol % of 1,4-cyclohexanedimethanol; 13 mol % to 15 mol % of isosorbide and 71 mol % to 87 mol % of 1,4-cyclohexanedimethanol; 14 mol % to 16 mol % of isosorbide and 70 mol % to 86 mol % of 1,4-cyclohexanedimethanol.

[0167] In embodiments, the diol component comprises the following residues: greater than 15 mol% and up to 21 mol% TMCD and 79 mol% and up to less than 85 mol% CHDM; greater than 15 mol% and up to 20 mol% TMCD and 80 mol% and up to less than 85 mol% CHDM; greater than 15 mol% and up to 19 mol% TMCD and 81 mol% and up to less than 85 mol% CHDM; greater than 15 mol% and up to 18 mol% TMCD and 82 mol% and up to less than 85 mol% CHDM. % to 85 mol% CHDM; 16 mol% to 22 mol% TMCD and 78 mol% to 84 mol% CHDM; 16 mol% to 21 mol% TMCD and 79 mol% to 84 mol% CHDM; 16 mol% to 20 mol% TMCD and 80 mol% to 84 mol% CHDM; 16 mol% to 19 mol% TMCD and 81 mol% to 84 mol% CHDM; 16 mol% to 18 mol% TMCD and 82 mol% to 84 mol% % to 83 mol% CHDM; 17 mol% to 22 mol% TMCD and 78 mol% to 83 mol% CHDM; 17 mol% to 21 mol% TMCD and 79 mol% to 83 mol% CHDM; 17 mol% to 20 mol% TMCD and 80 mol% to 83 mol% CHDM; 17 mol% to 19 mol% TMCD and 81 mol% to 83 mol% CHDM; 18 mol% to 22 mol% TMCD and 78 mol% to 82 mol% CHDM ; or 18 mol % to 21 mol % TMCD and 79 mol % to 82 mol % CHDM; or 18 mol % to 20 mol % TMCD and 80 mol % to 82 mol % CHDM; or 19 mol % to 22 mol % TMCD and 78 mol % to 81 mol % CHDM; or 19 mol % to 21 mol % TMCD and 79 mol % to 81 mol % CHDM; or 20 mol % to 22 mol % TMCD and 78 mol % to 80 mol % CHDM.

[0168] For certain embodiments of the present invention, the polyesters useful in the present invention may exhibit at least one of the following inherent viscosities measured in 60 / 40 (wt / wt) phenol / tetrachloroethane at a concentration of 0.5 g / 100 ml at 25° C.: 0.60 to 1.2 dL / g; 0.60 to 1.1 dL / g; 0.60 to 1 dL / g; 0.60 to less than 1 dL / g; 0.60 to 0.98 dL / g; 0.60 to 0.95 dL / g; 0.60 to 0.90 dL / g; 0.60 to 0.85 dL / g; 0.60 to 0.80 dL / g; 0.60 to 0.75 dL / g; 0.60 to less than 0.75 dL / g; 0.60 to 0.72 dL / g; 0 0.60 to 0.70 dL / g; 0.60 to less than 0.70 dL / g; 0.60 to 0.68 dL / g; 0.60 to less than 0.68 dL / g; 0.60 to 0.65 dL / g; 0.65 to 1.2 dL / g; 0.65 to 1.1 dL / g; 0.65 to 1 dL / g; 0.65 to less than 1 dL / g; 0 0.65 to 0.98 dL / g; 0.65 to 0.95 dL / g; 0.65 to 0.90 dL / g; 0.65 to 0.85 dL / g; 0.65 to 0.80 dL / g; 0.65 to 0.75 dL / g; 0.65 to less than 0.75 dL / g; 0.65 to 0.72 dL / g; 0.65 to 0.70 dL / g g; or 0.65 to less than 0.70 dL / g; 0.70 to 1.2 dL / g; 0.70 to 1.1 dL / g; 0.70 to 1 dL / g; 0.70 to less than 1 dL / g; 0.70 to 0.98 dL / g; 0.70 to 0.95 dL / g; 0.70 to 0.90 dL / g; 0.70 to 0.85 dL / g; 0.70 to 0.80 dL / g; 0.70 to 0.75 dL / g; 0.70 to less than 0.75 dL / g; 0.75 to 1.2 dL / g; 0.75 to 1.1 dL / g; 0.75 to 1 dL / g; 0.75 to less than 1 dL / g; 0.75 to 0.98 dL / g; 0.75 to 0.95 dL / g; 0. 75 to 0.90 dL / g; 0.75 to 0.85 dL / g; 0.75 to 0.80 dL / g; 0.75 to less than 0.80 dL / g; 0.80 to 1.2 dL / g; 0.80 to 1.1 dL / g; 0.80 to 1 dL / g; 0.80 to less than 1 dL / g; 0.80 to 0.98 dL / g; 0.80 to 0.95 dL / g; 0.80 to 0.90 dL / g; 0.80 to 0.85 dL / g; 0.80 to less than 0.85 dL / g; 0.85 to 1.2 dL / g; 0.85 to 1.1 dL / g; 0.85 to 1 dL / g; 0.85 to less than 1 dL / g; 0.85 to 0.98 dL / g; 0.85 to 0.95 dL / g; 0.85 to 0.90 dL / g; 0.85 to less than 0.90 dL / g; 0.90 to 1.2 dL / g; 0.90 to 1.1 dL / g; 0.90 to 1 dL / g; 0.90 to less than 1 dL / g; 0.90 to 0.98 dL / g; 0.90 to 0.95 dL / g; or 0.90 to less than 0.95 dL / g. It is contemplated that, unless otherwise stated, the polyester compositions of the present invention may have at least one of the inherent viscosity ranges described herein and at least one of the monomer ranges for the compositions described herein. It is also contemplated that, unless otherwise stated, the polyester compositions of the present invention may have at least one of the Tg ranges described herein, at least one of the inherent viscosity ranges described herein, and at least one of the monomer ranges for the compositions described herein.

[0169] For the desired polyester, the molar ratio of cis / trans 2,2,4,4-tetramethyl-1,3-cyclobutanediol may be different from the respective pure forms or mixtures thereof. In certain embodiments, the mole % of cis 2,2,4,4-tetramethyl-1,3-cyclobutanediol and / or trans 2,2,4,4-tetramethyl-1,3-cyclobutanediol is greater than 50 mole % cis and less than 50 mole % trans; or greater than 55 mole % cis and less than 45 mole % trans; or 30 mole % to 70 mole % cis and 70 mole % to 30 mole % trans; or 40 mole % to 60 mole % cis and 60 mole % to 40 mole % trans; or 50 mole % to 60 mole % The composition can be a mixture of cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol and trans-2,2,4,4-tetramethyl-1,3-cyclobutanediol, wherein the total molar percentage of cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol and trans-2,2,4,4-tetramethyl-1,3-cyclobutanediol is 100 mole%. The molar ratio of cis / trans 1,4-cyclohexanedimethanol can vary in the range of 50 / 50 to 0 / 100 (e.g., between 40 / 60 and 20 / 80). The cis / trans ratio of the composition can be determined by proton nuclear magnetic resonance (NMR) spectroscopy.

[0170] In certain embodiments, terephthalic acid or its ester (such as, for example, dimethyl terephthalate), or a mixture of terephthalic acid and its ester, constitutes most or all of the dicarboxylic acid component used to form the polyester that can be used in the present invention. In certain embodiments, terephthalic acid residues can constitute part or all of the dicarboxylic acid component used to form the polyester that can be used in the present invention, and the concentration of terephthalic acid residues is at least 70 mol%, such as at least 80 mol%, at least 90 mol%, at least 95 mol%, at least 99 mol% or in a preferred embodiment (e.g., reactor grade), 100 mol%. In certain embodiments, polyesters with higher amounts of terephthalic acid can be used to produce higher impact strength properties. For the purposes of this disclosure, the terms "terephthalic acid" and "dimethyl terephthalate" are used interchangeably herein. In one embodiment, dimethyl terephthalate is part or all of the dicarboxylic acid component used to prepare the polyester that can be used in the present invention. In all embodiments, a range of 70 mol% to 100 mol%; or 80 mol% to 100 mol%; or 90 mol% to 100 mol%; or 99 mol% to 100 mol%; or 100 mol% of terephthalic acid and / or dimethyl terephthalate and / or mixtures thereof may be used.

[0171] In certain embodiments, the dicarboxylic acid component of the polyesters useful in the present invention may comprise, in addition to terephthalic acid residues, up to 30 mol%, up to 20 mol%, up to 10 mol%, up to 5 mol%, or less than 5 mol%, or up to 3 mol%, or up to 2 mol%, or up to 1 mol% of one or more modified aromatic dicarboxylic acids. In a preferred embodiment, the polyester contains 0 mol% of modified aromatic dicarboxylic acids. Thus, if present, it is contemplated that the amount of one or more modified aromatic dicarboxylic acids may be within the range of any of these aforementioned endpoints, including, for example, 0.01 mol% to 30 mol%, 0.01 mol% to 20 mol%, 0.01 mol% to 10 mol%, 0.01 mol% to 5 mol%, 0.01 mol% to less than 5 mol%, 0.01 mol% to 4 mol%, 0.01 mol% to 3 mol%, 0.01 mol% to 2 mol%, or 0.01 mol% to 1 mol% of one or more modified aromatic dicarboxylic acids. In certain embodiments, the amount of the one or more modifying aromatic dicarboxylic acids may range from 1 mol% to 5 mol%, 1 mol% to less than 5 mol%, 1 mol% to 4 mol%, 1 mol% to 3 mol%, 1 mol% to 2 mol%, or 1.5 mol% to 5 mol%, 1.5 mol% to less than 5 mol%, 1.5 mol% to 4 mol%, 1.5 mol% to 3.5 mol%, 1.5 mol% to 3 mol%, 1.5 mol% to 2.5 mol%, 1.5 mol% to 2 mol%, or 2 mol% to 5 mol%, 2 mol% to less than 5 mol%, 2 mol% to 4 mol%, 2 mol% to 3.5 mol%. % to 3 mol%, 2 mol% to 2.5 mol%, or 2.5 mol% to 5 mol%, or 2.5 mol% to less than 5 mol%, or 2.5 mol% to 4 mol%, 2.5 mol% to 3.5 mol%, 2.5 mol% to 3 mol%, or 3 mol% to 5 mol%, 3 mol% to less than 5 mol%, 3 mol% to 4 mol%, 3 mol% to 3.5 mol%, or 3.5 mol% to 5 mol%, 3.5 mol% to less than 5 mol%, 3.5 mol% to 4 mol%, 4 mol% to 5 mol%, 4 mol% to less than 5 mol% of one or more modifying aromatic dicarboxylic acids.

[0172] In one embodiment, the modified aromatic dicarboxylic acids useful in the present invention include, but are not limited to, those having up to 20 carbon atoms, and may be linear, para-oriented, or symmetrical. Examples of modified aromatic dicarboxylic acids useful in the present invention include, but are not limited to, isophthalic acid, 4,4'-biphenyl dicarboxylic acid, 1,4-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, and trans-4,4'-stilbene dicarboxylic acid and esters thereof. In one embodiment, the modified aromatic dicarboxylic acid is isophthalic acid. A preferred embodiment of the present invention is a dicarboxylic acid component that is 100% based on terephthalic acid residues.

[0173] The carboxylic acid component that can be used for polyester of the present invention can further be modified with up to 10 moles %, such as up to 5 moles % or up to 1 mole % of one or more aliphatic dicarboxylic acids containing 2-16 carbon atoms (such as, for example malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and dodecanedioic acid).Some embodiment can also comprise 0.01 mole % or more moles %, for example 0.1 mole % or more moles %, 1 mole % or more moles %, 5 mole % or more moles % or 10 mole % or more moles % of one or more modified aliphatic dicarboxylic acids.In a preferred embodiment, polyester contains the modified aliphatic dicarboxylic acid of 0 mole %.Therefore, if exist, then consider that the amount of one or more modified aliphatic dicarboxylic acids can be in the scope of any one of these aforementioned endpoint values, including for example 0.01 mole % to 10 moles % and 0.1 mole % to 10 moles %.The total mole % of dicarboxylic acid component is 100 mole %.

[0174] Can use ester of terephthalic acid and other modified dicarboxylic acids or their corresponding ester and / or salt to replace dicarboxylic acid.Suitable example of dicarboxylic acid ester includes but not limited to dimethyl ester, diethyl ester, dipropyl ester, diisopropyl ester, dibutyl ester and diphenyl ester.In one embodiment, ester is selected from at least one of following: methyl ester, ethyl ester, propyl ester, isopropyl ester and phenyl ester.

[0175] 1,4-cyclohexanedimethanol may be cis, trans, or a mixture thereof, such as a cis / trans ratio of 60:40 to 40:60. In another embodiment, trans-1,4-cyclohexanedimethanol may be present in an amount of 60 mol% to 80 mol%.

[0176] In embodiments where the cyclic diol is TMCD, the diol component of the polyester portion of the polyester compositions useful in the present invention may contain 14 mol% or less of one or more modifying diols that are not 2,2,4,4-tetramethyl-1,3-cyclobutanediol or 1,4-cyclohexanedimethanol; in another embodiment, the polyesters useful in the present invention may contain 10 mol% or less of one or more modifying diols. In another embodiment, the polyesters useful in the present invention may contain 5 mol% or less of one or more modifying diols. In another embodiment, the polyesters useful in the present invention may contain 3 mol% or less of one or more modifying diols. In a preferred embodiment, the polyesters useful in the present invention may contain 0 mol% of modifying diols. Certain embodiments may also contain 0.01 mol% or more of one or more modifying diols, such as 0.1 mol% or more, 1 mol% or more, 5 mol% or more, or 10 mol% or more of one or more modifying diols. Thus, it is contemplated that the amount of modifying glycol(s), if present, can range between any of these aforementioned endpoints, including, for example, 0.1 mole % to 10 mole %.

[0177] In embodiments where the cyclic diol is TMCD, the modifying diols useful in the polyesters of the present invention are diols other than 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol and may contain from 2 to 16 carbon atoms. Examples of suitable modifying diols include, but are not limited to, ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, p-xylene glycol, or mixtures thereof. In one embodiment, the modifying diol is ethylene glycol. In another embodiment, the modifying diols include, but are not limited to, 1,3-propylene glycol and / or 1,4-butanediol. In another embodiment, ethylene glycol is excluded as a modifying diol. In another embodiment, 1,3-propylene glycol and 1,4-butanediol are excluded as modifying diols. In another embodiment, 2,2-dimethyl-1,3-propanediol is excluded as a modifying diol. Based on the total mole % of diol or diacid residues; respectively, the polyesters useful in the present invention may contain 0 to 10 mole %, for example, 0.01 to 5 mole %, 0.01 to 1 mole %, 0.05 to 5 mole %, 0.05 to 1 mole %, or 0.1 to 0.7 mole %, or 0.1 to 0.5 mole % of one or more residues of a branching monomer having 3 or more carboxyl substituents, hydroxyl substituents, or a combination thereof (also referred to herein as a branching agent). In certain embodiments, the branching monomer or branching agent may be added before and / or during and / or after polymerization of the polyester. Thus, the one or more polyesters useful in the present invention may be linear or branched. In certain embodiments, the branching monomer or branching agent may be added before and / or during and / or after polymerization.

[0178] Examples of branching monomers include, but are not limited to, polyfunctional acids or polyfunctional alcohols such as trimellitic acid, trimellitic anhydride, pyromellitic dianhydride, trimethylolpropane, glycerol, pentaerythritol, citric acid, tartaric acid, 3-hydroxyglutaric acid, and the like. In one embodiment, the branching monomer residues may comprise from 0.1 mol % to 0.7 mol % of one or more residues selected from at least one of trimellitic anhydride, pyromellitic dianhydride, glycerol, sorbitol, 1,2,6-hexanetriol, pentaerythritol, trimethylolethane, and / or trimesic acid. The branching monomers may be added to the polyester reaction mixture in the form of a concentrate or blended with the polyester, as described, for example, in U.S. Pat. Nos. 5,654,347 and 5,696,176, the disclosures of which regarding branching monomers are incorporated herein by reference.

[0179] The polyesters useful in the present invention can be prepared by methods known in the literature, such as, for example, by methods in homogeneous solution, by transesterification methods in the melt, and by two-phase interface methods. Suitable methods include, but are not limited to, the steps of reacting one or more dicarboxylic acids with one or more diols at a temperature of 100° C. to 315° C. and a pressure of 0.1 to 760 mmHg for a time sufficient to form the polyester. For methods of producing polyesters, see U.S. Pat. No. 3,772,405, the disclosure of which is hereby incorporated by reference herein.

[0180] The polyesters useful in the present invention can also be prepared by reactive melt blending and extrusion of two polyesters. For example, a polyester containing 100% terephthalic acid residues, 10 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, and 90 mol% 1,4-cyclohexanedimethanol can be prepared by reactive melt blending and extruding equal amounts of a polyester containing 100 mol% terephthalic acid residues and 100% 1,4-cyclohexanedimethanol with another polyester containing 100 mol% terephthalic acid residues, 80 mol% 1,4-cyclohexanedimethanol residues, and 20 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues.

[0181] In an embodiment, the at least one copolyester is a melt-blended polyester prepared by a process comprising melt blending at least two different starting polyesters to provide a final copolyester comprising the monomer residues contained in the starting polyesters. For example, a PCTA copolyester containing TPA, IPA, and CHDM residues is melt blended with a PCTM copolyester containing TPA, CHDM, and TMCD residues to provide a final copolyester having TPA, IPA, CHDM, and TMCD residues. In another embodiment, a PCT copolyester containing TPA and CHDM residues is melt blended with a PCTM copolyester containing TPA, CHDM, and TMCD residues to provide a final copolyester having TPA, CHDM, and TMCD residues (wherein the amount of TMCD is less than that of the starting PCTM copolyester). In another embodiment, a PCT copolyester containing TPA and CHDM residues is melt blended with an isosorbide copolyester containing TPA, CHDM, isosorbide, and EG residues to provide a final copolyester having TPA, CHDM, isosorbide, and EG residues (wherein the amount of isosorbide and EG is less than that of the starting isosorbide copolyester). In embodiments, the melt blended copolyester has a (net) amount of residues according to any of the embodiments of the copolyester (as described herein).

[0182] In embodiments, the polyesters of the present invention prepared in a reactor or by melt blending / extrusion may, if desired, subsequently be crystallized and solid-stateized by techniques known in the art to further increase IV.

[0183] In another aspect, there is provided a method for improving the aesthetic chemical resistance of a high Tg and high impact polyester (Polyester A) to degradation chemicals, the method comprising:

[0184] (1) Providing polyester A, which comprises:

[0185] (a) a dicarboxylic acid component comprising:

[0186] i) 70 to 100 mole percent of terephthalic acid residues;

[0187] (b) a diol component comprising:

[0188] i) greater than 15 mol% and up to 40 mol% of cyclic diol residues having a 2- to 5-membered ring structure or 5 mol% to 40 mol% of cyclic diol residues having a bicyclic structure wherein each individual ring of the bicyclic structure has 2 to 5 members; and

[0189] ii) 50 to 85 mole percent of 1,4-cyclohexanedimethanol residues, wherein the total mole percent of the dicarboxylic acid components is 100 mole percent and the total mole percent of the diol components is 100 mole percent; and wherein the intrinsic viscosity is from 0.55 to 1.2 dL / g, as measured at 25°C in 60 / 40 (wt / wt) phenol / tetrachloroethane at a concentration of 0.5 g / 100 ml; and wherein the polyester has a Tg of at least 100°C and a notched Izod impact strength greater than 500 J / m, as measured in accordance with ASTM D256 at 23°C using a 3.2 mm thick bar that has been subjected to 50% relative humidity at 23°C for 40 hours;

[0190] (2) combining polyester A with polyester B, wherein polyester B is included in an amount sufficient to improve the aesthetic chemical resistance of the combination to degradation chemicals as compared to polyester A, wherein polyester B comprises:

[0191] (a) a dicarboxylic acid component comprising:

[0192] i) 95 to 100 mole percent terephthalic acid residues; and

[0193] ii) 0 to 5 mole percent of isophthalic acid residues; and

[0194] (b) a diol component comprising:

[0195] i) 95 to 100 mole percent of 1,4-cyclohexanedimethanol residues, wherein the total mole percent of the dicarboxylic acid component is 100 mole percent and the total mole percent of the diol component is 100 mole percent;

[0196] (3) Blending polyester A with polyester B to provide a combined polyester composition.

[0197] In an embodiment, polyester A comprises:

[0198] (a) a dicarboxylic acid component comprising:

[0199] i) 100 mole % of terephthalic acid residues;

[0200] (b) a diol component comprising:

[0201] i) 20 to 25 mol% or 30 to 40 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and

[0202] ii) 75 to 80 mol% or 60 to 70 mol% of 1,4-cyclohexanedimethanol residues.

[0203] In an embodiment, polyester A comprises:

[0204] (a) a dicarboxylic acid component comprising:

[0205] i) 100 mole % of terephthalic acid residues;

[0206] (b) a diol component comprising:

[0207] i) 10 mol% to 35 mol%, or 15 mol% to 35 mol%, or 15 mol% to 25 mol% of isosorbide;

[0208] ii) 40 mol% to 80 mol%, or 50 mol% to 75 mol%, or 60 mol% to 75 mol% of 1,4-cyclohexanedimethanol residues; and

[0209] iii) 5 mol% to 30 mol%, or 7 mol% to 25 mol%, or 8 mol% to 16 mol% of ethylene glycol residues.

[0210] In an embodiment, polyester B comprises:

[0211] (a) a dicarboxylic acid component comprising:

[0212] i) 100 mole percent terephthalic acid residues; and

[0213] (b) a diol component comprising:

[0214] i) 100 mol % of 1,4-cyclohexanedimethanol residues.

[0215] In an embodiment, polyester B is included in an amount to provide a polyester A:polyester B weight ratio in the range of 90:10 to 50:50, or 90:10 to 60:40, or 90:10 to 65:35, or 85:15 to 50:50, or 85:15 to 60:40, or 85:15 to 65:35, or 80:20 to 50:50, or 80:20 to 60:40, or 80:20 to 65:35, or 80:20 to 70:30.

[0216] In embodiments, the blending step (3) comprises melt blending polyester A and polyester B.

[0217] In embodiments, articles made from the copolyester compositions may be amorphous. For purposes of this disclosure, amorphous means having a crystallinity of less than 1%. In other embodiments, articles made from the copolyester compositions may be semi-crystalline, such as by crystallization upon heating. In embodiments, articles of the present invention have a crystallinity of 1% to 40%, or 1% to 35%, or 1% to 30%, or 5% to 40%, or 5% to 35%, or 5% to 30%, or 10% to 40%, or 10% to 35%, or 10% to 30%.

[0218] In other embodiments, articles made from the copolyester compositions may exhibit strain-induced crystallinity. Strain-induced crystallization refers to a phenomenon in which an initially amorphous solid material undergoes a phase transition, where some of the amorphous domains are converted to crystalline domains due to applied strain. This phenomenon has a significant impact on strength and fatigue properties.

[0219] In embodiments, the articles of the present invention have a strain induced crystallinity of 1% to 40%, or 1% to 35%, or 1% to 30%, or 5% to 40%, or 5% to 35%, or 5% to 30%, or 10% to 40%, or 10% to 35%, or 10% to 30%, when stretched at a temperature above the Tg of the polyester, for example during a molding or forming process (e.g., stretch blow molding).

[0220] In an embodiment, the article is a transparent semi-crystalline article comprising a copolyester having a crystallization half-time of less than 10 minutes but greater than about 30 seconds. In an embodiment, the copolyester has a crystallization half-time of 30 seconds to 5 minutes, or 30 seconds to 3 minutes, or 30 seconds to 2 minutes, or 30 seconds to 1.5 minutes.

[0221] In embodiments, articles of the present invention may comprise polyesters of the present invention having a melting temperature (Tm) of from 260°C to 300°C.

[0222] In addition, the polyesters useful in the present invention may also contain from 0.01 to 25 wt % or from 0.01 to 20 wt % or from 0.01 to 15 wt % or from 0.01 to 10 wt % or from 0.01 to 5 wt % of conventional additives, such as colorants, dyes, mold release agents, reheat additives, flame retardants, plasticizers, stabilizers (including but not limited to UV stabilizers, heat stabilizers) and / or their reaction products, fillers, and impact modifiers, based on the total weight of the polyester composition. Examples of typical commercially available impact modifiers well known in the art and useful in the present invention include but are not limited to ethylene / propylene terpolymers; functionalized polyolefins, such as polyolefins containing methyl acrylate and / or glycidyl methacrylate; styrene-based block copolymer impact modifiers; and various acrylic core / shell impact modifiers. For example, UV additives may be incorporated into the manufactured article by addition to the main body, by applying a hardcoat, or by coextruding a cover layer. Residues of such additives are also contemplated as part of the polyester composition.

[0223] The polyesters useful in the present invention may contain at least one chain extender. Suitable chain extenders include, but are not limited to, multifunctional (including but not limited to difunctional) isocyanates, multifunctional epoxides (including, for example, epoxidized novolacs), and phenoxy resins. In certain embodiments, the chain extender may be added at the end of the polymerization process or after the polymerization process. If added after the polymerization process, the chain extender may be introduced by compounding or by addition during a conversion process (e.g., injection molding or extrusion). The amount of chain extender used may vary depending on the specific monomer composition used and the desired physical properties, but is typically from about 0.1% to about 10% by weight, preferably from about 0.1% to about 5% by weight, based on the total weight of the polyester.

[0224] Thermal stabilizers are compounds that stabilize polyesters during polyester manufacturing and / or post-polymerization, including but not limited to phosphorus compounds, including but not limited to phosphoric acid, phosphorous acid, phosphonic acid, phosphinic acid, phosphous acid, and various esters and salts thereof. These may be present in the polyester compositions useful in the present invention. Esters may be alkyl, branched alkyl, substituted alkyl, difunctional alkyl, alkyl ether, aryl, and substituted aryl groups. In one embodiment, the number of ester groups present in a particular phosphorus compound may vary from zero to a maximum value allowed by the number of hydroxyl groups present on the thermal stabilizer used. The term "thermal stabilizer" is intended to include reaction products thereof. The term "reaction product" used in conjunction with the thermal stabilizer of the present invention refers to any product of a polycondensation or esterification reaction between a thermal stabilizer and any of the monomers used to prepare the polyester, as well as the product of a polycondensation or esterification reaction between a catalyst and any other type of additive.

[0225] Reinforcement can be used in composition of the present invention.Reinforcement can include but not limited to carbon filament, silicate, mica, clay, talc, titanium dioxide, wollastonite, glass flake, glass beads and fiber and polymer fiber and combination thereof.In one embodiment, reinforcing material is glass, for example the mixture of fiber glass yarn, glass and talc, the mixture of glass and mica and the mixture of glass and polymer fiber.

[0226] In an embodiment, an article (configured to receive or accommodate contact with a chemical composition intended for body contact or a chemical composition for use on a high-contact article) may include, but is not limited to, injection blow molded articles, injection stretch blow molded articles, extrusion blow molded articles, extrusion stretch blow molded articles, calendared articles, compression molded articles, and solution cast articles. Methods of making the article include, but are not limited to, extrusion blow molding, extrusion stretch blow molding, injection blow molding, injection stretch blow molding, calendaring, compression molding, and solution casting.

[0227] In an embodiment, an article (e.g., configured to receive or accommodate contact with a chemical composition intended for body contact or a chemical composition on a high-contact article) may include one or more films and / or one or more sheets comprising a polyester composition formed into an article of the present invention. Methods of forming polyester into one or more films and / or one or more sheets are well known in the art. Examples of the one or more films and / or one or more sheets of the present invention include, but are not limited to, extruded one or more films and / or one or more sheets, calendered one or more films and / or one or more sheets, compression molded one or more films and / or one or more sheets, solution cast one or more films and / or one or more sheets. Methods of preparing films and / or sheets include, but are not limited to, extrusion, calendering, compression molding, and solution casting.

[0228] In an embodiment of the present invention, the copolyester composition has a notched Izod impact strength of at least 800 J / m or at least 900 J / m, as measured according to ASTM D256 using a 3.2 mm thick bar that has been subjected to 50% relative humidity at 23° C. for 48 hours. In certain embodiments, the polymer-based resin has a notched Izod impact strength of at least 1000 J / m or at least 1050 J / m, as measured according to ASTM D256 using a 3.2 mm thick bar that has been subjected to 50% relative humidity at 23° C. for 48 hours.

[0229] In an embodiment of the present invention, the polymer-based resin has a ΔE value of less than 25, or less than 20, or less than 15, or less than 14, or less than 13, or less than 12, or less than 11, or less than 10, or less than 9, or less than 8, or less than 7, or less than 6, or less than 5 using a 3.2 mm test plaque after injection molding with a barrel temperature of 249°C and a mold temperature of 80°C, where ΔE is determined by the following equation: ((L*-100) 2 +(a*-0) 2 +(b*-0) 2 ) 1 / 2 wherein the L*, a*, and b* color components are measured according to ASTM E 1348. In certain embodiments, the polymer-based resin has a ΔE value in the range of 2 to 25, or 2 to 20, or 2 to 15, or 2 to 14, or 2 to 13, or 2 to 12, or 2 to 11, or 2 to 10, or 2 to 9, or 2 to 8, or 2 to 7, or 2 to 6, or 2 to 5 using a 3.2 mm test plaque after injection molding with a barrel temperature of 249° C. and a mold temperature of 80° C., wherein ΔE is determined by the following equation: ((L*-100) 2 +(a*-0) 2 +(b*-0) 2 ) 1 / 2 wherein the L*, a* and b* color components are measured according to ASTM E1348.

[0230] In embodiments of the present invention, the polymer-based resin has an L* color of at least 85, or at least 86, or at least 87, or at least 88, or at least 89, or at least 90, or at least 91, or at least 92, or at least 93, or at least 94, or at least 95, as measured using a 3.2 mm test plaque after injection molding according to ASTM E1348 with a barrel temperature of 249° C. and a mold temperature of 80° C. In certain embodiments, the polymer-based resin has an L* color in the range of 85 to 98, or 85 to 97, or 85 to 96, or 85 to 95, as measured using a 3.2 mm test plaque after injection molding according to ASTM E1348 with a barrel temperature of 249° C. and a mold temperature of 80° C.

[0231] In embodiments of the present invention, the polymer-based resin has a b* value of less than 15, or less than 12, or less than 10, or less than 9, or less than 8, or less than 7, or less than 6, or less than 5, or less than 4, as measured using a 3.2 mm test plaque after injection molding according to ASTM E1348 with a barrel temperature of 249° C. and a mold temperature of 80° C. In certain embodiments, the polymer-based resin has a b* color in the range of 0 to 15, or 0 to 10, or 0 to 8, or 0 to 5, as measured using a 3.2 mm test plaque after injection molding according to ASTM E1348 with a barrel temperature of 249° C. and a mold temperature of 80° C.

[0232] In aspects of the present invention, shaped articles are related. In certain embodiments, the shaped article is not a continuously extruded film that is infinite (or continuous) in one direction and fixed in width and thickness in the other two directions, as is the case with rolled films. In certain embodiments, the film or sheet can be converted into a shaped article, for example, by thermoforming into a three-dimensional object (e.g., a cup or bowl). In embodiments of the present invention, the shaped article is not a film or is not a sheet. In embodiments of the present invention, the shaped article can be selected from injection molded articles, extrusion molded articles, rotational molded articles, compression molded articles, blow molded articles, injection blow molded articles, injection stretch blow molded articles, extrusion blow molded articles, sheet or film extruded articles, profile extruded articles, gas-assisted molded articles, structural foam molded articles, or thermoformed articles.

[0233] In an embodiment of the present invention, the shaped article is selected from a transparent article, a see-through article, a thin-walled article, a technical article (e.g., an article with a complex design), an article with high design specifications, an intricate design article, a container, a wearable article, a household article, a general consumer product, a packaging article, a medical article, a high-contact article, or a component thereof, wherein the article is configured to receive a chemical composition intended for body contact or a chemical composition that may come into contact with a high-contact article or to adapt to contact with a chemical composition intended for body contact or a chemical composition that may come into contact with a high-contact article.

[0234] In an embodiment, the article is a wearable article or device that may come into contact with a chemical composition intended for body contact, the chemical composition comprising one or more degradation chemicals. Examples of such wearable articles or devices include fitness trackers, headphones, earbuds, (smart) watches, AR / VR headsets, medical delivery devices, sporting goods (e.g., sunglasses, helmets, and scuba diving equipment), and cameras.

[0235] In an embodiment, the article is a high-contact article or device that may come into contact with a chemical composition (e.g., a disinfectant) used on such article or device that contains one or more degrading chemicals, such as sunscreen. Examples of such high-contact articles or devices include toys, protective cases, portable devices (e.g., smartphones, laptops, tablets), wine glasses, and drinkware.

[0236] In certain embodiments, the polyester composition can be once molded into a form such as a pellet, plaque, or parison, and then can be secondarily molded into an article, such as a catheter, tube, thin-walled container, or thick-walled container configured to receive a chemical composition intended for body contact or for use on a high-contact article.

[0237] Methods of forming the polyester composition into films, molded articles, and sheets can be according to methods known in the art. In embodiments, the polyester composition can be overmolded onto itself or onto a different polyester composition and maintain interfacial bond (or weld line) strength that does not separate (or delaminate) when the article (having such an overmolded interface) is used for its intended purpose.

[0238] In one aspect, an article or device is provided comprising a molded component that may come into contact with a chemical composition used on a high-contact article / device, wherein the molded component is formed from a plastic composition comprising a copolyester composition and having a Tg of at least 95°C.

[0239] In one aspect, an article is provided comprising a molded component configured to receive a chemical composition intended for body contact, wherein the molded component is formed from a plastic composition comprising a copolyester composition and having a Tg of at least 95°C.

[0240] Chemical compositions intended for body contact or for use on high-contact articles contain at least 1 wt%, or at least 5 wt%, or at least 10 wt%, or at least 15 wt%, or at least 20 wt%, or at least 25 wt% of one or more degradation chemicals. By degradation chemicals is meant chemicals that degrade the performance of one or more copolyesters (e.g., copolyesters containing CHDM or TMCD), wherein the degradation of performance is indicated by a decrease in optics or light transmittance when tested according to the methods disclosed herein. In embodiments, chemical compositions intended for body contact contain at least 0.01 wt%, or at least 0.05 wt%, or at least 0.1 wt%, or at least 0.5 wt%, or at least 1 wt%, or at least 5 wt%, or at least 10 wt% of total degradation chemicals.

[0241] In an embodiment, the degradation chemicals are selected from sunscreen components, insect repellent components, cosmetic components, perfume components, alcohols, glycols, oils, fats, waxes, plant-based oils or extracts, food ingredients, cleaning agents, disinfectants, detergents, or combinations thereof. In an embodiment, the sunscreen component may include a UV absorber / blocker such as, for example, oxybenzone, avobenzone, octisalate, octocrylene, homosalate, octinoxate, zinc oxide, titanium dioxide, or a combination thereof. In an embodiment, the insect repellent component may include an insect repellent active substance such as N,N-diethyl-m-toluamide (DEET), citronella, picardin, a plant oil or extract having insect repellent properties, or a combination thereof. In an embodiment, the cosmetic component may include an alcohol, glycol, amine, hydroxy acid, oil, fat, wax, glycerin, colorant, fragrance, or a combination thereof. In an embodiment, the perfume component may include a solvent, alcohol, glycol, hydroxy acid, oil, fragrance, or a combination thereof.

[0242] In an embodiment, the copolyester composition from which an article (e.g., an injection molded article) is formed is selected from any of the copolyester compositions discussed herein. In an embodiment, the copolyester composition from which an article (e.g., an injection molded article) is formed comprises at least one copolyester comprising:

[0243] (a) a dicarboxylic acid component comprising:

[0244] i) 92 to 100 mole percent terephthalic acid residues; and

[0245] ii) 0 to 2 mol% of isophthalic acid residues;

[0246] (b) a diol component comprising:

[0247] i) greater than 15 to 21 mole percent of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and

[0248] ii) 85 to 89 mol% of 1,4-cyclohexanedimethanol residues,

[0249] wherein the total mole % of the dicarboxylic acid components is 100 mole % and the total mole % of the diol components is 100 mole %; and wherein the intrinsic viscosity is from 0.70 to 1.0 dL / g or from 0.75 to 0.95 dL / g, as measured at 25°C in 60 / 40 (wt / wt) phenol / tetrachloroethane at a concentration of 0.5 g / 100 ml; and wherein the polyester has a Tg of at least 100°C to 115°C.

[0250] In one embodiment, a copolyester composition formed into an article (e.g., an injection molded article) comprises at least one copolyester comprising:

[0251] (a) a dicarboxylic acid component comprising:

[0252] i) 92 to 100 mole percent terephthalic acid residues; and

[0253] ii) 0 to 2 mol% of isophthalic acid residues;

[0254] (b) a diol component comprising:

[0255] i) 9 mol% to 16 mol% isosorbide; and

[0256] ii) 70 to 91 mol% of 1,4-cyclohexanedimethanol residues,

[0257] wherein the total mole % of the dicarboxylic acid component is 100 mole % and the total mole % of the glycol component is 100 mole %; and wherein the intrinsic viscosity is 0.70 to 1.0 dL / g or 0.75 to 0.95 dL / g, as measured at 25°C in 60 / 40 (wt / wt) phenol / tetrachloroethane at a concentration of 0.5 g / 100 ml; and wherein the polyester has a Tg of at least 95°C to 115°C. In one embodiment, the dicarboxylic acid is 100 mole % of terephthalic acid residues. In one embodiment, the glycol component further comprises 5 mole % to 10 mole %, or 5 mole % to 9 mole %, or 6 mole % to 10 mole %, or 6 mole % to 9 mole % of ethylene glycol.

[0258] The properties disclosed herein requiring a test method can be determined as follows:

[0259] Test Method

[0260] The properties disclosed throughout this application can be determined according to the test methods described herein.Samples are (or can be) evaluated using standard ASTM test methods under any of the specific conditions described below.

[0261] Test Method

[0262]

[0263]

[0264] The intrinsic viscosity of the polyesters is measured at 25°C in 60 / 40 (wt / wt) phenol / tetrachloroethane at a concentration of 0.5 g / 100 ml (according to ASTM D4603).

[0265] The diol composition was determined by proton nuclear magnetic resonance (NMR) spectroscopy. All NMR spectra were recorded on a JEOL EclipsePlus 600 MHz NMR spectrometer using chloroform-trifluoroacetic acid (70-30 vol / vol). Peak assignments for the 2,2,4,4-tetramethyl-1,3-cyclobutanediol resonances were made by comparison with model mono- and dibenzoates of 2,2,4,4-tetramethyl-1,3-cyclobutanediol. These model compounds closely resemble the resonance positions found in the polymer.

[0266] Crystallization half-time t 1 / 2 The light transmittance of a sample is measured over time on a temperature-controlled hot stage using a laser and a photodetector. max , and then cool it to the desired temperature. The sample is then maintained at the desired temperature by a hot stage while transmittance measurements are taken over time. Initially, the sample appears clear with high light transmittance, but becomes opaque as the sample crystallizes. The crystallization half-time is recorded as the time it takes for the light transmittance to be halfway between the initial transmittance and the final transmittance. max Defined as the temperature required to melt the crystalline domains of the sample (if any). The T reported in the following examples is max =T represents that each sample was heated to adjust the sample temperature before the crystallization half-time measurement. max The temperature depends on the composition and is typically different for each polyester. For example, PCT may need to be heated to a temperature above 290°C to melt the crystalline domains.

[0267] Differential Scanning Calorimetry (DSC) was performed using a TA Instruments Model 2920 equipped with a liquid nitrogen cooling accessory. Sample weights ranging from 8 to 12 mg were measured and recorded. The sample was first heated from 0°C to 320°C at 20°C / min (first heating scan), then cooled to 0°C at 20°C / min (cooling scan), and then heated again from 0°C to 320°C at 20°C / min. Various thermal parameters were measured and recorded. ΔH cc (cal / g) is the heat of crystallization measured from the cooling scan. T cc is the crystallization peak temperature on the cooling scan. T g is the glass transition temperature measured from the second heating scan. m is the melting point measured during the second heating scan. ΔH ch1 (cal / g) is the heat of crystallization measured during the first heating scan. ΔH m1 (cal / g) is the heat of fusion measured during the first heating scan.

[0268] The percentage of crystallinity formed during cooling was calculated by equation (1) assuming a specific heat of fusion of 29 cal / g (based on unmodified PCT).

[0269]

[0270] For unmodified PCT, the peak temperature in the crystallization exotherm (T cc ) occurs at 227°C.

[0271] Strain-induced crystallinity percentage ( c ) is determined by equation (2) from the first heating scan of the film evaluated in DSC.

[0272]

[0273] As used herein, the abbreviation "wt" means "weight."

[0274] The following examples further illustrate how to prepare and evaluate the composition of matter of the present invention and are intended to be purely exemplary embodiments of the present invention, rather than to limit its scope. Unless otherwise stated, parts are by weight, temperatures are degrees Celsius or room temperature, and pressures are equal to or near atmospheric pressure.

[0275] Example

[0276] Example A - Blend of Examples 1-10

[0277] Melt blended copolyester compositions were prepared by mixing amorphous polyester resin 1 with amorphous or semi-crystalline polyester resins 2 or 3. The compositions of the resins are shown below in Table 1. The blends of the resins are shown in Tables 2 and 3.

[0278] Table 1. Resins used to make blends

[0279]

[0280] Table 2. Blends with Resin 2

[0281]

[0282] Table 3. Blends with Resin 3

[0283]

[0284] The physical properties of the resin blends according to the examples are shown in Table 4 below.

[0285] Table 4 - General properties of resins of Examples 1-10

[0286]

[0287] Example B - Test Bar / Reverse Impact

[0288] Test rod production

[0289] Pellets of certain copolyester materials from Example A (Examples 5 and 7) were injection molded to form standard test bars measuring 0.5 inches by 5 inches by 0.125 inches (1.27 cm by 12.7 cm by 0.3 cm). The pellets were molded in a 110-ton Toyo injection molding machine with a 3.4 oz barrel capacity. The copolyester material was injection molded into four test bars per mold at an injection rate of 1 in / sec with a barrel temperature nominally at about 249° C. (480° F.) and a mold temperature of about 80° C.

[0290] Similar test bars were molded for the following commercial copolyesters (both available from Eastman Chemical Company): Tritan copolyester DX4001 (resin 4) and Tritan copolyester TX1501 (resin 5). Another blend (Example 11) was prepared with 60 wt% Resin 5 and 40 wt% Resin 3 and molded into test bars.

[0291] Test results

[0292] ESCR - Characteristic Retention in Reverse Impact

[0293] The test was conducted using injection molded flexible bars of 5.0", 0.5", and 0.125" length, width, and thickness, respectively. The bars were conditioned at 23°C / 50% RH for a minimum of 72 hours. The bars were clamped at 1.5% strain into a constant strain fixture or a 3-point bend fixture and exposed to the test oil using a cotton pad saturated with the test oil, which was placed on the top surface of the bar. After the test oil was applied to the side of the bar without the ejector pin marking, the strain fixture with the bar attached was sealed in a polyethylene bag at a nominal temperature of 23°C for 24 hours, after which the bar was wiped clean and removed from the strain fixture.

[0294] After exposure, the reverse side of the test rod was impacted at 23°C. The test apparatus was a CEAST pendulum impact tester equipped with a 15 joule hammer. The rod was placed in a fixture with a span of 2 inches, with the non-chemically exposed side facing the hammer. In addition to the rods exposed to the test oil, a control rod (exposed to water) was also impact tested. The comparison of the results between the control rod and the chemically exposed rod was used to calculate the percentage retention of the original impact energy. The test was repeated five times, and the result is the average of the five tests. The results are shown in Table 5 below.

[0295] Table 5 - Percentage Retention of Reverse Impact Strength After Exposure

[0296]

[0297] Review of Table 5 reveals that the copolyester of Example 7 had the best overall resistance to the panel of chemicals tested, but Example 5 showed better resistance to DEET 40% and limonene, and Example 11 showed better resistance to canola oil, Vitrex B, WD-40, and sebum.

[0298] Example C - Spiral Flow

[0299] The relative flow rates of certain copolyesters were examined by measuring the flow length through a standardized spiral die via injection molding of various test materials.The spiral flow test is described in more detail below.

[0300] spiral flow

[0301] 3.2mm thick rod

[0302] A reciprocating screw injection molding machine with 110 tons of clamping force and a 32mm screw diameter was equipped with a water-cooled cold runner mold featuring a spiral cavity measuring 0.50" wide x 0.125" deep x 60.00" long. The cavity was fed by a 3.5" long cold sprue with a nominal diameter of 0.400" and a 3-degree taper, followed by a 1.0" long cold runner with a nominal diameter of 0.30", followed by a rectangular gate 0.25" wide x 0.050" thick x 0.10" long. Controlled variables for the experimental range included resin drying, injection unit barrel temperature, mold temperature, initial injection velocity, injection pressure limit, screw speed and back pressure at screw reset, injection time, and cycle time.

[0303] For each variable combination, the response includes the actual melt temperature and the distance the melt travels in the spiral cavity, excluding runners and gates. The injection process is allowed to stabilize under each set of conditions (typically 10 to 15 shots), and then 10 molded samples are collected to obtain the average reported flow length.

[0304] All materials were molded using pressure control, with a mold temperature of 80°F, an initial injection velocity of 1 in / s, an injection unit pressure limit of 1000 psi, an injection time of 10 s, a cycle time of 38 s, a maximum cushion of 0.1″, a screw reset speed of 150 rpm, and a screw reset back pressure of 100 psi.

[0305] 0.8mm thick rod

[0306] A reciprocating screw injection molding machine with 110 tons of clamping force and a 32mm screw diameter was equipped with a water-cooled cold runner mold featuring a spiral cavity measuring 0.50" wide x 0.030" deep x 60.00" long. The cavity was fed by a 3.5" long cold sprue with a nominal diameter of 0.400" and a 3-degree taper, followed by a 1.0" long cold runner with a nominal diameter of 0.30", followed by a rectangular gate 0.25" wide x 0.030" thick x 0.10" long. Controlled variables for the experimental range included resin drying, injection unit barrel temperature, mold temperature, initial injection velocity, injection pressure limit, screw speed and backpressure at screw reset, injection time, and cycle time.

[0307] For each variable combination, the response includes the actual melt temperature and the distance the melt travels in the spiral cavity, excluding runners and gates. The injection process is allowed to stabilize under each set of conditions (typically 10 to 15 shots), and then 10 molded samples are collected to obtain the average reported flow length.

[0308] All materials were molded using pressure control, with a mold temperature of 120°F (49°C), an initial injection velocity of 1 in / s, an injection unit pressure limit of 2000 psi, an injection time of 5 s, a cycle time of 32 s, a maximum cushion of 0.2", a screw reset speed of 150 rpm, and a screw reset back pressure of 100 psi.

[0309] The spiral flow lengths of the copolyester of Example 7, Tritan copolyester TX1000 (resin 6), and Tritan copolyester TX1500 (resin 7) were measured when the polymer-based resins were molded using a spiral flow mold at a cylinder temperature of 260° C. to 282° C., a molding pressure of 13.8 MPa, a mold thickness of 0.8 mm, and a mold width of 12.7 mm. The results are listed in Table 6 below.

[0310] Table 6 - Spiral Flow Results

[0311]

[0312] Review of Table 6 reveals that the copolyester of Example 7 has a spiral flow length between the values ​​of Resin 6 and Resin 7 for the temperatures tested, with Example 7 performing closer to Resin 7.

[0313] The spiral flow lengths of Resin 6, Resin 7, Example 7, Example 11, and the copolyester of Bayblend 85XF (a PC / ABS blend from Covestro) (Resin 8) were measured when the polymer-based resins were molded using a spiral flow mold at a barrel temperature of 260° C. to 282° C., a molding pressure of 13.8 MPa, a mold thickness of 0.8 mm, and a mold width of 12.7 mm. The results are listed in Table 7 below.

[0314] Table 7 - Spiral Flow Results

[0315]

[0316] Example D - Sunscreen Testing

[0317] Pellets of each material from Examples 1-10 were injection molded to form standard test plaques measuring 4 inches by 4 inches by 0.125 inches thick (10.2 cm by 10.2 cm by 0.3 cm). The pellets were molded in a 110-ton Toyo injection molding machine with a 3.4 oz barrel capacity. The copolyester material was injection molded into four test bars per mold at an injection rate of 1 in / sec with a barrel temperature nominally at about 249° C. (480° F.) and a mold temperature of about 80° C.

[0318] Sunscreen is applied to the hands and rubbed with the other hand to evenly distribute the sunscreen. The test plate of each material is then touched with the finger rubbed in the sunscreen to show the fingerprint of the sunscreen on the surface. Each test plate is divided into 4 quadrants, and each quadrant is touched with different sunscreen products. Quadrant 1 uses Coppertone children's sports sunscreen spray spf50, and quadrant 2 uses Coppertone sports lotion spf50 (4 in 1 performance), and quadrant 3 uses equate sports sunscreen spf50, and quadrant 4 uses BananaBoat sport ultra spf 100. The test plate is then placed in 50 ℃ of ovens for 5 minutes. Then use Dawn detergent and water to wash each part, wipe with Kimwipe, and take the photo of each test plate to determine that the sunscreen remains / whitens. Then, 3-4 individuals are ranked based on the scale formed on the next slide to whiten.

[0319] Representative photographs of sunscreen fingerprints on test panels are shown in Figure 1 Medium. Rank the visual assessments according to the following scale:

[0320] 0 - Completely transparent; no signs of fingerprints from any angle.

[0321] 1- The fingerprint outline is partially visible under the right light and is still transparent.

[0322] 2 / 3 - Fingerprint outline visible under suitable light, still transparent.

[0323] 4- The details of the fingerprint begin to become visible and the print becomes more translucent.

[0324] 5- The print is clear / the lines may be visible, the print is translucent rather than transparent.

[0325] 6 / 7 - The print is clear / the lines are visible without any special angles / lighting; the print has increasing opacity.

[0326] 8 - Blots are very clear; visible without any special lighting, with increasing opacity.

[0327] 9 / 10 - The print is visible and very clear from all angles, completely opaque.

[0328] Representative photos of the test plates corresponding to the different scores are shown in Figure 2 middle.

[0329] The average score for all four quadrants of each test panel was determined. The results of the Average Sunscreen Rating Test are listed in Table 8 below.

[0330] Table 8 - Sunscreen Ratings for Resins of Examples 1-10

[0331]

[0332]

[0333] Haze and transmittance (%)

[0334] Haze and transmittance data were measured using Gardner Haze-gardplus using ASTM D1003 as the method. The results of the haze and transmittance tests are listed in Tables 9 and 10 below.

[0335] Table 9 - Haze values ​​after sunscreen testing by quadrant

[0336]

[0337] Table 10 - Transmittance of sunscreens tested by quadrant (%)

[0338]

[0339]

[0340] Review of Tables 9 and 10 reveals that blending Resin 2 or 3 into Resin 1 resulted in lower haze values ​​as the amount of Resin 2 or 3 increased, and that blending with Resin 3 reduced the haze value more than blending with Resin 2. Blending Resin 2 or 3 into Resin 1 resulted in higher % transmittance, with Examples 2 and 3 and Examples 7 and 8 having the highest transmittance for the Resin 2 and Resin 3 blends, respectively.

[0341] Example E - Whitening Test

[0342] To induce whitening, 1" x 1" test panels were placed in canola oil at 90°C for 24 hours, then removed and wiped with a Kimwipe until the oil was no longer visible on the part. Each sample was washed in a Dawn dishwashing detergent solution to remove any residual oil. The parts were placed in a sealed container with a Solid Power XL (SPXL) dishwashing detergent solution (2g powder / 1 liter of DI water) at 90°C for 24 hours. The samples were then removed from the SPXL solution and rinsed with DI water. Visual observations were made to determine the severity of whitening.

[0343] Examples 2 and 3 showed improvement (less whitening) compared to the Resin 1 test plaque, and Examples 7 and 8 showed additional improvement compared to Examples 2 and 3.

[0344] Example F - Additional Resin Blends

[0345] An additional melt-blended copolyester composition was prepared by mixing polyester resin 8 with resin 3. The compositions of resins 8 and 3 are shown below in Table 11. The blends of the resins are shown in Table 12.

[0346] Table 11. Resins used to make Blend A

[0347]

[0348] Table 12. Blends of Resin 4 and Resin 5

[0349]

[0350] The physical properties of the resin blends according to Table 12 are shown in Table 13 below.

[0351] Table 13. Properties of Comparative Examples 1, 2, and Examples 12 and 13

[0352]

[0353] Sunscreen Score, Haze, % Transmittance, and Whitening Testing similar to that described above for Example E were repeated for Comparative Examples 1 and 2, and Examples 12 and 13. The results for Sunscreen Score, Haze, and Transmittance are shown in Tables 14-16 below.

[0354] Table 14. Sunscreen Ratings for Comparative Examples 1 and 2, and Examples 12 and 13

[0355]

[0356]

[0357] Table 15. Haze values ​​of Comparative Examples 1 and 2, Examples 12 and 13

[0358]

[0359] Table 16. Transmittance (%) of Comparative Examples 1 and 2, and Examples 12 and 13

[0360]

[0361] A review of Tables 14 and 15 reveals that as the amount of Resin 3 increases, Examples 12 and 13 result in lower sunscreen scores and haze values, and Example 13 has a lower score and haze value than Example 12. Examples 12 and 13 have higher transmittance % than Comparative Example 1, and Example 13 has a higher transmittance than Example 12.

[0362] Furthermore, Comparative Example 1 and Examples 12 and 13 had similar whitening results with almost no whitening, while Comparative Example 2 had significant whitening.

[0363] By considering the description and practicing the embodiments disclosed herein, other embodiments will become apparent to those skilled in the art. It should be understood that variations and modifications can be realized within the spirit and scope of the disclosed embodiments. The description and examples are further intended to be considered as merely exemplary, with the true scope and spirit of the disclosed embodiments being indicated by the appended claims.

Claims

1. A transparent article configured to accommodate contact with a chemical composition intended for body contact and comprising one or more degradation chemicals, wherein the transparent article is formed from a copolyester composition comprising at least one copolyester comprising: (a) a dicarboxylic acid component comprising: i) 70 to 100 mole percent of terephthalic acid residues; (b) a diol component comprising: i) greater than 15 mol% and up to 33 mol% of cyclic diol residues having a 2- to 5-membered ring structure or 5 mol% to 33 mol% of cyclic diol residues having a bicyclic structure wherein each individual ring of the bicyclic structure has 2 to 5 members; and ii) 55 mol% to 95 mol% of 1,4-cyclohexanedimethanol residues, wherein the total mole % of the dicarboxylic acid component is 100 mole % and the total mole % of the glycol component is 100 mole %; and wherein the intrinsic viscosity is from 0.60 to 1.2 dL / g as measured at 25°C in 60 / 40 (wt / wt) phenol / tetrachloroethane at a concentration of 0.5 g / 100 ml; and wherein the polyester has a Tg of from 95°C to 115°C and has an average haze of less than 5 or less than 3 after exposure to a sunscreen (tested according to the Examples).

2. The article of claim 1, wherein the copolyester composition has a Tg in the range of 100°C to 115°C.

3. The article of claim 2, wherein the copolyester composition has an intrinsic viscosity of 0.70 to 1.0 dL / g or 0.75 to 0.95 dL / g.

4. The article of any one of claims 1 to 3, wherein the glycol component comprises: i) greater than 15 mol % and up to 22 mol % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) residues; and ii) 78 mol% to less than 85 mol% of 1,4-cyclohexanedimethanol (CHDM) residues.

5. The article of any one of claims 1 to 4, wherein the dicarboxylic acid component comprises 100 mole percent terephthalic acid residues.

6. The article of any one of claims 1 to 4, wherein the dicarboxylic acid component comprises: i) 95 to 100 mole percent terephthalic acid residues; and ii) 0 to 5 mole % of isophthalic acid residues.

7. The article of claim 6, wherein the dicarboxylic acid component comprises: i) 98 to 100 mole percent terephthalic acid residues; and ii) 0 to 2 mole % of isophthalic acid residues.

8. The article of any one of claims 1 to 7, wherein the copolyester composition has a crystallization half-time of 30 seconds to 5 minutes.

9. The article of any one of claims 1 to 8, wherein the article is selected from a wearable article, a high-contact article, a food or beverage container, or a packaging article.

10. The article according to any one of claims 1 to 9, wherein the chemical composition intended for body contact is a sunscreen.

11. The article of any one of claims 1 to 10, wherein the at least one copolyester has a total transmittance of at least 90% and a haze of less than 1%, the total transmittance and haze being measured according to ASTM D1003.

12. A method for improving the aesthetic chemical resistance of a high Tg and high impact polyester (Polyester A) to degradation chemicals, the method comprising: (1) Providing polyester A, which comprises: (a) a dicarboxylic acid component comprising: i) 70 to 100 mole percent of terephthalic acid residues; (b) a diol component comprising: i) greater than 15 mol% and up to 40 mol% of cyclic diol residues having a 2- to 5-membered ring structure or 5 mol% to 40 mol% of cyclic diol residues having a bicyclic structure wherein each individual ring of the bicyclic structure has 2 to 5 members; as well as ii) 40 to 85 mole percent of 1,4-cyclohexanedimethanol residues, wherein the total mole percent of the dicarboxylic acid component is 100 mole percent and the total mole percent of the diol component is 100 mole percent; and wherein the intrinsic viscosity is from 0.55 to 1.2 dL / g as measured in 60 / 40 (wt / wt) phenol / tetrachloroethane at a concentration of 0.5 g / 100 ml at 25° C.; and wherein the polyester has a Tg of at least 95° C. and a notched Izod impact strength greater than 500 J / m as measured in accordance with ASTM D256 at 23° C. using a 3.2 mm thick bar that has been subjected to 50% relative humidity at 23° C. for 40 hours; (2) combining polyester A with polyester B, wherein polyester B is included in an amount sufficient to improve the aesthetic chemical resistance of the combination of polyester A and polyester B to degradation chemicals as compared to polyester A, wherein polyester B comprises: (a) a dicarboxylic acid component comprising: i) 95 to 100 mole percent terephthalic acid residues; and ii) 0 to 5 mole percent of isophthalic acid residues; and (b) a diol component comprising: i) 95 to 100 mole percent of 1,4-cyclohexanedimethanol residues, wherein the total mole percent of the dicarboxylic acid component is 100 mole percent and the total mole percent of the diol component is 100 mole percent; (3) Blending polyester A with polyester B to provide a blended polyester composition.

13. The method of claim 12, wherein the blended polyester composition comprises: (a) a dicarboxylic acid component comprising: i) 70 to 100 net mole percent of terephthalic acid residues; (b) a diol component comprising: i) greater than 15 mol% and up to 22 mol% of cyclic diol residues having a 2- to 5-membered ring structure or 5 mol% to 22 mol% of cyclic diol residues having a bicyclic structure wherein each individual ring of the bicyclic structure has 2 to 5 members; and ii) 55 to 95 net mole % of 1,4-cyclohexanedimethanol residues, wherein the total neat mole % of the dicarboxylic acid component is 100 mole % and the total neat mole % of the glycol component is 100 mole %; and wherein the intrinsic viscosity is from 0.60 to 1.2 dL / g as measured at 25°C in 60 / 40 (wt / wt) phenol / tetrachloroethane at a concentration of 0.5 g / 100 ml; and wherein the polyester has a Tg of from 95°C to 115°C and has an average haze of less than 5 or less than 3 after exposure to a sunscreen (tested according to the Examples).

14. The method according to claim 12 or 13, wherein polyester A comprises: (a) a dicarboxylic acid component comprising: i) 100 mole % of terephthalic acid residues; (b) a diol component comprising: i) 20 to 25 mol% or 30 to 40 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and ii) 75 to 80 mol% or 60 to 70 mol% of 1,4-cyclohexanedimethanol residues.

15. The method according to claim 12 or 13, wherein polyester A comprises: (a) a dicarboxylic acid component comprising: i) 100 mole % of terephthalic acid residues; (b) a diol component comprising: i) 10 mol% to 25 mol% or 15 mol% to 25 mol% of isosorbide residues; ii) 50 to 80 or 60 to 75 mole percent of 1,4-cyclohexanedimethanol residues; and iii) 5 mol% to 25 mol% or 7 mol% to 17 mol% of ethylene glycol residues.

16. The process according to any one of claims 12 to 15, wherein polyester B comprises: (a) a dicarboxylic acid component comprising: i) 100 mole percent terephthalic acid residues; and (b) a diol component comprising: i) 100 mol % of 1,4-cyclohexanedimethanol residues.

17. The method of any one of claims 12 to 16, wherein polyester B is included in an amount to provide a polyester A:polyester B weight ratio in the range of 90:10 to 50:50, or 90:10 to 60:40, or 90:10 to 65:35, or 85:15 to 50:50, or 85:15 to 60:40, or 85:15 to 65:35, or 80:20 to 50:50, or 80:20 to 60:40, or 80:20 to 65:35, or 80:20 to 70:

30.

18. The method according to any one of claims 12 to 17, wherein the blending step (3) comprises melt blending polyester A and polyester B.

19. The method of any one of claims 12 to 18, wherein the blended polyester composition has a higher % transmittance and lower % haze after exposure to a sunscreen than Polyester A (tested according to the Examples).

20. The method of claim 19, wherein the blended polyester composition has a haze % after exposure to a sunscreen that is at least 50% lower than that of Polyester A (tested according to the Examples).

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