Polarizer protection films comprising amorphous copolyester compositions

Abstract

Described are polyester compositions comprising at least one amorphous copolyester which comprises combinations of terephthalic acid, an ester thereof, or mixtures thereof, ethylene glycol, 1,4-cyclohexanedimethanol, and 2,2,4,4-tetramethyl-1,3-cyclobutanediol, having high glass transition temperature and specific flexural properties. The polyester composition may be manufactured into articles such as fibers, films (e.g., polarizer protection films and / or compensation films), containers, bottles or sheets.

Description

[0001] POLARIZER PROTECTION FILMS COMPRISING AMORPHOUS COPOLYESTER COMPOSITIONS

[0002] FIELD OF THE INVENTION

[0003] The present invention relates to polyester compositions comprising at least one amorphous copolyester made from combinations of terephthalic acid, ethylene glycol, 1 ,4-cyclohexanedimethanol and 2,2,4,4-tetramethyl-1,3-cyclobutanediol, the amorphous copolyester having good dimensional stability at high temperature and are useful in polarizer protection films.

[0004] BACKGROUND OF THE INVENTION

[0005] The polycarbonate of 4,4'-isopropylidenediphenol (bisphenol A polycarbonate) is a well-known engineering molding plastic. Bisphenol A polycarbonate is a clear, high-performance plastic having good physical properties such as dimensional stability, high heat resistance, and good impact strength. Although bisphenol-A polycarbonate has many good physical properties, its relatively high melt viscosity leads to poor melt processability, and the polycarbonate exhibits poor chemical resistance. It can also be difficult to thermoform.

[0006] Amorphous copolyesters can have desirable properties, such as excellent clarity and color, toughness, chemical resistance and ease of processing. Such copolyesters are known to be useful for the manufacture of extruded sheets, packaging materials, and parts for medical devices.

[0007] However, when compared to certain other families of materials such as polycarbonates based on bisphenol A and certain acrylic resins such as polymethyl methacrylate, amorphous copolyesters generally have lower glass transition temperatures (Tg) and lower heat distortion temperatures (HDT). Lower Tgand HDT can limit applications and may not be useful where resistance to thermal deformation is important, for example, green house panels, skylights and other products prepared by extrusion or injection molding processes, where the intended use requires dimensional stability at higher temperatures. Although certain copolyesters have been described as having a higher Tg, they can exhibit high inherent viscosities and high melt viscosities along with the high Tg, such that the equipment used in industry may be insufficient (or have difficulty) to manufacture or post-polymerization process these materials.

[0008] There is a need for polymers that have high glass transition temperature that can be processed with typical melt-processing equipment, and that can maintain good mechanical properties, like flexural modulus and high heat distortion temperature.

[0009] Moreover, these polymers are useful in preparing films that can function as a polarizer protection film and / or as a viewing angle compensation film. These films provide high optical transmission, high Tggreater than or equal to 110°C, low in-plane retardation (“Re”), low out-of-plane retardation (“Rth”), low moisture uptake, and low water vapor transmission rate. The equations for Re and Rth follow: Equation 1. Re = (nx-ny)*d; Equation 2. Rth = -[nz-(nx+ny) / 2]*d; where nxand nyare the film refractive indices in the film plane x and y directions, nzis the film refractive index in the film thickness direction, and d is the film thickness.

[0010] SUMMARY OF THE INVENTION

[0011] It has been found that certain compositions comprising an amorphous copolyester formed from terephthalic acid residues, ethylene glycol residues, 1 ,4-cyclohexanedimethanol residues and 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol residues with certain glass transition temperatures can be provided that are superior to other polyesters and polycarbonates with respect to one or more of increased heat distortion temperature, increased flexural modulus, good color and clarity, and / or thermoformability, while maintaining other good (desired) physical properties.

[0012] The application discloses a polyester composition comprising at least one amorphous copolyester which comprises:

[0013] (a) a dicarboxylic acid component comprising: (i) 90 to 100 mole % of terephthalic acid residues;

[0014] (ii) 0 to 10 mole % of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, and;

[0015] (b) a glycol component comprising:

[0016] (i) 1-40 mole % of ethylene glycol residues; and

[0017] (ii) 1-60 mole % of 1 ,4-cyclohexanedimethanol residues; and

[0018] (iii) 40-65 mole % of 2,2,4, 4-tetramethyl-1 ,3-cyclobutanediol residues, and wherein the inherent viscosity of the material is 0.3-1 , or 0.3 to 0.7 dL / g in 60 / 40 (wt / wt) phenol / tetrachloroethan at a concentration of 0.5 g / 100 mL at 25 °C, a glass transition temperature of greater than 115 °C as determined using ASTM D3418 test method, and a flexural modulus greater than 1750 MPa as determined using the ASTM D790 test method.

[0019] The application also discloses a polyester composition comprising at least one amorphous copolyester which comprises:

[0020] (a) a dicarboxylic acid component comprising:

[0021] (i) 90 to 100 mole % of terephthalic acid residues;

[0022] (ii) 0 to 10 mole % of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, and;

[0023] (b) a glycol component comprising:

[0024] (i) 10-40 mole % of ethylene glycol residues; and

[0025] (ii) 1-50 mole % of 1 ,4-cyclohexanedimethanol residues; and

[0026] (iii) 40-65 mole % of 2,2,4, 4-tetramethyl-1 ,3-cyclobutanediol residues, and wherein the inherent viscosity of the material is 0.3-1 , or 0.3 to 0.7 dL / g in 60 / 40 (wt / wt) phenol / tetrachloroethan at a concentration of 0.5 g / 100 mL at 25 °C, a glass transition temperature of greater than 115 °C as determined using ASTM D3418 test method, and a flexural modulus greater than 1750 MPa as determined using the ASTM D790 test method.

[0027] The application also discloses a polyester composition comprising at least one amorphous copolyester which comprises:

[0028] (a) a dicarboxylic acid component comprising:

[0029] (i) 90 to 100 mole % of terephthalic acid residues; (II) 0 to 10 mole % of aromatic and / or aliphatic dicarboxyhc acid residues having up to 20 carbon atoms, and;

[0030] (b) a glycol component comprising:

[0031] (i) 10-40 mole % of ethylene glycol residues; and

[0032] (ii) 1-40 mole % of 1 ,4-cyclohexanedimethanol residues; and

[0033] (iii) 40-65 mole % of 2,2,4, 4-tetramethyl-1 ,3-cyclobutanediol residues, and wherein the inherent viscosity of the material is 0.3-1 , or 0.3 to 0.7 dL / g in 60 / 40 (wt / wt) phenol / tetrachloroethan at a concentration of 0.5 g / 100 mL at 25 °C, a glass transition temperature of greater than 115 °C as determined using ASTM D3418 test method, and a flexural modulus greater than 1750 MPa as determined using the ASTM D790 test method.

[0034] In another aspect, the invention relates to a polyester composition comprising at least one amorphous copolyester which comprises:

[0035] (a) a dicarboxylic acid component comprising:

[0036] (i) 90 to 100 mole % of terephthalic acid residues;

[0037] (ii) 0 to 10 mole % of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, and;

[0038] (b) a glycol component comprising:

[0039] (i) 10-40 mole % of ethylene glycol residues; and

[0040] (ii) 1-30 mole % of 1 ,4-cyclohexanedimethanol residues; and

[0041] (iii) 40-65 mole % of 2,2,4, 4-tetramethyl-1 ,3-cyclobutanediol residues, and wherein the inherent viscosity of the material is 0.3-1 , or 0.3 to 0.7 dL / g in 60 / 40 (wt / wt) phenol / tetrachloroethan at a concentration of 0.5 g / 100 mL at 25 °C, a glass transition temperature of greater than 115 °C as determined using ASTM D3418 test method, and a flexural modulus greater than 1750 MPa as determined using the ASTM D790 test method.

[0042] The application also discloses a polyester composition comprising at least one amorphous copolyester which comprises:

[0043] (a) a dicarboxylic acid component comprising:

[0044] (i) 90 to 100 mole % of terephthalic acid residues;

[0045] (ii) 0 to 10 mole % of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, and; (b) a glycol component comprising:

[0046] (i) 10-40 mole % of ethylene glycol residues; and

[0047] (ii) 8-30 mole % of 1 ,4-cyclohexanedimethanol residues; and

[0048] (iii) 40-65 mole % of 2,2,4, 4-tetramethyl-1 ,3-cyclobutanediol residues, and wherein the inherent viscosity of the material is 0.3-1 , or 0.3 to 0.7 dL / g in 60 / 40 (wt / wt) phenol / tetrachloroethan at a concentration of 0.5 g / 100 mL at 25 °C, a glass transition temperature of greater than 115 °C as determined using ASTM D3418 test method, and a flexural modulus greater than 1750 MPa as determined using the ASTM D790 test method.

[0049] The application also discloses a polyester composition comprising at least one amorphous copolyester which comprises:

[0050] (a) a dicarboxylic acid component comprising:

[0051] (i) 90 to 100 mole % of terephthalic acid residues;

[0052] (ii) 0 to 10 mole % of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms, and;

[0053] (b) a glycol component comprising:

[0054] (i) 15-40 mole % of ethylene glycol residues; and

[0055] (ii) 10-30 mole % of 1,4-cyclohexanedimethanol residues; and

[0056] (iii) 45-65 mole % of 2,2,4, 4-tetramethyl-1 ,3-cyclobutanediol residues, and wherein the inherent viscosity of the material is 0.3-1 , or 0.3 to 0.7 dL / g in 60 / 40 (wt / wt) phenol / tetrachloroethan at a concentration of 0.5 g / 100 mL at 25 °C, a glass transition temperature of greater than 115 °C as determined using ASTM D3418 test method, and a flexural modulus greater than 1750 MPa as determined using the ASTM D790 test method.

[0057] A film, comprising a polyester composition comprising at least one amorphous copolyester which comprises:

[0058] (a) a dicarboxylic acid component comprising:

[0059] (i) 90 to 100 mole % of terephthalic acid (“TPA”) residues;

[0060] (ii) 0 to 10 mole % of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; and

[0061] (b) a glycol component comprising: (i) 35 to 65 mole % of 2,2,4, 4-tetramethyl-1 ,3-cyclobutanediol (“TMCD”) residues,

[0062] wherein the total mole % of the acid component (a) is 100 mole % and the total mole % of the glycol component (b) is 100 mole %,

[0063] wherein the polyester exhibits an inherent viscosity (“IV”) in the range of from 0.5-0.7 dL / g in 60 / 40 (wt / wt) phenol / tetrachloroethan at a concentration of 0.5 g / 100 mL at 25°C, a glass transition temperature (“Tg”) in the range of from 110-150°C as determined using ASTM D3418 test method.

[0064] The application also discloses multilayer films, polarizers, liquid crystal displays, and organic light emitting diodes incorporating the films discloses herein.

[0065] DETAILED DESCRIPTION OF THE INVENTION

[0066] The present invention may be understood more readily by reference to the following detailed description of certain embodiments of the invention and the working examples. In accordance with the purpose(s) of this invention, certain embodiments of the invention are described in the Summary of the Invention and are further described herein below. Also, other embodiments or aspects of the invention are described herein.

[0067] It is believed that certain polyesters and / or polyester composition(s) of the invention formed from terephthalic acid, an ester thereof, and / or mixtures thereof, ethylene glycol, 1 ,4-cyclohexanedimethanol and 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol, can have a unique combination of two or more of the following properties: certain notched Izod impact strengths, certain inherent viscosities, certain glass transition temperature (Tg); certain flexural modulus, good clarity, good color, good thermal stability (e.g., high heat deflection temperature) for a selected IV. In certain embodiments of the invention, certain polyesters and / or polyester compositions of the invention can have a unique combination of three or more of certain notched Izod impact strengths, certain inherent viscosities, certain glass transition temperature (Tg); certain flexural modulus, good clarity, good color, good thermal stability (e.g., high heat deflection temperature) for a selected IV.

[0068] As used herein, the term "polyester" includes copolyesters and is understood to mean a synthetic polymer prepared by the reaction of one or more difunctional and / or multifunctional carboxylic acids with one or more difunctional hydroxyl compounds and / or multifunctional hydroxyl compounds. Typically, the difunctional carboxylic acid can be a dicarboxylic acid and the difunctional hydroxyl compound can be a dihydric alcohol such as, for example, glycols and diols. The term "glycol" as used in this application includes, but is not limited to, diols, glycols, and / or multifunctional hydroxyl compounds, for example, branching agents. Alternatively, the difunctional carboxylic acid may be a hydroxy carboxylic acid such as, for example, p-hydroxybenzoic acid, and the difunctional hydroxyl compound may be an aromatic nucleus bearing 2 hydroxyl substituents such as, for example, hydroquinone. The term "residue", as used herein, means any organic structure incorporated into a polymer through a polycondensation and / or an esterification reaction from the corresponding monomer. The term "repeating unit", as used herein, means an organic structure having a dicarboxylic acid residue and a diol residue bonded through a carbonyloxy group. Thus, for example, the dicarboxylic acid residues may be derived from a dicarboxylic acid monomer or its associated acid halides, esters, salts, anhydrides, or mixtures thereof. As used herein, therefore, the term dicarboxylic acid is intended to include dicarboxylic acids and any derivative of a dicarboxylic acid, including its associated acid halides, esters, half-esters, salts, half-salts, anhydrides, mixed anhydrides, or mixtures thereof, useful in a reaction process with a diol to make polyester. Furthermore, as used in this application, the term "diacid" includes multifunctional acids, for example, branching agents. As used herein, the term "terephthalic acid" is intended to include terephthalic acid itself and residues thereof as well as any derivative of terephthalic acid, including its associated acid halides, esters, half-esters, salts, half-salts, anhydrides, mixed anhydrides, or mixtures thereof or residues thereof useful in a reaction process with a diol to make polyester. The polyesters used in the present invention typically can be prepared from dicarboxylic acids and diols which react in substantially equal proportions and are incorporated into the polyester polymer as their corresponding residues. The polyesters of the present invention, therefore, can contain substantially equal molar proportions of acid residues (100 mole %) and diol (and / or multifunctional hydroxyl compound) residues (100 mole %) such that the total moles of repeating units are equal to 100 mole %. The mole percentages provided in the present disclosure, therefore, may be based on the total moles of acid residues, the total moles of diol residues, or the total moles of repeating units. For example, a polyester containing 10 mole % isophthalic acid, based on the total acid residues, means the polyester contains 10 mole % isophthalic acid residues out of a total of 100 mole % acid residues. Thus, there are 10 moles of isophthalic acid residues among every 100 moles of acid residues. In another example, a polyester containing 40 mole % 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol, based on the total diol residues, means the polyester contains 40 mole % 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol residues out of a total of 100 mole % diol residues. Thus, there are 40 moles of 2,2,4, 4-tetramethyl-1,3-cyclobutanediol residues among every 100 moles of diol residues.

[0069] In one embodiment or in combination with any other embodiment, wherein the ethylene glycol component (by mole % of the copolyester) is from 1-40%, or 1-35%, or 1-30%, or 1-25%, or 1-20%, or 1-15%, or 5-40%, or 5-35%, or 5-30%, or 5-25%, or 5-20%, or 5-15%, or 10-40%, or 10-35%, or 10-30%, or 10-25%, or 10-20%, or 10-15%, or 15-40%, or 15-35%, or 15-30%, or 15-25%, or 15-20%, or 20-40%, or 20-35%, or 20-30%, or 20-25%, or 25-40%, or 25-35%, or 25-30%, or 30-40%, or 30-35%, or 35-40%.

[0070] In one embodiment or in combination with any other embodiment, wherein the 1 ,4-cyclohexanedimethanol component (by mole % of the copolyester) is from 1-60%, or 1-55%, or 1-50%, or 1-45%, or 1-40%, or 1-35%, or 1-30%, or 1-25%, or 1-20%, or 1-15%, or 1-10%, or 1-5%, 5-60%, or 5-55%, or 5-50%, or 5-45%, or 5-40%, or 5-35%, or 5-30%, or 5-25%, or 5-20%, or 5-15%, or 5-10%, 10-60%, or 10-55%, or 10-50%, or 10-45%, or 10- 40%, or 10-35%, or 10-30%, or 10-25%, or 10-20%, or 10-15%, 15-60%, or 15-55%, or 15-50%, or 15-45%, or 15-40%, or 15-35%, or 15-30%, or 15-25%, or 15-20%, 20-60%, or 20-55%, or 20-50%, or 20-45%, or 20-40%, or 20-35%, or 20-30%, or 20-25%, 25-60%, or 25-55%, or 25-50%, or 25-45%, or 25-40%, or 25-35%, or 25-30%, 30-60%, or 30-55%, or 30-50%, or 30-45%, or 30-40%, or 30-35%, 35-60%, or 35-55%, or 35-50%, or 35-45%, or 35-40%, 40-60%, or 40-55%, or 40-50%, or 40-45%, or 45-60%, or 45-55%, or 45-50%, or 50-60%, or 50-55%.

[0071] In one embodiment or in combination with any other embodiment, wherein the 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol component (by mole % of the copolyester) is from 40-65%, or 40-60%, or 40-55%, or 40-50%, or 40-45%, 45-65%, or 45-60%, or 45-55%, or 45-50%, or 50-65%, or 50-60%, 50-55%.

[0072] In aspects of the invention, the glycol component for the polyesters useful in the invention includes but are not limited to at least one of the following combinations of ranges: 40 to 65 mole % 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol, 8 to 40 mole % 1,4-cyclohexanedimethanol, and 1 to 52 mole % ethylene glycol; 40 to 65 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 8 to 40 mole % 1 ,4-cyclohexanedimethanol, and 10 to 40 mole % ethylene glycol; 40 to 65 mole % 2, 2, 4, 4-tetramethyl-1 ,3-cyclobutanediol, 8 to 40 mole % 1 ,4-cyclohexanedimethanol, and 20 to 40 mole % ethylene glycol; 40 to 65 mole % 2, 2, 4, 4-tetramethyl-1 ,3-cyclobutanediol, 10 to 30 mole % 1,4-cyclohexanedimethanol, and 5 to 50 mole % ethylene glycol; 40 to 65 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 10 to 30 mole % 1,4-cyclohexanedimethanol, and 10 to 40 mole % ethylene glycol; 40 to 65 mole % 2, 2, 4, 4-tetramethyl-1 ,3-cyclobutanediol, 10 to 30 mole % 1,4-cyclohexanedimethanol, and 20 to 40 mole % ethylene glycol; 40 to 65 mole % 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol, 20 to 40 mole % 1 ,4-cyclohexanedimethanol, and 1 to 40 mole % ethylene glycol; 40 to 65 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 20 to 40 mole % 1,4-cyclohexanedimethanol, and 10 to 40 mole % ethylene glycol; 40 to 65 mole % 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol, 20 to 40 mole % 1 ,4-cyclohexanedimethanol, and 20 to 40 mole % ethylene glycol.

[0073] In aspects of the invention, the glycol component for the polyesters useful in the invention includes but are not limited to at least one of the following combinations of ranges: 45 to 65 mole % 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol, 8 to 40 mole % 1,4-cyclohexanedimethanol, and 1 to 47 mole % ethylene glycol; 45 to 65 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 8 to 40 mole % 1 ,4-cyclohexanedimethanol, and 10 to 40 mole % ethylene glycol; 45 to 65 mole % 2, 2, 4, 4-tetramethyl-1 ,3-cyclobutanediol, 8 to 40 mole % 1 ,4-cyclohexanedimethanol, and 20 to 40 mole % ethylene glycol; 45 to 65 mole % 2, 2, 4, 4-tetramethyl-1 ,3-cyclobutanediol, 10 to 30 mole % 1,4-cyclohexanedimethanol, and 5 to 45 mole % ethylene glycol; 45 to 65 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 10 to 30 mole % 1,4-cyclohexanedimethanol, and 10 to 40 mole % ethylene glycol; 45 to 65 mole % 2, 2, 4, 4-tetramethyl-1 ,3-cyclobutanediol, 10 to 30 mole % 1,4-cyclohexanedimethanol, and 20 to 40 mole % ethylene glycol; 45 to 65 mole % 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol, 20 to 40 mole % 1 ,4-cyclohexanedimethanol, and 1 to 35 mole % ethylene glycol; 45 to 65 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 20 to 40 mole % 1,4-cyclohexanedimethanol, and 10 to 35 mole % ethylene glycol; 45 to 65 mole % 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol, 20 to 40 mole % 1 ,4-cyclohexanedimethanol, and 20 to 35 mole % ethylene glycol.

[0074] In aspects of the invention, the glycol component for the polyesters useful in the invention includes but are not limited to at least one of the following combinations of ranges: 45 to 60 mole % 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol, 8 to 40 mole % 1,4-cyclohexanedimethanol, and 1 to 47 mole % ethylene glycol; 45 to 60 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 8 to 40 mole % 1 ,4-cyclohexanedimethanol, and 10 to 40 mole % ethylene glycol; 45 to 60 mole % 2, 2, 4, 4-tetramethyl-1 ,3-cyclobutanediol, 8 to 40 mole % 1 ,4-cyclohexanedimethanol, and 20 to 40 mole % ethylene glycol; 45 to 60 mole % 2, 2, 4, 4-tetramethyl-1 ,3-cyclobutanediol, 10 to 30 mole % 1,4-cyclohexanedimethanol, and 10 to 45 mole % ethylene glycol; 45 to 60 mole % 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol, 10 to 30 mole % 1,4-cyclohexanedimethanol, and 10 to 40 mole % ethylene glycol; 45 to 60 mole % 2, 2, 4, 4-tetramethyl-1 ,3-cyclobutanediol, 10 to 30 mole % 1,4-cyclohexanedimethanol, and 20 to 40 mole % ethylene glycol; 45 to 60 mole % 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol, 20 to 40 mole % 1 ,4-cyclohexanedimethanol, and 1 to 35 mole % ethylene glycol; 45 to 60 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 20 to 40 mole % 1,4-cyclohexanedimethanol, and 10 to 35 mole % ethylene glycol; 45 to 60 mole % 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol, 20 to 40 mole % 1 ,4-cyclohexanedimethanol, and 20 to 35 mole % ethylene glycol.

[0075] In other aspects of the invention, the Tgof the amorphous copolyesters useful in the polyester compositions of the invention can include, but are not limited to greater than 115°C; or greater than 118°C; or greater than 120°C; or greater than 125°C; or greater than 130°C; or greater than 135°C; or greater than 140°C; 115 to 200° C; 115 to 195°C.; 115 to 190°C.; 115 to 185°C.; 115 to 180° C.; 115 to 175° C.; 115 to 170° C.; 115 to 165° C. 115 to 160°C.; 115 to 155°C.; 115 to 150°C.; 115 to 145°C.; 115 to 140°C.; 115 to 138°C.; 115 to 135°C.; 115 to 125°C.; 115 to 120°C.; 120 to 200°C.; 120 to 195°C.; 120 to 190°C.; 120 to 185° C. 120 to 180° C.; 120 to 175° C. 120 to 170° C.; 120 to 165°C.; 120 to 160°C.; 120 to 155°C.; 120 to 150°C.; 120 to 145°C.; 120 to 140°C.; 120 to 138°C.; 120 to 135°C.; 125 to 180° C.; 125 to 170° C.; 125 to 160° C.; 125 to 155° C.; 125 to 150° C.; 125 to 145° C.; 125 to 140° C.; 125 to 138° C.; 125 to 135°C.; 135 to 180°C.; 127 to 180°C.; 127 to 170°C.; 127 to 160°C.; 127 to 150°C.; 127 to 145°C.; 127 to 140°C.; 127 to 138° C.; 127 to 135° C.; 130 to 200° C.; 130 to 195° C.; 130 to 190°C.; 130 to 185°C.; 130 to 180°C.; 130 to 175°C.; 130 to 170° C.; 130 to 165° C. 130 to 160° C.; 130 to 155° C.; 130 to 150°C.; 130 to 145°C.; 130 to 140°C.; 130 to 138°C.; 130 to 135°C.; 135 to 170°C.; 135 to 160°C.; 135 to 155°C.; 135 to 150° C.; 135 to 145° C.; 135 to 140° C.; 135 to 135° C.; 140 to 200° C.; 140 to 195°C.; 140 to 190°C. ; 140 to 185°C. ; 140 to 180°C. ; 140 to 170°C. ; 140 to 165°C. ; 140 to 160°C.; 140 to 155° C.; 140 to 150° C.; 140 to 145° C.; 148 to 200° C.; 148 to 190°C.; 148 to 180°C.; 148 to 170°C.; 148 to 160°C.; 148 to 155° C.; 148 to 150° C.; 150 to 200° C.; 150 to 195° C.; 150 to 190°C.; 150 to 185°C.; 150 to 180°C. ; 150 to 175°C. ; 150 to 170°C. ; 150 to 165°C. ; 150 to 160°C. ; 150 to 155°C. ; 155 to 200°C. ; 155 to 190°C. ; 155 to 180°C. ; 155 to 170°C. ; 155 to 160; 155 to 190° C.; 155 to 180° C.; 155 to 170° C.; and 155 to 165° C.; greater than 124° C. up to 200° C.; greater than 125° C. up to 200° C.; greater than 126° C. up to 200° C. ; greater than 148° C. up to 200° C.

[0076] In other aspects of the invention, the heat deflection temperature of the amorphous copolyesters useful in the polyester compositions of the invention is 100°C or greater measured according to ASTM D648 at 0.455 MPa and / or 85°C or greater measured according to ASTM D648 at 1.82 MPa. The heat deflection temperature (HDT) was determined according to ASTM D648 using a 3.2mm thick injection molded bar and 1.82 or 0.455 MPa applied stress. Samples were conditioned for 48 hrs at 23°C and 50%RH prior to testing.

[0077] In embodiments, the heat deflection temperature of the copolyester composition measured according to ASTM D648 at 0.455 MPa is greater than 100°C; or greater than 105°C; or greater than 110°C; or greater than 115°C; or greater than 120°C; 100 to 130° C; 100 to 125°C. ; 100 to 120°C. ; 100 to 115°C.; 100 to 110°C.; 100 to 105° C.; 105 to 130° C.; 105 to 125° C.; or 105 to 120°C. ; 105 to 115°C. ; 105 to 110°C. ; or 110 to 130°C. ; or 110 to 125°C. ; 110 to 120° C.; 110 to 115° C.; 115 to 130° C.; 115 to 125° C.; or 115 to 120° C; or 120 to 130°C.; or 120 to 125°C.; or 125 to 130°C.

[0078] In embodiments, the heat deflection temperature of the copolyester composition measured according to ASTM D648 at 1.82 MPa is greater than 85°C; or greater than 90°C; or greater than 95°C; or greater than 100°C; or greater than 105°C; 85 to 110° C; 85 to 105°C.; 85 to 100°C.; 85 to 95° C.; 85 to 90° C.; or 90 to 110° C; 90 to 105°C.; 90 to 100°C.; 90 to 95° C.; 95 to 110° C.; 95 to 105°C.; 95 to 100°C.; 100 to 110° C.; 100 to 105° C.; or 105 to 110°C.

[0079] For certain embodiments of the invention, the polyesters may exhibit any of the following inherent viscosities as determined in 60 / 40 (wt / wt) phenol / tetrachloroethane at a concentration of 0.25 g / 50 ml at 25° C.: 0.35 to less than 0.70 dL / g; 0.35 to 0.68 dL / g; 0.35 to less than 0.68 dL / g; 0.35 to 0.65 dL / g.; 0.40 to 0.70 dL / g; 0.40 to less than 0.70 dL / g; 0.40 to 0.68 dL / g; 0.40 to less than 0.68 dL / g; 0.40 to 0.65 dL / g.; 0.45 to less than 0.70 dL / g; 0.45 to 0.68 dL / g; 0.45 to less than 0.68 dL / g; 0.45 to 0.65 dL / g; 0.50 to less than 0.70 dL / g; 0.50 to 0.68 dL / g; 0.50 to less than 0.68 dL / g; 0.50 to 0.67 dL / g; 0.50 to 0.66 dL / g; 0.50 to 0.65 dL / g; 0.55 to less than 0.70 dL / g; 0.55 to 0.68 dL / g; 0.55 to less than 0.68 dL / g; 0.55 to 0.65 dL / g; 0.58 to less than 0.70 dL / g; 0.58 to 0.68 dL / g; 0.58 to less than 0.68 dL / g; or 0.58 to 0.65 dL / g.

[0080] For embodiments of the invention where the inherent viscosity ranges from 0.35 to 1.0dL / g, these polyesters may also exhibit any of the following inherent viscosities as determined in 60 / 40 (wt / wt) phenol / tetrachloroethane at a concentration of 0.25 g / 50 ml at 25° C.: 0.35 to 0.98 dL / g; 0.35 to 0.95 dL / g; 0.35 to 0.9 dL / g; 0.35 to 0.85 dL / g; 0.35 to 0.8 dL / g; 0.35 to 0.75 dL / g; 0.35 to less than 0.75 dL / g; 0.35 to 0.72 dL / g; 0.40 to 1.0 dL / g; 0.40 to less than i dL / g; 0.40 to 0.98 dL / g; 0.40 to 0.95 dL / g; 0.40 to 0.9 dL / g; 0.40 to 0.85 dL / g; 0.40 to 0.8 dL / g; 0.40 to 0.75 dL / g; 0.40 to less than 0.75 dL / g; 0.40 to 0.72 dL / g; greater than 0.42 to 1.0 dL / g; 0.42 to less than 1 dL / g; greater than 0.42 to 0.98 dL / g; greater than 0.42 to 0.95 dL / g; greater than 0.42 to 0.9 dL / g; greater than 0.42 to 0.85 dL / g; greater than 0.42 to 0.80 dL / g; greater than 0.42 to 0.75 dL / g; greater than 0.42 to less than 0.75 dL / g; 0.42 to 0.70 dL / g; 0.42 to less than 0.70 dL / g; greater than 0.42 to 0.72 dL / g; greater than 0.42 to 0.70 dL / g; greater than 0.42 to 0.68 dL / g; greater than 0.42 to less than 0.68 dL / g; 0.42 to 0.68 dL / g; greater than 0.42 to 0.65 dL / g; 0.45to 1 dL / g; 0.45 to 0.98 dL / g; 0.45 to 0.95 dL / g; 0.45 to 0.9 dL / g; 0.45 to 0.85 dL / g; 0.45 to 0.80 dL / g; 0.45 to 0.75 dL / g; 0.45 to less than 0.75 dL / g; 0.45 to 0.72 dL / g; 0.45 to 0.70 dL / g; 0.50 to 1 dL / g; 0.50 to less than 1 dL / g; 0.50 to 0.98 dL / g; 0.50 to 0.95 dL / g; 0.50 to 0.9 dL / g; 0.50 to 0.85 dL / g; 0.50 to 0.80 dL / g.; 0.50 to 0.75 dL / g; 0.50 to less than 0.75 dL / g; 0.50 to 0.72 dL / g; 0.50 to 0.70 dL / g; 0.55 to 1 dL / g; 0.55 to less than 1 dL / g; 0.55 to 0.98 dL / g; 0.55 to 0.95 dL / g; 0.55 to 0.9 dL / g; 0.55 to 0.85 dL / g; 0.55 to 0.80 dL / g; 0.55 to 0.75 dL / g; 0.55 to less than 0.75 dL / g; 0.55 to 0.72 dL / g; 0.55 to 0.70 dL / g; 0.58to 1 dL / g;0.58 to less than 1 dL / g; 0.58 to 0.98 dL / g; 0.58 to 0.95 dL / g; 0.58 to 0.9 dL / g; 0.58 to 0.85 dL / g; 0.58 to 0.80 dL / g; 0.58 to 0.75 dL / g; 0.58 to less than 0.75 dL / g; 0.58 to 0.72 dL / g; 0.58 to 0.70 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; 0.60 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 dL / g; 0.65 to less than 1 dL / g; 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; 0.65 to less than 0.70 dL / g; 0.68 to 1 dL / g; 0.68 to less than 1 dL / g; 0.68 to 0.98 dL / g; 0.68 to 0.95 dL / g; 0.68 to 0.90 dL / g; 0.68 to 0.85 dL / g; 0.68 to 0.80 dL / g; 0.68 to 0.75 dL / g; 0.68 to less than 0.75 dL / g; 0.68 to 0.72 dL / g; greater than 0.76 dL / g to 1 dL / g; greater than 0.76 dL / g to less than 1 dL / g; greater than 0.76 dL / g to 0.98 dL / g; greater than 0.76 dL / g to 0.95 dL / g; greater than 0.76 dL / g to 0.90 dL / g; greater than 0.80 dL / g to 1 dL / g; greater than 0.80 dL / g to less than 1 dL / g; greater than 0.80 dL / g to 0.98 dL / g; greater than 0.80 dL / g to 0.95 dL / g; greater than 0.80 dL / g to 0.90 dL / g.

[0081] In one embodiment, terephthalic acid may be used as the starting material. In another embodiment, dimethyl terephthalate may be used as the starting material. In another embodiment, mixtures of terephthalic acid and dimethyl terephthalate may be used as the starting material and / or as an intermediate material.

[0082] In certain embodiments, terephthalic acid or an ester thereof, such as, for example, dimethyl terephthalate or a mixture of terephthalic acid residues and an ester thereof can make up a portion or all of the dicarboxylic acid component used to form the polyesters useful in the invention. In certain embodiments, terephthalic acid residues can make up a portion or all of the dicarboxylic acid component used to form the polyesters useful in the invention. In certain embodiments, higher amounts of terephthalic acid can be used in order to produce a higher impact strength polyester. For purposes of this disclosure, the terms “terephthalic acid” and “dimethyl terephthalate” are used interchangeably herein. In one embodiment, dimethyl terephthalate is part, or all of the dicarboxylic acid component used to make the polyesters useful in the present invention. In embodiments, ranges of from 70 to 100 mole %; or 80 to 100 mole %; or 90 to 100 mole %; or 99 to 100 mole %; or 100 mole % terephthalic acid and / or dimethyl terephthalate and / or mixtures thereof may be used.

[0083] In addition to terephthalic acid, the dicarboxylic acid component of the polyesters useful in the invention can comprise up to 10 mole %, up to 5 mole %, or up to 1 mole % of one or more modifying aromatic dicarboxylic acids. Yet another embodiment contains 0 mole % modifying aromatic dicarboxylic acids. Thus, if present, it is contemplated that the amount of one or more modifying aromatic dicarboxylic acids can range from any of these preceding endpoint values including, for example, 0.01 to 10 mole %, from 0.01 to 5 mole % and from 0.01 to 1 mole %. In one embodiment, modifying aromatic dicarboxylic acids that may be used in the present invention include but are not limited to those having up to 20 carbon atoms, and which can be linear, para-oriented, or symmetrical. Examples of modifying aromatic dicarboxylic acids which may be used in this invention include, but are not limited to, isophthalic acid, 4,4'-biphenyldicarboxylic acid, 1,4-, 1,5-, 2,6-, 2,7-naphthalenedicarboxylic acid, and trans-4,4'-stilbenedicarboxylic acid, and esters thereof. In one embodiment, the modifying aromatic dicarboxylic acid is isophthalic acid.

[0084] The carboxylic acid component of the polyesters useful in the invention can be further modified with up to 10 mole %, such as up to 5 mole % or up to 1 mole % of one or more aliphatic dicarboxylic acids containing 2-16 carbon atoms, such as, for example, cyclohexanedicarboxylic, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic and dodecanedioic dicarboxylic acids. Certain embodiments can also comprise 0.01 to 10 mole %, such as 0.1 to 10 mole %, 1 or 10 mole %, 5 to 10 mole % of one or more modifying aliphatic dicarboxylic acids. Yet another embodiment contains 0 mole % modifying aliphatic dicarboxylic acids. The total mole % of the dicarboxylic acid component is 100 mole %. In one embodiment, adipic acid and / or glutaric acid are provided in the modifying aliphatic dicarboxylic acid component of the invention. Esters of terephthalic acid and the other modifying dicarboxyhc acids or their corresponding esters and / or salts may be used instead of the dicarboxylic acids. Suitable examples of dicarboxylic acid esters include, but are not limited to, the dimethyl, diethyl, dipropyl, diisopropyl, dibutyl, and diphenyl esters. In one embodiment, the esters are chosen from at least one of the following: methyl, ethyl, propyl, isopropyl, and phenyl esters.

[0085] For the desired polyester, the molar ratio of cis / trans 2 ,2 ,4,4-tetramethyl-1,3-cyclobutanediol can vary from the pure form of each and mixtures thereof. In certain embodiments, the molar percentages for cis and / or trans 2,2,4,4,-tetramethyl-1 ,3-cyclobutanediol are greater than 50 mole % cis and less than 50 mole % trans; or greater than 55 mole % cis and less than 45 mole % trans; or 50 to 70 mole % cis and 50 to 30 mole % trans; or 60 to 70 mole % cis and 30 to 40 mole % trans; or greater than 70 mole % cis and less than 30 mole % trans; wherein the total mole percentages for cisand trans-2, 2, 4, 4-tetramethyl-1 ,3-cyclobutanediol is equal to 100 mole %. In an additional embodiment, the molar ratio of cis / trans 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol can vary within the range of 50 / 50 to 0 / 100, for example, between 40 / 60 to 20 / 80.

[0086] In one embodiment, the glycol component of the polyester portion of the polyester compositions useful in the invention can contain up to 30 mole % of one or more modifying glycols which are not 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol, 1 ,4-cyclohexanedimethanol or ethylene glycol. In one embodiment, the glycol component of the polyester portion of the polyester compositions useful in the invention can contain up to 10 mole %, or 9 mole %, or 8 mole %, or 7 mole %, or 6 mole %, or less of one or more modifying glycols which are not 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1 ,4-cyclohexanedimethanol or ethylene glycol. In one embodiment, the glycol component of the polyester portion of the polyester compositions useful in the invention can contain up to 5 mole %, or 4 mole %, or 3 mole %, or 2 mole %, or 1 mole %, or less of one or more modifying glycols which are not 2, 2,4,4-tetramethyl-1 ,3-cyclobutanediol, 1 ,4-cyclohexanedimethanol or ethylene glycol. In certain embodiments, the polyesters useful in the invention can contain 3 mole % or less of one or more modifying glycols. In another embodiment, the polyesters useful in the invention can contain 2 mole % or less of one or more modifying glycols. In another embodiment, the polyesters useful in the invention can contain 0 mole % modifying glycols. It is contemplated however that some other glycol residuals may form in situ. For example, a certain amount of DEG will typically form in situ during the polymerization reactions. In some embodiments, DEG can be intentionally added as a monomer to the reaction mixture, and in other embodiments no DEG is intentionally added, but a small amount of DEG residues may be present in the final copolymer due to in situ formation.

[0087] In embodiments, modifying glycols for use in the polyesters can include diols other than 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol, 1 ,4-cyclohexanedimethanol and ethylene glycol and can contain 2 to 16 carbon atoms. Examples of modifying glycols include, but are not limited to, diethylene glycol, 1 ,2-propanediol, 1 ,3-propanediol, neopentyl glycol, 1,4-butanediol, 1 ,5-pentanediol, 1 ,6-hexanediol, p-xylene glycol, polytetramethylene glycol, and mixtures thereof. In another embodiment, the modifying glycols include, but are not limited to, at least one of 1 ,3-propanediol and 1 ,4-butanediol. In one embodiment, at least one modifying glycol is diethylene glycol. In one embodiment, the diethylene glycol is not added as a separate monomer but is formed during polymerization.

[0088] In some embodiments, the polyesters according to the invention can comprise from 0 to 10 mole percent, for example, from 0.01 to 5 mole percent, from 0.01 to 1 mole percent, from 0.05 to 5 mole percent, from 0.05 to 1 mole percent, or from 0.1 to 0.7 mole percent, based the total mole percentages of either the diol or diacid residues; respectively, of one or more residues of a branching monomer, also referred to herein as a branching agent, having 3 or more carboxyl substituents, hydroxyl substituents, or a combination thereof. In certain embodiments, the branching monomer or agent may be added prior to and / or during and / or after the polymerization of the polyester. In embodiments, the polyester(s) useful in the invention can thus be linear or branched. Examples of branching monomers include, but are not limited to, multifunctional acids or multifunctional 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 can comprise 0.1 to 0.7 mole percent of one or more residues chosen from at least one of the following: trimellitic anhydride, pyromellitic dianhydride, glycerol, sorbitol, 1 ,2,6-hexanetriol, pentaerythritol, trimethylolethane, and / or trimesic acid. The branching monomer may be added to the polyester reaction mixture or blended with the polyester in the form of a concentrate as described, for example, in U.S. Pat. Nos. 5,654,347 and 5,696,176, whose disclosure regarding branching monomers is incorporated herein by reference.

[0089] In one embodiment, certain polyesters useful in this invention can be visually clear. The term “visually clear” is defined herein as an appreciable absence of cloudiness, haziness, and / or muddiness, when inspected visually.

[0090] In one embodiment, the polyesters useful in the invention and / or the polyester compositions of the invention can have color values L* a* and b* which can be determined using a Hunter Lab Ultrascan Spectra Colorimeter manufactured by Hunter Associates Lab Inc., Reston, Va. The color determinations are averages of values measured on either pellets of the polyesters or plaques or other items injection molded or extruded from them. They are determined by the L*a*b* color system of the CIE (International Commission on Illumination) (translated), wherein L* represents the lightness coordinate, a* represents the red / green coordinate, and b* represents the yellow / blue coordinate. In various embodiments, the color values can be determined for polymers having the presence of and / or in the absence of toner(s).

[0091] In one embodiment, phosphorus compound(s) can be added to improve color of the copolyester composition. The phosphorus compound(s) can be an organic compound such as, for example, a phosphorus acid ester containing halogenated or non-halogenated organic substituents. In embodiments, the phosphorus compound(s) can comprise a wide range of phosphorus compounds, for example, phosphines, phosphites, phosphimtes, phosphonites, phosphinates, phosphonates, phosphine oxides, and phosphates.

[0092] Examples of phosphorus compounds that may be useful in the invention can include tributyl phosphate, triethyl phosphate, tri-butoxyethyl phosphate, t-butylphenyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, ethyl dimethyl phosphate, isodecyl diphenyl phosphate, trilauryl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, t-butylphenyl diphenylphosphate, resorcinol bis(diphenyl phosphate), tribenzyl phosphate, phenyl ethyl phosphate, trimethyl thionophosphate, phenyl ethyl thionophosphate, dimethyl methylphosphonate, diethyl methylphosphonate, diethyl pentylphosphonate, dilauryl methylphosphonate, diphenyl methylphosphonate, dibenzyl methylphosphonate, diphenyl cresylphosphonate, dimethyl cresylphosphonate, dimethyl methylthionophosphonate, phenyl diphenylphosphinate, benzyl diphenylphosphinate, methyl diphenylphosphinate, trimethyl phosphine oxide, triphenyl phosphine oxide, tribenzyl phosphine oxide, 4-methyl diphenyl phosphine oxide, triethyl phosphite, tributyl phosphite, trilauryl phosphite, triphenyl phosphite, tribenzyl phosphite, phenyl diethyl phosphite, phenyl dimethyl phosphite, benzyl dimethyl phosphite, dimethyl methylphosphonite, diethyl pentylphosphonite, diphenyl methylphosphonite, dibenzyl methylphosphonite, dimethyl cresylphosphonite, methyl dimethylphosphinite, methyl diethylphosphinite, phenyl diphenylphosphinite, methyl diphenylphosphinite, benzyl diphenylphosphinite, triphenyl phosphine, tribenzyl phosphine, and methyl diphenyl phosphine. In one embodiment, triphenyl phosphine oxide is excluded as a thermal stabilizer in the process(es) of making the polyesters of the invention and / or in the polyester composition(s) of the invention.

[0093] In one embodiment, phosphorus compounds useful in the invention can be any of the previously described phosphorus-based acids wherein one or more of the hydrogen atoms of the acid compound (bonded to either oxygen or phosphorus atoms) are replaced with alkyl, branched alkyl, substituted alkyl, alkyl ethers, substituted alkyl ethers, alkyl-aryl, alkylsubstituted aryl, aryl, substituted aryl, and mixtures thereof. In another embodiment, phosphorus compounds useful in the invention, include but are not limited to, the above described compounds wherein at least one of the hydrogen atoms bonded to an oxygen atom of the compound is replaced with a metallic ion or an ammonium ion.

[0094] The esters can contain alkyl, branched alkyl, substituted alkyl, alkyl ethers, aryl, and / or substituted aryl groups. The esters can also have at least one alkyl group and at least one aryl group. The number of ester groups present in the particular phosphorus compound can vary from zero up to the maximum allowable based on the number of hydroxyl groups present on the phosphorus compound used. For example, an alkyl phosphate ester can include one or more of the mono-, di-, and tri alkyl phosphate esters; an aryl phosphate ester includes one or more of the mono-, di-, and tri aryl phosphate esters; and an alkyl phosphate ester and / or an aryl phosphate ester also include, but are not limited to, mixed alkyl aryl phosphate esters having at least one alkyl and one aryl group.

[0095] In one embodiment, the phosphorus compounds useful in the invention include but are not limited to alkyl, aryl or mixed alkyl aryl esters or partial esters of phosphoric acid, phosphorus acid, phosphinic acid, phosphonic acid, or phosphonous acid. The alkyl or aryl groups can contain one or more substituents.

[0096] In one aspect, the phosphorus compounds useful in the invention comprise at least one phosphorus compound chosen from at least one of substituted or unsubstituted alkyl phosphate esters, substituted or unsubstituted aryl phosphate esters, substituted or unsubstituted mixed alkyl aryl phosphate esters, diphosphites, salts of phosphoric acid, phosphine oxides, and mixed aryl alkyl phosphites, reaction products thereof, and mixtures thereof. The phosphate esters include esters in which the phosphoric acid is fully esterified or only partially esterified.

[0097] In one embodiment, for example, the phosphorus compounds useful in the invention can include at least one phosphate ester. In one aspect, the phosphorus compounds useful in the invention comprise at least one phosphorus compound chosen from at least one of substituted or unsubstituted alkyl phosphate esters, substituted or unsubstituted aryl phosphate esters, substituted or unsubstituted mixed alkyl aryl phosphate esters, reaction products thereof, and mixtures thereof. The phosphate esters include esters in which the phosphoric acid is fully esterified or only partially esterified.

[0098] In one embodiment, for example, the phosphorus compounds useful in the invention can include at least one phosphate ester.

[0099] In another embodiment, the phosphate esters useful in the invention can include but are not limited to alkyl phosphate esters, aryl phosphate esters, mixed alkyl aryl phosphate esters, and / or mixtures thereof.

[0100] In certain embodiments, the phosphate esters useful in the invention are those where the groups on the phosphate ester include are alkyl, alkoxyalkyl, phenyl, or substituted phenyl groups. These phosphate esters are generally referred to herein as alkyl and / or aryl phosphate esters. Certain preferred embodiments include trialkyl phosphates, triaryl phosphates, alkyl diaryl phosphates, dialkyl aryl phosphates, and mixtures of such phosphates, wherein the alkyl groups are preferably those containing from 2 to 12 carbon atoms, and the aryl groups are preferably phenyl.

[0101] Representative alkyl and branched alkyl groups are preferably those containing from 1-12 carbon atoms, including, but not limited to, ethyl, propyl, isopropyl, butyl, hexyl, cyclohexyl, 2-ethylhexyl, octyl, decyl and dodecyl. Substituted alkyl groups include, but are not limited to, those containing at least one of carboxylic acid groups and esters thereof, hydroxyl groups, amino groups, keto groups, and the like.

[0102] Representative of alky l-ary I and substituted alky l-ary I groups are those wherein the alkyl portion contains from 1-12 carbon atoms, and the aryl group is phenyl or substituted phenyl wherein groups such as alkyl, branched alkyl, aryl, hydroxyl, and the like are substituted for hydrogen at any carbon position on the phenyl ring. Preferred aryl groups include phenyl or substituted phenyl wherein groups such as alkyl, branched alkyl, aryl, hydroxyl and the like are substituted for hydrogen at any position on the phenyl ring.

[0103] In one embodiment, the phosphate esters useful in the invention include but are not limited to dibutylphenyl phosphate, triphenyl phosphate, tricresyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, trioctyl phosphate, and / or mixtures thereof, including particularly mixtures of tributyl phosphate and tricresyl phosphate, and mixtures of isocetyl diphenyl phosphate and 2-ethylhexyl diphenyl phosphate.

[0104] In one embodiment, at least one phosphorus compound useful in the invention comprises at least one aryl phosphate ester.

[0105] In one embodiment, at least one phosphorus compound useful in the invention comprises at least one unsubstituted aryl phosphate ester.

[0106] In one aspect, at least one phosphorus compound useful in the invention comprises at least one aryl phosphate ester which is not substituted with benzyl groups.

[0107] In one aspect, any of the phosphorus compounds useful in the invention may comprise at least one alkyl phosphate ester.

[0108] In one embodiment, the phosphate esters useful in the invention as thermal stabilizers and / or color stabilizers include but are not limited to, at least one of the following: trialkyl phosphates, triaryl phosphates, alkyl diaryl phosphates, and mixed alkyl aryl phosphates.

[0109] In one embodiment, the phosphate esters useful in the invention as thermal stabilizers and / or color stabilizers include but are not limited to, at least one of the following: triaryl phosphates, alkyl diaryl phosphates, and mixed alkyl aryl phosphates.

[0110] In one embodiment, the phosphate esters useful as thermal stabilizers and / or color stabilizers in the invention can include but are not limited to, at least one of the following: triaryl phosphates and mixed alkyl aryl phosphates.

[0111] In one embodiment, at least one phosphorus compound useful in the invention can comprise, but is not limited to, triaryl phosphates, such as, for example, triphenyl phosphate. In one embodiment, at least one thermal stabilizer comprises, but is not limited to Merpol A. In one embodiment, at least one thermal stabilizer useful in the invention comprises, but is not limited to, at least one of tripheny I phosphate and Merpol A. Merpol A is a phosphate ester commercially available from Stepan Chemical Co and / or E.l. duPont de Nemours & Co. The CAS Registry number for Merpol A is believed to be CAS Registry #37208-27-8.

[0112] In one aspect, any of the phosphorus compounds useful in the invention may comprise at least one triaryl phosphate ester which is not substituted with benzyl groups.

[0113] In one embodiment, the polyester compositions and / or processes of the invention may comprise 2-ethylhexyl diphenyl phosphate.

[0114] In one embodiment, any of the processes described herein for making any of the polyester compositions and / or polyesters can comprise at least one mixed alkyl aryl phosphite, such as, for example, bis(2,4-dicumylphenyl)pentaerythritol diphosphite also known as Doverphos S-9228 (Dover Chemicals, CAS#15486243-8).

[0115] In one embodiment, any of the processes described herein for making any of the polyester compositions and / or polyesters can comprise at least one phosphine oxide.

[0116] In one embodiment, any of the processes described herein for making any of the polyester compositions and / or polyesters can comprise at least one salt of phosphoric acid such as, for example, KH2PO4and Zn3(PO4)2.

[0117] The term “thermal stabilizer” is intended to include the reaction product(s) thereof. The term “reaction product” as used in connection with the thermal stabilizers of the invention refers to any product of a polycondensation or esterification reaction between the thermal stabilizer and any of the monomers used in making the polyester as well as the product of a polycondensation or esterification reaction between the catalyst and any other type of additive.

[0118] In one embodiment of the invention, the phosphorus compounds useful in the invention may act as thermal stabilizers. In one embodiment of the invention, the phosphorus compounds useful in the invention may not act as a thermal stabilizer but may act as a color stabilizer. In one embodiment of the invention, the phosphorus compounds useful in the invention may act as both a thermal stabilizer and a color stabilizer.

[0119] When phosphorus is added to the polyesters and / or polyester compositions and / or process of making the polyesters of the invention, it is added in the form of a phosphorus compound, for example, at least one phosphate ester(s). The amount of phosphorus compound(s), (for example, at least one phosphate ester), is added to the polyesters of the invention and / or polyester compositions of the invention and / or processes of the invention can be measured in the form of phosphorus atoms present in the final polyester, for example, by weight measured in ppm.

[0120] In one embodiment, amounts of the phosphate ester of the invention added during polymerization are chosen from the following: 10 to 200 ppm based on the total weight of the polyester composition and as measured in the form of phosphorus atoms in the final polyester. In embodiments of the invention, phosphorus can be present in an amount of 5 to 100, or 5 to 80, or 10 to 80, or 10 to 75, or 10 to 70, or 10 to 65 ppm, based on the total weight of the polyester composition and as measured in the form of phosphorus atoms in the final polyester.

[0121] In embodiments of the invention, certain agents which colorize the polymer can be added to the melt. In one embodiment, a bluing toner is added to the melt in order to reduce the b* of the resulting polyester polymer melt phase product. Such bluing agents include blue inorganic and organic toner(s). In addition, red toner(s) can also be used to adjust the a* color.

[0122] Organic toner(s), e.g., blue and red organic toner(s), such as those toner(s) described in U.S. Pat. Nos. 5,372,864 and 5,384,377, which are incorporated by reference in their entirety, can be used. The organic toner(s) can be fed as a premix composition. The premix composition may be a neat blend of the red and blue compounds, or the composition may be pre-dissolved or slurried in one of the polyester's raw materials, e.g., ethylene glycol.

[0123] The total amount of toner components added can depend on the amount of inherent yellow color in the base polyester and the efficacy of the toner. In one embodiment, a concentration of up to about 15 ppm of combined organic toner components and a minimum concentration of about 0.5 ppm are used. In one embodiment, the total amount of bluing additive can range from 0.5 to 10 ppm. In an embodiment, the toner(s) can be added to the esterification zone or to the polycondensation zone. Preferably, the toner(s) are added to the esterification zone or to the early stages of the polycondensation zone, such as to a prepolymerization reactor.

[0124] The invention further relates to a polymer blend. In embodiments, the blend comprises:

[0125] (a) from 5 to 95 weight % of at least one of the polyesters described above; and

[0126] (b) from 5 to 95 weight % of at least one of the polymeric components. Suitable examples of the polymeric components include, but are not limited to, nylon; polyesters different than those described herein such as PET; polyamides such as ZYTEL® from DuPont; polystyrene; polystyrene copolymers; styrene acrylonitrile copolymers; acrylonitrile butadiene styrene copolymers; poly(methylmethacrylate); acrylic copolymers; poly(ether-imides) such as ULTEM® (a poly(ether-imide) from General Electric); polyphenylene oxides such as poly(2,6-dimethylphenylene oxide) or poly(phenylene oxide) / polystyrene blends such as NORYL 1000® (a blend of poly(2,6-dimethylphenylene oxide) and polystyrene resins from General Electric); polyphenylene sulfides; polyphenylene sulfide / sulfones; polyestercarbonates); polycarbonates such as LEXAN® (a polycarbonate from General Electric); polysulfones; polysulfone ethers; and poly(ether-ketones) of aromatic dihydroxy compounds; or mixtures of any of the foregoing polymers. The blends can be prepared by conventional processing techniques known in the art, such as melt blending or solution blending.

[0127] In embodiments, the polyester compositions and the polymer blend compositions can also contain from 0.01 to 25% by weight of the overall composition common additives such as colorants, toner(s), dyes, mold release agents, flame retardants, plasticizers, nucleating agents, stabilizers, including but not limited to, UV stabilizers, thermal stabilizers other than the phosphorus compounds describe herein, and / or reaction products thereof, fillers, and impact modifiers. Examples of commercially available impact modifiers include, but are not limited to, ethylene / propylene terpolymers, functionalized polyolefins such as those containing methyl acrylate and / or glycidyl methacrylate, styrene-based block copolymeric impact modifiers, and various acrylic core / shell type impact modifiers. Residues of such additives are also contemplated as part of the polyester composition.

[0128] Reinforcing materials may be added to the compositions of this invention. The reinforcing materials may include, but are not limited to, carbon filaments, silicates, mica, clay, talc, titanium dioxide, Wollastonite, glass flakes, glass beads and fibers, and polymeric fibers and combinations thereof. In one embodiment, the reinforcing materials include glass, such as, fibrous glass filaments, mixtures of glass and talc, glass and mica, and glass and polymeric fibers.

[0129] In one aspect, the invention relates to thermoplastic articles comprising the polyester compositions and / or polymer blends of the invention. In certain embodiments, the invention relates to film(s) and / or sheets comprising the polyester compositions and / or polymer blends of the invention. Methods of forming the polyesters and / or blends into film(s) and / or sheet(s) are well known in the art. Examples of film(s) and / or sheet(s) of the invention can include, without limitation, extruded film(s) and / or sheet(s), calendered film(s) and / or sheet(s), compression molded film(s) and / or sheet(s), solution casted film(s) and / or sheet(s), shrink films, pressure sensitive labels, stretched or stretchable films or sheets, uniaxially or biaxially oriented films, and / or multiwall films or sheets. Methods of making film and / or sheet include but are not limited to extrusion, calendering, compression molding, and solution casting.

[0130] In one embodiment, polyester compositions containing TMCD, CHDM and EG that provide improved calendering processes without the need for a branching monomer or branching agent are provided. In embodiments, the polyester compositions for calendering comprise: (a) at least one polyester comprising diacid residues, diol residues in which the polyester has a crystallization half time of at least 5 minutes and an inherent viscosity of about 0.50 to about 0.80 dL / g; and (b) at least one release additive effective to prevent sticking of the polyester to calendering rolls. It is believed the polyester compositions of the present disclosure have an unexpected combination of excellent melt strength and melt viscosity with a good shear response that allows higher calendering line speeds before melt fracture occurs. Higher calendering line speeds, in turn, provides for more economical production of polyester sheet or film in commercial applications. In various embodiments, any of the types and / or amounts of diacid residues and diol residues discussed herein can be used for the polyester calendering compositions. In one embodiment, the polyester calendering composition does not contain any branching monomers or agents.

[0131] In one aspect, the invention relates to injection molded and / or blow molded articles comprising the polyester compositions and / or polymer blends of the invention.

[0132] In embodiments of the invention, certain polyesters and / or polyester compositions of the invention can have a unique combination of all of the following properties: certain notched Izod impact strength, certain inherent viscosities, certain glass transition temperature (Tg), certain flexural modulus, good clarity, good color, and good thermal stability.

[0133] In one embodiment, the processes of making the polyesters useful in the invention can comprise a batch or continuous process.

[0134] In one embodiment, the processes of making the polyesters useful in the invention comprise a continuous process.

[0135] In embodiments of the invention, the Tgof the polyesters can be chosen from one of the following ranges: 115 to 145°C; 115 to 140°C; 120 to 145°C; 120 to 140°C; 125 to 145°C; 125 to 140°C; 130 to 145°C; 130 to 140°C; 135 to 145°C; 135 to 140°C.

[0136] Because of the long crystallization half-times (e.g., greater than 5 minutes) at 170°C exhibited by certain polyesters useful in the present invention, it can be possible to produce articles, including but not limited to, injection molded parts, injection blow molded articles, injection stretch blow molded articles, extruded film, extruded sheet, calendered film, shrink films, pressure sensitive labels, stretched or stretchable films or sheets, umaxially or biaxially oriented films, multiwall films or sheets, extrusion blow molded articles, extrusion stretch blow molded articles, and fibers. A thermoformable sheet is an example of an article of manufacture provided by this invention. The polyesters of the invention can be amorphous or semicrystalline. In one aspect, certain polyesters useful in the invention can have relatively low crystallinity. Certain polyesters useful in the invention can thus have a substantially amorphous morphology, meaning that the polyesters comprise substantially unordered regions of polymer.

[0137] Notched Izod impact strength, as described in ASTM D256, is a common method of measuring toughness. Notched Izod impact strength is measured herein at 23°C with a 10-mil notch in a 3.2mm (1 / 8-inch) thick bar determined according to ASTM D256. In one embodiment, certain polyesters useful in the invention can exhibit a notched Izod impact strength of at least 50 J / m at 23°C with a 10-mil notch in a 3.2mm (1 / 8-inch) thick bar determined according to ASTM D256. In one embodiment, certain polyesters useful in the invention can exhibit a notched Izod impact strength of from about 50 J / m (0.56 ft-lb / in) to about 900 J / m, or 100 J / m to 850 J / m at 23°C with a 10-mil notch in a 3.2mm (1 / 8-inch) thick bar determined according to ASTM D256.

[0138] In one embodiment, certain polyesters useful in the invention can exhibit at least one of the following densities: a density of greater than 1.2 g / ml at 23°C.

[0139] In one embodiment, certain polyesters useful in the invention can exhibit a flexural modulus at 23°C less than 2000 MPa (about 290,000 psi) as defined by ASTM D790. In another embodiment, certain polyesters useful in the invention can exhibit a flexural modulus at 23°C from about 1700 MPa to less than 2000 MPa as defined by ASTM D790. In another embodiment, certain polyesters useful in the invention can exhibit a flexural modulus at 23°C from about 1700 MPa to about 1900 MPa (377,100 psi) as defined by ASTM D790.

[0140] Certain polyesters useful in the invention can possess at least one of the following properties: a Tgof from about 115 to about 145 °C as measured by a TA 2100 Thermal Analyst Instrument at a scan rate of 20°C / min; a flexural modulus at 23°C less than 2000 MPa (about 290,000 psi), as defined by ASTM D790; and a notched Izod impact strength equal to or greater than 50 J / m and less than 900 J / m according to ASTM D256 with a 10-mil notch using a 1 / 8-inch thick bar at 23°C.

[0141] In one embodiment, the melt viscosity of the polyester(s) useful in the invention can be less than 30,000 poise as measured a 1 radian / second on a rotary melt rheometer at 290°C. In another embodiment, the melt viscosity of the polyester(s) useful in the invention can be less than 20,000 poise as measured a 1 radian / second on a rotary melt rheometer at 290°C.

[0142] In one embodiment, the melt viscosity of the polyester(s) useful in the invention can be less than 15,000 poise as measured at 1 radian / second (rad / sec) on a rotary melt rheometer at 290°C. In one embodiment, the melt viscosity of the polyester(s) useful in the invention can be less than 12,000 poise as measured at 1 radian / second (rad / sec) on a rotary melt rheometer at 290°C. In one embodiment, the melt viscosity of the polyester(s) useful in the invention in can be less than 10,000 poise as measured at 1 radian / second (rad / sec) on a rotary melt rheometer at 290°C.

[0143] In some embodiments, use of the polyester compositions useful in the invention minimizes and / or eliminates the drying step prior to melt processing and / or thermoforming.

[0144] In certain embodiments, the polyester compositions and / or polymer blends of the invention can be used in one or more of the following applications: graphic arts film, multiwall film or sheets, extruded articles, appliance parts, and glass laminates.

[0145] Graphic art films can be used in a variety of applications, such as, for example, in-mold decorated articles, embossed articles, hard-coated articles. The graphic art film can be smooth or textured.

[0146] Multiwall film or sheet refers to sheet extruded as a profile consisting of multiple layers that are connected to each other by means of vertical ribs. Examples of multiwall film or sheet include but are not limited to outdoor shelters (for example, greenhouses and commercial canopies). Examples of extruded articles comprising the polyester compositions useful in this invention include, but are not limited to, profile extruded tubing or channels, extrusion blow molded bottles, thermoformed sheet, film for graphic arts applications, outdoor signs, skylights, multiwall film, plastic film for plastic glass laminates, and liquid crystal display (LCD) films, including but not limited to, diffuser sheets, compensation films, and protective films for LCDs.

[0147] In one embodiment, the present invention comprises a thermoplastic article, typically in the form of sheet material, having a decorative material embedded therein which comprise any of the compositions described herein.

[0148] “Outdoor sign,” as used herein, refers to a surface formed from the polyester described herein, or containing symbols (e.g., numbers, letters, words, pictures, etc.), patterns, or designs coated with the polyester or polyester film described herein. In one embodiment, the outdoor sign comprises a polyester containing printed symbols, patterns, or designs. In one embodiment, the sign is capable of withstanding typical weather conditions, such as rain, snow, ice, sleet, high humidity, heat, wind, sunlight, or combinations thereof, for a sufficient period of time, e.g., ranging from one day to several years or more.

[0149] “Appliance parts,” as used herein, refers to a rigid piece used in conjunction with an appliance. In one embodiment, the appliance part is partly or wholly separable from the appliance. In another embodiment, the appliance part is one that is typically made from a polymer. In one embodiment, the appliance part is visually clear.

[0150] Exemplary appliance parts include those requiring toughness and durability, such as cups and bowls used with food processors, mixers, blenders, and choppers; parts that can withstand refrigerator and freezer temperatures (e.g., refrigerator temperatures ranging from greater than 0°C (e.g., 2°C) to 5°C, or freezer temperatures, e.g., at temperatures less than 0°C, such as temperatures ranging from -20 to 0°C, e.g., -18°C), such as refrigerator and freezer trays, bins, and shelves; parts having sufficient hydrolytic stability at temperatures above 90°C, such as washing machine doors, steam cleaner canisters, tea kettles, and coffee pots; and vacuum cleaner canisters and dirt cups.

[0151] In one embodiment, these appliance parts have at least one property chosen from toughness, clarity, chemical resistance, Tg, hydrolytic stability, and dishwasher stability. The appliance part can also be chosen from steam cleaner canisters, which, in one embodiment, can have at least one property chosen from toughness, clarity, chemical resistance, Tg, and hydrolytic stability.

[0152] In one embodiment, the polyesters useful have a heat deflection temperature at 264 psi greater than 90°C.

[0153] Films

[0154] “Extruded film” means a film that has been made by an extrusion process. “Melt” means a polymer composition that is flowable that has been heated above its melting temperature or glass transition temperature.

[0155] The present application discloses films comprising the polyesters disclosed herein.

[0156] The present application discloses a film, comprising a polyester composition comprising at least one amorphous copolyester which comprises: (a) a dicarboxylic acid component comprising: (i) 90 to 100 mole % of terephthalic acid (“TPA”) residues; (ii) 0 to 10 mole % of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; and (b) a glycol component comprising: (i) 35 to 65 mole % of 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol (“TMCD”) residues, wherein the total mole % of the acid component (a) is 100 mole % and the total mole % of the glycol component (b) is 100 mole %, wherein the polyester exhibits an inherent viscosity (“IV”) in the range of from 0.5-0.7 dL / g in 60 / 40 (wt / wt) phenol / tetrachloroethan at a concentration of 0.5 g / 100 mL at 25°C, a glass transition temperature (“Tg”) in the range of from 110-150°C as determined using ASTM D3418 test method.

[0157] In one embodiment, or in combination with any other embodiment, the TPA residues are present at from 92 to 100 mole%, or from 94 to 100 mole%, or from 96 to 100 mole%, or from 98 to 100 mole%, or at 100 mole%. In one class of this embodiment, or in combination with any other class, or embodiment, the aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms are present at from 0 to 8 mole%, or from 0 to 6 mole%, or from 0 to 4 mole%, or from 0 to 2 mole%, or from 2 to 10 mole%, or from 2 to 8 mole%, or from 2 to 6 mole%, or from 2 to 4 mole%, or from 4 to 10 mole%, or from 4 to 8 mole%, or from 4 to 6 mole%, or from 6 to 10 mole%, or from 6 to 8 mole%, or from 8 to 10 mole%.

[0158] In one embodiment, or in combination with any other embodiment, the TMCD residues are present at from 35 to 65 mole%, or 35 to 60 mole%, or from 35 to 55 mole%, or from 35 to 50 mole%, or from 35 to 45 mole%, or from 35 to 40 mole%, or from 40 to 65 mole%, or from 40 to 60 mole%, or from 40 to 55 mole%, or from 40 to 50 mole%, or from 40 to 45 mole%, or from 45 to 65 mole%, or from 45 to 60 mole%, or from 45 to 55 mole%, or from 45 to 50 mole%, or from 50 to 65 mole%, or from 50 to 60 mole%, or from 50 to 55 mole%, or from 55 to 65 mole%, or from 55 to 60 mole%, or from 60 to 65 mole%.

[0159] In one embodiment, or in combination with any other embodiment, the IV is in the range of from 0.3-0.6 dL / g, or from 0.3-0.5 dL / g, or from 0.3-0.4 dL / g, or from 0.4-0.7 dL / g, or from 0.4-0.6 dL / g, or from 0.4-0.5 dL / g, or from 0.5-0.7 dL / g, or from 0.5-0.6 dL / g, or from 0.6-0.7 dL / g.

[0160] In one embodiment, or in combination with any other embodiment, the Tgis from 110-145°C, or from 110-140°C, or from 110-135°C, or from 110-130°C, or from 110-125°C, or from 110-120°C, or from 110-115°C, or from 115-145°C, or from 115-140°C, or from 115-135°C, or from 115-130°C, or from 115-125°C, or from 115-120°C, or from 120-145°C, or from 120-140°C, or from 120-135°C, or from 120-130°C, or from 120-125°C, from 125-145°C, or from 125-140°C, or from 125-135°C, or from 125-130°C, or from 130-145°C, or from 130-140°C, or from 130-135°C, or from 135-145°C, or from 135-140°C from 140-145°C.

[0161] In one embodiment or in combination with any other embodiment, the film exhibits a total transmission (“TT%”) that is greater than 80%, or greater than 85%, or greater than 90%, or greater than 92%, or greater than 95% as measured using a HunterLab Ultrascan VIS colorimeter in diffused transmittance mode (1-inch diameter port) with a film thickness in the range of from 20-100 microns.

[0162] In one embodiment or in combination with any other embodiment, wherein the film exhibits a water vapor transmission rate (“WVTR”) that is less than 100 g / (m2x day), or less than 90 g / (m2x day), or less than 80 g / (m2x day), or less than 70 g / (m2x day), or less than 60 g / (m2x day), as measured at 38°C at a relative humidity (“RH”) of 50% using a Mocon PERMATRAN-W Model 3 / 34 G WVTR analyzer.

[0163] In one embodiment or in combination with any other embodiment, the film is a solvent cast film or an extruded film.

[0164] In one embodiment or in combination with any other embodiment, the film is unstretched or stretched. In one embodiment or in combination with any other embodiment, the film is uniaxially stretched, biaxial ly stretched, or 45 degree stretched.

[0165] In one embodiment or in combination with any other embodiment, the film is a polarizer protective film, a quarter wave retardation film, a half wave retardation film or a combination thereof.

[0166] In one embodiment or in combination with any other embodiment, the film exhibits an in-plane retardation as measured at 550 nm (“Re(550nm)”) is in the range of from 0-275 nm, or from 0-250 nm, or from 0-225nm, or from 0-200, or from 0-175nm, or from 0-150nm, or from 0-125nm, or from 0-100nm, or 50-275 nm, or from 50-250 nm, or from 50-225nm, or from 50-200, or from 50-175nm, or from 50-150nm, or from 50-125nm, or from 50-1 OOnm, or 1 GO-275 nm, or from 100-250 nm, or from 100-225nm, or from 100-200, or from 100-175nm, or from 100-160nm, or from 100-150nm, or from 100-125nm, or 150-275 nm, or from 150-250 nm, or from 150-225nm, or from 150-200, or from 150-175nm, or 200-275 nm, or from 200-250 nm, or from 200-225nm.

[0167] In one class of this embodiment, or in combination with any other class or embodiment, the thickness of the film is from 20-100 microns, 20-90 microns, or from 20-80 microns, or from 20-70 microns, or from 30-100 microns, or from 20-90 microns, or from 20-80 microns, or from 20-70 microns, or from 40-100 microns, or from 40-90 microns, or from 40-80 microns, or from 40-70 microns, or from 50-100 microns, or from 50-90 microns, or from 50-80 microns.

[0168] In one embodiment or in combination with any other embodiment, the film exhibits an out-of-plane retardation as measured at 550 nm (“Rth(550nm)”) is in the range of from -300 to 0 nm, or from -250 to Onm, or from -200 to Onm, or from -150 to Onm, or from -100 to Onm, or from -50 to 0 nm, or from -50 to -300nm, or from -50 to -250nm, or from -50 to -200nm, or from -50 to 150nm, or from -50 to -100nm, or from -100 to -300nm, from -100 to -250nm, or from -100 to -200nm, or from -100 to -150nm, or from -150 to -300nm, or from -150 to -250nm, or from -150 to -200nm, or from -200 to -300nm.

[0169] In one embodiment or in combination with any other embodiment, the film has a thickness in the range of from 20-100 microns, or from 20-90 microns, or from 20-80 microns, or from 20-60 microns, or from 20-40 microns, or from 30-100 microns, or from 30-80 microns, or from 30-60 microns, or from 30-40 microns, or from 40-100 microns, or from 40-80 microns, or from 40-60 microns, or from 50-100 microns, or from 50-80 microns, or from 60-100m icrons, or from 60-80 microns, or from 80-100 microns.

[0170] In one embodiment or in combination with any other embodiment, the film is a quarter wave retardation film, wherein the Re(550nm) is in the range of from 100-160nm, and the thickness of the film is in the range of from 20-80 microns.

[0171] In one embodiment or in combination with any other embodiment, the film further comprises an additive chosen from colorants, dyes, plasticizers, UV stabilizers, thermal stabilizers and / or reaction products thereof, impact modifiers, light absorbing molecules, or combinations thereof.

[0172] Glycol Component: CHDM

[0173] In one embodiment or in combination with any other embodiment disclosed herein, the glycol component further comprises: (ii) 35 to 45 mole %, 37 to 45 mole %, or 39 to 45 mole %, or 40 to 45 mole%, or 42 to 45 mole %, or 44 to 45 mole %, or 35 to 40 mole %, or 37 to 40 mole %, or 39 to 40 mole %, or 40 to 45 mole%, or 42 to 45 mole %, or 44 to 45 mole %,of 1 ,4-cyclohexandimethanol (“CHDM”) residues.

[0174] In one class of this embodiment, or in combination with any other class or embodiment, the TMCD residues are present at from 35 to 65 mole%, or 35 to 60 mole%, or from 35 to 55 mole%, or from 35 to 50 mole%, or from 35 to 45 mole%, or from 35 to 40 mole%, or from 40 to 65 mole%, or from 40 to 60 mole%, or from 40 to 55 mole%, or from 40 to 50 mole%, or from 40 to 45 mole%, or from 45 to 65 mole%, or from 45 to 60 mole%, or from 45 to 55 mole%, or from 45 to 50 mole%, or from 50 to 65 mole%, or from 50 to 60 mole%, or from 50 to 55 mole%, or from 55 to 65 mole%, or from 55 to 60 mole%, or from 60 to 65 mole%.

[0175] In one class of this embodiment, or in combination with any other class or embodiment, the Tgis from 130-140°C, or from 130-135°C, or from 135-140°C.

[0176] Glycol Component: CHDM and EG

[0177] In one embodiment or in combination with any other embodiment disclosed herein, the glycol component further comprises: (ii) 15 to 25 mole % of 1,4-cyclohexandiamethanol (“CHDM”) residues, and (iii) 15 to 25 mole % of ethylene glycol (“EG”) residues.

[0178] In one class of this embodiment, or in combination with any other class or embodiment, the TMCD residues are present at from 35 to 65 mole%, or 35 to 60 mole%, or from 35 to 55 mole%, or from 35 to 50 mole%, or from 35 to 45 mole%, or from 35 to 40 mole%, or from 40 to 65 mole%, or from 40 to 60 mole%, or from 40 to 55 mole%, or from 40 to 50 mole%, or from 40 to 45 mole%, or from 45 to 65 mole%, or from 45 to 60 mole%, or from 45 to 55 mole%, or from 45 to 50 mole%, or from 50 to 65 mole%, or from 50 to 60 mole%, or from 50 to 55 mole%, or from 55 to 65 mole%, or from 55 to 60 mole%, or from 60 to 65 mole%. In one class of this embodiment or in combination with any other class or embodiment, the CHDM residues are present at from 15 to 25 mole%, or 15 to 22 mole%, or 15 to 20 mole%, or 15 to 18 mole%, or 18 to 25 mole%, or 18 to 22 mole%, or 20 to 25 mole%, or 20 to 22 mole%. In one subclass of this class, or in combination with any other subclass, class, or embodiment, the EG residues are present at from 15 to 25 mole%, or 15 to 22 mole%, or 15 to 20 mole%, or 15 to 18 mole%, or 18 to 25 mole%, or 18 to 22 mole%, or 20 to 25 mole%, or 20 to 22 mole%.

[0179] In one class of this embodiment or in combination with any other class or embodiment, the EG residues are present at from 15 to 25 mole%, or 15 to 22 mole%, or 15 to 20 mole%, or 15 to 18 mole%, or 18 to 25 mole%, or 18 to 22 mole%, or 20 to 25 mole%, or 20 to 22 mole%. In one subclass of this class, or in combination with any other subclass, class, or embodiment, the CHDM residues are present at from 15 to 25 mole%, or 15 to 22 mole%, or 15 to 20 mole%, or 15 to 18 mole%, or 18 to 25 mole%, or 18 to 22 mole%, or 20 to 25 mole%, or 20 to 22 mole%.

[0180] In one class of this embodiment, or in combination with any other class or embodiment, the Tgis from 110-135°C, or from 110-130°C, or from 110-125°C, or from 110-115°C, or from 115-135°C, or from 115-130°C, or from 115-125 °C, or from 115-120 °C, or from 120-135 °C, or from 120-130, or from 120-125 °C, or from 125-135 °C, or from 125-130 °C, or from 130-135 °C. Glycol Component: EG

[0181] In one embodiment or in combination with any other embodiment disclosed herein, the glycol component further comprises: (iii) 15 to 25 mole%, or 15 to 22 mole%, or 15 to 20 mole%, or 15 to 18 mole%, or 18 to 25 mole%, or 18 to 22 mole%, or 20 to 25 mole%, or 20 to 22 mole% of ethylene glycol (“EG”) residues.

[0182] The present application discloses a multilayer film comprising the films disclosed herein. The present application discloses a polarizer incorporating the films or multilayer film disclosed herein. The present application discloses a liquid crystal display (“LCD”) or organic light emitting diode (“OLED”) comprising the film, multilayer film, or polarizer disclosed herein.

[0183] For the purposes of this invention, the term "wt" means "weight".

[0184] The following examples further illustrate how the polyesters of the invention can be made and evaluated and are intended to be purely exemplary of the invention and are not intended to limit the scope thereof. Unless indicated otherwise, parts are parts by weight, temperature is in degrees C or is at room temperature, and pressure is at or near atmospheric.

[0185] Specific Embodiments

[0186] Embodiment 1. A film, comprising a polyester composition comprising at least one amorphous copolyester which comprises:

[0187] (a) a dicarboxylic acid component comprising:

[0188] (i) 90 to 100 mole % of terephthalic acid (“TPA”) residues;

[0189] (ii) 0 to 10 mole % of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; and

[0190] (b) a glycol component comprising:

[0191] (i) 35 to 65 mole % of 2,2,4, 4-tetramethyl-1 ,3-cyclobutanediol (“TMCD”) residues,

[0192] wherein the total mole % of the acid component (a) is 100 mole % and the total mole % of the glycol component (b) is 100 mole %,

[0193] wherein the polyester exhibits an inherent viscosity (“IV”) in the range of from 0.3-0.7 dL / g in 60 / 40 (wt / wt) phenol / tetrachloroethan at a concentration of 0.5 g / 100 mL at 25°C, a glass transition temperature (“Tg”) in the range of from 110-150°C as determined using ASTM D3418 test method.

[0194] Embodiment 2. The film of Embodiment 1 , wherein the glycol component further comprises: (ii) 35 to 45 mole % of 1 ,4-cyclohexandimethanol (“CHDM”) residues. Embodiment 3. The film of any one of Embodiments 1 or 2, wherein the Tgis from 130-140°C.

[0195] Embodiment 4. The film of Embodiment 1 , wherein the glycol component further comprises: (ii) 15 to 25 mole % of 1 ,4-cyclohexandiamethanol (“CHDM”) residues, and (iii) 15 to 25 mole % of ethylene glycol (“EG”) residues.

[0196] Embodiment 5. The film of any one of Embodiments 1 or 5, wherein the Tgis from 130-140°C.

[0197] Embodiment 6. The film of Embodiment 1 , wherein the glycol component further comprises: (iii) 34 to 65 mole % of ethylene glycol (“EG”) residues.

[0198] Embodiment 7. The film of any one of Embodiments 1 or 6, wherein the Tgis from 110-135°C.

[0199] Embodiment 8. The film of any one of Embodiments 1-7, wherein the film exhibits a total transmission (“TT%”) that is greater than 80% as measured using a HunterLab Ultrascan VIS colorimeter in diffused transmittance mode (1-inch diameter port) with a film thickness in the range of from 20-100 microns.

[0200] Embodiment 9. The film of any one of Embodiments 1-8, wherein the film exhibits a water vapor transmission rate (“WVTR”) that is less than 100 g / (m2x day), as measured at 38°C at a relative humidity of 50% using a Mocon PERMATRAN-W Model 3 / 34 G WVTR analyzer.

[0201] Embodiment 10. The film of any one of Embodiments 1 -9, wherein the film is a solvent cast film or an extruded film. Embodiment 11. The film of any one of Embodiments 1 -10, wherein the film is unstretched or stretched.

[0202] Embodiment 12. The film of any one of Embodiments 1-11, wherein the film is uniaxially stretched, biaxial ly stretched, or 45 degree stretched.

[0203] Embodiment 13. The film of any one of Embodiments 1-12, wherein the film is a polarizer protective film, a quarter wave retardation film, a half wave retardation film or a combination thereof.

[0204] Embodiment 14. The film of any one of Embodiments 1-13, wherein the film exhibits an in-plane retardation as measured at 550 nm (“Re(550nm)”) is in the range of from 0-275 nm.

[0205] Embodiment 15. The film of any one of Embodiments 1-14, wherein the film exhibits an out-of-plane retardation as measured at 550 nm (“Rth(550nm)”) is in the range of from 0 to -300 nm.

[0206] Embodiment 16. The film of any one of Embodiments 1-15, wherein the film has a thickness in the range of from 20-100 microns.

[0207] Embodiment 17. The film of any one of Embodiments 1-16, wherein the film is a quarter wave retardation film, wherein the Re(550nm) is in the range of from 100-160nm, and the thickness of the film is in the range of from 20-80 microns.

[0208] Embodiment 18. A multilayer film comprising the film of any one of Embodiments 1-17.

[0209] Embodiment 19. A polarizer comprising the film of any one of Embodiments 1-18. Embodiment 20. A liquid crystal display (“LCD”) or an organic light emitting diode (“OLED”) comprising the film, multilayer film, or polarizer of any one of Embodiments 1-19.

[0210] EXAMPLES

[0211] Abbreviations

[0212] TPA is terephthalic acid, Ex is example(s); Comp Ex is comparative example(s); EG is ethylene glycol, CHDM is 1 ,4-cyclohexanedimethanol; TMCD is 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol; min is minute(s); g is gram(s); h is hour(s); mol% is mole percent; PET is polyethylene terephthalate; psi is pounds per square inch; PMMA is poly(methyl methacrylate); TAC is cellulose triacetate; Tgis glass transition temperature; RPM is revolutions per minute.

[0213] The following examples illustrate in general how a copolyester is prepared and the effect of using ethylene glycol, 1 ,4-cyclohexanedimethanol and 2,2,4,4-tetramethyl-L3 -cyclobutanediol on various polyester properties such as glass transition temperature, inherent viscosity, etc., compared to polyesters comprising 1 ,4-cyclohexanedimethanol and 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol, but lacking ethylene glycol, or compared to polyesters comprising 1,4-cyclohexanedimethanol and ethylene glycol, but lacking 2, 2, 4, 4-tetramethyl-1 ,3-cyclobutanediol. Additionally, based on the following examples, the skilled artisan will understand how the thermal stabilizers of the invention can be used in the preparation of polyesters containing them.

[0214] Measurement Method

[0215] The inherent viscosity of the polyesters was determined in 60 / 40 (wt / wt) phenol / tetrachloroethane at a concentration of 0.25 g / 50 ml at 25° C., and is reported in dL / g.

[0216] Unless stated otherwise, the Tgwas determined using a TA DSC 2920 instrument from Thermal Analyst Instruments at a scan rate of 20° C. / min according to ASTM D3418. The glycol content was determined by proton nuclear magnetic resonance (NMR) spectroscopy. All NMR spectra were recorded on a JEOL Eclipse Plus 600 MHz nuclear magnetic resonance spectrometer using either chloroform-trifluoroacetic acid (70-30 volume / volume) for polymers or, for oligomeric samples, 60 / 40 (wt / wt) phenol / tetrachloroethane with deuterated chloroform added for lock. Peak assignments for 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol resonances were made by comparison to model mono- and dibenzoate esters of 2,2,4, 4-tetramethyl-1,3-cyclobutanediol. These model compounds closely approximate the resonance positions found in the polymers and oligomers.

[0217] Mechanical properties of all resins were characterized using the following methods:

[0218] Heat deflection temperature, at 264 and 66 psi, was determined according to ASTM D648.

[0219] Flexural modulus and flexural strength were determined according to ASTM D790.

[0220] All flex bars were molded on the Boy22A injection molding. All resins were dried in forced-air ovens for 4-6 h at 20 °C below their Tgbefore molding. Once properly dried, the material was molded to give %x x5-inch and1 / 4x x5-inch flexure bars using a barrel temperature of 270-280 °C and a mold temperature of 40-46 °C, depending on the composition. To ensure there was no contamination, the first 10 flex bars were discarded. The bars were submitted to analytical for further testing.

[0221] Preparation of Copolyesters

[0222] The process for the preparation of the copolyesters in Ex 1-15 and Comp Ex 1-4 as shown in Table 1 is exemplified by the preparation of the copolyester of Ex 1, which has a target composition of 100 mol% terephthalic acid residues, 39.4 mol% EG residues, 45.2 mol% TMCD residues, and 15.4 mol% CHDM residues. A mixture of 145.65 g of terephthalic acid, 37.3 g of EG, 16.22 g of CHDM, 73.0 g of TMCD were placed in a 500-milliliter flask equipped with an inlet for nitrogen, a metal stirrer, and a short distillation column. 521 pL of a Titanium isopropoxide solution (0.01248 g / mL in n-butanol) and 0.23 g of a Fascat 4102 solution (2.82 wt% in n-butanol) were added to the flask. The flask was placed in a Wood’s metal bath already heated to 200 °C. The stirring speed was set to 200 RPM, and this was held for 60 min. The contents of the flask were heated to 210 °C over 10 minutes while the stirring, and then was held at that temperature for an additional 60 minutes. The contents were then raised to 275°C slowly over 45 minutes. The content remained at 275 °C while the pressure was reduced to 7.5 torr over 10 min, followed by a further pressure reduction to 0.3 torr over another 10 min period. Finally, the temperature was held at 275 °C while the stir rate slowly decreased to 150 RPM an over the course of 90 min. A high melt viscosity, visually yellow, but transparent, polymer was obtained with an inherent viscosity of 0.61 dl / g. NMR analysis confirmed target monomer incorporations.

[0223] Table 1. Composition of Ex 1-15, and Comp Ex 1-4.

[0224] Composition

[0225] IV

[0226] Ex TPA EG CHDM TMCD (dL / g)

[0227] (mole%) (mole%) (mole%) (mole%)

[0228] 1 100 39.4 15.4 45.2 0.61

[0229] 2 100 36.1 19.9 44 0.59

[0230] 3 100 27.8 21.3 50.9 0.54

[0231] 4 100 21 21.2 57.8 0.59

[0232] 5 100 13.4 27.5 59.1 0.62

[0233] 6 100 26.6 14.2 59.2 0.62

[0234] 7 100 31.1 8.2 60.7 0.53

[0235] 8 100 - 40 60 0.51

[0236] 9 100 - 50 50 0.60

[0237] 10 100 20 20 60 0.62

[0238] 11 100 20 21 59 0.55

[0239] 12 100 40 - 60 0.64

[0240] 13 100 39 - 61 0.52

[0241] 14 100 60 - 40 0.56

[0242] 15 100 50 - 50 0.57

[0243] Comp

[0244] 100 18.8 70 11.2 0.73

[0245] Ex 1

[0246] Comp

[0247] 100 0 78 22 0.72

[0248]

[0249] Ex 2 Composition

[0250] IV

[0251] Ex TPA EG CHDM TMCD (dL / g)

[0252] (mole%) (mole%) (mole%) (mole%)

[0253] Comp

[0254] 100 38 62 0 0.73

[0255] Ex 3

[0256] Comp

[0257] 100 31.6 34.5 33.9 0.66

[0258]

[0259] Ex 4

[0260] Table 2 provides thermal and mechanical properties for Ex 1-15, Comp Ex 1-4.

[0261] Table 2 Properties of Ex 1-15, and Comp Ex 1-4.

[0262] Thermal Properties Mechanical Properties

[0263] Ex Notched Izod HDT (264 Break Flexural

[0264] HDT (66 Impact Tg (°C) Psi) Stress Modulus

[0265] psi) (°C) Resistance (°C) (Mpa) (Mpa)

[0266] (J / M) 1 118.3 90.8 104.9 83.7 1922 112.8 2 121.1 92.8 107.1 105.6 1815.3 406.8 3 128.4 100.5 114.6 86 1853.1 764.4 4 139.6 107 124.8 74.6 1895.4 821.2 5 142.9 - - - - - 6 138.5 - - - - - 7 136 103.2 120.6 98.4 1976.1 541.8 8 139 - 9 132 50.4

[0267] 10 138

[0268] 11 134

[0269] 12 135

[0270] 13 132

[0271] 14 108

[0272] 15 119

[0273] Comp

[0274] 94 70.8 84.1 66.0 1704.9 1306.5 Ex 1

[0275] Comp

[0276] 108 85 99 58 1550 980

[0277] Ex 2

[0278] Comp

[0279] 86 64 74 52 1800 NB

[0280] Ex 3

[0281] Comp

[0282] 112 82.7 98.2 51.3 1929.1 1247.3

[0283]

[0284] Ex 4

[0285] *NB is indicative that a sample that did not break, even when hit with the max energy output of the instrument

[0286] Solvent Casting

[0287] These copolyester materials were solvent cast into films in following steps: 1. Copolyester materials are dissolved in the solvent, such as DCM / MeOH with ratio of 95 / 5 with solid concentration from 10wt% to 25wt%; 2. After copolyester and solvent mixtures are made, the bottles are put on the roller for 24 hours until the solids are fully dissolved and uniform dopes are obtained; 3. The uniform dope is cast onto a glass substrate using a doctor blade, which the knife gap is adjusted to give a film of desired thickness, in which the thicknesses ranged from 20pm to 150 pm can be obtained; 4.

[0288] Casting was conducted in a fume hood with RH controlled around 50%; 5. After casting, the film on the glass substrate was allowed to dry for 60 min under a cover pan (to minimize rate of solvent evaporation), 15 min with cover pan removed; 6. After this initial drying, the film was peeled from the glass substrate and annealed in a forced air oven for 10 min at 100°C. If necessary, the film could be annealed at a higher temp such as 110, 120°C for another 5 to 10 min.

[0289] Film Stretching

[0290] The cast films can also be uniaxially and biaxial ly stretched to increase the film size, reduce film thickness and improve film mechanical and optical properties.

[0291] Film stretching was done by Bruckner Karo IV laboratory film stretcher. Stretching conditions, such as, stretch speed, stretch ratio, stretch temperature, pre-heating and post-annealing temperature were varied to obtain specific optical retardation and dispersion according to the requirements of the applications. Films were cut into squares or rectangles. Film that underwent non-constrained stretch were held by clamps of stretcher on two sides (for example, on TD sides) while not held by clamps of stretcher on the other two sides (for example, on MD sides) during stretch. Films that underwent constrained stretch were held by clamps of stretcher on four sides (both TD and MD sides) during stretching.

[0292] Stretch ratio is defined as the end dimension of the film after stretching relative to the dimension of the film before stretching along one direction. For example, for films stretched uniaxially along MD from 100mm to 140mm, the stretch ratio is defined as 1.0 x 1.4. Optical Measurements

[0293] Film optical retardation and dispersion measurements were made using a J. A. Woollam M-2000V Spectroscopic Ellipsometer having a spectral range from 370 to 1000 nm or J. A. Woollam RC2 Ellipsometer having a spectral range from 250 - 2500 nm. RetMeas (Retardation Measurement) or CompleteEASE program from J. A. Woollam Co., Inc. was used to obtain optical Re and Rth. The thickness of the films was measured using a Metricon Prism Coupler 2010 (Metricon Corp.) or using a handheld Positector 6000. The haze and b* measurements were obtained using a HunterLab Ultrascan VIS colorimeter in diffused transmittance mode (1-inch diameter port).

[0294] The formulas for determination of Re and Rth are as follows:

[0295] Equation 1. Re = (nx-ny)*d;

[0296] Equation 2. Rth = -[nz-(nx+ny) / 2]*d;

[0297] where nxand nyare the film refractive indices in the film plane x and y directions, nzis the film refractive index in the film thickness direction, and d is the film thickness.

[0298] Protection films made by melt Extrusion

[0299] For melt extrusion techniques, the compositions can be extruded using a single-screw extruder, twin-screw extruder, roll-mill, or any other melt plastic processing equipment. Furthermore, as is more common the materials can be pre-compounded together on one system such as a twin-screw or roll-mill, pelletized, and then processed on a second extruder in conjunction with the film line. For single and twin-screw film extrusion, a gear pump can be used in between the extruder and die to ensure uniform flow rate. The extruded films can also be stretched for the application of polarizer protection films.

[0300] The results in Tables 3 and 4 show that films made from the copolyesters disclosed herein are excellent candidates for polarizer protection films. The retardation are below the observable interference color. Results for commercial PET, PMMA, and TAC films are provided for comparison. The total transmission is close to the commercial PMMA optical films and the WVTR is much lower than commercial TAC films. Table 3. Unstretched cast films of Ex 8-15, and for PET, PMMA, and TAC.

[0301] Thickness Re(nm) Rth(nm) Re(450nm) Re(650nm) Rth(450nm) Rth(650nm) WVTR (38C) Film #

[0302] (mm) TT%*

[0303] @550nm @550nm / Re(550nm) / Re(550nm) / Rth(550nm) / Rth(550nm) g / (m2*day) 8.1 35 7.37 -101.54 1.085 0.958 1.072 0.964

[0304] 8.2 76 2.64 -107.47 1.080 0.961 1.073 0.963 91.2 64.02 8.3 78 2.06 -119.80 1.072 0.963 1.064 0.968

[0305] 8.4 81 3.02 -123.83 1.081 0.941 1.068 0.965

[0306] 8.5 85 2.67 -101.23 1.083 0.956 1.060 0.970

[0307] 8.6 95 6.44 -63.57 1.077 0.962 1.052 0.972

[0308] 8.7 102 1.68 -75.09 1.086 0.949 1.048 0.974

[0309] 8.8 116 3.01 -77.96 1.083 0.956 1.033 0.982

[0310] 9.1 65 2.22 -245.65 1.061 0.974 1.058 0.969 91.2

[0311] 9.2 69 3.35 -273.81 1.076 0.966 1.054 0.972

[0312] 10.1 96 9.40 -73.07 1.09 0.964 1.082 0.959

[0313] 10.2 76 8.10 -103.10 1.09 0.967 1.088 0.956

[0314] 10.3 88 3.61 -97.97 1.09 0.969 1.088 0.956

[0315] 11.1 82 3.36 -79.86 1.08 0.958 1.087 0.955

[0316] 11.2 84 6.92 -129.56 1.08 0.951 1.101 0.949

[0317] 11.3 80 33.89 -58.07 1.09 0.962 1.065 0.966

[0318] 12.1 80 5.04 -66.06 1.079 0.972 1.089 0.957

[0319] 12.2 72 10.92 -72.52 1.088 0.964 1.087 0.956

[0320] 12.3 76 2.24 -80.13 1.116 0.966 1.092 0.956

[0321] 13.1 78 0.80 -44.12 1.044 0.962 1.089 0.955

[0322] 13.2 74 8.37 -46.65 1.084 0.966 1.089 0.956

[0323]

[0324] 13.3 72 2.33 -42.77 1.076 0.950 1.086 0.955 Thickness Re(nm) Rth(nm) Re(450nm) Re(650nm) Rth(450nm) Rth(650nm) WVTR (38C) Film # TT%*

[0325] (mm) @550nm @550nm / Re(550nm) / Re(550nm) / Rth(550nm) / Rth(550nm) g / (m2*day) 14.1 106 15.60 -57.30 1.081 0.960 1.085 0.957

[0326] 14.2 108 19.35 -70.49 1.081 0.960 1.084 0.957

[0327] 14.3 98 4.73 -57.87 1.081 0.959 1.081 0.958

[0328] 14.4 106 9.97 -60.45 1.085 0.958 1.085 0.956

[0329] 14.5 104 3.47 -60.82 1.079 0.967 1.079 0.958

[0330] 14.6 104 14.76 -55.09 1.084 0.959 1.091 0.953

[0331] 15.1 98 5.45 -24.60 1.095 0.954 1.072 0.963

[0332] 15.2 98 24.47 -31.47 1.089 0.957 1.085 0.958

[0333] 15.3 94 22.60 -21.84 1.083 0.960 1.083 0.957

[0334] 15.4 106 10.53 -48.28 1.081 0.961 1.086 0.956

[0335] 15.5 106 12.79 -45.35 1.091 0.954 1.082 0.961

[0336] 15.6 112 20.25 -44.86 1.089 0.956 1.092 0.952

[0337] PET 80 9226.64 -9294.85 1.085 0.967 1.07 0.964 89 9.3 PMMA 36 1.08 0.22 1.277 0.932 -22.532 10 91 68.8 PMMA 78 0.15 1.34 1.153 1.115 0.419 1.118 91 32.4

[0338]

[0339] TAC 60 0.25 -37.05 0.625 1.225 0.720 1.153 92 445.2 Table 4. Stretched cast films for Ex 8-15.

[0340] Film Stretching Stretching Thickness Re(450nm) Re(650nm) Rth(450nm) Rth(650nm)

[0341] Re(nm) Rth(nm)

[0342] # Temp (°C) Ratio (mm) / Re(550nm) / Re(550nm) / Rth(550nm) / Rth(550nm) 8.9 170 1.20 x 1.20 76 29.6 -142.55 1.082 0.961 1.072 0.963 8.10 175 1.30 x1.30 70 11.28 -169.14 1.076 0.963 1.076 0.961 8.11 175 1.40 x 1.40 44 7.08 -65.1 1.087 0.959 1.071 0.965 8.12 178 1.40 x 1.40 50 6.62 -61.79 1.083 0.96 1.077 0.959 8.13 180 1.30 x 1.30 70 4.24 -84.13 1.074 0.965 1.074 0.962 8.14 180 1.40 x 1.40 60 2.81 -77.48 1.079 0.961 1.078 0.959 8.15 180 1.50 x 1.50 52 5.21 -79.79 1.079 0.96 1.079 0.96 8.16 180 1.60 x 1.60 43 4.38 -63.47 1.078 0.964 1.078 0.96 8.17 180 1.50 x 1.50 36 6.31 -44.73 1.074 0.966 1.078 0.96 8.18 180 1.50 x 150 44 6.82 -54.6 1.081 0.96 1.069 0.965 9.3 180 1.20 x 1.20 60 3.46 -163.38 1.093 0.947 1.061 0.97 9.4 180 1.30 x 1.30 41 2.79 -167.08 1.056 0.972 1.067 0.966 9.5 180 1.30 x 1.30 48 4.45 -102.83 1.076 0.951 1.063 0.969 9.6 185 1.35 x 1.35 44 3.53 -90.13 1.077 0.963 1.063 0.967 10.4 170 1x1 ,3c* 94 187.00 -228.10 1.088 0.957 1.088 0.953 10.5 178 1x1 ,3c 92 99.07 -135.92 1.087 0.958 1.079 0.960 10.6 178 1x1 ,4c 60 101.16 -130.19 1.089 0.957 1.085 0.957 10.7 178 1.2 x 1.4 62 54.06 -151.13 1.088 0.957 1.087 0.957 10.8 178 1.2 x 1.4 47 20.51 -152.49 1.088 0.957 1.087 0.956 11.4 178 1x1 ,3c 90 45.29 -80.14 1.089 0.957 1.086 0.955 11.5 178 1x1 ,4c 56 39.47 -58.92 1.087 0.958 1.081 0.959

[0343]

[0344] 11.6 178 1.1 x 1.4 56 34.95 -74.52 1.087 0.958 1.086 0.957 Film Stretching Stretching Thickness Re(450nm) Re(650nm) Rth(450nm) Rth(650nm) # Temp (°C) Ratio (mm) Re(nm) Rth(nm) / Re(550nm) / Re(550nm) / Rth(550nm) / Rth(550nm) 11.7 178 1.2 x 1.4 52 23.16 -77.82 1.088 0.957 1.085 0.957 11.8 178 1.3x 1.4 50 12.88 -81.17 1.088 0.956 1.085 0.957 12.4 170 1x1.3 c 66 140.79 -170.19 1.090 0.956 1.087 0.956 12.5 170 1x1.35 c 78 176.18 -195.81 1.090 0.956 1.089 0.954 12.6 175 1x1.35 c 58 87.56 -120.53 1.091 0.956 1.091 0.955 12.7 175 1x1.4 c 58 100.20 -132.54 1.090 0.956 1.089 0.955 12.8 178 1x1.4 c 58 68.80 -92.96 1.090 0.956 1.086 0.956 13.4 178 1x1.4 c 58 13.12 -30.74 1.091 0.955 1.086 0.958 13.5 178 1.1 x 1.4 92 10.86 -39.44 1.089 0.958 1.086 0.956 13.6 178 1.2 x 1.4 50 5.65 -30.42 1.090 0.958 1.083 0.958 13.7 178 1.3x 1.4 54 3.02 -41.33 1.089 0.958 1.085 0.958 13.8 178 1.4 x 1.4 52 4.93 -52.43 1.087 0.956 1.085 0.959 14.7 120 1.2 x 1.2 80 10.75 -579.34 1.088 0.958 1.086 0.956 14.8 130 1.3x 1.3 70 21.75 -359.14 1.088 0.957 1.088 0.955 14.9 140 1.4 x 1.4 58 17.14 -161.64 1.085 0.959 1.090 0.954 14.10 140 1.5 x 1.5 54 24.75 -166.11 1.087 0.958 1.087 0.956 14.11 140 1x1.3 f 90 137.52 -76.57 1.088 0.957 1.096 0.950 15.7 170 1.2 x 1.2 78 3.76 -121.35 1.087 0.957 1.087 0.956 15.8 170 1.3x 1.3 72 4.45 -109.48 1.078 0.965 1.089 0.956 15.9 170 1.4 x 1.4 58 3.31 -79.96 1.088 0.958 1.084 0.956 15.10 170 1x1.4 c 68 35.12 -62.48 1.089 0.956 1.089 0.954

[0345]

[0346] 15.11 170 1x1.5 f 82 53.33 -24.74 1.089 0.957 1.093 0.953 The invention has been described in detail with reference to the embodiments disclosed herein, but it will be understood that variations and modifications can be affected within the spirit and scope of the invention.

Claims

What is claimed is:

1. A film, comprising a polyester composition comprising at least one amorphous copolyester which comprises:(a) a dicarboxylic acid component comprising:(i) 90 to 100 mole % of terephthalic acid (“TPA”) residues;(ii) 0 to 10 mole % of aromatic and / or aliphatic dicarboxylic acid residues having up to 20 carbon atoms; and(b) a glycol component comprising:(i) 35 to 65 mole % of 2,2,4, 4-tetramethyl-1 ,3-cyclobutanediol (“TMCD”) residues,wherein the total mole % of the acid component (a) is 100 mole % and the total mole % of the glycol component (b) is 100 mole %,wherein the polyester exhibits an inherent viscosity (“IV”) in the range of from 0.3-0.7 dL / g in 60 / 40 (wt / wt) phenol / tetrachloroethan at a concentration of 0.5 g / 100 mL at 25°C, a glass transition temperature (“Tg”) in the range of from 110-150°C as determined using ASTM D3418 test method.

2. The film of claim 1, wherein the glycol component further comprises: (ii) 35 to 45 mole % of 1 ,4-cyclohexandimethanol (“CHDM”) residues.

3. The film of any one of claims 1 or 2, wherein the Tgis from 130-140°C.

4. The film of claim 1, wherein the glycol component further comprises: (ii) 15 to 25 mole % of 1 ,4-cyclohexandiamethanol (“CHDM”) residues, and (iii) 15 to 25 mole % of ethylene glycol (“EG”) residues.

5. The film of any one of claims 1 or 4, wherein the Tgis from 130- 140°C.

6. The film of claim 1, wherein the glycol component further comprises: (iii) 34 to 65 mole % of ethylene glycol (“EG”) residues.

7. The film of any one of claims 1 or 6, wherein the Tgis from 110-135°C.

8. The film of any one of claims 1-7, wherein the film exhibits a total transmission (“TT%”) that is greater than 80% as measured using a HunterLab Ultrascan VIS colorimeter in diffused transmittance mode (1-inch diameter port) with a film thickness in the range of from 20-100 microns.

9. The film of any one of claims 1-8, wherein the film exhibits a water vapor transmission rate (“WVTR”) that is less than 100 g / (m2x day), as measured at 38°C at a relative humidity of 50% using a Mocon PERMATRAN-W Model 3 / 34 G WVTR analyzer.

10. The film of any one of claims 1-9, wherein the film is a solvent cast film or an extruded film.

11. The film of any one of claims 1 -10, wherein the film is unstretched or stretched.

12. The film of any one of claims 1-11, wherein the film is uniaxially stretched, biaxial ly stretched, or 45 degree stretched.

13. The film of any one of claims 1 -12, wherein the film is a polarizer protective film, a quarter wave retardation film, a half wave retardation film or a combination thereof.

14. The film of any one of claims 1 -13, wherein the film exhibits an inplane retardation as measured at 550 nm (“Re(550nm)”) is in the range of from 0-275 nm.

15. The film of any one of claims 1 -14, wherein the film exhibits an out-of-plane retardation as measured at 550 nm (“Rth(550nm)”) is in the range of from -300 to 0 nm.

16. The film of any one of claims 1 -15, wherein the film has a thickness in the range of from 20-100 microns.

17. The film of any one of claims 1 -16, wherein the film is a quarter wave retardation film, wherein the Re(550nm) is in the range of from 100-160nm, and the thickness of the film is in the range of from 20-80 microns.

18. A multilayer film comprising the film of any one of claims 1 -17.

19. A polarizer comprising the film of any one of claims 1 -18.

20. A liquid crystal display (“LCD”) or an organic light emitting diode (“OLED”) comprising the film, multilayer film, or polarizer of any one of claims 1-19.

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