Flame-retardant high-modulus copolyester composition

Abstract

A copolyester composition comprising a metal phosphinate flame retardant, an acrylic silicone impact modifier, and a silicate mineral, which provides high tensile and / or flexural modulus while maintaining thermal and impact properties and having improved flame retardant properties, a method for manufacturing the copolyester composition, and an article manufactured from the copolyester composition are provided.

Description

Technology Field

[0001] The present invention relates to using a combination of specific additives in a copolyester to improve the flame retardant properties of a copolyester composition while simultaneously providing a high flexural and / or tensile modulus. More specifically, the present invention relates to using a non-halogenated flame retardant in a copolyester to improve flame retardant properties while simultaneously providing a high flexural and / or tensile modulus, acceptable impact resistance, and glass transition temperature. Background Technology

[0002] Flame-retardant materials are added to some polymers to improve flame resistance, particularly to meet specific fire standards such as UL94 V-2. However, the addition of a sufficient amount of flame-retardant material to meet fire standards can have a detrimental effect on the specific physical properties of copolyesters containing an effective amount of flame-retardant material. Furthermore, the addition of large amounts of flame-retardant material will not be able to meet fire standards of UL94 V-0 or higher, regardless of the amount utilized, let alone maintain the essential physical properties of the polymer composition.

[0003] Copolyesters can be flame-retardantized by various means, but these methods have some drawbacks. Certain halogen compounds, such as Dechlorane Plus® (OxyChem®), decabromodiphenyl oxide, or decabromodiphenyl ether, can be effective flame retardants, but they may face opposition in the market due to potential concerns regarding bioaccumulation. Other halogen compounds may not have the same issues, but they can induce brittleness when used in amounts sufficient to flame-retard the copolyester. Liquid phosphorus compounds, such as triphenyl phosphite or triphenyl phosphate, can flame-retard the copolyester, but at effective usage levels, they plasticize and soften the copolyester, reducing its heat resistance to deformation. Solid flame retardants of the melamine and phosphorus classes can be used individually, but in the past, the concentrations required to achieve flame retardancy caused the copolyester to become brittle or reduced its tensile strength properties. Plastics used in many applications, such as electronic device applications, housings for handheld and stationary consumer electronics, and housings or shells for handheld and stationary power tools, all have flammability requirements specified in various codes or standards. These applications also have durability or physical property requirements in addition to flammability requirements.

[0004] There is a need for an improved copolyester composition containing an effective flame retardant that exhibits excellent flame resistance and high flexural and / or tensile modulus.

[0005] The applicant has unexpectedly discovered an improved copolyester composition comprising an effective amount of a combination of a specific non-halogenated flame retardant, a specific acrylic silicone polymer impact modifier, and a specific silane-modified silicate mineral reinforcing material, which is useful for manufacturing articles such as films, sheets, molded parts, or profiles that provide flexural and / or tensile modulus and exhibit excellent flame retardancy while maintaining other necessary physical properties.

[0006] In one embodiment, a copolyester composition is provided, which,

[0007] (a) A polyester component of about 50 to about 79 weight percent comprising at least one copolyester—the at least one copolyester,

[0008] (i) As a discrete component,

[0009] 70 to 100 mol% of terephthalic acid residue,

[0010] Residues of a modified aromatic diacid having 8 to 12 carbon atoms in an amount of 0 to 30 mol%, and

[0011] A discrete component comprising 0 to 10 mol% of a residue of an aliphatic dicarboxylic acid; and

[0012] (ii) As a glycol component,

[0013] 45 to 95 mol% of cyclohexanedimethanol (CHDM) residues,

[0014] 5 to 65 mol% of 2,2,4,4-tetramethylcyclobutane-1,3-diol (TMCD) residues, and

[0015] It comprises a glycol component comprising a modified glycol having 2 to 20 carbon atoms in an amount of 0 to 10 mol%, and

[0016] The intrinsic viscosity of the copolyester is 0.5 to 1.2 dL / g when determined in 60 / 40 (wt / wt) phenol / tetrachloroethane at a concentration of 0.5 g / 100 ml at 25°C, and

[0017] The weight % is based on the weight of the copolyester, the total mole % of the dicarboxylic acid component is 100 mole %, and the total mole % of the glycol component is 100 mole % - ; and

[0018] (b) About 8 to about 20 weight percent of a flame-retardant additive comprising a metal phosphinate compound; and

[0019] (c) About 3 to about 10 weight percent of an impact modifier component comprising an acrylic silicone polymer impact modifier;

[0020] (d) It comprises about 8 to about 25 weight%, or 10 to 25 weight%, of a reinforcing material component comprising a silane-modified silicate mineral having an average length greater than 10 micrometers and an aspect ratio greater than 8:1, and

[0021] The copolyester composition has a UL 94 V-0 rating or higher at 1.5 mm or less.

[0022] In an embodiment, the copolyester composition has a notched Izod impact strength of 60 J / m or more when measured according to ASTM D256, a flexural modulus of 2500 MPa or more when measured according to ASTM D790, and a tensile elongation at break of 10% or more when measured according to ASTM D638.

[0023] In an embodiment, the acrylic silicone impact modifier contains an acrylic content of less than 50 wt%, or less than 40 wt%, or less than 30 wt%, or less than 20 wt%, or less than 10 wt%, less than 5 wt%, or less than 3 wt%. In an embodiment, the acrylic silicone impact modifier is a core-shell impact modifier. In an embodiment, the silicone content is in the core of the core-shell impact modifier. In an embodiment, the acrylic content is in both the core and the shell of the core-shell impact modifier. In an embodiment, the acrylic content is in the shell of the core-shell impact modifier.

[0024] In certain embodiments, the impact modifier is classified as non-reactive. In certain embodiments, the impact modifier component does not contain ethylene acrylate glycidyl methacrylate (EA-GMA).

[0025] In an embodiment, the glycol component comprises 60 to 95 mol% of cyclohexanedimethanol residues and 5 to 40 mol% of 2,2,4,4-tetramethylcyclobutane-1,3-diol residues. In a specific embodiment, the glycol component comprises 70 to 95 mol% of cyclohexanedimethanol residues and 5 to 30, or 10 to 30, or 15 to 30, or 20 to 30, or 15 to 25 mol% of 2,2,4,4-tetramethylcyclobutane-1,3-diol residues. In a specific embodiment, the glycol component comprises 60 to 75 mol% of cyclohexanedimethanol residues and 25 to 40, or 30 to 40 mol% of 2,2,4,4-tetramethylcyclobutane-1,3-diol residues.

[0026] In the embodiment, the intrinsic viscosity of the copolyester is 0.55 to 0.85, or 0.55 to 0.65, or 0.65 to 0.80, or 0.65 to 0.75 dL / g.

[0027] In an embodiment, the flame retardant additive comprises an aluminum phosphinate-containing compound. In a specific embodiment, the flame retardant additive is aluminum diethyl phosphinate.

[0028] In an embodiment, the silane-modified silicate mineral has an average length greater than 10 micrometers, or greater than 12 micrometers, or greater than 14 micrometers, or greater than 16 micrometers, and an aspect ratio (length:diameter, or L:D) greater than 8:1, or greater than 9:1, or greater than 9.5:1. In an embodiment, the silane-modified silicate mineral has an average length in the range of 12 to 40 micrometers, or 12 to 30 micrometers, or 14 to 22 micrometers, or 16 to 20 micrometers. In an embodiment, the silane-modified silicate mineral is calcium metasilicate, for example, wollastonite (or CaSiO3). In an embodiment, the silane-modified silicate mineral is aminosilane-modified.

[0029] In an embodiment, the flame retardant additive is present in an amount of 8 to 20 weight%, or 8 to 18 weight%, or 8 to 15 weight% of the copolyester composition.

[0030] In an embodiment, the copolyester composition contains an impact modifier component in an amount greater than 3 to 10 weight%, or 4 to 9 weight%, or 4 to 8 weight%, or 5 to 10 weight%.

[0031] In an embodiment, the copolyester composition comprises a reinforcing material component in an amount of 8 to 28 weight%, or 10 to 28 weight%, or 15 to 28 weight%, or 18 to 27 weight%, or 20 to 25 weight%.

[0032] In an embodiment, the copolyester composition further comprises (e) about 0.1 to about 5 weight percent of a silicone compatibilizer. In an embodiment, the silicone compatibilizer is liquid at 25°C. In an embodiment, the liquid silicone compatibilizer is an alkyl, epoxy, amino, methacryloyloxy, phenyl, or alkyl-phenyl silicone resin that is liquid at 25°C. In an embodiment, the liquid silicone resin comprises hydroxy and / or cyclophenylmethicone groups.

[0033] In an embodiment, the copolyester composition further comprises (f) one or more antioxidants in an amount of about 0.05 to about 2.0 weight%. In an embodiment, the one or more antioxidants comprise at least one primary antioxidant.

[0034] In an embodiment, the copolyester composition further comprises (g) about 0.05 to about 0.5 weight% of a drip suppessant additive. In another embodiment, the copolyester composition does not comprise a drip suppessant additive.

[0035] In an embodiment, the copolyester composition comprises a drop inhibition additive in an amount of 0.05 to 0.4 weight%, or 0.05 to 0.25 weight%, or 0.1 to 0.2 weight%. The drop inhibition agent may comprise a fluoropolymer. The fluoropolymer is polytetrafluoroethylene (PTFE), for example, Teflon TM It may include, but is not limited to, polytetrafluoroethylene.

[0036] In an embodiment, the copolyester composition further comprises a chain extender. In a specific embodiment, the chain extender comprises a multifunctional epoxide chain extender.

[0037] In an embodiment, the copolyester composition has a notched Izod impact strength of 40, 50, 60, 70, 80, 90, or 100 J / m or more when measured according to ASTM D256. In one embodiment, the copolyester composition exhibits 100% ductile behavior when tested according to ASTM D256.

[0038] In an embodiment, the copolyester composition has a flexural modulus of 2500 MPa or more, or 3000 MPa or more, or 3500 MPa or more, or 4000 MPa or more when measured according to ASTM D790.

[0039] In an embodiment, the copolyester composition has a tensile elongation at break of 10% or more, or 15% or more, or 20% or more when measured according to ASTM D638.

[0040] In another aspect, an article comprising a copolyester composition according to one or more of the embodiments described herein, or any combination of the embodiments, is provided. In the embodiments, the article is in the form of a film, a sheet, a molded part, or a profile. Specific details for implementing the invention

[0041] The present invention can be more easily understood by referring to the following detailed description and examples of specific embodiments of the present invention.

[0042] In accordance with the purpose of the present invention, specific embodiments of the present invention are described in the content of the present invention and are further described below in this specification. Additionally, other embodiments of the present invention are described in this specification.

[0043] The present invention provides a copolyester composition comprising a copolyester component, a flame retardant additive, an impact modifier component, and a reinforcing material component, which exhibits excellent flame retardancy, high tensile and / or flexural modulus, and excellent toughness, an article prepared therefrom, and a method for preparing said composition and said article. The present invention relates to using a specific class of flame retardant additive, an impact modifier, and a silicate mineral to provide a relatively high modulus of elasticity and maintain excellent impact properties while simultaneously improving flame retardant properties.

[0044] In an embodiment, the flame retardant additive comprises a metal, for example, an aluminum phosphinate compound. When the flame retardant is added to the copolyester composition at an appropriate concentration, a flame-retardant composition may be provided having a flexural and / or tensile modulus of 2500 MPa or more, or 3000 MPa or more, or 3500 MPa or more, or 4000 MPa or more, or 4500 MPa or more, as measured according to ASTM D790. In an embodiment, the composition may also have a tensile elongation at break of 10% or more, or 15% or more, or 20% or more, as measured according to ASTM D638. In an embodiment, the composition may have a notched Izod impact strength greater than about 60 J / m, or 65, or 70, or 75, or 80, or 85, or 90, or 95, or 100 J / m or more, as measured according to ASTM D256.

[0045] Flammability was measured using the Underwriters Laboratories test standard UL 94 vertical combustion test. This test measures the ability of a plastic part to extinguish a flame and exhibit spot behavior after ignition in response to a small open flame or radiant heat source under controlled laboratory conditions. This test utilizes a specimen 13 mm wide x 126 mm long, which is fixed at one end in a vertical position and can be tested as a function of specimen thickness. A burner flame is applied to the free end of the specimen twice for 10 seconds, with an interval between the two flame applications equal to the time required for flame combustion to cease after the first application. The duration of the flame, spot behavior, and whether the spot sample ignites a piece of the surface beneath the specimen are all recorded. A combination of this data determines the UL 94 rating (V-2, V-1, V-0, 5VB, and 5VA, in order from highest to lowest flammability). Generally, a rating of V-0 or higher is desirable for selected applications where the plastic may come into contact with a power source, such as a battery, or be exposed to flame. UL 94 ratings are provided for specific materials at specific sample thicknesses (e.g., 0.8 mm, 1.2 mm, 1.5 mm, 1.6 mm, 3.0 mm, or 3.2 mm). For flame-retardant polymeric materials, thinner samples typically burn and / or ignite more easily, resulting in a lower rating. In an embodiment, the UL 94 rating is V-0 or higher at thicknesses of 3.2 mm or less, or 1.6 mm or less, or 1.5 mm or less, or 1.2 mm or less, or 1.0 mm or less, or 0.8 mm or less. In one embodiment, a copolyester composition has a UL 94 rating of V-0 or higher at a thickness of 1.5 mm.

[0046] In an embodiment, the metal phosphinate compound comprises a metal selected from calcium, magnesium, aluminum, and / or zinc. In an embodiment, the metal phosphinate compound is aluminum phosphinate. In an embodiment, the metal phosphinate is a metal dialkyl phosphinate. In an embodiment, the metal phosphinate is aluminum dialkyl phosphinate. In one embodiment, the aluminum dialkyl phosphinate compound is aluminum diethyl phosphinate. In an embodiment, the metal phosphinate compound, e.g., aluminum diethyl phosphinate, is present in an amount of 8 to 20 weight%, or 8 to 18 weight%, or 8 to 16 weight%, or 10 to 14 weight% of the copolyester composition.

[0047] In an embodiment, the copolyester composition comprises a first metal phosphinate flame retardant and at least one additional second flame retardant that is different from the first metal phosphinate flame retardant. In an embodiment, the copolyester composition comprises two or more metal phosphinate flame retardants that are different from each other. Different flame retardants mean chemically different and / or physically different. For example, a first aluminum diethyl phosphinate flame retardant having a first average particle size and a second aluminum diethyl phosphinate flame retardant having a second average particle size (different from the first average particle size) will be considered different flame retardants.

[0048] The particle size of an aluminum phosphinate compound can be described using the D(n) value. This value represents the particle diameter at (n)% of the cumulative distribution. For example, if D50 is 75 μm, 50% of the particles have a diameter larger than 75 μm, and 50% of the particles have a diameter smaller than 75 μm. If D95 is 10 μm, only 5% of the particles have a diameter larger than 10 μm, and 95% of the particles have a diameter smaller than 10 μm. The particle size distribution can be measured using one of many methods and instruments known in the art (particularly sieving, laser diffraction). Generally, the introduction of aluminum phosphinates with a smaller particle size distribution has been proven to exhibit improved toughness and lower notch sensitivity in these copolyester systems. A larger particle size distribution has exhibited improved flammability. For this reason, it is desirable to control the particle size distribution of the aluminum phosphinates used in the composition. In an embodiment, the aluminum phosphinate compound has a D50 value of less than 100 μm, less than 75 μm, less than 50 μm, less than 30 μm, or less than 25 μm. In an embodiment, the aluminum phosphinate compound has a D95 value of less than 50 μm, less than 30 μm, less than 20 μm, or less than 10 μm. In an embodiment, the aluminum phosphinate compound has a unimodal particle size distribution curve. In an embodiment, the aluminum phosphinate compound exhibits a bimodal or multimodal particle size distribution curve as a result of blending multiple particle sizes or by selecting a manufacturing method for generating a bimodal or multimodal particle size distribution curve.

[0049] In certain embodiments, the aluminum phosphinate compound may be a commercially available product such as OP 1240 or OP 935 (both derived from Clariant).

[0050] In an embodiment, the copolyester composition further comprises a small amount of a droplet suppression additive (as discussed herein), but less than 1 weight%, or less than 0.5 weight%, or less than 0.25 weight%, or less than 0.1 weight%, or less than 0.05 weight% of a flame retardant enhancer additive, or does not comprise a flame retardant enhancer additive. In an embodiment, the copolyester composition does not comprise a droplet suppression additive.

[0051] In the embodiments, a flame retardant enhancer may be used. In the embodiments, the flame retardant enhancer additive may comprise a phosphorus-containing compound selected from a phosphorus, nitrogen and / or sulfur-containing compound; a phosphazene compound; an oligomeric phosphate ester; or a combination thereof. Some examples of enhancers may include melamine polyphosphate (MPP), liquid phosphorus compounds, such as PhireGuard RDP and PhireGuard BDP, or other organophosphorus compounds containing phosphorus (V) having a double bond between P and N, for example.

[0052] With respect to the impact modifier component (c), the impact modifier component comprises one or more acrylic silicone polymer impact modifiers. These compounds are generally in the form of elastomer compounds or polymers that serve to absorb or dissipate the kinetic energy of an impact. In an embodiment, the impact modifier exists in a dispersed phase, and the copolyester is included in the continuous phase of the entire copolyester composition. One example comprises a core-shell polymer, wherein the core is composed of a rubbery polymer, for example, the core is composed of a silicone polymer or an acrylic silicone copolymer and the shell is composed of an acrylic polymer or an acrylic silicone copolymer. In a specific embodiment, the impact modifier component comprises an acrylic silicone polymer impact modifier and at least one additional impact modifier. Examples of additional impact modifiers that may be included in the impact modifier component include, in a specific embodiment, various known graft copolymers, other core-shell polymers, and block copolymers. These polymers may comprise at least one monomer selected from the group consisting of alkenes, alkadienes, arenes, acrylates, and alcohols. (See, for example, EP 1,694,771B1). An example of an additional impact modifier comprises a core-shell polymer, wherein the core is composed of a rubbery polymer and the shell is composed of a styrene copolymer (see, for example, U.S. Patent No. 5,321,056, by reference herein). Other examples comprise a core-shell and a functional polyolefin such as that described in U.S. 2014 / 0256848 A1, by reference herein. Also refer to EP 2 139 948 B1.

[0053] In a specific embodiment, the impact modifier component comprises an acrylic silicone impact modifier present as a dispersed phase in the composition. In a specific embodiment, the acrylic silicone impact modifier has a core-shell structure having a particle size (D50) in the range of 75 to 300 micrometers, 100 to 250 micrometers, or 100 to 200 micrometers. In a specific embodiment, the acrylic silicone impact modifier has a core-shell structure having an average particle size in the range of 650 to 1000 micrometers, or 700 to 950 micrometers, or 750 to 900 micrometers, or 800 to 900 micrometers. In an embodiment, the core-shell acrylic silicone impact modifier has a specific gravity in the range of 0.95 to 1.2 g / cm³, or 1.0 to 1.15 g / cm³, or 1.0 to 1.1 g / cm³. In an embodiment, the core-shell acrylic silicone impact modifier has a bulk density in the range of 0.25 to 0.45 g / cm³ or 0.30 to 0.40 g / cm³. In an embodiment, the acrylic silicone impact modifier contains an acrylic content of less than 50 wt%, or less than 40 wt%, or less than 30 wt%, or less than 20 wt%, or less than 10 wt%, or less than 5 wt%, or less than 3 wt%. In an embodiment, the acrylic content is in the shell of the core-shell impact modifier. In an embodiment, the acrylic content is in both the core and the shell of the core-shell impact modifier.

[0054] In an embodiment, the impact modifier component comprises an acrylic silicone polymer impact modifier in an amount of about 3 to about 10 weight%, or 3 to 9 weight%, or 4 to 8 weight%, or 5 to 7 weight% based on the total copolyester composition. In an embodiment, the copolyester composition contains any other impact modifier in an amount of less than 5 weight%, or less than 3 weight%, or less than 1 weight% based on the total weight of the copolyester composition. In an embodiment, the impact modifier component is an acrylic silicone polymer impact modifier, and the copolyester composition does not contain any other impact modifier.

[0055] In an embodiment, the acrylic silicone impact modifier is a core-shell impact modifier. In an embodiment, the silicone content is in the core of the core-shell impact modifier. In an embodiment, the acrylic content is in both the core and the shell of the core-shell impact modifier. In an embodiment, the acrylic content is in the shell of the core-shell impact modifier.

[0056] In certain embodiments, the impact modifier is classified as non-reactive. In certain embodiments, the impact modifier component does not contain ethylene acrylate glycidyl methacrylate (EA-GMA). In certain embodiments, the acrylic silicone impact modifier comprises a silicone / acrylate rubber having grafted maleic anhydride (MA) groups.

[0057] Commercially available acrylic silicone polymer impact modifiers include Kane Ace® MR-01, MR-02, MR-03, or MR-502 available from Kaneka Americas Holding, Inc., Metablen S-2100, S-2501, and S2200 available from Mitsubishi Chemical, BX IM 230 available from Baoxu Chemical, and TFL-205HC impact modifier available from Eversun Polycarnate Sci&Tech Co., LTD.

[0058] Examples of additional impact modifiers that may be used include, but are not limited to, ethylene / propylene terpolymers; functionalized polyolefins, such as those containing methyl acrylate and / or glycidyl methacrylate; styrene-based block copolymer impact modifiers; and various acrylic core / shell type impact modifiers. Residues of these additives are also considered as part of the polyester composition.

[0059] Commercially available products of additional shock modifiers include the following.

[0060] Modiper® 4300 and Modiper® 4400 available from Nippon Oil & Fat Corporation; Kane Ace® M300 available from Kaneka Americas Holding, Inc.; Kane Ace® B564 available from Kaneka Americas Holding, Inc.; Kane Ace® ECO 1000 available from Kaneka Americas Holding, Inc.; and Lotader® 8900 available from Arkema.

[0061] The impact modifier used as component (c) is generally present in an amount of about 3 to about 10 weight percent. In other embodiments, they are present in amounts greater than about 3 to 10 weight%, or 4 to 10 weight%, or 5 to 10 weight%, or greater than 5 to 10 weight%, or 6 to 10 weight%, or 3 to 9 weight%, or greater than 3 to 9 weight%, or 4 to 9 weight%, or 5 to 9 weight%, or greater than 5 to 9 weight%, or 6 to 9 weight%, or 3 to 8 weight%, or greater than 3 to 8 weight%, or 4 to 8 weight%, or 5 to 8 weight%, or greater than 5 to 8 weight%, or 6 to 8 weight%, or 3 to 7 weight%, or greater than 3 to 7 weight%, or 4 to 7 weight%, or 5 to 7 weight%, or greater than 5 to 7 weight%.

[0062] In an embodiment, the flame retardant (FR) and the impact modifier (IM) (as described herein) are present in the copolyester composition in a weight ratio of FR:IM greater than 1:1, or 1.1:1, or 1.25:1, or 1.4:1, or 1.5:1, or 1.75:1, or 2:1, or 2.25:1, or 2.5:1, or 2.75:1, or 3:1, or 3.25:1, or 3.5:1, or 3.75:1, or 4:1. In an embodiment, the weight ratio of FR:IM is 1.1 to 4.5:1, or 1.4 to 4.5:1, or 1.5 to 4.5:1, or 2 to 4.5:1, or 2.5 to 4.5:1, or 3 to 4.5:1, or 3.5 to 4.5:1, or 1.1 to 4.25:1, or 1.4 to 4.25:1, or 1.5 to 4.25:1, or 2 to 4.25:1, or 2.5 to 4.25:1, or 3 to 4.25:1, or 3.5 to 4.25:1, or 1.1 to 4:1, or 1.4 to 4:1, or 1.5 to 4:1, or 2 to 4:1, or 2.5 to 4:1, or 3 to 4:1, or 3.5 to 4:1, or 1.1 to 3.5:1, or 1.4 to 3.5:1, or 1.5 to 3.5:1, or 2 to 3.5:1, or 3.5 to 4.5:1, or 3 to 3.5:1, or 1.1 to 3:1, or 1.4 to 3:1, or 1.5 to 3:1, or 2 to 3:1, or 2.5 to 3:1, or 1.1 to 2.5:1, or 1.4 to 2.5:1, or 1.5 to 2.5:1, or 2 to 2.5:1, or 1.1 to 2:1, or 1.4 to 2:1, or 1.5 to 2:1, or 1.1 to 2:1, or 1.4 to 2:1, or 1.5 to 2:1, or 1.1 to 2:1, or 1.4 to It is in the range of 2:1, or 1.5 to 2:1.In certain embodiments, FR is an aluminum phosphinate, e.g., aluminum diethyl phosphinate, and IM is an acrylic silicone polymer, e.g., a core-shell acrylic silicone polymer. In embodiments, these FR and IM are present in one or more of the ratios discussed above.

[0063] In an embodiment, the silane-modified silicate mineral has an average length greater than 10 micrometers, or greater than 12 micrometers, or greater than 14 micrometers, or greater than 16 micrometers, and an aspect ratio (length:diameter, or L:D) greater than 8:1, or greater than 9:1, or greater than 9.5:1. In an embodiment, the silane-modified silicate mineral has an average length in the range of 12 to 40 micrometers, or 12 to 30 micrometers, or 14 to 22 micrometers, or 16 to 20 micrometers. In an embodiment, the silane-modified silicate mineral is calcium metasilicate, for example, wollastonite (or CaSiO3). In an embodiment, the silane-modified silicate mineral is aminosilane-modified.

[0064] In an embodiment, the copolyester composition comprises a reinforcing material component in an amount greater than 5 to less than 30 weight%, or 6 to 28 weight%, or 8 to 26 weight%, or 10 to 25 weight%, or 15 to 25 weight%, or 18 to 25 weight%, or 20 to 25 weight%, based on the total weight of the copolyester composition. In an embodiment, the reinforcing material component is essentially composed of a silane-modified silicate material, or is composed thereof.

[0065] Commercially available silane-modified silicate minerals include WLA-18 and WLA-6 aminosilane-modified wollastonite available from Muheng Material Technology (Shanghai) Co., Ltd., and Wollastokup available from Malvern Minerals Company.

[0066] The copolyester useful for the present invention comprises a residue of an aromatic diacid and a residue of two or more glycols.

[0067] The term 'copolyester' is understood to mean a synthetic polymer prepared by the reaction of one or more difunctional carboxylic acids and / or polyfunctional carboxylic acids with one or more difunctional hydroxyl compounds and / or polyfunctional hydroxyl compounds, intended to include 'polyester' as used herein. Typically, the difunctional carboxylic acid may be a dicarboxylic acid, and the difunctional hydroxyl compound may be a dihydric alcohol, such as a glycol, for example. Additionally, as used herein, the interchangeable terms 'diacid' or 'dicarboxylic acid' include polyfunctional acids, such as branching agents. The term 'glycol' includes, but is not limited to, diols, glycols, and / or polyfunctional hydroxyl compounds as used herein. Alternatively, the difunctional carboxylic acid may be a hydroxycarboxylic acid, for example, p-hydroxybenzoic acid, and the difunctional hydroxyl compound may be an aromatic nucleus having two hydroxyl substituents, for example, hydroquinone. As used herein, the term 'residue' refers to any organic structure incorporated into the polymer via polycondensation and / or esterification reactions from the corresponding monomer. As used herein, the term 'repeating unit' refers to an organic structure having a dicarboxylic acid residue and a diol residue connected via a carbonyloxy group. Thus, for example, the dicarboxylic acid residue may be derived from a dicarboxylic acid monomer or its associated acid halide, ester, salt, anhydride, or mixture thereof. Accordingly, as used herein, the term dicarboxylic acid is intended to include any derivative of a dicarboxylic acid, including its related acid halides, esters, semi-esters, salts, semi-salts, anhydrides, mixed anhydrides, or mixtures thereof, which are useful in the reaction process with a diol to form a polyester.As used herein, the term 'terephthalic acid' is intended to include terephthalic acid itself and its residues useful in the reaction process with a diol for producing a polyester, as well as its related acid halides, esters, semi-esters, salts, semi-salts, anhydrides, mixed anhydrides, or mixtures thereof, or any derivatives of terephthalic acid comprising residues thereof. The term 'modified aromatic diacid' means an aromatic dicarboxylic acid other than terephthalic acid. The term 'modified glycol' means a glycol other than cyclohexanedimethanol (CHDM) or 2,2,4,4-tetramethylcyclobutane-1,3-diol (TMCD).

[0068] In one embodiment, terephthalic acid may be used as a starting material. In another embodiment, dimethyl terephthalate may be used as a starting material. In yet another embodiment, a mixture of terephthalic acid and dimethyl terephthalate may be used as a starting material and / or an intermediate material.

[0069] The copolyester used in the present invention can typically be prepared from a dicarboxylic acid and a diol that react in substantially equal proportions and are incorporated into the copolyester polymer as their corresponding residues. Accordingly, the copolyester of the present invention may contain substantially equal molar ratios of acid residues (100 mol%) and diol (and / or polyfunctional hydroxyl compound) residues (100 mol%) such that the total moles of repeating units equal 100 mol%. Accordingly, the molar percentages provided in this disclosure may be based on the total moles of acid residues, the total moles of diol residues, or the total moles of repeating units. For example, a copolyester containing 30 mol% isophthalic acid based on total acid residues means that the copolyester contains 30 mol% isophthalic acid residues out of a total of 100 mol% acid residues. Thus, 30 moles of isophthalic acid residues are present out of 100 moles of all acid residues. In another example, a copolyester containing 30 mol% 1,4-cyclohexanedimethanol based on total diol residues means that the copolyester contains 30 mol% 1,4-cyclohexanedimethanol residues out of a total of 100 mol% diol residues. Thus, 30 mol of 1,4-cyclohexanedimethanol residues are present out of 100 mol of all diol residues.

[0070] In an embodiment, the copolyester comprises 70 to 100 mol% terephthalic acid (TPA). Alternatively, the copolyester comprises 80 to 100 mol% TPA, or 90 to 100 mol% TPA, or 95 to 100 mol% TPA, or 100 mol% TPA. For the purposes of the present invention, the terms 'terephthalic acid' and 'dimethyl terephthalate' are used interchangeably herein.

[0071] In addition to terephthalic acid, the dicarboxylic acid component of the copolyester useful in the present invention may comprise one or more modified aromatic dicarboxylic acids in an amount of up to 30 mol%, up to 20 mol%, up to 10 mol%, up to 5 mol%, or up to 1 mol%. Another embodiment contains 0 mol% of a modified aromatic dicarboxylic acid. Accordingly, it is considered that, where present, the amount of one or more modified aromatic dicarboxylic acids may be a range from any of these earlier endpoint values, including, for example, 0.01 to 30 mol%, 0.01 to 20 mol%, 0.01 to 10 mol%, 0.01 to 5 mol%, and 0.01 to 1 mol. In one embodiment, the modified aromatic dicarboxylic acids that may be used in the present invention include, but are not limited to, those having up to 20 carbon atoms, which may be linear, para-oriented, or symmetric. Examples of modified aromatic dicarboxylic acids that can be used in the present 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'-stilbendicarboxylic acid, and esters thereof. In one embodiment, the modified aromatic dicarboxylic acid is isophthalic acid.

[0072] The carboxylic acid component of the copolyester useful in the present invention may be further modified with one or more aliphatic dicarboxylic acids containing 2 to 16 carbon atoms, such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, souveric acid, azelaic acid, and dodecandioic dicarboxylic acid, in an amount of up to 10 mol%, e.g., up to 5 mol% or up to 1 mol%. Certain embodiments may also contain one or more modified aliphatic dicarboxylic acids in an amount of 0.01 mol% or more, e.g., 0.1 mol% or more, 1 mol% or more, 5 mol% or more, or 10 mol% or more. Additionally, another embodiment contains 0 mol% of modified aliphatic dicarboxylic acid. Accordingly, where present, the amount of one or more modified aromatic dicarboxylic acids is considered to be within the range of any of the aforementioned endpoint values, including, for example, 0.01 to 10 mol% and 0.1 to 10 mol%. The total mol% of the dicarboxylic acid components is 100 mol%.

[0073] Esters of terephthalic acid and other modified dicarboxylic acids, or their corresponding esters and / or salts, may be used instead of dicarboxylic acids. Suitable examples of dicarboxylic acid esters include, but are not limited to, dimethyl, diethyl, dipropyl, diisopropyl, dibutyl, and diphenyl esters. In one embodiment, the ester is selected from at least one of the following: methyl, ethyl, propyl, isopropyl, and phenyl esters.

[0074] A copolyester useful in the copolyester composition of the present invention may comprise, based on the total molar percentage of the diol or diacid residues, 0 to 10 mol%, e.g., 0.01 to 5 mol%, 0.01 to 1 mol%, 0.05 to 5 mol%, 0.05 to 1 mol%, or 0.1 to 0.7 mol%; each having three or more carboxyl substituents, hydroxyl substituents, or combinations thereof, and may comprise one or more residues of a branching monomer referred herein as a branching agent. In certain embodiments, the branching monomer or agent may be added before and / or during and / or after the polymerization of the polyester. Thus, the copolyester(s) useful in the present invention may be linear or branched.

[0075] Examples of branched monomers include, but are not limited to, polyfunctional acids or polyfunctional alcohols, such as trimellitic acid, trimellitic anhydride, pyromellitic dianhydride, trimethylolpropane, glycerol, pentaerythritol, citric acid, tartaric acid, 3-hydroxyglutarate, etc. In one embodiment, the branched monomer residue may comprise 0.1 to 0.7 mol% of one or more residues selected from at least one of the following: trimellitic anhydride, pyromellitic dianhydride, glycerol, sorbitol, 1,2,6-hexanetriol, pentaerythritol, trimethylolethane, and / or trimesic acid. The branched monomer may be added to a polyester reaction mixture in the form of a concentrate or blended with the polyester, for example, as described in U.S. Patent Nos. 5,654,347 and 5,696,176, whose disclosures regarding the branched monomer are incorporated herein by reference.

[0076] In an embodiment, CHDM may be 1,4-cyclohexanedimethanol. 1,4-cyclohexanedimethanol may be cis, trans, or a mixture thereof, for example, in a cis / trans ratio of 60:40 to 40:60. In another embodiment, trans-1,4-cyclohexanedimethanol may be present in an amount of 60 to 80 mol%. Alternatively, 1,2- and / or 1-3-cyclohexanedimethanol may be used individually or in combination with each other and / or 1,4-cyclohexanedimethanol.

[0077] In various embodiments, the glycol component of the copolyester portion of the useful copolyester composition may contain a modified glycol other than CHDM or TMCD, and in one embodiment, the useful copolyester of the present invention may contain one or more modified glycols in an amount of less than 15 mol% or 10 mol% or less.

[0078] The modified glycol useful in the copolyester useful in the embodiments refers to a diol other than CHDM or TMCD and may contain 2 to 20, or 2 to 16, carbon atoms. Examples of suitable modified glycols include, but are not limited to, ethylene glycol, 1,2-propanediol, 1,3-propanediol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, p-xylene glycol, isosorbide, or mixtures thereof. In another embodiment, the modified glycol is 1,3-propanediol and / or 1,4-butanediol.

[0079] In an embodiment, the copolyester composition comprises at least one polyester, and this,

[0080] (a) As a dicarboxylic acid component,

[0081] i) 70 to 100 mol% of terephthalic acid residues;

[0082] ii) an aromatic dicarboxylic acid residue having up to 20 carbon atoms in an amount of 0 to 30 mol%; and

[0083] iii) a dicarboxylic acid component comprising an aliphatic dicarboxylic acid residue having up to 16 carbon atoms in an amount of 0 to 10 mol%; and

[0084] (b) As a glycol component,

[0085] i) 5 to 55 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) residues; and

[0086] ii) comprising a glycol component containing 45 to 95 mol% of 1,4-cyclohexanedimethanol (CHDM) residues, wherein the total mol% of the dicarboxylic acid component is 100 mol% and the total mol% of the glycol component is 100 mol%, and

[0087] The intrinsic viscosity of the polyester is 0.5 to 1.2 dL / g when determined in 60 / 40 (wt / wt) phenol / tetrachloroethane at a concentration of 0.5 g / 100 ml at 25°C, and the polyester has a Tg of 100 to 200°C.

[0088] In an embodiment, the polyester composition comprises at least one polyester, and this,

[0089] (a) As a dicarboxylic acid component,

[0090] i) 70 to 100 mol% of terephthalic acid residues;

[0091] ii) an aromatic dicarboxylic acid residue having up to 20 carbon atoms in an amount of 0 to 30 mol%; and

[0092] iii) a dicarboxylic acid component comprising an aliphatic dicarboxylic acid residue having up to 16 carbon atoms in an amount of 0 to 10 mol%; and

[0093] (b) As a glycol component,

[0094] i) 20 to 40 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and

[0095] ii) comprising a glycol component containing 60 to 80 mol% of 1,4-cyclohexanedimethanol residues, wherein the total mol% of the dicarboxylic acid component is 100 mol% and the total mol% of the glycol component is 100 mol%, and

[0096] The intrinsic viscosity of the polyester is 0.35 to 0.85 dL / g when determined in 60 / 40 (wt / wt) phenol / tetrachloroethane at a concentration of 0.5 g / 100 ml at 25°C, and the polyester has a Tg of 100 to 120°C.

[0097] In an embodiment, the polyester composition comprises at least one polyester, and this,

[0098] (a) As a dicarboxylic acid component,

[0099] i) 70 to 100 mol% of terephthalic acid residues;

[0100] ii) an aromatic dicarboxylic acid residue having up to 20 carbon atoms in an amount of 0 to 30 mol%; and

[0101] iii) a dicarboxylic acid component comprising an aliphatic dicarboxylic acid residue having up to 16 carbon atoms in an amount of 0 to 10 mol%; and

[0102] (b) As a glycol component,

[0103] i) 40 to 55 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and

[0104] ii) comprising a glycol component containing 45 to 60 mol% of 1,4-cyclohexanedimethanol residues, wherein the total mol% of the dicarboxylic acid component is 100 mol% and the total mol% of the glycol component is 100 mol%, and

[0105] The intrinsic viscosity of the polyester is 0.35 to 0.85 dL / g when determined in 60 / 40 (wt / wt) phenol / tetrachloroethane at a concentration of 0.5 g / 100 ml at 25°C, and the polyester has a Tg of 120 to 140°C.

[0106] In an embodiment, the polyester composition comprises at least one polyester, and this,

[0107] (a) As a dicarboxylic acid component,

[0108] i) 70 to 100 mol% of terephthalic acid residues;

[0109] ii) an aromatic dicarboxylic acid residue having up to 20 carbon atoms in an amount of 0 to 30 mol%; and

[0110] iii) a dicarboxylic acid component comprising an aliphatic dicarboxylic acid residue having up to 16 carbon atoms in an amount of 0 to 10 mol%; and

[0111] (b) As a glycol component,

[0112] i) 15 to 70 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and

[0113] ii) comprising a glycol component containing 30 to 85 mol% of 1,4-cyclohexanedimethanol residues, wherein the total mol% of the dicarboxylic acid component is 100 mol% and the total mol% of the glycol component is 100 mol%, and

[0114] The intrinsic viscosity of the polyester is 0.35 to 0.85 dL / g when determined in 60 / 40 (wt / wt) phenol / tetrachloroethane at a concentration of 0.5 g / 100 ml at 25°C, and the polyester has a Tg of 100 to 140°C.

[0115] In an embodiment, the polyester composition comprises at least one polyester, and this,

[0116] (a) As a dicarboxylic acid component,

[0117] i) 70 to 100 mol% of terephthalic acid residues;

[0118] ii) an aromatic dicarboxylic acid residue having up to 20 carbon atoms in an amount of 0 to 30 mol%; and

[0119] iii) a dicarboxylic acid component comprising an aliphatic dicarboxylic acid residue having up to 16 carbon atoms in an amount of 0 to 10 mol%; and

[0120] (b) As a glycol component,

[0121] i) 15 to 90 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and

[0122] ii) comprising a glycol component containing 10 to 85 mol% of 1,4-cyclohexanedimethanol residues, wherein the total mol% of the dicarboxylic acid component is 100 mol% and the total mol% of the glycol component is 100 mol%, and

[0123] The intrinsic viscosity of the polyester is 0.1 to 1.2 dL / g when determined in 60 / 40 (wt / wt) phenol / tetrachloroethane at a concentration of 0.5 g / 100 ml at 25°C, and the polyester has a Tg of 100 to 200°C.

[0124] In an embodiment, any one of the polyester or polyester composition described herein may further comprise at least one residue of a branching agent. In an embodiment, any one of the polyester or polyester composition described herein may comprise at least one heat stabilizer or a reaction product thereof.

[0125] In an embodiment, the polyester may contain less than 15 mol% of ethylene glycol residues, for example, 0.01 mol% to less than 15 mol% of ethylene glycol residues. In an embodiment, the polyester useful in the present invention contains less than 10 mol%, or less than 5 mol%, or less than 4 mol%, or less than 2 mol%, or less than 1 mol% of ethylene glycol residues, such as 0.01 to less than 10 mol%, or 0.01 to less than 5 mol%, or 0.01 to less than 4 mol%, or 0.01 to less than 2 mol%, or 0.01 to less than 1 mol% of ethylene glycol residues. In one embodiment, the polyester useful in the present invention does not contain ethylene glycol residues.

[0126] In another embodiment, the glycol component for the polyester may include at least one of the combinations in the following range, but is not limited thereto.5 mol% to less than 55 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 45 mol% to 95 mol% 1,4-cyclohexanedimethanol; 5 mol% to less than 50 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 50 mol% to 95 mol% 1,4-cyclohexanedimethanol; 5 mol% to less than 45 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 55 mol% to 95 mol% 1,4-cyclohexanedimethanol; 5 mol% to less than 40 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 60 mol% to 95 mol% 1,4-cyclohexanedimethanol; 10 to 40 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 60 to 90 mol% 1,4-cyclohexanedimethanol; 10 to 35 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 65 to 90 mol% 1,4-cyclohexanedimethanol; 10 to 30 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 70 to 90 mol% 1,4-cyclohexanedimethanol; 10 to 25 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 75 to 90 mol% 1,4-cyclohexanedimethanol; 15 to 40 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 60 to 85 mol% 1,4-cyclohexanedimethanol; 15 to 35 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 65 to 85 mol% 1,4-cyclohexanedimethanol; 15 to 30 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 70 to 85 mol% 1,4-cyclohexanedimethanol; 15 to 25 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 75 to 85 mol% 1,4-cyclohexanedimethanol; 15 to 20 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 75 to 80 mol% 1,4-cyclohexanedimethanol; and 17 to 23 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 77 to 83 mol% 1,4-cyclohexanedimethanol.

[0127] In a specific embodiment, the glycol component of the polyester portion of the polyester composition may contain one or more modified glycols other than 2,2,4,4-tetramethyl-1,3-cyclobutanediol or 1,4-cyclohexanedimethanol in an amount of 25 mol% or less, and in one embodiment, the polyester useful in the present invention may contain one or more modified glycols in an amount of less than 15 mol%. In another embodiment, the polyester may contain one or more modified glycols in an amount of 10 mol% or less. In another embodiment, the polyester may contain one or more modified glycols in an amount of 5 mol% or less. In another embodiment, the polyester may contain one or more modified glycols in an amount of 3 mol% or less. In another embodiment, the polyester may contain 0 mol% modified glycols. Certain embodiments may contain one or more modified glycols in an amount of 0.01 mol% or more, e.g., 0.1 mol% or more, 1 mol% or more, 5 mol% or more, or 10 mol% or more. Accordingly, it is considered that, where present, the amount of one or more modified glycols may be a range from any of these earlier endpoint values, including, e.g., 0.01 to 15 mol% and 0.1 to 10 mol%.

[0128] In the embodiments, the modified glycol in the polyester may refer to a diol other than 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol and may contain 2 to 16 carbon atoms. Examples of suitable modified glycols include, but are not limited to, ethylene glycol, 1,2-propanediol, 1,3-propanediol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, p-xylene glycol, or mixtures thereof in certain embodiments. In one embodiment, the modified glycol is ethylene glycol. In another embodiment, the modified glycol is 1,3-propanediol and / or 1,4-butanediol. In yet another embodiment, ethylene glycol is excluded as the modified diol. In another embodiment, 1,3-propanediol and 1,4-butanediol are excluded as modified diols. In another embodiment, 2,2-dimethyl-1,3-propanediol is excluded as modified diols.

[0129] In an embodiment, the molar percentage of cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol in a specific polyester is greater than 50 molar% or greater than 55 molar% of cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol or greater than 70 molar% of cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol, and the total molar percentage of cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol and trans-2,2,4,4-tetramethyl-1,3-cyclobutanediol is equal to a total of 100 molar%.

[0130] In an embodiment, the molar percentage of the isomer of 2,2,4,4-tetramethyl-1,3-cyclobutanediol in a specific polyester is 30 to 70 molar% of cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol or 30 to 70 molar% of trans-2,2,4,4-tetramethyl-1,3-cyclobutanediol, or 40 to 60 molar% of cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol or 40 to 60 molar% of trans-2,2,4,4-tetramethyl-1,3-cyclobutanediol, wherein the total molar percentage of cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol and trans-2,2,4,4-tetramethyl-1,3-cyclobutanediol is equal to a total of 100 molar%.

[0131] In certain embodiments, the polyester may be amorphous or semi-crystalline. In one aspect, the certain polyester may have a relatively low degree of crystallinity. Thus, the certain polyester may have a substantially amorphous morphology, which means that the polyester contains substantially disordered polymer regions.

[0132] In an embodiment, the Tg of the polyester may be at least one of the following ranges: 100 to 200°C; 100 to 190°C; 100 to 180°C; 100 to 170°C; 100 to 160°C; 100 to 155°C; 100 to 150°C; 100 to 145°C; 100 to 140°C; 100 to 138°C; 100 to 135°C; 100 to 130°C; 100 to 125°C; 100 to 120°C; 100 to 115°C; 100 to 110°C; 105 to 200°C; 105 to 190°C; 105 to 180°C; 105 to 170°C; 105 to 160℃; 105 to 155℃; 105 to 150℃; 105 to 145℃; 105 to 140℃; 105 to 138℃; 105 to 135℃; 105 to 130℃; 105 to 125℃; 105 to 120℃; 105 to 115℃; 105 to 110℃; greater than 105 to 125℃; greater than 105 to 120℃; greater than 105 to 115℃; greater than 105 to 110℃; 110 to 200℃; 110 to 190℃; 110 to 180℃; 110 to 170℃; 110 to 160℃; 110 to 155℃; 110 to 150℃; 110 to 145℃; 110 to 140℃; 110 to 138℃; 110 to 135℃; 110 to 130℃; 110 to 125℃; 110 to 120℃; 110 to 115℃; 115 to 200℃; 115 to 190℃; 115 to 180℃; 115 to 170℃; 115 to 160℃; 115 to 155℃; 115 to 150℃; 115 to 145℃; 115 to 140℃; 115 to 138℃; 115 to 135℃; 110 to 130℃; 115 to 125℃; 115 to 120℃; 120 to 200℃; 120 to 190℃; 120 to 180℃; 120 to 170℃; 120 to 160℃; 120 to 155℃; 120 to 150℃; 120 to 145℃;120 to 140℃; 120 to 138℃; 120 to 135℃; 120 to 130℃; 125 to 200℃; 125 to 190℃; 125 to 180℃; 125 to 170℃; 125 to 160℃; 125 to 155℃; 125 to 150℃; 125 to 145℃; 125 to 140℃; 125 to 138℃; 125 to 135℃; 127 to 200℃; 127 to 190℃; 127 to 180℃; 127 to 170℃; 127 to 160℃; 127 to 150℃; 127 to 145℃; 127 to 140℃; 127 to 138℃; 127 to 135℃; 130 to 200℃; 130 to 190℃; 130 to 180℃; 130 to 170℃; 130 to 160℃; 130 to 155℃; 130 to 150℃; 130 to 145℃; 130 to 140℃; 130 to 138℃; 130 to 135℃; 135 to 200℃; 135 to 190℃; 135 to 180℃; 135 to 170℃; 135 to 160℃; 135 to 155℃; 135 to 150℃; 135 to 145℃; 135 to 140℃; 140 to 200℃; 140 to 190℃; 140 to 180℃; 140 to 170℃; 140 to 160℃; 140 to 155℃; 140 to 150℃; 140 to 145℃; 148 to 200℃; 148 to 190℃; 148 to 180℃; 148 to 170℃; 148 to 160℃; 148 to 155℃; 148 to 150℃; 150 to 200℃; 150 to 190℃; 150 to 180℃; 150 to 170℃; 150 to 160; 155 to 190℃; 155 to 180℃; 155 to 170℃; and 155 to 165℃.;

[0133] The glass transition temperature (Tg) of polyester can be determined using a TA DSC 2920 from Thermal Analyst Instrument at a scan rate of 20°C / min.

[0134] In certain embodiments, the polyester may exhibit at least one of the following intrinsic viscosities determined in 60 / 40 (wt / wt) phenol / tetrachloroethane at a concentration of 0.5 g / 100 ml at 25°C: 0.10 to 1.2 dL / g; 0.10 to 1.1 dL / g; 0.10 to 1 dL / g; 0.10 dL / g; less than 1 dL / g; 0.10 to 0.98 dL / g; 0.10 to 0.95 dL / g; 0.10 to 0.90 dL / g; 0.10 to 0.85 dL / g; 0.10 to 0.80 dL / g; 0.10 to 0.75 dL / g; 0.10 dL / g < 0.75 dL / g; 0.10 to 0.72 dL / g; 0.10 to 0.70 dL / g; 0.10 dL / g < 0.70 dL / g; 0.10 to 0.68 dL / g; 0.10 dL / g < 0.68 dL / g; 0.10 to 0.65 dL / g; 0.20 to 1.2 dL / g; 0.20 to 1.1 dL / g; 0.20 to 1 dL / g; 0.20 dL / g < 1 dL / g; 0.20 to 0.98 dL / g; 0.20 to 0.95 dL / g; 0.20 to 0.90 dL / g; 0.20 to 0.85 dL / g; 0.20 to 0.80 dL / g; 0.20 to 0.75 dL / g; 0.20 dL / g < 0.75 dL / g; 0.20 to 0.72 dL / g; 0.20 to 0.70 dL / g; 0.20 dL / g < 0.70 dL / g; 0.20 to 0.68 dL / g; 0.20 dL / g < 0.68 dL / g; 0.20 to 0.65 dL / g; 0.35 to 1.2 dL / g; 0.35 to 1.1 dL / g; 0.35 to 1 dL / g; 0.35 dL / g less than 1 dL / g; 0.35 to 0.98 dL / g; 0.35 to 0.95 dL / g; 0.35 to 0.90 dL / g; 0.35 to 0.85 dL / g; 0.35 to 0.80 dL / g; 0.35 to 0.75 dL / g; 0.35 dL / g less than 0.75 dL / g; 0.35 to 0.72 dL / g; 0.35 to 0.70 dL / g; 0.35 dL / g < 0.70 dL / g; 0.35 to 0.68 dL / g; 0.35 dL / g < 0.68 dL / g; 0.35 to 0.65 dL / g; 0.40 to 1.2 dL / g; 0.40 to 1.1 dL / g; 0.40 to 1 dL / g; 0.40 dL / g < 1 dL / g; 0.40 to 0.98 dL / g; 0.40 to 0.95 dL / g; 0.40 to 0.90 dL / g; 0.40 to 0.85 dL / g; 0.40 to 0.80 dL / g; 0.40 to 0.75 dL / g; 0.40 dL / g less than 0.75 dL / g; 0.40 to 0.72 dL / g; 0.40 to 0.70 dL / g; 0.40 dL / g less than 0.70 dL / g; 0.40 to 0.68 dL / g; 0.40 dL / g less than 0.68 dL / g; 0.40 to 0.65 dL / g; greater than 0.42 dL / g to 1.2 dL / g; greater than 0.42 dL / g to 1.1 dL / g; greater than 0.42 dL / g to 1 dL / g; Greater than 0.42 dL / g to less than 1 dL / g; greater than 0.42 dL / g to 0.98 dL / g; greater than 0.42 dL / g to 0.95 dL / g; greater than 0.42 dL / g to 0.90 dL / g; greater than 0.42 dL / g to 0.85 dL / g; greater than 0.42 dL / g to 0.80 dL / g; greater than 0.42 dL / g to 0.75 dL / g; greater than 0.42 dL / g to less than 0.75 dL / g; greater than 0.42 dL / g to 0.72 dL / g; greater than 0.42 dL / g to less than 0.70 dL / g; Greater than 0.42 dL / g to 0.68 dL / g; greater than 0.42 dL / g to less than 0.68 dL / g; and greater than 0.42 dL / g to 0.65 dL / g.

[0135] In certain embodiments, the polyester may exhibit at least one of the following intrinsic viscosities determined in 60 / 40 (wt / wt) phenol / tetrachloroethane at a concentration of 0.5 g / 100 ml at 25°C: 0.45 to 1.2 dL / g; 0.45 to 1.1 dL / g; 0.45 to 1 dL / g; 0.45 to 0.98 dL / g; 0.45 to 0.95 dL / g; 0.45 to 0.90 dL / g; 0.45 to 0.85 dL / g; 0.45 to 0.80 dL / g; 0.45 to 0.75 dL / g; less than 0.45 dL / g or less than 0.75 dL / g; 0.45 to 0.72 dL / g; 0.45 to 0.70 dL / g; 0.45 dL / g; less than 0.70 dL / g; 0.45 to 0.68 dL / g; 0.45 dL / g; less than 0.68 dL / g; 0.45 to 0.65 dL / g; 0.50 to 1.2 dL / g; 0.50 to 1.1 dL / g; 0.50 to 1 dL / g; 0.50 dL / g; less than 1 dL / g; 0.50 to 0.98 dL / g; 0.50 to 0.95 dL / g; 0.50 to 0.90 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 dL / g < 0.75 dL / g; 0.50 to 0.72 dL / g; 0.50 to 0.70 dL / g; 0.50 dL / g < 0.70 dL / g; 0.50 to 0.68 dL / g; 0.50 dL / g < 0.68 dL / g; 0.50 to 0.65 dL / g; 0.55 to 1.2 dL / g; 0.55 to 1.1 dL / g; 0.55 to 1 dL / g; 0.55 dL / g < 1 dL / g; 0.55 to 0.98 dL / g; 0.55 to 0.95 dL / g; 0.55 to 0.90 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 dL / g; less than 0.75 dL / g; 0.55 to 0.72 dL / g; 0.55 to 0.70 dL / g; 0.55 dL / g Less than 0.70 dL / g; 0.55 to 0.68 dL / g; 0.55 dL / g Less than 0.68 dL / g; 0.55 to 0.65 dL / g; 0.58 to 1.2 dL / g; 0.58 to 1.1 dL / g; 0.58 to 1 dL / g; 0.58 dL / g Less than 1 dL / g; 0.58 to 0.98 dL / g; 0.58 to 0.95 dL / g; 0.58 to 0.90 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 dL / g < 0.75 dL / g; 0.58 to 0.72 dL / g; 0.58 to 0.70 dL / g; 0.58 dL / g < 0.70 dL / g; 0.58 to 0.68 dL / g; 0.58 dL / g < 0.68 dL / g; 0.58 to 0.65 dL / g; 0.60 to 1.2 dL / g; 0.60 to 1.1 dL / g; 0.60 to 1 dL / g; 0.60 dL / g < 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 dL / g < 0.75 dL / g; 0.60 to 0.72 dL / g; 0.60 to 0.70 dL / g; 0.60 dL / g < 0.70 dL / g; 0.60 to 0.68 dL / g; 0.60 dL / g < 0.68 dL / g; 0.60 to 0.65 dL / g; 0.65 to 1.2 dL / g; 0.65 to 1.1 dL / g; 0.65 to 1 dL / g; 0.65 dL / g 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 dL / g less than 0.75 dL / g; 0.65 to 0.72 dL / g; 0.65 to 0.70 dL / g; 0.65 dL / g < 0.70 dL / g; 0.68 to 1.2 dL / g; 0.68 to 1.1 dL / g; 0.68 to 1 dL / g; 0.68 dL / g < 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 dL / g < 0.75 dL / g; 0.68 to 0.72 dL / g; >0.76 dL / g to 1.2 dL / g; >0.76 dL / g to 1.1 dL / g; >0.76 dL / g to 1 dL / g; >0.76 dL / g to less than 1 dL / g; >0.76 dL / g to 0.98 dL / g; >0.76 dL / g to 0.95 dL / g; >0.76 dL / g to 0.90 dL / g; >0.80 dL / g to 1.2 dL / g; >0.80 dL / g to 1.1 dL / g; >0.80 dL / g to 1 dL / g; >0.80 dL / g to 1 dL / g; >0.80 dL / g to less than 1 dL / g; >0.80 dL / g to 1.2 dL / g; >0.80 dL / g to 0.98 dL / g; >0.80 dL / g to 0.95 dL / g; >0.80 dL / g to 0.90 dL / g.

[0136] In certain embodiments, it is considered that the polyester composition may have at least one of the intrinsic viscosity ranges described herein and at least one of the monomer ranges for the composition described herein, unless otherwise noted. Additionally, it is considered that the polyester composition may have at least one of the Tg ranges described herein and at least one of the monomer ranges for the composition described herein, unless otherwise noted. Additionally, it is considered that the polyester composition may have at least one of the Tg ranges described herein, at least one of the intrinsic viscosity ranges described herein, and at least one of the monomer ranges for the composition described herein, unless otherwise noted.

[0137] In the embodiments, the molar ratio of cis / trans 2,2,4,4-tetramethyl-1,3-cyclobutanediol may vary in their respective pure forms or mixtures thereof. In certain embodiments, the molar percentage for cis and / or trans 2,2,4,4-tetramethyl-1,3-cyclobutanediol is greater than 50 mol% cis and less than 50 mol% trans; or greater than 55 mol% cis and less than 45 mol% trans; or 30 to 70 mol% cis and 70 to 30% trans; or 40 to 60 mol% cis and 60 to 40 mol% trans; or 50 to 70 mol% trans and 50 to 30% cis or 50 to 70 mol% cis and 50 to 30% trans; or 60 to 70 mol% cis and 30 to 40 mol% trans; or more than 70 moles cis and less than 30 moles trans, and the total sum of the mole percentages for cis- and trans-2,2,4,4-tetramethyl-1,3-cyclobutanediol is equal to 100 moles. The molar ratio of cis / trans 1,4-cyclohexanedimethanol may vary within the range of 50 / 50 to 0 / 100, e.g., 40 / 60 to 20 / 80.

[0138] The polyester portion of the polyester composition may be produced by processes known from the literature, such as, for example, by a process in a homogeneous solution, by a transesterification process in a melt, and by a two-phase interface process. Suitable methods include those disclosed in U.S. Publication Application 2006 / 0287484, the contents of which are incorporated herein by reference.

[0139] In an embodiment, the polyester may be produced by a method comprising reacting one or more dicarboxylic acids (or their derivatives) with one or more glycols under conditions providing the polyester, the step of reacting one or more dicarboxylic acids (or their derivatives) with one or more glycols at a temperature of 100°C to 315°C and a pressure of 0.1 to 760 mm Hg for a time sufficient to form the polyester, but not limited thereto. For a method of producing the polyester, refer to U.S. Patent No. 3,772,405, the disclosure relating to such method is incorporated herein by reference.

[0140] In an embodiment, the polyester composition may be a polymer blend, wherein the blend comprises: (a) 5 to 95 weight percent of at least one of the polyesters described herein; and (b) 5 to 95 weight percent of at least one polymer component. Suitable examples of the polymer component are nylon, polyesters different from those described herein, e.g., polyethylene or polybutylene terephthalate (PET or PBT), polycyclohexylenedimethylene terephthalate (PCT), polycyclohexylenedimethylene terephthalate modified with isophthalic acid (PCTA), polycyclohexylenedimethylene terephthalate modified with ethylene glycol (PCTG), or polyethylene terephthalate modified with cyclohexanedimethanol (PETG), and polyamides such as DuPont’s ZYTEL®; Polystyrene, polystyrene copolymer, styrene acrylonitrile copolymer, acrylonitrile butadiene styrene copolymer, poly(methyl methacrylate), acrylic copolymer, poly(ether-imide), e.g., ULTEM® (poly(etherimide) of General Electric); polyphenylene oxide (e.g., poly(2,6-dimethylphenylene oxide) or poly(phenylene oxide) / polystyrene blend), e.g., NORYL 1000® (poly(2,6-dimethylphenylene oxide) and polystyrene resin blend of General Electric); polyphenylene sulfide; polyphenylene sulfide / sulfone; poly(ester-carbonate); polycarbonate, e.g., LEXAN® (polycarbonate of General Electric); polysulfone; polysulfone ether; and poly(ether-ketone) of aromatic dihydroxy compounds; or any mixture of the above other polymers, but is not limited thereto. The blend can be prepared using conventional processing techniques known in the art, such as melt blending or solution blending. In one embodiment, polycarbonate is not present in the polyester composition.However, the polyester composition useful in the present invention also considers the exclusion of polycarbonate as well as the inclusion of polycarbonate.

[0141] In an embodiment, the polyester component comprises a blend of at least one copolyester and at least one second polyester different from the at least one copolyester. In an embodiment, the at least one second polyester is selected from PCT, PCTA, PCTG, PETG, or a combination thereof. In an embodiment, the polyester component comprises, based on the weight of the polyester component, a blend of the at least one copolyester in an amount of 25 to 99 weight% and the at least one second polyester in an amount of 1 to 75 weight%; or a blend of the at least one copolyester in an amount of 50 to 99 weight% and the at least one second polyester in an amount of 1 to 50 weight%; or a blend of the at least one copolyester in an amount of 75 to 99 weight% and the at least one second polyester in an amount of 1 to 25 weight%.

[0142] Additionally, the copolyester composition may further include one or more additional additives selected from colorants, dyes, release agents, additional flame retardants, plasticizers, processing aids, rheology modifiers, nucleation agents, additional antioxidants, light stabilizers, fillers, and additional reinforcing materials.

[0143] In the embodiments, the polyester composition and the polymer blend composition may contain 0.01 to 25 weight percent of general additives, such as colorants, dyes, release agents, additional flame retardants, plasticizers, nucleating agents, UV stabilizers, heat stabilizers, and / or reaction products thereof, fillers, and additional impact modifiers based on the weight of the total composition. For example, UV additives may be incorporated into articles (e.g., ophthalmic products) by adding them to the bulk or within a hard coat. Examples of typical commercially available impact modifiers widely known in the art and useful in the present invention include, but are not limited to, ethylene / propylene terpolymers; functionalized polyolefins, such as those containing methyl acrylate and / or glycidyl methacrylate; styrene-based block copolymer impact modifiers, epoxide-functionalized impact modifiers, and various acrylic core / shell type impact modifiers. Residues of these additives are also considered as part of the polyester composition. In one embodiment, the composition includes an epoxide-functionalized impact modifier.

[0144] In an embodiment, the polyester composition may include one or more UV stabilizers. In an embodiment, one or more UV stabilizers are present in an amount of 0.1 to 5 weight%, or 0.1 to 3 weight%, or 0.1 to 2 weight%, or 0.2 to 5 weight%, or 0.2 to 3 weight%, or 0.2 to 2 weight%, or 0.4 to 5 weight%, or 0.4 to 3 weight%, or 0.4 to 2 weight% based on the weight of the polyester composition. In an embodiment, one or more UV stabilizers may be selected from triazine, oxalanilide, cyanoacrylate, benzotriazole, naphthalene, benzophenone, and benzoxazine-4-one, or a combination thereof. In one embodiment, one or more UV stabilizers are selected from a triazine UV absorber, an oxalanilide UV absorber, or a combination of these UV absorbers. In the embodiments, one or more UV stabilizers are a combination of a triazine UV absorber and an oxalanilide UV absorber. In the embodiments, the triazine UV absorber and the oxalanilide UV absorber are each present in an amount of 0.1 to 2 weight%, or 0.1 to 1 weight%, or 0.2 to 2 weight%, or 0.2 to 1 weight%, or 0.4 to 2 weight%, or 0.4 to 1 weight%, or 0.4 to 0.8 weight% based on the weight of the polyester composition. Examples of suitable UV absorbers include Tiangang UV-630 triazine UV absorber available from Beijing Tiangang Auxiliary, and Hostavin VSU P or VSU P-S1000 oxalanilide UV absorber available from Clariant.

[0145] The polyester composition and the polymer blend composition contain, based on the total composition, a filler or additional reinforcing additive, such as glass (or other) fiber, in an amount of 1 to 45 wt%, or 1 to 40 wt%, or 1 to 35 wt%, or 1 to 30 wt%, or 5 to 45 wt%, or 5 to 40 wt%, or 5 to 35 wt%, or 5 to 30 wt%, or 10 to 45 wt%, or 10 to 40 wt%, or 10 to 35 wt%, or 10 to 30 wt%, or 15 to 45 wt%, or 15 to 40 wt%, or 15 to 35 wt%, or 15 to 30 wt%, or 20 to 45 wt%, or 20 to 40 wt%, or 20 to 35 wt%, or 20 to 30 wt%. It may contain. In certain embodiments comprising such fillers or additional reinforcing additives, the polyester composition and the polymer blend composition may contain 0.01% to 25%, 0.01% to 20%, or 0.01% to 15%, or 0.01% to 10% of general additives such as those discussed above, based on the weight of the total composition (in addition to the components and fillers / reinforcing additives described herein).

[0146] In certain embodiments, the polyester composition and the polymer blend composition may contain a coloring agent, such as TiO2, in an amount of 1 to 40 wt%, or 1 to 35 wt%, or 1 to 30 wt%, or 1 to 25 wt%, or 5 to 40 wt%, or 5 to 35 wt%, or 5 to 30 wt%, or 5 to 25 wt%, or 10 to 40 wt%, or 10 to 35 wt%, or 10 to 30 wt%, or 10 to 25 wt%, or 15 to 40 wt%, or 15 to 35 wt%, or 15 to 30 wt%, or 15 to 25 wt%, or 20 to 40 wt%, or 20 to 35 wt%, or 20 to 30 wt%, or 20 to 25 wt%, based on the total composition. In certain embodiments, the polyester composition and the polymer blend composition may contain a coloring agent, such as TiO2, in an amount of 0.1 to 15 weight%, or 0.1 to 10 weight%, or 0.1 to 8 weight%, or 0.1 to 6 weight%, or 0.5 to 15 weight%, or 0.5 to 10 weight%, or 0.5 to 8 weight%, or 0.5 to 6 weight%, or 1 to 15 weight%, or 1 to 10 weight%, or 1 to 8 weight%, or 1 to 6 weight%, or 2 to 15 weight%, or 2 to 10 weight%, or 2 to 8 weight%, or 2 to 6 weight%, or 5 to 15 weight%, or 5 to 10 weight%, or 8 to 15 weight%, or 10 to 15 weight%, based on the total composition. In certain embodiments comprising such coloring agents, the polyester composition and the polymer blend composition may contain 0.01% to 25%, 0.01% to 20%, or 0.01% to 15%, or 0.01% to 10% of general additives such as those discussed above, based on the weight of the total composition (in addition to the components and coloring agents described herein).

[0147] In one embodiment, the copolyester composition of the present invention comprises a polyester composition comprising any of the copolyesters or blends described above, a flame retardant additive, an impact modifier component, and a reinforcing mineral component.

[0148] In an embodiment, the copolyester composition further comprises (e) about 0.1 to about 5 wt%, or 0.1 to 3 wt%, or 0.1 to 2 wt%, or 0.1 to 1.5 wt%, or 0.1 to 1 wt%, or 0.2 to 5 wt%, or 0.2 to 3 wt%, or 0.2 to 2 wt%, or 0.2 to 1.5 wt%, or 0.2 to 1 wt%, or 0.5 to 5 wt%, or 0.5 to 3 wt%, or 0.5 to 2 wt%, or 0.5 to 1.5 wt%, or 0.5 to 1 wt% of a silicone compatibilizer. In an embodiment, the silicone compatibilizer is liquid at 25°C. In an embodiment, the liquid silicone compatibilizer is an alkyl, phenyl, or alkyl-phenyl silicone resin that is liquid at 25°C. In an embodiment, the liquid silicone resin comprises hydroxy and / or cyclophenylmethicone groups.

[0149] In an embodiment, the silicone resin, for example, phenyl silicone resin, is 1 to 10,000 cps, or 1 to 8,000 cps, or 1 to 6,000 cps, or 1 to 5,000 cps, or 1 to 3,000 cps, or 1 to 2,000 cps, or 1 to 1,000 cps, or 1 to 800 cps, or 1 to 600 cps, or 1 to 500 cps, or 1 to 300 cps, or 1 to 100 cps, or 1 to 50 cps, or 1 to 25 cps, or 1 to 20 cps, or 20 to 10,000 cps, or 20 to 8,000 cps, or 20 to 6,000 cps, or 20 to 5,000 cps, or 20 to 3000 cps, or 20 to 2000 cps, or 20 to 1000 cps, or 20 to 800 cps, or 20 to 600 cps, or 20 to 500 cps, or 20 to 300 cps, or 50 to 10,000 cps, or 50 to 8000 cps, or 50 to 6000 cps, or 50 to 5000 cps, or 50 to 3000 cps, or 50 to 2000 cps, or 50 to 1000 cps, or 50 to 800 cps, or 50 to 600 cps, or 50 to 500 cps, or 50 to 300 cps, or 100 to 10,000 cps, or 100 to 8000 cps, or 100 to 6000 cps, or 100 to 5000 cps, or 100 to 3000 cps, or 100 to 2000 cps, or 100 to 1000 cps, or 100 to 800 cps, or 100 to 600 cps, or 100 to 500 cps, or 100 to 300 cps, or 300 to 10,000 cps, or 300 to 8000 cps, or 300 to 6000 cps,or 300 to 5000 cps, or 300 to 3000 cps, or 300 to 2000 cps, or 300 to 1000 cps, or 300 to 800 cps, or 300 to 600 cps, or 300 to 500 cps, or 500 to 10,000 cps, or 500 to 8000 cps, or 500 to 6000 cps, or 500 to 5000 cps, or 500 to 3000 cps, or 500 to 2000 cps, or 500 to 1000 cps, or 1000 to 10,000 cps, or 1000 to 8000 cps, or 1000 to 6000 cps, or It has a viscosity in the range of 1,000 to 5,000 cps, or 1,000 to 3,000 cps, or 1,000 to 2,000 cps, or 2,000 to 10,000 cps, or 2,000 to 8,000 cps, or 2,000 to 6,000 cps, or 2,000 to 5,000 cps, or 2,000 to 3,000 cps, or 3,000 to 10,000 cps, or 3,000 to 8,000 cps, or 3,000 to 6,000 cps, or 3,000 to 5,000 cps, which can be measured at 25°C using a digital rotary viscometer NDJ-8T, and in the viscosity range of 1 to 100 cps, the viscosity can be measured using a #0 spindle and 6 to 60 rpm, and In the viscosity range of 100 to 5,000 cps, viscosity can be measured using spindle #1 or #2 and 1.5 to 60 rpm.

[0150] In the embodiment, the phenyl silicone resin is an alkyl phenyl silicone resin, for example, a methyl phenyl silicone resin or an octyl phenyl silicone resin. In an embodiment, the liquid methylphenyl silicone resin is 0.1 / 1.0 to 2.0 / 1.0, or 0.1 / 1.0 to 1.8 / 1.0, or 0.1 / 1.0 to 1.6 / 1.0, or 0.1 / 1.0 to 1.4 / 1.0, or 0.1 / 1.0 to 1.2 / 1.0, or 0.1 / 1.0 to 1.1 / 1.0, or 0.1 / 1.0 to 1.0 / 1.0, or 0.1 / 1.0 to 0.8 / 1.0, or 0.1 / 1.0 to 0.6 / 1.0, or 0.1 / 1.0 to 0.4 / 1.0, or 0.1 / 1.0 to 0.2 / 1.0, or 0.2 / 1.0 to 2.0 / 1.0, or 0.2 / 1.0 to 1.8 / 1.0, or 0.2 / 1.0 to 1.6 / 1.0, or 0.2 / 1.0 to 1.4 / 1.0, or 0.2 / 1.0 to 1.2 / 1.0, or 0.2 / 1.0 to 1.1 / 1.0, or 0.2 / 1.0 to 1.0 / 1.0, or 0.2 / 1.0 to 0.8 / 1.0, or 0.2 / 1.0 to 0.6 / 1.0, or 0.2 / 1.0 to 0.4 / 1.0, or 0.5 / 1.0 to 2.0 / 1.0, or 0.5 / 1.0 to 1.8 / 1.0, or 0.5 / 1.0 to 1.6 / 1.0, or 0.5 / 1.0 to 1.4 / 1.0, or 0.5 / 1.0 to 1.2 / 1.0, or 0.5 / 1.0 to 1.1 / 1.0, or 0.5 / 1.0 to 1.0 / 1.0, or 1.0 / 1.0 to 2.0 / 1.0, or 1.0 / 1.0 to 1.8 / 1.0, or 1.0 / 1.0 to 1.6 / 1.0, or 1.0 / 1.0 to 1.4 / 1.0, or 1.0 / 1.0 to 1.2 / 1.0, or 1.1 / 1.0 to 2.0 / 1.0, or 1.1 / 1.0 to 1.8 / 1.0, or 1.1 / 1.0 to 1.6 / 1.0, or 1.1 / 1.0 to 1.4 / 1.0, or 1.1 / 1.0 to 1.2 / 1.0, or 1.2 / 1.0 to 2.0 / 1.0, or 1.2 / 1.It has a phenyl / methyl molar ratio in the range of 0 to 1.8 / 1.0, or 1.2 / 1.0 to 1.6 / 1.0, or 1.2 / 1.0 to 1.4 / 1.0, or 1.4 / 1.0 to 2.0 / 1.0, or 1.4 / 1.0 to 1.8 / 1.0, or 1.4 / 1.0 to 1.6 / 1.0, or 1.6 / 1.0 to 2.0 / 1.0, or 1.6 / 1.0 to 1.8 / 1.0. In an embodiment, the liquid silicone resin has a solid content of 90% or more, or 95% or more. The solid content can be determined by weight loss after heating to 120°C for 2 hours to remove the liquid. In an embodiment, the liquid silicone resin is 1,000 to 50,000, or 1,000 to 40,000, or 1,000 to 30,000, or 1,000 to 20,000, or 1,000 to 10,000, or 1,000 to 5,000, or 2,000 to 5,000, or 2,000 to 40,000, or 2,000 to 30,000, or 2,000 to 20,000, or 2,000 to 10,000, or 2,000 to 5,000, 4,000 to 5,000, or 4,000 to 40,000, or 4,000 to 30,000, or 4,000 to 20,000, or 4,000 to 10,000, or It has a molecular weight (Mw) in the range of 8,000 to 50,000, or 8,000 to 40,000, or 8,000 to 30,000, or 8,000 to 20,000, or 8,000 to 15,000, or 10,000 to 50,000, or 10,000 to 40,000, or 10,000 to 30,000, or 10,000 to 20,000, 20,000 to 50,000, or 20,000 to 40,000, or 20,000 to 30,000, 30,000 to 50,000, or 30,000 to 40,000, or 40,000 to 50,000. The molecular weight can be determined by calculating the theoretical Mw based on the chemical composition.

[0151] Commercially available silicone compatibilizers include DOWSIL, available from Dow Chemical Company. TM 40-001 and DOWSIL TM Includes 4-7081.

[0152] In an embodiment, the copolyester composition further comprises (f) one or more antioxidants. In an embodiment, the copolyester composition may contain one or more antioxidants in an amount of 0.01 to 2 weight%, or 0.01 to 1.5 weight%, or 0.01 to 1 weight%, or 0.01 to 0.75 weight%, or 0.01 to 0.5 weight%, or 0.01 to 0.4 weight%, or 0.01 to 0.3 weight% based on the total composition. In an embodiment, one or more antioxidants comprise at least one primary antioxidant and / or at least one secondary antioxidant. In a specific embodiment, one or more antioxidants comprise at least one primary antioxidant and at least one secondary antioxidant. In an embodiment, at least one primary antioxidant and at least one secondary antioxidant are each present in an amount of 0.01 to 1 wt%, or 0.01 to 0.9 wt%, or 0.01 to 0.8 wt%, or 0.01 to 0.7 wt%, or 0.1 to 1 wt%, or 0.1 to 0.9 wt%, or 0.1 to 0.8 wt%, or 0.1 to 0.7 wt%, or 0.1 to 0.6 wt%, or 0.1 to 0.5 wt%, or 0.2 to 1 wt%, or 0.2 to 0.9 wt%, or 0.2 to 0.8 wt%, or 0.2 to 0.7 wt%, or 0.2 to 0.6 wt%, or 0.2 to 0.5 wt%, or 0.3 to 1 wt%, or 0.3 wt%, based on the total composition. It may be present in an amount of up to 0.9 wt%, or 0.3 to 0.8 wt%, or 0.3 to 0.7 wt%, or 0.3 to 0.6 wt%, or 0.1 to 0.5 wt%. Examples of antioxidants may include Irganox 1010, Irgafos 168, Doverfos S-9228, Ultranox 626, or combinations thereof.

[0153] In an embodiment, the copolyester composition further comprises (g) about 0.05 to about 0.5 weight% of a drop inhibition additive. In an embodiment, the drop inhibition additive is present in an amount of 0.05 to 0.4 weight%, or 0.05 to 0.25 weight%, or 0.1 to 0.2 weight%. The drop inhibition may comprise a fluoropolymer. The fluoropolymer is polytetrafluoroethylene (PTFE), for example, Teflon TM Polytetrafluoroethylene may be included, but is not limited thereto. Commercial examples include FA5601 PTFE available from Daikin Fluorochemicals (China) Co., Ltd., DB105 available from Union Chemical (Dongguan) CO., Ltd., FS-200 available from Han Nanotech CO., Ltd., and Blendex 6530 available from Galata Chemicals.

[0154] In an embodiment, the polyester may comprise at least one chain extender. Suitable chain extenders include, but are not limited to, polyfunctional (including but not limited to difunctional) isocyanates, for example, polyfunctional epoxides and phenoxy resins including epoxylated novolacs. In a specific embodiment, the chain extender may be added at the end of the polymerization process or after the polymerization process. If added after the polymerization process, the chain extender may be incorporated by formulation or by addition during a transition process such as injection molding or extrusion. The amount of chain extender used may vary depending on the specific monomer composition used and the desired physical properties, but is generally 0.1 to 10 weight percent, e.g., 0.1 to 5 weight percent, based on the total weight of the polyester.

[0155] A heat stabilizer is a compound that stabilizes a polyester during and / or after polymerization, and comprises, but is not limited to, phosphoric acid, phosphonic acid, phosphinic acid, phosphonose acid, and various esters and salts thereof, and phosphoric compounds. The esters may be alkyl, branched alkyl, substituted alkyl, difunctional alkyl, alkyl ether, aryl, and substituted aryl. In one embodiment, the number of ester groups present in a particular phosphoric compound may vary from 0 to a maximum allowable number based on the number of hydroxyl groups present on the heat stabilizer used. The term 'heat stabilizer' is intended to include its reaction product(s). As used in relation to the heat stabilizer of the present invention, the term 'reaction product' refers to any product of a polycondensation or esterification reaction between the heat stabilizer and any monomer used in the manufacture of the polyester, as well as any product of a polycondensation or esterification reaction between a catalyst and any other type of additive. In an embodiment, these may be present in a polyester composition.

[0156] In an embodiment, additional reinforcing materials may be useful in the polyester composition. Additional reinforcing materials may include, but are not limited to, carbon filaments, additional silicates, mica, clay, talc, titanium dioxide, additional wollastonite materials, glass flakes, glass beads and glass fibers, and polymeric fibers and combinations thereof. In one embodiment, additional reinforcing materials are glass, such as fibrous glass filaments, glass and talc, glass and mica, and glass and polymeric fibers.

[0157] In another aspect, the present invention relates to a copolyester composition comprising a copolyester produced by a process comprising the following steps.

[0158] (I) a step of heating a mixture containing monomers useful in any copolyester of the present invention at a temperature of 150 to 240°C in the presence of a catalyst for a time sufficient to produce an initial copolyester;

[0159] (II) A step of heating the initial copolyester of step (I) at a temperature of 240 to 320°C for 1 to 4 hours; and

[0160] (III) Step of removing any unreacted glycol.

[0161] Catalysts suitable for use in this process include, but are not limited to, organo-zinc or tin compounds. The use of such types of catalysts is widely known in the art. Examples of catalysts useful in the present invention include, but are not limited to, zinc acetate, butyltin tris-2-ethylhexanoate, dibutyltin diacetate, and dibutyltin oxide. Other catalysts include, but are not limited to, titanium, zinc, manganese, lithium, germanium, and cobalt-based catalysts. The amount of catalyst may be in the range of 10 ppm to 20,000 ppm, 10 to 10,000 ppm, 10 to 5,000 ppm, 10 to 1,000 ppm, 10 to 500 ppm, 10 to 300 ppm, or 10 to 250 ppm based on the catalyst metal and the weight of the final polymer. The process may be carried out as a batch or continuous process.

[0162] Typically, step (I) may be carried out until 50 weight percent or more of glycol is reacted. Step (I) may be carried out under a pressure ranging from atmospheric pressure to 100 psig. The term 'reaction product' as used in relation to any catalyst useful in the present invention refers to any product of a polycondensation or esterification reaction between the catalyst and any monomer used in the manufacture of the polyester, as well as any product of a polycondensation or esterification reaction between the catalyst and any other type of additive.

[0163] Typically, steps (II) and (III) can be performed simultaneously. These steps can be performed by methods known in the art, such as placing the reaction mixture under a pressure in the range of 0.002 psig to less than atmospheric pressure or blowing hot nitrogen gas onto the mixture.

[0164] Flame retardants, impact modifiers, and silicate minerals may be incorporated into the copolyester in the form of a concentrate by any conventional method for forming the final article. In certain embodiments, the flame retardant and impact modifier may be incorporated into the polymeric composition by blending and feeding into an extruder. In embodiments, reinforcing materials, such as silicate minerals, may be fed individually into the extruder, for example, through a side feed port.

[0165] A flame retardant may be incorporated in a plastic compounding line, such as a twin-screw compounding line, to form a concentrate of the copolyester composition. The pellets are then fed into the neck of an extruder and melted at 430°F to 520°F (221°C to 271°C) to produce a viscous thermoplastic material. Alternatively, an impact modifier may be added together with a weight-loss feeder or added to the weight-loss feeder alone. Alternatively, the flame retardant may be added in the form of a single powder to the weight-loss feeder or added to the weight-loss feeder alone. The rotation of the two screws disperses the flame retardant into the copolyester. The mixture may then be extruded through a die to produce multiple strands. In a specific embodiment, the strands are fed through a water tank to cool the pellets. As they exit the water tank, the strands may be dried and fed to a dicer to cut the strands into pellets. Alternatively, the mixture may be extruded into water through a circular flat die having multiple openings. A flat die has a rotary cutter that slices the strands as they are extruded from the die to produce pellets. A continuous flow of water cools the pellets and transports them to a drying section, typically a centrifuge, to separate the pellets from the water.

[0166] Alternatively, the flame retardant may be incorporated into a plastic blending line, such as a 2-rotor continuous blending mixer (e.g., a Farrell continuous mixer), to form a copolyester composition concentrate. In this case, the copolyester pellets are dried at 150 °F to 190 °F (65.6 °C to 87.8 °C) for 4 to 6 hours to reduce moisture. The copolyester pellets and flame retardant are fed into the neck of the continuous mixer and melted into a homogeneous mixture at 430 °F to 520 °F (221 °C to 271 °C). The output speed of the mixer is controlled by varying the area of ​​the discharge orifice. The melt can be sliced ​​into 'lumps' and fed into the neck of a 2-roll mill or a single-screw extruder. If the melt is fed into a 2-roll mill, the melt covers one of the rolls to form a sheet of concentrate, which is then cut into strips and fed into the neck of a single-screw extruder. Subsequently, the mixture can be extruded through a die to produce multiple strands. The strands are fed through a water tank to cool the pellets. As they emerge from the water tank, the strands can be dried and fed to a dicer to cut the strands into pellets. Alternatively, the mixture can be extruded into water through a circular flat die having multiple openings. The flat die has a rotary cutter that slices the strands as they are extruded from the die to produce pellets. A continuous flow of water cools the pellets and transports them to a drying section, typically a centrifuge, to separate the pellets from the water. When a 'lump' (a relatively large amount of concentrate) is fed into a single-screw extruder, the mixture can be extruded through a die to produce multiple strands. The strands can be fed through a water tank to cool the pellets. As they emerge from the water tank, the strands can be dried and fed to a dicer to cut the strands into pellets. Alternatively, the mixture can be extruded into water through a circular flat die having multiple openings.A flat die has a rotary cutter that slices the strands as they are extruded from the die to produce pellets. A continuous flow of water cools the pellets and transports them to a drying section, typically a centrifuge, to separate the pellets from the water.

[0167] Alternatively, the flame retardant can be incorporated into a high-strength mixer, such as a Banbury® batch mixer, to form a concentrate of the copolyester composition. In this case, the copolyester pellets can be dried at 150 °F to 190 °F (65.6 °C to 87.8 °C) for 4 to 6 hours to reduce moisture. The copolyester pellets and flame retardant are loaded into the high-strength mixer, and the ram is lowered to compress the pellet / flame retardant mixture into the mixing chamber. Two rotary mixer blades melt the pellets and disperse the flame retardant into the melt. Once the desired temperature is reached, the door at the bottom of the mixer is opened, and the mixture is dropped onto a 2-roll mill. The ribbon from the 2-roll mill can then be fed into a single-screw extruder. The mixture can then be extruded through a die to produce multiple strands. The strands can be fed through a water tank to cool the pellets. As the strands emerge from the water tank, they can be dried and fed into a dicer to cut them into pellets. Alternatively, the mixture can be extruded into water through a circular flat die having multiple openings. The flat die has a rotary cutter that slices the strands as they are extruded from the die to produce pellets. A continuous flow of water cools the pellets and transports them to a drying section, typically a centrifuge, to separate the pellets from the water.

[0168] The present invention comprises a plastic article comprising a copolyester composition. The plastic article may be manufactured by a process including, but not limited to, extrusion of the copolyester composition to produce a continuous flat sheet or profile, injection molding to produce a separate article, calendering to produce a continuous film or sheet, or additional manufacturing of a powder or filament to produce a three-dimensional shape.

[0169] The films and / or sheets useful in the present invention may have any thickness obvious to a person skilled in the art. In one embodiment, the film of the present invention has a thickness of less than 30 mil, less than 20 mil, less than 10 mil, or less than 5 mil. In one embodiment, the sheet of the present invention has a thickness greater than 30 mil. In one embodiment, the sheet of the present invention has a thickness of 30 mil to 100 mil, 30 mil to 200 mil, or 30 mil to 500 mil.

[0170] The present invention further relates to films and / or sheets comprising the polyester composition of the present invention. Methods for forming polyester into films and / or sheets are widely known in the art. Examples of films and / or sheets of the present invention include, but are not limited to, extruded films and / or sheets, calendered films and / or sheets, compression-molded films and / or sheets, injection-molded films or sheets, and solution-cast films and / or sheets. Methods for manufacturing films and / or sheets include, but are not limited to, extrusion, calendering, extrusion molding, compression molding, and solution casting. These films or sheets may be subjected to or manufactured with further processing, such as orientation (uniaxial or biaxial), heat curing, surface treatment, etc.

[0171] One embodiment of the present invention comprises a flat sheet or profile. The sheet or profile is manufactured by extruding a copolyester composition to produce a flat sheet or profile. In this case, pellets of the copolyester composition are dried at 150 °F to 190 °F (65.6 °C to 87.8 °C) for 4 to 6 hours and then fed into a single-screw extruder, a twin-screw extruder, or a conical twin-screw extruder. The pellets of the copolyester composition are conveyed along the extruder barrel by the screw(s) and compressed to melt the pellets and discharge the molten material from the end of the extruder. The molten material is fed through a screening device to remove debris and / or through a melt pump to reduce pressure fluctuations induced by the extruder. The molten material is then fed through a die to produce a continuous flat sheet or fed into a profile die to produce a continuous shape. In one embodiment of the present invention comprising a flat sheet die, the molten material is extruded onto a series of metal rolls, typically three rolls, to cool the molten material and impart a finish to the sheet. The flat sheet is then transported from the continuous sheet over a distance or period sufficient for sheet cooling. The sheet is then trimmed to a desired width and then rolled onto rolls or sheared or sawed into a sheet of desired dimensions. The flat sheet may also be formed into a desired article through mechanical means to form a desired article, and then cooled by spraying with water, by transporting through a water container, or by blowing air onto the article. The article is then sawed or sheared to a desired length. In the case of a profile die, the die is designed to produce a profile of a desired shape. Then, after exiting the die, the profile is cooled by spraying with water, by transporting through a water container, or by blowing air onto the profile. The profile is then sawed or sheared to a desired length.In the case of fibers, the fibers can be drawn from an extrusion die to a desired fiber diameter and crystallized to improve physical properties.

[0172] Another embodiment of the present invention comprises mixing pure copolyester pellets with a flame retardant concentrate and then extruding the copolyester composition. The flame retardant concentrate may be incorporated as pellets. Before extrusion, the pellets are dried at 150 °F to 190 °F (65.6 °C to 87.8 °C) for 4 to 6 hours. After blending in a low-strength mixer, such as a ribbon blender, tumbler, or conical screw blender, the pellets are dried. The pellets are then fed into an extruder, including but not limited to a single-screw extruder, a twin-screw extruder, or a conical twin-screw extruder. The pellets are conveyed along the extruder barrel by screw(s) and compressed to melt the pellets, and the melt is discharged from the end of the extruder. The melt is fed through a screening device to remove debris and / or through a melt pump to reduce pressure fluctuations caused by the extruder. Next, the molten material is fed through a die to produce a continuous flat sheet or fed into a profile die to produce a continuous shape. In the case of a flat sheet die, the molten material is extruded onto a series of metal rolls, typically three rolls, to cool the molten material and impart a finish to the sheet. The flat sheet is then transported from the continuous sheet over a distance or period sufficient for sheet cooling. It can then be trimmed to a desired width and rolled, or sheared or sawed into a sheet. The flat sheet can also be formed into a desired shape using mechanical means and then cooled by spraying water, through a water container, or by blowing air onto the molded part. It can then be sawed or sheared to a desired length. In the case of a film, the film can be produced and wound into a roll. In the case of a profile die, the die is designed to produce the desired shape of the article. After exiting the die, the profile can be cooled by spraying water, through a water container, or by blowing air onto the profile.Next, it can be sawed or sheared to a desired length. In the case of fibers, the fibers can be drawn from an extrusion die spinning tube to a desired fiber diameter and crystallized to improve physical properties.

[0173] Another embodiment may involve mixing pure copolyester pellets with a flame retardant and / or impact modifier concentrate and then extruding them into short and long strands of glass fiber reinforcement or into a continuous glass fiber composite film, sheet, or tape. The flame retardant may be incorporated into a single pellet. The pellets are dried at 150°F to 190°F (65.6°C to 87.8°C) for 4 to 6 hours prior to extrusion. After blending in a low-strength mixer, such as a ribbon blender, tumbler, or conical screw blender, the pellets may be dried separately or together. The pellets are then fed into a single-screw extruder, a twin-screw extruder, or a conical twin-screw extruder. The pellets are conveyed along the extruder barrel by the screw(s) and compressed to melt the pellets, and the melt is discharged from the end of the extruder. Typically, the molten material can be fed through a screening device to remove debris and / or through a melt pump to reduce pressure fluctuations caused by the extruder. The molten material can then be fed through a die to produce a continuous flat sheet or into a profile die to produce a continuous shape. In the case of a flat sheet die, the molten material is extruded onto a series of metal rolls, typically three rolls, to cool the molten material and impart a finish to the sheet. The flat sheet is then transported from the continuous sheet to cool the sheet. It can then be trimmed to the desired width and rolled, or sheared or sawed into a sheet form. The flat sheet can also be shaped using mechanical means to form the desired shape and then cooled by spraying water, through a water tank, or by blowing air onto the profile. It can then be cut or sheared, such as by sawing, to the desired length, or a film can be produced and wound onto a roll. In the case of a profile die, the die is designed to produce the desired shape of the article.After exiting the die, it can be cooled by spraying water, through a water tank, or by blowing air onto the profile. It can then be cut or sheared to a desired length. In the case of fibers, the fibers can be drawn from the extrusion die spinnerets to a desired fiber diameter and crystallized to improve physical properties.

[0174] Another embodiment may involve producing an injection-molded article by extruding fully blended pellets of a copolyester composition comprising a copolyester, flame retardant(s), impact modifier(s), and silicate mineral(s). In this case, the pellets are dried at 150°F to 190°F (65.6°C to 87.8°C) for 4 to 6 hours and then fed into an injection molding machine for drying. When the pellets reach the desired temperature, the gate at the end of the extruder is opened, and the molten plastic is pumped by a screw into a heated mold to form an article of the desired shape. Once the mold is filled, a coolant is pumped through the mold to cool it and the molten plastic. Once the plastic solidifies, the mold is opened, and the article is removed from the mold.

[0175] Another embodiment may comprise mixing pure copolyester pellets with a flame retardant and / or impact modifier and / or silicate mineral concentrate to form a copolyester composition, optionally including or excluding short or long fiber glass fibers, and then molding the copolyester composition to produce an injection-molded article. The pellets are dried at 150 °F to 190 °F (65.6 °C to 87.8 °C) for 4 to 6 hours and then fed to an injection molding machine. When the pellets reach the desired temperature, the gate at the end of the extruder is opened, and the molten plastic is pumped by a screw into the heated mold to form an article of the desired shape. Once the mold is filled, a coolant is pumped through the mold to cool it and the molten plastic. Once the plastic solidifies, the mold is opened, and the article is removed from the mold.

[0176] Another embodiment may include mixing pure copolyester pellets with a concentrate of a flame retardant, an impact modifier, and / or a silicate mineral to form a copolyester composition, and then calendering the copolyester composition to produce a film product. Calendering is a widely known process for forming a film or sheet through continuous co-rotating parallel rollers. In a specific calendering process, if the processing temperature is sufficiently low (e.g., 350 °F to 400 °F; 177 °C to 204 °C), the pellets may not need to be pre-dried. In this case, significant decomposition and hydrolysis of the polyester may not occur. The copolyester and the flame retardant / impact modifier / silicate mineral composition may be melted using a high-strength mixer or extruder, including but not limited to a Buss Ko-kneader, a planetary gear extruder, a Farrell continuous mixer, a twin-screw extruder, or a Banbury® type mixer. The melt is then transferred to a calender. A calender typically consists essentially of a system of three or more large-diameter heated rollers that convert high-viscosity plastics into films or sheets. Flat sheets or films are conveyed from a continuous web to dry the sheets. They can then be trimmed to a desired width and then rolled into rolls, or sheared or sawed into sheet form.

[0177] A copolyester composition may be prepared by mixing or blending a flame retardant and / or impact modifier and / or silicate mineral concentrate with a copolyester, but alternatively, the copolyester composition may be prepared by directly blending the flame retardant, impact modifier, and silicate mineral with the copolyester using any mixing or blending previously described for preparing a copolyester composition by blending the flame retardant / impact modifier concentrate with the copolyester. The flame retardant, impact modifier, and silicate mineral may be mixed or blended with the copolyester simultaneously or sequentially.

[0178] In an embodiment, an article comprising any copolyester composition (as described herein) may be an article or component of an article configured or otherwise useful for use in any application where flame-retardant properties are beneficial, for example, in one or more of the following applications: medical device housings or components; housings for electronic devices or peripherals; personal electronic device components; television or monitor housings or components; power tool housings or components; power adapter housings or components; home automation device components; gaming device housings or components; building and construction materials and components; furniture and home decoration components; wiring and connector housings or components; and automotive structural or decorative components.

[0179] The present invention may be further illustrated by the following examples of specific embodiments thereof, but it will be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the invention unless otherwise specifically indicated.

[0180] Examples

[0181] The following abbreviations are used. J stands for slash, J / m stands for slash per meter, MPa stands for megapascal, FR stands for flame retardant, DS stands for drip inhibitor, IM stands for impact modifier, ST stands for stabilizer, FOT stands for flame cessation time, wt% stands for weight percent, TPA stands for terephthalic acid, TMCD stands for 2,2,4,4-tetramethylcyclobutane-1,3-diol, and 1,4-CHDM stands for 1,4-cyclohexanedimethanol. PCTM stands for glycol-modified polyethylene cyclohexanedimethanol terephthalate. The materials used in the test are listed in Table 1.

[0182]

[0183] Copolyester compositions were prepared by blending the combination of materials via an extrusion process using a 26 mm twin-screw extruder (Coperion ZSK 26 Mc18) and a 3.5 mm - 2-hole die. All pelletized polymers and additives were mixed prior to feeding through the primary pellet feeder, except that OP 1240 and other powdered additives were blended and fed through a separate powder feeder. When used, silicone oil was pre-mixed with OP1240. Processing conditions are shown in Table 2.

[0184]

[0185] The extruded strands were pelletized using a water tank / cutter or an underwater pelletizer system to achieve a pellet size and shape suitable for further processing.

[0186] The copolyester composition was formed into a test portion via an injection molding process using a FANUC100 injection molding machine. The barrel temperature was in the range of 265-275°C, and the water-cooled mold temperature was in the range of 35-45°C. Test bars were formed to thicknesses of 1.5 mm (for UL 94 testing) and 3.2 mm (for notched Izod and tensile testing).

[0187] Examples 1-4

[0188] Examples 1 to 4 were prepared as described above. UL 94 vertical combustion and notched Izod impact were measured for each example. The UL 94 vertical combustion test results included FOT (seconds for 5 test rods), UL94 classification, and phenomenon. The compositions and test results are listed in Table 3 below.

[0189]

[0190] Comparing Example-1 and Example-3, it can be seen that the elastic modulus increases as the particle size of the talc increases. Example-2, which has a smaller particle size, passed V0 at 1.5 mm and maintained a relatively high elastic modulus and impact strength.

[0191] A comparison of Example-1 and Example-4 shows the effects of 035B and various impact modifiers on elastic modulus and impact properties. Compared to PFLD, H92, and 3CA, 035B had the least effect on increasing the elastic modulus.

[0192] Examples 5-8

[0193] Examples 5 to 8 were prepared as described above. UL 94 vertical combustion and notched Izod were measured for each embodiment similar to those in Table 3. The compositions and test results are listed in Table 4 below.

[0194]

[0195] Reviewing Table 4, it can be seen that the type or mineral additive may affect flame retardant properties. When AX8900 is used as an impact modifier, a comparison of Example 5 and Example 7 shows that WLA-18 passes V0 at 1.5 mm, while PFLD does not. Additionally, WLA-18 exhibited superior flexural strength at yield and elongation at break. When TFL-205HC is used as an impact modifier, a comparison of Example 6 and Example 8 shows that both PFLD and WLA-18 passed V0 at 1.5 mm and achieved similar flexural moduli of approximately 4500 MPa, indicating that WLA-18 possesses superior toughness compared to PFLD.

[0196] Comparing Example 5 with Example 8, TFL-205HC was effective in further increasing elasticity and flame retardancy using WLA-18 or PFLD as a filler, indicating that WLA-18 and TFL-205HC are effective mineral fillers and impact modifier additives.

[0197] Examples 9-13

[0198] Examples 9 to 13 were prepared as described above. UL 94 vertical combustion and notched Izod were measured for each embodiment similar to those in Table 3. The compositions and test results are listed in Table 5 below.

[0199]

[0200] Reviewing Table 5, it can be seen that a balance of relatively high elastic modulus, good toughness, and V-0 FR can be achieved with the tested composition, particularly in the case of Example-10 containing the DOWSIL-40-001 additive. Comparing Example-9 and Example-11, it can be seen that the composition with WLA-18 and TFL-205 HC in the TX1501 system had both high elastic modulus and V-0 at 1.5 mm, but toughness decreased with increasing WLA-18. Comparing Example-9, Example-12, and Example-13, it can be seen that adding TX1001 increases the elastic modulus but lowers the FR grade, and reducing TFL-205HC allows V-0 at 1.5 mm to be achieved. In addition, comparing Example-9 and Example-10, DOWSIL-40-001 was an effective additive for increasing elongation at break and improving FR performance, where the formulation of Example-10 achieved V0 at 1.2 mm.

[0201] Examples 14-33

[0202] Example 24 was prepared as described above. UL 94 vertical combustion and notched Izod were measured for each embodiment similar to those in Table 3. The compositions and test results are listed in Tables 6 and 7 below.

[0203]

[0204]

[0205] The review of Tables 6 and 7 indicates that a balance of relatively high elastic modulus, good toughness, and V-0 FR can be achieved with the tested compositions of Examples 14 through 18. Comparing Example 14 with Example 19, it can be seen that the composition containing AX-8900 showed reduced notch impact compared to TFL-205 HC. Comparing Examples 14 through 16 with Example 20 indicates that the type of silicate mineral can affect physical properties, where PFLD resulted in lower impact and elongation at fracture compared to WLA-18. Comparing Examples 14 through 19 with Examples 21 and 22, it can be seen that the amount of silicate mineral affects physical properties and FR grade. Comparing Example 15 with Example 23, it can be seen that the physical form of the silicate mineral affects physical properties and FR grade. Comparing Example 18 and Example 24, it can be seen that the type of polyester can affect the physical properties of the composition.

[0206] Although the present invention has been described in detail with reference to the embodiments disclosed herein, it will be understood that variations and modifications may be made within the spirit and scope of the invention.

Claims

Claim 1 (a) a polyester component comprising about 50 to about 79 weight% of at least one copolyester, comprising (i) a diacid component comprising 70 to 100 mol% of a residue of terephthalic acid, 0 to 30 mol% of a residue of a modified aromatic diacid having 8 to 12 carbon atoms, and 0 to 10 mol% of a residue of an aliphatic dicarboxylic acid; and (ii) a glycol component comprising 45 to 95 mol% of cyclohexanedimethanol (CHDM) residues, 5 to 65 mol% of 2,2,4,4-tetramethylcyclobutane-1,3-diol (TMCD) residues, and 0 to 10 mol% of a modified glycol having 2 to 20 carbon atoms, wherein the intrinsic viscosity of the copolyester is 0.5 to 1.2 dL / g when determined in 60 / 40 (wt / wt) phenol / tetrachloroethane at a concentration of 0.5 g / 100 ml at 25°C, where the weight% is based on the weight of the copolyester, the total mol% of the dicarboxylic acid component is 100 mol%, and the total mol% of the glycol component is 100 mol%; (b) about 8 to about 20 comprising a metal phosphinate compound A copolyester composition comprising: (c) a flame retardant additive in weight%; (c) an impact modifier component in weight% of about 3 to about 10 weight% comprising an acrylic silicone polymer impact modifier; and (d) a reinforcing material component in weight% of about 8 to about 25 weight%, or 10 to 25 weight% comprising a silane-modified silicate mineral having an average length greater than 10 micrometers and an aspect ratio greater than 8:1, wherein the copolyester composition has a UL 94 V-0 grade or higher at 1.5 mm or less, a notched Izod impact strength of 60 J / m or more when measured according to ASTM D256, a flexural modulus of 2500 MPa or more when measured according to ASTM D790, and a tensile elongation at break of 10% or more when measured according to ASTM D638. Claim 2 A copolyester composition according to claim 1, wherein the metal phosphinate compound is aluminum diethyl phosphinate. Claim 3 A copolyester composition according to claim 1, wherein the flame-retardant additive comprises a combination of two or more metal phosphinate compounds. Claim 4 A copolyester composition according to any one of claims 1 to 3, wherein the impact modifier component comprises a core-shell impact modifier present in an amount of more than 3 to 10 weight% or 5 to 10 weight% based on the total weight of the copolyester composition. Claim 5 A copolyester composition according to any one of claims 1 to 4, wherein the at least one copolyester glycol component comprises 60 to 95 mol% of a cyclohexanedimethanol residue; and 5 to 40 mol%, or 5 to 30 mol%, or 10 to 30 mol%, or 15 to 30 mol%, or 20 to 30 mol%, or 15 to 25 mol% of a 2,2,4,4-tetramethylcyclobutane-1,3-diol residue. Claim 6 A copolyester composition according to any one of claims 1 to 4, wherein the at least one copolyester glycol component comprises 60 to 75 mol% of a cyclohexanedimethanol residue; and 25 to 40 mol%, or 30 to 40 mol%, of a 2,2,4,4-tetramethylcyclobutane-1,3-diol residue. Claim 7 A copolyester composition according to any one of claims 1 to 6, wherein the intrinsic viscosity of at least one copolyester is 0.55 to 0.85 dL / g, or 0.55 to 0.65 dL / g, or 0.65 to 0.80 dL / g, or 0.65 to 0.75 dL / g. Claim 8 A copolyester composition according to any one of claims 1 to 7, wherein the polyester component comprises a blend of at least one copolyester and at least one second polyester different from the at least one copolyester. Claim 9 In claim 8, the polyester component comprises, based on the weight of the polyester component, a blend of at least one copolyester in an amount of 25 to 99 weight% and at least one second polyester in an amount of 1 to 75 weight%; a blend of at least one copolyester in an amount of 50 to 99 weight% and at least one second polyester in an amount of 1 to 50 weight%; or a blend of at least one copolyester in an amount of 75 to 99 weight% and at least one second polyester in an amount of 1 to 25 weight%, wherein the at least one second polyester is selected from PCT, PCTA, PCTG, PETG and combinations thereof, a copolyester composition. Claim 10 A copolyester composition according to any one of claims 1 to 9, wherein the copolyester composition further comprises (e) about 0.1 to about 5 weight% of a silicone compatibilizer, said silicone compatibilizer being liquid at 25°C, and said liquid silicone compatibilizer being selected from alkyl, epoxy, amino, methacryloyloxy, phenyl, and alkyl-phenyl silicone resins being liquid at 25°C. Claim 11 In claim 10, the liquid silicone resin is a copolyester composition comprising hydroxy and / or cyclophenylmethicone groups. Claim 12 A copolyester composition according to any one of claims 1 to 11, wherein the copolyester composition further comprises (f) one or more antioxidants, wherein the one or more antioxidants comprise at least one primary antioxidant and / or at least one secondary antioxidant. Claim 13 A copolyester composition according to any one of claims 1 to 12, wherein the copolyester composition further comprises (g) about 0.05 to about 0.5 weight% of a drip suppressant additive. Claim 14 A copolyester composition according to any one of claims 1 to 13, wherein the flame-retardant additive is present in an amount of 11 to 20 weight%, or 12 to 20 weight%, or 15 to 20 weight% of the copolyester composition. Claim 15 A copolyester composition according to any one of claims 1 to 14, wherein the copolyester composition has a notched Izod impact strength of 60 J / m or 80 J / m or more when measured according to ASTM D256. Claim 16 A copolyester composition according to any one of claims 1 to 15, wherein the copolyester composition has a flexural modulus of 2500 MPa or more, or 3000 MPa or more, or 3500 MPa or more when measured according to ASTM D790. Claim 17 A copolyester composition according to any one of claims 1 to 16, wherein the copolyester composition has a tensile elongation at break of 10% or more, or 15% or more, when measured according to ASTM D638. Claim 18 A copolyester composition according to any one of claims 1 to 17, wherein the copolyester composition further comprises one or more additional additives selected from additional polymeric components, colorants, dyes, release agents, additional flame retardants, plasticizers, processing aids, rheological modifiers, nucleation agents, additional antioxidants, light stabilizers, fillers, and reinforcing materials. Claim 19 An article comprising a copolyester composition according to any one of claims 1 to 18, wherein the article is in the form of a film, sheet, molded part or profile. Claim 20 In paragraph 19, the article is selected from medical device housings or components, housings for electronic devices or peripheral devices, personal electronic device components, television or monitor housings or components, power tool housings or components, power adapter housings or components, home automation device components, gaming device housings or components, building and construction materials and components, furniture and home decoration components, wiring and connector housings or components, and structural or decorative components of automobiles.

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