Dual shell dental device and material construction

Abstract

To provide a dental appliance and a polymer sheet composition that can dissipate impact forces, is thin, and does not interfere with a person's natural occlusion or speaking.SOLUTION: The improved dental appliances and polymer sheets are useful for making dental appliances having an outer layer comprising a material having a modulus of elasticity of about 1, 000 MPa to 2, 500 MPa ("hard") and an inner core comprising an elastomeric material (s) having a modulus of elasticity of about 50 MPa to 500 MPa ("soft "), exhibiting improved flexibility and strength, and better stain resistance than currently available materials and dental appliances.SELECTED DRAWING: None

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001]

[0001] This application claims the benefit of U.S. Provisional Patent Application No. 62 / 512,786, filed May 31, 2017, and U.S. Provisional Patent Application No. 62 / 590,627, filed November 26, 2017, both of which are incorporated herein by reference in their entireties. [Technical Field]

[0002]

[0002] Disclosed is a composition in the form of a polymer sheet, useful, for example, for dental appliances, which is composed of layers that impart flexibility, strength, and stain resistance to devices made from the sheet.

[0003]

[0003] There is a need for improved orthodontic and dental appliances that can facilitate orthodontic tooth movement, stabilize tooth position, or protect teeth from potentially damaging external forces. Existing materials and products are constructed from single-, two-, or three-ply materials with limited functionality and can suffer from performance deficiencies. Aligners are plastic shells that fit over the teeth and are designed to apply translational or rotational forces to the teeth. Their ability to precisely move teeth is limited by their effective modulus of elasticity, resilience, and ability to resist creep and stress relaxation. Additionally, they should generally exhibit stain and environmental stress crack resistance.

[0004]

[0004] Devices for protecting teeth, such as sports mouth guards and dental splints, have conflicting requirements: on the one hand, they should be able to dissipate impact forces, and on the other hand, they should be thin and not interfere with the natural occlusion of a person's teeth or hinder speech. (Brief summary)

[0005]

[0005] In one embodiment, a composition is provided that includes at least two outer layers A and C and an intermediate layer B. The A and C layers each include a thermoplastic polymer having a modulus of elasticity of about 1,000 MPa to 2,500 MPa and a glass transition temperature and / or melting point of about 80°C to 180°C, and the intermediate B layer includes at least an elastomer having one or more of a modulus of elasticity of about 50 MPa to about 500 MPa and a glass transition temperature and / or melting point of about 90°C to about 220°C.

[0006] In one embodiment, the A and C layers comprise one or more of a copolyester, a polycarbonate, a polyester-polycarbonate blend, a polyurethane, a polyamide, or a polyolefin.

[0007]

[0007] In another embodiment, the intermediate B layer comprises one or more of polyurethane elastomers, polyolefin elastomers, polyester elastomers, styrene-based elastomers, polyamide elastomers, cyclic olefin elastomers, acrylic elastomers, aromatic or aliphatic polyethers, and polyester polyurethanes.

[0008] In yet another embodiment, the intermediate B layer material has a compression set after 22 hours at 25°C of less than 35%, less than 30%, less than 25%, less than 20%, or less than 10%.

[0009] In yet another embodiment, the A and C layers have a displacement of 1 cm when displaced 0.05 mm to 0.1 mm relative to each other. 2 Less than 100N (Newtons) per 1cm 2 Less than 50N per 1cm 2 Less than 25N per 1cm 2 It has a lateral restoring force of less than 10N per

[0010] In another embodiment, the delamination strength between layers A and C and layer B is greater than 50 N per 2.5 cm.

[0011]

[0011] In one embodiment, the combined thickness of the A, B, and C layers is from about 250 microns to about 2,000 microns, and the combined thickness of the A and C layers is from 25 microns to 750 microns, 50 microns to 1000 microns, 100 microns to 700 microns, 150 microns to 650 microns, or 200 microns to 600 microns.

[0012]

[0012] In yet another embodiment, one or more of the A and C layers contain a microcrystalline polyamide comprising 50 to 100 mole % of a C6 to C14 aliphatic diacid moiety and about 50 to 100 mole % of 4,4'-methylene-bis(cyclohexylamine) (CAS [1761-71-3]), and having a glass transition of about 100°C to 180°C, a heat of fusion of less than 20 J / g, and a light transmittance of greater than 80%.

[0013] In another embodiment, one or more of the A and C layers comprises a copolyester, the copolyester comprising (a) a dicarboxylic acid component comprising 70 mol % to 100 mol % of terephthalic acid residues, and (b) a diol component, the diol component comprising: i) 0 to 95 mol % of ethylene glycol; ii) 5 mol % to 50 mol % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; iii) 50 mol % to 95 mol % of 1,4-cyclohexanedimethanol residues; and / or iv) 0 to 1 % of a polyol having three or more hydroxyl groups, wherein the sum of the mol % of the diol residues i) and / or ii) and / or iii) and / or iv) amounts to 100 mol %, and the copolyester exhibits a glass transition temperature, Tg, of 80°C to 150°C.

[0014]

[0014] In another embodiment, the intermediate B layer comprises an aromatic polyether polyurethane having a Shore hardness of about A90 to D55 and a compression set of less than 35%, and the interlayer peel strength between the A and C layers and the B layer is greater than 50 N per 2.5 cm.

[0015]

[0015] In one embodiment, one or more of the A and C layers contain a polyurethane, the polyurethane comprising (a) a diisocyanate comprising 80 mol% to 100 mol% of methylene diphenyl diisocyanate residues, and / or hydrogenated methylene diphenyl diisocyanate, and (b) a diol component, the diol component comprising i) 0 to 100 mol% hexamethylene diol, and ii) 0 to 50 mol% 1,4-cyclohexanedimethanol, the sum of i) and ii) being greater than 90 mol%, and the polyurethane having a glass transition temperature Tg of about 85°C to about 150°C.

[0016] In another aspect, a dental appliance that conforms to one or more teeth is made from a composition or polymer sheet as described herein.

[0017]

[0017] In one embodiment of the dental device, the combined thickness of the A, B, and C layers is from about 250 microns to about 2,000 microns, and the combined thickness of the A and C layers is from 25 microns to 750 microns, 50 microns to 1000 microns, 100 microns to 700 microns, 150 microns to 650 microns, or 200 microns to about 600 microns.

[0018] In another aspect, there is provided a reversibly deformable dental appliance comprising a composition or polymeric sheet material as described herein, wherein the elastomeric intermediate layer and outer layer are reversibly movable relative to one another and have a resilience of 1 cm when displaced 0.05 mm to 0.1 mm relative to one another. 2 Less than 100N per 1cm 2 Less than 50N per 1cm 2 Less than 25N per 1cm 2 A dental appliance is provided having a lateral restoring force of less than 10 N per tooth.

[0019] In one embodiment, the elastomeric intermediate layer comprises a polyurethane having a hardness of about A80 to D75, A85 to D65, or A90 to D55.

[0020]

[0020] In another aspect, there is provided a composition, polymer sheet, or dental device having environmental stress resistance and comprising at least two outer layers and an elastomeric inner layer, wherein one or more of the outer layers is a polyester or copolyester having a modulus of elasticity of about 1,000 MPa to 2,500 MPa, and the inner layer comprises an elastomer having a modulus of elasticity of about 50 MPa to about 500 MPa, and wherein the interlayer peel strength between at least one outer layer and the elastomer is greater than about 50 N / inch.

[0021]

[0021] In another aspect, a reversibly deformable dental device is provided, wherein the outer A layer has a thickness of about 175 to about 250 microns, the outer C layer has a thickness of about 175 to about 250 microns, the middle B layer has a thickness of 300 to 500 microns, and the total thickness of the A, B, and C layers is 850 to 1,000 microns. [Brief explanation of the drawings]

[0022] [Figure 1A] 1 is a schematic diagram of a cross-section of a three-layer sheet of the present invention having a simple ABC configuration. Layers A and C may be the same or different materials, and each layer may comprise one or more materials, or a blend or alloy. Layer B may be a single material, a blend of materials, or an alloy. [Figure 1B] 1B is a schematic diagram of a cross-sectional view of a multilayer sheet. Each layer A, B, and C may comprise a single layer or multiple layers, and each layer may comprise one or more materials or a blend of materials. As illustrated in FIG. 1B, layer A may comprise more than one layer, e.g., layers a and a'; layer B may comprise more than one layer, e.g., layers b and b'; and layer C may comprise more than one layer, e.g., layers c and c'. [Figure 2A]FIG. 2A is a schematic diagram of an exemplary test specimen for determining the displacement (FIG. 2A) of a simple three-layer sheet comprising two rigid outer layers and an inner elastomeric layer, where A, B, and C are the individual layers of the sheet. In this example, layers A and C are reversibly translated relative to one another, with layer B providing the restoring force. In one more specific example, layers A, B, and C are each approximately 250 microns thick, and layers A, B, and C may comprise one or more materials and may each individually comprise one or more layers. [Figure 2B] FIG. 2B is a schematic diagram of an exemplary test specimen for determining the restoring force (translation; FIG. 2B) of a simple three-layer sheet comprising two rigid outer layers and an inner elastomeric layer, where A, B, and C are the individual layers of the sheet. In this example, layers A and C are reversibly translated relative to one another, with layer B providing the restoring force. In one more specific example, layers A, B, and C are each approximately 250 microns thick, and layers A, B, and C may comprise one or more materials and may each individually comprise one or more layers. [Figure 3A] 1 is a graphical depiction of the displacement / force curves of elastomers with different hardnesses. The graph shows the restoring force (N / cm2) resulting from the translation of layer A relative to layer C, with an intermediate layer B comprising a TPU elastomer of different hardness, and the effect of the hardness of the elastomer on the displacement and restoring force. A harder thermoplastic urethane (TPU) generates a larger restoring force, but may limit the amount of movement. [Figure 3B] 1 is a graphical depiction of recovery force (N / cm2) as a function of time (0-48 hours) for a given displacement between layers A and C, with the intermediate layer B having a TPU elastomer of different hardness in the B layer. TPU 75A has a low compression set and exhibits the least initial force, but its force decays only slightly over time. TPU 75D has a high compression set and exhibits a much higher initial recovery force, but its force decays rapidly over time. [Figure 4] 1 is a graphical depiction of the retention force at 5% stress of different configurations exposed to 37° C. and water for 48 hours.

[0023]

[0028] It should be understood that the configurations and characteristics illustrated in Figures 1-4 are specific examples and are not intended to limit the scope of configurations and tests that may be used. Other materials, configurations, and step sequences may also be implemented according to alternative embodiments. For example, alternative embodiments may include additional layers, including tie layers, pigments, optical additives, or reinforcing agents, and may be constructed by any means known in the art, such as flat extrusion, coextruded blown film, calendaring, lamination, and adhesive bonding. Structures (or polymer sheets) and devices may, in some embodiments, be fabricated by 3D printing or dip coating. Those skilled in the art will recognize and appreciate the many variations, modifications, and alternatives of the configurations.

[0024]

[0029] Accordingly, the specification and drawings are to be regarded in an illustrative rather than a restrictive sense, although it will be evident that various modifications and changes may be made thereto without departing from the broader spirit and scope of the disclosure as set forth in the appended claims.

[0025]

[0030] Other variations are within the spirit of the present disclosure. Accordingly, while the disclosed embodiments are susceptible to various modifications and alternative constructions, specific illustrated embodiments thereof have been shown in the drawings and are described herein. It should be understood, however, that there is no intention to limit the disclosure to the particular form(s) disclosed, but on the contrary, the intention is to cover all modifications, alternative constructions, and equivalents falling within the spirit and scope of the present disclosure as defined by the appended claims. DETAILED DESCRIPTION

[0026]

[0031] Current orthodontic aligners have a very limited elastic range (typically 4%-7%) and exhibit rapid decay of resilience when deformed. As a result, appliances may need to be replaced frequently, which increases manufacturing costs, teeth may not move as desired, and patients may experience discomfort from excessively high initial forces. Attempts to improve the elastic range by providing a thin outer layer of elastomer (typically polyurethane, as described, for example, in U.S. Pat. No. 9,655,693 B2) result in tooth contact surfaces that deform easily, which may reduce the accuracy of tooth movement and increase the tendency for unsightly staining from common foods, beverages, or tobacco. U.S. Pat. No. 6,524,101 describes dental appliances with regions having different elastic moduli and appliances with added reinforcing elements. Non-staining polyurethanes used to make dental appliances, such as Zendura® A available from Bay Materials, LLC (Fremont, CA), have excellent properties, but are hygroscopic, require rigorous drying before thermoforming, can be initially uncomfortable, are difficult to clean, and may not be ideal for some applications.

[0027]

[0032] Many other polyurethanes also must be dried before thermoforming, adding time and cost to the manufacturing process. Aromatic polyesters or copolyesters may be used to form aligners; however, they exhibit poor chemical resistance and low impact and tear strength. Aligners constructed from stiff materials, such as polyesters or rigid polyurethanes, have a high modulus of elasticity, e.g., greater than about 1,000 or 1,500 MPa, and if deformed, can exert excessive force on the teeth, causing discomfort and potential damage to the roots. High-elasticity polymers, such as thermoplastic polyurethane elastomers (TPUs), styrene-based elastomers (e.g., SBS, SEBS, SIS, etc.), have a low modulus of elasticity (typically less than 100 MPa or 200 MPa), which may be insufficient for tooth movement and are easily stained, limiting their usefulness for producing aligners.

[0028]

[0033] The present disclosure is based on the discovery that many of the defects in prior art materials, and dental appliances constructed therefrom, can be reduced or eliminated using a sheet or device having an outer layer comprising a material having a modulus of elasticity of about 1,000 MPa up to greater than 2,500 MPa, and an inner elastomeric layer or core comprising an elastomeric material(s) having a modulus of elasticity of about 50 MPa to 500 MPa, which may be non-staining, is lower in cost than rigid urethanes, exhibits improved elastic properties, and has surprisingly greater environmental stress crack resistance.

[0029]

[0034] The polymer sheet or device may include more than two rigid layers; for example, a third rigid layer may be disposed between two or more elastomeric layers. The multi-layer construction provides a dual-shell dental appliance that can be adapted to move teeth, hold teeth in their existing positions, or protect teeth from impact. As disclosed herein, the outer shell material that contacts the teeth can be substantially rigid to precisely engage with the teeth and provide precise force while maintaining the ability to exert a more constant force over longer distances.

[0030]

[0035] By selecting appropriate elastic moduli and thicknesses of the outer and inner materials, two or more substantially rigid shells can be reversibly displaced relative to one another to a greater extent than rigid materials of comparable thickness and shape, providing a dental appliance that can apply desired forces to teeth over a greater range of movement while not generating excessive forces or exhibiting excessive stress relaxation when deformed. While not limiting the present disclosure to a specific configuration, the sheet or dental appliance may be referred to herein as a "dual-shell" sheet or appliance. A "dual-shell" sheet or appliance may include two or more shells or layers. The shells or layers may have the same or different thicknesses. A series of dental appliances including this "dual-shell" configuration may be used to move teeth in stages, and the two or more appliances may be constructed from the same or different materials. The dental appliance may be constructed by thermoforming the dual-shell material onto one or more dental models, or by sequentially thermoforming rigid and elastomeric precursor sheets, or by sequentially dip-coating the models with polymer solutions or polymer-forming monomers or oligomers, which may be optionally cured or otherwise post-treated. The inventors have discovered that this unique configuration can significantly reduce the amount of stress cracking that a shell or material exhibits, thereby expanding the range of materials that can be used for the sheet or device.

[0031] definition

[0036] The use of the terms "a," "an," and "the," and similar referents in the context of describing the disclosed embodiments (particularly in the context of the claims below), should be interpreted to encompass both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The terms "comprising," "having," "including," and "containing" should be interpreted as open-ended terms (i.e., meaning "including, but not limited to"), unless otherwise noted. The term "connected" should be interpreted as partly or wholly contained within, associated with, or joined together, even if there is something intervening. The phrase "based on" should be understood to be open-ended and in no way limiting, and is intended to be interpreted or otherwise read as "based at least in part on," where appropriate. The recitation of ranges of values ​​herein is merely intended to serve as a shorthand method of individually referring to each separate value falling within that range, unless otherwise indicated herein, and each separate value is incorporated into this specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or clearly contradicted by context. The use of any and all examples, or exemplary language provided herein (e.g., "such as"), is intended merely to facilitate a better understanding of embodiments of the disclosure and does not limit the scope of the disclosure unless otherwise claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the disclosure.

[0032]

[0037] The term "dental appliance" is used herein to refer to any device that is placed in or on a subject's teeth. Dental appliances include, but are not limited to, orthodontic, prosthetic, retaining, snoring / airway, cosmetic, therapeutic, protective (e.g., mouthguards), and habit correction devices.

[0033]

[0038] The term "ASTM D638" is used herein in reference to testing for tensile strength of plastics.

[0034]

[0039] The term "ASTM D1364" is used herein in reference to the test for delamination strength.

[0035]

[0040] The term "compression set" is used herein to refer to the permanent deformation of a material when a force is applied and removed.

[0036]

[0041] The term "flexural modulus" is used herein in reference to the stiffness of a material and / or its resistance to deformation in bending. The higher the flexural modulus of a material, the more resistant it is to bending. For an isotropic material, the modulus measured in all directions is the same.

[0037]

[0042] The term "hardness" is used herein in reference to the Shore hardness scale. Shore hardness and elastic modulus are generally correlated and can be converted by approximation when only one value is known.

[0038]

[0043] The terms "elastic modulus" or "tensile modulus" are used herein in reference to the stiffness of a material and / or its resistance to stretching. The higher the modulus of a material, the stiffer it is. The flexural and tensile moduli of a material may be the same or different. For isotropic materials such as A, B, and C, the flexural and elastic moduli (sometimes also called tensile moduli) are substantially the same, and either one can be measured depending on the situation.

[0039]

[0044] The term "polymer sheet" is used interchangeably herein with the term "plastic sheet."

[0040]

[0045] The term "lateral restoring force" with respect to the A and C layers of a polymer sheet is used in reference to the force that may be exerted by one layer being translated relative to another layer that is fixed in place. If the A and C layers were moved independently of each other, they would later return to their original positions if not restrained.

[0041]

[0046] The term "shear force," as used herein, means a translational force applied to two surfaces connected by an elastic material.

[0042]

[0047] The term "shell" is used herein in reference to a polymeric shell that fits over and is removably positionable on a tooth.

[0043]

[0048] The term "stain resistant" is used herein in reference to materials that are designed to resist being stained.

[0044]

[0049] The term "thermoplastic polymer" is used herein to refer to a polymer that becomes flexible or moldable above a particular temperature and solidifies upon cooling, unless heat and pressure chemically degrade the polymer.

[0045]

[0050] The term "tooth(s)" includes natural teeth, including natural teeth that have been modified with a filling or crown, implant teeth, artificial teeth that are part of a bridge or other appliance that are fixed to one or more natural or implant teeth, and artificial teeth that are part of a removable appliance.

[0046]

[0051] In the following description, various embodiments are described. For purposes of explanation, specific configurations and details are set forth in order to provide a thorough understanding of the embodiments. However, it will be apparent to one skilled in the art that the embodiments may be practiced without the specific details. Furthermore, well-known features may be omitted or simplified so as not to obscure the described embodiments.

[0047] Embodiment

[0052] In some embodiments (referred to herein as Embodiment #1), the thermoformable polymer sheet includes at least two outer layers, A and C, and a middle layer, B, wherein the A and C layers have a pressure of greater than about 1,000 MPa, for example, 1,000 MPa to 1,500 MPa; 1,100 MPa to 1,600 MPa; 1,200 MPa to 1,700 MPa; 1,300 MPa to 1,800 MPa; 1,400 MPa to 1,900 MPa; 1,500 MPa to 2,000 MPa; 1,100 MPa; 1,200 MPa; 1,300 MPa; 1,400 MPa; 1,500 MPa; 1,600 MPa; 1,700 MPa; 1,800 MPa, 1,900 MPa; 2000 MPa; or up to 2,500 MPa; and a glass transition temperature (Tg) and / or melting point of about 80°C to 180°C; 90°C to 170°C; 100°C to 160°C; 110°C to 150°C; 120°C to 150°C; 130°C to 170°C; 140°C to 180°C; 80°C; 90°C; 100°C; 110°C; 120°C; 130°C; 140°C; 150°C; 160°C; 170°C; or 180°C.

[0048]

[0053] In such embodiments, the intermediate B layer may be from about 50 MPa to about 500 MPa; 60 MPa to 470 MPa; 70 MPa to 440 MPa; 80 MPa to 400 MPa; 100 MPa to 350 MPa; 150 MPa to 300 MPa; 200 MPa to 400 MPa; 60 MPa, 70 MPa; 80 MPa, 90 MPa; 100 MPa; 110 MPa; 120 MPa; 130 MPa; 140 MPa; 150 MPa, 160 MPa a; 170 MPa; 180 MPa; 190 MPa; 200 MPa, 250 MPa, 300 MPa, 350 MPa, 400 MPa, 450 MPa, or up to 500 MPa, and one or more of (a) a glass transition temperature, or (b) a melting point, of about 90° C. to about 220° C.; 100° C. to about 200° C.; 120° C. to about 180° C.; 140° C. to 220° C.; or 160° C. to about 220° C. In some embodiments, the intermediate B layer is an elastomeric layer or shell and may comprise one or more materials and one or more layers.

[0049]

[0054] In embodiment #1, layers A and C may comprise polyester or copolyester, polyurethane, polyamide, polyolefin, (meth)acrylic polymer, polycarbonate, vinyl polymer such as polyvinyl chloride, or fluoropolymer.

[0050]

[0055] In embodiment #1, Layer B may comprise a polyurethane elastomer, a polyester elastomer, a styrenic elastomer, a polyamide elastomer, a siloxane elastomer, a polyether elastomer, a polyolefin elastomer, an olefin copolymer, an acrylic elastomer, or a fluoroelastomer.

[0051]

[0056] In embodiment #1, the B layer material has a compression set at 25°C for 22 hours of less than about 35%, less than 30%, less than 25%, less than 20%, less than 10%, i.e., less than 35%, less than 34%, less than 33%, less than 32%, less than 31%, less than 30%, less than 29%, less than 28%, less than 27%, less than 26%, less than 25%, less than 24%, less than 23%, less than 22%, less than 21%, less than 20%, less than 19%, less than 18%, less than 17%, less than 16%, less than 15%, less than 14%, less than 13%, less than 12%, less than 11%, or less than 10%. Contrary to the findings of U.S. Patent No. 9,655,693 B2, where an elastomer is used as the outer layer, applicants have discovered that a lower compression set is more effective, rather than a higher compression set.

[0052]

[0057] In a particular aspect of Embodiment #1, the sheet has a total thickness of about 250 microns to about 2,000 microns.

[0053]

[0058] In certain aspects of Embodiment #1, the combined thickness of the A and C layers is from about 25 microns to about 1000 microns, 50 microns to 750 microns, 100 to 750 microns, 250 microns to 750 microns, or 250 microns to about 600 microns.

[0054]

[0059] In certain aspects of Embodiment #1, the thermoformable sheet has a flexural modulus of about 100 MPa to about 2,000 MPa, about 250 MPa to about 2,000 MPa, about 500 MPa to 1,500 MPa, about 750 MPa to about 2,000 MPa, or about 750 microns to about 1,500 MPa.

[0055]

[0060] In certain aspects of Embodiment #1, the A and C layers have a Tg between about 80 and 150°C, and the B layer has a Tg or melting point between about 180 and 220°C and a heat of fusion of about 5 Joules / g to about 20 Joules / g, or 5 Joules / g to 15 Joules / g.

[0056]

[0061] In certain aspects of Embodiment #1, the peel strength of Layer A is greater than about 50 N / inch, greater than about 60 N / inch, or greater than about 70 N / inch.

[0057]

[0062] In a specific aspect of embodiment #1, the A and C layers each have a thickness of 25 microns to about 1000 microns, 50 microns to 750 microns, 100 to 750 microns, 125 to 300 microns, 250 microns to 750 microns, or 250 microns to about 600 microns, and may have a total thickness of about 250 microns to about 600 microns, and comprise a rigid copolyester or polyurethane having a Tg between 95°C and 150°C, a modulus of elasticity of 1000 MPa to 2,500 MPa, and the elastomeric B layer having a thickness of about 200 microns to about 1,000 microns or 200 to 500 microns has a hardness of about D35 to about D65 and a modulus of elasticity of about 35%, less than 30%, less than 25%, less than 20%, less than 10%, i.e., less than 35%, less than 34%, less than 33%, less than 32%, less than 35%, less than 36%, less than 37%, less than 38%, less than 39%, less than 40%, less than 41%, less than 42%, less than 43%, less than 44%, less than 45%, less than 46%, less than 47%, less than 48%, less than 49%, less than 50%, less than 51%, less than 52%, less than 53%, less than 54%, less than 55%, less than 56%, less than 57%, less than 58%, less than 59%, less than 60%, less than 61%, less than 62%, less than 63%, less than 64%, less than 65%, less than 66%, less than 67%, less than 68%, less than 69%, less than the polymer sheet comprises a polyether or polyester polyurethane having a compression set at 25°C for 22 hours of less than 1%, less than 30%, less than 29%, less than 28%, less than 27%, less than 26%, less than 25%, less than 24%, less than 23%, less than 22%, less than 21%, less than 20%, less than 19%, less than 18%, less than 17%, less than 16%, less than 15%, less than 14%, less than 13%, less than 12%, less than 11%, or less than 10%, and an A layer having an interlayer peel strength of greater than about 50 N / inch, greater than about 60 N / inch, or greater than about 70 N / inch, and the polymer sheet has a flexural modulus of about 750 MPa to about 1,500 MPa; about 100 MPa to about 2,000 MPa; about 250 MPa to about 2,000 MPa; about 500 MPa to 1,500 MPa; or about 750 MPa to about 2,000 MPa.

[0058]

[0063] In some aspects of Embodiment #1, thin layers of additional polymers (tie layers) may be present to improve adhesion of polymer layers that do not naturally adhere to each other; for example, a layer of maleic anhydride grafted polypropylene may be used to increase adhesion between a polypropylene A layer and a polyester or polyamide B layer.

[0059]

[0064] In some embodiments (herein referred to as Embodiment #2), the A and C layers of the sheet or device are 1 cm 2 Less than 100N per 1cm 2Less than 50N per 1cm 2 Less than 25N per 1cm 2 They can reversibly move relative to each other (eg, translationally) by about 0.05 mm to about 0.1 mm with a force of less than 10 N per one.

[0060]

[0065] In some aspects of embodiment #2, the A and C layers of the sheet or device have a total thickness of about 500 microns to 1,000 microns and are less than 1 cm 2 Less than 100N per 1cm 2 Less than 50N per 1cm 2 Less than 25N per 1cm 2 They can reversibly move relative to each other by a distance of 0.05 mm to 0.1 mm with a force of less than 10 N each.

[0061]

[0066] In some aspects of Embodiment #2, the B Layer material has a compression set at 25°C for 22 hours of less than about 35%, less than 30%, less than 25%, less than 20%, less than 10%, i.e., less than 35%, less than 34%, less than 33%, less than 32%, less than 31%, less than 30%, less than 29%, less than 28%, less than 27%, less than 26%, less than 25%, less than 24%, less than 23%, less than 22%, less than 21%, less than 20%, less than 19%, less than 18%, less than 17%, less than 16%, less than 15%, less than 14%, less than 13%, less than 12%, less than 11%, or less than 10%.

[0062]

[0067] In some embodiments (referred to herein as Embodiment #3), one or more of the A and C layers contains a microcrystalline polyamide comprising 50-100, 50-90, 50-80, 50-70, 60-90, 60-80, or 70-90 mole % of a C6-C14 aliphatic diacid moiety and about 50-100, 50-90, 50-80, 50-70, 60-90, 60-80, or 70-90 mole % of 4,4'-methylene-bis(cyclohexylamine) (CAS [1761-71-3]), wherein the microcrystalline polyamide has a glass transition temperature between about 100°C and 180°C and a heat of fusion of less than 20 J / g, e.g., 5 Joules / g to about 20 Joules / g, or 5 Joules / g to 15 Joules / g. See, for example, German Patent Application Publication No. 4310970 (Embodiment 3). In some aspects of Embodiment #3, the combined thickness of the A and C layers is less than about 500 microns, less than about 400 microns, or less than about 300 microns.

[0063]

[0068] In some embodiments (referred to herein as Embodiment #4), a dental appliance conforming to one or more teeth includes at least two outer layers A and C and a middle layer B, wherein the A and C layers have a resistance greater than about 1,000 MPa, e.g., 1,000 MPa to 1,500 MPa; 1,100 MPa to 1,600 MPa; 1,200 MPa to 1,700 MPa; 1,300 MPa to 1,800 MPa; 1,400 MPa to 1,900 MPa; 1,500 MPa to 2,000 MPa; 1,100 MPa; 1,200 MPa; 1,300 MPa; 1,400 MPa; 1,500 MPa; 1,600 MPa a; 1,700 MPa; 1,800 MPa, 1,900 MPa; 2000 MPa; up to greater than 2,500 MPa, and in certain embodiments greater than 1,500 MPa; and a glass transition temperature and / or melting point of about 80°C to 180°C; 90°C to 170°C; 100°C to 160°C; 110°C to 150°C; 120°C to 150°C; 130°C to 170°C; 140°C to 180°C; 80°C; 90°C; 100°C; 110°C; 120°C; 130°C; 140°C; 150°C; 160°C; 170°C; or 180°C, and in certain embodiments 80 to 150°C or 95 to 150°C. In such an embodiment, the intermediate B layer comprises at least an elastomer having one or more of a modulus of elasticity of about 50 MPa to 500 MPa; 70 MPa to 450 MPa; 80 MPa to 400 MPa; 100 MPa to 350 MPa; 150 MPa to 300 MPa; 200 MPa to 400 MPa; 60 MPa, 70 MPa; 80 MPa, 90 MPa; 100 MPa; 110 MPa; 120 MPa; 130 MPa; 140 MPa; 150 MPa, 160 MPa; 170 MPa; 180 MPa; 190 MPa; 200 MPa, up to 250 MPa, and a glass transition temperature or melting point of about 90°C to about 220°C.

[0064]

[0069] In some aspects of Embodiment #4, the A and C layers have a combined thickness of about 25 microns to about 600 microns, e.g., 250 microns, 300 microns, 350 microns, 400 microns, 450 microns, 500 microns, 550 microns, or 600 microns, and can be heated to temperatures between 80°C and 180°C; 90°C and 170°C; 100°C and 160°C; 110°C and 150°C; 120°C and 150°C; 130°C and 170°C; 140°C and 180°C; 80°C; 90°C; 100°C; 110°C; 120°C; 130°C; 140°C; 150°C; 160°C; 170°C; or 180°C, e.g., 80°C to 150°C or 95°C. Included are rigid copolyesters or polyurethanes having a Tg of up to 150°C and a modulus of elasticity greater than 1,000 MPa, for example, 1,000 MPa to 1,500 MPa; 1,100 MPa to 1,600 MPa; 1,200 MPa to 1,700 MPa; 1,300 MPa to 1,800 MPa; 1,400 MPa to 1,900 MPa; 1,500 MPa to 2,000 MPa; 1,100 MPa; 1,200 MPa; 1,300 MPa; 1,400 MPa; 1,500 MPa; 1,600 MPa; 1,700 MPa; 1,800 MPa, 1,900 MPa; 2000 MPa; or up to 2,500 MPa.

[0065]

[0070] In some aspects of Embodiment #4, the elastomeric B layer has a thickness of about 200 microns to about 1,000 microns, e.g., 100 microns, 200 microns, 250 microns, 300 microns, 350 microns, 375 microns, 400 microns, 500 microns, 750 microns, or 1,000 microns, a hardness of about D35 to about D65, and a hardness of about less than 35%, less than 34%, less than 33%, less than 32%, less than 31%, less than 30%, less than 29%, less than 28%, less than 27%, less than 26%, less than 25%, less than 24%, less than 23%, less than 22%, less than 21%, less than 20%, less than 19%, less than 18%. the polymer sheet comprises an A layer comprising a polyether or polyester polyurethane having a compression set at 25°C for 22 hours of less than 17%, less than 16%, less than 15%, less than 14%, less than 13%, less than 12%, less than 11%, or less than 10%, and having an interlayer peel strength of greater than about 50 N / inch, greater than about 55 N / inch, greater than about 60 N, or greater than about 70 N, and the polymer sheet has a flexural modulus of about 100 MPa to about 2,000 MPa, about 250 MPa to about 2,000 MPa, about 500 MPa to 1,500 MPa, or about 750 MPa to about 2,000 MPa, for example, about 750 microns to about 1,500 MPa.

[0066]

[0071] In some aspects of Embodiment #4, the A and C layers are 1 cm 2 Less than 100N per 1cm 2 Less than 50N per 1cm 2 Less than 25N per 1cm 2 With a force of less than 10N, it has a lateral restoring force of 0.05mm to 0.1mm.

[0067]

[0072] In some embodiments (referred to herein as Embodiment #5), the dental appliance is formed by thermoforming a multi-layer sheet onto a dental model, the thermoforming being carried out at a temperature at least above the glass transition temperature and / or melting point of the outer layer and at least below the upper glass transition temperature and / or melting point of the inner layer elastomeric material.

[0068]

[0073] In one embodiment of Embodiment #5, the dental device is prepared by thermoforming a multilayer sheet having at least A and C layers having a Tg of about 80°C-180°C; 90°C-170°C; 100°C-160°C; 110°C-150°C; 120°C-150°C; 130°C-170°C; 140°C-180°C; 80°C; 90°C; 100°C; 110°C; 120°C; 130°C; 140°C; 150°C; 160°C; 170°C; or 180°C, wherein the B layer has a glass transition temperature and / or melting point of about 90°C-220°C, e.g., 180°C-220°C, and a heat of fusion of about 5 J / g to about 20 J / g, e.g., about 5 J / g to about 20 Joules / g, or 5 Joules / g to 15 Joules / g.

[0069]

[0074] In one aspect of embodiment #5, the A and C layers comprise a copolyester or polyurethane having a Tg of about 90°C to about 120°C, the B layer comprises a polyurethane having a modulus of about 50 MPa to 500 MPa and a glass transition temperature and / or melting point of about 170°C to about 220°C, and thermoforming is carried out at a temperature between about 150°C and 200°C.

[0070]

[0075] It should be understood that elements of more than one embodiment may be combined.

[0071]

[0076] In some embodiments, a thermoformable polymer sheet includes at least two outer layers, A and C, and an intermediate layer, B, wherein one or more of the A and C layers contains a microcrystalline polyamide comprising 50-100 mole % of a C6-C14 aliphatic diacid moiety and about 50-100 mole % of 4,4'-methylene-bis(cyclohexylamine) (CAS [1761-71-3]), wherein the microcrystalline polyamide has a glass transition of about 100°C to 180°C, a heat of fusion of less than 20 J / g, and a light transmittance of greater than 80%.

[0072]

[0077] In some embodiments, a thermoformable polymer sheet includes at least two outer layers, A and C, and a middle layer, B, wherein one or more of the A and C layers comprises a copolyester, the copolyester including a dicarboxylic acid component comprising 70 mol % to 100 mol % of terephthalic acid residues, and a diol component, the diol component including (i) 0 to 95 mol % ethylene glycol, (ii) 5 mol % to 50 mol % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, (iii) 50 mol % to 95 mol % of 1,4-cyclohexanedimethanol residues, and / or (iv) 0 to 1 % of a polyol having three or more hydroxyl groups, wherein the sum of the mol % of the diol residues (i), (ii), (iii), and / or (iv) amounts to 100 mol %, and the copolyester exhibits a glass transition temperature, Tg, of 80° C. to 150° C. In some aspects of this embodiment, the thermoformable polymer sheet includes an intermediate B layer comprising an aromatic polyether polyurethane having a Shore hardness of about A90 to D55 and a compression set of less than 35%, and the interlayer peel strength between the A and C layers and the B layer is greater than 50 N per 2.5 cm.

[0073]

[0078] In some embodiments, dental appliances that conform to one or more teeth are made from the microcrystalline polyamides or copolyesters described above.

[0074] How to configure

[0079] Multi-layer sheets may be manufactured by several means, including but not limited to, hot or cold lamination, adhesive lamination, melt lamination, co-extrusion, multi-layer extrusion, or other known methods. The sheet may be fully manufactured before being formed into an orthodontic appliance, or the appliance may be produced using a series of individual thermoforming steps that create the multiple layers.

[0075]

[0080] Thermoforming of sheets to produce test specimens or dental appliances may be performed using a "Biostar" pressure former available from Great Lakes Orthodontics, using procedures commonly used in the industry. Alternatively, thermoforming may be performed using a roll-fed thermoformer, vacuum former, or other known thermoforming techniques. Thermoforming may be performed using different conditions, configurations, or patterns to vary the stretch ratio and thickness of the molded article. Multilayer devices may be fabricated via one or more 3D printing processes, or by sequential dip coating, spray coating, powder coating, or similar processes known to produce films, sheets, and 3D structures.

[0076]

[0081] The temperature of the sheet during thermoforming can be measured using an infrared thermometer or a surface thermocouple.

[0077] usefulness

[0082] The sheets and materials described herein have utility as thermoformable materials with excellent dimensional stability, impact cushioning, and resilience. The sheets can be converted into several types of oral appliances, for example, for tooth movement, for use as sports mouthguards with improved impact resistance, and for use as orthodontic retainers. Compared to currently available materials and appliances, the improved properties of the materials and appliances described herein include, but are not limited to, greater flexibility resulting in improved end-user comfort, improved tooth movement results, greater stain and stress crack resistance, and superior cosmetology, all of which promote more consistent wear by the subject.

[0078] Test Method

[0083] Tensile properties were measured using an Instron Universal Materials Tester, following ASTM D638 procedures unless otherwise noted. Color and clarity were measured using a BYK Gardner Spin colorimeter.

[0079]

[0084] Impact resistance was measured using a Gardner impact tester. Tear strength was measured using a materials testing machine at a speed of 250 mm per minute.

[0080]

[0085] The stress relaxation of the samples in water at 37° C. was measured by the method described in US Pat. No. 8,716,425 B2.

[0081]

[0086] Stain resistance was measured by exposing the test specimens to a staining medium such as mustard or coffee at 37°C for 24 hours and measuring the color on a white tile before and after exposure.

[0082]

[0087] The translational recovery force was measured by constructing a three-layer structure (or polymer sheet) as shown in Figures 1 and 2. The sample was displaced from 0 to 0.5 mm, and the force was measured in N / cm 2 reported in.

[0083]

[0088] Peel strength is measured at a rate of 50 mm / min and may be reported as Newtons (N) per inch or per 2.54 cm (N). Details can be found in test method ASTM D3164.

[0084]

[0089] Thermal testing to determine glass transition temperature, melting point and freezing point was measured using a differential scanning calorimeter at heating and cooling rates of 10° C. per minute unless otherwise indicated.

[0085]

[0090] Environmental stress crack resistance may be determined by clamping a sheet sample around a cylindrical mandrel, subjecting the outer surface to a specific strain, e.g., 3% or 5%, and exposing the sample to a specific environment, e.g., a saliva-mimicking solution, mouthwash, or other solution of interest, for a specified period of time. The response can be measured semi-quantitatively by visual observation of the type and number of cracks, or quantitatively by subsequent measurement of mechanical properties such as tear strength.

[0086] Materials and Methods.

[0091] Materials of Construction. Numerous commercially available materials are available for use in producing the sheets and devices described herein. Table 1 provides a list of exemplary materials for use in the A or C components. Table 2 provides a list of exemplary materials for use in the B component. Similar or related materials may be obtained from other manufacturers or produced by known methods.

[0087] [Table 1]

[0088] [Table 2]

[0089]

[0092] Further suitable materials for the A, B, or C layers can include compatible or incompatible blends, such as blends of two or more copolyesters, blends of polypropylene and polyethylene and ethylene propylene elastomers, fluoropolymers such as polyvinylidene fluoride or copolymers thereof, styrene acrylonitrile resins, acrylonitrile styrene butadiene resins (ABS), polyurethanes containing polycarbonate soft blocks, siloxane soft blocks, silicone elastomers such as Geniomer™, siloxane urea copolymers, and cyclic olefin copolymers and elastomers. [Example]

[0090]

[0093] The present disclosure is further illustrated by the following examples, which are provided for illustrative purposes only and should not be construed as limiting the scope or content of the present invention in any way.

[0091] Example 1

[0094] A series of single-layer and multi-layer sheets with a nominal total thickness of 0.76 mm were prepared as shown in Table 3. Test Samples 1-4 were prepared by compression molding and heat laminating individual films or by extrusion laminating. Examples of prior art materials P1, P2, and P3 were prepared by compression molding films and optionally heat laminating them.

[0092]

[0095] Press lamination was performed at 200-220° C., extrusion lamination was performed using a polyurethane melt temperature of 210-240° C., and coextrusion was performed using a polyester melt temperature of 240-260° C. and a polyurethane melt temperature of 210-240° C. The time, temperature, and pressure conditions were varied to maximize structural (polymer sheet) quality, thickness, and adhesion.

[0093]

[0096] Mechanical properties, optical properties, stress relaxation, and shape recovery rates were measured to compare the suitability of the resulting structures (polymer sheets).

[0094] [Table 3]

[0095]

[0097] Prior art material P1 is a commercially available thermoformable aligner material supplied by Bay Materials, LLC, Fremont, Calif. Prior art material P2 is a polyester manufactured by Eastman Chemical, sold under the trade name Eastar 6763, having a glass transition temperature of approximately 90°C. Prior art material P3 is described in U.S. Pat. No. 9,655,693 B2. Test samples 1-4 are multilayer laminates (as described herein) that demonstrate improved stress relaxation properties, increased tear strength, and excellent stain resistance.

[0096]

[0098] Compared to prior art materials, Test Samples 1-4 exhibited several unexpected properties. Comparing Test Samples 1-4 and prior art materials P1 and P2, Test Samples 1-4 exhibit substantially lower initial force in stress relaxation tests (believed to translate into better user comfort), but surprisingly, maintain force over a longer period of time. This contradicts the teachings of U.S. Pat. No. 9,655,693 B2, which teaches that an elastomeric outer layer is necessary to protect the inner rigid layer. The ability of the multilayer sheet to maintain adequate force levels over time under demanding conditions is readily apparent in Figure 4. Samples A and B in Figure 4 are single-layer sheets, while Samples 1 and 2 are multilayer sheets as described in Table 3.

[0097]

[0099] Tear strength is an important property of dental appliances. Materials with low tear strength are less durable and may crack at locations of concentrated stress. Comparing the tear strength of prior art materials P1, P2, and P3 with test samples 1-4 shows that such multilayer structures (or polymer sheets) including an elastomer B layer have significantly higher tear strength than comparable single layer structures or prior art multilayer structures.

[0098]

[0100] To further investigate the effect of construction on tear strength, another laminate (#5) was prepared with 0.25 mm A and C layers containing Eastar 6763, a copolyester available from Eastman Chemical, having a Tg of 86°C, and a 0.2 mm B layer of a Shore 50D urethane elastomer, for a total thickness of 0.7 mm. The tear strength of this sample was compared to prior art materials P1, P2, and P3. Sample #5 exhibited a tear strength of 120 N, more than 200% of the value of prior art material P3, but with a similar ratio of polyurethane and polyester.

[0099] Example 2 (Measurement of translational force)

[0101] A three-layer sheet was prepared as described in Example 1 for Test Material 2. A 2.54 cm x 1 cm piece of the sheet was bonded between two 2.54 cm wide pieces of rigid polyester, creating a 0.5 cm overlap ("Multilayer Sample A2"). A control test sample was prepared using the same size and thickness of Polyester A (prior art) between two pieces of rigid polyester. The displacement / force response was measured at a rate of 0.04 MPa / min, and the results are reported in Table 4. The multilayer configuration allows the two outer layers (or two shells) of the device to accommodate greater elastic movement at moderate forces than the prior art configuration.

[0100] [Table 4]

[0101]

[0102] Orthodontic devices were made using the materials and methods described herein and compared to devices of the same shape and thickness made from Zendura A and Essix Plus. The disclosed devices were substantially more resilient and more comfortable to wear. Because the inner and outer shells can deform independently of each other, they can accommodate larger offsets between the actual teeth and the appliances without causing unnecessary discomfort to the patient, and can exert a nearly constant force over time to precisely move teeth.

[0102] Example 3

[0103] A 0.25 mm thick clear polypropylene film designated BFI 257, supplied by Blue Ridge Films (Petersburg, Virginia), was laminated to both sides of a 0.25 mm thick film prepared from Kraton GF (maleic acid-modified SEBS, available from Kraton Polymers) in a hot press at 180°F, cooled, and cut into 125 mm circles. The modulus of elasticity of polypropylene is reported at 1,100 MPa. The SEBS elastomer has a reported hardness of 71 A and a modulus of elasticity of 25 MPa. The multilayer film exhibited low staining and was thermoformable on dental models to produce retainers with excellent elastic recovery properties.

[0103] Example 4

[0104] Because dental appliances are known to be easily damaged by alcohol and / or surfactants, the durability of sheet materials in the presence of mouthwash was investigated. Test sheets with a thickness of 0.75 mm were prepared, measuring 2.54 cm wide and 12 cm long. Prior art materials P1, P2, and P3, as well as multilayer sheet (test material) #2, were wound around a mandrel of sufficient diameter to induce a 5% strain. The samples were immersed in mouthwash and maintained at 37°C. This environment is known to promote environmental stress cracking, inducing strain that causes the material to assume a hoop shape instead of a flat surface. After 24 hours, the samples were rinsed with deionized water, and the amount of recovery was measured immediately at ambient temperature and again after 24 and 48 hours. The samples were then viewed under a microscope to determine the amount of stress cracking on the side that had been under tension. Samples that returned completely flat were scored as having 100% recovery. Stress cracking was rated from 1 to 5, with 5 being no visible cracking and 1 being severe cracking. Shape recovery of the samples is shown in Table 5. The multilayer sheet (#2) recovered more rapidly and completely than the prior art materials P1, P2, and P3.

[0104] [Table 5]

[0105] Example 5 Three laminates were prepared as in Example 1, Sample 2, and designated Samples #6, #7, and #8. Sample #6 was an extrusion laminated with untreated polyester film at a roll temperature of 40°C, Sample #7 was an extrusion laminated with corona-treated polyester film at a roll temperature of 60°C, and Sample #8 was an extrusion laminated with corona-treated film at a roll temperature of 80°C. Corona treatment is commonly used to activate film surfaces to increase their polarity. A control sample of Polyester A was designated Sample #9. The mechanical properties and environmental stress crack resistance of the three samples are shown in Table 6.

[0106] [Table 6]

[0107] The dramatic improvement in environmental resistance observed in Samples #7 and #8 compared to Samples #6 and #9 is unexpected and unexpected. In each case, the materials exposed to the environment are chemically identical and under equal amounts of stress. While not wishing to be bound by theory, Applicants hypothesize that some concentrated strain-induced stress present in the outer polyester layer is transferred to the elastomeric material, and that force transfer is more efficient in materials with higher interlayer bond strength. However, Applicants are not aware of any precedent for this result.

[0108] It is well known that thermoplastic amorphous copolyesters (PETG and PCTG) have poor environmental stress crack resistance and tend to degrade rapidly when used as dental appliances. U.S. Pat. No. 9,655,691 teaches that coating both sides of such copolyesters with thermoplastic polyurethane elastomers having hardnesses of about 60A to about 85D surprisingly increased the durability of dental aligners made from such materials (described as "a hard polymer layer disposed between two soft polymer layers"). Presumably, the outer material provides a physical and / or chemical protective layer. Disadvantages of such materials include poor stain resistance, and the disclosed multilayer structures have poor tear resistance.

[0109] The present inventors have unexpectedly discovered that the stress crack resistance of amorphous polyester films, sheets, or thermoformed parts prepared therefrom can be dramatically improved by bonding an elastomeric material, such as polyurethane, between two layers of polyester. The resulting structure, having a soft polymer layer disposed between two hard polymer layers, has excellent chemical resistance, high transparency, and excellent stain resistance. Furthermore, the tear resistance of the multilayer structure exceeds that of either polyester or elastomer alone. The inventors have also discovered that the improved properties require high bond strength between the layers, and that materials with poorly bonded layers have poor crack resistance and poor tear strength.

[0110] It is known in the art that rigid polyurethane sheets have very good stress crack resistance by themselves. Unexpectedly, Applicants observed that a three-layer ABA structure having a rigid polyurethane A (exterior) layer and an elastomeric B (interior) layer with excellent adhesion had poorer environmental stress crack resistance than rigid polyurethane alone, with the opposite effect observed with the polyester exterior layer.

[0111] Example 6 Tests were conducted to investigate the effect of heat treatment and thermoforming conditions on the performance of devices made from the sheets. Three sheets of Test Material 2 (2A, 2B, and 2C) (three layers: polyester, polyurethane, polyester) were dried at 60°C under vacuum for 12 hours. The samples were placed in moisture-proof bags and subjected to the heat treatment and thermoforming conditions shown in Table 7. Sample 2A was maintained at 22°C, while Samples 2B and 2C were annealed at 100°C for 24 hours. The samples were then thermoformed to produce plaques using different thermoforming temperatures. Samples 2A and 2B were thermoformed at temperatures below the upper end of the polyurethane's melting range, while Sample 2C was thermoformed at a temperature above the polyurethane's melting range.

[0112] [Table 7]

[0113] Test specimens were cut from the thermoformed samples, analyzed by DSC, and subjected to stress relaxation tests in water at 37°C. DSC showed that the melting point and heat of fusion of the samples increased with annealing at 100°C, and that thermoforming reduced the heat of fusion and melting range. However, samples thermoformed below the upper limit of the polyurethane's melting range retained more crystallinity and performed well in stress relaxation tests. The conditions for Sample 2B in Table 7 were used to fabricate dental appliances.

[0114] Example 7 Further constructions can be made by selecting appropriate layer materials with modulus and elasticity differentials as shown in Table 8.

[0115] [Table 8]

[0116] Example 8

[0113] A 2 mm thick sheet was prepared by laminating two outer films of 0.250 mm thick polypropylene homopolymer (Blue Ridge Films BFI 3270, 1,200 MPa modulus) and an inner layer of 1.50 mm thick ethylene propylene microcrystalline elastomer (Noito PN 2070, Mitsui Chemical, 150 MPa modulus). The sheet was cut into 125 mm diameter discs and thermoformed and shaped to individual maxillary tooth casts to create high impact resistant sports mouthguards. Surprisingly, the mouthguards provided better impact protection and were more comfortable than standard devices made from 4 mm thick ethylene vinyl acetate copolymer sold by Dreve under the trademark Drufosoft.

[0117] Example 9 Aligners were fabricated by thermoforming a three-layer sheet onto a dental model. The two outer layers comprised a rigid polyurethane with a Tg of approximately 120°C, and the inner B layer comprised an aromatic polyether polyurethane with a Shore A of 85, having a hard block melting point of 160-195°C and a heat of fusion of 8 J / gram. The devices were annealed at 100°C, below the Tg of the outer layers, for 24 hours. No deformation was observed. Testing demonstrated that the devices were more elastic and had lower load creep than before annealing at 100°C. The improvement was likely due to an improved microstructure of the polyurethane elastomer.

[0118] In a second test, multilayer and single-layer devices were compared, with Zendura A material used as the A / C or A / B / C material, respectively, in each case. The devices were annealed at 90°C for 24 hours. It was observed that the single-layer device deformed extensively, while the multilayer device maintained its shape. It is hypothesized that in the multilayer device, the elastomer maintains a stabilizing force on the stiffer material during annealing to prevent undesired dimensional changes.

Claims

1. at least two outer layers A and C and an intermediate layer B; the A and C layers each comprise a thermoplastic polymer having a modulus of elasticity of about 1,000 MPa to 2,500 MPa and a glass transition temperature and / or melting point of about 80°C to 180°C; The polymer sheet construction, wherein the intermediate B layer at least comprises an elastomer having one or more of a modulus of elasticity of about 50 MPa to about 500 MPa and a glass transition temperature and / or a melting point of about 90°C to about 220°C.

2. 10. The polymer sheet construction of claim 1, wherein the A and C layers comprise one or more of a copolyester, a polycarbonate, a polyester-polycarbonate blend, a polyurethane, a polyamide, or a polyolefin.

3. 3. The polymer sheet construction of claim 2, wherein the intermediate B layer comprises one or more of a polyurethane elastomer, a polyolefin elastomer, a polyester elastomer, a styrenic elastomer, a polyamide elastomer, a cyclic olefin elastomer, an acrylic elastomer, an aromatic or aliphatic polyether, and a polyester polyurethane.

4. 4. The polymer sheet construction of claim 3, wherein the intermediate B layer material has a compression set of less than 35%, less than 30%, less than 25%, less than 20%, or less than 10% after 22 hours at 25°C.

5. When the A and C layers are displaced relative to each other by 0.05 mm to 0.1 mm, ２ Less than 100N (Newtons) per 1cm ２ Less than 50N per 1cm ２ Less than 25N per cm ２ 3. The polymer sheet construction of claim 2, having a lateral restoring force of less than 10 N per unit area.

6. 4. The polymer sheet construction of claim 3, wherein the interlayer peel strength between the A and C layers and the B layer exceeds 50 N per 2.5 cm.

7. the combined thickness of the A, B, and C layers is from about 250 microns to about 2,000 microns; 4. The polymer sheet construction of claim 3, wherein the combined thickness of the A and C layers is from 25 microns to 750 microns, from 50 microns to 1000 microns, from 100 microns to 700 microns, from 150 microns to 650 microns, or from 200 microns to 600 microns.

8. one or more of the A and C layers comprises a microcrystalline polyamide comprising 50 to 100 mole % of a C6 to C14 aliphatic diacid moiety and about 50 to 100 mole % of 4,4'-methylene-bis(cyclohexylamine) (CAS [1761-71-3]); 3. The polymer sheet composition of claim 2, wherein the microcrystalline polyamide has a glass transition of about 100° C. to 180° C., a heat of fusion of less than 20 J / g, and a light transmittance of greater than 80%.

9. one or more of the A and C layers comprises a copolyester; The copolyester is (a) a dicarboxylic acid component containing 70 mol % to 100 mol % terephthalic acid residues; (b) i) 0-95% ethylene glycol; ii) 5 mol % to 50 mol % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; iii) 50 mol % to 95 mol % of 1,4-cyclohexanedimethanol residues, and iv) 0-1% polyols with 3 or more hydroxyl groups and a diol component comprising: the sum of the mole percentages of the diol residues i), ii), iii), and iv) amounts to 100 mole percent; 4. The polymer sheet composition of claim 3, wherein the copolyester exhibits a glass transition temperature, Tg, of 80°C to 150°C.

10. the intermediate B layer comprises an aromatic polyether polyurethane having a Shore hardness of about A90 to D55 and a compression set of less than 35%; 10. The polymer sheet construction of claim 9, wherein the interlayer peel strength between the A and C layers and the B layer exceeds 50 N per 2.5 cm.

11. one or more of the A and C layers comprises a polyurethane; The polyurethane is (a) a diisocyanate containing 80 mol % to 100 mol % of methylene diphenyl diisocyanate residues and / or hydrogenated methylene diphenyl diisocyanate; (b) i) 0 to 100 mole % of hexamethylene diol; ii) 0 to 50 mole % of 1,4-cyclohexanedimethanol and a diol component comprising: The total of i) and ii) exceeds 90 mol % 4. The polymer sheet composition of claim 3, wherein the polyurethane has a glass transition temperature, Tg, of from about 85°C to about 150°C.

12. 10. A dental appliance conforming to one or more teeth made from the polymer sheet composition of claim 3.

13. the combined thickness of the A, B, and C layers is from about 250 microns to about 2,000 microns; 13. The dental device of claim 12, wherein the combined thickness of the A and C layers is from 25 microns to 750 microns, from 50 microns to 1000 microns, from 100 microns to 700 microns, from 150 microns to 650 microns, or from 200 microns to about 600 microns.

14. 14. The dental device of claim 13, comprising the polymer sheet composition of claim 8.

15. 14. The dental device of claim 13, comprising the polymer sheet composition of claim 9.

16. 14. The dental device of claim 13, comprising the polymer sheet composition of claim 10.

17. 14. The dental device of claim 13, comprising the polymer sheet composition of claim 11.

18. The polymer sheet composition of claim 3, The elastomeric intermediate layer and the outer layer are reversibly movable relative to each other and have a tensile strength of 1 cm when displaced 0.05 mm to 0.1 mm relative to each other. ２ Less than 100N per 1cm ２ Less than 50N per 1cm ２ Less than 25N per cm ２ 1. A reversibly deformable dental device having a lateral restoring force of less than 10 N per tooth.

19. 19. The reversibly deformable dental device of claim 18, wherein the elastomeric intermediate layer comprises polyurethane having a hardness of about A80 to D75, A85 to D65, or A90 to D55.

20. 1. An environmental stress resistant sheet or dental device comprising at least two outer layers and an elastomeric inner layer, one or more of the outer layers is a polyester or copolyester having a modulus of elasticity of about 1,000 MPa to 2,500 MPa; the inner layer comprises an elastomer having a modulus of elasticity of about 50 MPa to about 500 MPa; A sheet or dental device having a delamination strength between at least one outer layer and said elastomer of greater than about 50 N / inch.

21. the outer A layer has a thickness of about 175 to about 250 microns; the outer C layer has a thickness of about 175 to about 250 microns; the thickness of the intermediate B layer is 300 to 500 microns; 4. The reversibly deformable dental device of claim 3, wherein the combined thickness of the A, B, and C layers is between 850 and 1,000 microns.

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