# US 10,870,263 B2 · Dual shell dental appliance and material constructions > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,870,263 B2 - Document ID: US10870263B2 - Status: Granted - Kind: B2 - Application number: 16/719,256 - Filed: 2019-12-18 - Published: 2020-04-30 - Granted: 2020-12-22 - Earliest claimed: 2017-05-31 - Assignees: Bay Materials, LLC - Applicants: Bay Materials, LLC - Inventors: Ray F. Stewart; John Lahlouh - Web page: https://patentgrep.com/patent/US10870263B2 ## CPC - B32B 27/08: of synthetic resin - A61C 7/08: Mouthpiece-type retainers {or positioners, e.g. for both the lower and upper arch (arch-shaped medicament applicators for teeth or gums A61C19/063; mouthguards for protecting the teeth of sportsmen A63B71/085)} - B32B 7/022: Mechanical properties - B32B 7/023: Optical properties - B32B 25/08: of synthetic resin - B32B 25/14: comprising {synthetic rubber copolymers (B32B25/18 and B32B25/20 take precedence)} - B32B 27/302: {comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers} - B32B 27/304: {comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF} - B32B 27/308: {comprising acrylic (co)polymers} - B32B 27/32: comprising polyolefins {(comprising vinyl (co)polymers or acrylic (co)polymers B32B27/30)} - B32B 27/325: {comprising polycycloolefins} - B32B 27/34: comprising polyamides - B32B 27/36: comprising polyesters - B32B 27/365: {comprising polycarbonates} - B32B 27/40: comprising polyurethanes - B32B 2250/03: 3 layers - B32B 2250/24: All layers being polymeric - B32B 2270/00: Resin or rubber layer containing a blend of at least two different polymers - B32B 2307/40: having particular optical properties - B32B 2307/536: Hardness - B32B 2307/546: Flexural strength; Flexion stiffness - B32B 2307/732: Dimensional properties - B32B 2535/00: Medical equipment, e.g. bandage, prostheses or catheter - B32B: LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM - A61C: DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE (non-driven toothbrushes A46B; {tongue scrapers A61B17/24;} preparations for dentistry A61K6/00; preparations for cleaning the teeth or mouth A61K8/00, A61Q11/00) ## Abstract Improved dental appliances and polymeric sheet compositions are disclosed. The polymeric sheet compositions are useful for making dental appliances having outer layers comprised of a material having a modulus of from about 1,000 MPA to 2,500 MPA (“hard”) and an inner core comprised of elastomeric material or materials having a modulus of from about 50 MPa to 500 MPa (“soft”), which exhibit improved flexibility and strength, and better stain and tear resistance than currently available materials and dental appliances. ## Claims ### Claim 1 A polymeric sheet composition, comprising: at least two outer layers A and C and an elastomeric inner layer B, wherein one or both of the outer layers A and C individually comprise a thermoplastic polymer having a flexural modulus of from about 1,000 MPa to 2,500 Mpa, and the inner layer B is comprised of an elastomeric material having a hardness from about A 60 to D 85. ### Claim 2 (depends on 1) The polymeric sheet composition of claim 1, wherein the A, B and C layers of the polymeric sheet composition have a combined thickness of from 250 microns to 2,000 microns and a flexural modulus of from 500 MPa to 1,500 MPa. ### Claim 3 (depends on 2) The polymeric sheet composition of claim 2, wherein the outer layers A and C comprise one or more of a polyester, a co-polyester, a polycarbonate, a polyester polycarbonate blend, a polyurethane, a polyamide, a polyolefin, a microcrystalline polyamide, a co-polyester of terephthalic acid, cyclohexane dimethanol, and 2,2,4,4-tetramethyl-1,3-cyclobutanediol, a co-polyester of terephthalic acid, ethylene glycol and diethylene glycol, an aromatic polyurethane based on MDI and hexanediol, an aromatic polyurethane with aliphatic diols, a co-polymer of propylene, ethylene and C4 to C8 alpha olefin, a cycloaliphatic polyamide, a (meth) acrylic polymer, a vinyl polymer such a polyvinyl chloride, and a fluoropolymer. ### Claim 4 (depends on 2) The polymeric sheet composition of claim 2, wherein the inner layer B comprises one or more of a polyurethane elastomer, an aromatic polyether polyurethane, a polyolefin elastomer, a polyester elastomer, a styrenic elastomer, a polyamide elastomer, a polyether polyamide (polypropylene oxide-based or polytetramethlene oxide-based), a cyclic olefin elastomer, an acrylic elastomer, an aromatic or aliphatic polyether, a polyester polyurethane, a siloxane elastomer, a polyether elastomer, a polyolefin elastomer, an olefin copolymer, and a fluoroelastomer. ### Claim 5 (depends on 3) The polymeric sheet composition of claim 3, wherein one or more of outer layers A and C comprise a microcrystalline polyamide having heat of fusion of less than 20 J/g and a light transmission of greater than 80%. ### Claim 6 (depends on 4) The polymeric sheet composition of claim 4, wherein the inner layer B comprises an anhydride functionalized styrenic elastomer having a hardness of from about A60 to D50. ### Claim 7 (depends on 2) The polymeric sheet composition of claim 2, wherein one or more of the A and C layers comprises a co-polyester having a: (a) a dicarboxylic acid component and (b) a diol component, wherein the-copolyester exhibits a glass transition temperature (Tg) from 80° C. to 150° C. ### Claim 8 (depends on 2) The polymeric sheet composition of claim 2, wherein one or more of the A and C layers comprises a polyurethane comprised of: (a) a di-isocyanate, and (b) a diol component comprising one or more of hexane diol and cyclohexane dimethanol wherein the polyurethane has a glass transition temperature Tg from about 85° C. to about 150° C. ### Claim 9 (depends on 2) The polymeric sheet composition of claim 2, wherein the inner layer B comprises an aromatic polyether polyurethane having a compression set of less than 35%. ### Claim 10 (depends on 2) The polymeric sheet composition according to claim 2, wherein the inner layer B comprises an aromatic polyether polyurethane having an interlayer peel strength between the A and C layers and the B layer of greater than 50 N per 2.5 cm. ### Claim 11 A polymeric sheet composition comprised of at least two rigid or hard outer layers A and C, at least two soft inner layers B and B′, and at least a rigid or hard inner layer, D, wherein the rigid or hard layers, A, C and D, individually comprise a thermoplastic polymer having a modulus of from about 1,000 MPa to 2,500 MPa and the soft inner layers B and B′ individually comprise an elastomeric material having a hardness from about A 60 to D 85. ### Claim 12 (depends on 11) The polymeric sheet composition of claim 11, wherein the polymeric sheet composition has a combined thickness of from 250 microns to 2,000 microns and a flexural modulus of from 500 MPa to 1,500 MPa. ### Claim 13 (depends on 12) The polymeric sheet composition of claim 12, wherein the rigid or hard layers, A, C and D individually comprise one or more of a polyester, a co-polyester, a polycarbonate, a polyester polycarbonate blend, a polyurethane, a polyamide, a polyolefin, a microcrystalline polyamide, a co-polyester of terephthalic and/or isophthalic acid, cyclohexane dimethanol, and 2,2,4,4-tetramethyl-1,3-cyclobutanediol, a co-polyester of terephthalic and/or isophthalic acid, ethylene glycol and diethylene glycol, an aromatic polyurethane based on MDI and hexanediol, an aromatic polyurethane with aliphatic diols, a co-polymer of propylene, ethylene and C4 to C8 alpha olefin, a cycloaliphatic polyamide, a (meth) acrylic polymer, a vinyl polymer such as a polyvinyl chloride, and a fluoropolymer. ### Claim 14 (depends on 12) The polymeric sheet composition of claim 12, wherein the soft inner layers B and B′ individually comprise one of more of a polyurethane elastomer, an aromatic polyether polyurethane, a polyolefin elastomer, a polyester elastomer, a styrenic elastomer, an anhydride functionalized styrenic elastomer, a polyamide elastomer, a polyether polyamide (polypropylene oxide-based or polytetramethylene oxide-based), a cyclic olefin elastomer, an acrylic elastomer, an aromatic or aliphatic polyether, a polyester polyurethane, a siloxane elastomer, a polyether elastomer, a polyolefin elastomer, an olefin copolymer, an acrylic elastomer and a fluoroelastomer. ### Claim 15 (depends on 14) The polymeric sheet composition of claim 14, wherein one or more of the soft inner layers B and B′ comprise an anhydride functionalized styrenic elastomer having a hardness of from about A60 to D50. ### Claim 16 (depends on 14) The polymeric sheet composition of claim 14, wherein the rigid or hard layers, A, C and D have a combined thickness of from about 100 microns to about 750 microns. ### Claim 17 (depends on 14) The polymeric sheet composition of claim 14, wherein the soft layers, B and B′ have a combined thickness of from about 150 microns to about 1,000 microns. ### Claim 18 (depends on 12) A dental appliance conformal to one or more teeth comprising a polymeric sheet composition according to claim 12. ### Claim 19 A polymeric sheet composition, comprising: three or more layers, A, A1, and B, wherein the outermost layers, A and A1 have different thicknesses from one another and individually comprise a thermoplastic polymer having a flexural modulus of from about 1,000 MPa to 2,500 MPa, and wherein the inner layer B is comprised of an elastomeric material having a hardness from about A 60 to D 85. ### Claim 20 (depends on 19) The polymeric sheet composition of claim 19, wherein the A, A1 and B layers of the polymeric sheet composition have a combined thickness of from about 500 microns to 2,000 microns. ### Claim 21 (depends on 20) The polymeric sheet composition of claim 20, wherein the outermost layer A1 has a thickness of from about 25 to about 250 microns. ### Claim 22 (depends on 20) The polymeric sheet composition of claim 20, wherein the ratio of the thickness of the outermost layer A1 to the thickness of the outermost layer A is from about 0.9 to about 0.2. ### Claim 23 (depends on 20) The polymeric sheet composition of claim 20, wherein the outermost layer A and outermost layer A1 are comprised of one or more of a polyester, a co-polyester, a polycarbonate, a polyester polycarbonate blend, a polyurethane, a polyamide, and a polyolefin. ### Claim 24 (depends on 20) The polymeric sheet composition according to claim 20, wherein the outer layers A and A1 comprise the same material. ### Claim 25 (depends on 20) The polymeric sheet composition according to claim 20, wherein the outer layers A and A2 comprise different materials. ### Claim 26 (depends on 20) The polymeric sheet composition of claim 20, wherein the middle layer B is comprised of 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. ### Claim 27 (depends on 20) A dental appliance conformal to one or more teeth comprising a polymeric sheet composition according to claim 20. ### Claim 28 (depends on 27) The dental appliance of claim 27, wherein the dental appliance exhibits improved tear resistance relative to the A, C or D layer alone. ### Claim 29 (depends on 27) The dental appliance of claim 27, wherein the dental appliance exhibits improved environmental stress resistance relative to the A, C or D layer alone. ### Claim 30 A polymeric sheet composition, comprising: at least two outer layers A and C and an elastomeric inner layer B, wherein (i) one or both of the outer layers A and C individually comprise a thermoplastic polymer having a flexural modulus of from about 1,000 MPa to 2,500 Mpa, (ii) the inner layer B is comprised of an elastomeric material having a hardness from about A 60 to D 85, (iii) the A, B and C layers of the polymeric sheet composition have a combined thickness of from 250 microns to 2,000 microns and a flexural modulus of from 500 MPa to 1,500 Mpa, and (iv) the inner layer B comprises an anhydride functionalized styrenic elastomer having a hardness of from about A60 to D50. ### Claim 31 A polymeric sheet composition, comprising: at least two outer layers A and C and an elastomeric inner layer B, wherein (i) one or both of the outer layers A and C individually comprise a thermoplastic polymer having a flexural modulus of from about 1,000 MPa to 2,500 Mpa, (ii) the inner layer B is comprised of an elastomeric material having a hardness from about A 60 to D 85, (iii) the A, B and C layers of the polymeric sheet composition have a combined thickness of from 250 microns to 2,000 microns and a flexural modulus of from 500 MPa to 1,500 Mpa, and (iv) one or more of the A and C layers comprises a co-polyester having a: (c) a dicarboxylic acid component and (d) a diol component, wherein the-copolyester exhibits a glass transition temperature (Tg) from 80° C. to 150° C. ### Claim 32 A polymeric sheet composition, comprising: at least two outer layers A and C and an elastomeric inner layer B, wherein (i) one or both of the outer layers A and C individually comprise a thermoplastic polymer having a flexural modulus of from about 1,000 MPa to 2,500 Mpa, (ii) the inner layer B is comprised of an elastomeric material having a hardness from about A 60 to D 85, (iii) the A, B and C layers of the polymeric sheet composition have a combined thickness of from 250 microns to 2,000 microns and a flexural modulus of from 500 MPa to 1,500 Mpa, and (iv) one or more of the A and C layers comprises a polyurethane comprised of: (c) a di-isocyanate, and (d) a diol component comprising one or more of hexane diol and cyclohexane dimethanol wherein the polyurethane has a glass transition temperature Tg from about 85° C. to about 150° C. ### Claim 33 A polymeric sheet composition, comprising: at least two outer layers A and C and an elastomeric inner layer B, wherein (i) one or both of the outer layers A and C individually comprise a thermoplastic polymer having a flexural modulus of from about 1,000 MPa to 2,500 Mpa, (ii) the inner layer B is comprised of an elastomeric material having a hardness from about A 60 to D 85, (iii) the A, B and C layers of the polymeric sheet composition have a combined thickness of from 250 microns to 2,000 microns and a flexural modulus of from 500 MPa to 1,500 Mpa, and (iv) the inner layer B comprises an aromatic polyether polyurethane having a compression set of less than 35%. ### Claim 34 A polymeric sheet composition, comprising: at least two outer layers A and C and an elastomeric inner layer B, wherein (i) one or both of the outer layers A and C individually comprise a thermoplastic polymer having a flexural modulus of from about 1,000 MPa to 2,500 Mpa, (ii) the inner layer B is comprised of an elastomeric material having a hardness from about A 60 to D 85, (iii) the A, B and C layers of the polymeric sheet composition have a combined thickness of from 250 microns to 2,000 microns and a flexural modulus of from 500 MPa to 1,500 Mpa, and (iv) the inner layer B comprises an aromatic polyether polyurethane having an interlayer peel strength between the A and C layers and the B layer of greater than 50 N per 2.5 cm.