Bondable orthodontic assemblies and bonding methods - Patents.com

Abstract

Orthodontic appliances, methods for making and fastening the orthodontic appliances, and kits including the orthodontic appliances are described.

Description

[Background technology]

[0001] Crooked jaws and malpositioned teeth are often prevented and treated with orthodontic appliances. In many situations, the appliances are temporarily bonded to the tooth structure with an adhesive. When the appliance is secured against the tooth surface, excess adhesive, which is often used to fill the gap between the appliance base and the tooth surface, seeps past the periphery of the appliance base. The seeped adhesive, known in the art as "flash," is manually removed by the practitioner before hardening, but this procedure is time-consuming and incomplete removal can be structurally problematic. For example, accidental movement of the appliance during burr removal can adversely affect bond reliability. Furthermore, incomplete removal of excess adhesive is not only uncomfortable for the patient, but also promotes bacterial accumulation, which can ultimately deteriorate the underlying tooth structure, resulting in demineralization and discoloration.

[0002] Cinader previously developed a strategy for reducing burrs (see U.S. Patent No. 10,492,890). Cinader discovered that incorporating a compressible mat into the appliance base and soaking the mat with unfilled or lightly filled adhesive was effective in causing the adhesive to leach out and fill the gap between the appliance base and the tooth surface, forming a meniscus around the edge of the appliance when the appliance was secured, thereby eliminating the need for burr removal of excess adhesive.

[0003] Although progress has been made, there is a continuing interest in developing tools that bond efficiently, avoid burr removal, and reduce manufacturing costs. Summary of the Invention

[0004] In one embodiment, an orthodontic appliance is described. The orthodontic appliance includes a base and a hardenable adhesive layer disposed on the base. The hardenable adhesive layer includes a first region and a second region, the first region being at least partially surrounded by the second region, the first region and the second region being configured to contact a tooth surface. The first region is 1s -1 the second region includes a high viscosity adhesive composition characterized by a viscosity of 10 Pa·s to about 1,500,000 Pa·s at a shear rate of 1 s -1 The low viscosity adhesive composition is characterized by a viscosity of about 0.1 Pa·s to about 100 Pa·s at a shear rate of 100° C. The high viscosity adhesive composition has a viscosity higher than that of the low viscosity adhesive composition.

[0005] In one embodiment, a method for securing an orthodontic appliance to a tooth surface is described that includes providing an orthodontic appliance as described herein, contacting the orthodontic appliance to a tooth surface, applying pressure to the orthodontic appliance such that the hardenable adhesive layer is compressed against the tooth surface, and hardening the hardenable adhesive layer to form a hardened adhesive.

[0006] In one embodiment, a method is described for manufacturing the orthodontic appliance described herein. The method includes providing a base and applying a high viscosity adhesive composition to the base in a first region and applying a low viscosity adhesive composition to the base in a second region to form a hardenable adhesive layer. The first region is at least partially surrounded by the second region.

[0007] In one embodiment, a kit is described that includes an orthodontic appliance as described herein and a set of instructions instructing a user to perform the method steps described herein for securing the orthodontic appliance to a tooth surface.

[0008] In one embodiment, a kit is described that includes a base, a high viscosity adhesive composition as described herein, a low viscosity adhesive composition as described herein, and a set of instructions instructing a user to perform the steps described herein to make an orthodontic appliance of the present disclosure. [Brief description of the drawings]

[0009] [Figure 1A] FIG. 1 is a side view of an orthodontic appliance of the present disclosure having a hardenable adhesive layer in an uncompressed state. [Figure 1B] FIG. 1 is a side view of an orthodontic appliance of the present disclosure having a hardenable adhesive layer in a compressed state. [Figure 1C] FIG. 2 is a bottom view of an orthodontic appliance of the present disclosure having a hardenable adhesive layer in an uncompressed state. [Figure 1D] FIG. 2 is a bottom view of an orthodontic appliance of the present disclosure having a hardenable adhesive layer in a compressed state. [Figure 1E] FIG. 2 is a top view of an orthodontic appliance of the present disclosure having a hardenable adhesive layer in an uncompressed state. [Figure 1F] FIG. 2 is a top view of an orthodontic appliance of the present disclosure having a hardenable adhesive layer in a compressed state. [Figure 2A] FIG. 1 is a cross-sectional side view of an orthodontic appliance of the present disclosure having a hardenable adhesive layer in an uncompressed state. [Figure 2B] FIG. 1 is a cross-sectional side view of an orthodontic appliance of the present disclosure having a hardenable adhesive layer in a compressed state. [Figure 3A] FIG. 1 is a cross-sectional side view of an orthodontic appliance of the present disclosure having a hardenable adhesive layer in an uncompressed state. [Figure 3B] FIG. 1 is a cross-sectional side view of an orthodontic appliance of the present disclosure having a hardenable adhesive layer in a compressed state. [Figure 4A] FIG. 1 is a cross-sectional side view of an orthodontic appliance of the present disclosure having a hardenable adhesive layer in an uncompressed state. [Figure 4B] FIG. 1 is a cross-sectional side view of an orthodontic appliance of the present disclosure having a hardenable adhesive layer in a compressed state. [Figure 5A] FIG. 1 is a side view of a comparable orthodontic appliance not of the present disclosure having a compressible mat. [Figure 5B] FIG. 1 is a side view of a comparable orthodontic appliance not of the present disclosure having a compressible mat. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] The present disclosure is directed to orthodontic appliances that use differential adhesive placement to provide superior tooth bonding while eliminating the need for burr removal.

[0011] It is a common practice to use adhesives to bond orthodontic appliances to teeth. The adhesive is generally coated on the bonding surface of the appliance. After the appliance is attached to the tooth, the adhesive is cured to create a strong bond. A suitable orthodontic adhesive must provide high strength to maintain a consistent and secure bond between the appliance and the tooth throughout the course of orthodontic treatment, which can last for more than two years. However, the adhesive bond should not be so strong that it becomes excessively difficult to remove the appliance at the end of treatment. An ideal adhesive should also have an appropriate degree of tack and viscosity to avoid drift after placing the appliance on the tooth and to facilitate handling by the orthodontic practitioner. Conventional orthodontic adhesives are polymerizable resins filled with a significant amount of hard fillers, such as quartz or silica fillers. Because the bonding procedure requires the adhesive to act as a gap filler (i.e., occupy all the space between the tooth surface and the appliance), an excess of adhesive is usually applied to the bonding surface of the appliance. In other words, if there is a mismatch between the tooth surface and the adhesive surface of the appliance, the adhesive fills the space between the appliance and the tooth, maintaining the bond and preventing the formation of voids that can trap food and accumulate plaque. When the appliance is fully secured against the tooth, excess adhesive oozes out along the periphery of the base. This excess adhesive, known as "burr," is manually removed by the practitioner before the adhesive is allowed to harden. The presence of adhesive burr can be disadvantageous. Removal of burr is time-consuming, especially since accidental movement of the appliance can adversely affect the adhesive reliability. Furthermore, incomplete removal of excess adhesive is problematic. Incomplete removal is particularly common in posterior areas and behind hooked appliances where access is limited. If not completely removed, excess adhesive provides a site for bacterial accumulation. Such bacteria can attack and degrade the underlying tooth structure, resulting in demineralization and discoloration of the tooth. Furthermore, the exposed adhesive surface is susceptible to contamination by food or beverages. Finally, the presence of hard fillers in the adhesive composition makes the adhesive difficult to remove once it has cured in the case of indirect adhesives, and uncomfortable for the patient.

[0012] It is understood that adhesives with sufficient filler content provide better tooth bonding but require burr removal. Fillers increase flow resistance (i.e., increase viscosity), which allows more adhesive to remain in contact with the appliance-tooth interface (i.e., fill the gap between the orthodontic appliance and the tooth surface), likely due at least in part to the more easily formed gap configuration. Filling this gap is particularly important for tooth structures with significant curvature, irregularly shaped teeth, molars, and the like. However, the exuded viscous adhesive (burr) takes on a convex shape that must be removed, and burrs that are not removed are prone to contamination and create an environment for the accumulation of bacteria that cause tooth decay.

[0013] It is further understood that adhesives with little or no filler result in a softer adhesive (i.e., lower viscosity) that is manifested by a concave meniscus-like shape (not considered a "burr") that may not need to be removed. However, low viscosity adhesives do not adequately fill the gap between the orthodontic appliance and the tooth structure, resulting in insufficient tooth adhesion, which may lead to displacement or "drift" of the appliance, or even complete failure of adhesion. Furthermore, poorly filled gaps may contain food material that may contribute to tooth decay. Previous solutions to adequately fill the gap between the orthodontic appliance and the tooth structure while mitigating burrs with low viscosity adhesives have been achieved through the use of compressible mats, as described in U.S. Pat. No. 10,492,890.

[0014] The inventors of the present disclosure have discovered that by incorporating a hardenable adhesive layer having a high viscosity adhesive composition at least partially surrounded by a low viscosity adhesive composition, sufficient gap filling is provided while allowing only the low viscosity adhesive composition to bleed out when securing an orthodontic appliance to a tooth surface (no flash removal required). The high viscosity adhesive composition effectively displaces the low viscosity adhesive composition that surrounds it, preventing the high viscosity adhesive from bleed-out beyond the base (forming a flash; requiring removal). Furthermore, the high viscosity adhesive composition is dispensed to maximize the contact area between the base and the tooth structure. In addition, the adhesive layer does not flow from the base in any orientation for any period of time, allowing for complete assembly and dispensing. This ingenious construction ensures excellent bond strength without the need for flash removal, avoids the use of compressible mats and associated manufacturing costs, and limits in-chair preparation.

[0015] 1A illustrates a side view of an orthodontic appliance 100. The orthodontic appliance 100 includes a base 102 having a hardenable adhesive layer 104 disposed thereon. The hardenable adhesive layer 104 includes a high viscosity adhesive composition 106 surrounded by a low viscosity adhesive composition 108. The hardenable adhesive layer 104 is shown in an uncompressed configuration, i.e., prior to pressing the orthodontic appliance 100 against a tooth surface (not shown). In one particular embodiment, the orthodontic appliance 100 has a maximum thickness of 0.508 mm and a maximum length of 1.24 mm. 3 and covering 24% of the area of ​​the base; and 3 and a low viscosity composition 108 that is present in a volume of 100% and covers 76% of the area of ​​the base.

[0016] 1B shows a side view of the orthodontic appliance 100 in a compressed state, i.e., after the orthodontic appliance 100 has been pressed against a tooth surface (not shown). As shown, only the low viscosity adhesive composition 108 extends beyond the base 102. In one particular embodiment, the orthodontic appliance 100 has a high viscosity composition 106 that covers 47% of the area of ​​the base after compression, and a low viscosity composition 108 that covers 53% of the area of ​​the base after compression, as described above in FIG. 1A.

[0017] FIG. 1C illustrates a bottom view of the orthodontic appliance 100 in an uncompressed state.

[0018] FIG. 1D illustrates a bottom view of the orthodontic appliance 100 in a compressed state.

[0019] FIG. 1E illustrates a top view of the orthodontic appliance 100 in an uncompressed state.

[0020] IF shows a top view of the orthodontic appliance 100 in a compressed state. As shown, only the low viscosity adhesive composition 108 extends beyond the base 102.

[0021] 2A illustrates a cross-sectional side view of an orthodontic appliance 200. The orthodontic appliance 200 includes a base 202 and a hardenable adhesive layer 204 disposed thereon. The hardenable adhesive layer 204 is shown in an uncompressed configuration. As shown, the high viscosity adhesive composition 206 has a greater volume than the low viscosity adhesive 208. In one particular embodiment, the orthodontic appliance 200 has a maximum thickness of 0.508 mm and a maximum length of 1.72 mm. 3 and a high viscosity composition 206 present in a volume of 1.41 mm with a maximum thickness of 0.508 mm and an average thickness of about 0.250 mm. 3 and a low viscosity composition 208 that is present in a volume of 100% and covers 68% of the area of ​​the base.

[0022] 2B shows a cross-sectional side view of the orthodontic appliance 200 in a compressed state. The high viscosity adhesive composition 206 is shown spreading toward the edges of the base 202, and the low viscosity adhesive composition 204 is shown spreading beyond the edges of the base 202 in a concave configuration. The extent to which the high viscosity adhesive composition 204 spreads toward the edges of the base 202 depends at least on the volume of high viscosity adhesive composition used. In one particular embodiment, the orthodontic appliance 200 has the high viscosity composition 206 covering 66% of the area of ​​the base after compression, as described above in FIG. 2A, and the low viscosity composition 208 covering 34% of the area of ​​the base after compression.

[0023] 3A shows a cross-sectional side view of an orthodontic appliance 300 in an uncompressed state, similar to the orthodontic appliance 300, but with a different volume (and therefore area coverage) of deposited high viscosity adhesive composition 306. In one particular embodiment, the orthodontic appliance 300 has a maximum thickness of 0.381 mm and a maximum width of 2.67 mm. 3 and a high viscosity composition 306 present in a volume of 0.46 mm with a maximum thickness of 0.266 mm and an average thickness of 0.133 mm covering 67% of the area of ​​the base. 3 and a low viscosity composition 308 that is present in a volume of about 100 μm and covers 33% of the area of ​​the base.

[0024] 3B shows a cross-sectional side view of an orthodontic appliance 300 in a compressed state similar to orthodontic appliance 300, but with a different area A covered by high viscosity adhesive composition 306. In one particular embodiment, orthodontic appliance 300 has high viscosity composition 306 covering 100% of the area of ​​the base after compression, as described above in FIG.

[0025] 4A shows a cross-sectional side view of an orthodontic appliance 400 in an uncompressed state, similar to orthodontic appliance 400, but with a different height and area covered by high viscosity adhesive composition 406. In one particular embodiment, orthodontic appliance 400 has a maximum thickness of 1.15 mm and a maximum width of 1.26 mm. 3 and a high viscosity composition 406 present in a volume of 1.87 mm with a maximum thickness of 0.56 mm and an average thickness of 0.33 mm covering 24% of the area of ​​the base. 3and a low viscosity composition 408 that is present in a volume of 100% and covers 76% of the area of ​​the base.

[0026] 4B shows a cross-sectional side view of an orthodontic appliance 400 in a compressed state, similar to orthodontic appliance 200, but with a different area A covered by high viscosity adhesive composition 406. In one particular embodiment, orthodontic appliance 400 has high viscosity composition 306 covering 47% of the area of ​​the base after compression, and low viscosity composition 408 covering 53% of the area of ​​the base after compression, as described above in FIG.

[0027] 5A shows an example of an orthodontic appliance 500 having a compressible material 510 and adhesive 506 / 508 (high viscosity adhesive and / or low viscosity adhesive composition) disposed therein and / or thereon (not part of this disclosure; see U.S. Pat. No. 9,480,540). The orthodontic appliance 500 is shown in an uncompressed state. The compressible material has been used to prevent the adhesive composition from spreading beyond the base 502 of the device. The orthodontic appliance of the present disclosure does not have such compressible material as described herein.

[0028] FIG. 5B is a cross-sectional view of the orthodontic appliance 500 showing the compressible material 510 in an uncompressed configuration.

[0029] definition As used herein, "about" means plus or minus ten percent of a given value. For example, about ten means from nine to eleven.

[0030] As used herein, an "acid functional group" refers to a functional group that has an acidic hydrogen (i.e., a pKa of less than about 5). Organic functional groups, such as -COH, -P(O)(OH), -S(O)OH, etc., are considered "acid functional groups."

[0031] As used herein, "alkyl" refers to a straight or branched monovalent saturated carbon chain, e.g., a C1 alkyl is methyl (-CH3), a C2 alkyl is ethyl (-CH2CH3), a C4 alkyl can be butyl (-CH2CH2CH2CH3), sec-butyl (-CH(CH-3)CH2CH3), iso-butyl (-CH2CH(CH3)2), or tert-butyl (-C(CH3)3), etc.

[0032] As used herein, "alkylene" refers to a straight or branched divalent saturated carbon chain, e.g., a C1 alkylene is methylene (-CH2-), a C2 alkylene is ethylene (-CH2CH2-), a C4 alkylene can be -CH2CH2CH2CH2-, -CH(CH-3)CH2CH2-, -CH2CH(CH3)CH2-, or -C(CH3)2CH2-, etc.

[0033] As used herein, “alkyl (alk)acrylate” refers to an alkyl acrylate ester (i.e., C(R 1 )(R 1 )=C(R 2 )C(O)O-alkyl), where R 1 is optional (e.g., -H or C 1~4 alkyl), R 2 is -H), or alkyl substituted alkyl acrylate esters (i.e., C(R 1 )(R 1 )=C(R 2 )C(O)O-(alkyl), where R 1 is optional (e.g., -H or C 1~4 alkyl), R 2 refers to an alkyl (e.g., methyl ("meth")). A "hydroxy-substituted (alkyl) acrylate" refers to a hydroxy-substituted (alkyl) acrylate of the formula C(R 1 )(R 1 )=C(R 2 )C(O)OR 3 ) in which R 1 , R 2 , or R 3At least one of the alkyl groups is an alkyl group substituted with —OH. In some cases, the (alkyl)acrylate may be a dimer, e.g., C(R 1 )(R 1 )=C(CH3)C(O)OR 2 OC(O)OC(CH3)=C(R 1 )(R 1 ), wherein R 2 is a linking group, e.g., C 2~8 It is alkylene.

[0034] As used herein, "base" refers to the surface of an orthodontic appliance that is intended to contact the tooth structure. The base of an orthodontic appliance may be composed of metal, plastic, ceramic, or a combination thereof.

[0035] As used herein, "unsaturated" and "unsaturated organic group" refer to an olefin unit. An olefin is an olefin having a -C(R 1 )=C(R 2 )-, wherein R 1 and R 2 is arbitrary, for example, each R 1 is H or C 1~6 alkyl; each R 2 is -C(O)(C 1~6 alkyl), -COH, -O(C 1~6 The term "unsaturated monomer" refers to a polymerizable compound that contains an olefin unit.

[0036] As used herein, "compressible material" or "compressible mat" refers to any non-adhesive material, particularly a porous material, that reduces in volume when compressed. Exemplary compressible materials include foams (e.g., cellulose, glass, polymer), sponges, nonwovens, glass wool, cotton fibers, and cellulose fibers. Further examples of compressible materials are disclosed in U.S. Pat. Nos. 10,492,890 and 9,480,540 and the references cited therein, each of which is incorporated herein by reference in its entirety. The orthodontic appliance of the present disclosure does not have a compressible material on the base.

[0037] As used herein, the phrase "one or more of" when used in phrases such as "one or more of A and B" or "one or more of at least one A and at least one B" means that the composition may include at least one A, more than one A, at least one B, more than one B, at least one A and at least one B, more than one A and more than one B. In other words, the phrase is not intended to mean that the composition must have at least one of each A and B.

[0038] As used herein, "orthodontic appliance" refers to any device that is intended to be attached to tooth structure, such as orthodontic brackets, buccal tubes, lingual anchors, orthodontic bands, mouth gag devices, buttons, prefabricated attachments, and cleats.

[0039] As used herein, a "curable adhesive" refers to a composition that includes a polymerizable component (i.e., a resin), with or without a filler, that can be cured or solidified, for example, by heating to cause polymerization or chemical crosslinking.

[0040] As used herein, "cured adhesive" refers to a composition that includes polymerized components, with or without fillers, that are derived from a curable adhesive.

[0041] As used herein, a "high viscosity adhesive composition" is defined as a composition having one or more polymerizable components that upon curing provide a polymerized adhesive. The nature of the polymerizable components (i.e., monomers), alone or in combination with additives, such as fillers, can affect the 1s -1The high viscosity adhesive composition provides a viscosity of about 10 Pa·s to about 1,500,000 Pa·s at a shear rate of 100 / s. The high viscosity adhesive composition is a filling (e.g., composite) material (e.g., dental or orthodontic material) that can be applied or adhered (i.e., for indirect bonding) to a tooth surface or a tooth replica surface, such as a stone model or a plaster model. High viscosity adhesive compositions include, for example, orthodontic adhesives, cements (e.g., glass ionomer cements, resin modified glass ionomer cements, and / or orthodontic cements), and restoratives (e.g., restorative filling materials). The high viscosity adhesive composition may be photopolymerizable and / or redox polymerizable.

[0042] As used herein, a "low viscosity adhesive composition" is defined as a composition having one or more monomers that upon curing provide a polymerized adhesive. The nature of the polymerizable component (i.e., monomer), alone or in combination with additives, such as fillers, determines the 1s -1 The adhesive composition provides a viscosity of about 1 Pa·s to about 100 Pa·s at a shear rate of 100° C. The low viscosity adhesive composition is a non-filled or lightly filled material (e.g., dental or orthodontic materials) that can be applied or adhered to a tooth surface or a tooth replica surface. Low viscosity adhesive compositions include, for example, dental adhesives, primers (e.g., orthodontic primers), liners, sealants, and coatings. The low viscosity adhesive composition may be photopolymerizable and / or redox polymerizable.

[0043] As used herein, a "layer" is defined as a plane parallel to the length of the base. The plane must intersect each component in the layer for the component to be considered part of the layer. The composition forming the layer may extend above and / or below the plane.

[0044] As used herein, "thickness" defined in terms of the dimensions defining the placement of the low viscosity adhesive composition and the high viscosity adhesive composition is measured as the vertical distance from the base of the orthodontic appliance to the highest point of the composition. "Maximum thickness" refers to the maximum distance measured within an area. "Average thickness" refers to the average of the distances measured over the entire area.

[0045] As used herein, the term "resin" refers to a polymerizable component that includes one, two, three, or more polymerizable groups. Exemplary polymerizable groups include, but are not limited to, acrylate groups, epoxy (oxirane) groups, and vinyl ether groups. Resins can often be cured by radiation-induced polymerization or crosslinking, or by using redox initiators. The term "resin" is used interchangeably with "polymerizable component" and "adhesive."

[0046] As used herein, "yield stress" is the minimum stress required to cause a material to flow.

[0047] Orthodontic appliances In various embodiments, an orthodontic appliance is described. The orthodontic appliance can include a base and a hardenable adhesive layer disposed on the base. The hardenable adhesive layer can include a first region and a second region, the first region being at least partially surrounded by the second region, the first region and the second region being configured to contact a tooth surface. The first region is 1s -1 The first region may include a high viscosity adhesive composition characterized by a viscosity of about 10 Pa·s to about 1,500,000 Pa·s at a shear rate of 1 s. -1 The low viscosity adhesive composition is characterized by a viscosity of about 0.1 Pa·s to about 100 Pa·s at a shear rate of 100° C. The high viscosity adhesive composition has a viscosity higher than that of the low viscosity adhesive composition.

[0048] In some embodiments, the orthodontic appliance consists essentially of a base and a hardenable adhesive layer.

[0049] In some embodiments, the orthodontic appliance may exclude a compressible mat. Compressible mats have been used to fill gaps between the surface of a base and tooth structure. Compressible materials and mats made therefrom can be found, for example, in U.S. Patent No. 10,492,890 and U.S. Patent No. 9,480,540, each of which is incorporated herein by reference in its entirety. For example, the compressible mat may include foam, sponge, nonwoven fabric, glass wool, cotton fiber, cellulose fiber, combinations thereof, and the like. In some embodiments, the compressible material may have a thickness of about 0.2 mm to about 1 mm, for example, 0.5 mm. Specific materials are described, for example, in U.S. Pat. Nos. 4,605,402; 4,865,596; 5,614,570; 6,027,795; 6,645,618; Japanese Patent No. JP63170437; and Nacht et al., "The microsponge: a novel topical programmable delivery system," in Topical Drug Delivery Formulations, DW Osborn and AH Amman (Eds.), Marel Dekker, New York, pp. 299-325 (1990), U.S. Pat. No. 5,770,636 (Wernsing et al.) and U.S. Pat. No. 5,817,704 (Shively et al.); see, e.g., Westerman et al., British Journal of Sports No. 6,750,261, each of which is incorporated herein by reference in its entirety. For example, the compressible mat may comprise or consist essentially of polypropylene.

[0050] Orthodontic appliance base In some embodiments, the base is about 8.0 mm 2 ~about 20mm 2 may have an area of

[0051] In some embodiments, the base may be a base for an orthodontic appliance (e.g., a lingual bracket, a self-ligating bracket, a Roth bracket, an MBT bracket, etc.), a buccal tube, a band, a button, a spacer retainer, a lingual anchoring device, a custom base for a bracket or buccal tube, etc.

[0052] In some embodiments, the base may comprise a material selected from ceramic, cobalt chrome, composite material, gold, plastic, stainless steel, titanium, or combinations thereof.

[0053] Curable adhesive layer In some embodiments, the curable adhesive layer may further comprise a filler as described herein. The filler may be present in the high viscosity adhesive composition, the low viscosity adhesive composition, or a combination thereof. In many embodiments, the high viscosity adhesive composition may comprise a greater amount of filler than the amount of filler present in the low viscosity adhesive composition. In some embodiments, the high viscosity adhesive may be based on the same resin as the low viscosity adhesive, the composition differing in the amount of filler present such that the viscosities described for the high viscosity adhesive composition and the low viscosity adhesive composition are achieved. In other embodiments, the high viscosity adhesive and the low viscosity adhesive are based on different resins, i.e., the adhesives comprise or are derived from one or more different monomers.

[0054] In some embodiments, the high viscosity adhesive composition and the low viscosity adhesive composition may differ in viscosity by at least 5 times, at least 6 times, at least 7 times, at least 8 times, at least 9 times, at least 10 times, at least 12 times, at least 15 times, at least 18 times, at least 20 times, at least 50 times, at least 100 times, or a value within a range between any of the foregoing values, such as from about 8 times to about 12 times, from about 10 times to about 15 times, etc.

[0055] In some embodiments, the high viscosity adhesive composition may be present on the base at a maximum thickness (in an uncompressed state) of about 0.3 mm to about 2.0 mm. For example, the high viscosity adhesive composition may be present on the base at a maximum thickness of about 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, or 2.0 mm, or a value within a range between any of the aforementioned values, such as about 0.3 to about 0.5 mm, about 0.5 to about 1.6 mm, etc. In some embodiments, the high viscosity adhesive composition may be present on the base at a maximum thickness of about 1.0 mm. 3 ~ approx. 3.0 mm 3 For example, the high viscosity adhesive composition may be present on the base in a volume of about 1.0, 1.2, 1.4, 1.6, 1.8, 2.0, 2.2, 2.4, 2.6, 2.8, or 3.0 mm. 3 or a value within a range between any of the preceding values, e.g., from about 1.2 to about 1.5 mm 3 , about 1.8 to about 2.8 mm 3 and the like may be present on the base.

[0056] In some embodiments, the low viscosity adhesive composition may be present on the base at a maximum thickness (in an uncompressed state) of about 0.2 mm to about 1.5 mm. For example, the low viscosity adhesive composition may be present on the base at a maximum thickness of about 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, or 2.0 mm, or a value within a range between any of the aforementioned values, such as about 0.3 to about 0.5 mm, about 0.5 to about 1.6 mm, etc. In some embodiments, the low viscosity adhesive composition may be present on the base at a maximum thickness of about 0.3 mm. 3 ~ approx. 2.0 mm 3 For example, the low viscosity adhesive composition may be present on the base in a volume of about 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0 mm 3 or a value within a range between any of the preceding values, e.g., from about 1.4 to about 1.9 mm 3, about 0.4 to about 0.8 mm 3 and the like may be present on the base.

[0057] In some embodiments, the ratio of the maximum thickness of the high viscosity adhesive composition (uncompressed) to the average thickness of the low viscosity adhesive composition (uncompressed) may be at least 2:1, at least 3:1, at least 4:1, at least 5:1, at least 6:1, at least 7:1, at least 8:1, at least 9:1, at least 10:1, at least 11:1, at least 12:1, at least 13:1, at least 14:1, at least 15:1, at least 16:1, at least 17:1, at least 18:1, at least 19:1, at least 20:1, or a ratio between any of the foregoing values, such as from about 2:1 to about 4:1, from about 12:1 to about 15:1, etc.

[0058] In some embodiments, the high viscosity adhesive composition may cover (in an uncompressed state) about 20% to about 75% of the area of ​​the base. For example, the high viscosity adhesive composition may cover (in an uncompressed state) about 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, or a value within a range between any of the aforementioned values, such as about 20% to about 55%, about 60% to about 70%, etc.

[0059] In some embodiments, the low viscosity adhesive composition may cover (in an uncompressed state) about 25% to about 80% of the area of ​​the base. For example, the low viscosity adhesive composition may cover (in an uncompressed state) about 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, or 80% of the area of ​​the base, or a value within a range between any of the aforementioned values, such as about 30% to about 40%, about 45% to about 80%, etc. The low viscosity adhesive composition may cover the difference in the area of ​​the base not occupied by the high viscosity adhesive composition.

[0060] In some embodiments, the total area of ​​the base may be covered by the first region (comprising the high viscosity adhesive composition in an uncompressed state) and the second region (comprising the low viscosity adhesive composition in an uncompressed state) in a ratio of about 1:1, 1:1.2, 1:1.4, 1:1.6, 1:1.8, 1:2, 1:2.2, 1:2.4, 1:2.6, 1:2.8, 1:3, 1:3.2, 1:3.4, 1:3.6, 1:3.8, 1:4, 1:4.2, 1:4.4, 1:4.6, 1:4.8, 1:5, or a ratio between any of the aforementioned values, such as from about 1:1.6 to about 1:2.5, from about 1:3 to about 1:4, etc.

[0061] In some embodiments, the high viscosity adhesive composition may cover (after compression) about 40% to about 100% of the base area. For example, the high viscosity adhesive composition may cover (after compression) about 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, or 100% of the base area, or a value within a range between any of the aforementioned values, such as about 45% to about 70%, about 50% to about 95%, etc.

[0062] In some embodiments, the low viscosity adhesive composition may cover (after compression) about 0% to about 60% of the area of ​​the base. For example, the low viscosity adhesive composition may cover (after compression) about 0%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, or 60% of the area of ​​the base, or a value within a range between any of the aforementioned values, such as about 5% to about 50%, about 30% to about 55%, etc. The low viscosity adhesive composition may cover the difference in the area of ​​the base not occupied by the high viscosity adhesive composition.

[0063] In some embodiments, the high viscosity adhesive composition and the low viscosity adhesive composition can be selected from any of the compositions described herein, including any filler amount, and any combination of those compositions. For example, the high viscosity adhesive can be 3M Transbond™ XT Adhesive or 3M Transbond™ PLUS Color Change Adhesive, and the low viscosity adhesive can be 3M Transbond™ XT Primer, 3M Clinpro Sealant, or 3M Scotchbond Universal Adhesive.

[0064] In some embodiments, at least one of the high viscosity adhesive and the low viscosity adhesive in the curable adhesive layer may further include an initiator system. The initiator system may be present in the low viscosity adhesive composition, the high viscosity adhesive composition, or a combination thereof. In some embodiments, the initiator system may include one or more photoinitiators. The photoinitiator initiates the polymerization (curing) of the adhesive composition. Examples of photoinitiators are described in U.S. Pat. Nos. 5,545,676 and 7,674,850, and 7,816,423, such as diaryliodonium salts, metal complex salts, and the like. Other examples of polymerization initiators include ketones, such as benzil, benzoin, acyloin, acyloin ethers, and the like. Specific examples of polymerization initiators include 2,2-dimethoxy-2-phenylacetophenone (i.e., IRGACURE 651) and 2-methoxy-2-phenylacetophenone (Ciba Specialty Chemicals Corp., Tarrytown, NY). In some embodiments, the photoinitiator may be present in the curable adhesive layer in an amount of about 0.01% to about 10% by weight, based on the weight of the curable adhesive layer. For example, the photoinitiator may be present in an amount of about 0.01, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, or 10.0% by weight, or a range of values ​​between any of the foregoing values, such as about 5.0% to about 8.0% by weight, about 0.1% to about 3.5% by weight, etc.

[0065] In other embodiments, the initiator system may include a redox initiator. The redox initiator may include one or more redox agents, i.e., a reducing agent and an oxidizing agent. The reducing agent and the oxidizing agent may react to generate a free radical species that can initiate polymerization. Suitable redox agents can be found, for example, in U.S. Pat. No. 7,173,074 and U.S. Pat. No. 6,982,288. For example, ascorbic acid and its salts, derivatives or metal complexes are suitable reducing agents, as well as amines (e.g., 4-tert-butyldimethylaniline; p-toluenesulfinate and benzenesulfinate), thioureas (e.g., 1-ethyl-2-thiourea, tetraethylthiourea, tetramethylthiourea, 1,1-dibutylthiourea and 1,3-dibutylthiourea), cobalt(II) chloride, ferrous chloride, ferrous sulfate, hydrazine, hydroxylamine, sulfites and dithionites. Preferred oxidizing agents include, for example, persulfuric acid and its salts, alkylammonium salts, peroxides (e.g., benzoyl peroxide; hydroperoxides such as cumyl hydroperoxide, t-butyl hydroperoxide, amyl hydroperoxide), salts of transition metals such as cobalt(III) chloride, ferric chloride, cerium(IV) sulfate, perboric acid and its salts, permanganic acid and its salts, perphosphoric acid and its salts, etc. Enzymes, such as those disclosed in U.S. Patent Application Publication No. 2004 / 0122126, can also function as redox initiators.

[0066] In some embodiments, the initiator system may further include one or more sensitizers (e.g., ketones, coumarin dyes, xanthene dyes, acridine dyes, thiazole dyes, thiazine dyes, oxazine dyes, azine dyes, aminoketone dyes, porphyrins, aromatic polycyclic hydrocarbons, p-substituted aminostyryl ketone compounds, aminotriarylmethanes, merocyanines, squarylium dyes, and pyridinium dyes, etc.). Specific examples of sensitizers include camphorquinone, glyoxal, biacetyl, 3,3,6,6-tetramethylcyclohexanedione, 3,3,7,7-tetramethyl-1,2-cycloheptanedione, 3,3,8,8-tetramethyl-1,2-cyclooctanedione, 3,3,18,18-tetramethyl-1,2-cyclooctadecanedione, dipivaloyl, benzyl, furyl, hydroxybenzyl, 2,3-butanedione, 2,3-pentanedione, 2,3-hexanedione, 3,4-hexanedione, 2,3-heptanedione, 3,4-heptanedione, 2,3-octanedione, 4,5-octanedione, and 1,2-cyclohexanedione. In some embodiments, the initiator system may further include one or more electron donors, such as amines, amides, ethers, thioethers, urea, thiourea, ferrocene, sulfonic acids or their salts, ferrocyanide salts, ascorbic acid or its salts, dithiocarbamic acid or its salts, xanthates, ethylenediaminetetraacetates, tetraphenylboronic acid salts, etc. In some embodiments, the initiator system may further include one or more hydrogen donors, such as amines.

[0067] In some embodiments, the curable adhesive layer may further comprise a glass ionomer cement, a resin modified glass ionomer cement, or a combination thereof.

[0068] In some embodiments, at least one of the high viscosity adhesive and the low viscosity adhesive in the curable adhesive layer may further comprise one or more fluoride-releasing agents. Incorporating one or more fluoride-releasing agents into the high viscosity adhesive composition and / or the low viscosity adhesive composition may enable delivery of fluoride to the tooth surface under and immediately surrounding the orthodontic appliance, thereby protecting the tooth surface from corrosion. Examples of fluoride-releasing agents include fluoroaluminosilicate glasses, inorganic fluoride salts, organic fluoride salts, fluoride-containing complexes, and the like. Specific fluoride-releasing agents may be found, for example, in the following disclosures: U.S. Pat. No. 3,814,717, U.S. Pat. No. 5,332,429, U.S. Pat. No. 6,126,922, and International Patent Publication No. WO 2000 / 69393. In some embodiments, the curable adhesive layer may comprise a fluoride-releasing agent present in an amount of about 0.1% to about 85% by weight based on the weight of the curable adhesive layer. For example, the fluoride releasing agent may be present in an amount of about 0.1, 0.5, 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, or 85% by weight, based on the weight of the curable adhesive layer, or a range of values ​​between any of the foregoing values, such as about 20% to about 30% by weight, about 45% to about 60% by weight, etc.

[0069] Adhesive Composition In many embodiments, the high viscosity adhesive composition comprises a resin and a filler as described herein. In many embodiments, the low viscosity adhesive composition comprises a resin and optionally a filler as described herein. The high viscosity adhesive resin and the low viscosity adhesive resin may comprise the same or different polymerizable components, and compositions having the same resin may differ based on the type and / or amount of filler.

[0070] In some embodiments, the high viscosity adhesive resin and the low viscosity adhesive resin may independently comprise one or more polymerizable components with or without acid functionality, or a combination thereof.

[0071] Polymerizable components without acid functionality include, for example, PEGDMA (polyethylene glycol dimethacrylate with a molecular weight of about 400), bisGMA, UDMA (urethane dimethacrylate), GDMA (glycerol dimethacrylate), TEGDMA (triethylene glycol dimethacrylate), bisEMA6 as described in US Patent 6,030,606 (Holmes), and NPGDMA (neopentyl glycol dimethacrylate).Other examples include those described in US Patent 6,187,836 (Oxman et al.) and US Patent 6,084,004 (Weinmann et al.), US Patent 6,245,828 (Weinmann et al.), US Patent 5,037,861 (Crivello et al.), and US Patent 6,779,656 (Klettke et al.), US Patent 3,018,262 (Schroeder), and WO 01 / 51540 (Klettke et al.). No. 7,262,228 (Oxman et al.), and epoxy resins such as those listed in "Handbook of Epoxy Resins" by Lee and Neville, McGraw-Hill Book Co., New York (1967), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-2-methylcyclohexylmethyl-3,4-epoxy-2-methylcyclohexanecarboxylate, and bis(3,4-epoxy-6-methylcyclohexyl-methyl)adipate, octadecylene oxide, epichlorohydrin, styrene oxide, vinylcyclohexene oxide, glycidol, glycidyl methacrylate, diglycidyl ethers of bisphenol A. These references are incorporated herein in their entireties.

[0072] Examples of polymerizable components having an acid functional group include α,β-unsaturated acidic compounds, such as glycerol phosphate mono(meth)acrylate, glycerol phosphate di(meth)acrylate, hydroxyethyl(meth)acrylate (e.g., HEMA) phosphate, bis((meth)acryloxyethyl)phosphate, ((meth)acryloxypropyl)phosphate, bis((meth)acryloxypropyl)phosphate, bis((meth)acryloxy)propyloxyphosphate, (meth)acryloxyhexyl phosphate, bis((meth)acryloxyhexyl)phosphate, (meth)acryloxyoctyl phosphate, bis((meth)acryloxyethyl)phosphate, ( ... )acryloyloxyoctyl)phosphate, (meth)acryloyloxydecyl phosphate, bis((meth)acryloyloxydecyl)phosphate, caprolactone methacrylate phosphate, citric acid di- or tri-methacrylate, poly(meth)acrylated oligomaleic acid, poly(meth)acrylated polymaleic acid, poly(meth)acrylated poly(meth)acrylic acid, poly(meth)acrylated polycarboxyl-polyphosphonic acid, poly(meth)acrylated polychlorophosphoric acid, poly(meth)acrylated polysulfonate, poly(meth)acrylated polyboric acid, etc., may be used as a component of the solidifying component system. Also, unsaturated carbonic acid, such as (meth)acrylic acid, aromatic (meth)acrylated acid (e.g., methacrylated trimellitic acid), and their anhydrides, etc., may be used as a component of the solidifying component system. Some of these compounds can be obtained, for example, as the reaction product between an isocyanatoalkyl (meth)acrylate and a carboxylic acid. Additional compounds of this type having both acid-functional and ethylenically unsaturated components are described in U.S. Patent No. 4,872,936 (Engelbrecht) and U.S. Patent No. 5,130,347 (Mitra).For example, polymerizable bisphosphonic acids, such as those disclosed in U.S. Patent Publication No. 2004 / 0206932 (Abuelyaman et al.); AA:ITA:IEM (copolymers of acrylic acid:itaconic acid having pendant methacrylates prepared, for example, by reacting an AA:ITA copolymer, such as that described in Example 11 of U.S. Patent No. 5,130,347 (Mita), with sufficient 2-isocyanatoethyl methacrylate to convert a portion of the acid groups of the copolymer to pendant methacrylate groups); and polymerizable bisphosphonic acids, such as those disclosed in U.S. Patent Publication No. 4,259,075 (Yamauchi et al.), U.S. Patent No. 4,499,251 (Omura et al.), U.S. Patent No. 4,537,940 (Omura et al.), U.S. Patent No. 4,539,382 (Omura et al.), U.S. Patent No. 5,530,038 (Yamamoto et al.), U.S. Patent No. 6,458,868 (Okada et al.), and European Patent Publication No. 712,622 (Tokuyama et al.) Corp. and No. 1,051,961 (Kuraray Co., Ltd.). Further examples of polymerizable components having acid functionality include (meth)acryloxy groups and at least one -OP(O)(OH). x A group (wherein x=1 or 2 and at least one -OP(O)(OH) x group and at least one (meth)acryloxy group are linked together by a C1-C4 hydrocarbon group; at least one (meth)acryloxy group and at least one -OP(O)(OH) x A second compound comprising a group, where x=1 or 2 and at least one -OP(O)(OH) xThe (meth)acryloxy group and at least one (meth)acryloxy group are linked together by a C5-C12 hydrocarbon group; an ethylenically unsaturated compound without acid functionality; an initiator system; and a filler. Such compositions are described, for example, in U.S. Patent Application Publication No. 2007 / 0248927 (Luchterhandt et al.). See also U.S. Patent No. 7,449,499 (Bradley et al.) and U.S. Patent No. 7,452,924 (Aasen et al.); and U.S. Patent Application Publication Nos. 2005 / 0175966 (Falsafi et al.), 2009 / 0011388 (Bradley et al.), and 2009 / 0035728 (Aasen et al.). These references are incorporated herein in their entirety.

[0073] In some embodiments, the high viscosity adhesive resin and the low viscosity adhesive resin may independently comprise a polymerizable component selected from unsaturated monomers (e.g., (meth)acrylates, epoxy (meth)acrylates, hydroxy-substituted (meth)acrylates, (meth)acrylic acids, hydroxy-substituted (meth)acrylic acids, vinyl ethers), epoxy resins, and the like. For example, the one or more unsaturated monomers may be selected from methyl (meth)acrylate, ethyl acrylate, isopropyl methacrylate, n-hexyl acrylate, stearyl acrylate, allyl acrylate, glycerol triacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, 1,3-propanediol di(meth)acrylate, trimethylolpropane triacrylate, 1,2,4-butanetriol trimethacrylate, 1,4-cyclohexanediol diacrylate, pentaerythritol tetra(meth)acrylate, sorb ... tallhexaacrylate, tetrahydrofurfuryl(meth)acrylate, bis[1-(2-acryloxy)]-p-ethoxyphenyldimethylmethane, bis[1-(3-acryloxy-2-hydroxy)]-p-propoxyphenyldimethylmethane, ethoxylated bisphenol A di(meth)acrylate, and trishydroxyethyl-isocyanurate trimethacrylate; (meth)acrylamides (i.e., acrylamide and methacrylamide), such as (meth)acrylamide, methylene bis-(meth)acrylamide, and diacetone (meth)acrylamide; urethane (meth)acrylates;Bis-(meth)acrylate of polyethylene glycol (preferably, molecular weight 200-500), bisphenol A bis(2-hydroxyethyl ether) dimethacrylate, 2-hydroxy-1,2,3-propane tricarboxylic acid, CDMA (reaction product of 2-hydroxy-1,2,3-propane tricarboxylic acid and 2-isocyanatoethyl methacrylate), decamethylene dimethacrylate, methacryloxydecyl phosphate (MDP) and other acrylic phosphates, acrylic acid and other acrylic acids, acrylic acid and itacon. The copolymers may be selected from copolymers of acids, copolymerizable mixtures of acrylated monomers such as those described in U.S. Pat. No. 4,652,274 (Boettcher et al.), acrylated oligomers such as those described in U.S. Pat. No. 4,642,126 (Zador et al.), and polyunsaturated carbamoyl isocyanurates such as those described in U.S. Pat. No. 4,648,843 (Mitra); and vinyl compounds such as styrene, diallyl phthalate, divinyl succinate, divinyl adipate, and divinyl phthalate. Other suitable free radically polymerizable compounds include siloxane-functional (meth)acrylates, such as those disclosed in, for example, WO 00 / 38619 (Guggenberger et al.), WO 01 / 92271 (Weinmann et al.), WO 01 / 07444 (Guggenberger et al.), and WO 00 / 42092 (Guggenberger et al.), as well as those disclosed in, for example, U.S. Pat. No. 5,076,844 (Fock et al.), U.S. Pat. No. 4,356,296 (Griffith et al.), European Patent No. 0373384 (Wack et al.), and the like. fluoropolymer-functional (meth)acrylates such as those disclosed in EP 0201031 (Reiners et al.), EP 0201778 (Reiners et al.), hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; glycerol mono- or di-(meth)acrylate; trimethylolpropane mono- or di-(meth)acrylate; pentaerythritol mono-, di-, and tri-(meth)acrylate;Sorbitol mono-, di-, tri-, tetra-, or penta-(meth)acrylates; and 2,2-bis[4-(2-hydroxy-3-ethacryloxypropoxyphenyl]propane (bisGMA), PEGDMA (polyethylene glycol dimethacrylate having a molecular weight of about 400), UDMA (urethane dimethacrylate), GDMA (glycerol dimethacrylate), TEGDMA (triethylene glycol dimethacrylate), bisEMA6 as described in U.S. Pat. No. 6,030,606 (Holmes), and NPGDMA (neopentyl glycol dimethacrylate). These references are incorporated herein in their entireties;

[0074] In some embodiments, the high viscosity adhesive resin and the low viscosity adhesive resin may independently comprise one or more polymerizable components independently selected from bisphenol A bis(2-hydroxyethyl ether) dimethacrylate, bisphenol A diglycidyl ether dimethacrylate, CDMA (citric acid dimethacrylate, a reaction product of 2-hydroxy-1,2,3-propane tricarboxylic acid and 2-isocyanatoethyl methacrylate), polyethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 2-hydroxylethyl methacrylate, decamethylene dimethacrylate, methacryloxydecyl phosphate, dimethylaminoethyl methacrylate, and copolymers of acrylic acid and itaconic acid.

[0075] In some embodiments, the high viscosity adhesive resin may include one or more polymerizable components selected from bisphenol A bis(2-hydroxyethyl ether) dimethacrylate, bisphenol A diglycidyl ether dimethacrylate, CDMA (citric acid dimethacrylate, a reaction product of 2-hydroxy-1,2,3-propanetricarboxylic acid and 2-isocyanatoethyl methacrylate), and polyethylene glycol dimethacrylate.

[0076] In some embodiments, the high viscosity adhesive resin may include one or more polymerizable components selected from bisphenol A bis(2-hydroxyethyl ether) dimethacrylate and bisphenol A diglycidyl ether dimethacrylate. In some embodiments, the low viscosity adhesive resin may include one or more polymerizable components selected from bisphenol A bis(2-hydroxyethyl ether) dimethacrylate, bisphenol A diglycidyl ether dimethacrylate, triethylene glycol dimethacrylate, 2-hydroxyethyl methacrylate, decamethylene dimethacrylate, methacryloxydecyl phosphate, dimethylaminoethyl methacrylate, and copolymers of acrylic acid and itaconic acid.

[0077] In some embodiments, the low viscosity adhesive resin may include one or more polymerizable components selected from bisphenol A bis(2-hydroxyethyl ether) dimethacrylate and bisphenol A diglycidyl ether dimethacrylate.

[0078] In some embodiments, the low viscosity adhesive resin may include one or more polymerizable components selected from triethylene glycol dimethacrylate and bisphenol A diglycidyl ether dimethacrylate.

[0079] In some embodiments, the low viscosity adhesive resin may include one or more polymerizable components selected from 2-hydroxyethyl methacrylate, bisphenol A diglycidyl ether dimethacrylate, decamethylene dimethacrylate, methacryloxydecyl phosphate, dimethylaminoethyl methacrylate, and copolymers of acrylic acid and itaconic acid.

[0080] In some embodiments, the low viscosity adhesive resin may include water, an alcohol solvent, such as ethanol, or a combination thereof.

[0081] In some embodiments, the high viscosity adhesive composition may include one or more adhesive compositions sold under the names Transbond XT Adhesive (3M Unitek, Monrovia, CA), Transbond PLUS Color Change Adhesive (3M Unitek, Monrovia, CA), and Transbond Supreme LV Adhesive (3M Unitek, Monrovia, CA), including the adhesives in those devices. In some embodiments, the low viscosity adhesive composition may include one or more adhesive compositions sold under the names Transbond XT Primer (3M Unitek, Monrovia CA), Clinpro Sealant (3M ESPE, St. Paul, MN), and Scotchbond Universal Adhesive (3M ESPE, St. Paul, MN), including the adhesives in those devices. Alternatively, the high viscosity adhesive composition and the low viscosity adhesive composition may independently include one or more resins in the aforementioned adhesive compositions, although they differ in the type and / or amount of filler.

[0082] In some embodiments, the high viscosity adhesive composition may include one or more fillers described herein present in an amount of about 50% to about 90% by weight based on the weight of the high viscosity adhesive composition. For example, the high viscosity adhesive composition may include a filler in an amount of about 50, 52, 54, 56, 58, 60, 62, 64, 66, 68, 70, 72, 74, 76, 78, 80, 82, 84, 86, 88, 90% by weight based on the weight of the high viscosity adhesive composition, or a range of values ​​between any of the foregoing values, such as about 50% to about 86%, about 70% to about 80%, etc.

[0083] In some embodiments, the low viscosity adhesive composition may include one or more fillers described herein present in an amount of about 0% to about 65% by weight based on the weight of the low viscosity adhesive composition. For example, the low viscosity adhesive composition may include a filler in an amount of about 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, or 65% by weight based on the weight of the low viscosity adhesive composition, or a range of values ​​between any of the foregoing values, such as about 25% to about 35% by weight, about 10% to about 20% by weight, etc.

[0084] In some embodiments, the high viscosity adhesive composition is -1 For example, a high viscosity adhesive composition may be characterized by a viscosity of about 10 Pa·s to about 1,500,000 Pa·s at a shear rate of 1 s. -1 At shear rates of about 10, 50, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1500, 2000, 2500, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10000, 12000, 13000, 14000, 15000, 20000, 40000, 60000, 800 In some embodiments, the high viscosity adhesive composition may be characterized by a viscosity of 1 s, 100,000, 200,000, 300,000, 400,000, 500,000, 600,000, 700,000, 800,000, 900,000, 1,000,000, 1,500,000 Pa·s, or a value within a range between any of the aforementioned values, such as from about 500 to about 1,000, from about 10,000 to about 100,000 Pa·s, etc. -1 For example, a high viscosity adhesive composition may be characterized by a viscosity of about 1500 Pa·s to about 5000 Pa·s at a shear rate of 1 s. -1The composition may be characterized by a viscosity of about 1500, 1600, 1700, 1800, 1900, 2000, 2100, 2200, 2300, 2400, 2500, 2600, 2700, 2800, 2900, 3000, 3100, 3200, 3300, 3400, 3500, 3600, 3700, 3800, 3900, 4000, 4100, 4200, 4300, 4400, 4500, 4600, 4700, 4800, 4900, or 5000 Pa·s, or a value within a range between any of the aforesaid values, such as, for example, about 1800 to about 1900, about 4000 to about 4100 Pa·s, at a shear rate of about 1500, 1600, 1700, 1800, 1900, 2000, 2100, 2200, 2300, 2400, 2500, 2600, 2700, 2800, 2900, 3000, 3100, 3200, 3300, 3400, 3500, 3600, 3700, 3800, 3900, 4000, 4100, 4200, 4300, 4400, 4500, 4600, 4700, 4800, 4900, or 5000 Pa·s. In some embodiments, the high viscosity adhesive composition has a viscosity of 0.1 s -1 For example, a high viscosity adhesive composition may be characterized by a viscosity of about 4000 Pa·s to about 8000 Pa·s at a shear rate of 0.1 s. -1 At shear rates of about 4000, 4100, 4200, 4300, 4400, 4500, 4600, 4700, 4800, 4900, 5000, 5100, 5200, 5300, 5400, 5500, 5600, 5700, 5800, 5900, 6000, 6100, 6200, 6300, 6400, 6500, 66 In some embodiments, the high viscosity adhesive composition may be characterized by a viscosity of 10 s, 6700, 6800, 6900, 7000, 7100, 7200, 7300, 7400, 7500, 7600, 7700, 7800, 7900, or 8000 Pa·s, or a value within a range between any of the foregoing values, such as, for example, from about 5000 to about 7000 Pa·s. -1 For example, a high viscosity adhesive composition may be characterized by a shear rate of about 300 Pa·s to about 2000 Pa·s at a shear rate of 10 s. -1 The composition may be characterized by a viscosity of about 300, 400, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, or 2000 Pa·s, or a value within a range between any of the aforementioned values, e.g., about 400 to about 600, about 1500 to about 1700 Pa·s, etc., at a shear rate of about 100 to about 2000 Pa·s.

[0085] In some embodiments, the low viscosity adhesive composition is-1 For example, a low viscosity adhesive composition may be characterized by a viscosity of about 0.1 Pa·s to about 100 Pa·s at a shear rate of 1 s. -1 The low viscosity adhesive composition may be characterized by a viscosity of about 0.1, 0.5, 1.0, 5.0, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100 Pa·s, or a value within a range between any of the aforementioned values, such as about 40 to about 100, about 1 to about 5, about 0.1 to about 1 Pa·s, etc., at a shear rate of 1 s. -1 For example, a low viscosity adhesive composition may be characterized by a viscosity of about 0.5 Pa·s to about 50 Pa·s at a shear rate of 1 s. -1 The low viscosity adhesive composition may be characterized by a viscosity of about 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 68, or 50 Pa·s, or a value within a range between any of the foregoing values, such as from about 0.7 to about 1, from about 30 to about 40 Pa·s, etc., at a shear rate of 0.1 s. -1 For example, a low viscosity adhesive composition may be characterized by a viscosity of about 0.5 Pa·s to about 50 Pa·s at a shear rate of 0.1 s. -1 In some embodiments, the low viscosity adhesive composition may be characterized by a viscosity of about 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 68, or 50 Pa·s, or a value within a range between any of the foregoing values, such as from about 0.7 to about 1, from about 30 to about 40 Pa·s, etc., at a shear rate of 10 s. -1 For example, a low viscosity adhesive composition may be characterized by a viscosity of about 0.5 Pa·s to about 50 Pa·s at a shear rate of 10 s. -1The composition may be characterized by a viscosity of about 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 68, or 50 Pa s, or a value within a range between any of the aforementioned values, such as, for example, about 0.7 to about 1, about 20 to about 30 Pa s, etc., at a shear rate of about 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 68, or 50 Pa s, or a value within a range between any of the aforementioned values, such as, for example, about 0.7 to about 1, about 20 to about 30 Pa s, etc.

[0086] In some embodiments, one or more of the high viscosity adhesive composition and the low viscosity adhesive composition may further comprise a filler as described herein. Those skilled in the art will understand how to adjust the viscosity of the composition by including a viscosity adjusting filler.

[0087] In some embodiments, the high viscosity adhesive composition may be a paste. A paste is defined herein as a viscous mass of solids dispersed in a liquid that can be molded prior to curing. In some embodiments, the high viscosity adhesive composition has a viscosity of at least 1000 dynes / cm as measured by the method described in Rheology Principles, Measurements, and Applications, CIW. 2 The adhesive composition may be characterized by a yield stress of about 1000 dynes / cm. See C.W. Macosko, VCH Publishers, Inc., New York, 1994, p. 92. Measurement of the yield stress and viscosity of adhesive test samples may be performed using a suitable device such as a Rheometrics ARES controlled strain rheometer (Advanced Rheometric Expansion System, Rheometric Scientific, Inc., Piscataway, NJ). In some embodiments, the high viscosity adhesive composition has a yield stress of about 1000 dynes / cm. 2 ~ approx. 10,000 dynes / cm 2For example, the high viscosity adhesive composition may be characterized by a yield stress of about 1000, 2000, 3000, 4000, 5000, 6000, 7000, 7200, 7400, 7600, 7800, 8000, 8200, 8400, 8600, 8800, 9000, 9200, 9400, 9600, 9800, 10000 dynes / cm at 28°C. 2 or a value within a range between any of the aforementioned values, e.g., about 7500 to about 8000, about 7400 to about 9200 dynes / cm 2 The strength may be characterized by a static yield stress such as:

[0088] In some embodiments, the low-viscosity adhesive composition is a flowable solution or flowable suspension. It can flow with moderate force and cannot be molded before curing. Although the low-viscosity adhesive composition described herein is flowable, the low-viscosity adhesive does not flow significantly from a base held vertically as measured by the vertical flow test (see Example 4), and the difference in thickness of the adhesive composition at the top and bottom due to surface tension within the curable adhesive layer configuration in contact with the base after the base is held vertically at room temperature (23°C) for 6 hours and at 40°C for 5 minutes is less than about 15%.

[0089] First Area In many embodiments, the first region may comprise any of the high viscosity adhesive compositions described herein.

[0090] In some embodiments, the first region may include a high viscosity adhesive composition having a maximum thickness of about 0.3 mm to about 1.5 mm. For example, the high viscosity adhesive composition may have a maximum thickness of about 0.3, 0.32, 0.34, 0.36, 0.38, 0.40, 0.42, 0.44, 0.46, 0.48, 0.50, 0.55, 0.60, 0.65, 0.70, 0.75, 0.80, 0.85, 0.90, 0.95, 1.00, 1.05, 1.10, 1.15, 1.20, 1.25, 1.30, 1.35, 1.40, 1.45, 1.50 mm, or a value within a range between any of the aforementioned values, such as about 0.38 to about 1.2 mm, about 0.60 to about 0.90 mm, etc.

[0091] In some embodiments, the first region may include a high viscosity adhesive composition having a volume that is about 40 percent to about 85 percent of the total volume of the curable adhesive layer. For example, the volume of the high viscosity adhesive composition may be about 40, 45, 50, 55, 60, 65, 70, 75, 80, 85 percent of the total volume of the curable adhesive layer, or a value within a range between any of the foregoing values, such as about 45 to about 55, about 60 to about 75 percent, etc.

[0092] In some embodiments, the first region may extend over about 20 percent to about 50 percent of the total area of ​​the base. For example, the first region comprising the high viscosity adhesive composition may extend over a percentage of the total area of ​​the base of about 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50 percent, or any value between any of the foregoing values, such as about 30 to about 40, about 26 to about 48 percent, etc.

[0093] In some embodiments, the first region may comprise a high viscosity adhesive composition that has a shape that represents a Gaussian curve, a triangle, or a trapezoid when viewed from a cross-sectional side view of the base.

[0094] In some embodiments, the first region may comprise a high viscosity adhesive composition in a shape that represents a circle, a polygon, or a square when viewed perpendicular to the base.

[0095] Second Area In many embodiments, the second region may comprise any of the low viscosity adhesive compositions described herein.

[0096] In some embodiments, the second region may include a low-viscosity adhesive composition having an average thickness of about 0.05 mm to about 0.20 mm. For example, the low-viscosity adhesive composition may have an average thickness of about 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.12, 0.14, 0.16, 0.18, 0.20 mm, or a value within a range between any of the foregoing values, such as about 0.06 to about 0.16 mm, about 0.10 to about 0.14 mm, etc.

[0097] In some embodiments, the second region may include the low viscosity adhesive composition that extends over about 50 percent to about 80 percent of the total area of ​​the base. For example, the second region including the low viscosity adhesive composition may extend over a percentage of the total area of ​​the base of about 50, 55, 60, 65, 70, 75, 80 percent, or a value within a range between any of the foregoing values, such as about 60 to about 70, about 55 to about 75 percent, etc.

[0098] In some embodiments, the second region may comprise a low viscosity adhesive composition in a shape that represents a circular or rectangular ring when viewed perpendicular to the plane defined by the base.

[0099] Filler In some embodiments, the filler may be an inorganic material selected from non-acid-reactive (e.g., quartz, submicron silica, zirconia, submicron zirconia, non-vitreous microparticles), acid-reactive (e.g., metal oxides (e.g., barium oxide, calcium oxide, magnesium oxide, zinc oxide), glasses (e.g., borate glasses, phosphate glasses, fluoroaluminosilicate glasses), metal salts), and combinations thereof.

[0100] In some embodiments, the filler may be silanized glass, silanized quartz, silanized fumed silica, silanized silica, silanized zirconia, silanized ceramic, or combinations thereof.

[0101] In some embodiments, the surface of the filler can be treated with a coupling agent to enhance adhesion between the filler and the adhesive polymer (resin). Suitable coupling agents include, for example, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, or the like.

[0102] In some embodiments, the filler has a unimodal or multimodal particle size distribution. The maximum particle size may be less than 30 μm. For example, the maximum particle size may be less than 30, less than 25, less than 20, less than 15, less than 10, less than 5, less than 1, less than 0.5, less than 0.1, less than 0.075, less than 0.05, less than 0.025 μm, or a value within a range between any of the aforementioned values, such as about 0.025 to about 0.5, about 5 to about 1, about 30 to about 10 μm, etc.

[0103] In some embodiments, the filler is selected from the group consisting of quartz, silica, silica nitride, feldspar, borosilicate glass, kaolin, talc, zirconia, titania, glasses derived from Zr, Sr, Ce, Sb, Sn, Ba, Zn, Al, feldspar, submicron silica particles, such as those available under the trade name AEROSIL (e.g., OX50), silica from Degussa Corp (Akron, OH), silica from Cabot Corp (Tuscola, IL), ground polycarbonate, methacrylates of polycaprolactone, polyepoxides, metal oxides (e.g., barium oxide, calcium oxide, magnesium oxide, zinc oxide), glasses (borate glasses, phosphate glasses, fluoroaluminosilicate glasses, metal salts, non-vitreous microparticles such as those described in U.S. Pat. No. 4,503,169 (incorporated herein by reference in its entirety), Iow glass particles such as those described in U.S. Pat. No. 5,695,251 (incorporated herein by reference in its entirety), and the like. The fillers may be selected from the group consisting of cellulose, cellulose acetate, cellulose esters ...

[0104] In some embodiments, the high viscosity adhesive composition may include one or more fillers present in a total amount of about 1% to about 85% by weight based on the weight of the high viscosity adhesive composition. For example, the high viscosity adhesive composition may include one or more fillers present in a total amount of about 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, or 85% by weight, or a value within a range between any of the foregoing values, such as about 50 to about 75% by weight, about 25 to about 60% by weight, etc. In some embodiments, the high viscosity adhesive composition may include silanized glass, silanized quartz, silanized silica, or a combination thereof.

[0105] In some embodiments, the low-viscosity adhesive composition may include one or more fillers present in a total amount of about 0% to about 50% by weight. For example, the low-viscosity adhesive composition may include one or more fillers present in a total amount of about 0, 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 25, 30, 40, 50% by weight, or a value within a range between any of the aforementioned values, such as about 1 to about 5% by weight, about 2 to about 3% by weight, etc. In some embodiments, the low-viscosity adhesive composition may include a silane-treated ceramic, a silane-treated silica, titanium dioxide, or a combination thereof.

[0106] Method for fastening orthodontic appliances - Patents.com In various embodiments, a method for securing an orthodontic appliance to a tooth surface is described. The method may include providing an orthodontic appliance as described herein, contacting the orthodontic appliance to the tooth surface, applying pressure to the orthodontic appliance such that the hardenable adhesive layer is compressed against the tooth surface, and hardening the hardenable adhesive layer to form a hardened adhesive.

[0107] In some embodiments, the method may further include applying one or more orthodontic appliances to a prefabricated tray prior to contacting the orthodontic appliances to the tooth surfaces. The prefabricated tray may be a custom replica of the subject's teeth and may assist in accurate placement of the orthodontic appliances on the subject's teeth. This technique is commonly referred to as indirect bonding.

[0108] In some embodiments, the low viscosity adhesive composition can spread beyond the base perimeter upon application of pressure to the orthodontic appliance, forming a concave meniscus relative to the point defined by the appliance-tooth interface. In some embodiments, the method may further include removing the low viscosity adhesive composition that has spread beyond the base perimeter from the tooth surface. Removal of the low viscosity adhesive composition may include brushing, wiping, picking, scraping, rinsing, or a combination thereof. In some embodiments, minimal burrs need not be removed.

[0109] In many embodiments, the high viscosity adhesive composition can at least partially fill the gap between the base and the tooth surface upon application of pressure to the orthodontic appliance. In some embodiments, the high viscosity adhesive composition can cover from about 50 percent to about 100 percent of the total area of ​​the base upon application of pressure to the orthodontic appliance. For example, the high viscosity adhesive composition can cover a percentage of the total area of ​​the base of about 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100 percent, or a value within a range between any of the aforementioned values, such as about 75 to about 95, about 80 to about 90 percent, etc. The contour of a tooth surface (e.g., molar, canine, bicuspid, etc.) may not match the contour of the base surface. The high viscosity adhesive composition can function to at least partially fill any gap between the tooth surface and the base surface depending on the area of ​​the base that is covered upon application of pressure to the tooth surface. The base coverage can be varied according to the selection of the thickness and volume of the high viscosity adhesive composition used.

[0110] In many embodiments, the high viscosity adhesive composition will not spread more than 0.2 mm beyond the perimeter of the base upon application of pressure to the orthodontic appliance and upon curing of the curable adhesive layer. The high viscosity adhesive composition may spread beyond the perimeter of the base by less than 0.2 mm, less than 0.18, less than 0.16, less than 0.14, less than 0.12, less than 0.10, less than 0.08, less than 0.06, less than 0.04, less than 0.02, 0 mm, or a value within a range between any of the foregoing values, such as from about 0 to about 0.10 mm, from about 0.04 to about 0.14 mm, etc.

[0111] In some embodiments, curing may provide an adhesive strength of at least 5.0 MPa as measured by the Adhesive Strength Test described herein. In some embodiments, curing may provide an adhesive strength of at least 5.0, at least 6.0, at least 7.0, at least 8.0, at least 9.0, at least 10.0, at least 11.0, at least 12.0, at least 13.0, at least 14.0, at least 15.0, at least 16.0, at least 17.0, at least 18.0, at least 19.0, at least 20.0, at least 21 MPa, or a value within a range between any of the foregoing values, such as, for example, about 8.0 to about 15.0 MPa, about 10.0 to about 20.0 MPa, etc.

[0112] In some embodiments, the method may further comprise pretreating the tooth surface with a fluoride composition, described below, prior to contacting the orthodontic appliance with the tooth surface.

[0113] Fluoride Pretreatment In some embodiments, the fluoride composition may include: 1) a fluoride-releasing composition effective to release fluoride to a tooth surface, a crosslinked polyacid polymer, a polyvalent cation salt, a pharma- ceutically acceptable buffer, and water; 2) a curable resin composition comprising a silver-fluoride composition comprising a source of silver cations, a source of fluoride anions, a source of iodide or thiocyanate anions, and water, and at least one (meth)acrylate monomer; or 3) a fluoride composition comprising a zinc carboxylate, an amine-containing ligand, a fluoride anion source effective to provide fluoride in an amount of at least 4% by weight based on the weight of the fluoride composition, and water, wherein the fluoride composition has a pH of at least 8, and wherein the fluoride composition is a homogeneous solution at a temperature of about 20° C. to 25° C.

[0114] In some embodiments, the method may further comprise pretreating the dental surface with a fluoride composition as described in 1) above. Further details regarding fluoride compositions and methods for pretreating dental surfaces can be found in WO 2019 / 048962, which is incorporated herein by reference in its entirety.

[0115] In some embodiments, the method may further comprise pretreating the dental surface with a fluoride composition as described in 2) above. Further details regarding fluoride compositions and methods for pretreating dental surfaces can be found in U.S. Provisional Patent Applications Nos. 62 / 956,008 and 62 / 968115, each of which is incorporated herein by reference in its entirety.

[0116] In some embodiments, the method may further comprise pretreating the dental surface with a fluoride composition as described above in 3). Further details regarding fluoride compositions and methods for pretreating dental surfaces can be found in U.S. Provisional Patent Application No. 62 / 955,975, the contents of which are incorporated by reference in their entirety.

[0117] Method for manufacturing an orthodontic appliance In various embodiments, methods are described for manufacturing the orthodontic appliances described herein that can include providing a base and forming a hardenable adhesive layer by applying a high viscosity adhesive composition to the base in a first region and applying a low viscosity adhesive composition to the base in a second region, the second region at least partially surrounding the first region.

[0118] In some embodiments, forming the curable adhesive layer may include first applying a high viscosity adhesive composition to a base in a first region, followed by applying a low viscosity adhesive composition to the base in a second region.

[0119] In some embodiments, applying one or more of the high viscosity adhesive composition and the low viscosity adhesive composition may include extruding.

[0120] In some embodiments, applying one or more of the high viscosity adhesive composition and the low viscosity adhesive composition may include additive manufacturing practices.

[0121] In some embodiments, applying one or more of the high viscosity adhesive composition and the low viscosity adhesive composition may include manual application in a dental office.

[0122] In some embodiments, the method may further include partially curing one or more of the high viscosity adhesive composition and the low viscosity adhesive composition.

[0123] In some embodiments, the method may further include molding one or more of the high viscosity adhesive composition and the low viscosity adhesive composition or removing excess adhesive from the base.

[0124] In some embodiments, the method may further include packaging the orthodontic appliance in a package described herein.

[0125] kit Kits for use In various embodiments, kits are described that include an orthodontic appliance as described herein and a set of instructions instructing a user to perform the method steps described herein for securing the orthodontic appliance to a tooth surface.

[0126] In some embodiments, the kit may further include a package for housing the orthodontic appliance. In some embodiments, the orthodontic appliance may be suspended within the package. The package may be in the form of a blister pack. The package may further include a mount for mounting the orthodontic appliance. The mount may secure the orthodontic appliance such that the hardenable adhesive layer is protected against deformation upon handling of the package. In some embodiments, the orthodontic appliance may be packaged within a package described in WO 2019 / 175726, the entirety of which is incorporated herein by reference.

[0127] In some embodiments, the kit may include two or more orthodontic appliances.

[0128] Manufacturing kit In one embodiment, a kit is described that includes a base, a container having therein a high viscosity adhesive composition as described herein, a container having therein a low viscosity adhesive composition as described herein, and a set of instructions instructing a user to carry out the method steps described herein to manufacture an orthodontic appliance of the present disclosure.

[0129] In some embodiments, the kit may include two or more bases.

[0130] In some embodiments, one or more of the containers may be graduated. The graduated compartments may allow the user to vary the amount of adhesive composition desired based on factors such as base size, tooth structure, etc. The graduated compartments may also allow the user to apply the adhesive composition to multiple bases from the same container.

[0131] In some embodiments, the kit may further include one or more extrusion devices, hi some embodiments, the extrusion device may be configured to mate with the adhesive composition container. EXAMPLES

[0132] The objects and advantages of the present disclosure are further illustrated by the following examples, but the particular materials and amounts thereof recited in these examples, as well as other conditions and details, should not be construed to unduly limit the disclosure. These examples are merely for illustrative purposes and are not intended to limit the scope of the appended claims.

[0133] material: HVA1 - High Viscosity Adhesive Composition #1: Contains 5-15% Bisphenol A bis(2-hydroxyethyl ether) dimethacrylate, 5-15% Bisphenol A diglycidyl ether dimethacrylate, 70-80% silane treated quartz, less than 2% silane treated silica and camphorquinone initiator system.

[0134] HVA2 - High Viscosity Adhesive Composition #2: 5-15% reaction product of 2-hydroxy-1,2,3-propanetricarboxylic acid and 2-isocyanatoethyl methacrylate, 5-15% polyethylene glycol dimethacrylate, 1-10% bisphenol A diglycidyl ether dimethacrylate, 35-45% silane treated glass, 35-45% silane treated quartz, 1-5% silane treated silica and camphorquinone initiator system.

[0135] LVA1 - Low Viscosity Adhesive Composition #1: Contains 44% Bisphenol A bis(2-hydroxyethyl ether) dimethacrylate, 44% Bisphenol A diglycidyl ether dimethacrylate, 11% silane treated ceramic, 0.25% camphorquinone, 1% ethyl 4-dimethylaminobenzoate, 0.15% diphenyliodonium hexafluorophosphate and 0.1% butylated hydroxytoluene (viscosity of about 20-100 Pa-s).

[0136] LVA2 - Low Viscosity Adhesive Composition #2: 40-50% triethylene glycol dimethacrylate, 40-50% bisphenol A diglycidyl ether dimethacrylate, 6% silane treated fumed silica, less than 5% tetrabutylammonium tetrafluoroborate, less than 0.5% titanium dioxide, less than 0.05% Rose Bengal dye, and an initiator system based on camphorquinone, a tertiary amine, and an iodonium salt (viscosity of about 0.5-5 Pa-s).

[0137] LVA3 - Low Viscosity Adhesive Composition #3: 15-25% 2-hydroxyethyl ether methacrylate, 15-25% bisphenol A diglycidyl ether dimethacrylate, 5-15% decamethylene dimethacrylate, 1-10% methacryloxydecyl phosphate, less than 2% dimethylaminoethyl methacrylate, 1-5% copolymer of acrylic acid and itaconic acid, 5-15% silane treated silica, 10-15% ethanol, 10-15% water, and camphorquinone initiator system (viscosity of about 0.1-1 Pa-s).

[0138] The nonwoven mat used in the comparative examples was a compressible material composed of polypropylene with individual fibers approximately 6 microns in diameter.

[0139] Viscosity measurement The viscosity of the high viscosity adhesives was tested using a controlled strain rheometer (Model ARG2, TA Instruments, Eden Prairie, MN). The adhesive samples were placed between two parallel plates (diameter 8 mm) with a gap of 0.15 mm. Viscosity measurements were taken at 25°C for 0.01 s-1 at shear rate steps spaced at 23 logarithmic intervals. -1 Starting from 10s -1 Before the measurement, the sample was shaken for 10 s. -1 The mixture was presheared at 40° C. for 3 minutes and equilibrated at 25° C. for 5 minutes. [Table 1]

[0140] The viscosity of the low viscosity adhesives was tested using a controlled strain rheometer (Model ARG2, TA Instruments, Eden Prairie, MN). The adhesive samples were placed between two parallel plates (diameter 40 mm) with a gap of 0.50 mm. Viscosity measurements were taken at 25°C for 0.01 s-1 at shear rate steps spaced at 23 logarithmic intervals. -1 Starting from 200s -1 Before the measurement, the sample was shaken for 10 s. -1 The mixture was presheared at 40° C. for 3 minutes and equilibrated at 25° C. for 5 minutes. [Table 2]

[0141] Comparative Example CE1: Bracket with High Viscosity Adhesive Composition #1 (HVA1) Comparative Example 1 was the commercial product 3M™ SmartClip™ SL3 Self-Ligating Brackets with APC™ II Adhesive precoat (catalog number 3004-301) available from 3M™ Company, St. Paul, MN, USA. The APC™ II adhesive is a high viscosity paste adhesive called HVA1.

[0142] Comparative Example CE2: Brackets with only high viscosity adhesive composition #2 (HVA2) Comparative Example 2 was the commercial product SmartClip™ SL3 with APC™ PLUS Adhesive precoat (catalog number 5004-301) available from 3M Company, St. Paul, MN, USA. The APC™ PLUS adhesive is a high viscosity paste adhesive called HVA2.

[0143] Comparative Example CE3: Bracket with only low viscosity adhesive composition (LVA1) Comparative Example 3 was prepared by coating the base of a commercially available orthodontic bracket, SmartClip™ SL3 (3M catalog number 004-301), with the low viscosity adhesive (LVA1) described in the materials section.

[0144] Example 1: Bracket with High Viscosity Adhesive Composition #1 (HVA1) Surrounded by Low Viscosity Adhesive (LVA1) Example 1 was made by modifying the commercially available 3M™ SmartClip™ SL3 Self-Ligating Brackets with APC™ II Adhesive precoat (catalog number 3004-301) of Comparative Example 1. The high viscosity paste adhesive (HVA1) around the bracket base was removed using a razor blade, leaving the inner center portion of the bracket base with the APC™ II adhesive. A low viscosity adhesive (LVA1) was then applied to the bracket base around the remaining inner portion of HVA1. The low viscosity adhesive (LVA1) used is listed in the materials section. HVA1 weighed 4.2 mg (68 wt%, 54 vol%) and LVA1 weighed 2.0 mg (32 wt%, 46 vol%).

[0145] Example 2: Brackets with High Viscosity Adhesive Composition #2 (HVA2) Surrounded by Low Viscosity Adhesive (LVA1) Example 2 was made by modifying the commercially available SmartClip™ SL3 with APC™ PLUS Adhesive precoat (catalog number 5004-301) of Comparative Example 2. The high viscosity paste adhesive (HVA2) around the bracket base was removed using a razor blade, leaving the inner central portion of the bracket base with the APC™ PLUS adhesive. A low viscosity adhesive (LVA1) was then applied to the bracket base around the remaining inner portion of HVA2. The low viscosity adhesive (LVA1) used is listed in the materials section. HVA2 weighed 4.2 mg (68 wt%, 54 vol%) and LVA1 weighed 2.0 mg (32 wt%, 46 vol%).

[0146] Adhesion Procedure Bovine teeth were cleaned and partially embedded in circular polymethylmethacrylate disks exposing the labial tooth surface. The teeth were drilled, etched, primed with TRANSBOND Plus Self Etching Primer (SEP) (available from 3M Company, catalog number 712-090) for 3-5 seconds and dried with a 3-second blast of air. The precoated brackets were bonded to the bovine teeth. For Examples 1-2 (with LVA in the outer regions) and Comparative Example 3 (with only LVA), no adhesive flash (excess) removal was required when securing the brackets to the teeth. However, for Comparative Examples 1-2, which had only HVA paste adhesive, excess adhesive flash was removed around the base of the brackets as per standard clinical bracket bonding practices. All adhesives for Examples 1-2 and Comparative Examples 1-3 were light cured using an Ortholux™ Luminous Curing Light (available from 3M Company, St. Paul, MN, USA; catalog number 704-460). The curing light was applied to the cases for 3 seconds mesial and 3 seconds distal unless otherwise noted.

[0147] Shear Peel Adhesion Strength Test Procedure Shear peel bond strength was measured either 15 minutes after bonding or 16-24 hours after bonding using the following standardized method. Each bond specimen was first mounted with the gingival tie wing facing up (unless otherwise noted) in a test fixture attached to a QTEST / 5 brand mechanical tester (MTS Systems Corporation, Eden Prairie, Minn.). A standard circular wire, 0.020 inches (0.051 centimeters) in diameter, was looped under the occlusal bond wing and attached to the crosshead of the tester. The initial crosshead position was adjusted to snug the wire, and then translated upward at 0.2 inches per minute (5 millimeters per minute) until the bracket was debonded. The maximum force was recorded and divided by the measured surface area of ​​the bracket base to obtain the bond strength measurement. Each reported bond strength value represents the average of 10 replicate measurements unless otherwise noted. [Table 3]

[0148] Examples Ex.1 and Ex.2 showed acceptable adhesive strength compared to the commercially available comparative examples CE1 and CE2. Additionally, Examples Ex.1 and Ex.2 also had the advantage that no adhesive flash removal was required since the peripheral LVA1 adhesive provided a low profile / minimal flash.

[0149] Example Ex.3: Buccal tube with high viscosity adhesive #1 (HVA1) surrounded by low viscosity adhesive (LVA1) Example 3 was made by modifying a commercially available 3M product: Victory Series™ buccal tubes with APC™ II Adhesive precoat (3M catalog number 3066-4082). The high viscosity paste adhesive (HVA1) already present on the commercially available product was partially removed in the area around the base using a razor blade, leaving the inner central portion of the base covered with HVA1 (APC™ II adhesive). A low viscosity adhesive (LVA1) was then applied to the base around the remaining inner portion of HVA1. The low viscosity adhesive (LVA1) used is listed in the materials section. HVA1 weighed 9.6 mg (82 wt%, 72 vol%) and LVA1 weighed 2.1 mg (18 wt%, 28 vol%).

[0150] Comparative Example CE4: Buccal tube with high viscosity adhesive #1 (HVA1) Comparative Example 4 was a commercially available 3M product: Victory Series™ buccal tubes with APC™ II Adhesive precoat (3M catalog number 3066-4082). The APC™ II adhesive present on this product is a high viscosity paste adhesive called HVA1.

[0151] Comparative Example CE5: Buccal tube with low viscosity adhesive (LVA1) Comparative Example 5 was prepared by coating the base of a commercially available 3M Victory Series™ buccal tube (3M catalog number 066-4082) with only the low viscosity adhesive (LVA1) described in the Materials section.

[0152] Comparative Example CE6: Buccal tube with low viscosity adhesive (LVA1) with nonwoven mat Comparative Example 6 was prepared similarly to Comparative Example CE5, except that the nonwoven mat described in the Materials section was also cut to the shape of the base and placed over the base of the buccal tube. The nonwoven mat was completely saturated with the low viscosity adhesive (LVA1) described in the Materials section. When the appliance was secured, the low viscosity adhesive (LVA1) oozed out and filled the gap between the appliance base and the tooth surface, forming a meniscus around the edge of the base, thereby eliminating the need to remove excess adhesive flash.

[0153] During the bonding procedure, removal of adhesive flash (excess) was not required for Example 3 (with LVA in the outer area), Comparative Example 5 (with only LVA) and Comparative Example 6 (LVA and nonwoven mat). However, for Comparative Example 4 with only HVA paste adhesive, excess adhesive flash was removed around the base of the buccal tube as per standard clinical bracket bonding practice. The cure times used for the buccal tube examples in Table 2 were 6 seconds mesial and 6 seconds occlusal.

[0154] In the shear-peel adhesion strength test procedure, these buccal tube examples in Table 2 were peeled with the hook facing down. [Table 4]

[0155] Example Ex.3 showed acceptable adhesive strength compared to the commercial product Comparative Example CE4. Additionally, Example Ex.3 did not require adhesive flash removal as the peripheral LVA1 adhesive provided a low profile / minimal flash.

[0156] Example Ex.4: Low Profile Bracket with High Viscosity Adhesive #1 (HVA1) Surrounded by Low Viscosity Adhesive (LVA1) Example 4 was made by modifying a commercially available 3M product: Victory Series™ Low Profile bracket with APC™ II Adhesive precoat (3M catalog number 3024-890). The high viscosity paste adhesive (HVA1) already present on the commercially available product was partially removed in the area around the base using a razor blade, leaving the inner central portion of the base covered with HVA1. A low viscosity adhesive (LVA1) was then applied to the base around the remaining inner portion of HVA1. The low viscosity adhesive (LVA1) used was listed in the materials section. The weight of HVA1 was 3.5 mg (69 wt%, 55 vol%) and the weight of LVA1 was 1.6 mg (31 wt%, 45 vol%).

[0157] Vertical flow test Five copies of Example 4 were made and tested for vertical flow of the adhesive. The bracket was placed so that the base was vertical (90 degrees to the horizontal). After 6 hours at room temperature, the profile of the bracket of Example 4 was observed. No flow of the adhesive (HVA1 or LVA1) was observed, and there was no change in the thickness of the adhesive at the top of the bracket versus the bottom of the bracket. The bracket of Example 4 was then treated at 40° C. for 5 minutes (also in a vertical position). Again, no (undesirable) flow of the adhesive was observed. Furthermore, the viscosity difference between HVA1 and LVA1 was large enough that they remained separate and did not mix into one.

[0158] Comparative Example 7: Low Profile Bracket with High Viscosity Adhesive #1 (HVA1) Comparative Example 7 was a commercially available 3M product: Victory Series™ Low Profile Brackets with APC™ II Adhesive precoat (3M catalog number 3024-890). The APC™ II adhesive present on this product is a high viscosity paste adhesive called HVA1.

[0159] Comparative Example 8: Low Profile Bracket with Low Viscosity Adhesive #1 (LVA1) Comparative Example 8 was prepared by coating the base of a commercially available orthodontic bracket, Victory Series™ Low Profile (3M Catalog No. 024-890), with the low viscosity adhesive (LVA1) described in the Materials section.

[0160] During the bonding procedure, no adhesive flash (excess) removal was required for Example 4 (with LVA on the outer / second area) and Comparative Example 8 (with only LVA). However, for Comparative Example 7, which only had HVA paste adhesive, excess adhesive flash was removed around the base of the bracket as per standard clinical bracket bonding practice. During the shear-peel bond strength test procedure, this bracket type in Table 3 was peeled with the gingival tiewing facing down. [Table 5]

[0161] Example Ex.4 showed acceptable adhesive strength compared to the commercial product Comparative Example CE7. Additionally, Example Ex.4 did not require adhesive flash removal as the peripheral LVA1 adhesive provided a low profile / minimal flash.

[0162] Example Ex.5: Low Profile Bracket with High Viscosity Adhesive Composition #1 (HVA1) Surrounded by Low Viscosity Adhesive (LVA2) Example 5 was made by modifying a commercially available 3M product: Victory Series™ Low Profile bracket with APC™ II Adhesive precoat (3M catalog number 3024-875). The high viscosity paste adhesive (HVA1) already present on the commercially available product was partially removed in the area around the base using a razor blade, leaving the inner central portion of the base covered with HVA1. A low viscosity adhesive (LVA2) was then applied to the base around the remaining inner portion of HVA1. HVA1 weighed 4.0 mg (68% by weight, 55% by volume) and LVA2 weighed 1.9 mg (32% by weight, 45% by volume).

[0163] Comparative Example 9: Low Profile Bracket with High Viscosity Adhesive Composition #1 (HVA1) Comparative Example 9 was a commercially available 3M product: APC II Victory Series™ Low Profile Brackets (3M catalog number 3024-875). The APC™ II adhesive present on this product is a high viscosity paste adhesive called HVA1.

[0164] Comparative Example 10: Low Profile Bracket with Low Viscosity Adhesive Composition #2 (LVA2) Comparative Example 10 was prepared by coating the base of a commercially available orthodontic bracket, Victory Series™ Low Profile (3M catalog number 024-875 or 024-775) with 3M CLINPRO Sealant, available from 3M Company, St. Paul, Minn., USA. 3M CLINPRO Sealant is a low viscosity adhesive called LVA2.

[0165] During the bonding procedure, no adhesive flash (excess) removal was required for Example 5 (with LVA on the outer / second area) and Comparative Example 10 (with only LVA). However, for Comparative Example 9, which has only HVA paste adhesive, excess adhesive flash was removed around the base of the bracket as per standard clinical bracket bonding practices. In Table 4, the reported shear peel bond strength test values ​​represent the average of 10 replicate measurements for Comparative Example 9, or the average of 8 replicate measurements for Example 5 and Comparative Example 10. [Table 6]

[0166] Example Ex.5 showed acceptable adhesive strength compared to the commercial product Comparative Example CE9. Additionally, Example Ex.5 did not require adhesive flash removal as the peripheral LVA2 adhesive provided a low profile / minimal flash.

[0167] Example Ex.6: Low Profile Bracket with High Viscosity Adhesive Composition #1 (HVA1) Surrounded by Low Viscosity Adhesive (LVA3) Example 6 was made by modifying a commercially available 3M product: Victory Series™ Low Profile bracket with APC™ II Adhesive precoat (3M catalog number 3024-890). The high viscosity paste adhesive (HVA1) already present on the commercially available product was partially removed in the area around the base using a razor blade, leaving the inner central portion of the base covered with HVA1. A low viscosity adhesive (LVA3) was then applied to the base around the remaining inner portion of HVA1. The low viscosity adhesive (LVA3) used was a self-etching adhesive: Scotchbond Universal Adhesive (3M catalog number 41528) with a pH of 2.7. The weight of HVA1 was 3.6 mg (69 wt%, 55 vol%) and the weight of LVA3 was 1.6 mg (31 wt%, 45 vol%). After application of LVA3, the solvent was dried for 5 seconds using an air syringe. Etching and priming the teeth with TRANSBOND Plus Self Etching Primer (SEP) was omitted in the bonding procedure.

[0168] Comparative Example 11: Low Profile Bracket with High Viscosity Adhesive Composition #1 (HVA1) Comparative Example 11 was a commercially available 3M product: Victory Series™ Low Profile Brackets with APC II Adhesive precoat (3M catalog number 3024-890). The APC™ II adhesive present on this product is a high viscosity paste adhesive called HVA1.

[0169] In the bonding procedure, no adhesive flash (excess) removal was required for Example 6 (having LVA on the outer / second area). However, for Comparative Example 11, which had only HVA paste adhesive, the excess adhesive flash around the base of the bracket was removed as per standard clinical bracket bonding practice. In the shear-peel bond strength test procedure, this type of bracket in Table 5 (same as used in Table 3) was peeled with the gingival tiewing facing down. [Table 7]

[0170] Example Ex.6 demonstrated acceptable bond strength compared to the commercial product Comparative Example CE11. Example Ex.6 eliminated the need for tooth etching / priming as a result of the acidic functionality of the low viscosity adhesive LVA3. Additionally, Example Ex.6 did not require adhesive flash removal as the peripheral low viscosity adhesive LVA3 resulted in a low profile / minimal flash.

[0171] Equivalent Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments specifically described herein which equivalents are intended to be encompassed by the following claims.

Claims

**Claim 1** A dental orthodontic appliance, comprising: a base; a curable adhesive layer disposed on the base; and the curable adhesive layer includes a first region and a second region; wherein the first region comprises a high-viscosity adhesive composition characterized by having a viscosity of about 10 Pa·s to about 1,500,000 Pa·s at a shear rate of 1 s －１ ; wherein the second region comprises a low-viscosity adhesive composition characterized by having a viscosity of from about 0.1 Pa·s to about 100 Pa·s at a shear rate of 1 s －１ -1 the first region is at least partially surrounded by the second region; the first region and the second region are configured to contact the surface of a tooth; a dental orthodontic appliance, wherein the viscosity of the high-viscosity adhesive composition is higher than the viscosity of the low-viscosity adhesive composition. **Claim 2** The dental orthodontic appliance according to claim 1, wherein the high-viscosity adhesive composition includes a filler present in an amount of about 50 wt% to about 86 wt% based on the weight of the high-viscosity adhesive composition. **Claim 3** The high-viscosity adhesive composition is characterized by a static yield stress of at least 7,000 dynes / cm at 28°C ２ and The dental orthodontic appliance according to claim 1, wherein the low-viscosity adhesive composition is characterized by a flow such that, when measured by a vertical flow test, the difference in the thickness of the adhesive composition at the top and bottom is less than about 15%. The dental orthodontic appliance according to claim 1, characterized by one or more of the above. **Claim 4** The dental orthodontic appliance according to claim 1, wherein the curable adhesive layer has a shape representing a Gaussian curve, a triangle, or a trapezoid when viewed from a cross-sectional side view of the base. **Claim 5** The dental orthodontic appliance according to claim 1, wherein the high-viscosity adhesive composition has a shape representing a circle, a polygon, or a quadrilateral when viewed from a direction perpendicular to the base. **Claim 6** The dental orthodontic appliance according to claim 1, wherein the high-viscosity adhesive composition has a volume that is about 40 percent to about 85 percent of the volume of the curable adhesive layer. **Claim 7** The dental orthodontic appliance according to claim 1, wherein the high-viscosity adhesive composition extends over about 20 percent to about 50 percent of the total area of the base. **Claim 8** The dental orthodontic appliance according to claim 1, wherein the low-viscosity adhesive composition has a filler amount of about 0 to about 50 wt%. **Claim 9** The dental orthodontic appliance according to claim 1, wherein the low-viscosity adhesive composition has a shape of an annular ring or a rectangular ring when viewed from a direction perpendicular to the base. **Claim 10** The dental orthodontic appliance according to claim 1, wherein the low-viscosity adhesive composition extends over about 50 percent to about 80 percent of the total area of the base. **Claim 11** The high-viscosity adhesive composition has a viscosity of about 100 Pa·s to about 13,000 Pa·s at a shear rate of 1 s －１ and is characterized by this viscosity the low-viscosity adhesive composition is characterized by a viscosity of about 0.1 Pa·s to about 10 Pa·s at a shear rate of 1 s−1; and the high-viscosity adhesive composition and the low-viscosity adhesive composition differ in viscosity by at least 10 times. The dental orthodontic appliance according to claim 1, characterized by one or more of the following.

12. The high-viscosity adhesive composition has a maximum thickness greater than the average thickness of the low-viscosity adhesive composition, The low-viscosity adhesive composition has a thickness of about 0.06 mm to about 0.16 mm, and The high-viscosity adhesive composition has a thickness of about 0.38 mm to about 1.2 mm, The dental orthodontic appliance according to claim 1, characterized by one or more of the following.

13. The dental orthodontic appliance according to claim 1, having no compressible mat.

14. A dental orthodontic appliance according to any one of claims 1 to 13, and A set of instructions for instructing the user to fix the dental orthodontic appliance to the surface of the teeth, or A base, A container containing a high-viscosity adhesive composition therein, A container containing a low-viscosity adhesive composition therein, A kit including a set of instructions for instructing the user to prepare the dental orthodontic appliance.

15. A method of manufacturing a dental orthodontic appliance according to any one of claims 1 to 13, the method comprising: Preparing a base, and Forming a curable adhesive layer on the base, wherein the forming includes: Applying a high-viscosity adhesive composition to the base in a first region, and Applying a low-viscosity adhesive composition to the base in a second region, The method, wherein the first region is at least partially surrounded by the second region.

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