Bondable orthodontic assembly and method for bonding

Abstract

Orthodontic appliances, methods of preparing and seating the same, and kits comprising the same are described.

Description

Background Technology

[0001] Misalignment and misaligned teeth are often prevented and treated with orthodontic appliances. In many cases, the appliances are temporarily bonded to the tooth structure with adhesive. When the appliance is positioned against the tooth surface, excess adhesive, typically used to fill the gap between the base of the appliance and the tooth surface, is squeezed out beyond the periphery of the appliance base. This squeezed adhesive, referred to in the art as "burrs," is usually removed manually by the dentist before hardening; however, this procedure is time-consuming, and incomplete removal can cause structural problems. For example, accidental disturbance of the appliance during burr removal can negatively impact the reliability of the bond. Furthermore, incomplete removal of excess adhesive not only causes patient discomfort but also promotes bacterial buildup, which can eventually degrade the underlying tooth structure, leading to demineralization and discoloration.

[0002] Cinader previously developed a strategy for reducing burrs (see U.S. Patent No. 10,492,890). Cinader found that combining a compressible pad at the base of the aligner and soaking the pad with unfilled or slightly filled adhesive was effective in allowing the adhesive to seep out to fill the gap between the aligner base and the tooth surface and to form a meniscus around the edge of the aligner during placement, thereby eliminating the need for removing excess adhesive burrs.

[0003] Despite progress, we remain focused on developing correctors that offer effective adhesion, avoid removing burrs, and reduce manufacturing costs. Summary of the Invention

[0004] In one embodiment, a malocclusion correction appliance is described. The malocclusion correction 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, wherein the first region is at least partially surrounded by the second region, and the first and second regions are configured to contact a tooth surface. The first region includes features characterized in that, in 1s -1 A high-viscosity adhesive composition with a viscosity of about 10 Pa·s to about 1,500,000 Pa·s at a shear rate, and the second region comprising a feature characterized in that at 1 s -1 Low-viscosity adhesive compositions have a viscosity of about 0.1 Pa·s to about 100 Pa·s at a shear rate. High-viscosity adhesive compositions have a viscosity greater than that of low-viscosity adhesive compositions.

[0005] In one embodiment, a method for placing a malocclusion appliance onto a tooth surface is described. The method includes: providing the malocclusion appliance described herein; contacting the malocclusion appliance with a tooth surface; applying pressure to the malocclusion appliance to press a hardenable adhesive layer against the tooth surface; and hardening the hardenable adhesive layer to form a hardened adhesive.

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

[0007] In one embodiment, a kit is described. The kit includes the orthodontic appliance described herein and a set of instructions to guide the user in performing the steps described herein to place the orthodontic appliance onto the tooth surface.

[0008] In one embodiment, a kit is described. The kit includes a base, the high-viscosity adhesive composition described herein, the low-viscosity adhesive composition described herein, and a set of instructions guiding the user to perform the steps described herein to prepare the orthodontic appliance of this disclosure. Attached Figure Description

[0009] Figure 1A A side view of the orthodontic appliance of this disclosure having a hardenable adhesive layer in an uncompressed state.

[0010] Figure 1B A side view of the orthodontic appliance of this disclosure having a compressible, hardenable adhesive layer.

[0011] Figure 1C A bottom view of the orthodontic appliance of this disclosure having a hardenable adhesive layer in an uncompressed state.

[0012] Figure 1D A bottom view of the orthodontic appliance of this disclosure having a compressible, hardenable adhesive layer.

[0013] Figure 1E A top view of the orthodontic appliance of this disclosure having a hardenable adhesive layer in an uncompressed state.

[0014] Figure 1F A top view of the orthodontic appliance of this disclosure having a compressible, hardenable adhesive layer.

[0015] Figure 2A A cross-sectional side view of the orthodontic appliance of this disclosure having a hardenable adhesive layer in an uncompressed state.

[0016] Figure 2B A cross-sectional side view of the orthodontic appliance of this disclosure having a compressible, hardenable adhesive layer.

[0017] Figure 3A A cross-sectional side view of the orthodontic appliance of this disclosure having a hardenable adhesive layer in an uncompressed state.

[0018] Figure 3B A cross-sectional side view of the orthodontic appliance of this disclosure having a compressible, hardenable adhesive layer.

[0019] Figure 4A A cross-sectional side view of the orthodontic appliance of this disclosure having a hardenable adhesive layer in an uncompressed state.

[0020] Figure 4B A cross-sectional side view of the orthodontic appliance of this disclosure having a compressible, hardenable adhesive layer.

[0021] Figure 5A Side view of a comparable orthodontic appliance with a compressible pad, not disclosed herein.

[0022] Figure 5B Side view of a comparable orthodontic appliance with a compressible pad, not disclosed herein. Detailed Implementation

[0023] This invention relates to an orthodontic appliance that uses an arrangement of different adhesives to provide excellent tooth adhesion while eliminating the need for burr removal.

[0024] Using adhesives to bond orthodontic appliances to teeth is a common procedure. The adhesive is typically applied to the bonding surface of the appliance. After the appliance is fitted to the teeth, the adhesive hardens to create a strong bond. A suitable orthodontic adhesive should provide high strength to maintain a continuous and secure bond between the appliance and teeth throughout orthodontic treatment, which can last for two years or longer. However, the adhesive should not be so strong that removing the appliance at the end of treatment becomes too difficult. An ideal adhesive should also have appropriate adhesion and viscosity to prevent the appliance from shifting after it has been placed on the teeth and to facilitate handling by the orthodontist. Conventional orthodontic adhesives are polymerizable resins filled with a large amount of hard filler, such as quartz or silica filler. During the bonding procedure, excess adhesive is often applied to the bonding surface of the appliance because the adhesive needs to act as a gap filler (i.e., occupying all the space between the tooth surface and the appliance). In other words, when a mismatch exists between the tooth surface and the bonding surface of the braces, the adhesive fills the space between the braces and the teeth to maintain adhesion and prevent the formation of voids that can trap food and accumulate plaque. When the braces are fully pressed against the teeth, excess adhesive is squeezed out along the periphery of the base. This excess adhesive, called "burrs," is usually removed manually by the dentist before the adhesive hardens. The presence of adhesive burrs can be detrimental. Burr removal is time-consuming, especially since accidental disturbance of the braces can negatively impact bonding reliability. Furthermore, incomplete removal of excess adhesive is problematic. Incomplete removal is particularly common in the posterior region and after hook braces, where the excess is limited. If not completely removed, the excess adhesive provides a site for bacterial accumulation. Such bacteria can attack and degrade the underlying tooth structure, leading to demineralization and discoloration of the teeth. Additionally, exposed adhesive surfaces are easily stained by food or beverages. Finally, the presence of hard fillers within the adhesive composition makes the adhesive difficult to remove once it hardens in the case of indirect bonding, causing discomfort to the patient.

[0025] It should be understood that adhesives with sufficient filler loading provide better tooth adhesion, but require burr removal. The filler increases flow resistance (i.e., increases viscosity), which presumably allows more adhesive to remain in contact with the brace-tooth interface (i.e., filling the gap between the brace and the tooth surface), at least partly due to the ease with which the structure forms this gap. Filling this gap is particularly important for tooth structures with considerable curvature, irregular shapes, molars, etc. However, the extruded viscous adhesive (burrs) takes on a convex shape that must be removed, and any burrs that are not removed are susceptible to staining and create an environment conducive to the accumulation of bacteria that cause tooth decay.

[0026] It should also be understood that adhesives with almost no filler content result in a softer adhesive (i.e., lower viscosity), which manifests as a concave, meniscus-like shape that may not need to be removed (not considered "burrs"). However, low-viscosity adhesives cannot adequately fill the gaps between the orthodontic appliance and the tooth structure, leading to poor tooth adhesion, which can cause appliance displacement or "drift," and even complete adhesive failure. Furthermore, the inadequately filled gaps contain food matter that can contribute to tooth decay. Previous solutions for adequately filling the gaps between the orthodontic appliance and the tooth structure while mitigating burrs with low-viscosity adhesives have been achieved using compressible pads as described in U.S. Patent No. 10,492,890.

[0027] The inventors of this disclosure have discovered that a hardenable adhesive layer, incorporating a high-viscosity adhesive composition at least partially surrounded by a low-viscosity adhesive composition, provides sufficient gap filling while allowing the low-viscosity adhesive composition to be extruded only when the orthodontic appliance is placed onto the tooth surface (eliminating the need for burr removal). The high-viscosity adhesive composition effectively displaces the surrounding low-viscosity adhesive composition and prevents the high-viscosity adhesive from extruding beyond the base (forming burrs; requiring removal). Furthermore, the high-viscosity adhesive composition is distributed to maximize the contact area between the base and the tooth structure. Additionally, the adhesive layer does not flow out of the base in any orientation at any time, allowing for complete assembly and distribution. This ingenious construction ensures excellent bond strength without the need for burr removal, avoids the use of compressible pads and associated manufacturing costs, and limits in-chair fabrication.

[0028] Figure 1A A side view of an orthodontic appliance 100 is shown. The orthodontic appliance 100 includes a base 102 and 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 depicted in an uncompressed configuration, i.e., before the orthodontic appliance 100 is pressed against a tooth surface (not shown). In one particular embodiment, the orthodontic appliance 100 has the high-viscosity composition 106, which has a viscosity of 1.24 mm. 3 The volume exists, with a maximum thickness of 0.508 mm, and covers 24% of the base area; and the low viscosity composition 108, which has a thickness of 1.84 mm. 3 The volume exists, with an average thickness of 0.238 mm, and covers 76% of the base area.

[0029] Figure 1BA side view of the orthodontic appliance 100 in a compressed state is shown, i.e., a side view 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, as described above... Figure 1A The orthodontic appliance 100 described herein has a high-viscosity composition 106 that covers 47% of the base area after compression and a low-viscosity composition 108 that covers 53% of the base area after compression.

[0030] Figure 1C A bottom view of the orthodontic appliance 100 in its uncompressed state is shown.

[0031] Figure 1D A bottom view of the orthodontic appliance 100 in a compressed state is shown.

[0032] Figure 1E A top view of the orthodontic appliance 100 in its uncompressed state is shown.

[0033] Figure 1F A top view of the orthodontic appliance 100 in a compressed state is shown. As shown, only the low-viscosity adhesive composition 108 extends beyond the base 102.

[0034] Figure 2A A cross-sectional side view of a malocclusion corrector 200 is shown. The malocclusion corrector 200 includes a base 202 and a hardenable adhesive layer 204 disposed thereon. The hardenable adhesive layer 204 is depicted as having an uncompressed configuration. As shown, the high-viscosity adhesive composition 206 has a larger volume than the low-viscosity adhesive 208. In one particular embodiment, the malocclusion corrector 200 has a high-viscosity composition 206, which has a volume of 1.72 mm. 3 The volume exists, with a maximum thickness of 0.508 mm, and covers 32% of the base area; and the low viscosity composition 208, which has a thickness of 1.41 mm. 3 The volume exists, with a maximum thickness of 0.508 mm and an average thickness of approximately 0.250 mm, and it covers 68% of the base area.

[0035] Figure 2B A cross-sectional side view of a malocclusion appliance 200 in a compressed state is shown. A high-viscosity adhesive composition 206 is shown extending toward the edge of the base 202, and a low-viscosity adhesive composition 206 is shown extending beyond the edge of the base 202 in a concave configuration. The extent to which the high-viscosity adhesive composition 204 extends toward the edge of the base 202 depends at least on the volume of the high-viscosity adhesive composition used. In one particular embodiment, as described above... Figure 2AThe orthodontic appliance 200 described herein has a high-viscosity composition 206 that covers 66% of the base area after compression and a low-viscosity composition 208 that covers 34% of the base area after compression.

[0036] Figure 3A A cross-sectional side view of an orthodontic appliance 300 in an uncompressed state is shown, which is similar to a cross-sectional side view of an orthodontic appliance 300, but the volume (and therefore the area coverage) of the high-viscosity adhesive composition 306 is different. In one particular embodiment, the orthodontic appliance 300 has a high-viscosity composition 306 with a volume of 2.67 mm. 3 The volume exists, with a maximum thickness of 0.381 mm, and covers 67% of the base area; and the low viscosity composition 308, which has a thickness of 0.46 mm. 3 The volume exists, with a maximum thickness of 0.266 mm and an average thickness of 0.133 mm, and covers 33% of the base area.

[0037] Figure 3B A cross-sectional side view of a malocclusion braces 300 in a compressed state is shown, which is similar to the cross-sectional side view of the malocclusion braces 300, but the area A covered by the high-viscosity adhesive composition 306 is different. In a particular embodiment, as described above... Figure 3A The orthodontic appliance 300 described herein has a high-viscosity composition 306 that covers 100% of the base area after compression.

[0038] Figure 4A A cross-sectional side view of an uncompressed orthodontic appliance 400 is shown, which is similar to an orthodontic appliance 400, but differs in the height and area covered by the high-viscosity adhesive composition 406. In one particular embodiment, the orthodontic appliance 400 has the high-viscosity composition 406, which has a viscosity of 1.26 mm. 3 The volume exists, with a maximum thickness of 1.15 mm, and covers 24% of the base area; and the low viscosity composition 408, which has a thickness of 1.87 mm. 3 The volume exists, with a maximum thickness of 0.56 mm and an average thickness of 0.33 mm, and it covers 76% of the base area.

[0039] Figure 4B A cross-sectional side view of a malocclusion appliance 400 in a compressed state is shown, which is similar to the cross-sectional side view of a malocclusion appliance 200, but the area A covered by the high-viscosity adhesive composition 406 is different. In one particular embodiment, as described above... Figure 4A The orthodontic appliance 400 described herein has a high-viscosity composition 306 that covers 47% of the base area after compression and a low-viscosity composition 408 that covers 53% of the base area after compression.

[0040] Figure 5A An example of a malocclusion device 500 having a compressible material 510 and an adhesive 506 / 508 (a high-viscosity adhesive and / or a low-viscosity adhesive composition) disposed therein and / or on it is shown (not part of this disclosure; see U.S. Patent No. 9,480,540). The malocclusion device 500 is shown in an uncompressed state. The compressible material is used to prevent the adhesive composition from extending beyond the base 502 of the device. The malocclusion device of the present invention does not contain such a compressible material as described herein.

[0041] Figure 5B A cross-sectional view of the orthodontic appliance 500 is shown, illustrating the compressible material 510 in an uncompressed configuration.

[0042] definition

[0043] As used in this article, “about” means ±10% of a given value. For example, “about 10” means 9 to 11.

[0044] As used in this article, "acid functional group" refers to a functional group with acidic hydrogen (i.e., a pKa of less than about 5). Organic acid functional groups such as -CO2H, -P(O)(OH)2, and -S(O)2OH are considered "acid functional groups".

[0045] As used in this article, "alkyl" refers to a straight-chain or branched monovalent saturated carbon chain. For example, C1 alkyl is methyl (-CH3), C2 alkyl is ethyl (-CH2CH3), and C4 alkyl can be butyl (-CH2CH2CH2CH3), sec-butyl (-CH(CH-3)CH2CH3), isobutyl (-CH2CH(CH3)2), or tert-butyl (-C(CH3)3), etc.

[0046] As used in this article, "alkylene" refers to a straight-chain or branched divalent saturated carbon chain. For example, C1 alkylene is methylene (-CH2-), C2 alkylene is ethylene (-CH2CH2-), and C4 alkylene can be -CH2CH2CH2CH2-, -CH(CH-3)CH2CH2-, -CH2CH(CH3)CH2-, or -C(CH3)2CH2-, etc.

[0047] As used in this article, "(alkyl)acrylate" refers to alkyl acrylate (i.e., C(R) acrylate). 1 (R) 1 )=C(R 2 )C(O)O-alkyl)), wherein R 1 It can be arbitrary (e.g., -H or C). 1-4 alkyl) and R 2 It is an alkyl substituted acrylate (i.e., C(R)-H) or alkyl-substituted alkyl acrylate (i.e., C(R)-H ...""" alkyl acrylate (i.e., C(R)-H)-H)-H) 1 (R)1 )=C(R 2 )C(O)O-(alkyl), wherein R 1 It can be arbitrary (e.g., -H or C). 1-4 alkyl) and R 2 It is an alkyl group (e.g., methyl (“methyl(meth)”)). “Hydroxy-substituted (alkyl)acrylate” refers to the formula C(R) 1 (R) 1 )=C(R 2 )C(O)OR 3 Compounds of which R 1 R 2 or R 3 At least one of them is an alkyl group substituted with -OH. In some cases, (alkyl)acrylates can be dimers, such as C(R) 1 (R) 1 )=C(CH3)C(O)OR 2 -OC(O)C(CH3)=C(R 1 (R) 1 ), where R 2 It is a linking group, such as C 2-8 Alkylene.

[0048] As used in this article, "base" refers to the surface of an orthodontic appliance designed to contact the dental structure. The base of an orthodontic appliance may be constructed of metal, plastic, ceramic, or a combination thereof.

[0049] As used in this article, "unsaturated" and "unsaturated organic group" refer to olefin units. Olefins are -C(R) 1 )=C(R 2 )-, where R 1 and R 2 It can be any group, such as each R 1 Is it H or C? 1-6 Alkyl; each R 2 It is -C(O)(C 1-6 Alkyl groups, -CO2H, -O(C) 1-6 Alkyl groups, etc. The term "unsaturated monomer" refers to a polymerizable compound containing an olefin unit.

[0050] As used herein, "compressible material" or "compressible pad" means any non-sticky material, especially porous material, that decreases in volume when compressed. Exemplary compressible materials include foams (e.g., cellulose, glass, polymers), sponges, nonwoven fabrics, glass wool, cotton fibers, and cellulose fibers. Other examples of compressible materials are disclosed in US 10,492,890 and US 9,480,540 and the references described therein, each of which is incorporated herein by reference in its entirety. The orthodontic appliance of the present invention does not have compressible material at its base.

[0051] As used herein, the phrase “one or more of A and B” or “at least one A and at least one B” means that the composition may contain 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 imply that the composition must have at least one of each of A and B.

[0052] As used in this article, “orthodontic appliance” refers to any device designed to be bonded to the dental structure, such as orthodontic brackets, oral tubes, lingual retainers, orthodontic braces, bite openers, snaps, prefabricated attachments, and wedges.

[0053] As used herein, "curable adhesive" refers to a composition containing a polymerizable component (i.e., a resin), with or without fillers, which can be cured or solidified, for example, by heating to induce polymerization or chemical crosslinking.

[0054] As used herein, “hardening adhesive” means a composition comprising polymeric components, with or without fillers, derived from a hardening adhesive.

[0055] As used herein, a “high viscosity adhesive composition” is defined as a composition having one or more polymerizable components, wherein the adhesive provides polymerization upon curing. The polymerizable component (i.e., monomer) alone or in combination with additives such as fillers provides properties that enable polymerization within 1 second. -1 Viscosity from about 10 Pa·s to about 1,500,000 Pa·s at shear rates. High-viscosity adhesive compositions are filled (e.g., composite) materials (e.g., dental or orthodontic materials) capable of being applied to or adhered to the surface of a tooth or a tooth replica, such as a stone model or plaster model (i.e., for indirect bonding). High-viscosity adhesive compositions include, for example, orthodontic adhesives, adhesives (e.g., glass ionomer adhesives, resin-modified glass ionomer adhesives, and / or orthodontic adhesives), and restorative agents (e.g., restorative filling materials). High-viscosity adhesive compositions may be photopolymerizable and / or redox-polymerizable.

[0056] As used herein, a “low-viscosity adhesive composition” is defined as a composition having one or more monomers, wherein the adhesive provides polymerization upon curing. The polymerizable component (i.e., the monomer) alone or in combination with additives such as fillers provides the properties of polymerizable components within 1 second. -1 Viscosity from about 1 Pa·s to about 100 Pa·s at a shear rate. Low-viscosity adhesive compositions are unfilled or lightly filled materials (e.g., dental or orthodontic materials) that can be applied to or adhered to the surface of a tooth or a tooth replica. Low-viscosity adhesive compositions include, for example, dental adhesives, primers (e.g., orthodontic primers), linings, sealants, and coatings. Low-viscosity adhesive compositions may be photopolymerizable and / or redox polymerizable.

[0057] As used herein, a “layer” is defined as a plane parallel to the length of the base. This plane must pass through each component within the layer so that those components are considered part of the layer. The composition forming the layer may extend above and / or below this plane.

[0058] As used herein, “thickness,” defined relative to the dimensions of the arrangement of the low-viscosity and high-viscosity adhesive compositions, 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 that area. “Average thickness” refers to the average of the distances measured over the entire area.

[0059] As used herein, the term "resin" refers to a polymerizable component comprising one, two, three, or more polymerizable groups. Exemplary polymerizable groups include, but are not limited to, acrylate groups, epoxy (ethylene oxide) groups, and vinyl ether groups. Resins are typically cured by radiation-induced polymerization or crosslinking, or by using a redox initiator. The term "resin" is used synonymously with "polymerizable component" and "adhesive."

[0060] As used in this article, "yield stress" is the minimum stress required for a material to flow.

[0061] Orthodontic appliance

[0062] In various embodiments, an orthodontic appliance is described. The orthodontic appliance may include a base and a hardenable adhesive layer disposed on the base. The hardenable adhesive layer may include a first region and a second region, wherein the first region is at least partially surrounded by the second region, and the first and second regions are configured to contact a tooth surface. The first region may include features characterized in that, within 1 second... -1 A high-viscosity adhesive composition with a viscosity of about 10 Pa·s to about 1,500,000 Pa·s at a shear rate, and the second region comprising a feature characterized in that at 1 s -1Low-viscosity adhesive compositions have a viscosity of about 0.1 Pa·s to about 100 Pa·s at a shear rate. High-viscosity adhesive compositions have a viscosity greater than that of low-viscosity adhesive compositions.

[0063] In some implementations, orthodontic appliances consist essentially of a base and a hardenable adhesive layer.

[0064] In some embodiments, orthodontic appliances may not include compressible pads. Compressible pads have been used to fill the gap between the base surface and the tooth structure. Compressible materials and pads made therefrom can be found, for example, in U.S. Patent Nos. 10,492,890 and 9,480,540, each of which is incorporated herein by reference in its entirety. For example, compressible pads may include foam, sponge, nonwoven fabric, glass wool, cotton fibers, cellulose fibers, combinations thereof, etc. In some embodiments, the compressible material may have a thickness of about 0.2 mm to about 1 mm (e.g., 0.5 mm). Specific materials are described in, for example, U.S. Patent 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, eds. D. W. W. Born and A. H. A. M. Man (Marel Dekker, New York, pp. 299–325 (1990); U.S. Patent Nos. 5,770,636 (Wernsing et al.) and 5,817,704 (Shively et al.); and, for example, Westerman et al., British Journal of Sports. Closed-cell foams as described in Medicine, 36:205-208 (2002) (Westerman et al., British Journal of Sports Medicine, Vol. 36, pp. 205-208, 2002); U.S. Patent No. 6,645,618; and U.S. Patent No. 6,750,261, each of which is incorporated herein by reference in its entirety. For example, compressible pads may comprise or be substantially composed of polypropylene.

[0065] Base of orthodontic appliance

[0066] In some implementations, the base may have approximately 8.0 mm. 2 approximately 20mm2 The area.

[0067] In some implementations, the base can be the base of an orthodontic appliance (e.g., lingual bracket, self-binding bracket, Roth bracket, MBT bracket, etc.), an oral tube, dental band, dental clip, spacer retainer, lingual retainer, bracket, or a custom base of an oral tube, etc.

[0068] In some embodiments, the base may include a material selected from ceramics, cobalt-chromium, composites, gold, plastics, stainless steel, titanium, or combinations thereof.

[0069] Hardenable adhesive layer

[0070] In some embodiments, the curable adhesive layer may also include the fillers described herein. The fillers 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 contain a greater amount of filler than is 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, wherein their compositions differ in the amount of filler present, thereby achieving the aforementioned viscosities of both the high-viscosity and low-viscosity adhesive compositions. In other embodiments, the high-viscosity and low-viscosity adhesives are based on different resins, i.e., the adhesives comprise or are derived from one or more different monomers.

[0071] In some embodiments, the viscosities of the high-viscosity adhesive composition and the low-viscosity adhesive composition may differ 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 any of the foregoing values ​​(e.g., between about 8 and about 12 times, between about 10 and about 15 times, etc.).

[0072] In some embodiments, the high-viscosity adhesive composition may be present on the substrate (in an uncompressed state) with a maximum thickness of about 0.3 mm to about 2.0 mm. For example, the high-viscosity adhesive composition may be present on the substrate with a maximum thickness (in mm) of values ​​ranging from 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, or between any of the foregoing values ​​(e.g., between about 0.3 and about 0.5, between about 0.5 and about 1.6, etc.). In some embodiments, the high-viscosity adhesive composition may be about 1.0 mm thick. 3 To approximately 3.0mm 3The volume exists at the base (in an uncompressed state). For example, the high viscosity adhesive composition may have a volume (in mm) 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 or between any of the foregoing values ​​(e.g., between about 1.2 and about 1.5, between about 1.8 and about 2.8, etc.). 3 The (calculation) exists on the base.

[0073] In some embodiments, the low-viscosity adhesive composition may be present on the substrate (in an uncompressed state) with a maximum thickness of about 0.2 mm to about 1.5 mm. For example, the high-viscosity adhesive composition may be present on the substrate with a maximum thickness (in mm) 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, or between any of the foregoing values ​​(e.g., between about 0.3 and about 0.5, between about 0.5 and about 1.6, etc.). In some embodiments, the low-viscosity adhesive composition may be about 0.3 mm thick. 3 To approximately 2.0mm 3 The volume exists at the base (in an uncompressed state). For example, the low viscosity adhesive composition may have a volume (in mm) 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 or any of the foregoing values ​​(e.g., between about 1.4 and about 1.9, between about 0.4 and about 0.8, etc.). 3 The (calculation) exists on the base.

[0074] In some embodiments, the ratio of the maximum thickness of the high-viscosity adhesive composition (in its uncompressed state) to the average thickness of the low-viscosity adhesive composition (in its uncompressed state) 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 any of the foregoing values ​​(e.g., between about 2:1 and about 4:1, between about 12:1 and about 15:1, etc.).

[0075] In some embodiments, the high-viscosity adhesive composition may cover about 20% to about 75% of the substrate area (in an uncompressed state). For example, the high-viscosity adhesive composition may cover the substrate area (in an uncompressed state) of about 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, or any of the foregoing values ​​(e.g., between about 20% and about 55%, between about 60% and about 70%, etc.).

[0076] In some embodiments, the low-viscosity adhesive composition may cover about 25% to about 80% of the substrate area (in an uncompressed state). For example, the low-viscosity adhesive composition may cover the substrate area (in an uncompressed state) of about 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, or 80%, or any value between the foregoing values ​​(e.g., between about 30% and about 40%, between about 45% and about 80%, etc.). The low-viscosity adhesive composition may cover the difference in substrate area not occupied by the high-viscosity adhesive composition.

[0077] In some embodiments, the total base area may be covered by a first region (comprising an uncompressed high-viscosity adhesive composition) and a second region (comprising an uncompressed low-viscosity adhesive composition) at ratios 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 any of the foregoing values ​​(e.g., between about 1:1.6 and about 1:2.5, between about 1:3 and about 1:4, etc.).

[0078] In some embodiments, the high-viscosity adhesive composition may cover about 40% to about 100% of the substrate area (after compression). For example, the high-viscosity adhesive composition may cover the substrate area (after compression) of about 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, or 100% or any of the foregoing values ​​(e.g., between about 45% and about 70%, between about 50% and about 95%, etc.).

[0079] In some embodiments, the low-viscosity adhesive composition may cover about 0% to about 60% of the substrate area (after compression). For example, the low-viscosity adhesive composition may cover the substrate area (after compression) of about 0%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, or 60%, or values ​​within any of the foregoing values ​​(e.g., between about 5% and about 50%, between about 30% and about 55%, etc.). The low-viscosity adhesive composition may cover the difference in substrate area not covered by the high-viscosity adhesive composition.

[0080] In some embodiments, the high-viscosity adhesive composition and the low-viscosity adhesive composition may be selected from any composition described herein, including any filler loading and any combination of compositions thereof. For example, the high-viscosity adhesive may be 3M Transbond. TM XT adhesive or 3M Transbond TM PLUS color-changing adhesive, while low-viscosity adhesives can be 3M Transbond. TM XT primer, 3M Clinpro sealant, or 3M Scotchbond universal adhesive.

[0081] In some embodiments, at least one of the high-viscosity adhesive and the low-viscosity adhesive within the curable adhesive layer may further comprise 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 comprise one or more photoinitiators. The photoinitiator initiates the polymerization (curing) of the adhesive composition. Examples of photoinitiators are described in U.S. Patent Nos. 5,545,676, 7,674,850, and 7,816,423, such as diaryliodomonium salts, metal complex salts, etc. Other exemplary polymerization initiators include ketones, such as benzyl, benzoin, azoin, azoin ethers, etc. 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 from about 0.01% by weight to about 10% by weight relative to 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 relative to the weight of the curable adhesive layer, or between any of the foregoing values ​​(e.g., between about 5.0 and about 8.0, between about 0.1 and about 3.5, etc.).

[0082] 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 oxidizing agent can react to generate a free radical capable of initiating polymerization. Suitable redox agents are found, for example, in U.S. Patent Nos. 7,173,074 and 6,982,288. For example, ascorbic acid and its salts, derivatives, or metal complexes are suitable reducing agents; 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 are also suitable reducing agents. Suitable oxidants include, for example, persulfate and its salts, alkylammonium salts, peroxides (e.g., benzoyl peroxide, hydroperoxides such as cumyl hydroperoxide, tert-butyl hydroperoxide, pentyl hydroperoxide), transition metal salts such as cobalt(III) chloride, ferric chloride, cerium(IV) sulfate, perboric acid and its salts, permanganic acid and its salts, superphosphate and its salts, etc. Enzymes, such as those disclosed in U.S. Patent Publication No. 2004 / 0122126, can also be used as redox initiators.

[0083] In some embodiments, the initiator system may also include one or more sensitizers (e.g., ketones, coumarin dyes, xanthan dyes, acridine dyes, thiazole dyes, thiazine dyes, oxazine dyes, acridine dyes, aminoketone dyes, porphyrins, aromatic polycyclic hydrocarbons, p-substituted aminostyryl ketone compounds, aminotriarylmethane, phthalocyanine, squaric acid dyes, pyridine dyes, etc.). Specific examples of sensitizers include camphorquinone, glyoxal, diacetyl, 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, dipentanoyl, biphenylyl, furozyloyl, hydroxybiphenylyl, 2,3-butanedione, 2,3-pentanedione, 2,3-hexanedione, 3,4-hexanedione, 2,3-heptanedione, 3,4-heptanedione, 2,3-octanedione, 4,5-octanedione, 1,2-cyclohexanedione, etc. In some embodiments, the initiator system may further include one or more electron donors, such as amines, amides, ethers, thioethers, ureas, thioureas, ferrocene, sulfinic acid or its salts, ferrocyanide salts, ascorbic acid or its salts, dithiocarbamate or its salts, xanthates, ethylenediaminetetraacetic acid, tetraphenylborate, etc. In some embodiments, the initiator system may further include one or more hydrogen donors, such as amines.

[0084] In some embodiments, the curable adhesive layer may also comprise a glass ionomer adhesive, a resin-modified glass ionomer adhesive, or a combination thereof.

[0085] In some embodiments, at least one of the high-viscosity and low-viscosity adhesives within the curable adhesive layer may further comprise one or more fluoride-releasing agents. Incorporation of one or more fluoride-releasing agents into the high-viscosity and / or low-viscosity adhesive compositions allows fluoride delivery to the tooth surfaces beneath and around the orthodontic appliance, thereby protecting the tooth surfaces from decay. Examples of fluoride-releasing agents include fluoroaluminosilicate glass, inorganic fluoride salts, organic fluoride salts, fluorine-containing metal complexes, etc. Specific fluoride-releasing agents can be found, for example, in the following disclosures: U.S. Patent Nos. 3,814,717, 5,332,429, 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 from about 0.1% by weight to about 85% by weight relative to the weight of the curable adhesive layer. For example, the fluoride releaser may be present in an amount of 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 relative to the curable adhesive layer, or in a range between any of the aforementioned values ​​(e.g., between about 20 and about 30, between about 45 and about 60, etc.).

[0086] Adhesive composition

[0087] In many embodiments, the high-viscosity adhesive composition comprises the resin and filler described herein. In many embodiments, the low-viscosity adhesive composition comprises the resin and optional filler described herein. The high-viscosity adhesive resin and the low-viscosity adhesive resin may comprise the same or different polymerizable components, wherein compositions having the same resin may differ based on the type and / or amount of filler.

[0088] 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 functional groups, or combinations thereof.

[0089] Polymerizable components that do not have acid functional groups may 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 U.S. Patent No. 6,030,606 (Holmes), and NPGDMA (neopentyl glycol dimethacrylate). Other examples include epoxy resins such as those listed in U.S. Patent Nos. 6,187,836 (Oxman et al.) and 6,084,004 (Weinmann et al.), 6,245,828 (Weinmann et al.), 5,037,861 (Crivello et al.), 6,779,656 (Klettke et al.), 3,018,262 (Schroeder), WO 01 / 51540 (Klettke et al.), 7,262,228 (Oxman et al.), and Lee and Neville’s “Handbook of Epoxy Resins” (McGraw-Hill Book Co., New York (1967)). 3,4-Epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, 3,4-epoxy-2-methylcyclohexylmethyl-3,4-epoxy-2-methylcyclohexane carboxylate and bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate, octadecyl oxide, epichlorohydrin, styrene oxide, vinyl cyclohexene oxide, glycidyl methacrylate, and diglycidyl ether of bisphenol A. These references are incorporated herein by reference in their entirety.

[0090] Polymerizable components having acidic functional groups may include, for example, α,β-unsaturated acidic compounds such as glyceryl phosphate mono(meth)acrylate, glyceryl phosphate di(meth)acrylate, hydroxyethyl methacrylate (e.g., HEMA) phosphate, bis((meth)acryloyloxyethyl) phosphate, ((meth)acryloyloxypropyl) phosphate, bis((meth)acryloyloxypropyl) phosphate, bis((meth)acryloyloxy)propoxy phosphate, (meth)acryloyloxyhexyl phosphate, bis((meth)acryloyloxyhexyl) phosphate, (meth)acryloyloxyoctyl phosphate, bis((meth)propoxy)propoxy phosphate, bis((meth)propoxyhexyl) phosphate, bis((meth)propoxy)propoxy phosphate, bis((meth)propoxyhexyl) phosphate, bis((meth)propoxy)propoxy phosphate, bis((meth)propoxyhexyl) phosphate, bis((meth)propoxyhexyl) phosphate, bis((meth)propoxyhexyl)propoxy ...meth)propoxyhexyl)propoxy phosphate, bis(meth)propoxyhexyl)propoxy phosphate, bis(meth)propoxyhexyl)propoxy phosphate, bis(meth)propoxyhexyl)propoxyhexyl)propoxy phosphate, bis(meth)propoxyhexyl)propoxyhexyl)propoxy phosphate, bis(meth)propoxyhexyl)propoxyhexyl)propoxy Acryloyloxyoctyl phosphoric acid, (meth)acryloyloxydecyl phosphoric acid, bis((meth)acryloyloxydecyl) phosphoric acid, caprolactone phosphate, di- or tri-methacrylate of citrate, poly(meth)acrylated oligomeric maleic acid, poly(meth)acrylated polymaleic acid, poly(meth)acrylated poly(meth)acrylic acid, poly(meth)acrylated polycarboxy-polyphosphonic acid, poly(meth)acrylated polychlorophosphonic acid, poly(meth)acrylated polysulfonic acid, poly(meth)acrylated polyboronic acid, etc., can be used as components in curable component systems. Unsaturated carbonic acids such as (meth)acrylic acid, aromatic (meth)acrylated acids (e.g., trimellitic acid methacrylated), and their anhydrides, monomers, oligomers, and polymers are also used. Some of these compounds can be obtained, for example, as reaction products between isocyanatoalkyl (meth)acrylates and carboxylic acids. Other compounds of this kind, which simultaneously possess acidic functional components and olefinically unsaturated components, are described in U.S. Patent Nos. 4,872,936 (Engelbrecht) and 5,130,347 (Mitra).For example, polymerizable bisphosphonic acids disclosed in U.S. Patent Publication No. 2004 / 0206932 (Abuelyaman et al.); AA:ITA:IEM (an acrylic acid:itaconic acid copolymer with side-chain methacrylates obtained by reacting an AA:ITA copolymer with sufficient 2-isocyanate methacrylate to convert some of the acidic groups in the copolymer into side-chain methacrylate groups, as described in Example 11 of U.S. Patent No. 5,130,347 (Mita); and U.S. Patent Nos. 4,259,075 (Yamauchi et al.), 4,499,251 (Omura et al.), 4,537,940 (Omura et al.), 4,539,382 (Omura et al.), 5,530,038 (Yamamoto et al.), 6,458,868 (Okada et al.), and European Patent Application Publication No. EP Those cited in 712,622 (Tokuyama Corp.) and EP 1,051,961 (Kuraray Co., Ltd.). Other examples of polymerizable components having acid functional groups include (meth)acryloyloxy groups and at least one -OP(O)(OH). x A group, wherein x = 1 or 2, and wherein at least one is -OP(O)(OH). x The first compound comprises a group and at least one (meth)acryloyloxy group linked together by a C1-C4 hydrocarbon group; the second compound comprises at least one (meth)acryloyloxy group and at least one -OP(O)(OH) group. x A group, wherein x = 1 or 2, and wherein at least one is -OP(O)(OH). x The composition comprises a group and at least one (meth)acryloyloxy group linked together by a C5-C12 hydrocarbon group; an olefinic unsaturated compound free of acidic functional groups; an initiator system; and a filler. Such compositions are described, for example, in published U.S. Patent Application No. 2007 / 0248927 (Luchterhandt et al.). See also U.S. Patent Nos. 7,449,499 (Bradley et al.) and 7,452,924 (Aasen et al.); and published U.S. Patent Application Nos. 2005 / 0175966 (Falsafi et al.), 2009 / 0011388 (Bradley et al.), and 2009 / 0035728 (Aasen et al.). These references are incorporated herein by reference in their entirety.

[0091] In some embodiments, the high-viscosity adhesive resin and the low-viscosity adhesive resin may independently include polymerizable components selected from unsaturated monomers (e.g., (meth)acrylates, epoxy (meth)acrylates, hydroxy-substituted (meth)acrylates, (meth)acrylic acid, hydroxy-substituted (meth)acrylic acid, vinyl ethers), epoxy resins, etc. For example, one or more unsaturated monomers may be selected from methyl (meth)acrylate, ethyl acrylate, isopropyl methacrylate, n-hexyl acrylate, octadecyl acrylate, allyl acrylate, glyceryl 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, sorbitol Hexaacrylate, tetrahydrofurfuryl (meth)acrylate, bis[1-(2-acryloyloxy)]-p-ethoxyphenyl dimethylmethane, bis[1-(3-acryloyloxy-2-hydroxy)]-p-propoxyphenyl dimethylmethane, ethoxylated bisphenol A di(meth)acrylate and trihydroxyethyl isocyanurate; (meth)acrylamide (i.e. acrylamide and methacrylamide) such as (meth)acrylamide, methylene bis(meth)acrylamide and acetylacetone (meth)acrylamide; ureaalkyl (meth)acrylate; Polyethylene glycol bis(meth)acrylate (preferably with a molecular weight of 200-500), bisphenol A bis(2-hydroxyethyl ether) dimethacrylate, 2-hydroxy-1,2,3-propanetricarboxylic acid, CDMA (the reaction product of 2-hydroxy-1,2,3-propanetricarboxylic acid and 2-isocyanate ethyl methacrylate), decamethyl dimethacrylate, methacryloyloxydecyl phosphate (MDP) and other propionyl phosphates, acrylic acid and other acrylic acids, copolymers of acrylic acid and itaconic acid, and acrylate esterified monomers. Copolymerizable blends (such as those in U.S. Patent No. 4,652,274 (Boettcher et al.), acrylated oligomers (such as those in U.S. Patent No. 4,642,126 (Zador et al.), and polyunsaturated carbamoyl isocyanurates (such as those disclosed in U.S. Patent No. 4,648,843 (Mitra); and vinyl compounds such as styrene, diallyl phthalate, divinyl succinate, divinyl adipate, and divinyl phthalate.Other suitable free radical polymerizable compounds include, for example, siloxane-functionalized (meth)acrylates disclosed in 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, for example, U.S. Patent 5,076,844 (Fock et al.), U.S. Patent 4,356,296 (Griffith et al.), EP-0373 384 (Wagenknecht et al.), EP-0201 031 (Reiners et al.), and EP-0201 Fluoropolymer-functionalized (meth)acrylates, hydroxyalkyl (meth)acrylates, such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate, disclosed in 778 (Reiners et al.); glyceryl mono(meth)acrylates or glyceryl di(meth)acrylates; trimethylolpropane mono(meth)acrylates or trimethylolpropane di(meth)acrylates; pentaerythritol mono(meth)acrylates, pentaerythritol di(meth)acrylates, and pentaerythritol tri(meth)acrylates; sorbitol mono(meth)acrylates, sorbitol di(meth)acrylates, and sorbitol tri(meth)acrylates. Sorbitol esters, sorbitol tetra(meth)acrylates, or sorbitol penta(meth)acrylates; and 2,2-bis[4-(2-hydroxy-3-ethylacryloyloxypropoxy)phenyl]propane (bisGMA), PEGDMA (polyethylene dimethacrylate with a molecular weight of about 400), UDMA (polyurethane dimethacrylate), GDMA (glyceryl dimethacrylate), TEGDMA (triethylene dimethacrylate), bisEMA6 as described in U.S. Patent No. 6,030,606 (Holmes), and NPGDMA (neopentyl dimethacrylate). These references are incorporated herein by reference in their entirety.

[0092] In some embodiments, the high-viscosity adhesive and the low-viscosity adhesive may independently comprise one or more polymerizable components selected independently from the following: bisphenol A bis(2-hydroxyethyl ether) dimethacrylate, bisphenol A diglycidyl ether dimethacrylate, CDMA (the reaction product of dimethicone citrate, 2-hydroxy-1,2,3-propanetricarboxylic acid and 2-isocyanate ethyl methacrylate), polyethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 2-hydroxyethyl methacrylate, decamethyl dimethacrylate, methacryloyloxydecyl phosphate, dimethylaminoethyl methacrylate, and copolymers of acrylic acid and itaconic acid.

[0093] In some embodiments, the high-viscosity adhesive may include one or more polymerizable components selected from the following: bisphenol A bis(2-hydroxyethyl ether) dimethacrylate, bisphenol A diglycidyl ether dimethacrylate, CDMA (the reaction product of citrate dimethacrylate, 2-hydroxy-1,2,3-propanetricarboxylic acid and 2-isocyanate ethyl methacrylate), and polyethylene glycol dimethacrylate.

[0094] In some embodiments, the high-viscosity adhesive may contain one or more polymerizable components selected from the following: bisphenol A bis(2-hydroxyethyl ether) dimethacrylate and bisphenol A diglycidyl ether dimethacrylate.

[0095] In some embodiments, the low-viscosity adhesive may contain one or more polymerizable components selected from the following: bisphenol A bis(2-hydroxyethyl ether) dimethacrylate, bisphenol A diglycidyl ether dimethacrylate, triethylene glycol dimethacrylate, 2-hydroxyethyl methacrylate, decamethyl dimethacrylate, methacryloxydecyl phosphate, dimethylaminoethyl methacrylate, and copolymers of acrylic acid and itaconic acid.

[0096] In some embodiments, the low-viscosity adhesive may contain one or more polymerizable components selected from the following: bisphenol A bis(2-hydroxyethyl ether) dimethacrylate and bisphenol A diglycidyl ether dimethacrylate.

[0097] In some embodiments, the low-viscosity adhesive resin may contain one or more polymerizable components selected from the following: triethylene glycol dimethacrylate and bisphenol A diglycidyl ether dimethacrylate.

[0098] In some embodiments, the low-viscosity adhesive resin may contain one or more polymerizable components selected from the following: 2-hydroxyethyl methacrylate, bisphenol A diglycidyl ether dimethacrylate, decamethyl dimethacrylate, methacryloyloxydecyl phosphate, dimethylaminoethyl methacrylate, and copolymers of acrylic acid and itaconic acid.

[0099] In some embodiments, the low-viscosity adhesive resin may contain water, an alcohol solvent (e.g., ethanol), or a combination thereof.

[0100] In some embodiments, the high-viscosity adhesive composition may comprise one or more adhesive compositions sold under the names Transbond XT Adhesive (3M Unitek, Monrovia, CA), Transbond PLUS Color-Changing Adhesive (3M Unitek, Monrovia, CA), and Transbond Supreme LV Adhesive (3M Unitek, Monrovia, CA), including adhesives within their respective devices. In other embodiments, the low-viscosity adhesive composition may comprise 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 General Purpose Adhesive (3M ESPE, St. Paul, MN), including adhesives within their respective devices. Alternatively, the high-viscosity and low-viscosity adhesive compositions may independently comprise one or more resins in the aforementioned adhesive compositions, although the filler type and / or filler amount may differ.

[0101] In some embodiments, the high-viscosity adhesive composition may contain one or more fillers described herein in an amount of about 50% to about 90% by weight relative to the weight of the high-viscosity adhesive composition. For example, the high-viscosity adhesive composition may contain fillers 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 relative to the weight of the high-viscosity adhesive composition, or in a range between any of the foregoing values ​​(e.g., between about 50 and about 86, between about 70 and about 80, etc.).

[0102] In some embodiments, the low-viscosity adhesive composition may contain one or more fillers described herein in an amount from about 0% to about 65% by weight relative to the weight of the low-viscosity adhesive composition. For example, the low-viscosity adhesive composition may contain fillers in an amount of about 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60 or 65% by weight relative to the weight of the low-viscosity adhesive composition, or in a range between any of the foregoing values ​​(e.g., between about 25 and about 35, between about 10 and about 20, etc.).

[0103] In some embodiments, the high-viscosity adhesive composition is characterized by a viscosity of 1 second. -1 Viscosity at shear rates from about 10 Pa·s to about 1,500,000 Pa·s. For example, a high-viscosity adhesive composition may be characterized by a viscosity of about 1 s.-1 At shear rates (Pa·s), approximately 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, 40 Viscosities ranging from 0.000, 60000, 80000, 100000, 200000, 300000, 400000, 500000, 600000, 700000, 800000, 900000, 1000000, 1500000, or any of the foregoing values ​​(e.g., between about 500 and about 1000, between about 10000 and about 100000, etc.). In some embodiments, the high-viscosity adhesive composition is characterized by a viscosity of 1 second. -1 Viscosity at shear rates of approximately 1500 Pa·s to approximately 5000 Pa·s. For example, a high-viscosity adhesive composition may be characterized by a viscosity of approximately 1500 Pa·s to approximately 5000 Pa·s at a shear rate. -1 Viscosity in Pa·s at shear rates of approximately 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 or any of the foregoing values ​​(e.g., between approximately 1800 and approximately 1900, between approximately 4000 and approximately 4100, etc.). In some embodiments, the high-viscosity adhesive composition is characterized by a viscosity of 0.1s. -1 Viscosity at a shear rate of approximately 4000 Pa·s to approximately 8000 Pa·s. For example, a high-viscosity adhesive composition may be characterized by a viscosity of approximately 0.1 s⁻¹. -1Viscosity in Pa·s at shear rates of approximately 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, 6600, 6700, 6800, 6900, 7000, 7100, 7200, 7300, 7400, 7500, 7600, 7700, 7800, 7900 or 8000 or between any of the foregoing values ​​(e.g., between approximately 5000 and approximately 7000, etc.). In some embodiments, the high-viscosity adhesive composition is characterized by a viscosity of 10s. -1 Viscosity at shear rates of approximately 300 Pa·s to approximately 2000 Pa·s. For example, a high-viscosity adhesive composition may be characterized by a viscosity of approximately 10 s. -1 Viscosity in Pa·s at shear rates of approximately 300, 400, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900 or 2000 or between any of the foregoing values ​​(e.g., between approximately 400 and approximately 600, between approximately 1500 and approximately 1700, etc.).

[0104] In some embodiments, the low-viscosity adhesive composition is characterized by a viscosity of 1 second. -1 Viscosity from about 0.1 Pa·s to about 100 Pa·s at a shear rate. For example, a low-viscosity adhesive composition may be characterized by a viscosity of about 1 s. -1 Viscosity in Pa·s at shear rates 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, or between any of the foregoing values ​​(e.g., between about 40 and about 100, between about 1 and about 5, between about 0.1 and about 1, etc.). In some embodiments, the low-viscosity adhesive composition is characterized by a viscosity of about 0.1 Pa·s. -1The viscosity at a shear rate is from about 0.5 Pa·s to about 50 Pa·s. For example, a low-viscosity adhesive composition may be characterized by a viscosity in Pa·s 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 or any of the foregoing values ​​(e.g., between about 0.7 and about 1, between about 30 and about 40, etc.) at a shear rate of 0.1 s⁻¹. In some embodiments, the low-viscosity adhesive composition may be characterized by a viscosity at a shear rate of 0.1 s⁻¹. -1 Viscosity at a shear rate of about 0.5 Pa·s to about 50 Pa·s. For example, a low-viscosity adhesive composition may be characterized by a viscosity of about 0.1 Pa·s. -1 Viscosity at shear rates 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 between any of the foregoing values ​​(e.g., between about 0.7 and about 1, between about 30 and about 40, etc.). In some embodiments, the low-viscosity adhesive composition is characterized by a viscosity of about 10 s. -1 Viscosity at a shear rate of about 0.5 Pa·s to about 50 Pa·s. For example, a low-viscosity adhesive composition may be characterized by a viscosity in Pa·s 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 or any of the foregoing values ​​(e.g., between about 0.7 and about 1, between about 20 and about 30, etc.).

[0105] In some embodiments, one or more of the high-viscosity adhesive composition and the low-viscosity adhesive composition may also contain the fillers described herein. Those skilled in the art will understand how the viscosity of the composition can be adjusted by including viscosity-modifying fillers.

[0106] In some embodiments, the high-viscosity adhesive composition may be a paste. A paste is defined herein as a viscous substance with solids dispersed in a liquid, which can be shaped before curing. In some embodiments, the high-viscosity adhesive composition may be characterized by at least 1000 dynes / cm². 2The yield stress is determined as described in Rheology Principles, Measurements, and Applications, CIW See CW Macosko, VCH Publishers, Inc., New York, 1994, page 92. The yield stress and viscosity of the adhesive test sample can be measured using suitable equipment, such as the Rheometrics ARES controlled strain rheometer (Advanced Rheometric Expansion System, Rheometric Scientific, Inc., Piscataway, NJ). In some embodiments, the high-viscosity adhesive composition may be characterized by approximately 1000 dynes / cm². 2 Approximately 10,000 dynes / cm 2 The yield stress. For example, a high-viscosity adhesive composition may be characterized by a yield stress of dynes / cm at 28°C. 2 Static yield stresses are defined as values ​​in the range of approximately 1000, 2000, 3000, 4000, 5000, 6000, 7000, 7200, 7400, 7600, 7800, 8000, 8200, 8400, 8600, 8800, 9000, 9200, 9400, 9600, 9800, 10000, or any of the aforementioned values ​​(e.g., between approximately 7500 and approximately 8000, between approximately 7400 and approximately 9200, etc.).

[0107] In some embodiments, the low-viscosity adhesive composition is a flowable solution or flowable suspension. It is capable of flowing with moderate force and cannot be molded before curing. Although the low-viscosity adhesive composition described herein is flowable, as determined by a vertical flow test (see Example 4), the low-viscosity adhesive does not flow significantly from a vertically held substrate, wherein after being vertically held at room temperature (23°C) for six hours and then vertically held at 40°C for five minutes, the thickness difference of the adhesive composition at the top and bottom is less than about 15% due to surface tension within the curable adhesive layer structure in contact with the substrate.

[0108] First District

[0109] In many embodiments, the first region may include any high-viscosity adhesive composition described herein.

[0110] 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 in mm ranging from 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 or any of the foregoing values ​​(e.g., between about 0.38 and about 1.2, between about 0.60 and about 0.90, etc.).

[0111] In some embodiments, the first region may include a high-viscosity adhesive composition comprising about 40% to about 85% of the total volume of the curable adhesive layer. For example, the volume of the high-viscosity adhesive composition may be a value in percentages of about 40, 45, 50, 55, 60, 65, 70, 75, 80, 85 or any of the foregoing values ​​(e.g., between about 45 and about 55, between about 60 and about 75, etc.) relative to the total volume of the curable adhesive layer.

[0112] In some embodiments, the first region may extend over about 20% to about 50% of the total base area. For example, the first region comprising the high-viscosity adhesive composition may extend over about 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50% of the total base area or between any of the foregoing values ​​(e.g., between about 30 and about 40, between about 26 and about 48, etc.).

[0113] In some embodiments, the first region may include a high-viscosity adhesive composition that, when viewed from a cross-sectional side view of the base, exhibits a Gaussian curve, a triangle, or a trapezoidal shape.

[0114] In some embodiments, the first region may include a high-viscosity adhesive composition that, when viewed from a direction perpendicular to the base, takes the shape of a circle, polygon, or quadrilateral.

[0115] Second Zone

[0116] In many embodiments, the second region may include any low-viscosity adhesive composition described herein.

[0117] In some embodiments, the second region may include a low-viscosity adhesive composition with 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 in mm ranging from about 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.12, 0.14, 0.16, 0.18, 0.20 or any of the foregoing values ​​(e.g., between about 0.06 and about 0.16, between about 0.10 and about 0.14, etc.).

[0118] In some embodiments, the second region may include a low-viscosity adhesive composition extending over about 50% to about 80% of the total base area. For example, the second region including the low-viscosity adhesive composition may extend over about 50, 55, 60, 65, 70, 75, 80 percent of the total base area or within a range of any of the foregoing values ​​(e.g., between about 60 and about 70, between about 55 and about 75, etc.).

[0119] In some embodiments, the second region may include a low-viscosity adhesive composition that, when viewed from a direction perpendicular to the plane defined by the base, is ring-shaped or rectangular.

[0120] filler

[0121] In some embodiments, the filler may be an inorganic material selected from the following: non-acid reactants (e.g., quartz, submicron silica, zirconium oxide, submicron zirconium oxide, non-glassy microparticles), acid reactants (e.g., metal oxides (e.g., barium oxide, calcium oxide, magnesium oxide, zinc oxide), glass (e.g., borate glass, phosphate glass, fluoroaluminosilicate glass), metal salts), and combinations thereof.

[0122] In some embodiments, the filler may be silane-treated glass, silane-treated quartz, silane-treated pyrolytic silica, silane-treated silicon dioxide, silane-treated zirconium oxide, silane-treated ceramic, or a combination thereof.

[0123] In some implementations, to enhance the adhesion between the filler and the adhesive polymer (resin), the surface of the filler can be treated with a coupling agent. Suitable coupling agents include, for example, γ-methacryloyloxypropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, etc.

[0124] In some embodiments, the packing material may have a unimodal or multimodal particle size distribution. The maximum particle size may be less than 30 μm. For example, the maximum particle size in μm 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, or a value within any of the foregoing values ​​(e.g., between about 0.025 and about 0.5, between about 5 and about 1, between about 30 and about 10, etc.).

[0125] In some embodiments, the filler may be selected from quartz, silica, silica nitride, feldspar, borosilicate glass, kaolin, talc, zirconium oxide, titanium dioxide, glass 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., OX 50)), silica from Degussa Corp (Akron, OH) of Akron, Ohio, or Cabot Corporation of Tuscora, Illinois. Silica, pulverized polycarbonate, methacrylate of polycaprolactone, polyepoxides, metal oxides (e.g., barium oxide, calcium oxide, magnesium oxide, zinc oxide), glass (borate glass, phosphate glass, fluoroaluminosilicate glass, metal salts), non-vitreous microparticles (e.g., those described in U.S. Patent No. 4,503,169, which are incorporated herein by reference in their entirety), low Mohs hardness fillers (e.g., those described in U.S. Patent No. 5,695,251, which are incorporated herein by reference in their entirety), or combinations thereof. Other suitable fillers are described in U.S. Patent Nos. 6,387,981; 6,572,693; International Publications WO 01 / 30305; WO 01 / 30306; WO 01 / 30307; and WO 03 / 063804 (each of which is incorporated herein by reference in its entirety). Suitable nanofillers are described in U.S. Patent Nos. 7,090,721; 7,090,722; 7,156,911; and U.S. Patent Publication No. 2005 / 0256223 (each of which is incorporated herein by reference in its entirety).

[0126] In some embodiments, based on the weight of the high-viscosity adhesive composition, the high-viscosity adhesive composition may contain one or more fillers present in a total amount of about 1% to about 85% by weight. For example, the high-viscosity adhesive composition may contain one or more fillers present in a total amount of values ​​in the range of about 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, or 85% by weight, or between any of the foregoing values ​​(e.g., between about 50 and about 75, between about 25 and about 60, etc.). In some embodiments, the high-viscosity adhesive composition may contain silane-treated glass, silane-treated quartz, silane-treated silica, or combinations thereof.

[0127] In some embodiments, the low-viscosity adhesive composition may comprise one or more fillers present in a total amount from about 0% to about 50% by weight. For example, the low-viscosity adhesive may comprise one or more fillers present in a total amount of values ​​in the range 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 any of the foregoing values ​​(e.g., between about 1 and about 5, between about 2 and about 3, etc.). In some embodiments, the low-viscosity adhesive composition may comprise silane-treated ceramics, silane-treated silica, titanium dioxide, or combinations thereof.

[0128] Methods for installing orthodontic appliances

[0129] In various embodiments, a method for placing an orthodontic appliance onto a tooth surface is described. The method may include providing the orthodontic appliance described herein; contacting the orthodontic appliance with a tooth surface; applying pressure to the orthodontic appliance to press a hardenable adhesive layer against the tooth surface; and hardening the hardenable adhesive layer to form a hardened adhesive.

[0130] In some implementations, the method may further include applying one or more orthodontic appliances to a prefabricated tray before bringing the orthodontic appliance into contact with the tooth surface. The prefabricated tray may be a custom replica of the subject's teeth and can help to accurately place the orthodontic appliance onto the subject's teeth. This technique is often referred to as indirect bonding.

[0131] In some embodiments, when pressure is applied to the orthodontic appliance, the low-viscosity adhesive composition may extend beyond the base periphery to form 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 from the tooth surface that has extended beyond the base periphery. Removal of the low-viscosity adhesive composition may include brushing, wiping, picking up, scraping, rinsing, or a combination thereof. In some embodiments, it is not necessary to remove the minimum roughness.

[0132] In many embodiments, when pressure is applied to the orthodontic appliance, the high-viscosity adhesive composition can at least partially fill the gap between the base and the tooth surface. In some embodiments, when pressure is applied to the orthodontic appliance, the high-viscosity adhesive composition can cover about 50% to about 100% of the total base area. For example, the high-viscosity adhesive composition can cover about 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 100% of the total base area, or values ​​within the range of any of the foregoing values ​​(e.g., between about 75% and about 95%, between about 80% and about 90%, etc.). The contours of the tooth surface (e.g., molars, canines, premolars, etc.) may not match the contours of the base surface. Depending on the base area covered when pressure is applied to the tooth surface, the high-viscosity adhesive composition can be used to at least partially fill any gap between the tooth surface and the base surface. The base coverage can be varied depending on the selection of the thickness and volume of the high-viscosity adhesive composition used.

[0133] In many embodiments, the high-viscosity adhesive composition may not extend beyond the base perimeter by more than 0.2 mm when pressure is applied to the orthodontic appliance and when the hardenable adhesive layer hardens. The high-viscosity adhesive composition may extend beyond the base perimeter by values ​​in mm ranging from 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, or any of the foregoing values ​​(e.g., between about 0 and about 0.10, between about 0.04 and about 0.14, etc.).

[0134] In some embodiments, the curing provides an adhesive strength of at least 5.0 MPa, as measured by the adhesive strength test described herein. In some embodiments, the curing provides an adhesive strength in MPa 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, or in any of the foregoing values ​​(e.g., between about 8.0 and about 15.0, between about 10.0 and about 20.0, etc.).

[0135] In some embodiments, the method may further include pretreating the tooth surface with the following fluoride composition before bringing the orthodontic appliance into contact with the tooth surface.

[0136] Fluoride pretreatment

[0137] In some embodiments, the fluoride composition may comprise:

[0138] 1) A fluoride-releasing composition that effectively releases fluoride onto the tooth surface, a cross-linked polyacid polymer, a polyvalent cationic salt, a pharmaceutically acceptable buffer, and water;

[0139] 2) A silver fluoride composition comprising a silver cation source, a fluoride anion source, an iodide or thiocyanate anion source, and water; and a curable resin composition comprising at least one (meth)acrylate monomer. Or

[0140] 3) Zinc carboxylate, an amine ligand, a fluoride anion source for effectively providing fluoride in an amount of at least 4% by weight relative to 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.

[0141] In some embodiments, the method may further include pretreating the tooth surface with the fluoride composition described in 1) above. Further details regarding the fluoride composition and the method for pretreating the tooth surface can be found in WO 2019 / 048962, which is incorporated herein by reference in its entirety.

[0142] In some embodiments, the method may further include pretreating the tooth surface with the fluoride composition described in 2) above. Further details regarding the fluoride composition and the method for pretreating the tooth surface 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.

[0143] In some embodiments, the method may further include pretreating the tooth surface with the fluoride composition described in 3) above. Further details regarding the fluoride composition and the method for pretreating the tooth surface can be found in U.S. Provisional Patent Application No. 62 / 955,975, which is incorporated herein by reference in its entirety.

[0144] Methods for preparing orthodontic appliances

[0145] In various embodiments, a method for preparing the orthodontic appliance described herein is described. The method may include providing a base and forming a curable adhesive layer by applying a high-viscosity adhesive composition to a first region of the base and applying a low-viscosity adhesive composition to a second region of the base, wherein the second region at least partially surrounds the first region.

[0146] In some embodiments, the formation of the curable adhesive layer may include first applying a high-viscosity adhesive composition to a first region of the substrate, followed by applying a low-viscosity adhesive composition to a second region of the substrate.

[0147] In some embodiments, applying one or more of the high-viscosity adhesive composition and the low-viscosity adhesive composition may include extrusion.

[0148] In some embodiments, applying one or more of a high-viscosity adhesive composition and a low-viscosity adhesive composition may include additive manufacturing practices.

[0149] 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 clinic.

[0150] 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.

[0151] In some embodiments, the method may also include shaping one or more of the high-viscosity adhesive composition and the low-viscosity adhesive composition, or otherwise removing excess adhesive from the base.

[0152] In some implementations, the method may also include packaging the orthodontic appliance in the packaging described herein.

[0153] kit

[0154] Use the kit

[0155] In various embodiments, a kit is described. The kit may include the orthodontic appliance described herein and a set of instructions to guide the user in performing the steps described herein to place the orthodontic appliance onto the tooth surface.

[0156] In some embodiments, the kit may also include packaging for housing the orthodontic appliance. In some embodiments, the orthodontic appliance may be suspended within the packaging. The packaging may be in the form of a blister pack. The packaging may also include mounting elements for attaching the orthodontic appliance. The mounting elements secure the orthodontic appliance, protecting the hardenable adhesive layer from deformation during handling of the packaging. In some embodiments, the orthodontic appliance may be packaged in the packaging described in WO 2019 / 175726, which is incorporated herein by reference in its entirety.

[0157] In some implementations, the kit may include more than one orthodontic appliance.

[0158] Preparation kit

[0159] In one embodiment, a kit is described. The kit may include a base, a container containing the high-viscosity adhesive composition described herein, a container containing the low-viscosity adhesive composition described herein, and a set of instructions instructing a user to perform the steps of the methods described herein to prepare the orthodontic appliance of this disclosure.

[0160] In some implementations, the kit may include more than one base.

[0161] In some embodiments, one or more of the containers may be graduated. Graduated compartments allow the user to vary the desired amount of adhesive composition based on factors such as base size and tooth structure. Graduated compartments also allow the user to apply the adhesive composition from the same container to multiple bases.

[0162] In some embodiments, the kit may also include one or more extrusion devices. In some embodiments, the extrusion devices may be configured to cooperate with the adhesive composition container.

[0163] Example

[0164] While the objects and advantages of this disclosure are further illustrated by the following embodiments, the specific materials and quantities listed in these embodiments, as well as other conditions and details, should not be construed as undue limitation of this disclosure. These embodiments are for illustrative purposes only and are not intended to limit the scope of the appended claims.

[0165] Material :

[0166] HVA1-High Viscosity Adhesive Composition #1: Contains 5% to 15% bisphenol A bis(2-hydroxyethyl ether) dimethacrylate, 5% to 15% bisphenol A diglycidyl ether dimethacrylate, 70% to 80% silane-treated quartz, <2% silane-treated silica, and a camphorquinone initiator system.

[0167] HVA2-High Viscosity Adhesive Composition #2: Contains 5% to 15% of the reaction product of 2-hydroxy-1,2,3-propanetricarboxylic acid and ethyl 2-isocyanate methacrylate, 5% to 15% polyethylene glycol dimethacrylate, 1% to 10% bisphenol A diglycidyl ether dimethacrylate, 35% to 45% silane-treated glass, 35% to 45% silane-treated quartz, 1% to 5% silane-treated silica, and a camphorquinone initiator system.

[0168] 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 from about 20 Pa·s to 100 Pa·s).

[0169] LVA2-Low Viscosity Adhesive Composition #2: Contains 40% to 50% triethylene glycol dimethacrylate, 40% to 50% bisphenol A diglycidyl ether dimethacrylate, 6% silane-treated pyrolytic silica, <5% tetrabutylammonium tetrafluoroborate, <0.5% titanium dioxide, <0.05% rose red dye, and an initiator system based on camphorquinone, tertiary amines, and iodonium salts (viscosity approximately 0.5 Pa·s to 5 Pa·s).

[0170] LVA3 - Low viscosity adhesive composition #3: comprising 15% to 25% 2-hydroxyethyl methacrylate, 15% to 25% bisphenol A diglycidyl ether dimethacrylate, 5% to 15% decamethyl dimethacrylate, 1% to 10% methacryloyloxydecyl phosphate, <2% dimethylaminoethyl methacrylate, 1% to 5% copolymer of acrylic acid and itaconic acid, 5% to 15% silane-treated silica, 10% to 15% ethanol, 10% to 15% water and camphorquinone initiator system (viscosity about 0.1 Pa·s to 1 Pa·s).

[0171] The nonwoven mat used for comparison is a compressible material made of polypropylene with a single fiber having a diameter of about 6 micrometers.

[0172] Viscosity measurement

[0173] The viscosity of the high-viscosity adhesive was tested using a controlled strain rheometer (model ARG2, TA Instruments, Eden Prairie, MN). The adhesive sample was placed between two parallel plates (8 mm diameter) with a 0.15 mm gap. The viscosity was measured at 0.01 s⁻¹. -1 up to 10s-1 Viscosity was measured at 25°C in 23 logarithmically spaced shear rate steps. Before measurement, the sample was subjected to shear rate conditions for 10 seconds. -1 Pre-shear for 3 minutes and then equilibrate at 25°C for 5 minutes.

[0174]

[0175] The viscosity of the low-viscosity adhesive was tested using a controlled strain rheometer (model ARG2, TA Instruments, Eden Prairie, MN). The adhesive sample was placed between two parallel plates (40 mm in diameter) with a 0.50 mm gap. The viscosity was measured at 0.01 s⁻¹. -1 up to 200s -1 Viscosity was measured at 25°C in 23 logarithmically spaced shear rate steps. Before measurement, the sample was subjected to shear rate conditions for 10 seconds. -1 Pre-shear for 3 minutes and then equilibrate at 25°C for 5 minutes.

[0176]

[0177] Comparative Example CE1: A bracket having a high-viscosity adhesive composition #1 (HVA1)

[0178] Comparative Example 1 is a commercially available product with APC. TM II. 3M Adhesive Pre-coating TM SmartClip TM The SL3 self-binding tray (catalog number 3004-301) is available from 3M Company of St. Paul, MN, USA. APC TM II adhesive is a high-viscosity paste adhesive, known as HVA1.

[0179] Comparative Example CE2: A bracket containing only high-viscosity adhesive composition #2 (HVA2)

[0180] Comparative Example 2 is a commercially available product with APC. TM PLUS Adhesive Pre-coated SmartClip TM SL3 (catalog number 5004-301) is commercially available from 3M Company of St. Paul, MN, USA. (APC) TM PLUS adhesive is another type of high-viscosity paste adhesive called HVA2.

[0181] Comparative Example CE3: A bracket containing only a low-viscosity adhesive composition (LVA1)

[0182] Comparative Example 3: A commercially available orthodontic bracket, SmartClip, was coated with a low-viscosity adhesive (LVA1) described below. TM It is prepared from the base of SL3 (3M catalog number 004-301).

[0183] Example Ex.1: A high-viscosity adhesive composition #1 (HVA1) surrounded by a low-viscosity adhesive (LVA1) bracket

[0184] Example 1 modifies a commercially available material with APC from Comparative Example 1. TM II. 3M Adhesive Pre-coating TM SmartClip TM SL3 self-binding brackets (catalog number 3004-301) are prepared by removing the high-viscosity paste adhesive (HVA1) around the base of the bracket using a razor blade, leaving APC-coated brackets. TM II. The inner central portion of the bracket base is then coated with adhesive. A low-viscosity adhesive (LVA1) is then applied to the remaining inner portion of the bracket base surrounding HVA1. The low-viscosity adhesive (LVA1) used is described below. The weight of HVA1 is 4.2 mg (68 wt%, 54 vol%), and the weight of LVA1 is 2.0 mg (32 wt%, 46 vol%).

[0185] Example Ex.2: A high-viscosity adhesive composition #2 (HVA2) surrounded by a low-viscosity adhesive (LVA1). bracket

[0186] Example 2 modified the commercially available product of Comparative Example 2, which has APC TM PLUS Adhesive Pre-coated SmartClip TM Prepared using SL3 (catalog number 5004-301). The high-viscosity paste-like adhesive (HVA2) surrounding the bracket base is removed using a razor blade, leaving APC-like material. TM The inner central portion of the bracket base is treated with PLUS adhesive. Then, a low-viscosity adhesive (LVA1) is applied to the bracket base surrounding the remaining inner portion of HVA2. The low-viscosity adhesive (LVA1) used is described below. The weight of HVA2 is 4.2 mg (68 wt%, 54 vol%), and the weight of LVA1 is 2.0 mg (32 wt%, 46 vol%).

[0187] Adhesion process

[0188] Bovine teeth were cleaned and partially embedded in a circular polymethyl methacrylate (PMMA) disc, exposing the labial tooth surfaces. The teeth were prophied, etched with TRANSBOND Plus self-etching primer (SEP) (available from 3M, catalog number 712-090), and primed for 3 to 5 seconds, followed by air drying for 3 seconds. The pre-coated brackets were then bonded to the bovine teeth. When placing the brackets onto the teeth, Examples 1-2 (using LVA in the outer area) and Comparative Example 3 (using LVA only) did not require removal of excess adhesive burrs. However, according to standard clinical bracket bonding practice, for Comparative Examples 1-2, which only used HVA paste adhesive, excess adhesive burrs around the bracket base were removed. Ortholux was then applied... TM A light-curing lamp (available from 3M Company, St. Paul, Minnesota, USA; product number 704-460) was used to light-cur all adhesives in Examples 1 to 2 and Comparative Examples 1 to 3; unless otherwise indicated, the curing light irradiated the near-mid surface of the examples for 3 seconds and the far-mid surface for 3 seconds.

[0189] Shear peel bond strength test procedure

[0190] Shear peel bond strength was determined 15 minutes or 16 to 24 hours after bonding using the following standardized method. First, each bonded specimen was mounted in a test fixture attached to a QTEST / 5 mechanical testing machine (MTS Systems Corporation, Eden Prairie, Minn.) using an upward-oriented gingival mating wing (unless otherwise indicated). A standard round wire with a diameter of 0.020 inches (0.051 cm) was looped under the mating wing and attached to the test machine's chuck. After adjusting the initial chuck position to allow the wire to adhere, it was translating upwards at a rate of 0.2 inches per minute (5 mm per minute) until the bracket detached. The maximum force was recorded and divided by the surface area of ​​the measured bracket base to obtain the bond strength. Unless otherwise indicated, each reported bond strength value represents the average of ten repeated measurements.

[0191] Table 1. Adhesive strength of Comparative Examples 1 to 3 and Examples 1 to 2

[0192]

[0193] Compared to commercially available comparative examples CE1 and CE2, Examples Ex.1 and Ex.2 exhibit acceptable adhesive strength. Furthermore, Examples Ex.1 and Ex.2 also have the advantage of not requiring the removal of adhesive burrs, as the peripheral LVA1 adhesive results in a low profile / minimal burrs.

[0194] Example Ex.3: A dental tube having a high-viscosity adhesive #1 (HVA1) surrounded by a low-viscosity adhesive (LVA1).

[0195] Example 3: Modification of a commercially available 3M product: featuring APC TM II Adhesive Pre-coated VictorySeries TM The oral tube (3M catalog number 3066-4082) is used for preparation. Using a razor blade, the high-viscosity paste adhesive (HVA1) already present on the commercially available product is partially removed from the area surrounding the base, leaving an coating of HVA1 (APC). TM The inner central portion of the base of the HVA1 is then applied. A low-viscosity adhesive (LVA1) is then applied to the remaining inner base surrounding the HVA1. The low-viscosity adhesive (LVA1) used is described below. The weight of HVA1 is 9.6 mg (82 wt%, 72 vol%), and the weight of LVA1 is 2.1 mg (18 wt%, 28 vol%).

[0196] Comparative Example CE4: Oral tube with high viscosity adhesive #1 (HVA1)

[0197] Comparative Example 4 is a commercially available 3M product: featuring APC TM II Adhesive Pre-coated Victory Series TM Oral tube (3M catalog number 3066-4082). APC present on this product. TM II adhesive is a high-viscosity paste adhesive, known as HVA1.

[0198] Comparative Example CE5: Oral tube with low viscosity adhesive (LVA1)

[0199] Comparative Example 5: Coating a commercially available 3M Victory Series using only the low-viscosity adhesive (LVA1) described in the Materials section. TM It is prepared from the base of the oral tube (3M catalog number 066-4082).

[0200] Comparative Example CE6: Oral tube with low viscosity adhesive (LVA1) and nonwoven pad

[0201] Comparative Example 6 was prepared in the same manner as Comparative Example CE5, except that the nonwoven pad, which will be described under “Materials”, was also cut into the shape of the base and installed on the base of the oral tube. The nonwoven pad was completely saturated with a low-viscosity adhesive (LVA1) described under “Materials”. During the placement of the orthodontic appliance, the low-viscosity adhesive (LVA1) seeps out to fill the gap between the base of the appliance and the tooth surface and forms a meniscus around the edge of the base, thereby eliminating the need for removal of excess adhesive burrs.

[0202] In the bonding process, Example 3 (using LVA in the external area), Comparative Example 5 (using LVA only), and Comparative Example 6 (LVA and nonwoven pad) did not require removal of adhesive burrs (excess). However, according to standard clinical bracket bonding practice, for Comparative Example 4, which only had HVA paste adhesive, excess adhesive burrs around the base of the oral tube were removed. The curing times for the oral tube examples in Table 2 were 6 seconds for the mesial surface and 6 seconds for the occlusal surface.

[0203] In the shear-peel adhesive strength test procedure, these oral tube examples in Table 2 were debonded using downward-oriented hooks.

[0204] Table 2. Adhesive strength of Comparative Examples 4 to 6 and Example 3

[0205]

[0206] Compared to the commercially available product Comparative Example CE4, Example Ex.3 exhibits acceptable adhesive strength. Furthermore, Example Ex.3 does not require removal of adhesive burrs because the peripheral LVA1 adhesive results in a low profile / minimal burrs.

[0207] Example Ex.4: A low profile of high viscosity adhesive #1 (HVA1) surrounded by a low viscosity adhesive (LVA1). bracket

[0208] Example 4: Modification of commercially available 3M products: featuring APC TM II Adhesive Pre-coated VictorySeries TM The low-profile bracket (3M catalog number 3024-890) was prepared. Using a razor blade, a high-viscosity paste adhesive (HVA1) already present on the commercially available product was partially removed from the area surrounding the base, leaving an inner central portion of the base covered with HVA1. A low-viscosity adhesive (LVA1) was then applied to the remaining inner base surrounding the HVA1. The low-viscosity adhesive (LVA1) used is described below. 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%).

[0209] Vertical flow test

[0210] Five replicate samples of Example 4 were prepared and the vertical flow of the adhesive was tested. The tray was positioned so that the base was vertical (90 degrees from the horizontal). After 6 hours at room temperature, the profile of the Example 4 tray was observed. No flow of the adhesive (HVA1 or LVA1) was observed; the thickness of the adhesive at the top and bottom of the tray did not change. The Example 4 tray was then subjected to 40°C for 5 minutes (also in a vertical position). Again, no (undesirable) adhesive flow was observed. In addition, the viscosity difference between HVA1 and LVA1 was large enough that they remained separate and did not mix.

[0211] Comparative Example 7: Low Profile Tray with High Viscosity Adhesive #1 (HVA1)

[0212] Comparative Example 7 is a commercially available 3M product: featuring APC TM II Adhesive Pre-coated Victory Series TM Low-profile bracket (3M catalog number 3024-890). APC present on this product. TM II adhesive is a high-viscosity paste adhesive, known as HVA1.

[0213] Comparative Example 8: Low Profile Tray with Low Viscosity Adhesive #1 (LVA1)

[0214] Comparative Example 8: Victory Series commercially available orthodontic brackets were coated with the low-viscosity adhesive (LVA1) described in the Materials section below. TM It is prepared using the base of Low Profile (3M catalog number 024-890).

[0215] In the bonding procedure, Example 4 (using LVA in the outer / second region) and Comparative Example 8 (using LVA only) did not require removal of adhesive burrs (excess). However, according to standard clinical bracket bonding practice, for Comparative Example 7, which only used HVA paste adhesive, excess adhesive burrs around the bracket base were removed. In the shear peel bond strength test procedure, examples of this type of bracket in Table 3 were debonded using downward-oriented gingival wings.

[0216] Table 3. Adhesive strength of Comparative Examples 7 to 8 and Example 4

[0217]

[0218] Compared to the commercially available product Comparative Example CE7, Example Ex.4 exhibits acceptable adhesive strength. Furthermore, Example Ex.4 does not require removal of adhesive burrs because the peripheral LVA1 adhesive results in a low profile / minimal burrs.

[0219] Example Ex.5: A high-viscosity adhesive composition #1 (HVA1) surrounded by a low-viscosity adhesive (LVA2). Low profile bracket

[0220] Example 5: Modification of commercially available 3M products with APC TM II Adhesive Pre-coated VictorySeries TM The low-profile bracket (3M catalog number 3024-875) was prepared. Using a razor blade, a high-viscosity paste adhesive (HVA1) already present on the commercially available product was partially removed from the area surrounding the base, leaving an inner central portion of the base covered with HVA1. A low-viscosity adhesive (LVA2) was then applied to the remaining inner base surrounding the HVA1. The weight of HVA1 was 4.0 mg (68 wt%, 55 vol%), and the weight of LVA2 was 1.9 mg (32 wt%, 45 vol%).

[0221] Comparative Example 9: Low-profile bracket with high-viscosity adhesive composition #1 (HVA1)

[0222] Comparative Example 9 is a commercially available 3M product: APC II Victory Series TM Low-profile bracket (3M catalog number 3024-875). APC present on this product. TM II adhesive is a high-viscosity paste adhesive, known as HVA1.

[0223] Comparative Example 10: Low-profile bracket with low-viscosity adhesive composition #2 (LVA2)

[0224] Comparative Example 10 involved coating a commercially available orthodontic bracket, Victory Series, with 3M CLINPRO sealant, which is available from 3M Company in St. Paul, Minnesota, USA. TM It is prepared using the base of Low Profile (3M catalog number 024-875 or 024-775). 3M CLINPRO sealant is a low-viscosity adhesive called LVA2.

[0225] In the bonding process, Example 5 (using LVA in the outer / second area) and Comparative Example 10 (using LVA only) did not require removal of adhesive burrs (excess). However, according to standard clinical bracket bonding practice, for Comparative Example 9, which only had HVA paste adhesive, excess adhesive burrs around the base of the bracket were removed. In Table 4, the reported shear peel bond strength test values ​​represent the average of ten repeated measurements in Comparative Example 9 or the average of eight repeated measurements in Examples 5 and Comparative Example 10.

[0226] Table 4. Adhesive strength of Comparative Examples 9 to 10 and Example 5

[0227]

[0228] Compared to the commercially available product Comparative Example CE9, Example Ex.5 exhibits acceptable adhesive strength. Furthermore, Example Ex.5 does not require removal of adhesive burrs because the peripheral LVA2 adhesive results in a low profile / minimal burrs.

[0229] Example Ex. 6: A high-viscosity adhesive composition #1 (HVA1) surrounded by a low-viscosity adhesive (LVA3). Low profile bracket

[0230] Example 6: Modification of commercially available 3M products with APC TM II Adhesive Pre-coated VictorySeries TM The low-profile bracket (3M catalog number 3024-890) was prepared. Using a razor blade, a high-viscosity paste adhesive (HVA1) already present on the commercially available product was partially removed from the area surrounding the base, leaving the inner center portion of the base covered with HVA1. A low-viscosity adhesive (LVA3) was then applied to the remaining inner base surrounding the 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 applying LVA3, the solvent was dried for 5 seconds using an air syringe. Etching and priming with TRANSBOND Plus Self-Etching Primer (SEP) were omitted in the bonding process.

[0231] Comparative Example 11: Low-profile bracket with high-viscosity adhesive composition #1 (HVA1)

[0232] Comparative Example 11 is a commercially available 3M product: the Victory Series with APC II adhesive pre-coating. TM Low-profile bracket (3M catalog number 3024-890). APC present on this product. TM II adhesive is a high-viscosity paste adhesive, known as HVA1.

[0233] In the bonding procedure, Example 6 does not require removal of adhesive burrs (excess) (using LVA in the outer / secondary area). However, according to standard clinical bracket bonding practice, for Comparative Example 11, which only has HVA paste adhesive, excess adhesive burrs around the base of the bracket are removed. In the shear peel bond strength test procedure, examples of this type of bracket in Table 5 (the same as those used in Table 3) are debonded with downward-oriented gingival wings.

[0234] Table 5. Adhesion strength of Comparative Example 11 and Example 6

[0235]

[0236] Compared to the commercially available product Comparative Example CE11, Example Ex.6 exhibits acceptable adhesive strength. Due to the acidic properties of the low-viscosity adhesive LVA3, Example Ex.6 eliminates the need for etching / priming. Furthermore, Example Ex.6 does not require burr removal because the peripheral low-viscosity adhesive LVA3 results in a low profile / minimal burr.

[0237] Equivalent solution

[0238] Those skilled in the art will recognize or be able to determine numerous equivalents of the specific embodiments described herein using only conventional experiments. Such equivalents are intended to be included within the scope of the following claims.

Claims

1. A malocclusion correction appliance, the malocclusion correction appliance comprising: Base; as well as A hardenable adhesive layer disposed on the base. The curable adhesive layer includes a first region and a second region, each of the first region and the second region being on the base. The first zone comprises a high viscosity adhesive composition, characterized by a viscosity of 100 Pa s to 1 500 000 Pa s at 25°C under a shear rate of 1 s -1 1 s-1 1 s-1 The second region comprises a low-viscosity adhesive composition, characterized in that it reacts at 25°C for 1 second. -1 It has a viscosity ranging from 0.1 Pa·s to 100 Pa·s at shear rates. The first region is at least partially surrounded by the second region. The first region and the second region are configured to contact the tooth surface. The low-viscosity adhesive composition has a thickness of 0.06 mm to 0.16 mm, and The viscosity of the high-viscosity adhesive composition is greater than that of the low-viscosity adhesive composition.

2. The orthodontic appliance of claim 1, wherein when the hardenable adhesive layer is pressed against the tooth surface, the high-viscosity adhesive composition does not extend beyond the base by more than 0.2 mm.

3. The orthodontic appliance of claim 1, wherein the high-viscosity adhesive composition comprises filler present in an amount of 50% to 86% by weight relative to the weight of the high-viscosity adhesive.

4. The orthodontic appliance according to claim 1, wherein the high-viscosity adhesive composition comprises one or more unsaturated monomers having or not having acid functional groups, or combinations thereof.

5. The orthodontic appliance according to claim 1, wherein the high-viscosity adhesive composition is a paste.

6. The orthodontic appliance of claim 1, wherein the high-viscosity adhesive composition comprises a filler selected from pyrolytic silica, silane-treated glass, silane-treated quartz, silane-treated silica, and combinations thereof.

7. The orthodontic appliance of claim 1, wherein the high-viscosity adhesive composition is characterized by having a viscosity of at least 7000 dynes / cm at 28°C. 2 The static yield stress.

8. The orthodontic appliance of claim 1, wherein the high-viscosity adhesive composition has a thickness of 0.38 mm to 1.2 mm.

9. The orthodontic appliance of claim 1, wherein, when viewed from a cross-sectional side view of the base, the shape of the hardenable adhesive layer presents a Gaussian curve, a triangle, or a trapezoid.

10. The orthodontic appliance of claim 1, wherein the high-viscosity adhesive composition is circular, polygonal, or quadrilateral when viewed from a direction perpendicular to the base.

11. The orthodontic appliance of claim 1, wherein the volume of the high-viscosity adhesive composition is 40% to 85% of the volume of the hardenable adhesive layer.

12. The orthodontic appliance of claim 1, wherein the high-viscosity adhesive composition extends over 20% to 50% of the total area of ​​the base.

13. The orthodontic appliance of claim 1, wherein the low-viscosity adhesive composition is a flowable solution or a flowable suspension.

14. The orthodontic appliance of claim 1, wherein the low viscosity adhesive composition has a filler loading of 0% to 50% by weight.

15. The orthodontic appliance of claim 1, wherein the low-viscosity adhesive composition comprises a filler selected from pyrolytic silica, silane-treated glass, silane-treated quartz, silane-treated silica, and combinations thereof.

16. The orthodontic appliance of claim 1, wherein the low viscosity adhesive composition is characterized by its flowability, wherein the thickness difference between the top and bottom of the adhesive composition, as determined by a vertical flow test, is less than 15%.

17. The orthodontic appliance of claim 1, wherein the low-viscosity adhesive composition is ring-shaped when viewed from a direction perpendicular to the base.

18. The orthodontic appliance according to claim 17, wherein the ring is a rectangular ring.

19. The orthodontic appliance of claim 1, wherein the low-viscosity adhesive composition extends over 50% to 80% of the total area of ​​the base.

20. The orthodontic appliance of claim 1, wherein the low-viscosity adhesive composition comprises one or more unsaturated monomers having or not having acid functional groups, or combinations thereof.

21. The orthodontic appliance according to claim 1, wherein the high-viscosity adhesive composition is characterized in that it reacts at 25°C for 1 second. -1 Viscosities from 1500 Pa·s to 5000 Pa·s at shear rates.

22. The orthodontic appliance of claim 1, wherein the low-viscosity adhesive composition is characterized in that it reacts at 25°C for 1 second. -1 Viscosities from 0.1 Pa·s to 10 Pa·s at shear rates.

23. The orthodontic appliance of claim 1, wherein the viscosity of the high-viscosity adhesive composition and the low-viscosity adhesive composition differs by at least 10 times.

24. The orthodontic appliance of claim 1, wherein the maximum thickness of the high-viscosity adhesive composition is greater than the average thickness of the low-viscosity adhesive composition.

25. The orthodontic appliance according to claim 1, wherein the orthodontic appliance comprises the base and the hardenable adhesive layer.

26. The orthodontic appliance according to claim 1, wherein the orthodontic appliance does not have a compressible pad.

27. A non-therapeutic method for placing an orthodontic appliance onto a tooth surface, the method comprising: Provide a malocclusion correction appliance according to any one of claims 1 to 26; The orthodontic appliance is brought into contact with the tooth surface; Pressure is applied to the orthodontic appliance to press the hardenable adhesive layer against the tooth surface; and The hardenable adhesive layer is hardened to form a hardened adhesive.

28. The non-treatment method according to claim 27, wherein the tooth surface is the surface of a molar, canine, or premolar.

29. The non-treatment method of claim 27, wherein when pressure is applied to the orthodontic appliance, the low-viscosity adhesive composition extends beyond the periphery of the base and forms a concave meniscus relative to the point defined by the appliance-tooth junction.

30. The non-treatment method of claim 27, wherein when pressure is applied to the orthodontic appliance, the high-viscosity adhesive composition fills the gap between the base and the tooth surface.

31. The non-treatment method according to claim 27, wherein the high-viscosity adhesive composition does not extend beyond the periphery of the base by more than 0.2 mm after pressure is applied and the material is hardened.

32. The non-treatment method according to claim 27, wherein when the adhesive layer is pressed against the tooth surface, the high-viscosity adhesive composition covers 50% to 100% of the base.

33. The non-treatment method according to claim 27, wherein the hardened adhesive bonding the orthodontic appliance to the tooth surface, as measured by an adhesive strength test, has an adhesive strength of at least 5.0 MPa.

34. The non-treatment method of claim 27, wherein the hardening comprises applying light to the hardenable adhesive layer for a period of time.

35. The non-treatment method of claim 27, further comprising pretreating the tooth surface with a fluoride composition before bringing the orthodontic appliance into contact with the tooth surface. The pretreatment includes contacting the fluoride composition with the tooth surface. The fluoride composition comprises: A fluoride-releasing composition that effectively releases fluoride onto the tooth surface; Cross-linked polyacid polymers; Polyvalent cation salts; Pharmaceutically acceptable buffers; and water.

36. The non-treatment method of claim 27, further comprising pretreating the tooth surface with a fluoride composition before bringing the orthodontic appliance into contact with the tooth surface. The pretreatment includes contacting the fluoride composition with the tooth surface. The fluoride composition comprises: Silver fluoride composition, said silver fluoride composition comprising: Silver cation source; Fluoride anion source; Iodide or thiocyanate anion source; and Water; and A curable resin composition comprising: At least one (meth)acrylate monomer.

37. The non-treatment method of claim 27, further comprising pretreating the tooth surface with a fluoride composition. The pretreatment includes contacting the fluoride composition with the tooth surface. The fluoride composition comprises: Zinc carboxylate; Amine-containing ligands; A fluoride anion source for the fluoride is effectively provided in an amount of at least 4% by weight relative to the weight of the fluoride composition; and water, in: The fluoride composition has a pH of at least 8, and The fluoride composition is a homogeneous solution at a temperature of 20°C to 25°C.

38. A kit comprising: Orthodontic appliance according to any one of claims 1 to 26; and A set of instructions that guides the user in placing the orthodontic appliance onto the tooth surface.

39. The kit of claim 38, further comprising blister packaging.

40. The kit of claim 38, further comprising packaging, wherein the orthodontic appliance is suspended within the packaging.

41. A method for preparing a malocclusion appliance according to any one of claims 1 to 26, the method comprising: Provide the base; as well as A hardenable adhesive layer is formed on the base, the formation comprising: The high-viscosity adhesive composition is applied to a first region of the base, and The low-viscosity adhesive composition is applied to the second region of the base. The first region is at least partially surrounded by the second region.

42. A kit comprising: Base; A container containing a high-viscosity adhesive composition; A container containing a low-viscosity adhesive composition; and A set of instructions that guides the user to perform the steps of the method according to claim 41.

43. The kit of claim 42, further comprising one or more containers containing one or more fillers.

44. The kit of claim 43, wherein the instruction manual further instructs the user to combine one or more of the high-viscosity adhesive composition and the low-viscosity adhesive composition with one or more fillers.

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