Adhesive orthodontic assemblies and bonding methods

Abstract

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

Description

[Background technology]

[0001] Crooked jaws and abnormally positioned 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 fixed to the tooth surface, excess adhesive, often used to fill the gap between the appliance base and the tooth surface, seeps beyond the periphery of the appliance base. This seeped adhesive, known in the art as "flash," is manually removed by the practitioner before it hardens, but this procedure is time-consuming, and incomplete removal can cause structural problems. For example, accidental movement of the appliance during flash removal can negatively affect the reliability of the bond. Furthermore, incomplete removal of excess adhesive is not only uncomfortable for the patient but can also promote bacterial accumulation, which can ultimately degrade the underlying tooth structure, leading to demineralization and discoloration.

[0002] Cinader had previously developed a strategy to reduce burrs (see U.S. Patent No. 10,492,890). Cinader found that incorporating a compressible mat into the instrument base and immersing the mat in an unfilled or slightly filled adhesive was effective in allowing the adhesive to leach out and fill the gap between the instrument base and the tooth surface, forming a meniscus around the edge of the instrument when the instrument is secured, thereby eliminating the need to deburr excess adhesive.

[0003] Despite progress, there remains a continuing interest in developing tools that bond efficiently, avoid burr removal, and reduce manufacturing costs. [Overview of the Initiative]

[0004] In one embodiment, an orthodontic appliance is described. The orthodontic appliance includes a base and a curable adhesive layer disposed on the base. The curable adhesive layer includes a first region and a second region, the first region being at least partially surrounded by the second region, and the first and second regions are configured to be in contact with the surface of a tooth. The first region is 1s -1 The present invention comprises a high-viscosity adhesive composition characterized by a viscosity of 10 Pa·s to approximately 1,500,000 Pa·s at a shear rate, the second region being 1s -1 The present invention includes low-viscosity adhesive compositions characterized by a viscosity of approximately 0.1 Pa·s to approximately 100 Pa·s at a shear rate. High-viscosity adhesive compositions have a higher viscosity than the low-viscosity adhesive compositions.

[0005] One embodiment describes a method for fixing an orthodontic appliance to the surface of a tooth. This method includes preparing the orthodontic appliance described herein, bringing the orthodontic appliance into contact with the surface of a tooth, applying pressure to the orthodontic appliance so that a curable adhesive layer is compressed against the surface of the tooth, and curing the curable adhesive layer to form a curable adhesive.

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

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

[0008] In one embodiment, a kit is described. The kit includes a base, a high-viscosity adhesive composition described herein, a low-viscosity adhesive composition described herein, and a set of instructions instructing the user to carry out the steps described herein for manufacturing the orthodontic appliance of the present disclosure. [Brief explanation of the drawing]

[0009] [Figure 1A] This is a side view of an orthodontic appliance of the present disclosure having an uncompressible curable adhesive layer. [Figure 1B] This is a side view of an orthodontic appliance of the present disclosure having a curable adhesive layer in a compressed state. [Figure 1C] This is a bottom view of an orthodontic appliance of the present disclosure having an uncompressed curable adhesive layer. [Figure 1D] This is a bottom view of an orthodontic appliance of the present disclosure having a curable adhesive layer in a compressed state. [Figure 1E] This is a top view of the orthodontic appliance of the present disclosure having an uncompressed curable adhesive layer. [Figure 1F] This is a top view of the orthodontic appliance of the present disclosure having a curable adhesive layer in a compressed state. [Figure 2A] This is a cross-sectional side view of an orthodontic appliance of the present disclosure having an uncompressible curable adhesive layer. [Figure 2B] This is a cross-sectional side view of an orthodontic appliance of the present disclosure having a curable adhesive layer in a compressed state. [Figure 3A] This is a cross-sectional side view of an orthodontic appliance of the present disclosure having a curable adhesive layer in an uncompressed state. [Figure 3B] This is a cross-sectional side view of an orthodontic appliance of the present disclosure having a curable adhesive layer in a compressed state. [Figure 4A] This is a cross-sectional side view of an orthodontic appliance of the present disclosure having an uncompressible curable adhesive layer. [Figure 4B] This is a cross-sectional side view of an orthodontic appliance of the present disclosure having a curable adhesive layer in a compressed state. [Figure 5A] This is a side view of an equivalent orthodontic appliance, not subject to this disclosure, having a compressible mat. [Figure 5B] This is a side view of an equivalent orthodontic appliance, not subject to this disclosure, having a compressible mat. [Modes for carrying out the invention]

[0010] This disclosure relates to orthodontic appliances that use different adhesive arrangements to provide superior tooth adhesion while simultaneously eliminating the need for burr removal.

[0011] Using adhesive to bond orthodontic appliances to teeth is a common method. The adhesive is typically coated onto the bonding surface of the appliance. After the appliance is attached to the teeth, the adhesive hardens to create a strong bond. A suitable orthodontic adhesive must provide high strength to maintain consistent and secure adhesion between the appliance and the teeth throughout the course of orthodontic treatment, which can last for more than two years. However, the adhesive bond should not be so strong that it becomes excessively difficult to remove the appliance at the end of treatment. An ideal adhesive should also have an appropriate degree of tackiness and viscosity to avoid drift after the appliance is placed on the teeth and to facilitate handling by the orthodontist. Conventional orthodontic adhesives are polymerizable resins filled with a considerable amount of hard filler, such as quartz or silica filler. Since the bonding procedure requires the adhesive to act as a gap filler (i.e., occupying all the space between the tooth surface and the appliance), excess adhesive is usually applied to the bonding surface of the appliance. In other words, if there is a mismatch between the tooth surface and the bonding surface of the instrument, the adhesive fills the space between the instrument and the tooth, maintaining adhesion and preventing the formation of gaps that can trap food and accumulate plaque. Once the instrument is fully fixed to the tooth, excess adhesive seeps out along the base. This excess adhesive, known as "burr," is manually removed by the practitioner before the adhesive hardens. The presence of adhesive burrs can be detrimental. Removing burrs is time-consuming, especially since accidental movement of the instrument can negatively affect adhesive reliability. Furthermore, incomplete removal of excess adhesive is problematic. Incomplete removal is particularly common in posterior areas where access is limited and behind hooked instruments. If not completely removed, excess adhesive provides a site for bacterial accumulation. Such bacteria can attack and break down the underlying tooth structure, potentially leading to tooth demineralization and discoloration. Additionally, exposed adhesive surfaces are susceptible to contamination by food or beverages. Ultimately, the presence of hard fillers in the adhesive composition makes it difficult to remove the adhesive once it has hardened, especially in the case of indirect bonding, which can be unpleasant for the patient.

[0012] Adhesives with a sufficient amount of filler provide better tooth adhesion, but it is understood that burr removal is necessary. The filler increases flow resistance (i.e., increases viscosity), which is at least partly due to the formation of gaps, allowing more adhesive to remain in contact with the appliance-tooth junction (i.e., filling the gap between the orthodontic appliance and the tooth surface). Filling this gap is especially important for tooth structures with considerable curvature, irregularly shaped teeth, molars, etc. However, the viscous adhesive that seeps out (burr) takes on a convex shape that must be removed, and burrs that are not removed are prone to contamination and create an environment for the accumulation of bacteria that cause tooth decay.

[0013] It is further understood that adhesives containing little to no filler result in softer adhesives (i.e., lower viscosity) that are represented by concave, meniscus-like shapes (not considered "burrs") that may not need to be removed. However, low-viscosity adhesives may not adequately fill the gaps between orthodontic appliances and tooth structures, resulting in poor tooth adhesion, which may lead to appliance displacement or "drift," and even complete adhesion failure. Furthermore, poorly filled gaps can contain food particles that can contribute to tooth decay. Previous solutions for adequately filling the gaps between orthodontic appliances and tooth structures while reducing burrs with low-viscosity adhesives have been achieved by using compressible mats, such as those described in U.S. Patent No. 10,492,890.

[0014] The inventors of this disclosure have discovered that by incorporating a curable adhesive layer having a high-viscosity adhesive composition at least partially surrounded by a low-viscosity adhesive composition, sufficient gap filling is provided while allowing only the low-viscosity adhesive composition to seep out (without requiring burr removal) when fixing orthodontic appliances to the tooth surface. The high-viscosity adhesive composition effectively moves the surrounding low-viscosity adhesive composition, preventing the high-viscosity adhesive from seeping 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. In addition, the adhesive layer does not flow from the base in any orientation over any period of time, allowing for complete assembly and distribution. This ingenious structure ensures excellent adhesive strength without requiring burr removal, avoids the use of compressible mats and associated manufacturing costs, and limits in-chair preparation.

[0015] Figure 1A shows a side view of the orthodontic appliance 100. The orthodontic appliance 100 includes a base 102 and a curable adhesive layer 104 placed thereon. The curable adhesive layer 104 includes a high-viscosity adhesive composition 106 surrounded by a low-viscosity adhesive composition 108. The curable adhesive layer 104 is shown in an uncompressed configuration, i.e., before the orthodontic appliance 100 is pressed against the surface of a tooth (not shown). In one particular embodiment, the orthodontic appliance 100 has a maximum thickness of 0.508 mm and a thickness of 1.24 mm. 3 A high-viscosity composition 106 exists in a volume and covers 24% of the base area, and 1.84 mm with an average thickness of 0.238 mm. 3 It has a low viscosity composition 108 that exists in a volume and covers 76% of the base area.

[0016] Figure 1B shows a side view of the orthodontic appliance 100 in a compressed state, i.e., after the orthodontic appliance 100 has been pressed against the surface of a tooth (not shown). As shown, only the low-viscosity adhesive composition 108 has spread beyond the base 102. In one particular embodiment, the orthodontic appliance 100 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, as described above in Figure 1A.

[0017] Figure 1C shows a bottom view of the orthodontic appliance 100 in its uncompressed state.

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

[0019] Figure 1E shows a top view of the orthodontic appliance 100 in its uncompressed state.

[0020] Figure 1F shows a top view of the compressed orthodontic appliance 100. As shown, only the low-viscosity adhesive composition 108 extends beyond the base 102.

[0021] Figure 2A shows a cross-sectional side view of the orthodontic appliance 200. The orthodontic appliance 200 includes a base 202 and a curable adhesive layer 204 disposed thereon. The curable adhesive layer 204 is shown in an uncompressible configuration. As shown, the high-viscosity adhesive composition 206 has a larger volume than the low-viscosity adhesive 208. In one particular embodiment, the orthodontic appliance 200 has a maximum thickness of 0.508 mm and a thickness of 1.72 mm 3 A high-viscosity composition 206 exists in a volume that covers 32% of the base area, and a layer with a maximum thickness of 0.508 mm and an average thickness of approximately 0.250 mm, totaling 1.41 mm 3 It comprises a low-viscosity composition 208 that exists in volume and covers 68% of the base area.

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

[0023] Figure 3A shows a cross-sectional side view of an orthodontic appliance 300 in an uncompressed state, which is similar to the orthodontic appliance 300 but has a different volume (and thus covered area) of the high-viscosity adhesive composition 306 disposed thereon. In a particular embodiment, the orthodontic appliance 300 has a high-viscosity composition 306 that exists with a volume of 2.67 mm at a maximum thickness of 0.381 mm and covers 67% of the area of the base, and a low-viscosity composition 308 that exists with a volume of 0.46 mm at a maximum thickness of 0.266 mm and an average thickness of 0.133 mm and covers 33% of the area of the base. 3 of the base. 3

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

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

[0026] Figure 4B shows a cross-sectional side view of a compressed orthodontic appliance 400, similar to the orthodontic appliance 200, but with a different area A covered by the high-viscosity adhesive composition 406. In one particular embodiment, the orthodontic appliance 400 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, as described above in Figure 4A.

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

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

[0029] definition As used herein, "about" means ±10 percent of a given value. For example, about 10 means between 9 and 11.

[0030] As used herein, “acidic functional group” refers to a functional group having acidic hydrogen (i.e., a pKa of less than about 5). Organic functional groups, such as -CO2H, -P(O)(OH)2, and -S(O)2OH, are considered “acidic functional groups.”

[0031] As used herein, "alkyl" refers to a monovalent saturated carbon chain, whether linear or branched, for example, a C1 alkyl is methyl (-CH3), a C2 alkyl is ethyl (-CH2CH3), and a C4 alkyl may be butyl (-CH2CH2CH2CH3), sec-butyl (-CH(CH-3)CH2CH3), iso-butyl (-CH2CH(CH3)2), or tert-butyl (-C(CH3)3).

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

[0033] As used herein, "alkyl(alkyl)acrylate" means alkyl acrylate ester (i.e., C(R) 1 )(R 1 )=C(R 2 )C(O)O-alkyl), where R 1 This is optional (for example, -H or C) 1~4 Alkyl), R 2 (is -H), or alkyl-substituted alkyl acrylate ester (i.e., C(R 1 )(R 1 )=C(R 2 )C(O)O-(alkyl), where R 1 This is optional (for example, -H or C) 1~4 Alkyl), R 2 C(R) refers to an alkyl group (for example, methyl ("meth")). A "hydroxy-substituted (alkyl) acrylate" is defined by the formula C(R) 1 )(R 1 )=C(R 2 )C(O)OR 3 This refers to a compound of ), in which R 1 , R 2 , or R 3At least one of them is an alkyl group substituted with -OH. In some cases, (alkyl)acrylates are dimers, e.g., C(R 1 )(R 1 )=C(CH3)C(O)OR 2 OC(O)OC(CH3)=C(R 1 )(R 1 ) may also be, and in the formula, R 2 is a linking group, for example, C 2~8 It is alkylene.

[0034] As used herein, “base” refers to the surface of an orthodontic appliance intended to come into contact with a tooth structure. The base of an orthodontic appliance may be made of metal, plastic, ceramic, or a combination thereof.

[0035] As used herein, "unsaturated" and "unsaturated organic group" refer to olefin units. Olefins are -C(R 1 )=C(R 2 )- and in the formula, R 1 and R 2 is arbitrary, for example, each R 1 H or C 1~6 It is alkyl; each R 2 is -C(O)(C 1~6 Alkyl), -CO2H, -O(C 1~6 Examples include alkyl groups. The term "unsaturated monomer" refers to polymerizable compounds that contain olefin units.

[0036] As used herein, “compressible material” or “compressible mat” refers to any non-adhesive material, particularly porous material, that decreases in volume when compressed. Exemplary compressible materials include foams (e.g., cellulose, glass, polymers), sponges, nonwovens, glass wool, cotton fibers, and cellulose fibers. Further examples of compressible materials are disclosed in U.S. Patent No. 10,492,890 and U.S. Patent No. 9,480,540 and the references cited therein, each of which is incorporated herein by reference in whole. The orthodontic appliances of this disclosure do not have compressible material on their bases.

[0037] As used herein, the phrase "one or more of A and B" or "at least one A and at least one B" means that a 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, this phrase is not intended to mean that a composition must each have at least one A and one B.

[0038] As used herein, “orthodontic appliance” means any device intended to be bonded to a tooth structure, such as orthodontic brackets, buccal tubes, tongue restraints, orthodontic bands, mouth openers, buttons, prefabricated attachments, and cleats.

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

[0040] As used herein, “curing adhesive” refers to a composition comprising a polymer component, with or without a filler, derived from a curing adhesive.

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

[0042] As used herein, “low viscosity adhesive composition” is defined as a composition having one or more monomers that, upon curing, provides a polymerizable adhesive. The properties of the polymerizable components (i.e., monomers) are as follows: alone or in combination with additives, such as fillers. -1 It provides a viscosity of about 1 Pa·s to about 100 Pa·s at a shear rate. Low viscosity adhesive compositions are non-filling or light-filling materials (e.g., dental or orthodontic materials) that can be applied to or bonded to the surface of a tooth or a replica tooth surface. Examples of low viscosity adhesive compositions include dental adhesives, primers (e.g., orthodontic primers), liners, sealants, and coatings. Low viscosity adhesive compositions may be photopolymerizable and / or redox polymerizable.

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

[0044] As used herein, “thickness” as defined with respect to the dimensions defining the placement of 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 the area. “Average thickness” refers to the average of the distances measured over the entire area.

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

[0046] As used herein, “yield stress” is the minimum stress required for a material to flow.

[0047] Orthodontic appliances Various embodiments describe orthodontic appliances. An orthodontic appliance may include a base and a curable adhesive layer disposed on the base. The curable adhesive layer may include a first region and a second region, the first region being at least partially surrounded by the second region, and the first and second regions being configured to contact the surface of a tooth. The first region is 1s -1 The high-viscosity adhesive composition may include a viscosity of approximately 10 Pa·s to approximately 1,500,000 Pa·s at a shear rate, and the second region is 1s -1 The present invention includes low-viscosity adhesive compositions characterized by a viscosity of approximately 0.1 Pa·s to approximately 100 Pa·s at a shear rate. High-viscosity adhesive compositions have a higher viscosity than the low-viscosity adhesive compositions.

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

[0049] In some embodiments, the orthodontic appliance may omit a compressible mat. Compressible mats have been used to fill the gap between the base surface and the tooth structure. Compressible materials and mats manufactured therefrom can be found, for example, in U.S. Patent No. 10,492,890 and U.S. Patent No. 9,480,540, each of which is incorporated herein by reference in whole. For example, compressible mats may include foams, sponges, nonwovens, glass wool, cotton fibers, cellulose fibers, and combinations thereof. In some embodiments, the compressible material may have a thickness of about 0.2 mm to about 1 mm, for example, 0.5 mm. Specific materials include, 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, DWOsborn and AHAmman (Eds.), Marel Dekker, New York, pp. 299-325 (1990), U.S. Patent No. 5,770,636 (Wernsing et al.), and U.S. Patent No. 5,817,704 (Shively et al.); for example, Westerman et al., British Journal of Sports Closed-cell foams are described in Medicine, 36:205-208 (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 whole. For example, a compressible mat may contain or be essentially made of polypropylene.

[0050] Base of orthodontic appliance In some embodiments, the base is approximately 8.0 mm 2 ~about 20mm 2 It may have an area of ​​.

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

[0052] In some embodiments, the base may include a material selected from ceramic, cobalt-chromium, composite materials, gold, plastic, stainless steel, titanium, or a combination thereof.

[0053] Curable adhesive layer In some embodiments, the curable adhesive layer may further contain fillers as described herein. The fillers may be present in a high-viscosity adhesive composition, a low-viscosity adhesive composition, or a combination thereof. In many embodiments, the high-viscosity adhesive composition may contain a greater amount of filler than that 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, with its composition differing in the amount of filler present so as to achieve the viscosities described for 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 contain or are derived from one or more different monomers.

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

[0055] 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 of about 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, or 2.0 mm, or within a range between any of the aforementioned values, for example, about 0.3 to about 0.5 mm, about 0.5 to about 1.6 mm, etc. In some embodiments, the high-viscosity adhesive composition may be present on the substrate with a maximum thickness of about 1.0 mm 3 ~approximately 3.0mm 3 It may exist on the base (in an uncompressed state) in a volume of . For example, the high viscosity adhesive composition may be about 1.0, 1.2, 1.4, 1.6, 1.8, 2.0, 2.2, 2.4, 2.6, 2.8, or 3.0 mm 3 In volume, or within the range of any of the aforementioned values, for example, approximately 1.2 to approximately 1.5 mm 3 Approximately 1.8 to 2.8 mm 3 They may be present on the base, for example.

[0056] 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 low-viscosity adhesive composition may be present on the substrate with a maximum thickness of about 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, or 2.0 mm, or within a range of any of the aforementioned values, for example, about 0.3 to about 0.5 mm, about 0.5 to about 1.6 mm, etc. In some embodiments, the low-viscosity adhesive composition may be present on the substrate with a maximum thickness of about 0.3 mm 3 ~approximately 2.0 mm 3 It may exist on the base (in an uncompressed state) in a volume of . For example, low viscosity adhesive compositions may be present in volumes of approximately 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, and 2.0 mm. 3 In volume, or within the range of any of the aforementioned values, for example, approximately 1.4 to approximately 1.9 mm 3Approximately 0.4 to 0.8 mm 3 They may be present on the base, for example.

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

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

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

[0060] In some embodiments, the total surface area of ​​the base may be covered by a first region (containing a high-viscosity adhesive composition in an uncompressible state) and a second region (containing a low-viscosity adhesive composition in an uncompressible state) in ratios of approximately 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 ratios between any of the aforementioned values, for example, approximately 1:1.6 to approximately 1:2.5, approximately 1:3 to approximately 1:4, etc.

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

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

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

[0064] In some embodiments, at least one of the high-viscosity and low-viscosity adhesives within the curable adhesive layer may further contain 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 contain one or more photoinitiators. The photoinitiators initiate polymerization (curing) of the adhesive composition. Examples of photoinitiators are described in U.S. Patents 5,545,676, 7,674,850, and 7,816,423, and include diaryliodonium salts, metal complex salts, etc. Examples of other polymerization initiators include ketones, such as benzyl, benzoin, acyloin, and acyloin ethers. Specific examples of polymerization initiators include 2,2-dimethoxy-2-phenylacetophenone (i.e., IRGACURE 651) and 2-methoxy-2-phenylacetophenone (Ciba Specialty Chemicals Corp., Tarrytown, NY). In some embodiments, the photoinitiator may be present in the curable adhesive layer in an amount of about 0.01% to about 10% by weight 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 in a range of any of the aforementioned values, for example, about 5.0% to about 8.0% by weight, about 0.1% to about 3.5% by weight, etc.

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

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

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

[0068] In some embodiments, at least one of the high-viscosity and low-viscosity adhesives within the curable adhesive layer may further contain one or more fluoride release agents. Incorporating one or more fluoride release agents into the high-viscosity and / or low-viscosity adhesive compositions allows for the delivery of fluoride to the tooth surface beneath and immediately surrounding the orthodontic appliance, thereby protecting the tooth surface from corrosion. Examples of fluoride release agents include fluoroaluminosilicate glass, inorganic fluoride salts, organofluoride salts, and fluoride-containing complexes. Specific fluoride release agents can be found, for example, in the following disclosures: U.S. Patent No. 3,814,717, U.S. Patent No. 5,332,429, U.S. Patent No. 6,126,922, and International Patent Publication No. 2000 / 69393. In some embodiments, the curable adhesive layer may contain a fluoride release agent present in an amount of about 0.1% to about 85% by weight relative to the weight of the curable adhesive layer. For example, the fluoride release agent may be present in an amount of approximately 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 weight of the curable adhesive layer, or in a range between any of the aforementioned values, for example, approximately 20% to approximately 30% by weight, approximately 45% to approximately 60% by weight, etc.

[0069] Adhesive composition 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 optionally filler described herein. The high-viscosity adhesive resin and the low-viscosity adhesive resin may contain the same or different polymerizable components, and compositions having the same resin may differ based on the type and / or amount of filler.

[0070] In some embodiments, the high-viscosity adhesive resin and the low-viscosity adhesive resin may independently contain one or more polymerizable components having or not having acidic functional groups, or a combination thereof.

[0071] Examples of polymerizable components that do not have acidic functional groups include PEGDMA (polyethylene glycol dimethacrylate with a molecular weight of approximately 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 Japanese Patent No. 6,187,836 (Oxman et al.) and U.S. Patent No. 6,084,004 (Weinmann et al.), U.S. Patent No. 6,245,828 (Weinmann et al.), U.S. Patent No. 5,037,861 (Crivello et al.), and U.S. Patent No. 6,779,656 (Klettke et al.), U.S. Patent No. 3,018,262 (Schroeder), and International Publication No. 01 / 51540 (Klettke et al.). Examples include epoxy resins such as those listed in U.S. Patent No. 7,262,228 (Oxman et al.) and "Handbook of Epoxy Resins" by Lee and Neville, McGraw-Hill Book Co., New York (1967), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-2-methylcyclohexylmethyl-3,4-epoxy-2-methylcyclohexanecarboxylate, and bis(3,4-epoxy-6-methylcyclohexyl-methyl) adipate, octadecylen oxide, epichlorohydrin, styrene oxide, vinylcyclohexene oxide, glycidol, glycidyl methacrylate, and diglycidyl ether of bisphenol A. These references are incorporated herein by reference in their entirety.

[0072] Polymerizable components having acidic functional groups include, for example, α,β-unsaturated acidic compounds such as glycerol phosphate mono(meth)acrylate, glycerol phosphate di(meth)acrylate, hydroxyethyl (meth)acrylate (e.g., HEMA) phosphate, bis((meth)acrylooxyethyl) phosphate, ((meth)acrylooxypropyl) phosphate, bis((meth)acrylooxypropyl) phosphate, bis((meth)acrylooxy)propyl phosphate, (meth)acrylooxyhexyl phosphate, bis((meth)acrylooxyhexyl) phosphate, (meth)acrylooxyoctyl phosphate, bis((meth) Examples include (acrylooxyoctyl) phosphate, (meth)acrylooxydecyl phosphate, bis((meth)acrylooxydecyl) phosphate, caprolactone methacrylate phosphate, di- or tri-methacrylate citrate, poly(meth)acrylated oligomaleic acid, poly(meth)acrylated polymaleic acid, poly(meth)acrylated poly(meth)acrylic acid, poly(meth)acrylated polycarboxyl-polyphosphonic acid, poly(meth)acrylated polychlorophosphate, poly(meth)acrylated polysulfonate, and poly(meth)acrylated polyboric acid, which may be used as components of the solidification system. Other examples include unsaturated carbonic acid, such as (meth)acrylic acid, aromatic (meth)acrylated acids (e.g., methacrylated trimellitic acid), and monomers, oligomers, and polymers of these, such as their anhydrides. Some of these compounds can be obtained, for example, as reaction products between isocyanatoalkyl (meth)acrylates and carboxylic acids. Additional compounds of this type having both acidic and ethylenically unsaturated components are described in U.S. Patent No. 4,872,936 (Engelbrecht) and U.S. Patent No. 5,130,347 (Mitra).For example, polymerizable bisphosphonic acid as disclosed in U.S. Patent Publication No. 2004 / 0206932 (Abuelyaman et al.); AA:ITA:IEM (for example, an acrylic acid:itaconic acid copolymer having pendant methacrylate produced by reacting an AA:ITA copolymer, such as described in Example 11 of U.S. Patent No. 5,130,347 (Mita), with sufficient 2-isocyanatoethyl methacrylate to convert some of the acid groups of the copolymer into pendant methacrylate groups); and U.S. Patents No. 4,259,075 (Yamauchi et al.), No. 4,499,251 (Omura et al.), No. 4,537,940 (Omura et al.), No. 4,539,382 (Omura et al.), No. 5,530,038 (Yamamoto et al.), No. 6,458,868 (Okada et al.), and European Patent Application Publication No. 712,622 (Tokuyama et al.). These are listed in Corp. and No. 1,051,961 (Kuraray Co., Ltd.). Further examples of polymerizable components having acidic functional groups include (meth)acrylooxy groups and at least one -OP(O)(OH). x Base (where x=1 or 2, and at least one -OP(O)(OH) x The group and at least one (meth)acrylooxy group are linked together by a C1-C4 hydrocarbon group; at least one (meth)acrylooxy group and at least one -OP(O)(OH) x A second compound containing the group (wherein x=1 or 2, and at least one -OP(O)(OH) xThe composition comprises a group and at least one (meth)acrylooxy group linked together by a C5-C12 hydrocarbon group; an ethylenically unsaturated compound without an acidic functional group; an initiator system; and a filler. Such compositions are described, for example, in U.S. Patent Application Publication 2007 / 0248927 (Luchterhandt et al.), U.S. Patent No. 7,449,499 (Bradley et al.) and U.S. Patent No. 7,452,924 (Aasen et al.); and also see U.S. Patent Application Publications 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.

[0073] In some embodiments, the high-viscosity adhesive resin and the low-viscosity adhesive resin may independently contain polymerizable components selected from unsaturated monomers (e.g., (meth)acrylate, epoxy (meth)acrylate, hydroxy-substituted (meth)acrylate, (meth)acrylic acid, hydroxy-substituted (meth)acrylic acid, vinyl ether), epoxy resin, etc. For example, one or more unsaturated monomers may be methyl (meth)acrylate, ethyl acrylate, isopropyl methacrylate, n-hexyl acrylate, stearyl acrylate, allyl acrylate, glycerol triacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, 1,3-propanediol di(meth)acrylate, trimethylolpropane triacrylate, 1,2,4-butanetriol trimethacrylate, 1,4-cyclohexanediol diacrylate, pentaerythritol tetra(meth)acrylate, sorbitan Tall hexaacrylate, tetrahydrofurfuryl (meth)acrylate, bis[1-(2-acrylooxy)]-p-ethoxyphenyldimethylmethane, bis[1-(3-acrylooxy-2-hydroxy)]-p-propoxyphenyldimethylmethane, ethoxylated bisphenol A di(meth)acrylate, and trishydroxyethyl isocyanurate trimethacrylate; (meth)acrylamides (i.e., acrylamides and methacrylamides), e.g., (meth)acrylamide, methylenebis-(meth)acrylamide, and diacetone(meth)acrylamide; urethane(meth)acrylate;bis-(meth)acrylate of polyethylene glycol (preferably molecular weight 200-500), bisphenol A bis(2-hydroxyethyl ether) dimethacrylate, 2-hydroxy-1,2,3-propanetricarboxylic acid, CDMA (reaction product of 2-hydroxy-1,2,3-propanetricarboxylic acid and 2-isocyanatoethyl methacrylate), decamethylenedimethacrylate, methacrylateoxydecyl phosphate (MDP) and other acrylic phosphates, acrylic acid and other acrylic acids, acrylic acid and itacone Acid copolymers, copolymerizable mixtures of acrylated monomers as described in U.S. Patent No. 4,652,274 (Boettcher et al.), acrylated oligomers as described in U.S. Patent No. 4,642,126 (Zador et al.), and polyunsaturated carbamoyl isocyanurates as described in U.S. Patent No. 4,648,843 (Mitra); and vinyl compounds, which may be selected from, for example, 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 International Publication No. 00 / 38619 (Guggenberger et al.), International Publication No. 01 / 92271 (Weinmann et al.), International Publication No. 01 / 07444 (Guggenberger et al.), and International Publication No. 00 / 42092 (Guggenberger et al.), as well as, for example, U.S. Patent No. 5,076,844 (Fock et al.), U.S. Patent No. 4,356,296 (Griffith et al.), and European Patent No. 0373384 (Wa Hydroxyalkyl (meth)acrylates such as fluoropolymer-functional (meth)acrylates, 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate, as disclosed in Genknecht et al., European Patent No. 0201031 (Reiners et al.), and European Patent No. 0201778 (Reiners et al.); glycerol mono- or di-(meth)acrylate; trimethylolpropane mono- or di-(meth)acrylate; pentaerythritol mono-, di-, and tri-(meth)acrylate;Examples include sorbitol mono-, di-, tri-, tetra-, or penta-(meth)acrylates; and 2,2-bis[4-(2-hydroxy-3-ethacryloxypropoxyphenyl)]propane (bisGMA), PEGDMA (polyethylene glycol dimethacrylate having a molecular weight of about 400), UDMA (urethane dimethacrylate), GDMA (glycerol dimethacrylate), TEGDMA (triethylene glycol dimethacrylate), bisEMA6 as described in U.S. Patent No. 6,030,606 (Holmes), and NPGDMA (neopentyl glycol dimethacrylate). These references are incorporated herein by reference in their entirety.

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

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

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

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

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

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

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

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

[0082] In some embodiments, the high-viscosity adhesive composition may contain one or more fillers described herein, present 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, or 90% by weight relative to the weight of the high-viscosity adhesive composition, or in a range between any of the aforementioned values, for example, about 50% to about 86% by weight, about 70% to about 80% by weight, etc.

[0083] In some embodiments, the low viscosity adhesive composition may contain one or more fillers described herein, present in an amount of 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 aforementioned values, for example, about 25% to about 35% by weight, about 10% to about 20% by weight, etc.

[0084] In some embodiments, the high-viscosity adhesive composition is 1s -1 It can be characterized by a viscosity of approximately 10 Pa·s to approximately 1,500,000 Pa·s at a shear rate of 1 s -1 At shear rates of 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, 40000, 60000, and 800, the shear rates are approximately 10, 50, 100, 2000, 3000, 40000, 60000, and 800. Viscosities of 00, 100000, 200000, 300000, 400000, 500000, 600000, 700000, 800000, 900000, 1000000, 1500000 Pa·s may be characterized by values ​​within a range between any of the aforementioned values, for example, about 500 to about 1000, about 10000 to about 100000 Pa·s, etc. In some embodiments, the high-viscosity adhesive composition is 1s -1 It can be characterized by a viscosity of approximately 1500 Pa·s to approximately 5000 Pa·s at a shear rate of 1s. -1At shear rates, it can be characterized by a viscosity 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 Pa·s, or a value within any of the aforementioned ranges, for example, approximately 1800 to approximately 1900, approximately 4000 to approximately 4100 Pa·s, etc. In some embodiments, the high-viscosity adhesive composition is 0.1s -1 It can be characterized by a viscosity of approximately 4000 Pa·s to approximately 8000 Pa·s at a shear rate of 0.1s. -1 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, 66 The high-viscosity adhesive composition may be characterized by a viscosity of 0, 6700, 6800, 6900, 7000, 7100, 7200, 7300, 7400, 7500, 7600, 7700, 7800, 7900, or 8000 Pa·s, or a value within a range between any of the aforementioned values, for example, a viscosity of about 5000 to about 7000 Pa·s. In some embodiments, the high-viscosity adhesive composition is 10s -1 The shear rate can be characterized by approximately 300 Pa·s to approximately 2000 Pa·s. For example, a high-viscosity adhesive composition may have a shear rate of 10s -1 At shear rates, it can be characterized by a viscosity of approximately 300, 400, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, or 2000 Pa·s, or a value within any of the aforementioned ranges, for example, a viscosity of approximately 400 to 600, or approximately 1500 to 1700 Pa·s.

[0085] In some embodiments, the low viscosity adhesive composition is 1s-1 Viscosity can be characterized by a shear rate of approximately 0.1 Pa·s to approximately 100 Pa·s. For example, a low-viscosity adhesive composition may have a shear rate of 1 s -1 At shear rates, viscosities of approximately 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, and 100 Pa·s may be characterized by values ​​within any of the aforementioned ranges, for example, approximately 40 to approximately 100, approximately 1 to approximately 5, approximately 0.1 to approximately 1 Pa·s, etc. In some embodiments, low viscosity adhesive compositions are 1s -1 It can be characterized by a viscosity of approximately 0.5 Pa·s to approximately 50 Pa·s at a shear rate of 1s. -1 At shear rates, the viscosity may be characterized by approximately 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 68, or 50 Pa·s, or a value within a range between any of the aforementioned values, for example, approximately 0.7 to approximately 1, approximately 30 to approximately 40 Pa·s, etc. In some embodiments, the low viscosity adhesive composition is 0.1 s -1 It can be characterized by a viscosity of approximately 0.5 Pa·s to approximately 50 Pa·s at a shear rate of 0.1s -1 At shear rates, the viscosity may be characterized by approximately 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 68, or 50 Pa·s, or a value within a range between any of the aforementioned values, for example, viscosities of approximately 0.7 to approximately 1, approximately 30 to approximately 40 Pa·s. In some embodiments, the low viscosity adhesive composition is 10s -1 It can be characterized by a viscosity of approximately 0.5 Pa·s to approximately 50 Pa·s at a shear rate of 10s. -1At shear rates, viscosities of approximately 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 may be characterized by values ​​within any of the aforementioned ranges, for example, approximately 0.7 to approximately 1, approximately 20 to approximately 30 Pa·s, etc.

[0086] In some embodiments, one or more of the high-viscosity adhesive compositions and low-viscosity adhesive compositions may further contain the fillers described herein. Those skilled in the art will understand how the viscosity of the composition is adjusted by including viscosity-modifying fillers.

[0087] In some embodiments, the high-viscosity adhesive composition may be a paste. A paste is defined herein as a solid viscous mass dispersed in a liquid that can be molded before curing. In some embodiments, the high-viscosity adhesive composition has a viscosity of at least 1000 dynes / cm³ when measured by the method described in Rheology Principles, Measurements, and Applications, CIW. 2 It can be characterized by its yield stress. See CW Macosko, VCH Publishers, Inc., New York, 1994, p. 92. The yield stress and viscosity of adhesive test specimens can be measured using appropriate equipment such as a Rheometrics ARES controlled strain rheometer (Advanced Rheometric Expansion System, Rheometric Scientific, Inc., Piscataway, NJ). In some embodiments, high-viscosity adhesive compositions are approximately 1000 dynes / cm³. 2 ~Approximately 10,000 dynes / cm 2High viscosity adhesive compositions can be characterized by their yield stress. For example, high viscosity adhesive compositions may have yield stresses of approximately 1000, 2000, 3000, 4000, 5000, 6000, 7000, 7200, 7400, 7600, 7800, 8000, 8200, 8400, 8600, 8800, 9000, 9200, 9400, 9600, 9800, and 10000 dynes / cm² at 28°C. 2 , or a value within the range between any of the aforementioned values, for example, approximately 7500 to 8000, or approximately 7400 to 9200 dynes / cm². 2 It can be characterized by static yield stresses such as those mentioned above.

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

[0089] First domain In many embodiments, the first region may include any high-viscosity adhesive composition described herein.

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

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

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

[0093] 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, represents a Gaussian curve, a triangle, or a trapezoid.

[0094] In some embodiments, the first region may include a high-viscosity adhesive composition that, when viewed from a direction perpendicular to the base, represents a circular, polygonal, or quadrilateral shape.

[0095] Second Domain In many embodiments, the second region may include any low-viscosity adhesive composition described herein.

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

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

[0098] 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, represents a ring or rectangular ring.

[0099] Filler In some embodiments, the filler may be an inorganic material selected from non-acid-reactive materials (e.g., quartz, submicron silica, zirconia, submicron zirconia, non-vitreous microparticles), acid-reactive materials (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.

[0100] In some embodiments, the filler may be silane-treated glass, silane-treated quartz, silane-treated fumed silica, silane-treated silica, silane-treated zirconia, silane-treated ceramic, or a combination thereof.

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

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

[0103] In some embodiments, the fillers include quartz, silica, silica nitride, feldspar, borosilicate glass, kaolin, talc, zirconia, titania, glass derived from Zr, Sr, Ce, Sb, Sn, Ba, Zn, Al, feldspar, submicron silica particles, e.g., those available under trade name AEROSIL (e.g., OX50), silica from Degussa Corp (Akron,OH), silica from Cabot Corp (Tuscola,IL), 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-glassy fine particles such as those described in U.S. Patent No. 4,503,169 (which is incorporated herein by reference in its entirety), and Iow, e.g., those described in U.S. Patent No. 5,695,251 (which is incorporated herein by reference in its entirety). Mohs fillers or combinations thereof may be selected. Other suitable fillers are described in U.S. Patent Nos. 6,387,981, 6,572,693, International Publication Nos. 01 / 30305, 01 / 30306, 01 / 30307, ​​and 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).

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

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

[0106] Methods for securing orthodontic appliances Various embodiments describe methods for fixing orthodontic appliances to the surface of teeth. These methods may include preparing the orthodontic appliances described herein, bringing the orthodontic appliances into contact with the surface of teeth, applying pressure to the orthodontic appliances so that a curable adhesive layer is compressed against the surface of teeth, and curing the curable adhesive layer to form a curable adhesive.

[0107] In some embodiments, the method may further include pre-applying one or more orthodontic appliances to a pre-fabricated tray before contacting the tooth surface. The pre-fabricated tray may be a custom replica of the tooth in question and may help to precisely position the orthodontic appliance on the tooth in question. This technique is commonly referred to as indirect bonding.

[0108] In some embodiments, when pressure is applied to the orthodontic appliance, the low-viscosity adhesive composition may spread beyond the base circumference, forming a concave meniscus at a point defined by the appliance-tooth joint. In some embodiments, the method may further include removing the low-viscosity adhesive composition that has spread beyond the base circumference from the tooth surface. Removal of the low-viscosity adhesive composition may include brushing, wiping, picking, scraping, rinsing, or a combination thereof. In some embodiments, minimal burr removal is not required.

[0109] In many embodiments, a high-viscosity adhesive composition can at least partially fill the gap between the base and the tooth surface when pressure is applied to the orthodontic appliance. In some embodiments, a high-viscosity adhesive composition can cover about 50 percent to about 100 percent of the total area of ​​the base when pressure is applied to the orthodontic appliance. For example, a high-viscosity adhesive composition can cover a percentage of the total area of ​​the base, such as about 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100 percent, or values ​​within any of the aforementioned ranges, for example, about 75 to about 95 percent, about 80 to about 90 percent. The contours of the tooth surface (e.g., molars, canines, premolars, etc.) may not coincide with the contours of the base surface. Depending on the area of ​​the base covered when pressure is applied to the tooth surface, the high-viscosity adhesive composition may function to at least partially fill any gaps between the tooth surface and the base surface. The base coverage can be varied according to the selection of the thickness and volume of the high-viscosity adhesive composition used.

[0110] In many embodiments, the high-viscosity adhesive composition does not spread beyond 0.2 mm around the base when pressure is applied to the orthodontic appliance and when the curable adhesive layer is cured. The high-viscosity adhesive composition may spread beyond the base to a value within the range of less than 0.2 mm, less than 0.18 mm, less than 0.16 mm, less than 0.14 mm, less than 0.12 mm, less than 0.10 mm, less than 0.08 mm, less than 0.06 mm, less than 0.04 mm, less than 0.02 mm, or 0 mm, or any of the aforementioned values, for example, about 0 to about 0.10 mm, about 0.04 to about 0.14 mm, etc.

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

[0112] In some embodiments, the method may further include pre-treating the tooth surface with a fluoride composition described below before bringing the orthodontic appliance into contact with the tooth surface.

[0113] Fluoride pretreatment In some embodiments, the fluoride composition may include: 1) A fluoride-releasing composition effective for releasing fluoride onto the tooth surface, a cross-linked polyacid polymer, a polyvalent cationic salt, a pharmaceutically acceptable buffer, and water; 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 3) The fluoride composition comprises zinc carboxylate, an amine-containing ligand, a fluoride anion source effective in 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 is a homogeneous solution at a temperature of about 20°C to 25°C.

[0114] In some embodiments, the method may further include pre-treating the tooth surface with the fluoride composition described in 1) above. Further details of fluoride compositions and methods for pre-treating tooth surfaces can be found in International Publication No. 2019 / 048962, which is incorporated herein by reference in its entirety.

[0115] In some embodiments, the method may further include pre-treating the tooth surface with the fluoride composition described in 2) above. Further details regarding the fluoride composition and the method for pre-treating the tooth surface can be found in U.S. Provisional Patent Applications No. 62 / 956,008 and No. 62 / 968,115, each of which is incorporated herein by reference in whole.

[0116] In some embodiments, the method may further include pre-treating the tooth surface with the fluoride composition described in 3) above. Further details regarding the fluoride composition and the method for pre-treating the tooth surface can be found in U.S. Provisional Patent Application No. 62 / 955,975, the contents of which are incorporated in whole by reference.

[0117] Method for manufacturing orthodontic appliances Various embodiments describe methods for manufacturing the orthodontic appliances described herein. These methods may include preparing a base, applying a high-viscosity adhesive composition to the base in a first region, and applying a low-viscosity adhesive composition to the base in a second region to form a curable adhesive layer, wherein the second region at least partially surrounds the first region.

[0118] In some embodiments, forming a curable adhesive layer may involve first applying a high-viscosity adhesive composition to the base in a first region, and then applying a low-viscosity adhesive composition to the base in a second region.

[0119] In some embodiments, applying one or more of the high-viscosity adhesive compositions and low-viscosity adhesive compositions may include extrusion molding.

[0120] In some embodiments, the application of one or more high-viscosity and low-viscosity adhesive compositions may include the practice of additive manufacturing.

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

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

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

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

[0125] kit Kit for use In various embodiments, a kit is described. The kit includes an orthodontic appliance as described herein and a set of instructions instructing the user to perform the method steps described herein for fixing the orthodontic appliance to the surface of the teeth.

[0126] In some embodiments, the kit may further include a package for housing the orthodontic appliance. In some embodiments, the orthodontic appliance may be suspended within the package. The package may be in the form of a blister pack. The package may further include a mount for attaching the orthodontic appliance. The mount may secure the orthodontic appliance so that a curing adhesive layer protects it from deformation during handling of the package. In some embodiments, the orthodontic appliance may be packaged within a package described in International Publication No. 2019 / 175726, which is incorporated herein by reference in its entirety.

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

[0128] Manufacturing kit In one embodiment, a kit is described. The kit includes a base, a container containing a high-viscosity adhesive composition described herein, a container containing a low-viscosity adhesive composition described herein, and a set of instructions instructing the user to carry out the method steps described herein for manufacturing the orthodontic appliance of the Disclosure.

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

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

[0131] In some embodiments, the kit may further include one or more extruders. In some embodiments, the extruders may be configured to fit with an adhesive composition container. [Examples]

[0132] The purposes and advantages of this disclosure are further illustrated by the following examples, but the specific materials and quantities thereof, as well as other conditions and details described in these examples, should not be construed as unduly limiting this disclosure. These examples are for illustrative purposes only and are not intended to limit the scope of the appended claims.

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

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

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

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

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

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

[0139] Viscosity measurement The viscosity of high-viscosity adhesives 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 in diameter) with a 0.15 mm gap. Viscosity measurements were performed at 25°C with a shear rate step of 0.01 s at 23 logarithmic intervals. -1 Starting from 10s -1 The measurement was performed at shear rates up to [value]. Before measurement, the sample was 10s -1 The material was pre-sheared for 3 minutes and then equilibrated at 25°C for 5 minutes. [Table 1]

[0140] 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 with a 0.50-mm gap between two parallel plates (40 mm in diameter). Viscosity measurements were performed at 25 °C at shear rates starting from 0.01 s -1 and up to 200 s -1 at shear rate intervals of 23 logarithms. Before measurement, the sample was pre-sheared for 10 s -1 for 3 minutes and equilibrated for 5 minutes at 25 °C.

Table 2

[0141] Comparative Example CE1: Bracket with high-viscosity adhesive composition #1 (HVA1) Comparative Example 1 was a commercially available product 3M™ SmartClip™ SL3 Self-Ligating Brackets with APC™ II Adhesive precoat (Catalog No. 3004 - 301) commercially available from 3M Company (St. Paul, MN, USA). The APC™ II adhesive is a high-viscosity paste adhesive called HVA1.

[0142] Comparative Example CE2: Bracket having only high-viscosity adhesive composition #2 (HVA2) Comparative Example 2 was a commercially available product SmartClip™ SL3 with APC™ PLUS Adhesive precoat (Catalog No. 5004 - 301) commercially available from 3M Company (St. Paul, MN, USA). The APC™ PLUS adhesive is a high-viscosity paste adhesive called HVA2.

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

[0144] Example 1: Bracket having a high-viscosity adhesive composition #1 (HVA1) surrounded by a low-viscosity adhesive (LVA1). Example 1 was prepared by modifying the commercially available 3M® SmartClip® SL3 Self-Ligating Brackets with APC® II Adhesive precoat (catalog no. 3004-301) from Comparative Example 1. The high-viscosity paste adhesive (HVA1) around the bracket base was removed using a razor blade, leaving the inner central portion of the bracket base with APC® II adhesive. Then, a low-viscosity adhesive (LVA1) was applied to the bracket base around the remaining inner portion of HVA1. The low-viscosity adhesive (LVA1) used is described in the Materials section. The weight of HVA1 was 4.2 mg (68 wt%, 54 vol%) and the weight of LVA1 was 2.0 mg (32 wt%, 46 vol%).

[0145] Example 2: Bracket having a high-viscosity adhesive composition #2 (HVA2) surrounded by a low-viscosity adhesive (LVA1). Example 2 was prepared by modifying the commercially available SmartClip® SL3 with APC® PLUS Adhesive precoat (catalog number 5004-301) from Comparative Example 2. The high-viscosity paste adhesive (HVA2) around the bracket base was removed using a razor blade, leaving the inner central portion of the bracket base with APC® PLUS adhesive. Then, a low-viscosity adhesive (LVA1) was applied to the bracket base around the remaining inner portion of HVA2. The low-viscosity adhesive (LVA1) used is described in the Materials section. The weight of HVA2 was 4.2 mg (68 wt%, 54 vol%) and the weight of LVA1 was 2.0 mg (32 wt%, 46 vol%).

[0146] Bonding procedure Bovine teeth were cleaned and partially embedded in circular polymethyl methacrylate discs with the labial surface of the teeth exposed. The teeth were perforated, etched, and primed with TRANSBOND Plus Self Etching Primer (SEP) (commercially available from 3M Company, catalog number 712-090) for 3-5 seconds, followed by air blowing for 3 seconds to dry. The pre-coated brackets were bonded to the bovine teeth. In Examples 1-2 (with LVA in the outer region) and Comparative Example 3 (with LVA only), deburring of the adhesive was not necessary when fixing the brackets to the teeth. However, for Comparative Examples 1-2, which had only HVA paste adhesive, deburring of the adhesive around the base of the brackets was performed according to standard clinical bracket bonding procedures. All adhesives in Examples 1-2 and Comparative Examples 1-3 were photocured using Ortholux® Luminous Curing Light (available from 3M Company (St. Paul, MN, USA); catalog number 704-460). Unless otherwise specified, the curing light was applied to the sample for 3 seconds mesially and 3 seconds centrifugally.

[0147] Shear peel adhesion strength test procedure Shear peel bond strength was measured either 15 minutes or 16–24 hours after bonding using the following standardized method. First, each bonded specimen was mounted with the gingival tie wing facing upward (unless otherwise specified) to a test fixture attached to a QTEST / 5 brand mechanical tester (MTS Systems Corporation, Eden Prairie, Minn). A standard 0.020 inch (0.051 cm) diameter circular wire was looped under the occlusal bond wing and attached to the crosshead of the tester. After adjusting the initial crosshead position to ensure the wire was tight, the tester was moved parallel upward at 0.2 inches per minute (5 mm per minute) until the bracket peeled off. The maximum force was recorded and divided by the measured surface area of ​​the bracket base to obtain the bond strength value. Each reported bond strength value represents the average of 10 repeated measurements unless otherwise specified. [Table 3]

[0148] Examples Ex.1 and Ex.2 demonstrated acceptable adhesive strength compared to comparative examples CE1 and CE2, which are commercially available products. Furthermore, Examples Ex.1 and Ex.2 also had the advantage of eliminating the need to remove adhesive burrs, as the peripheral LVA1 adhesive resulted in a low profile / minimal burrs.

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

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

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

[0152] Comparative Example CE6: Buccal tube with a nonwoven mat and low-viscosity adhesive (LVA1) Comparative Example 6 was manufactured in the same manner as Comparative Example CE5, but the nonwoven mat described in the Materials section was also cut to the shape of the base and placed on the base of the buccal tube. The nonwoven mat was completely saturated with the low-viscosity adhesive (LVA1) described in the Materials section. When the instrument was fixed, the low-viscosity adhesive (LVA1) seeped out and filled the gap between the instrument base and the tooth surface, forming a meniscus around the edge of the base, thereby eliminating the need to remove excess adhesive burrs.

[0153] In the bonding procedure, removal of excess adhesive burrs was not necessary for Example 3 (with LVA in the outer region), Comparative Example 5 (with LVA only), and Comparative Example 6 (with LVA and nonwoven mat). However, for Comparative Example 4, which had only HVA paste adhesive, excess adhesive burrs around the base of the buccal tube were removed according to the standard clinical bracket bonding procedure. The curing times used for the buccal tube examples in Table 2 were 6 seconds mesially and 6 seconds occlusally.

[0154] In the shear-peel adhesion strength test procedure, the examples of these buccal tubes in Table 2 were peeled with the hooks facing downwards. [Table 4]

[0155] Example Ex.3 demonstrated acceptable adhesive strength compared to Comparative Example CE4, a commercially available product. Furthermore, Example Ex.3 resulted in a low profile / minimal burr due to the surrounding LVA1 adhesive, eliminating the need for adhesive burr removal.

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

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

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

[0159] Comparative Example 8: Low-profile bracket with low-viscosity adhesive #1 (LVA1) Comparative Example 8 was manufactured by coating the base of a commercially available orthodontic bracket, Victory Series® Low Profile (3M catalog number 024-890), with the low-viscosity adhesive (LVA1) described in the Materials section.

[0160] In the bonding procedure, in Example 4 (with LVA in the outer / secondary region) and Comparative Example 8 (with LVA only), deburring of the adhesive (excess) was not necessary. However, for Comparative Example 7, which had only HVA paste adhesive, the excess adhesive burr around the base of the bracket was removed according to the standard clinical bracket bonding procedure. In the shear-peel bond strength test procedure, the bracket types in Table 3 were peeled with the gingival tie wing facing downwards. [Table 5]

[0161] Example Ex.4 demonstrated acceptable adhesive strength compared to Comparative Example CE7, a commercially available product. Furthermore, Example Ex.4 resulted in a low profile / minimal burr due to the surrounding LVA1 adhesive, eliminating the need for adhesive burr removal.

[0162] Example Ex.5: Low-profile bracket having a high-viscosity adhesive composition #1 (HVA1) surrounded by a low-viscosity adhesive (LVA2). Example 5 was manufactured by modifying a commercially available 3M product: Victory Series® Low Profile bracket with APC® II Adhesive precoat (3M catalog number 3024-875). The high-viscosity paste adhesive (HVA1) already present on the commercially available product was partially removed around the base using a razor blade, leaving the inner central portion of the base covered with HVA1. Then, the low-viscosity adhesive (LVA2) was applied to the base around the remaining inner portion of 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%).

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

[0164] Comparative Example 10: Low-profile bracket having low-viscosity adhesive composition #2 (LVA2) Comparative Example 10 was manufactured by coating the base of a commercially available orthodontic bracket, Victory Series® Low Profile (3M catalog number 024-875 or 024-775), with 3M CLINPRO sealant, which is commercially available from 3M Company (St. Paul, MN, USA). 3M CLINPRO sealant is a low-viscosity adhesive called LVA2.

[0165] In the bonding procedure, deburring of the adhesive was not necessary in Example 5 (with LVA in the outer / second region) and Comparative Example 10 (with LVA only). However, for Comparative Example 9, which had only HVA paste adhesive, deburring of the excess adhesive around the base of the bracket was performed according to the standard procedure for clinical bracket bonding. In Table 4, the reported shear peel bond strength test values ​​represent the average of 10 repeated measurements in Comparative Example 9, or the average of 8 repeated measurements in Example 5 and Comparative Example 10. [Table 6]

[0166] Example Ex.5 demonstrated acceptable adhesive strength compared to Comparative Example CE9, a commercially available product. Furthermore, Example Ex.5 resulted in a low profile / minimal burr due to the surrounding LVA2 adhesive, eliminating the need for adhesive burr removal.

[0167] Example Ex.6: Low-profile bracket having a high-viscosity adhesive composition #1 (HVA1) surrounded by a low-viscosity adhesive (LVA3). Example 6 was prepared by modifying a commercially available 3M product: Victory Series® Low Profile bracket with APC® II Adhesive precoat (3M catalog no. 3024-890). The high-viscosity paste adhesive (HVA1) already present on the commercially available product was partially removed around the base using a razor blade, leaving the inner central portion of the base covered with HVA1. Then, a low-viscosity adhesive (LVA3) was applied to the base around the remaining inner portion of HVA1. The low-viscosity adhesive (LVA3) used was a self-etching adhesive: Scotchbond Universal Adhesive with a pH of 2.7 (3M catalog no. 41528). The weight of HVA1 was 3.6 mg (69 wt%, 55 vol%) and the weight of LVA3 was 1.6 mg (31 wt%, 45 vol%). After application of LVA3, the solvent was dried for 5 seconds using an air syringe. In the bonding procedure, tooth etching and priming with TRANSBOND Plus Self Etching Primer (SEP) were omitted.

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

[0169] In the bonding procedure, in Example 6 (with LVA in the outer / second region), deburring of the adhesive (excess) was not necessary. However, for Comparative Example 11, which had only HVA paste adhesive, the excess adhesive burr around the base of the bracket was removed according to the standard clinical bracket bonding procedure. In the shear-peel bond strength test procedure, this type of bracket in Table 5 (the same as the one used in Table 3) was peeled with the gingival tie wing facing downwards. [Table 7]

[0170] Example Ex.6 demonstrated acceptable adhesive strength compared to Comparative Example CE11, a commercially available product. Example Ex.6 eliminated the need for tooth etching / priming as a result of the acidic properties of the low-viscosity adhesive LVA3. Furthermore, Example Ex.6 eliminated the need for adhesive burr removal because the surrounding low-viscosity adhesive LVA3 resulted in a low profile / minimal burr.

[0171] Equivalents Those skilled in the art will be able to recognize or identify numerous equivalents to the specific embodiments described herein using experimental methods that are merely routine practice. Such equivalents are intended to be covered by the following claims. Examples of embodiments of the present invention are listed in the following sections [Aspect 1] to [Aspect 44]. [Aspect 1] It is a dental orthodontic appliance, The base and, The base comprises a curable adhesive layer disposed on the base, The curable adhesive layer includes a first region and a second region, The first region is 1s -1 The present invention comprises a high-viscosity adhesive composition characterized by having a viscosity of approximately 10 Pa·s to approximately 1,500,000 Pa·s at a shear rate, The second region is 1s -1 The present invention comprises a low-viscosity adhesive composition characterized by having a viscosity of approximately 0.1 Pa·s to approximately 100 Pa·s at a shear rate, The first region is at least partially surrounded by the second region, The first region and the second region are configured to contact the surface of the tooth, An orthodontic appliance wherein the viscosity of the high-viscosity adhesive composition is higher than the viscosity of the low-viscosity adhesive composition. [Aspect 2] The orthodontic appliance according to embodiment 1, wherein the high-viscosity adhesive composition does not spread beyond the base by more than 0.2 mm when the curable adhesive layer is compressed against the tooth surface. [Aspect 3] The orthodontic appliance according to embodiment 1 or 2, wherein the high-viscosity adhesive composition contains a filler present in an amount of about 50% to about 86% by weight relative to the weight of the high-viscosity adhesive composition. [Aspect 4] The orthodontic appliance according to any one embodiment of Embodiments 1 to 3, wherein the high-viscosity adhesive composition comprises one or more unsaturated monomers having or not having an acidic functional group, or a combination thereof. [Aspect 5] The orthodontic appliance according to any one of embodiments 1 to 4, wherein the high-viscosity adhesive composition is a paste. [Aspect 6] An orthodontic appliance according to any one embodiment of embodiments 1 to 5, wherein the high-viscosity adhesive composition comprises a filler selected from fumed silica, silane-treated glass, silane-treated quartz, silane-treated silica, and combinations thereof. [Aspect 7] The aforementioned high-viscosity adhesive composition has a viscosity of at least 7000 dynes / cm³ at 28°C. 2 An orthodontic appliance according to any one of embodiments 1 to 6, characterized by its static yield stress. [Aspect 8] The orthodontic appliance according to any one of embodiments 1 to 7, wherein the high-viscosity adhesive composition has a thickness of about 0.38 mm to about 1.2 mm. [Aspect 9] The orthodontic appliance according to any one of embodiments 1 to 8, wherein the curable adhesive layer has a shape that represents a Gaussian curve, a triangle, or a trapezoid when viewed from a cross-sectional side view of the base. [Aspect 10] The orthodontic appliance according to any one of embodiments 1 to 9, wherein the high-viscosity adhesive composition has a circular, polygonal, or quadrilateral shape when viewed from a direction perpendicular to the base. [Aspect 11] The orthodontic appliance according to any one embodiment of embodiments 1 to 10, wherein the high-viscosity adhesive composition has a volume of about 40 percent to about 85 percent of the volume of the curable adhesive layer. [Aspect 12] The orthodontic appliance according to any one embodiment of embodiments 1 to 11, wherein the high-viscosity adhesive composition is spread over approximately 20 percent to approximately 50 percent of the total surface area of ​​the base. [Aspect 13] The orthodontic appliance according to any one embodiment of embodiments 1 to 12, wherein the low-viscosity adhesive composition is a fluid solution or a fluid suspension. [Aspect 14] The orthodontic appliance according to any one embodiment of embodiments 1 to 13, wherein the low-viscosity adhesive composition has a filler content of about 0 to about 50% by weight. [Aspect 15] An orthodontic appliance according to any one embodiment of embodiments 1 to 14, wherein the low-viscosity adhesive composition comprises a filler selected from fumed silica, silane-treated glass, silane-treated quartz, silane-treated silica, and combinations thereof. [Aspect 16] An orthodontic appliance according to any one embodiment of embodiments 1 to 15, wherein the low-viscosity adhesive composition is characterized by a flow such that, when measured by a vertical flow test, the difference in thickness of the adhesive composition at the top and bottom is less than approximately 15%. [Aspect 17] The orthodontic appliance according to any one embodiment of embodiments 1 to 16, wherein the low-viscosity adhesive composition has a thickness of about 0.06 mm to about 0.16 mm. [Aspect 18] The orthodontic appliance according to any one of embodiments 1 to 17, wherein the low-viscosity adhesive composition is in the shape of a ring or a rectangular ring when viewed from a direction perpendicular to the base. [Aspect 19] An orthodontic appliance according to any one embodiment of embodiments 1 to 18, wherein the low-viscosity adhesive composition is spread over approximately 50 percent to approximately 80 percent of the total surface area of ​​the base. [Aspect 20] The orthodontic appliance according to any one embodiment of embodiments 1 to 19, wherein the low-viscosity adhesive composition comprises one or more unsaturated monomers having or not having an acidic functional group, or a combination thereof. [Aspect 21] The aforementioned high-viscosity adhesive composition, -1 An orthodontic appliance according to any one of embodiments 1 to 20, characterized by a viscosity of approximately 100 Pa·s to approximately 13,000 Pa·s at a shear rate. [Aspect 22] The low viscosity adhesive composition, -1 An orthodontic appliance according to any one of embodiments 1 to 21, characterized by a viscosity of approximately 0.1 Pa·s to approximately 10 Pa·s at a shear rate. [Aspect 23] An orthodontic appliance according to any one embodiment of embodiments 1 to 22, wherein the high-viscosity adhesive composition and the low-viscosity adhesive composition differ by at least 10 times in viscosity. [Aspect 24] The orthodontic appliance according to any one embodiment of embodiments 1 to 23, wherein the high-viscosity adhesive composition has a maximum thickness greater than the average thickness of the low-viscosity adhesive composition. [Aspect 25] An orthodontic appliance according to any one embodiment of embodiments 1 to 24, comprising essentially the base and the curable adhesive layer. [Aspect 26] An orthodontic appliance according to any one of embodiments 1 to 25, which does not have a compressible mat. [Aspect 27] A method for fixing orthodontic appliances to the surface of teeth, Prepare an orthodontic appliance as described in any one of the embodiments 1 to 26, The orthodontic appliance is brought into contact with the surface of the tooth, Applying pressure to the orthodontic appliance so that the curing adhesive layer is compressed against the surface of the tooth, A method comprising curing the aforementioned curable adhesive layer to form a cured adhesive. [Aspect 28] The method according to embodiment 27, wherein the tooth surface is a molar, canine, or premolar. [Aspect 29] The method according to embodiment 27 or 28, wherein when pressure is applied to the orthodontic appliance, the low-viscosity adhesive composition spreads beyond the outer circumference of the base and forms a concave meniscus at a point defined by the appliance-tooth joint. [Aspect 30] The method according to any one embodiment of embodiments 27 to 29, wherein when pressure is applied to the orthodontic appliance, the high-viscosity adhesive composition substantially fills the gap between the base and the surface of the tooth. [Aspect 31] The method according to any one embodiment of embodiments 27 to 30, wherein the high-viscosity adhesive composition does not spread beyond 0.2 mm around the outer circumference of the base when cured under pressure. [Aspect 32] The method according to any one embodiment of embodiments 27 to 31, wherein the high-viscosity adhesive composition covers about 50% to about 100% of the base when the adhesive layer is compressed against the surface of the tooth. [Aspect 33] The method according to any one embodiment of embodiments 27 to 32, wherein the curing provides an adhesive strength of at least 5.0 MPa as measured by an adhesive strength test. [Aspect 34] The method according to any one embodiment of embodiments 27 to 33, wherein the curing includes exposing the curable adhesive layer to light for a certain period of time. [Aspect 35] The method further includes pre-treating the surface of the teeth with a fluoride composition before bringing the orthodontic appliance into contact with the surface of the teeth. The aforementioned pretreatment includes bringing the fluoride composition into contact with the tooth surface, The fluoride composition is A fluoride-releasing composition effective in releasing fluoride onto the tooth surface, Cross-linked polyacid polymer and Polyvalent cation salts, Pharmaceutically acceptable buffering agents, The method according to any one embodiment of embodiments 27 to 34, comprising water. [Aspect 36] The method further includes pre-treating the surface of the teeth with a fluoride composition before bringing the orthodontic appliance into contact with the surface of the teeth. The aforementioned pretreatment includes bringing the fluoride composition into contact with the tooth surface, The fluoride composition is A silver-fluoride composition, Silver cation source and Fluoride anion source and A source of iodide or thiocyanate anion, A silver-fluoride composition containing water, A curable resin composition, A curable resin composition comprising at least one (meth)acrylate monomer, The method according to any one embodiment of embodiments 27 to 34, including the method described herein. [Aspect 37] The method further includes pre-treating the tooth surface with a fluoride composition, The aforementioned pretreatment includes bringing the fluoride composition into contact with the tooth surface, The fluoride composition is Zinc carboxylate and Amine-containing ligands and A fluoride anion source effective in providing fluoride in an amount of at least 4% by weight relative to the weight of the fluoride composition, Water, and the contents The fluoride composition has a pH of at least 8, The method according to any one embodiment of embodiments 27 to 34, wherein the fluoride composition is a homogeneous solution at a temperature of about 20 to 25°C. [Aspect 38] An orthodontic appliance described in any one of embodiments 1 to 26, A kit including a set of instructions that instruct the user to perform the steps described in any one of embodiments 27 to 37. [Aspect 39] The kit according to embodiment 38, further comprising packaging in the form of a blister pack. [Aspect 40] The kit according to embodiment 38 or 39, further comprising a package, wherein the orthodontic appliance is suspended within the package. [Aspect 41] A method for manufacturing an orthodontic appliance according to any one of embodiments 1 to 26, wherein the method is To prepare the base, This includes forming a curable adhesive layer on the base, and the formation is Applying a high-viscosity adhesive composition to the base in the first region, The method includes applying a low-viscosity adhesive composition to the base in a second region, A method wherein the first region is at least partially surrounded by the second region. [Aspect 42] The base and, A container containing a high-viscosity adhesive composition, A container containing a low-viscosity adhesive composition, A kit including a set of instructions that instruct the user to perform the steps described in Embodiment 41. [Aspect 43] The kit according to embodiment 42, further comprising one or more containers containing one or more fillers. [Aspect 44] The kit according to embodiment 43, wherein the set of instructions further instructs the user to combine one or more of the high-viscosity adhesive compositions and the low-viscosity adhesive compositions with one or more fillers.

Claims

1. It is a dental orthodontic appliance, The base and, The base comprises a curable adhesive layer disposed on the base, The curable adhesive layer includes a first region and a second region, the first region and the second region each being located on a base. The first region is 25°C for 1 second. －１ The present invention comprises a high-viscosity adhesive composition characterized by having a viscosity of approximately 100 Pa·s to approximately 1,500,000 Pa·s at a shear rate, The second region is 25°C for 1 second. －１ The present invention comprises a low-viscosity adhesive composition characterized by having a viscosity of approximately 0.1 Pa·s to approximately 100 Pa·s at a shear rate, The first region is at least partially surrounded by the second region, The first region and the second region are configured to contact the surface of the tooth. The low-viscosity adhesive composition has a thickness of about 0.06 mm to about 0.16 mm. An orthodontic appliance wherein the viscosity of the high-viscosity adhesive composition is higher than the viscosity of the low-viscosity adhesive composition.

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

3. The aforementioned high-viscosity adhesive composition has a viscosity of at least 7000 dynes / cm² at 28°C. ２ Characterized by its static yield stress, and The low-viscosity adhesive composition is characterized by a flow such that, when measured by a vertical flow test, the difference in thickness of the adhesive composition at the top and bottom is less than approximately 15%. An orthodontic appliance according to claim 1, characterized by one or more of the following.

4. The orthodontic appliance according to claim 1, wherein the curable adhesive layer has a shape that represents a Gaussian curve, a triangle, or a trapezoid when viewed from a cross-sectional side view of the base.

5. The orthodontic appliance according to claim 1, wherein the high-viscosity adhesive composition has a shape that represents a circle, polygon, or square when viewed from a direction perpendicular to the base.

6. The orthodontic appliance according to claim 1, wherein the high-viscosity adhesive composition has a volume of about 40 percent to about 85 percent of the volume of the curable adhesive layer.

7. The orthodontic appliance according to claim 1, wherein the high-viscosity adhesive composition is spread over approximately 20 percent to approximately 50 percent of the total surface area of ​​the base.

8. The orthodontic appliance according to claim 1, wherein the low-viscosity adhesive composition has a filler amount of about 0 to about 50% by weight.

9. The orthodontic appliance according to claim 1, wherein the low-viscosity adhesive composition has the shape of a ring or a rectangular ring when viewed from a direction perpendicular to the base.

10. The orthodontic appliance according to claim 1, wherein the low-viscosity adhesive composition is spread over approximately 50 percent to approximately 80 percent of the total surface area of ​​the base.

11. The aforementioned high-viscosity adhesive composition, at 25°C, 1 s －１ It is characterized by a viscosity of approximately 1500 Pa·s to approximately 5000 Pa·s at a shear rate. The low viscosity adhesive composition, at 25°C, 1 s －１ It is characterized by a viscosity of approximately 0.1 Pa·s to approximately 10 Pa·s at a shear rate, and The high-viscosity adhesive composition and the low-viscosity adhesive composition differ in viscosity by at least 10 times. An orthodontic appliance according to claim 1, characterized by one or more of the following.

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

13. The orthodontic appliance according to claim 1, which does not have a compressible mat.

14. An orthodontic appliance according to any one of claims 1 to 13, Includes a set of instructions that instruct the user on how to fix the orthodontic appliance to the surface of the teeth, or The base and, A container containing a high-viscosity adhesive composition, A container containing a low-viscosity adhesive composition, A kit including a set of instructions that instruct the user on how to prepare the aforementioned orthodontic appliance.

15. A method for manufacturing an orthodontic appliance according to any one of claims 1 to 13, wherein the method is To prepare the base, This includes forming a curable adhesive layer on the base, and the formation is Applying a high-viscosity adhesive composition to the base in the first region, The method includes applying a low-viscosity adhesive composition to the base in a second region, A method wherein the first region is at least partially surrounded by the second region.

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