Two-part dental sealant, application method using a syringe device, and kit

Abstract

A method for applying a two-part dental sealant is described, including providing a syringe device (1) with a cartridge (10) including first and second chambers. The first chamber contains a first part of the dental sealant, including a (meth)acrylate resin and an oxidative curing agent. The second chamber contains a second part of the dental sealant, including a (meth)acrylate resin and a reductive curing agent that reacts with the oxidative curing agent in the first chamber. The first and / or second parts of the dental sealant further include a component or components that neutralize acid and promote remineralization. The syringe device includes a static mixer and a dispensing nozzle (17) with an outlet at one end of the cartridge, and a plunger (20) at the opposite end of the cartridge. Also described is a kit for storing and applying dental sealants.

Description

[Background technology]

[0001] Sealants are often used to prevent tooth decay, which is caused by the accumulation of caries-causing microorganisms on a patient's teeth. Of the various areas of tooth shape, the area where sealant treatment is most desirable is generally referred to as the pits and fissures. Sealants are used to fill in the pits and fissures, creating a smooth shape and preventing the accumulation of microorganisms without negatively affecting chewing ability.

[0002] Conventional dental sealants are provided in either a transparent composition or a composition containing an opacifying filler to impart whiteness. For example, U.S. Patent No. 4,150,012 teaches a dental composition prepared in a two-part system, each of which comprises a polymerizable resin and an opacifying filler, except that the first container contains a catalyst and the second container contains an accelerator that reacts with the catalyst in the first container. This dental material chemically hardens (via an oxidation-reduction reaction) and becomes an opaque dental material upon hardening.

[0003] As another example of a dental sealant, U.S. Patent No. 6,444,725 teaches an aesthetic dental sealant comprising a curable resin, a curing agent, and a coloring agent, wherein the composition has an initial color before exposure to chemical radiation and a final color (e.g., a tooth-like color) after the composition has been exposed to chemical radiation that is different from the initial color. [Overview of the Initiative]

[0004] While coloring may offer the advantage of precise application of dental sealants, the industry will likely find more benefits in application methods that minimize sealant waste, reduce the time required for sealant application, and offer other advantages.

[0005] In one embodiment, a method of applying a two-component dental sealant is described, which includes providing a syringe device comprising a cartridge having first and second chambers. The first chamber contains a first portion of the dental sealant, which includes a (meth)acrylate resin and an oxidative curing agent. The second chamber contains a second portion of the dental sealant, which includes a (meth)acrylate resin and a reductive curing agent that reacts with the oxidative curing agent of the first chamber. The first and / or second portion of the dental sealant further includes one or more components that neutralize acids and promote remineralization. The syringe device includes a static mixer and a dispensing nozzle having an outlet at one end of the cartridge, and a plunger at the opposite end of the cartridge. The plunger includes two rods, one end of each rod sealing the first and second portions of the dental sealant within the chambers, and the opposite ends of the plunger rods being connected. The method includes manually applying pressure to the plunger, thereby transporting the first and second portions of the dental sealant through the static mixer and outlet of the dispensing nozzle onto the surface of a tooth.

[0006] In another embodiment, a kit for storing and applying a dental sealant includes: i) a syringe device comprising a) a cartridge having first and second chambers, wherein the first chamber contains a (meth)acrylate resin and an oxidative curing agent, the second chamber contains a (meth)acrylate resin and a reductive curing agent that reacts with the oxidative curing agent of the first chamber, and the first and / or second chamber further includes one or more components that neutralize acids and promote remineralization; b) a plunger at one end of the cartridge, the plunger including two rods, one end of each rod sealing the first and second portions of the dental sealant within the chambers, and the opposite ends of the plunger rods being connected; ii) at least one detachable dispensing nozzle having a static mixer attached to the opposite end of the cartridge.

[0007] In another embodiment, a two-component dental sealant composition is provided, comprising a first part containing a (meth)acrylate resin and an oxidation curing agent, and a second chamber part containing a (meth)acrylate resin and a reduction curing agent that reacts with the oxidation curing agent in the first chamber, wherein the first and second parts each have a viscosity of 5000 cps or less, and the two-component dental sealant composition further comprises a single component or a plurality of components that neutralize acids and promote remineralization.

Brief Description of the Drawings

[0008] [Figure 1] A perspective view of an exemplary syringe. [Figure 2] A cross-sectional view of an exemplary syringe. [Figure 3] A cross-sectional view of an exemplary syringe (modified from FIG. 3 of U.S. Patent Application Publication No. 2016 / 0270879). [Figure 4] A side view of an exemplary static mixer (FIG. 2 of International Publication No. 2016 / 205181 (FN76390)).

Modes for Carrying Out the Invention

[0009] Herein, a method of applying a dental sealant using a syringe device, and a kit for storing and applying a dental sealant comprising a syringe device for containing a two-component dental sealant, a detachable dispensing nozzle attached to the syringe device, and a two-component dental sealant composition are described.

[0010] FIG. 1 shows an exemplary syringe device 1 suitable for dispensing a two-component dental sealant material. The syringe device includes a cartridge 10 (e.g., cylindrical), a plunger 20, and a dispensing nozzle 17.

[0011] The cartridge 10 typically has a cylindrical shape. In a typical embodiment, the cartridge further comprises a finger rest 113. The shape of the finger rest 113 includes a flat portion or support point that prevents the cartridge 10 from rolling when placed on a flat surface. Thus, when the syringe 1 is placed on a flat surface such as a table, the flat portion of the finger rest 113 of the cartridge 10 prevents the syringe from rolling off the table.

[0012] The cartridge 10 of syringe 1 is pre-filled with a two-component dental sealant. One part of the two-component dental sealant is housed in the first chamber 111, and the second part of the two-component dental sealant is housed in the second chamber 112.

[0013] As best shown in the cross-sectional view of Figure 2, syringe 1 has a plunger 20 comprising a first plunger rod 121 and a second plunger rod 122. One end of each rod 121, 122 is configured to seal the first and second portions of the dental sealant in chambers 111 and 112. The opposite ends of the plunger rods are connected at the rear end 16 of plunger 20.

[0014] The cartridge contains a sufficient amount of two-component dental sealant to seal one or more teeth. Typically, the amount of two-component dental sealant is sufficient to seal all the teeth of one patient. In some embodiments, the amount of two-component dental sealant is sufficient to seal all the teeth of two or more patients, and the removable nozzle is replaced for each patient. In a typical embodiment, the syringe is pre-filled by the manufacturer with the two-component dental sealant composition. In some embodiments, the (e.g., pre-filled) syringe, the two-component dental sealant composition, and one or more removable dispensing nozzles are combined to form a kit for storing and applying dental sealant. The kit typically further includes instructions for using the kit and for attaching the removable nozzle to the syringe.

[0015] To facilitate oral use and minimize waste of dental sealant, the syringe device is relatively small. In some embodiments, the total length of the filled syringe (without nozzle) before engagement with the plunger, as shown in Figures 1 and 2, is 200 mm, 190 mm, 180 mm, 170 mm, 160 mm, 150 mm, or 140 mm or less. The total length of the filled syringe (without nozzle) is typically 100 mm, 110 mm, 120 mm, or 130 mm or more. In some embodiments, the total length of the cartridge is typically 100 mm, 95 mm, 90 mm, 85 mm, 80 mm, or 75 mm or less. The total length of the cartridge is typically 50 mm, 55 mm, 60 mm, or 65 mm or more. The length of the internal chamber is shorter than the total length of the cartridge. In some embodiments, the total length of the internal chamber is 70 mm, or 65 mm or less. The outer diameter of the cartridge is typically 15mm, 14mm, 13mm, 12mm, 11mm, 10mm, 9mm, or 8mm or less. The outer diameter is typically 5mm, 5.5mm, 6mm, 6.5mm, 7mm, or 7.5mm or more. The total internal volume of the cartridge is typically 5, 4.5, 4, 3.5, 3, or 2.5cc or less.

[0016] In a typical embodiment, the first chamber and the second chamber have a volume ratio of approximately 1:1. Other volume ratios can also be adopted. For example, the volume ratio of the chambers may be in the range of 1:1 to approximately 2:1 or 3:1.

[0017] When a 1:1 volume ratio mixture of the first and second parts is intended, the first and second chambers each contain approximately half of the total volume of the cartridge. Thus, the total internal volume of each chamber is typically 2.5, 2, 1.75, 1.5, or 1.25 cc or less.

[0018] Figure 3 shows a cross-sectional view of syringe 1 through cartridge 10. Cartridge 10 has two chambers 111, 112 extending through cartridge 10. In some embodiments, the chambers have a substantially D-shaped cross-section, such as that described in U.S. Patent Application Publication 2016 / 0270879, which is incorporated herein by reference.

[0019] Specifically, the outer perimeter of the D-shape is defined solely by multiple arches 19a, 19b, 19c, and 19d. (Arches 19a, 19b, 19c, and 19d correspond to the first, third, second, and fourth arches, respectively.) The arch 19a adjacent to the separation wall has a different radius than the opposite arch 19c adjacent to the outer wall 17. Specifically, arch 19a has a larger radius than arch 19c. Thus, while an almost D-shape is achieved, having a cross-section based solely on circular structures allows for more reliable sealing compared to a cross-section with one or more linear structures. Furthermore, the arches 19a, 19b, 19c, and 19d are joined at the joints of two arches such that the tangents of each arch passing through the joint coincide. That is, the arches 19a, 19b, 19c, and 19d smoothly integrate with each other to form a closed line that defines the outer perimeter of the cross-section.

[0020] In a preferred embodiment, the radius of the first arc may be in the range of 10 mm to 20, 30, 40, or 50 mm, the radius of the second arc may be in the range of 2 mm to 5, 10, 15, or 20 mm, and the radii of the third and fourth arcs may be in the range of 0.3 mm to 1, 2, or 3 mm. In one embodiment, radius 19a is approximately 14 mm, radius 19b is approximately 1 mm, and radius 19c is approximately 4 mm.

[0021] As shown in the figure, the two roughly D-shaped forms are arranged mirror-like to each other, and the cartridge 10 has a generally cylindrical outer shape at one end and an outer wall 117 at the other end with a separating wall 118 having a substantially uniform wall thickness. The substantially uniform wall thickness facilitates the manufacture of the cartridge by, for example, injection molding (e.g., polypropylene).

[0022] In some embodiments, the plunger rods 121 and 122 are configured to be pressed into the respective chambers of the cartridge. The plunger rods may contain a material that is more rigid than the cartridge. In some embodiments, the plunger rods are injection molded from polypropylene containing 50% glass fiber. The cross-sectional shape of each plunger rod typically corresponds to the cross-sectional shape of the respective chamber. Therefore, if the chamber has a substantially D-shaped cross-section, the plunger rod also has a substantially D-shaped cross-section.

[0023] In some embodiments, the end portions of the plunger rods 121 and 122 that seal the two-component dental sealant within the chamber are preferably larger in dimension than the cross-sectional shape of the respective chamber, specifically being two-dimensionally enlarged by a certain offset. In one embodiment, each plunger rod 121 and 122 has a skirt-type lip seal, which is described in more detail in U.S. Patent Application Publication No. 2016 / 0270879 cited above.

[0024] The chambers and plunger rods may have various other designs and cross-sectional shapes so that the two-component dental sealant is sealed within each chamber before use.

[0025] The dispensing nozzle 17 is detachably mounted on the front end 15 of the cartridge 10. In some embodiments, the nozzle is rotatably mounted on the front end of the cartridge 10. The cartridge, nozzle, or combination thereof includes a valve capable of providing or preventing fluid communication between the two-component dental sealant of the cartridge 10 and the dispensing nozzle 17. In some embodiments, the combination of the cartridge 10 and nozzle 17 forms a rotary slide valve. Further details relating to the valve are described in International Publication No. 2018 / 057503 and U.S. Patent No. 9,427,290, which are incorporated herein by reference.

[0026] The dispensing nozzle 17 further comprises a cannula 172 including a static mixer 40 (not shown in Figure 1, but shown in Figures 2 and 4).

[0027] The volume and design are selected to maximize mixing efficiency and reduce waste. In some embodiments, the total volume of the dispensing nozzle without a static mixer is typically 0.25, 0.20, 0.15, or 0.10 cc or less. In some embodiments, the total volume of the dispensing nozzle is 0.09, 0.08, 0.07, 0.06, 0.05, 0.04, or 0.03 cc or less. The cannula has an external shape with a width of 2, 2.5, or 3 mm and a length of approximately 75 to 150 mm.

[0028] Various static mixers can be used. Figure 4 shows a preferred static mixer 40 which may be placed in the dispensing nozzle shown in Figures 1 and 2. Such a static mixer is described in International Publication No. 2015 / 205181, which is incorporated herein by reference. The static mixer 40 has a series of mixing elements 41a / 41b. Each mixing element 41a / 41b is based on a helical shape or helical body. The structure of such a helical mixing element can be envisioned as basically a planar sheet material held at both ends and twisted 180 degrees or wound, but typically other methods (e.g., injection molding) are used to manufacture such a structure. The overall shape of such a mixing element 41a / 41b is based on a columnar helix. Thus, each mixing element has an outer diameter D. Each mixing element has an inlet edge 42a / 42b and an outlet edge 43a / 43b of material. With respect to the flow F of dental material passing through the mixing unit, the material enters each mixing element 41a / 41b at the inlet edge 42a / 42b and exits each mixing element 41a / 41b at the outlet edge 43a / 43b. The static mixer 40 has a plurality of mixing elements 41a / 41b arranged in a continuous pattern. The inlet edges 42a / 42b and outlet edges 43a / 43b of two adjacent mixing elements 41a / 41b are offset from each other at a certain angle. Thus, the flow of two components of the dental material is divided as the dental material flows through the mixing unit 40, and the divided partial flows merge multiple times. Thus, the dental material (for example, two parts of it) is mixed. The offset angle between the inlet edges 42a / 42b and the outlet edges 43a / 43b is measured at a point on the major axis A of the mixing unit in a plane perpendicular to the major axis A. In this example, the offset angle between the inlet edge 42a / 42b and the outlet edge 43a / 43b is 90 degrees. In other words, the inlet edge 42a / 42b and the outlet edge 43a / 43b of adjacent mixing elements 41a / 41b are positioned to intersect each other.

[0029] As shown in the figure, the mixing unit 40 has a right-handed mixing element 41a and a left-handed mixing element 41b, which are arranged continuously in an alternating order along the long axis A. The right-handed mixing element 41 and the left-handed mixing element 41b have different helical winding directions.

[0030] In some embodiments, the mixing elements 41a / 41b have an outer diameter D of 1.5 mm to 1.6 mm. Furthermore, each mixing element has a length L of 0.6 mm to 1.2 mm, preferably 0.78 mm. The diameter D and length L are preferably the same for all mixing elements 41a / 41b of the mixing unit 40. This specific range of diameter D for the mixing elements 41a / 41b can improve mixing.

[0031] The tip 173 of the dispensing nozzle can be rigid or flexible. This nozzle tip can be formed from a thermoplastic material or may be a hollow needle made of metal. In some embodiments, the tip of the dispensing nozzle extends from the cannula with an internal angle in the range of 90° to 180°. In some embodiments, the internal angle is 95, 100, 105, or 110° or greater. In some embodiments, the internal angle is 170, 160, 150, 140, or 130° or less. In some embodiments, the length of the tip can be in the range of about 5 mm to 15 mm or 20 mm. In some embodiments, the length of the tip is 14, 13, 12, 11, or 10 mm or less. The outlet is typically round and has a diameter narrower than that of the cannula. In some embodiments, the diameter of the outlet is in the range of 0.5, 0.6, 0.7, or 0.8 mm or more, and 1, 1.1, 1.2, 1.3, 1.4, or 1.5 mm or less.

[0032] Syringe 1 may optionally include an actuator for progressively engaging the plunger toward the front end of the syringe. The inclusion of an actuator is useful for dispensing a predetermined amount (e.g., a single dose) of dental sealant material. This feature may be useful for precisely applying the appropriate amount, i.e., an amount sufficient to fill pits and fissures, but not an excess that would allow the patient to detect hardened sealant during chewing. An example of a syringe with an actuator is further described in International Publication No. 2017 / 180545, incorporated herein by reference.

[0033] During use of the syringe device, the nozzle rotates so that the slide valve opens and the fluid contained in the chamber can be transported through the nozzle. A finger (e.g., index and middle finger) contacts the finger rest 113, and the thumb pushes the rear end 16 of the plunger, typically moving the first plunger rod 121 and the second plunger rod 122 toward the front end 15 of the syringe device. By applying pressure to the rear end of the plunger by hand, the first and second portions of the dental sealant are transported onto the tooth surface (e.g., onto the enamel) via the static mixer and outlet.

[0034] The two components are combined by merging in a static mixer. Each component preferably has a viscosity of 5000 cps or less at 23°C, as measured according to the test method described in the examples. In some embodiments, the viscosity of each component is 4500, 4000, 3500, or 3000 cps or less at 23°C. Typically, the viscosity of each component is 200, 300, 400, or 500 cps or more at 23°C.

[0035] Furthermore, the viscosities of the two components are typically similar, differing by only 50, 45, 40, 35, 30, 25, 20, 15, or 10% or less, for example, the higher viscosity material. When the viscosity of each component being mixed and the viscosity difference are within a suitable range, a sufficiently homogeneous mixture can be dispensed through the outlet. Moreover, the components can be transported through a static mixer with a relatively low pressurizing force. Such a low pressurizing force can typically be generated by a manually operated system.

[0036] In some embodiments, a method for applying a dental sealant further includes pre-treating the tooth surface before applying the dental sealant. Such pre-treatment may include (e.g., acid) etching, priming, polishing, or a combination thereof, as is known in the art.

[0037] Each component of a dental sealant contains a polymerizable resin. The polymerizable resin is typically a mixture of (meth)acrylate monomers. One common acrylic monomer is described in U.S. Patent No. 3,066,112. Such an acrylic monomer is a reaction product of bisphenol A or other bisphenol with glycidyl methacrylate, and the reaction product is commonly referred to in the art as Bis-GMA monomer. Typically, this monomer is combined with various other monomers (e.g., low molecular weight, low viscosity) such as di(meth)acrylate monomers (e.g., tetraethylene glycol dimethacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, etc.) or monofunctional (meth)acrylate monomers (e.g., methyl methacrylate).

[0038] The dental sealants described herein include a "redox" curing system. In a redox process, a reducing agent is oxidized by losing electrons, and an oxidizing agent is reduced by gaining electrons. When an oxidizing agent and a reducing agent are combined, an initiator species (such as a free radical or cation) is generated that has the ability to cause curing (e.g., polymerization and / or crosslinking) of the curable resin. Typically, the redox pair is activated at temperatures below approximately 40°C.

[0039] Suitable oxidizing agents include peroxide compounds (i.e., peroxy compounds), which include hydrogen peroxide, as well as inorganic and organic peroxide compounds (e.g., "per" compounds, i.e., salts having a peroxoanion). Suitable oxidizing agents include, but are not limited to, peroxides such as benzoyl peroxide, phthaloyl peroxide, substituted benzoyl peroxide, acetyl peroxide, caproyl peroxide, lauroyl peroxide, cinnamoyl peroxide, acetylbenzoyl peroxide, methyl ethyl ketone peroxide, sodium peroxide, hydrogen peroxide, di-tert-butyl peroxide, tetralin peroxide, urea peroxide, and cumene peroxide; and hydroxides such as p-methane hydroxide, diisopropylbenzene hydroxide, tert-butyl hydroxide, methyl ethyl ketone hydroxide, and 1-hydroxycyclohexyl hydroperoxide-1.

[0040] Other oxidizing compounds include persulfate compounds (e.g., ammonium persulfate, potassium persulfate), perborate compounds (e.g., sodium perborate), perchlorate compounds (e.g., sodium perchlorate), ozone, ozone compounds, etc. These oxidizing agents may be used alone or in combination with each other.

[0041] The first initiator system may contain one or more oxidizing agents in an amount sufficient to initiate the curing process and provide a desired curing rate. Dental sealants typically consist of 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09 or 1% by weight or more, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5 or 10% by weight or less of the oxidizing agent, based on the total weight of all components of the dental material. In some embodiments, the dental sealant consists of 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5 or 5% by weight or more of the oxidizing agent.

[0042] The first initiator system also includes a reducing agent having one or more functional groups for activating the oxidizing agent and initiating curing. The functional groups are typically selected from amines, mercaptans, or mixtures thereof. If two or more functional groups are present, they may be part of the same compound or provided by different compounds.

[0043] Preferred reducing agents are aromatic tertiary amines. Examples of useful tertiary amines include those shown in the following formula: [ka]

[0044] In the formula, each R group may be H or an organic group that does not adversely affect the initiation of hardening of the dental material. The organic group generally does not sterically or electronically interfere with the function of the reducing agent. Examples of such compounds are disclosed in International Publication No. 97 / 35916, published on October 2, 1997.

[0045] Preferably R 1 R is an aliphatic group, 2 and R 3 These are independently (i.e., may be the same or different) H, an aromatic group, and / or an aliphatic group (preferably containing up to 20 carbon atoms). Preferably, R 2 and R 3 Only one of them is an aromatic group. More preferably, R1 is an alkyl group optionally substituted with a hydroxy group (preferably containing up to 10 carbon atoms), R 2 and R 3 is H or an alkyl group optionally substituted with a hydroxyl group (preferably containing up to 10 carbon atoms). In certain preferred embodiments, R 1 , R 2 , and R 3 can also contain a polymerizable functional group that reacts with a functional group of the resin. Preferably, at least one of R 1 , R 2 , and R 3 contains a functional group such as acrylate, methacrylate, acrylamide, vinyl, or other functional groups present in the above resin.

[0046] Preferably, R 4 , R 5 , R 6 , R 7 , and R 8 are independently H or an aliphatic group (preferably containing up to 20 carbon atoms). More preferably, R 4 , R 5 , R 6 , R 7 , and R 8 are independently H or an alkyl group optionally substituted with a hydroxy group (preferably containing up to 10 carbon atoms). In certain preferred embodiments, R 4 , R 5 , R 6 , R 7 , and R 8 can also contain a polymerizable functional group that reacts with a functional group of the resin. Preferably, at least one of R 4 , R 5 , R 6 , R 7 , and R 8 contains a functional group such as acrylate, methacrylate, acrylamide, vinyl, or other functional groups present in the above resin.

[0047] Particularly preferred aromatic tertiary amines are N,N-bis(2-hydroxyethyl)-p-toluidine (DHEPT), 2-(4-dimethylaminophenyl)ethyl alcohol (DMAPE), and 4-tert-butyldimethylaniline. Other preferred compounds include, for example, DMAPE having difunctional or polyfunctional acid compounds such as adipic acid, sebacic acid, 1,3,5-benzenetricarboxylic acid, and 1,2,4,5-benzenetetracarboxylic acid, or compounds derived from DMAPE having difunctional or polyfunctional isocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, and desmodul N-330 (trifunctional isocyanate).

[0048] The tertiary amine may be polymerizable. Particularly preferred polymerizable aromatic tertiary amines include, but are not limited to, adducts of IEM (2-isocyanatoethyl methacrylate) to N,N-bis(2-hydroxyethyl)-p-toluidine (DHEPT-di-IEM or bis-N,N-[2-(2-methacryloloxyethyl (methacryloloxyethyl)aminocarbonyloxy)ethyl]-p-toluidine), VDM (2-vinyl-4,4-dimethylazulactone) (DMAPE-VDM or 4-[ Examples include adducts of DMAPE to 2(2-acrylamido-2-methylpropionyloxy)ethyl)-N,N-dimethylaniline), adducts of methacrylate diesters to DHEPT (DHEPT-di-ester or bis-N,N-(2-methacryloxyethyl)-p-toluidine), and adducts of DHEPT to VDM (DHEPT-di-VDM or bis-N,N-[2-(2-acrylamido-2-methylpropionyloxy)ethyl]-p-toluidine).

[0049] Another preferred reducing agent is a mercaptan, which may contain aromatic and / or aliphatic groups and optionally polymerizable groups. Preferred mercaptans have a molecular weight greater than about 200 because they have less odor. Particularly preferred mercaptans are isooctylthioglycolate (IOTG) and pentaerythritol tetrakis(3-mercaptopropionate) (PETMP).

[0050] The tertiary amines and mercaptans may be used individually or in combination with each other. For example, a first initiator system may include one aromatic tertiary amine and one mercaptan, two aromatic tertiary amines, two mercaptans, and one polymerizable aromatic tertiary amine. Other reducing agents such as sulfinic acid, formic acid, ascorbic acid, hydrazine, and salts thereof may also be used herein to initiate free radical polymerization. However, preferably, the first initiator system comprises an aromatic tertiary amine, a mercaptan, or a mixture thereof. Such reducing agents may function as either a component of the first initiator system or a component of the second initiator system.

[0051] When using two or more reducing agents, they are preferably selected such that at least one of them has a faster activation rate than the other reducing agents.

[0052] The first initiator system may contain one or more reducing agents in an amount sufficient to initiate the curing process and provide a desired curing rate. Dental sealants typically contain a reducing hardener in the range of 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09 or 1% by weight or more, and 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5 or 10% by weight or less, based on the total weight of all components of the dental material. In some embodiments, the dental sealant contains 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5 or 5% by weight or more of reducing hardener.

[0053] A small amount of transition metal compound may be added to accelerate the redox curing rate. In some embodiments, it may be preferable to include a second ionic salt to enhance the stability of the polymerizable composition, as described in U.S. Patent Application Publication No. 2003 / 0195273 (Mitra et al.). The concentrations of the oxidizing agent and the reductive curing agent are selected to provide an optimal reaction rate. If the reaction rate is too fast, the dental sealant may harden prematurely in the dispensing nozzle. If the reaction rate is too slow, the overall treatment may be prolonged. In some embodiments, the dental sealant hardens within 5, 4, 3, 2, or 1 minute.

[0054] The dental sealant may further include a second initiator system. The second initiator system includes one or more initiators commonly used in free radical polymerization. The second initiator is preferably a free radical photoinitiator, which can be activated by irradiation with a chemical beam (using conventional dental curing light) to initiate polymerization (or curing) of the free radical polymerizable composition.

[0055] Photoinitiators can typically generate free radicals for addition polymerization when exposed to light energy having a wavelength of 400–800 nm. If the dental sealant is photocurable with conventional dental curing light, the sealant may also further contain rose bengal or other photobleaching colorants, such that the dental sealant is colored before curing but becomes tooth-colored after curing, as described in U.S. Patent No. 6,444,726 incorporated herein by reference. A variety of photoinitiators suitable for dental compositions are known.

[0056] In some embodiments, the dental sealant further comprises a sensitizer. The sensitizer may be co-initiated with an amine reducing agent.

[0057] The sensitizer is preferably soluble in the monomer and capable of absorbing light at any wavelength in the range of over 400 to 800 nanometers, more preferably 400 to about 500 nanometers. The sensitizer may also be sensitized to 2-methyl-4,6-bis(trichloromethyl)-s-triazine using the test procedure described in U.S. Patent No. 3,729,313, which is incorporated herein by reference. Preferably, in addition to passing this test, the sensitizer is also selected with some consideration for storage stability.

[0058] In addition to the colors imparted by dyes or pigments, photobleaching colors may be imparted by sensitizers. For example, camphorquinone can impart yellow to the material of the present invention, and rose bengal can impart a reddish color to the material.

[0059] Suitable sensitizers include compounds in the categories of ketones, coumarin dyes (e.g., ketocoumarins), xanthene dyes, fluorone acridine dyes, thiazole dyes, thiazine dyes, oxazine dyes, azine dyes, aminoketone dyes, porphyrins, polycyclic aromatic hydrocarbons, p-substituted aminostyryl ketone compounds, aminotrialylmethane, merocyanines, squarylium dyes, and pyridinium dyes. Xanthene dyes include dyes whose molecular structure is related to xanthenes and which have a color index in the range of 45,000 to 45,999. Ketones (e.g., monoketones or α-diketones), ketocoumarins, aminoaryl ketones, and p-substituted aminostyryl ketone compounds are preferred sensitizers. For applications requiring high sensitivity, it is preferable to use a sensitizer containing a julolidinil moiety.

[0060] For example, a preferred class of ketone sensitizers has the following formula: ACO(X) b B

[0061] Suitable ketones for the above formula include monoketones (b=0), such as 2,2-, 4,4- or 2,4-dihydroxybenzophenone, di-2-pyridyl ketone, di-2-furanyl ketone, di-2-thiophenyl ketone, benzoin, fluorenone, chalcone, Michler ketone, 2-fluoro-9-fluorenone, 2-chlorothioxanthone, acetophenone, benzophenone, 1- or 2-acetonaphthone, 9-acetylanthracene, 2-, 3- or 9-acetylphenanthrene, 4-acetylbiphenyl, propiophenone, n-butyrophenone, valerophenone, 2-, 3- or 4-acetylpyridine, and 3-acetylcoumarin. Suitable diketones include aralkyl diketones such as anthraquinone, phenanthrenequinone, o-, m- and p-diacetylbenzene, 1,3-, 1,4-, 1,5-, 1,6-, 1,7- and 1,8-diacetylnaphthalene, and 1,5-, 1,8- and 9,10-diacetylanthracene. Suitable α-diketones (b=1 and X=CO) include 2,3-butanedione, 2,3-pentanedione, 2,3-hexanedione, 3,4-hexanedione, 2,3-heptanedione, 3,4-heptanedione, 2,3-octanedione, 4,5-octanedione, benzyl, 2,2'-3,3'- and 4,4'-dihydroxylbenzyl, furyl, di-3,3'-indolethanedione, 2,3-bornanedione (camphorquinone), biacetyl, 1,2-cyclohexanedione, 1,2-naphthaquinone, and acenaphthaquinone.

[0062] Dental sealants (for example, first and / or second parts thereof) further contain components that promote remineralization, such as materials that release calcium ions, phosphorus-containing ions (e.g., phosphates), fluoride ions, or combinations thereof. In some embodiments, the dental sealant further contains a calcium ion-releasing compound, such as a calcium salt. Examples of calcium salts include calcium glycerol phosphate, calcium carbonate, calcium chloride, calcium caseinate, calcium citrate, calcium glubionate, calcium gluceptate, calcium gluconate, calcium hydroxide, calcium hydroxyapatite, calcium lactate, calcium oxalate, calcium oxide, calcium pantothenate, calcium phosphate, calcium polycarbophil calcium, calcium propionate, calcium pyrophosphate, and calcium sulfate. In some embodiments, for example, in the case of calcium oxide, the calcium ion-releasing compound also neutralizes the acid. Thus, a single component promotes remineralization and neutralizes the acid. In other embodiments, the calcium ion-releasing compound does not neutralize the acid. In this embodiment, the dental sealant further comprises another component which is a basic material.

[0063] In some embodiments, dental sealants include materials that promote remineralization by releasing fluoride ions, such as AlF3, Na2AlF3, and mixtures thereof. Other components that release fluoride ions include silanol-treated fluoroaluminosilicate glass fillers, such as those described in U.S. Patent No. 5,332,429. Organic fluoride sources, such as those described in U.S. Patent No. 4,871,786, are also preferred.

[0064] In some embodiments, dental sealants further include materials that promote remineralization by releasing phosphorus ions. Suitable phosphorus compounds include P2O5, AlPO4, and mixtures thereof. Some salts, such as calcium glycerol phosphate, release both calcium and phosphorus ions.

[0065] The concentration of such remineralization-promoting components is typically 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, or 5% by weight or more of the total dental sealant, and typically about 10% by weight or less. However, higher concentrations may be used if the remineralization-promoting component also neutralizes the acid.

[0066] The first and / or second portion of the dental sealant further comprises an acid-neutralizing basic component. In the case of dental sealants, this basic component is presumed to be able to neutralize acids originating from bacteria or food sources that come into contact with the hardened dental sealant.

[0067] The acid-neutralizing component is typically combined with (e.g., a second) component of the dental sealant, which includes a polymerizable resin and a reducing agent.

[0068] In a preferred embodiment, the dental sealant comprises an encapsulated material containing a basic core material. In one preferred embodiment, an inorganic shell material surrounds the core material. The shell material and the thickness of the shell can be selected to allow control and / or delayed release or reaction of the basic core material. In some embodiments, the release of the basic core material is utilized to increase basicity after a long period of time. Such encapsulated materials are further described in U.S. Patent Application Publication No. 2017 / 063829, which is incorporated herein by reference.

[0069] Alternatively, dental sealants may contain unencapsulated basic materials. Therefore, the following description of a “basic core” also applies to unencapsulated “basic materials.”

[0070] The encapsulated packing material includes a basic core material. The basic (e.g., core) material, as well as the material (e.g., compound) that forms the core, is generally solid at 25°C. The basic (e.g., core) material may be a single particle or a group of smaller associated particles. As used herein, the term “associated” refers to a group of two or more primary particles that are aggregated and / or agglomerated. Similarly, the term “non-associated” refers to a group of two or more primary particles that do not involve aggregation and / or agglomeration.

[0071] In some embodiments, the basic (e.g., core) material may contain multiple aggregated particles. "Aggregation" or "coagulation" refers to a strong association between primary particles. For example, primary particles can be chemically bonded to one another. When a basic (e.g., core) material is prepared such that aggregated basic (e.g., core) particles remain as aggregates, and during encapsulation, typically, the aggregates do not break down into smaller particles (e.g., primary particles). Similarly, the term "non-aggregated" refers to primary particles that do not exhibit strong association with other primary particles.

[0072] In other embodiments, the basic (e.g., core) material may contain multiple agglomerated particles. As used herein, the terms “agglomeration” or “agglomeration” refer to the weak association of primary particles. For example, primary particles may be held together by charge or polarity. During the preparation and encapsulation of the basic (e.g., core) material, agglomerations may decompose into smaller particles (e.g., primary particles). Similarly, the term “non-agglomerated” refers to primary particles that do not have weak associations with other primary particles.

[0073] The average particle size of basic (e.g., core) material (e.g., primary particles, aggregated particles, or agglomerated particles) is typically 0.2, 0.5, 1, 2, 3, 4, or 5 micrometers or larger, and typically 1 mm, 750 micrometers, or 500 micrometers or smaller, as measured, for example, using a sedimentation analyzer. In some embodiments, the average particle size of basic (e.g., core) material (e.g., primary particles, aggregated particles, or agglomerated particles) is typically 250, 200, 150, 100, or 50 micrometers or smaller. In some embodiments, the average particle size of basic (e.g., core) material (e.g., primary particles, aggregated particles, or agglomerated particles) is typically 45, 40, 35, 30, 25, or 20 micrometers or smaller. Since the shell is typically thin, the enclosed material may also fall within the average particle size range described above.

[0074] The core material is basic. Chemically basic materials are those that donate electrons, accept protons, and typically provide hydroxyl ions to aqueous solutions.

[0075] Materials, including the core of the encapsulated material, are considered basic if they have or exhibit one or more of the following properties, including containing a sufficient amount of high pKa components, resulting in a basic pH when added to deionized water (according to the test methods further described in the Examples), or resulting in a basic pH when added to an acidic buffer (according to the test methods further described in the Examples).

[0076] Basic materials function to react with acids and acidic buffers to produce an increase in pH. The change in pH and the rate of pH change depend on the strength of the basic component, the chemical and physical form of the basic component within it, and the amount of the basic component in the basic (e.g., core) material.

[0077] In some embodiments, the basic material (e.g., the core of the encapsulated material) is strongly basic. The strongly basic material typically comprises and is prepared from a sufficient amount of a strongly basic material (e.g., a compound) having a pKa in the range of about 11–14. Examples of strongly basic compounds include oxides and hydroxides of alkali and alkaline earth metals, and strongly basic salts such as alkali phosphates. Specific examples of strongly basic (e.g., core) compounds include oxides and hydroxides of Na, K, Ca, Sr, and Ba; silicates of Na, K, Ca, Sr, and Ba; and aluminates of Na, K, Ca, Sr, and Ba. Strongly basic silicates and glasses typically contain at least 1, 2, or 3 moles of a strongly basic (e.g., core) compound (e.g., CaO) per mole of silica, on a cation molar basis. Similarly, strongly basic aluminates typically contain at least 1, 2, or 3 moles of a strongly basic (e.g., core) compound (e.g., CaO) per mole of alumina, on a cation molar basis.

[0078] In some embodiments, the strongly basic material may be a heterogeneous physical mixture of at least one strongly basic compound and a weakly basic or neutral material. For example, the strongly basic material may be a physical mixture of silica and sodium hydroxide. Sodium hydroxide is a strongly basic material having a pKa of 13.8. A 0.1N aqueous solution of sodium hydroxide has a pH of 13. On a weight percentage basis, 1 gram of a mixture of 96 wt% silica and 4 wt% sodium hydroxide in 1 liter of water will provide a 0.1N aqueous solution of sodium hydroxide. If the enclosed material is a physical mixture, substantially all strongly basic compounds are accessible upon shell decomposition. Therefore, in this embodiment, the basic (e.g., core) material may be present in small amounts (e.g., at least 1, 2, or 3 wt% of the strongly basic material) to provide a delayed pH of 8.5 or 9 or higher in deionized water (according to the test method described in the examples). However, higher concentrations of the chemically basic (e.g., core) material may be required to provide a delayed pH of 8.5 or 9 or higher in an acidic buffer solution. For example, depending on the pKa of the strongly basic material, the amount of the strongly basic material may be 5, 6, 7, 8, 9, or 10% or more by weight of the total encapsulated material.

[0079] In other embodiments, the basic material (e.g., the core of the encapsulated material) is a multicomponent crystalline compound comprising at least one strongly basic material (e.g., a compound) and other components (such as alkaline earth silicates) prepared therefrom. In yet another embodiment, the basic material (e.g., the core of the encapsulated material) can be characterized as a multicomponent amorphous glass prepared from at least one strongly basic material (e.g., a compound). The strongly basic material (e.g., a compound) can be distributed homogeneously or heterogeneously within the glass structure. When the basic material (e.g., the core of the encapsulated material) is a molten multicomponent material such as glass, the concentration of the strongly basic compound (which can be determined by X-ray fluorescence (XRF) or inductively coupled plasma (ICP)) is typically in the range of 25, 30, 35, 40, 45, or 50% by weight or more, 75% by weight or less, or greater, based on the entire basic (e.g., core) material.

[0080] In some preferred embodiments, the basic (e.g., core) material comprises and is prepared from CaO having a pKa of 11.6. CaO can be used in combination with providing a calcium ion source to result in both a delay in the rise of pH. The amount of CaO can typically be 5, 10, 15, 20, or 25% by weight or more, 75% by weight or less, or more. The amount of Ca is about 71% of such values. Specific examples of strongly basic multicomponent (e.g., core) materials containing CaO include Portland cement (reported to contain 60-70% by weight of CaO), tricalcium silicate (containing about 75% by weight of CaO), and bioactive glass (containing about 25% by weight of CaO and about 25% by weight of Na2O), such as that available from 3M Advanced Material Division.

[0081] In other embodiments, the basic material of the encapsulated material (e.g., the core of the encapsulated material) is weakly basic. The weakly basic material comprises a substantial amount of at least one material (e.g., a compound) having a pKa in the range of 8 or greater but less than 11. In some embodiments, the weakly basic material has pKas of 8.5, 9, 9.5, 10, 10.5 or greater. Examples of weakly basic (e.g., core) compounds include oxides of Cu, Zn, and Fe, as well as weakly basic salts such as NaF, calcium acetate, and hydrogen phosphate.

[0082] Alternatively, a weakly basic (e.g., core) material may contain or be prepared from a smaller amount of a strongly basic compound. A weakly basic (e.g., core) material alone typically cannot provide a sufficient amount of hydroxyl ions to adequately raise the pH of an acidic solution. However, a weakly basic (e.g., core) material alone can provide a sufficient amount of hydroxyl ions to adequately raise the pH of water. Furthermore, a weakly basic (e.g., core) material (e.g., encapsulated) can be used in combination with a strongly basic (e.g., core) material (e.g., encapsulated).

[0083] For example, the encapsulated basic material is typically not a reducing agent in a redox curing system. The encapsulation of a reducing agent will delay the redox curing reaction. Furthermore, since reducing agents are typically weak bases used at relatively low concentrations, the encapsulated reducing agent alone will not produce the desired increase in pH.

[0084] In preferred embodiments, the basic (e.g., core) material further comprises and is prepared from one or more neutral compounds, which are defined herein as having a pKa of 6, 6.5, or 7 or greater but less than 8. In some embodiments, such neutral compounds exhibit low solubility in deionized water and / or weak acid solutions and / or weak base solutions. Weak acid solutions typically have a pH of less than 7 but greater than 4. Weak base solutions typically have a pH greater than 7 but less than 10. Low solubility means that less than 100 grams (i.e., 10% by weight) dissolves per liter. In some embodiments, less than 50, 25, 5, or 1 gram dissolves per liter. Examples of neutral compounds include silica, zirconia, titania, alumina, and combinations thereof. A pKa greater than 7 is slightly basic, but such basicity is less than that of weak basic (e.g., core) materials and significantly less than that of strongly basic (e.g., core) materials, as described above.

[0085] If a (e.g., core) material is prepared from only a basic material (e.g., a compound) or from a combination of a basic material and a neutral material, the basicity of the (e.g., core) material can be estimated based on the weight of the components. Thus, the (e.g., core) material contains the aforementioned amount of basic material (e.g., a compound). However, if the core material further contains an acidic material (e.g., a compound), the estimation of basicity can become more difficult. In particular, for embodiments where it is difficult to estimate the basicity of the (e.g., core) material based on its composition or compositional analysis, the basicity of a basic (e.g., core) material or an enclosed core material can be defined by the change in pH of a specific amount of the material in deionized water or an acidic (e.g., buffer) solution. These tests can also be used to confirm that the (e.g., core) material or an enclosed core material is indeed basic.

[0086] For example, fluoroaluminosilicate (FAS) glass is a homogeneous glass structure prepared from approximately 19% by weight of a strongly basic compound (SrO), with the remainder being neutral (SiO2) and other compounds. When tested in deionized water according to the test method described in 78772 cited above, FAS glass reduces the pH to 6.5 within 15 minutes and is therefore considered a weakly acidic core material.

[0087] In some embodiments, the basicity of the (e.g., core) material or the encapsulated core material can be determined by the pH change of a specific amount (0.25 g) of the material in 25 g of deionized water. An unencapsulated basic (e.g., core) material typically changes the pH of the deionized water from neutral to 8.5 or 9 or higher. This typically occurs within 1, 2, 3, 4, or 5 minutes, but may take up to 1 or 24 hours.

[0088] In preferred embodiments, the basicity of a basic (e.g., core) material or encapsulated material can be determined by the pH change of a specific amount (0.25 g) of the material in a buffer solution, which is 15 g of deionized water and 10 g of aqueous potassium bituminate buffer (e.g., buffer BDH5018) having a pH of 4, adjusted to 4.00 at 25°C (with hydrochloric acid). This test is referred to herein as the “buffer test”. When a strongly basic (e.g., core) material or encapsulated material is subjected to the buffer test, it may reach a pH of 8.5 or 9 or higher. It is understood that a larger amount of hydroxyl ions is required to change an acidic solution to a basic pH compared to deionized water. Therefore, this pH change may take a longer time compared to the same material in deionized water. In some embodiments, such a pH change occurs within 5, 10, or 15 minutes, but may take up to 1 hour or 24 hours.

[0089] A weakly basic (e.g., core) material may result in a small increase in pH when tested according to a buffering test. For example, the pH may rise from 4 to 5. However, a weakly basic (e.g., core) material does not provide a sufficient amount of hydroxyl ions to reach a pH of 8.5 or 9 or higher when tested according to a buffering test.

[0090] Therefore, when the enclosed basic core material is added to water or buffer solution, the pH does not change initially (i.e., immediately after immersion of the material in water or buffer solution), as described herein, but the pH increases at various rates depending on the shell and basic core material.

[0091] In some embodiments, the basic (e.g., core) material is curable or self-curing when mixed with water, as in the case of various natural and synthetic cements. Conventional natural (e.g., Portland) cements and synthetic cements typically contain large amounts of calcium silicate (e.g., 3CaO-SiO2, 2CaO-SiO2) alone or in combination with one or more calcium aluminates (e.g., 3CaO-Al2O3, 4CaO-Al2O3-Fe2O3).

[0092] In some embodiments, the encapsulated material is an encapsulated (e.g., dental) filler.

[0093] The encapsulated (e.g., dental) filling material may contain a substantial amount of neutral metal oxide having low solubility in water or an acidic solution having a pH of 3-4, as described above. Examples of neutral metal oxides include silica, zirconia, titania, and alumina. The amount of neutral metal oxide may range from 10, 15, 20, 25, 30% by weight or more, to 50, 60, 70, 80, or 90% by weight or less, of the total weight of the basic (e.g., core) material. Calcium silicate and encapsulated calcium silicate may also be characterized as filling materials because they contain silica.

[0094] Dental sealants contain materials that promote remineralization, as described above. These materials can be present within the core of the encapsulated sealant, provided as a second filler such as FAS glass, or provided as separate components in a curable dental sealant composition.

[0095] In some embodiments, the core or second filler material comprises and is prepared from fluoride compounds such as AlF3, Na2AlF3, and mixtures thereof in an amount ranging from about 5 to 40% by weight. In some embodiments, the amount of AlF3 is in the range of 10 to 30% by weight of the core or second filler material. In some embodiments, the amount of Na2AlF3 is in the range of 2 to 10% by weight of the core or second filler material.

[0096] In some embodiments, the core or second filler material contains and is prepared from phosphorus compounds such as P2O5, AlPO4, and mixtures thereof in an amount ranging from 2 to 25% by weight. In some embodiments, the amount of P2O5 is in the range of 2 to 15% by weight of the core or second filler material. In some embodiments, the amount of AlPO4 is in the range of 2 to 10% by weight of the core or second filler material.

[0097] Basic (e.g., core) materials can be encapsulated by any preferred method. In some embodiments, basic (e.g., core) materials can be encapsulated in an inorganic shell containing a metal oxide by any preferred method, such as vapor deposition, atomic layer deposition (ALD), sputtering, or evaporation, which are well known in the art.

[0098] The shell material may be a weakly basic material. However, the basicity of the shell material is not sufficient to produce the desired pH change, particularly according to the buffering test or disk buffering test described above (as described below).

[0099] In some embodiments, the shell, or in other words, the encapsulating material, has an average thickness of 5, 10, 15, 20, or 25 nm or more. The shell thickness may be in the range of 250, 500, 750, or 1000 nm (1 micrometer) or more. In some embodiments, for example, in the case of encapsulated dental fillings, the shell thickness is typically in the range of 50, 75, 100, 150, or 200 nm or less.

[0100] On a weight percentage basis, the shell material is typically 0.1, 0.2, 0.3, 0.4, or 0.5% or more of the total encapsulated material. The amount of shell material on a weight percentage basis may range up to 15 or 20% or less of the total encapsulated material, but more typically it is 10, 9, 8, 7, 6, or 5% or less. In some embodiments, the amount of shell material on a weight percentage basis is 4.5, 4, 3.5, 3, 2, or 1% or less.

[0101] In a preferred embodiment, the shell material and shell thickness can be selected to allow control and / or delayed release or reaction of the basic core material.

[0102] In a preferred embodiment, the shell is initially impermeable (i.e., materials from the composition and core material cannot interact by simple diffusion through the shell). Interaction occurs after the shell has been altered by interaction with other materials (e.g., decomposition, corrosion, or dissolution). The composition (e.g., a two-part composition) may be designed to contain a component such as water or an acid that decomposes the shell. In other embodiments, decomposition of the shell may occur by contact with water or an acidic component during use. In this embodiment, the source or water or acidic component may be a biological fluid (e.g., saliva or water retained within the soft tissue surrounding a tooth or bone).

[0103] In some embodiments, the concentration of the basic material (e.g., encapsulated) is typically in the range of 2, 3, 4, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, or 65% by weight or more, and 100% by weight or less, of the second portion of the curable dental sealant composition. The whole curable (e.g., dental composition) contains half of such a concentration of the basic material (e.g., encapsulated). Thus, the concentration of the basic material (e.g., encapsulated) is typically in the range of 1, 1.5, 2, 2.5, 5, 7.5, 10, 12.5, 15, 17.5, 20, 22.5, 25, 27.5, 30, or 32.5% by weight or more, and 50% by weight or less, of the whole curable dental sealant composition. The concentration can be selected based on the strength of the basic (e.g., encapsulated) material and the intended properties of the dental sealant composition.

[0104] Referring to Tables 4-7 of 78772WO003 cited earlier, in one embodiment, an unencapsulated (e.g., Portland cement or tricalcium silicate) basic material yields a basic pH (e.g., 8.5, 9, 9.5, 10, or 10.5 or higher) within 1 minute when subjected to the buffering test described above. However, an encapsulated (e.g., Portland cement or tricalcium silicate) basic material does not yield a basic pH (e.g., 8.5, 9, 9.5, 10, or 10.5 or higher) for 2, 3, 4, 5, 6, 7, 8, 9, or 10 minutes or longer according to this buffering test. In some embodiments, an encapsulated (e.g., Portland cement) basic material does not yield a basic pH (e.g., 8.5, 9, 9.5, 10, or 10.5 or higher) for 15, 20, 25, 30, 35, 40, or 45 minutes. In some embodiments, the encapsulated basic material (e.g., Portland cement) does not result in a basic pH (e.g., 8.5, 9, 9.5, 10, or 10.5 or higher) for 100, 200, or 300 minutes.

[0105] In another embodiment, an unencapsulated (e.g., bioactive glass) basic material, when subjected to the aforementioned buffering test, yields a basic pH (e.g., 8.5, 9, 9.5, 10, or 10.5 or higher) within 5 minutes. However, an encapsulated (e.g., bioactive glass) basic material, according to this buffering test, does not yield a basic pH (e.g., 8.5, 9, 9.5, 10, or 10.5 or higher) for 30 to 40 minutes.

[0106] In another embodiment, an unencapsulated basic material (e.g., Portland cement) yields a basic pH of 11.5 within 20 seconds when tested in deionized water. However, an encapsulated basic material (e.g., Portland cement) yields a basic pH of 8.5 or higher within 20 seconds when tested in deionized water. In yet another embodiment, an unencapsulated basic material (e.g., bioactive glass) yields a basic pH of 10.5 within 20 seconds when tested in deionized water. However, an encapsulated basic material (e.g., bioactive glass) yields a basic pH of 9.8 or higher within 20 seconds when tested in deionized water. Therefore, the pH change of an acidic (e.g., buffer solution) can occur at a significantly slower rate than in deionized water.

[0107] In preferred embodiments, the delayed release or reaction of a basic (e.g., core) material can be utilized to improve the basicity of the cured dental sealant material, thereby neutralizing acids that subsequently form in the oral environment near the cured dental sealant. Unencapsulated strong basic materials can produce a desired, significant (but undesirably rapid) increase in pH. Encapsulated, the same basic material can produce the desired increase in pH, but only after a long time, i.e., by slowly and continuously releasing the basic material (e.g., hydroxyl ions).

[0108] The basicity of a carrier material (e.g., a biological carrier material), such as a cured dental sealant composition containing encapsulated or unencapsulated basic material, can be evaluated by measuring the pH change of a disk (3.1 mm × 1.3 mm high) of hardened (i.e., cured) material immersed in 1.5 mL of 10 mM Na₂HPO₄ (commonly known as PBS) buffer contained in a 2 mL plastic centrifuge tube. PBS buffer can be prepared by dissolving 8 g of NaCl, 0.2 g of KCl, 1.44 g of Na₂HPO₄, and 0.24 g of KH₂PO₄ in 800 mL of distilled H₂O, adjusting the pH to 7.4 with HCl, adjusting the volume to 1 L with additional distilled water, and sterilizing by autoclaving. This test is subsequently referred to herein as the “disk buffering test.”

[0109] Representative two-component curable dental sealant compositions that may be used in disc buffering tests are further described in the following examples.

[0110] In some embodiments, a cured dental sealant composition containing encapsulated or unencapsulated basic material raises the pH of the buffer by 0.05, 0.10, 0.15, 0.20, 0.25, or 0.30 or more within 15 or 39 hours.

[0111] The cured dental sealant composition is initially neutral in water (pH 7–7.5), and becomes basic (pH 8, 8.5, 9, 9.5, 10, 10.5, or 11 or higher) after various periods ranging from 1 hour to 1 day, and in some embodiments, 2, 3, 4, 5, 6, or 7 days or longer. However, as the released base neutralizes the acids present in the oral environment, the cured dental sealant composition may remain neutral (pH 7–7.5) due to a neutralization reaction that proceeds at a rate equal to the release rate of the basic (e.g., core) material.

[0112] In one embodiment, encapsulated or unencapsulated basic material, in the case of a composition containing more than 16.25% by weight of encapsulated basic material, results in a basic pH (e.g., 8.5, 9, 9.5, 10, or 10.5 or higher) within 46, 72, 100, 147, 260, 360, or 500 hours.

[0113] The dental sealant composition may optionally include additional additives suitable for use in the oral environment, including flavorings, antibacterial agents, fragrances, stabilizers, viscosity modifiers, rheological modifiers, inhibitors, and (in embodiments where the dental sealant is not cured by exposure to UV light) ultraviolet (UV) absorbers. Other suitable additives include fluorescent and / or opalescent agents.

[0114] In some embodiments, the cured dental sealant has a tooth-like white appearance. In this embodiment, at least one portion of the dental sealant typically further comprises an opacifying filler. Preferred fillers include, for example, titania, zirconia, alumina, or silica. The average particle size of the opacifying filler is typically in the range of 0.1 or 0.2 microns or more and 0.7 or 1 micron or less. In some embodiments, the encapsulated material, comprising a basic core material and an inorganic shell material, is a single or primary opacifying filler, as described later.

[0115] The concentration of the opacifying filler may typically be in the range of 0.05, 0.10, 0.15, 0.2% by weight or more, and 5% by weight or less.

[0116] The preferred amount of opacifying filler varies depending on the particle size distribution and refractive index of the opacifying filler and the curing resin system. The greater the difference in refractive index between the filler and the curing resin, the more efficient the filler is in terms of opacity.

[0117] In typical embodiments, suspending agents such as fumed silica can be used. Fumed silica is commercially available from Cabot Corporation under the trade name "Cab-O-Sil" and from Degussa, Inc. under the trade name "Aerosil". Suspending agents can thicken the composition, thereby increasing its viscosity.

[0118] The concentration of the suspending agent may typically be in the range of 0.05, 0.10, 0.15, 0.2% by weight or more, and 5% by weight or less. When higher concentrations of basic materials are used, the concentration of the suspending agent may be reduced to maintain a sufficiently low viscosity.

[0119] In typical embodiments, the opacifying filler and suspending agent include a hydrophobic (e.g., organosilane) surface treatment. The filler can be treated using the procedure described in U.S. Patent No. 3,066,112, which is incorporated herein by reference. A reactive organosilane useful for this purpose is γ-methacrylateoxypropyltrimethoxysilane (commercially available from Union Carbide as "A-174").

[0120] The dental sealant compositions described herein are typically prepared by first mixing a polymerizable resin with an oxidizing or reducing agent and other optional additives. The opacifying filler and suspending agent are then mixed under high shear force until a homogeneous dispersion is obtained.

[0121] The present invention will be further explained by the following examples. [Examples]

[0122] material Camphorquinone (CPQ), benzoyl peroxide-LUPEROX A75 (BPO), 2-(4-dimethylamino)phenyl)ethanol (DMAPE), triethylene glycol dimethacrylate (TEGDMA), and bisphenol A glyceroate dimethacrylate (BisGMA) were obtained from Sigma-Aldrich.

[0123] 2,6-di-tert-butyl-4-methylphenol (BHT) was obtained from PMC Specialties Incorporated (Cincinnati,OH).

[0124] The fumed silica (AEROSIL R972) was obtained from Evonik Corporation (Piscataway, NJ).

[0125] Portland cement: White Portland cement (Federal White Type 1, ASTM designation C150) was purchased from Federal White Cement (Woodstock, Ontario, Canada). The main components of the composition reported by the manufacturer are tricalcium silicate (3CaO-SiO2), dicalcium silicate (2CaO-SiO2), tricalcium aluminate (3CaO-Al2O3), tetracalcium aluminoferrite (4CaO-Al2O3-Fe2O3), magnesium oxide, calcium oxide, potassium sulfate, and sodium sulfate. Portland cement is a strongly basic material containing multiple components. Each major component (excluding the trace components of magnesium oxide, potassium sulfate, and sodium sulfate) contains a considerable amount of strong base (CaO). Portland cement typically contains approximately 61%–69% CaO, 18%–24% SiO2, 2%–6% Al2O3, 1%–6% Fe2O3, and 0.5%–5% MgO.

[0126] calculation The shell thickness, weight % of core material, and weight % of shell material for the encapsulated material prepared by the processes described in Examples 1 and 2 were calculated using the following equations 1 to 6. In the calculation, the total surface area of ​​the core material was calculated by treating the particles of the core material powder as spheres (surface area = 4π(d / 2)). 2 Volume = (4 / 3)(π)(d / 2) 3 This was determined by expressing it as follows:

[0127] Formula 1:

number

[0128] Formula 2:

number

[0129] Formula 3:

number

[0130] Formula 4:

number

[0131] Formulas 5 and 6 - Weight percentage (Wt%) of the enclosed material:

number

[0132] measurement Viscosity measurements were taken using a Brookfield DV-I+ viscometer with a HELIPATH stand and a Type AT bar spindle (AMETEK Brookfield (Middleboro, MA)). Measurements were taken at 23°C for 100 seconds. -1 The test was conducted at the specified shear rate. Test results were obtained when the viscosity measurement stabilized (typically within 0.5–2 minutes). Viscosity is reported in centipoise (cP) units.

[0133] Example 1. Enclosed material 1 (PC core and AO shell) Portland cement (PC) was sealed with aluminum oxide (AO)-based material using atmospheric pressure chemical vapor deposition (APCVD). The Portland cement powder was coated with trimethylalumina (obtained from Strem Chemicals (Newburyport, MA) and dispensed from a stainless steel bubbler) by reacting it with water vapor in a fluidized bed reactor. The reactor was a glass frit funnel tube (12 cm in diameter, 30 cm in height). The reactor had an inlet tube extending from below the frit, routed parallel to the reactor body, and an extended top region above the frit, allowing for the desired reactor height and fittings for the precursor injector tube and exhaust outlet. The temperature was controlled to 180°C using an oil bath. Nitrogen carrier gas was used in a standard bubbler configuration for the liquid precursor. The bubbler was maintained at an ambient temperature of approximately 22°C. The flow rate through the trimethylalumina (TMA) bubbler was 1773 cm³. 3 The flow rate through the water bubbler was 5307 cm³ / min. 3 The rate was per minute. The total coating time was 120 minutes. The amount of Portland cement added to the reactor was 800 g, and the particle size of the Portland cement powder was 20 microns.

[0134] Before adding to the reactor, fine and coarse particles were removed from the Portland cement sample using an AVEKA CCE centrifugal air classifier Model 100 (AVEKA CCE LLC (Cottage Grove, MN)). In the first step, approximately 24% of the coarse portion of the initial sample was removed, and in the second step, approximately 25% of the fine portion was removed from the remaining sample. The resulting Portland cement powder had an average particle size of 20 microns (measured using a Coulter Counter Multisizer 3 (Beckman Coulter Company (Brea, CA))).

[0135] The enclosed material 1 was calculated to have a shell thickness of 46 nm. The calculated weight percentages (wt%) were 98.8 wt% core material and 1.2 wt% shell material.

[0136] Example 2. Encapsulated material 2 (PC core and AO shell) Portland cement (PC) was sealed with aluminum oxide (AO)-based material using atmospheric pressure chemical vapor deposition (APCVD). The Portland cement powder was coated with trimethylaluminum (obtained from Strem Chemicals and dispensed from a stainless steel bubbler) by reacting it with steam in a fluidized bed reactor. The reactor was a glass frit funnel tube (12 cm in diameter, 30 cm in height). The reactor had an inlet tube extending from below the frit, routed parallel to the reactor body, and an extended top region above the frit, allowing for the desired reactor height and fittings for the precursor injector tube and exhaust outlet. The temperature was controlled to 180°C using an oil bath. Nitrogen carrier gas was used in a standard bubbler configuration for the liquid precursor. The bubbler was maintained at an ambient temperature of approximately 22°C. The flow rate through the trimethylalumina (TMA) bubbler was 2670 cm³. 3 The flow rate through the water bubbler was 8032 cm³ / min. 3The rate was per minute. The total coating time was 190 minutes. The amount of Portland cement added to the reactor was 1500 g, and the particle size of the Portland cement powder was 20 microns.

[0137] Before adding to the reactor, fine and coarse particles were removed from the Portland cement sample using an AVEKA CCE centrifugal air classifier Model 100 (AVEKA CCE LLC). In the first step, approximately 24% of the coarse portion of the initial sample was removed, and then in the second step, approximately 25% of the fine portion was removed from the remaining sample. The resulting Portland cement powder had an average particle size of 20 microns (measured using a Coulter Counter Multisizer 3 (Beckman Coulter Company)).

[0138] The enclosed material 2 was calculated to have a shell thickness of 58 nm. The calculated weight percentages (wt%) were 98.5 wt% core material and 1.5 wt% shell material.

[0139] Example 3. The composition of Paste AA-1 is reported in Table 1 (each component is reported in weight %). Paste AA-1 was prepared in bulk. BisGMA and TEGDMA were combined (1:1 weight ratio) and stirred until homogeneous. In a mixing cup, the BisGMA / TEGDMA mixture was mixed with BPO and CPQ. The filled cup was placed in a FlackTek SPEEDMIXER (FlackTek Incorporated (Landrum, SC)) and the contents were mixed at 2400 rpm until a homogeneous mixture was obtained. Fumed silica (AEROSIL R972) was added to the cup. The cup was placed in the FlackTek SPEEDMIXER and the contents were mixed at 2400 rpm until a homogeneous mixture of Paste AA-1 was obtained. The viscosity of Paste AA-1 was 1130 ± 9 cP (23℃, shear rate 100 s). -1 ) was.

[0140] The composition of Paste BB-1 is reported in Table 2 (each component is reported in weight %). BisGMA and TEGDMA were combined (1:1 weight ratio) and stirred until homogeneous. In a mixing cup, the BisGMA / TEGDMA mixture was mixed with DMAPE and BHT. The filled cup was placed in a FlackTek SPEEDMIXER and the contents were mixed at 2400 rpm until a homogeneous mixture was obtained. Fumed silica (AEROSIL R972) was added to the cup. The cup was placed in a FlackTek SPEEDMIXER and the contents were mixed at 2400 rpm until a homogeneous mixture was obtained. Enclosed material 1 was added to the cup. The cup was placed in a FlackTek SPEEDMIXER and the contents were mixed at 2400 rpm until a homogeneous mixture of Paste BB-1 was obtained. The viscosity of Paste BB-1 was 1450 ± 12 cP (23℃, shear rate 100 s). -1 ) was.

[0141] [Table 1]

[0142] [Table 2]

[0143] Example 4. The composition of Paste BB-2 is reported in Table 3 (each component is reported in weight %). BisGMA and TEGDMA were combined (1:1 weight ratio) and stirred until homogeneous. In a mixing cup, the BisGMA / TEGDMA mixture was mixed with DMAPE and BHT. The filled cup was placed in a FlackTek SPEEDMIXER and the contents were mixed at 2400 rpm until a homogeneous mixture was obtained. Fumed silica (AEROSIL R972) was added to the cup. The cup was placed in a FlackTek SPEEDMIXER and the contents were mixed at 2400 rpm until a homogeneous mixture was obtained. Enclosed material 2 was added to the cup. The cup was placed in a FlackTek SPEEDMIXER and the contents were mixed at 2400 rpm until a homogeneous mixture of Paste BB-1 was obtained.

[0144] Pastes AA-1 and BB-2 were equilibrated in a chamber at 37°C, and then mixed on a mixing plate in a volume ratio of approximately 1:1. The resulting sealant composition cured after 2 minutes.

[0145] When AA-1 and BB-2 were mixed in a 1:1 volume ratio on a mixing plate at room temperature (approximately 23°C) without using a curing light (dark curing), the sample did not harden after 2 minutes.

[0146] Alternatively, pastes AA-1 and BB-2 were mixed in a 1:1 volume ratio on a mixing plate at room temperature (approximately 23°C) and immediately cured using an Elipar® DeepCure-S LED curing light (3M Oral Care (Maplewood, MN)). The sealant composition cured after being exposed to light for 10 seconds.

[0147] [Table 3]

[0148] Example 5. The composition of Paste AA-2 is reported in Table 4 (each component is reported in weight %). Paste AA-2 was prepared in bulk. BisGMA and TEGDMA were combined (1:1 by weight ratio) and stirred until homogeneous. In a mixing cup, the BisGMA / TEGDMA mixture was mixed with BPO and CPQ. The filled cup was placed in a FlackTek SPEEDMIXER and the contents were mixed at 2400 rpm until a homogeneous mixture was obtained. Fumed silica (AEROSIL R972) was added to the cup. The cup was placed in a FlackTek SPEEDMIXER and the contents were mixed at 2400 rpm until a homogeneous mixture of Paste AA-2 was obtained.

[0149] The composition of Paste BB-3 is reported in Table 5 (each component is reported in weight %). BisGMA and TEGDMA were combined (1:1 weight ratio) and stirred until homogeneous. In a mixing cup, the BisGMA / TEGDMA mixture was mixed with DMAPE and BHT. The filled cup was placed in a FlackTek SPEEDMIXER and the contents were mixed at 2400 rpm until a homogeneous mixture was obtained. Fumed silica (AEROSIL R972) was added to the cup. The cup was placed in a FlackTek SPEEDMIXER and the contents were mixed at 2400 rpm until a homogeneous mixture was obtained. Enclosed material 2 was added to the cup. The cup was placed in a FlackTek SPEEDMIXER and the contents were mixed at 2400 rpm until a homogeneous mixture of Paste BB-2 was obtained.

[0150] Pastes AA-2 and BB-3 were mixed in a 1:1 volume ratio on a mixing plate at room temperature (approximately 23°C) without the use of curing light (dark curing). The resulting sealant composition cured within 1 minute.

[0151] Alternatively, pastes AA-2 and BB-3 were mixed in a 1:1 volume ratio on a mixing plate at room temperature (approximately 23°C) and immediately cured using an Elipar® DeepCure-S LED curing light (3M Oral Care). The resulting sealant composition cured after being exposed to light for 10 seconds.

[0152] [Table 4]

[0153] [Table 5]

[0154] Example 6. A two-chamber syringe device equipped with the dispensing nozzle and static mixer shown in Figures 1 to 4 was used. The dimensions of the syringe device were as follows: cartridge length = 73.8 mm, cartridge outer diameter = 8.4 mm, volume of each chamber = 1 mL, total volume of dispensing nozzle = 0.03 mL, diameter of dispensing nozzle outlet orifice = 0.85 mm, nozzle tip length = 9 mm, and internal clamping angle of nozzle tip = 120°. The static mixer shown in Figure 4 was inserted into the cannula portion of the dispensing nozzle. The total length of the series of mixing paddles was 15 mm. Each of the two chambers had a roughly D-shaped cross-section, and the D-shapes were oriented mirror-like relative to each other.

[0155] One chamber of the syringe was partially filled with paste AA-2 (2 / 3 by volume). The second chamber was partially filled with paste BB-3 (2 / 3 by volume). When the plunger was pressed down, the filled syringe dispensed paste AA-2 and paste BB-3 in a 1:1 volume ratio into the dispensing nozzle. A typodont model of the upper dental arch in a human mouth was used, with deep fissures in each tooth. Using the syringe device, a thin coating of the sealant composition was applied to the surface of 10 teeth on the model. During application, penetration of the sealant composition into the fissures was observed. The total time to apply the sealant composition to the 10 teeth was approximately 45 seconds. The sealant composition hardened approximately 45 seconds after application to the teeth.

[0156] Example 7. A two-chamber syringe apparatus described in Example 6 was used. One chamber of the syringe was partially filled with paste AA-1 (2 / 3 by volume). The second chamber was partially filled with paste BB-1 (2 / 3 by volume). When the plunger was pressed down, the filled syringe metered paste AA-1 and paste BB-1 in a 1:1 volume ratio into the dispensing nozzle. Using the syringe apparatus, a Teflon disc mold (3.1 mm in diameter, 1.3 mm in height) was filled with the paste. The paste was then cured by applying ELIPAR S10 curing light (3M Oral Care) to each side of the mold for 20 seconds. The resulting molded disc was immediately removed from the mold and placed in a 2 mL plastic centrifuge tube containing 0.5 mL of buffer solution mixed with 15 g of deionized water and 10 g of pH 4 buffer solution (Buffer BDH5018, VWR International). The disc was completely immersed in the buffer solution. The tube was stoppered and stored at room temperature.

[0157] The pH of the buffer solution was measured using an ORION PERPHECT ROSS pH Micro Electrode (catalog number 8220BNWP, Thermo Fisher Scientific Company (Waltham, PA)). The sample was gently shaken before each measurement. pH measurements were performed immediately after immersion of the disk in the buffer solution ("0 hours" in the table), 15 hours after immersion, and 39 hours after immersion.

[0158] A comparative example molded disc was prepared and tested according to the described procedure, with the only change being that paste BB-1 was replaced with paste BB-C1, which did not contain encapsulated material 1 (Table 6). The pH characteristics are reported in Table 7.

[0159] [Table 6]

[0160] Example 8. Next, the same procedure and test method as described in Example 7 were followed, with the only change being that paste BB-1 did not contain material 2 containing the encapsulated material 1, and the encapsulated material 1 in paste BB-1 was replaced with an equal amount of unencapsulated Portland cement (10% by weight). The pH characteristics are reported in Table 6.

[0161] [Table 7]

[0162] Example 9. The composition of Paste BB-4 is reported in Table 8 (each component is reported in weight %). BisGMA and TEGDMA can be mixed by stirring until homogeneous (1:1 weight ratio). Mix the BisGMA / TEGDMA mixture with DMAPE and BHT in a mixing cup. Place the filled cup in a FlackTek SPEEDMIXER and mix the contents at approximately 2400 rpm until a homogeneous mixture is obtained. Add fumed silica (AEROSIL R972) to the cup. Place the cup in a FlackTek SPEEDMIXER and mix the contents at approximately 2400 rpm until a homogeneous mixture is obtained. Add enclosed material 1 to the cup. Place the cup in a FlackTek SPEEDMIXER and mix the contents at approximately 2400 rpm until a homogeneous mixture of Paste BB-4 is obtained.

[0163] The sealant composition is obtained by mixing pastes AA-1 and BB-4 on a mixing plate in a volume ratio of approximately 1:1.

[0164] Example 10. The composition of Paste BB-5 is reported in Table 8 (each component is reported in weight %). BisGMA and TEGDMA can be mixed by stirring until homogeneous (1:1 weight ratio). Mix the BisGMA / TEGDMA mixture with DMAPE and BHT in a mixing cup. Place the filled cup in a FlackTek SPEEDMIXER and mix the contents at approximately 2400 rpm until a homogeneous mixture is obtained. Add fumed silica (AEROSIL R972) to the cup. Place the cup in a FlackTek SPEEDMIXER and mix the contents at approximately 2400 rpm until a homogeneous mixture is obtained. Add enclosed material 1 to the cup. Place the cup in a FlackTek SPEEDMIXER and mix the contents at approximately 2400 rpm until a homogeneous mixture of Paste BB-5 is obtained.

[0165] The sealant composition is obtained by mixing pastes AA-1 and BB-5 on a mixing plate in a volume ratio of approximately 1:1.

[0166] Example 11. The composition of Paste BB-6 is reported in Table 8 (each component is reported in weight %). BisGMA and TEGDMA can be mixed by stirring until homogeneous (1:1 weight ratio). Mix the BisGMA / TEGDMA mixture with DMAPE and BHT in a mixing cup. Place the filled cup in a FlackTek SPEEDMIXER and mix the contents at approximately 2400 rpm until a homogeneous mixture is obtained. Add fumed silica (AEROSIL R972) to the cup. Place the cup in a FlackTek SPEEDMIXER and mix the contents at approximately 2400 rpm until a homogeneous mixture is obtained. Add enclosed material 1 to the cup. Place the cup in a FlackTek SPEEDMIXER and mix the contents at approximately 2400 rpm until a homogeneous mixture of Paste BB-6 is obtained.

[0167] The sealant composition is obtained by mixing pastes AA-1 and BB-6 on a mixing plate in a volume ratio of approximately 1:1.

[0168] Example 12. The composition of Paste BB-7 is reported in Table 8 (each component is reported in weight %). BisGMA and TEGDMA can be mixed by stirring until homogeneous (1:1 weight ratio). Mix the BisGMA / TEGDMA mixture with DMAPE and BHT in a mixing cup. Place the filled cup in a FlackTek SPEEDMIXER and mix the contents at approximately 2400 rpm until a homogeneous mixture is obtained. Add fumed silica (AEROSIL R972) to the cup. Place the cup in a FlackTek SPEEDMIXER and mix the contents at approximately 2400 rpm until a homogeneous mixture is obtained. Add enclosed material 1 to the cup. Place the cup in a FlackTek SPEEDMIXER and mix the contents at approximately 2400 rpm until a homogeneous mixture of Paste BB-7 is obtained.

[0169] The sealant composition is obtained by mixing paste AA-1 and BB-7 on a mixing plate in a volume ratio of approximately 1:1.

[0170] Example 13. The composition of Paste BB-8 is reported in Table 8 (each component is reported in weight %). BisGMA and TEGDMA can be mixed by stirring until homogeneous (1:1 weight ratio). Mix the BisGMA / TEGDMA mixture with DMAPE and BHT in a mixing cup. Place the filled cup in a FlackTek SPEEDMIXER and mix the contents at approximately 2400 rpm until a homogeneous mixture is obtained. Add fumed silica (AEROSIL R972) to the cup. Place the cup in a FlackTek SPEEDMIXER and mix the contents at approximately 2400 rpm until a homogeneous mixture is obtained. Add enclosed material 1 to the cup. Place the cup in a FlackTek SPEEDMIXER and mix the contents at approximately 2400 rpm until a homogeneous mixture of Paste BB-8 is obtained.

[0171] The sealant composition is obtained by mixing paste AA-1 and BB-8 on a mixing plate in a volume ratio of approximately 1:1.

[0172] Example 14. The composition of Paste BB-9 is reported in Table 8 (each component is reported in weight %). BisGMA and TEGDMA can be mixed by stirring until homogeneous (1:1 weight ratio). Mix the BisGMA / TEGDMA mixture with DMAPE and BHT in a mixing cup. Place the filled cup in a FlackTek SPEEDMIXER and mix the contents at approximately 2400 rpm until a homogeneous mixture is obtained. Add fumed silica (AEROSIL R972) to the cup. Place the cup in a FlackTek SPEEDMIXER and mix the contents at approximately 2400 rpm until a homogeneous mixture is obtained. Add enclosed material 1 to the cup. Place the cup in a FlackTek SPEEDMIXER and mix the contents at approximately 2400 rpm until a homogeneous mixture of Paste BB-9 is obtained.

[0173] The sealant composition is obtained by mixing pastes AA-1 and BB-9 on a mixing plate in a volume ratio of approximately 1:1.

[0174] [Table 8]

Claims

1. It's a kit, Syringe device, A cartridge including a first chamber and a second chamber, A plunger comprising a first rod and a second rod, wherein the first rod seals the first chamber and the second rod seals the second chamber, A static mixer and at least one detachable dispensing nozzle having an outlet, wherein the at least one detachable dispensing nozzle is attached to the end of the cartridge opposite to the plunger, Syringe devices including, Two-part dental sealant composition Includes, The aforementioned two-component dental sealant composition is A first portion comprising a (meth)acrylate resin and an oxidative curing agent, characterized by a viscosity of 5000 cps or less, A second portion comprising a (meth)acrylate resin and a reducing curing agent, characterized by a viscosity of 5000 cps or less, The enclosed materials and, It contains, The enclosed material is, It is the core, Basic materials or basic compounds characterized by a pKa of 8 to 14, A core comprising a calcium ion source which is derived from the basic material or the basic compound, or a calcium compound other than the basic material or the basic compound, or a combination thereof, Shells containing metal oxides Includes, The shell surrounds the core, The aforementioned shell, upon contact with acidic components, decomposes, dissolves, or corrodes. A kit in which the first part is located in the first chamber and the second part is located in the second chamber.

2. The cartridge has a volume of 5 cc or less. The dispensing nozzle has a volume of 0.25 cc or less. The kit according to claim 1, wherein the outlet has a diameter of 1.5 mm or less.

3. The kit according to claim 1, wherein the first chamber and the second chamber have a volume ratio of approximately 1:

1.

4. The kit according to any one of claims 1 to 3, wherein the (meth)acrylate resin of the first portion and the (meth)acrylate resin of the second portion each comprise bisphenol A glycidyl methacrylate and triethylene glycol dimethacrylate.

5. The kit according to any one of claims 1 to 4, wherein the oxidative curing agent is a peroxide and the reductive curing agent is an amine.

6. The kit according to any one of claims 1 to 5, wherein the core further comprises a phosphorus ion source, a fluoride ion source, or a combination thereof.

7. The kit according to any one of claims 1 to 6, wherein the core comprises tricalcium silicate, dicalcium silicate, calcium silicate, tricalcium aluminate, tetracalcium iron aluminate, or a combination thereof.

8. The kit according to any one of claims 1 to 7, wherein the core further comprises magnesium oxide, calcium oxide, potassium sulfate, sodium sulfate, or a combination thereof.

9. The kit according to any one of claims 1 to 8, wherein the core comprises bioactive glass.

10. The kit according to any one of claims 1 to 9, wherein the basic material or basic compound is present in an amount of at least 25% by weight based on the weight of the core.

11. The kit according to any one of claims 1 to 10, wherein the shell has a maximum thickness of 500 nm.

12. The kit according to any one of claims 1 to 11, wherein the second portion comprises the enclosed material.

13. The kit according to any one of claims 1 to 12, wherein the two-component dental sealant composition further comprises a photoinitiator.

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