Dental adhesive composition

Abstract

Provided is a dental adhesive composition containing a first polymerizable monomer, a second polymerizable monomer, and a third polymerizable monomer. The dental adhesive composition is characterized in that: the first polymerizable monomer has only one group selected from the group consisting of a urethane group, a urea group, and a carbonate group; the second polymerizable monomer has a (meth)acrylamide group; and the third polymerizable monomer has an acid group.

Description

Dental adhesive composition

[0001] The present invention relates to a dental adhesive composition.

[0002] Dental adhesive compositions are used in the field of dentistry to bond tooth structures (enamel and dentin) to dental restorative materials such as dental composite resins and dental cements.

[0003] As a conventional dental adhesive composition, for example, a one-component non-solvent dental adhesive composition containing an acidic group-containing polymerizable monomer, a polymerizable monomer having no acidic group, a photopolymerization initiator, and a polymerizable group-containing benzotriazole-based compound of a specific structure has been disclosed (see, for example, Patent Document 1).

[0004] Patent No. 6763764

[0005] However, conventional dental adhesive compositions have a storage problem in that they gel after long-term storage, and there is a demand for dental adhesive compositions that have even stronger adhesion to tooth structures.

[0006] Therefore, an object of the present invention is to provide a dental adhesive composition that has high adhesion to tooth structure and good storage stability.

[0007] The dental adhesive composition of the present invention as a means for solving the problems is a dental adhesive composition comprising a first polymerizable monomer, a second polymerizable monomer, and a third polymerizable monomer, wherein the first polymerizable monomer has only one group selected from the group consisting of a urethane group, a urea group, and a carbonate group, the second polymerizable monomer has a (meth)acrylamide group, and the third polymerizable monomer has an acid group.

[0008] According to the present invention, a dental adhesive composition having high adhesion to tooth structure and high storage stability can be provided.

[0009] Next, an embodiment of the present invention will be described.

[0010] (Dental Adhesive Composition) The dental adhesive composition of the present invention contains a first polymerizable monomer, a second polymerizable monomer, and a third polymerizable monomer, and may further contain other components as necessary.

[0011] <First Polymerizable Monomer> The first polymerizable monomer in the present invention has only one group (hereinafter, may be referred to as a urethane group, etc.) selected from the group consisting of a urethane group, a urea group, and a carbonate group, and may further have other groups as necessary.

[0012] The first polymerizable monomer having only one urethane group or the like has only one urethane group or the like, and does not have two or more urethane groups or the like.

[0013] The first polymerizable monomer imparts mechanical strength to the cured product obtained by curing the dental adhesive composition.

[0014] The urethane group is a linking group represented by -NHCOO-, the urea group is a linking group represented by -NHCONH-, and the carbonate group is a linking group represented by -OCOO-.

[0015] The first polymerizable monomer is not particularly limited as long as it has only one urethane group or the like and can be appropriately selected depending on the purpose, and examples thereof include (meth)acrylates having only one urethane group or the like.

[0016] In this specification, (meth)acrylate refers to a compound having a methacryloyloxy group and / or an acryloyloxy group (hereinafter referred to as a (meth)acryloyloxy group).

[0017] The (meth)acrylate having only one urethane group or the like is not particularly limited and can be appropriately selected depending on the purpose, but a (meth)acrylate having two or more (meth)acryloyloxy groups is preferred.

[0018] The (meth)acrylate having only one urethane group or the like is not particularly limited and can be appropriately selected depending on the purpose, but is preferably represented by the following formula (1).

[0019] (In formula (1), A １ and A ２are each independently a (meth)acryloyloxy group or a (meth)acrylamide group which may have an alkyl group having 3 or less carbon atoms on the side chain, B is a urethane group, and R １ and R ２ are each independently an alkylene group having 8 or less carbon atoms which may have a (meth)acryloyloxy group or a (meth)acrylamide group on the side chain.

[0020] In this specification, the term "(meth)acrylamide group" refers to a methacrylamide group and / or an acrylamide group. ３ R ４ CO(CH=CH ２ ) represents a substituent represented by R ３ and R ４ represents a hydrogen atom or an alkyl group which may have a substituent, R ３ and R ４ may be bonded to each other to form a cyclic structure.

[0021] In the formula (1), A １ and A ２ Preferably, the number of carbon atoms in the alkyl group on the side chain of the (meth)acryloyloxy group or (meth)acrylamide group is 2 or less, and more preferably, the side chain of the (meth)acryloyloxy group or (meth)acrylamide group does not have an alkyl group.

[0022] In the formula (1), R １ and R ２ The alkylene group preferably has 5 or less carbon atoms. １ and R ２ When the alkylene group has 8 or less carbon atoms, distortion of the polymerizable monomer having only one urethane group or the like is suppressed, and the cured product obtained by curing the dental adhesive composition has sufficient mechanical strength.

[0023] Specific examples of the (meth)acrylate containing only one urethane group or the like represented by the formula (1) include (meth)acrylates represented by the following formulas (2) to (6). These may be used alone or in combination of two or more.

[0024] The compound represented by the formula (2) is sometimes called mUDMA.

[0025] The compound represented by the formula (3) is sometimes referred to as mUA / MA-1.

[0026]

[0027]

[0028]

[0029] The content of the first polymerizable monomer is not particularly limited and can be selected appropriately depending on the purpose, but from the viewpoint of imparting high mechanical strength to the cured product of the dental adhesive composition, it is preferably 3% by mass or more and 70% by mass or less, more preferably 5% by mass or more and 60% by mass or less, and even more preferably 10% by mass or more and 50% by mass or less, relative to the total amount of the dental adhesive composition.

[0030] <Second Polymerizable Monomer> The second polymerizable monomer in the present invention has a (meth)acrylamide group, and further has other groups as required.

[0031] The second polymerizable monomer inhibits gelation of the dental adhesive composition and improves its storage stability.

[0032] The second polymerizable monomer is not particularly limited as long as it has a (meth)acrylamide group and can be appropriately selected depending on the purpose, and examples thereof include those not having a cyclic structure such as dimethyl(meth)acrylamide, diethyl(meth)acrylamide, hydroxyethyl(meth)acrylamide, and (meth)acrylamide, and those having a cyclic structure such as 4-(meth)acryloylmorpholine. These may be used alone or in combination of two or more.

[0033] The content of the second polymerizable monomer is not particularly limited and can be selected appropriately depending on the purpose, but from the viewpoint of suppressing gelation of the dental adhesive composition and improving its storage stability, it is preferably 3% by mass or more and 60% by mass or less, more preferably 5% by mass or more and 50% by mass or less, and even more preferably 10% by mass or more and 40% by mass or less, relative to the total amount of the dental adhesive composition.

[0034] <Third Polymerizable Monomer> The third polymerizable monomer in the present invention has an acid group, and further has other groups as required.

[0035] The third polymerizable monomer improves the adhesiveness of the dental adhesive composition to tooth structure.

[0036] The acid group is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include a phosphate group, a pyrophosphate group, a thiophosphate group, a carboxylic acid group, a sulfonic acid group, and a phosphonic acid group.

[0037] The third polymerizable monomer is not particularly limited as long as it has an acid group, and can be appropriately selected depending on the purpose. From the viewpoint of improving the adhesion of the dental adhesive composition to tooth structure, 10-methacryloyloxydecyl dihydrogen phosphate (also referred to as MDP) is preferred.

[0038] The content of the third polymerizable monomer is not particularly limited and can be selected appropriately depending on the purpose, but from the viewpoint of improving the adhesion of the dental adhesive composition to tooth structure, it is preferably 0.1% by mass or more and 40% by mass or less, more preferably 1% by mass or more and 25% by mass or less, and even more preferably 3% by mass or more and 20% by mass or less, relative to the total amount of the dental adhesive composition.

[0039] <Other Components> The other components are not particularly limited and can be appropriately selected within a range that does not impair the effects of the present invention. Examples thereof include solvents, other polymerizable monomers, photopolymerization initiators, chemical polymerization initiators, polymerization inhibitors, silane coupling agents, and fillers.

[0040] -Solvent- Examples of the solvent include organic solvents and water.

[0041] The organic solvent is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include ethanol, acetone, isopropyl alcohol, etc. These may be used alone or in combination of two or more.

[0042] The content of the solvent is not particularly limited and can be selected appropriately depending on the purpose, but from the viewpoint of improving the storage stability and adhesion to tooth structure of the dental adhesive composition, the content of the solvent is preferably 0.01% by mass or more and 80% by mass or less, more preferably 1% by mass or more and 70% by mass or less, and even more preferably 3% by mass or more and 60% by mass or less, relative to the total amount of the dental adhesive composition.

[0043] The content of the organic solvent is not particularly limited and can be selected appropriately depending on the purpose, but from the viewpoint of improving the storage stability and adhesion to tooth structure of the dental adhesive composition, it is preferably 0.01% by mass or more and 30% by mass or less, more preferably 1% by mass or more and 20% by mass or less, and even more preferably 3% by mass or more and 15% by mass or less, of the total amount of the dental adhesive composition.

[0044] -Other polymerizable monomers- In the present invention, other polymerizable monomers refer to polymerizable monomers that do not fall into any of the first polymerizable monomer, the second polymerizable monomer, and the third polymerizable monomer.

[0045] There are no particular restrictions on the other polymerizable monomers, and the physical properties of the dental adhesive composition can be adjusted by appropriately selecting the type and content of the other polymerizable monomers within a range that does not impair the effects of the present invention.

[0046] Examples of other polymerizable monomers include, but are not limited to, dimethacrylates such as glycerol dimethacrylate, triethylene glycol dimethacrylate, and di-2-methacryloyloxyethyl-2,2,4-trimethylhexamethylene dicarbamate.

[0047] -Photopolymerization initiator- The photopolymerization initiator is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include camphorquinone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl 4-dimethylaminobenzoate, etc. These may be used alone or in combination of two or more.

[0048] The content of the photopolymerization initiator is not particularly limited and can be selected appropriately depending on the purpose, but from the viewpoint of improving the curability of the dental adhesive composition, it is preferably from 0.01% by mass to 10% by mass, more preferably from 0.05% by mass to 8% by mass, and even more preferably from 1% by mass to 6% by mass, relative to the total amount of the dental adhesive composition.

[0049] Chemical Polymerization Initiator There are no particular limitations on the chemical polymerization initiator, and it can be appropriately selected depending on the purpose. For example, copper acetylacetonate can be used.

[0050] The content of the chemical polymerization initiator is not particularly limited and can be selected appropriately depending on the purpose, but from the viewpoint of improving the curability of the dental adhesive composition, it is preferably from 0.001% by mass to 5% by mass, more preferably from 0.001% by mass to 3% by mass, and even more preferably from 0.001% by mass to 1% by mass, relative to the total amount of the dental adhesive composition.

[0051] -Polymerization Inhibitor- There are no particular limitations on the polymerization inhibitor, and it can be appropriately selected depending on the purpose. For example, dibutylhydroxytoluene and the like can be used.

[0052] The content of the polymerization inhibitor is not particularly limited and can be selected appropriately depending on the purpose, but from the viewpoint of improving the curability of the dental adhesive composition, it is preferably from 0.01% by mass to 5% by mass, more preferably from 0.05% by mass to 4% by mass, and even more preferably from 0.1% by mass to 3% by mass, relative to the total amount of the dental adhesive composition.

[0053] -Silane Coupling Agent- There are no particular limitations on the silane coupling agent, and it can be appropriately selected depending on the purpose. For example, 3-methacryloxypropyltrimethoxysilane can be used.

[0054] The content of the silane coupling agent is not particularly limited and can be selected appropriately depending on the purpose, but for example, it is preferably 0.01% by mass or more and 20% by mass or less, more preferably 0.1% by mass or more and 15% by mass or less, and even more preferably 0.5% by mass or more and 10% by mass or less, relative to the total amount of the dental adhesive composition.

[0055] Filler There are no particular limitations on the filler, and it can be appropriately selected depending on the purpose. For example, fumed silica can be used.

[0056] The content of the filler is not particularly limited and can be selected appropriately depending on the purpose, but for example, it is preferably 0.1% by mass or more and 50% by mass or less, more preferably 0.5% by mass or more and 40% by mass or less, and even more preferably 1% by mass or more and 30% by mass or less, relative to the total amount of the dental adhesive composition.

[0057] Examples of the present invention will be described below, but the present invention is not limited to these examples in any way.

[0058] (Examples 1 to 10, Comparative Examples 1 to 4) Dental adhesive compositions of Examples 1 to 10 and Comparative Examples 1 to 4 were obtained by mixing the components according to the compositions (unit: mass %) shown in Tables 1 to 3.

[0059] The components indicated by symbols or abbreviations in Tables 1 to 3 are as follows: Omnirad 819: phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (manufactured by IGM Resins) CQ: camphorquinone EPA: ethyl 4-dimethylaminobenzoate AACu: acetylacetonate copper BHT: dibutylhydroxytoluene mUDMA: compound represented by the above formula (2) mUA / MA-1: compound represented by the above formula (3) DEAA: N,N-diethylacrylamide DMAA: N,N-dimethylacrylamide ACMO: 4-acryloylmorpholine HEAA: N-(2-hydroxyethyl)acrylamide AA: acrylamide MDP: 10-methacryloyloxydecyl dihydrogen phosphate GDMA: glycerol dimethacrylate TEGDMA: triethylene glycol dimethacrylate UDMA: di-2-methacryloyloxyethyl-2,2,4-trimethylhexamethylene dicarbamate KBM-503: 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) RX50: fumed silica (manufactured by Nippon Aerosil Co., Ltd.)

[0060] <Adhesion Strength to Enamel> Bovine teeth were polished with #400 polishing paper to expose the enamel, thereby preparing enamel adherends.

[0061] After polishing the enamel adherend, the water on the surface was dried by air blowing. A sample of the dental adhesive composition prepared in each of the Examples and Comparative Examples was applied to the dried, smooth surface by agitation for 10 seconds, and then, without air drying, was irradiated with light for 10 seconds using a dental visible light irradiator (G-Light Prima II Plus, manufactured by GC Corporation). A mold (manufactured by Ultradent) with a circular hole having a diameter of 2.38 mm was placed on the surface to which the dental adhesive composition sample had been applied, and a composite resin (Clearfil AP-X, manufactured by Kuraray Noritake Dental Co., Ltd.) was filled in. After 20 seconds of light irradiation, the sample was removed from the mold, burrs were removed with a razor, and the sample was immersed in 37°C water for 24 hours to obtain a test specimen.

[0062] The prepared specimens were sheared using an autograph (Shimadzu Corporation, EZ-Test EZ-SX) at a crosshead speed of 1 mm / min to measure the adhesive strength to enamel. The evaluation criteria are as follows: a rating of A (excellent) or B (good) was deemed to have sufficient adhesive strength, and a rating of C (poor) was deemed to have insufficient adhesive strength. [Evaluation criteria] A (excellent): adhesive strength of 20 MPa or more B (good): adhesive strength of 15 MPa or more but less than 20 MPa C (poor): adhesive strength less than 15 MPa

[0063] <Adhesive Strength to Dentin> Bovine teeth were polished with #400 polishing paper to expose the dentin, thereby preparing dentin adherends.

[0064] The bond strength to dentin was measured in the same manner as for the bond strength to enamel, except that a dentin adherend was used instead of an enamel adherend. The evaluation criteria were the same as for the bond strength to enamel.

[0065] <Adhesion Strength to Etched Dentin> A dentin adherend was treated with GC Etchant (manufactured by GC Corporation) for 10 seconds and then washed with water to prepare an etched dentin adherend.

[0066] The bond strength to etched dentin was measured in the same manner as for the bond strength to enamel, except that the etched dentin was used instead of the enamel. The evaluation criteria were the same as for the bond strength to enamel.

[0067] <Storability> 5 g of each sample of the dental adhesive composition prepared in the Examples and Comparative Examples was filled into a bottle and left at 60°C. After a predetermined number of days had passed (3, 5, 7, 14, 21, and 28 days), the bottle was opened and the presence or absence of gelation of the contents was confirmed. The evaluation criteria were as follows: a rating of A (excellent) or B (good) was deemed to have sufficient storage stability, and a rating of C (poor) was deemed to have insufficient storage stability. [Evaluation criteria] A (excellent): Gelling days were 28 days or more B (good): Gelling days were 7 days or more but less than 28 days C (poor): Gelling days were less than 7 days

[0068]

[0069]

[0070]

[0071] From the results shown in Tables 1 and 2, the dental adhesive compositions of Examples 1 to 10 were rated A (excellent) or B (good) in all evaluation items, and it can be seen that they are dental adhesive compositions with high adhesion to tooth structure and high preservability.

[0072] On the other hand, as shown in Table 3, it was confirmed that the dental adhesive compositions of Comparative Examples 1 to 4, which did not contain the first polymerizable monomer and / or the second polymerizable monomer, were insufficient in at least one of adhesion to tooth structure and storage stability.

[0073] Although the embodiments of the present invention have been described above, the present invention is not limited to the specific embodiments, and various modifications and changes are possible within the scope of the invention described in the claims.

[0074] This application claims priority based on Japanese Patent Application No. 2024-103711, filed on June 27, 2024, the entire contents of which are incorporated herein by reference.

Claims

1. A dental adhesive composition comprising a first polymerizable monomer, a second polymerizable monomer, and a third polymerizable monomer, wherein the first polymerizable monomer has only one group selected from the group consisting of a urethane group, a urea group, and a carbonate group, the second polymerizable monomer has a (meth)acrylamide group, and the third polymerizable monomer has an acid group.

2. The dental adhesive composition according to claim 1, which contains N,N-diethylacrylamide as the second polymerizable monomer.

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