Dental primer composition

Abstract

This dental primer composition contains a (meth)acrylate and a siloxane compound represented by general formula (1) and is characterized by being substantially free from water. In general formula (1), X1 to X6 each independently represent an alkyl group having 1 to 6 carbon atoms or an ethylenically unsaturated group, X3 and X4 may be different from each other in the same repeating unit, m represents an integer of 0-500, Y1 and Y2 each independently represent a linear or branched hydrocarbon group that has 1 to 20 carbon atoms and may have an ether bond, Z1 to Z4 each independently represent a hydrogen atom or an ethylenically unsaturated group, and at least one of X1 to X6 and Z1 to Z4 represents an ethylenically unsaturated group.

Description

Dental primer composition

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

[0002] In the dental field, it is known that the adhesion of the adherend can be improved by applying a dental primer composition before applying a dental adhesive, dental cement, or the like to the tooth surface.

[0003] As a dental primer composition, for example, when a dental adhesive restorative material such as a resin cement is bonded to a substrate such as the enamel or dentin of natural teeth or a prosthetic restoration, a primer composition that can impart strong adhesion and durability between the two without performing a treatment such as an acid treatment has been disclosed (see, for example, Patent Document 1).

[0004] Japanese Patent Application Publication No. 3-240712

[0005] In recent years, super engineering plastics, which have excellent mechanical strength, heat resistance, and chemical stability, have become popular as dental prostheses. However, due to their chemical stability, these super engineering plastics have the problem of being difficult to bond by chemical bonding. The primer composition described in Patent Document 1 does not take into consideration adhesion to dental prostheses containing super engineering plastics, and there is room for improvement.

[0006] Therefore, an object of the present invention is to provide a dental primer composition that has excellent adhesion to dental materials containing super engineering plastics.

[0007] The dental primer composition of the present invention as a means for solving the problems is a dental primer composition that contains a (meth)acrylate and a siloxane compound represented by general formula (1), and is substantially free of water.

[0008] (In general formula (1), X １ ~X ６each independently represents an alkyl group having 1 to 6 carbon atoms or an ethylenically unsaturated group, m represents an integer of 0 to 500, and when m is 2 or more, X ３ and X ４ may be different from one another within the same repeating unit, and Y １ and Y ２ each independently represents a linear or branched hydrocarbon group having from 1 to 20 carbon atoms which may have an ether bond; Z １ ~Z ４ each independently represents a hydrogen atom or an ethylenically unsaturated group; X １ ~X ６ and Z １ ~Z ４ At least one of represents an ethylenically unsaturated group.

[0009] According to the present invention, a dental primer composition having excellent adhesion to dental materials including super engineering plastics can be provided.

[0010] The present invention will be described in detail below.

[0011] (Dental Primer Composition) The dental primer composition of the present invention contains a (meth)acrylate and a siloxane compound represented by general formula (1), and may also contain a polymerization initiator and / or a polymerization accelerator, and other components, as necessary.

[0012] The dental primer composition of the present invention is substantially free of water.

[0013] <(Meth)acrylate> The (meth)acrylate contained in the dental primer composition of the present invention is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include monofunctional (meth)acrylates and polyfunctional (meth)acrylates.

[0014] 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).

[0015] <<Monofunctional (meth)acrylate>> Examples of the monofunctional (meth)acrylate include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, and hydroxyethyl methacrylate.

[0016] The content of the monofunctional (meth)acrylate is not particularly limited and can be selected appropriately depending on the purpose, but is preferably 1% by mass or more and 90% by mass or less, more preferably 20% by mass or more and 80% by mass or less, and even more preferably 30% by mass or more and 60% by mass or less, relative to the total amount of the dental primer composition.

[0017] As the monofunctional (meth)acrylate, an appropriately synthesized product or a commercially available product may be used.

[0018] Commercially available monofunctional (meth)acrylates include, for example, Methyl Methylacrylate (stabilized with 6-tert-butyl-2,4-xylenol, manufactured by Tokyo Chemical Industry Co., Ltd.).

[0019] <<Polyfunctional (meth)acrylates>> Examples of polyfunctional (meth)acrylates include triethylene glycol dimethacrylate, 2-hydroxy-1,3-dimethacryloxypropane, 2,2-bis-(4-(2-methacryloxyethoxy)phenyl)propane, [2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)]dimethacrylate, trimethylolpropane trimethacrylate, dipentaerythritol polyacrylate, and 1,3,5-(tris(1,3-bis(methacryloxy)-2-propoxycarbonylaminohexane)-1,3,5-(1H,3H,5H)triazine-2,4,5-trione.

[0020] The content of the polyfunctional (meth)acrylate is not particularly limited and can be selected appropriately depending on the purpose, but is preferably 1% by mass or more and 90% by mass or less, more preferably 20% by mass or more and 80% by mass or less, and even more preferably 30% by mass or more and 50% by mass or less, relative to the total amount of the dental primer composition.

[0021] The analytical method for confirming whether or not the dental primer composition of the present invention contains the (meth)acrylate is not particularly limited and can be appropriately selected depending on the purpose. For example, confirmation can be made by high performance liquid chromatography (HPLC).

[0022] As the polyfunctional (meth)acrylate, a suitably synthesized product or a commercially available product may be used.

[0023] Commercially available polyfunctional (meth)acrylates include, for example, NK Ester 3G (triethylene glycol dimethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0024] <Siloxane Compound Represented by General Formula (1)> The dental primer composition of the present invention contains a siloxane compound represented by the following general formula (1).

[0025] By containing the siloxane compound represented by general formula (1), the dental primer composition of the present invention has improved adhesion to dental materials including super engineering plastics.

[0026] (In general formula (1), X １ ~X ６ each independently represents an alkyl group having 1 to 6 carbon atoms or an ethylenically unsaturated group; X ３ and X ４ may be different from one another within the same repeating unit, m represents an integer of 0 to 500, and Y １ and Y ２ each independently represents a linear or branched hydrocarbon group having from 1 to 20 carbon atoms which may have an ether bond; Z １ ~Z ４ each independently represents a hydrogen atom or an ethylenically unsaturated group; X １ ~X ６ and Z １ ~Z ４ At least one of represents an ethylenically unsaturated group.

[0027] The siloxane compound represented by the general formula (1) may be either linear or branched.

[0028] The content of the siloxane compound represented by general formula (1) is not particularly limited and can be selected appropriately depending on the purpose, but is preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.1% by mass or more and 5% by mass or less, even more preferably 0.1% by mass or more and 3% by mass or less, and particularly preferably 0.1% by mass or more and 1% by mass or less, relative to the total amount of the dental primer composition.

[0029] When the content of the siloxane compound represented by general formula (1) is 0.1% by mass or more and 10% by mass or less based on the total amount of the dental primer composition, the adhesiveness is improved.

[0030] The analytical method for confirming whether or not the dental primer composition of the present invention contains the siloxane compound represented by general formula (1) is not particularly limited and can be appropriately selected depending on the purpose. For example, confirmation can be made by high performance liquid chromatography (HPLC).

[0031] The siloxane compound represented by the general formula (1) may be suitably synthesized or may be a commercially available product.

[0032] Commercially available linear siloxanes containing (meth)acryloyl groups at both ends include, for example, trade names such as X-22-164, X-22-164AS, X-22-164A, X-22-164B, X-22-164C, X-22-164E, KP-410, KP-411, KP-412, KP-413, KP-414, KP-415, and KP-423 (all manufactured by Shin-Etsu Chemical Co., Ltd.), and DMS-C21, DMS-E21, DMS-T21, and DMS-U21 (all manufactured by Gelest).

[0033] Commercially available linear siloxanes containing a (meth)acryloyloxy group at one end include, for example, trade names such as X-22-174ASX, X-22-174BX, KF-2012, X-22-2426, X-22-2404, KP-416, KP-418, and KP-422 (all manufactured by Shin-Etsu Chemical Co., Ltd.).

[0034] An example of a commercially available linear siloxane containing a (meth)acryloyloxy group in the side chain is KP-420 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0035] The dental primer composition of the present invention is substantially free of water.

[0036] Here, in this specification, "substantially free of water" means that the water content is 5% by mass or less, preferably 1% by mass or less, more preferably 0.1% by mass or less, and even more preferably 0% by mass, i.e., below the detection limit, relative to the total amount of the dental primer composition.

[0037] The method for measuring the water content in the dental primer composition is not particularly limited and can be appropriately selected depending on the purpose. For example, the water content can be measured using a Karl Fischer moisture meter.

[0038] <Polymerization Initiator and / or Polymerization Accelerator> The dental primer composition of the present invention may contain a polymerization initiator and / or a polymerization accelerator.

[0039] The polymerization initiator is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include camphorquinone and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

[0040] The polymerization accelerator is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include ethyl 4-dimethylaminobenzoate.

[0041] The content of the polymerization initiator and / or polymerization accelerator is not particularly limited and can be selected appropriately depending on the purpose, but is preferably 0.1% by mass or more and 10% by mass or less, and more preferably 0.1% by mass or more and 5% by mass or less, relative to the total amount of the dental primer composition.

[0042] The polymerization initiator and / or polymerization accelerator may be suitably synthesized or may be a commercially available product.

[0043] Commercially available polymerization initiators and / or polymerization accelerators include, for example, the trade name Diphenyl(2,4,6-trimethylbenzoyl)phosphine Oxide (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0044] <Other Components> The dental primer composition of the present invention may contain other components within the range that does not impair the effects of the present invention.

[0045] The other components are not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include a polymerization inhibitor and a thickener.

[0046] The polymerization inhibitor is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include dibutylhydroxytoluene (2,6-di-tert-butyl) cresol, 2,4-diethyl-9H-thioxanden-9-one, 6-tert-butyl-2,4-xylenol, and 4-methoxyphenol.

[0047] The thickener is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include silica particles and fumed silica.

[0048] The contents of other components can be appropriately set depending on the contents of the above-mentioned materials.

[0049] The other components may be appropriately synthesized or commercially available.

[0050] <Method for manufacturing dental primer composition> The method for preparing the dental primer composition is not particularly limited and can be selected appropriately depending on the purpose. For example, the dental primer composition can be prepared by blending the various materials described above in a sample tube and mixing them using a magnetic stirrer.

[0051] The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples. In the following examples and comparative examples, unless otherwise specified, parts mean parts by mass and % means % by mass.

[0052] Examples 1 to 4 and Comparative Examples 1 and 2 Based on the materials and compositions shown in Table 1, the materials were compounded in a sample tube, and the various materials were mixed using a magnetic stirrer to obtain each dental primer composition.

[0053] Details of the components indicated by symbols or abbreviations in Table 1 are as follows:

[0054] - Monofunctional monomer - MMA: methyl methacrylate

[0055] - Polyfunctional Monomer - ADPH: Dipentaerythritol polyacrylate

[0056] -Siloxane Compounds- KP410 (linear siloxane containing (meth)acryloyl groups at both ends, manufactured by Shin-Etsu Chemical Co., Ltd.) KP422 (linear siloxane containing a (meth)acryloyloxy group at one end, manufactured by Shin-Etsu Chemical Co., Ltd.) KP423 (linear siloxane containing (meth)acryloyl groups at both ends, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0057] - Polymerization initiator, polymerization accelerator - TPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide

[0058] -Polymerization inhibitor- DET: 2,4-diethyl-9H-thioxanden-9-one

[0059] - Thickener - R812: Aerosil (registered trademark) R812 (manufactured by Nippon Aerosil Co., Ltd.)

[0060] [Adhesion Evaluation] A PEEK material was polished flat with #600 waterproof abrasive paper, and a 100 μm thick polytetrafluoroethylene seal (FEP adhesive sheet film: manufactured by Fluoro Industries Co., Ltd.) with a 3 mm diameter hole was attached to the polished surface to define the area of ​​the adherend. Each dental primer composition was applied to the adherend surface of the PEEK material and dried with an air blower. An appropriate amount of GC G-Cem ONE (manufactured by GC Corporation), a self-adhesive resin cement, was applied to a tensile test jig and then pressed against the adherend surface of the PEEK material. The tensile test jig used was a 10 mm diameter stainless steel rod polished with #120 waterproof abrasive paper and then sandblasted. Excess cement was removed with a probe, and the test specimen was immersed in 37°C water for 24 hours.

[0061] Tensile tests were carried out on five specimens using a precision universal testing machine Autograph AG-1 (manufactured by Shimadzu Corporation) at a crosshead speed of 1 mm / min. The average of the obtained values ​​was calculated, and the adhesiveness was evaluated based on the following evaluation criteria. The results are shown in Table 1. -Adhesion evaluation criteria- Excellent: 10 MPa or more Poor: 5 MPa or more but less than 10 MPa Unacceptable: Less than 5 MPa

[0062]

[0063] As can be seen from Table 1, the dental primer compositions containing (meth)acrylate and the siloxane compound represented by general formula (1) and substantially no water had excellent adhesion (Examples 1 to 4).

[0064] In contrast, Table 1 shows that the dental primer composition not containing the siloxane compound represented by general formula (1) and the dental primer composition containing water had poor or no adhesion (Comparative Examples 1 and 2).

[0065] 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.

[0066] The present invention includes, for example, the following aspects.

[0067] <1> A dental primer composition comprising a (meth)acrylate and a siloxane compound represented by general formula (1), and substantially free of water.

[0068] (In general formula (1), X １ ~X ６ each independently represents an alkyl group having 1 to 6 carbon atoms or an ethylenically unsaturated group; X ３ and X ４ may be different from one another within the same repeating unit, m represents an integer of 0 to 500, and Y １ and Y ２ each independently represents a linear or branched hydrocarbon group having from 1 to 20 carbon atoms which may have an ether bond; Z １ ~Z ４ each independently represents a hydrogen atom or an ethylenically unsaturated group; X １ ~X ６ and Z １ ~Z ４ At least one of represents an ethylenically unsaturated group.

[0069] The dental primer composition described in <1> can solve the various problems of the prior art and achieve the object of the present invention.

[0070] This application claims priority based on Japanese Patent Application No. 2024-048972, filed on March 26, 2024, the entire contents of which are incorporated herein by reference.

Claims

1. A dental primer composition comprising a (meth)acrylate and a siloxane compound represented by general formula (1), and substantially free of water. (In general formula (1), X １ ~X ６ each independently represents an alkyl group having 1 to 6 carbon atoms or an ethylenically unsaturated group; X ３ and X ４ may be different from one another within the same repeating unit, m represents an integer of 0 to 500, and Y １ and Y ２ each independently represents a linear or branched hydrocarbon group having from 1 to 20 carbon atoms which may have an ether bond; Z １ ~Z ４ each independently represents a hydrogen atom or an ethylenically unsaturated group; X １ ~X ６ and Z １ ~Z ４ At least one of represents an ethylenically unsaturated group.

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