JP7204476B2 - Non-solvent dental composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a dental composition used in the field of dentistry, and more particularly to a non-solvent-based dental composition substantially free of water and organic solvents.

In the restoration of tooth structure (enamel, dentin, and cementum) damaged by caries, etc., filling materials such as filling composite resins and filling compomers (filling glass ionomer resins), metal alloys, porcelain, Dental restorative materials such as crown restorative materials such as resin materials are used. Generally, these dental restorative materials themselves do not have adhesive properties to the tooth substance. Therefore, various bonding systems using bonding materials (adhesives) have been adopted for bonding tooth substance and dental restorative materials. As a conventional adhesive system, an acid etching agent such as an aqueous solution of phosphoric acid is used to etch the surface of the dentin, and then a primer is applied to the surface of the dentin, and then a bonding material is applied. There are so-called acid-etched bonding systems for bonding with dental restorative materials.

On the other hand, there is a so-called self-etching adhesive system as an adhesive system that does not use an acid etchant. As this adhesive system, conventionally, after applying a self-etching primer containing an acidic group-containing monomer, a hydrophilic monomer and water to the surface of the tooth, a bonding solution containing a cross-linking monomer and a polymerization initiator is applied. A two-step adhesive system that applies a material was the mainstream, but recently a one-step adhesive system using a one-liquid bonding material that has both the function of a self-etching primer and the function of a bonding material has been developed. there is

Conventional one-liquid type bonding materials further contain water and hydrophilic volatile organic solvents in addition to polymerizable monomers such as acidic group-containing monomers, hydrophilic monomers, and crosslinkable monomers. . Since such water and organic solvents cause poor curing and delay in curing of the bonding material, it is necessary to remove the water and organic solvent contained in the bonding material by air blow etc. before curing the bonding material. becomes. However, in addition to such operation itself being complicated, the operation is highly dependent on the technique of the operator, such as air blow time and pressure. sometimes decreased. Therefore, there is an increasing demand for a non-solvent-based dental adhesive composition that does not substantially contain water or organic solvents and that can omit operations such as air blowing.

Regarding the non-solvent-based dental adhesive composition, Patent Document 1 discloses a specific non-solvent-based dental adhesive composition containing a phosphoric acid-based monomer, a sulfonic acid-based monomer, an aromatic amine having an electron-withdrawing group, and a polymerization initiator. According to the non-solvent-based adhesive composition for dental use, it is possible to omit a process such as air blowing for removing water and organic solvents, and it is also possible to remove enamel and ivory. It is described that the non-solvent-based dental adhesive composition can be used for bonding materials, self-adhesive composite resins, and the like.

JP 2016-56145 A

However, the non-solvent-based dental adhesive composition described in Patent Literature 1, particularly in terms of adhesion (initial adhesive strength and adhesion durability) to wet tooth substance (especially dentin), needs further improvement. There was room.

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a non-solvent-based dental composition that exhibits high adhesiveness (initial adhesive strength and adhesive durability) even to wet dentin.

The inventors of the present invention have made intensive studies to achieve the above object, and found that a non-solvent-based dental composition having a viscosity and a specific gravity within a specific range exhibits high adhesion even to wet tooth structure. The present inventors have found that a dental composition exhibits excellent properties (initial adhesive strength and adhesive durability), and have completed the present invention through further studies based on this finding.

That is, the present invention relates to the following.
[1] A non-solvent dental composition having a viscosity of 1 to 700 cP at 30°C and a specific gravity of 1.10 or more at 20°C.
[2] The non-solvent-based dental composition according to [1], which contains a monomer (A) having an acidic group.
[3] The non-solvent-based dental composition according to [1] or [2], which contains a hydrophobic monomer (B) having no acidic group.
[4] The non-solvent-based dental composition according to any one of [1] to [3], which contains a hydrophilic monomer (C) having no acidic group.
[5] A hydrophobic monomer (B) having no acidic group, comprising a hydrophobic monomer (B) having no acidic group and a hydrophilic monomer (C) having no acidic group The non-solvent-based dental composition according to any one of [1] to [4], wherein the content of the hydrophilic monomer (C) having no acidic group is 50% by mass or less relative to the total mass.
[6] The non-solvent-based dental composition according to any one of [1] to [5], which contains a polymerization initiator (D).
[7] The non-solvent-based dental composition according to any one of [1] to [6], wherein the polymerization initiator (D) contains a water-soluble photopolymerization initiator (D-1).
[8] The non-solvent-based dental composition according to any one of [1] to [7], which contains a filler (F).
[9] The non-solvent-based dental composition of [8], wherein the filler (F) has an average primary particle size of 0.001 to 50 µm.
[10] The non-solvent-based dental composition according to any one of [1] to [9], which is a dental bonding material.
[11] The non-solvent-based dental composition according to any one of [1] to [9], which is a dental primer.
[12] The non-solvent-based dental composition according to any one of [1] to [9], which is a dental coating material.

INDUSTRIAL APPLICABILITY According to the present invention, there is provided a non-solvent-based dental composition that exhibits high adhesiveness (initial adhesive strength and adhesive durability) even to wet dentin.

<<Non-solvent-based dental composition>>
The non-solvent-based dental composition of the present invention has a viscosity of 1 to 700 cP at 30°C and a specific gravity of 1.10 or more at 20°C.

Since the non-solvent-based dental composition of the present invention does not substantially contain solvents (i.e., water and organic solvents) that cause poor curing or retardation of curing, the solvent is removed by air blowing or the like when curing. A process can be omitted. Here, "substantially free of solvent" means that the solvent content in the solvent-free dental composition of the present invention is 3% by mass or less, and the content is 2% by mass. It is preferably 1% by mass or less, more preferably 1% by mass or less, and may be 0.5% by mass or less, further 0.1% by mass or less. Such non-solvent-based dental compositions use raw materials with a low solvent content (in some cases, commercially available materials subjected to a solvent-removing operation). etc. can be obtained.

As described above, the non-solvent dental composition of the present invention has a viscosity of 1 to 700 cP at 30°C and a specific gravity of 1.10 or more at 20°C. With this structure, the non-solvent-based dental composition exhibits high adhesiveness (initial adhesive strength and adhesive durability) even to wet tooth substance. The reason why the non-solvent-based dental composition of the present invention exhibits high adhesiveness even to the tooth substance in a wet state is not necessarily clear, and the present invention is not limited in any way, but the following reasons are presumed. be done.
That is, normally, tooth substance, especially dentin, contains water which causes poor hardening or delay of hardening. Since the moisture derived from the tooth was also removed before polymerization and curing, it was possible to form a strong adhesive layer. On the other hand, when a non-solvent-based dental composition is used, solvent removal such as air blowing is usually not performed, so water derived from the tooth remains, and this is noticeable in moist tooth. Become.
Conventional non-solvent-based dental compositions have low viscosity but low specific gravity. Otherwise, a layer of the non-solvent-based dental composition is formed in a state of absorption of water to form a brittle adhesive layer, resulting in poor adhesiveness. It was easy to drop. In addition, when a non-solvent-based dental composition having a relatively high specific gravity is used, such as conventionally known self-adhesive composite resins, the difference in specific gravity from the water existing on the tooth surface may cause the dental Although the adhesive composition can sink into the dentin surface and can improve the adhesion to the dentin to some extent, such self-adhesive composite resins generally have high viscosity and adhere to the dentin surface. Sufficient adhesion could not be obtained for fine irregularities.
In contrast, the viscosity and specific gravity of the non-solvent dental composition of the present invention are within specific ranges. It can sink into the dentin surface to improve adhesion to the dentin, and can follow minute irregularities on the dentin surface to further improve adhesion to the dentin. The high fluidity makes it easier for components such as polymerizable monomers contained in the non-solvent-based dental composition to penetrate into the tooth. As a result, it is considered that the non-solvent-based dental composition of the present invention exhibits high adhesiveness even to wet dentin.

The non-solvent-based dental composition of the present invention has a viscosity of 1 to 700 cP (centipoise) at 30°C. As used herein, the viscosity of a non-solvent-based dental composition refers to the viscosity of a portion of the non-solvent-based dental composition, such as the viscosity of one composition that separates during storage. It means the viscosity of the dental composition as a whole. That is, for example, when separation or sedimentation occurs during storage of the non-solvent-based dental composition, the viscosity of the non-solvent-based dental composition of the present invention is measured after making it uniform by shaking, stirring, or the like. of the non-solvent-based dental composition can be determined. The viscosity can be measured using a rotational viscometer, and more specifically by the method described later in Examples. The method for adjusting the viscosity of the non-solvent-based dental composition of the present invention is not particularly limited. Hydrophobic monomer (B) that does not have an acidic group, hydrophilic monomer (C) that does not have an acidic group, etc.) type and blending amount, type and blending amount of filler (F), etc. are appropriately selected and adjusted. The viscosity can be easily adjusted by using, more specifically, for example, using a relatively low-viscosity polymerizable monomer and using a filler (F) having a relatively large average primary particle size. The viscosity can be adjusted to the desired range. If the viscosity is too high, the fluidity of the non-solvent-based dental composition is reduced, making it difficult for the composition to follow minute irregularities on the surface of the tooth, and the penetration into the dentin is reduced. , resulting in poor adhesion. From the viewpoint of adhesiveness and operability when applied to tooth substance, the viscosity is preferably 5 cP or more, more preferably 10 cP or more, and 30 cP or more. It is more preferably 35 cP or more, most preferably 50 cP or more, and preferably 600 cP or less, more preferably 500 cP or less, further preferably 400 cP or less, and 300 cP. It is particularly preferably 200 cP or less, and may be 100 cP or less.

The non-solvent-based dental composition of the present invention has a specific gravity of 1.10 or more at 20°C. As used herein, the specific gravity of the non-solvent-based dental composition is not the specific gravity of a portion of the non-solvent-based dental composition, such as the specific gravity of one composition separated during storage, but rather the specific gravity of the non-solvent-based dental composition. It means the specific gravity of the entire dental composition. That is, for example, when separation or sedimentation occurs during storage of the non-solvent-based dental composition, the specific gravity of the non-solvent-based dental composition is measured after making it uniform by shaking, stirring, etc. of the non-solvent-based dental composition can be determined. The specific gravity can be measured using a density meter, and more specifically by the method described later in Examples. The method for adjusting the specific gravity of the non-solvent-based dental composition of the present invention is not particularly limited. can be adjusted to If the specific gravity is too low, the difference in specific gravity from the water existing on the tooth surface becomes small, and when the non-solvent-based dental composition is applied, it is below the water existing on the tooth surface. It becomes difficult to penetrate, and the adhesion to the tooth substance is lowered, resulting in a decrease in adhesiveness. From the viewpoint of the adhesiveness, etc., the specific gravity is preferably 1.15 or more, more preferably 1.20 or more, further preferably 1.25 or more, and 1.30 or more. is particularly preferred. From the viewpoint of storage stability of the non-solvent-based dental composition, the specific gravity is preferably 3.00 or less, more preferably 2.50 or less, and 2.00 or less. is more preferable, 1.80 or less is particularly preferable, and 1.50 or less is most preferable.

[Monomer (A) having an acidic group]
The non-solvent-based dental composition of the present invention preferably contains a monomer (A) having an acidic group. The monomer (A) having an acidic group can contribute to demineralizing action and penetrating action, and imparts an acid etching function and a primer treatment function to the non-solvent-based dental composition of the present invention. can be done. Moreover, the polymerization of the monomer (A) having an acidic group can also contribute to the curing action. These improve the adhesion to the tooth substance.

As the monomer (A) having an acidic group, for example, a polymerizable monomer having at least one acidic group and at least one polymerizable group such as an acryloyl group, a methacryloyl group, a vinyl group, a styrene group, etc. and the like, and (meth)acrylic monomers having an acidic group, such as (meth)acrylic esters having an acidic group and (meth)acrylamide having an acidic group, are preferred, and (meth)acrylic monomers having an acidic group are preferred. Acid esters are more preferred, and methacrylic acid esters having an acidic group are even more preferred. In this specification, the term "(meth)acryl" is used in the sense of including both methacryl and acryl.
Examples of the acidic group include a phosphoric acid group, a pyrophosphoric acid group, a thiophosphoric acid group, a phosphonic acid group, a sulfonic acid group, and a carboxylic acid group. You may have only 1 type in an acidic group, and may have 2 or more types.
Monomer (A) which has an acidic group may be used individually by 1 type, and may use 2 or more types together. Specific examples of monomers having various acidic groups that can be preferably used as the monomer (A) having an acidic group are shown below.

Examples of monomers having a phosphate group include 2-(meth)acryloyloxyethyl dihydrogen phosphate, 3-(meth)acryloyloxypropyl dihydrogen phosphate, 4-(meth)acryloyloxybutyl dihydrogen Phosphate, 5-(meth)acryloyloxypentyl dihydrogen phosphate, 6-(meth) acryloyloxyhexyl dihydrogen phosphate, 7-(meth) acryloyloxyheptyl dihydrogen phosphate, 8-(meth) acryloyloxyoctyl dihydrogen phosphate hydrogen phosphate, 9-(meth)acryloyloxynonyl dihydrogen phosphate, 10-(meth)acryloyloxydecyldihydrogenphosphate, 11-(meth)acryloyloxyundecyldihydrogenphosphate, 12-(meth)acryloyl oxidodecyl dihydrogen phosphate, 16-(meth) acryloyloxyhexadecyl dihydrogen phosphate, 20-(meth) acryloyloxy eicosyl dihydrogen phosphate, bis[2-(meth) acryloyloxyethyl] hydrogen phosphate, Bis[4-(meth)acryloyloxybutyl]hydrogen phosphate, bis[6-(meth)acryloyloxyhexyl]hydrogenphosphate, bis[8-(meth)acryloyloxyoctyl]hydrogenphosphate, bis[9-( meth) acryloyloxynonyl] hydrogen phosphate, bis [10-(meth) acryloyloxydecyl] hydrogen phosphate, 1,3-bis [(meth) acryloyloxy] propan-2-yl dihydrogen phosphate, 2-(meth) ) acryloyloxyethylphenyl hydrogen phosphate, 2-(meth)acryloyloxyethyl-2-bromoethyl hydrogen phosphate, bis[2-(meth)acryloyloxy-(1-hydroxymethyl)ethyl] hydrogen phosphate, and these acid anhydrides, acid halides (acid chlorides, etc.), alkali metal salts, ammonium salts, and the like.

Examples of the monomer having a pyrophosphate group include bis[2-(meth)acryloyloxyethyl] pyrophosphate, bis[4-(meth)acryloyloxybutyl] pyrophosphate, bis[6-(meth)pyrophosphate acryloyloxyhexyl], bis[8-(meth)acryloyloxyoctyl] pyrophosphate, bis[10-(meth)acryloyloxydecyl] pyrophosphate, and their acid anhydrides and acid halides (acid chlorides, etc.), Examples include alkali metal salts and ammonium salts.

Monomers having a thiophosphate group include, for example, 2-(meth)acryloyloxyethyl dihydrogenthiophosphate, 3-(meth)acryloyloxypropyl dihydrogenthiophosphate, 4-(meth)acryloyloxybutyldi hydrogenthiophosphate, 5-(meth)acryloyloxypentyl dihydrogenthiophosphate, 6-(meth)acryloyloxyhexyldihydrogenthiophosphate, 7-(meth)acryloyloxyheptyldihydrogenthiophosphate, 8-( meth)acryloyloxyoctyl dihydrogenthiophosphate, 9-(meth)acryloyloxynonyl dihydrogenthiophosphate, 10-(meth)acryloyloxydecyldihydrogenthiophosphate, 11-(meth)acryloyloxyundecyldihydro gentiophosphate, 12-(meth)acryloyl oxide decyl dihydrogenthiophosphate, 16-(meth) acryloyloxyhexadecyl dihydrogenthiophosphate, 20-(meth) acryloyloxy eicosyl dihydrogenthiophosphate, and these acid anhydrides, acid halides (acid chlorides, etc.), alkali metal salts, ammonium salts, and the like.

Examples of monomers having a phosphonic acid group include 2-(meth)acryloyloxyethylphenylphosphonate, 5-(meth)acryloyloxypentyl-3-phosphonopropionate, 6-(meth)acryloyloxyhexyl- 3-phosphonopropionate, 10-(meth)acryloyloxydecyl-3-phosphonopropionate, 6-(meth)acryloyloxyhexylphosphonoacetate, 10-(meth)acryloyloxydecylphosphonoacetate, and These acid anhydrides, acid halides (acid chlorides, etc.), alkali metal salts, ammonium salts and the like are included.

Examples of monomers having a sulfonic acid group include 2-(meth)acrylamido-2-methylpropanesulfonic acid, styrenesulfonic acid, 2-sulfoethyl (meth)acrylate, and their acid anhydrides and acid halides ( acid chlorides, etc.), alkali metal salts, ammonium salts, and the like.

The monomer having a carboxylic acid group includes a monomer having one carboxyl group in the molecule and a monomer having a plurality of carboxyl groups in the molecule.

Examples of monomers having one carboxyl group in the molecule include (meth)acrylic acid, N-(meth)acryloylglycine, N-(meth)acryloylaspartic acid, O-(meth)acryloyltyrosine, N- (Meth) acryloyltyrosine, N-(meth)acryloylphenylalanine, N-(meth)acryloyl-p-aminobenzoic acid, N-(meth)acryloyl-o-aminobenzoic acid, p-vinylbenzoic acid, 2-(meth) ) acryloyloxybenzoic acid, 3-(meth)acryloyloxybenzoic acid, 4-(meth)acryloyloxybenzoic acid, N-(meth)acryloyl-5-aminosalicylic acid, N-(meth)acryloyl-4-aminosalicylic acid, 2-(meth)acryloyloxyethyl hydrogensuccinate, 2-(meth)acryloyloxyethylhydrogenphthalate, 2-(meth)acryloyloxyethylhydrogenmalate, and their acid anhydrides and acid halides (acid chlorides substances, etc.), alkali metal salts, ammonium salts, and the like.

Examples of monomers having multiple carboxyl groups in the molecule include 6-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 9-(meth)acryloyloxynonane-1,1-dicarboxylic acid, 10- (Meth) acryloyloxydecane-1,1-dicarboxylic acid, 11-(meth)acryloyloxyundecane-1,1-dicarboxylic acid, 12-(meth)acryloyloxyundecane-1,1-dicarboxylic acid, 13-(meth) ) acryloyloxytridecane-1,1-dicarboxylic acid, 4-(meth)acryloyloxyethyl trimellitate, 4-(meth)acryloyloxybutyl trimellitate, 4-(meth)acryloyloxyhexyl trimellitate, 4 -(meth)acryloyloxydecyl trimellitate, 2-(meth)acryloyloxyethyl-3′-(meth)acryloyloxy-2′-(3,4-dicarboxybenzoyloxy)propylsuccinate, and acids thereof Anhydrides, acid halides (acid chlorides, etc.), alkali metal salts, ammonium salts and the like can be mentioned.

Among the above-mentioned monomers (A) having an acidic group, monomers having a phosphate group and/or having a pyrophosphate group can exhibit superior adhesiveness to tooth substance. A monomer is preferred, and a monomer having a phosphate group is more preferred. Among them, divalent phosphorus having an alkyl or alkylene group with a carbon number of 6 to 20 as the main chain in the molecule, because it exhibits high deashing property in the absence of an organic solvent and exhibits high adhesiveness. A (meth)acrylic monomer having an acid group is preferred, and a (meth)acrylic monomer having a divalent phosphoric acid group having an alkylene group having 8 to 12 carbon atoms as a main chain in the molecule is more preferred. 10-methacryloyloxydecyl dihydrogen phosphate is particularly preferred.

The content of the monomer (A) having an acidic group is not particularly limited. It is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, further preferably 1 part by mass or more, and preferably 2 parts by mass or more. Particularly preferably, it is 2.5 parts by mass or more, and may be 3 parts by mass or more, and is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and 30 parts by mass or less. It is more preferably 20 parts by mass or less, and may be 10 parts by mass or less, or even 5 parts by mass or less.

[Hydrophobic monomer (B) having no acidic group]
The non-solvent-based dental composition of the present invention preferably contains a hydrophobic monomer (B) having no acidic group. The hydrophobic monomer (B) having no acidic group can contribute to the curing action by being polymerized, and the resulting cured product (cured layer) has improved mechanical strength and adhesiveness. improves. In addition, the inclusion of the hydrophobic monomer (B) having no acidic group improves the handleability of the non-solvent-based dental composition.

The hydrophobic monomer having no acidic group (B) is a polymerizable monomer having no acidic group and having at least one polymerizable group such as an acryloyl group, a methacryloyl group, a vinyl group, a styrene group, etc. (particularly radically polymerizable monomers) can be preferably used. As the polymerizable group, a (meth)acryloyloxy group and a (meth)acrylamide group are preferable, and a methacryloyloxy group and a methacrylamide group are more preferable, because radical polymerization is easy. As the hydrophobic monomer (B) having no acidic group, those having a solubility in water (pure water) at 25° C. of less than 10% by mass can be used. Polymers, bifunctional aliphatic monomers, crosslinkable monomers such as trifunctional or higher monomers, and the like can be preferably used.

Examples of aromatic bifunctional monomers include 2,2-bis((meth)acryloyloxyphenyl)propane, 2,2-bis[4-(3-(meth)acryloyloxy-2-hydroxy propoxy)phenyl]propane, 2,2-bis(4-(meth)acryloyloxyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane, 2,2-bis(4 -(meth)acryloyloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxytriethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxytetraethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypentaethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxydipropoxyphenyl)propane, 2-(4-(meth)acryloyloxydiethoxy) Phenyl)-2-(4-(meth)acryloyloxyethoxyphenyl)propane, 2-(4-(meth)acryloyloxydiethoxyphenyl)-2-(4-(meth)acryloyloxytriethoxyphenyl)propane, 2 -(4-(meth)acryloyloxydipropoxyphenyl)-2-(4-(meth)acryloyloxytriethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypropoxyphenyl)propane, 2, 2-bis(4-(meth)acryloyloxyisopropoxyphenyl)propane and the like. Among these, 2,2-bis[4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane (commonly known as "Bis-GMA"), 2,2-bis(4-(meth)acryloyloxyethoxyphenyl ) propane, 2,2-bis(4-methacryloyloxypolyethoxyphenyl)propane (those with an average number of added moles of ethoxy groups of 2.6, commonly known as “D-2.6E”), 2,2-bis(4 -(meth)acryloyloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxytriethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxytetraethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypentaethoxyphenyl)propane is preferred, and Bis-GMA, D-2.6E is more preferred.

Examples of aliphatic bifunctional monomers include glycerol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di( meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 1,6-hexane Diol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,2-bis(3-(meth)acryloyloxy-2-hydroxypropoxy)ethane, 2,2,4-trimethylhexamethylene bis (2-carbamoyloxyethyl) di(meth)acrylate, N-methacryloyloxyethyl acrylamide, N-methacryloyloxypropylamide and the like. Among these, triethylene glycol diacrylate, triethylene glycol dimethacrylate (commonly known as "3G"), neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,10-decanediol di Methacrylate (commonly known as "DD"), 1,2-bis(3-methacryloyloxy-2-hydroxypropoxy)ethane, 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl) dimethacrylate (commonly known as "UDMA" ), N-methacryloyloxyethylacrylamide (commonly known as “MAEA”) are preferred, and 3G, DD, UDMA and MAEA are more preferred.

Tri- or higher functional monomers include, for example, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolmethane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol Tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, N,N-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)propane-1,3-diol]tetra(meth) Acrylate, 1,7-di(meth)acryloyloxy-2,2,6,6-tetra(meth)acryloyloxymethyl-4-oxyheptane and the like. Among these, N,N-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)propane-1,3-diol]tetramethacrylate is preferred.

Among the above-mentioned hydrophobic monomers (B) having no acidic group, aromatic bifunctional monomers, aliphatic bifunctional monomers are preferred, and aliphatic bifunctional monomers are more preferred. The hydrophobic monomer (B) having no acidic group may be used alone or in combination of two or more.

Although the content of the hydrophobic monomer (B) having no acidic group is not particularly limited, from the viewpoint of improving adhesiveness, etc., the entire polymerizable monomer contained in the non-solvent-based dental composition of the present invention is With respect to 100 parts by mass of the monomer, it is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, further preferably 30 parts by mass or more, and 50 parts by mass or more. Particularly preferably, it may be 70 parts by mass or more, and is preferably 99 parts by mass or less, more preferably 95 parts by mass or less, further preferably 90 parts by mass or less, and 80 parts by mass. The following are particularly preferred. When the content is at least the above lower limit, the mechanical strength of the cured product (cured layer) is further improved. In addition, when the content is equal to or less than the above upper limit, the penetration of the non-solvent-based dental composition into the dentin is further improved.

[Hydrophilic monomer (C) having no acidic group]
The non-solvent-based dental composition of the present invention may contain a hydrophilic monomer (C) having no acidic group. The hydrophilic monomer (C) that does not have an acidic group can improve adhesiveness by its polymerization, and in addition, each component contained in the non-solvent-based dental composition permeates into the dentin. In addition, the adhesiveness can be improved by permeating the dentin itself and adhering to the organic component (collagen) in the dentin.

The hydrophilic monomer (C) having no acidic group is a polymerizable monomer having no acidic group and having at least one polymerizable group such as an acryloyl group, a methacryloyl group, a vinyl group, or a styrene group. (particularly radically polymerizable monomers) can be preferably used. As the polymerizable group, a (meth)acryloyloxy group and a (meth)acrylamide group are preferable, and a methacryloyloxy group and a methacrylamide group are more preferable, because radical polymerization is easy. As the hydrophilic monomer (C) having no acidic group, those having a solubility in water (pure water) at 25° C. of 10% by mass or more can be used, and those having a solubility of 30% by mass or more can be used. Preferred are those that are soluble in water at 25° C. in any proportion.

As the hydrophilic monomer (C) having no acidic group, those having a hydrophilic group such as a hydroxyl group, an oxymethylene group, an oxyethylene group, an oxypropylene group, and an amide group are preferred. ethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 1,3-dihydroxy-2-propyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, 2 - (meth)acrylic acid esters such as (meth)acryloyloxyethyltrimethylammonium chloride, polyethylene glycol di(meth)acrylate (having 9 or more oxyethylene groups); N-monosubstituted (meth)acrylamides (e.g., N-methylol (meth)acrylamide, N-hydroxyethyl (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, diacetone (meth)acrylamide, etc.), 4-(meth)acryloylmorpholine and monofunctional (meth)acrylamides such as N,N-disubstituted (meth)acrylamides represented by the following general formula (1).

In the above general formula (1), R ¹ is an alkyl group having 1 to 3 carbon atoms (eg, methyl group, ethyl group, n-propyl group, isopropyl group, etc.) optionally having a substituent (eg, hydroxyl group, etc.) ), multiple R ¹ may be the same or different, and R ² is a hydrogen atom or a methyl group.

Examples of the N,N-disubstituted (meth)acrylamide represented by the general formula (1) include N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-bis( 2-hydroxyethyl)(meth)acrylamide and the like, and from the viewpoint of storage stability, N,N-dimethylacrylamide and N,N-diethylacrylamide are preferred, and N,N-diethylacrylamide is more preferred.

Among these hydrophilic monomers (C) having no acidic group, 2-hydroxyethyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, monofunctional 2-hydroxyethyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, diacetone (meth)acrylamide, N,N-disubstituted represented by the general formula (1) (Meth)acrylamide is more preferred, and 2-hydroxyethyl (meth)acrylate is even more preferred. The hydrophilic monomer (C) having no acidic group may be used singly or in combination of two or more.

When the non-solvent-based dental composition of the present invention contains a hydrophilic monomer (C) having no acidic group, the content of the hydrophilic monomer (C) having no acidic group is particularly limited. However, since the mechanical strength of the cured product (cured layer) is improved and the adhesiveness is further improved, the total amount of polymerizable monomers contained in the non-solvent-based dental composition of the present invention is 100 parts by mass. is preferably 90 parts by mass or less, more preferably 50 parts by mass or less, even more preferably 30 parts by mass or less, particularly preferably 25 parts by mass or less, and 1 It is preferably at least 5 parts by mass, more preferably at least 5 parts by mass, even more preferably at least 10 parts by mass, and particularly preferably at least 15 parts by mass.

In addition, when the non-solvent-based dental composition of the present invention contains the above-described hydrophobic monomer (B) having no acidic group, high adhesiveness can be expressed regardless of the state of tooth substance. From the above, the hydrophilic monomer (C) having no acidic group with respect to the total mass of the hydrophobic monomer (B) having no acidic group and the hydrophilic monomer (C) having no acidic group The content of is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, particularly preferably 20% by mass or less, and 10% by mass % or less, 5% by mass or less, or even 0% by mass (that is, it does not contain a hydrophilic monomer (C) having no acidic group).

[Polymerization initiator (D)]
The solvent-free dental composition of the present invention preferably contains a polymerization initiator (D). By containing the polymerization initiator (D), the curability of the non-solvent-based dental composition of the present invention is improved. A known polymerization initiator can be used as the polymerization initiator (D), for example, water-soluble photopolymerization initiator (D-1), water-insoluble photopolymerization initiator (D-2), chemical polymerization initiator Agent (D-3) and the like can be used. The polymerization initiator (D) may be used alone or in combination of two or more. For example, a water-soluble photopolymerization initiator (D-1) and a water-insoluble photopolymerization initiator (D-1) At least one of the agents (D-2) and the chemical polymerization initiator (D-3) may be used in combination. The polymerization initiator (D) preferably contains at least one of a water-soluble photopolymerization initiator (D-1) and a water-insoluble photopolymerization initiator (D-2), and a water-soluble photopolymerization initiator ( D-1) is more preferably included.

- Water-soluble photopolymerization initiator (D-1)
As the water-soluble photopolymerization initiator (D-1), a photopolymerization initiator having a solubility of 10 g or more in 1 L of water (pure water) at 25° C. can be used. The water-soluble photopolymerization initiator (D-1) can be dissolved in the tooth surface or in the water in the wet state due to its high solubility in water, and the tooth structure and non-solvent-based dental High curability can be exhibited at the interface with the composition, and adhesiveness is improved. The water-soluble photopolymerization initiator (D-1) may be used alone or in combination of two or more. The solubility of the water-soluble photopolymerization initiator (D-1) in 1 L of water (pure water) at 25° C. is preferably 15 g or more, more preferably 20 g or more, and even more preferably 25 g or more. .

Examples of the water-soluble photopolymerization initiator (D-1) include water-soluble (bis)acylphosphine oxides, water-soluble thioxanthones, α-hydroxyalkylphenones, α-aminoalkylphenones and the like.

Examples of the water-soluble (bis)acylphosphine oxides include water-soluble acylphosphine oxides represented by the following general formula (2) and water-soluble bisacylphosphine oxides represented by the following general formula (3).

In the above general formula (2), R ³ is an alkyl group having 1 to 4 carbon atoms or a halogen atom, multiple R ³ may be the same or different, and M is M ⁿ⁺ Hydrogen ions, alkali metal ions, alkaline earth metal ions, optionally substituted pyridinium ions, or HN ⁺ (R ⁴ ) ₃ (wherein R ⁴ is a hydrogen atom or an organic group, and a plurality of R ⁴ may be the same or different), and n is 1 or 2.

In the above general formula (3), R ³ is an alkyl group having 1 to 4 carbon atoms or a halogen atom, multiple R ³ may be the same or different, and M is M ⁿ⁺ Hydrogen ions, alkali metal ions, alkaline earth metal ions, optionally substituted pyridinium ions, or HN ⁺ (R ⁴ ) ₃ (wherein R ⁴ is a hydrogen atom or an organic group, and a plurality of R ⁴ may be the same or different), and n is 1 or 2.

In the above general formulas (2) and (3), the C 1-4 alkyl group represented by R ³ may be linear or branched, and may be methyl, ethyl, n- Examples include propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and tert-butyl group. Among these, from the viewpoint of storage stability and color stability in non-solvent-based dental compositions, R ³ is preferably a methyl group. is preferably a ^methyl group.

Examples of alkali metal ions represented by M in the general formulas (2) and (3) include lithium ions, sodium ions, potassium ions, rubidium ions, and cesium ions.
In the general formulas (2) and (3), examples of alkaline earth metal ions represented by M include magnesium ion, calcium ion, strontium ion, barium ion, and radium ion.
In the above general formulas (2) and (3), examples of substituents (typically, substituents bonded to the pyridine ring) that may be possessed when M is a pyridinium ion include halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom), carboxyl group, linear or branched acyl group having 2 to 6 carbon atoms, linear or branched alkyl group having 1 to 6 carbon atoms, carbon Linear or branched alkoxy groups of numbers 1 to 6 and the like can be mentioned.
In the above general formulas (2) and (3), when M is an ammonium ion represented by HN ⁺ (R ⁴ ) ₃ , the organic group represented by R ⁴ includes, for example, a carboxyl group and A linear or branched acyl group, a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched alkoxy group having 1 to 6 carbon atoms, and the like. Specific examples of the ammonium ion include ammonia, trimethylamine, diethylamine, dimethylaniline, ethylenediamine, triethanolamine, N,N-dimethylaminomethacrylate, N,N-dimethylaminobenzoic acid or its alkyl ester, N,N - Ammonium ions of amines such as diethylaminobenzoic acid or its alkyl esters, morpholine and diethanol p-toluidine.
In the above general formulas (2) and (3), M is an alkali metal ion, an alkaline earth metal ion, a pyridinium ion which may have a substituent, or an ammonium represented by HN ⁺ (R ⁴ ) ₃ It is preferably an ion.

Among these water-soluble (bis)acylphosphine oxides, phenyl(2,4,6-trimethylbenzoyl)phosphinic acid sodium salt, phenyl(2,4,6-trimethylbenzoyl)phosphinic acid lithium salt, bis( 2,4,6-trimethylbenzoyl)phosphinic acid sodium salt, bis(2,4,6-trimethylbenzoyl)phosphinic acid lithium salt are preferred, bis(2,4,6-trimethylbenzoyl)phosphinic acid sodium salt is particularly preferred.

Water-soluble (bis)acylphosphine oxides can be synthesized according to known methods, for example, according to the methods described in JP-A-57-197289 and WO 2014/095724. Can be synthesized. Moreover, you may use a commercial item as water-soluble (bis) acyl phosphine oxides.

Examples of the water-soluble thioxanthones include 2-hydroxy-3-(9-oxo-9H-thioxanthen-4-yloxy)-N,N,N-trimethyl-1-propanaminium chloride, 2-hydroxy- 3-(1-methyl-9-oxo-9H-thioxanthen-4-yloxy)-N,N,N-trimethyl-1-propanaminium chloride, 2-hydroxy-3-(9-oxo-9H-thio xanthen-2-yloxy)-N,N,N-trimethyl-1-propanaminium chloride, 2-hydroxy-3-(3,4-dimethyl-9-oxo-9H-thioxanthen-2-yloxy)-N , N,N-trimethyl-1-propanaminium chloride, 2-hydroxy-3-(3,4-dimethyl-9H-thioxanthen-2-yloxy)-N,N,N-trimethyl-1-propanaminium chloride, 2-hydroxy-3-(1,3,4-trimethyl-9-oxo-9H-thioxanthen-2-yloxy)-N,N,N-trimethyl-1-propanaminium chloride and the like.

As the α-hydroxyalkylphenones, for example, a (poly)ethylene glycol chain is introduced into the hydroxyl group of 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methylpropan-1-one. _{1 -} hydroxycyclohexylphenyl ^ketone in which a (poly) ^ethylene glycol chain is introduced into the hydroxyl group and/or phenyl group; 2-hydroxy-2-methyl-1-phenylpropan-1-one in which a (poly)ethylene glycol chain is introduced into the hydroxyl group and/or phenyl group, 2-hydroxy-2-methyl-1-phenylpropane-1- Examples include those in which —OCH ₂ CO ₂ ^{−Na +} is introduced into the phenyl group of on.

Examples of the α-aminoalkylphenones include, for example, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one whose amino group is converted into a quaternary ammonium salt, 2-benzyl-2 A quaternary ammonium salt of the amino group of -(dimethylamino)-1-(4-morpholinophenyl)butan-1-one can be mentioned.

The water-soluble photopolymerization initiator (D-1) is in a form capable of dissolving in the surface of the dentin in a moist state or water in the dentin to improve the polymerization curability of the adhesive interface and the inside of the resin-impregnated layer. Preferably, the water-soluble photopolymerization initiator (D-1) may be dissolved or dispersed in the non-solvent dental composition.

When the water-soluble photopolymerization initiator (D-1) is dispersed in the non-solvent-based dental composition, if the average particle size of the dispersed particles is too large, they tend to settle. is preferably 500 μm or less, more preferably 100 μm or less, even more preferably 50 μm or less. On the other hand, if the average particle size is too small, the specific surface area of the dispersed particles tends to be too large and the amount that can be dispersed in the non-solvent-based dental composition tends to decrease. It is preferably 01 μm or more. Here, the average particle diameter is based on electron micrographs of 100 or more particles, and after image analysis using image analysis type particle size distribution measurement software (such as "Mac-View" manufactured by Mountech Co., Ltd.) It can be calculated as a volume average particle size.

The non-solvent-based dental composition in which the water-soluble photopolymerization initiator (D-1) is dispersed can be obtained by using the powdery water-soluble photopolymerization initiator (D-1) as a raw material. can. The shape of individual particles of the powdery water-soluble photopolymerization initiator (D-1) is not particularly limited, and examples thereof include spherical, needle-like, plate-like, and crushed shapes. The method for preparing the powdery water-soluble photopolymerization initiator (D-1) is not particularly limited. can be obtained by the following method.
Method 1: A method of preparing an aqueous solution of the water-soluble photopolymerization initiator (D-1), freezing this aqueous solution (for example, at about −50° C.), and vacuum-drying it in a frozen state (freeze-drying method).
Method 2: Prepare an aqueous solution (eg, saturated aqueous solution) of the water-soluble photopolymerization initiator (D-1), pour this aqueous solution into cooled ethanol (eg, about 0 ° C.), filter off the resulting crystals, and Wash with ethanol and air dry (reprecipitation method).
Method 3: Prepare an aqueous solution (eg, saturated aqueous solution) of the water-soluble photopolymerization initiator (D-1), rapidly cool the aqueous solution (eg, about 0° C.), filter off the resulting crystals, and air dry. Method.
Method 4: By mechanical grinding and sieving.

Among these, the freeze-drying method (Method 1) and the reprecipitation method (Method 2) are preferred, and the freeze-drying method (Method 1) is more preferred, from the viewpoint of the average particle size of the resulting powder.

In the case where the non-solvent-based dental composition of the present invention contains the water-soluble photopolymerization initiator (D-1), the content of the water-soluble photopolymerization initiator (D-1) is not particularly limited, but From the viewpoint of the curability and adhesiveness of the non-solvent-based dental composition, as well as sufficient dissolution, dispersion or diffusion of the water-soluble photopolymerization initiator (D-1), the non-solvent-based dental composition of the present invention It is preferably in the range of 0.01 to 20 parts by mass with respect to 100 parts by mass of the total polymerizable monomer contained in the non-solvent-based dental solvent of the present invention from the viewpoint of further improving adhesiveness. It is more preferably in the range of 0.05 to 10 parts by mass, more preferably in the range of 0.1 to 5 parts by mass, based on 100 parts by mass of the total polymerizable monomers contained in the composition for More preferred.

・ Water-insoluble photopolymerization initiator (D-2)
As the water-insoluble photopolymerization initiator (D-2), a photopolymerization initiator having a solubility of less than 10 g in 1 L of water (pure water) at 25°C can be used. By including the water-insoluble photopolymerization initiator (D-2), the curability of the non-solvent-based dental composition and the mechanical strength of the resulting cured product (cured layer) can be increased, thereby improving adhesion. do. The water-insoluble photopolymerization initiator (D-2) may be used alone or in combination of two or more.

Examples of the water-insoluble photopolymerization initiator (D-2) include (bis)acylphosphine oxides, thioxanthones, ketals, α-diketones other than the water-soluble photopolymerization initiator (D-1) described above. , coumarins, anthraquinones, benzoin alkyl ether compounds, α-aminoketone compounds, and the like.

Among the (bis)acylphosphine oxides, acylphosphine oxides include, for example, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, and 2,6-dichlorobenzoyldiphenylphosphine. oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, benzoyldi(2,6-dimethyl phenyl) phosphonates and the like.

Among the (bis)acylphosphine oxides, the bisacylphosphine oxides include, for example, bis(2,6-dichlorobenzoyl)phenylphosphine oxide, bis(2,6-dichlorobenzoyl)-2,5-dimethylphenyl Phosphine oxide, bis(2,6-dichlorobenzoyl)-4-propylphenylphosphine oxide, bis(2,6-dichlorobenzoyl)-1-naphthylphosphine oxide, bis(2,6-dimethoxybenzoyl)phenylphosphine oxide, bis (2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,5-dimethylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis(2,3,6-trimethylbenzoyl)-2,4,4-trimethylpentylphosphine oxide and the like.

Examples of the thioxanthones include thioxanthone and 2-chlorothioxanthene-9-one.

Examples of the ketals include benzyl dimethyl ketal and benzyl diethyl ketal.

Examples of the α-diketones include diacetyl, benzyl, camphorquinone, 2,3-pentadione, 2,3-octadione, 9,10-phenanthrenequinone, 4,4′-oxybenzyl, acenaphthenequinone, and the like. be done. Among these, camphorquinone is particularly preferable from the viewpoint of having a maximum absorption wavelength in the visible light region.

Examples of the coumarins include 3,3′-carbonylbis(7-diethylaminocoumarin), 3-(4-methoxybenzoyl)coumarin, 3-thienylcoumarin, 3-benzoyl-5,7-dimethoxycoumarin, 3- Benzoyl-7-methoxycoumarin, 3-benzoyl-6-methoxycoumarin, 3-benzoyl-8-methoxycoumarin, 3-benzoylcoumarin, 7-methoxy-3-(p-nitrobenzoyl)coumarin, 3-(p-nitro benzoyl)coumarin, 3,5-carbonylbis(7-methoxycoumarin), 3-benzoyl-6-bromocoumarin, 3,3′-carbonylbiscoumarin, 3-benzoyl-7-dimethylaminocoumarin, 3-benzoylbenzo[ f]coumarin, 3-carboxycoumarin, 3-carboxy-7-methoxycoumarin, 3-ethoxycarbonyl-6-methoxycoumarin, 3-ethoxycarbonyl-8-methoxycoumarin, 3-acetylbenzo[f]coumarin, 3-benzoyl -6-nitrocoumarin, 3-benzoyl-7-diethylaminocoumarin, 7-dimethylamino-3-(4-methoxybenzoyl)coumarin, 7-diethylamino-3-(4-methoxybenzoyl)coumarin, 7-diethylamino-3- (4-diethylamino)coumarin, 7-methoxy-3-(4-methoxybenzoyl)coumarin, 3-(4-nitrobenzoyl)benzo[f]coumarin, 3-(4-ethoxycinnamoyl)-7-methoxycoumarin, 3-(4-dimethylaminocinnamoyl)coumarin, 3-(4-diphenylaminocinnamoyl)coumarin, 3-[(3-dimethylbenzothiazol-2-ylidene)acetyl]coumarin, 3-[(1-methylnaphtho[ 1,2-d]thiazol-2-ylidene)acetyl]coumarin, 3,3′-carbonylbis(6-methoxycoumarin), 3,3′-carbonylbis(7-acetoxycoumarin), 3,3′-carbonyl Bis(7-dimethylaminocoumarin), 3-(2-benzothiazolyl)-7-(diethylamino)coumarin, 3-(2-benzothiazolyl)-7-(dibutylamino)coumarin, 3-(2-benzo imidazoyl)-7-(diethylamino)coumarin, 3-(2-benzothiazolyl)-7-(dioctylamino)coumarin, 3-acetyl-7-(dimethylamino)coumarin, 3,3′-carbonylbis(7 -dibutylaminocoumarin), 3,3'- Carbonyl-7-diethylaminocoumarin-7′-bis(butoxyethyl)aminocoumarin, 10-[3-[4-(dimethylamino)phenyl]-1-oxo-2-propenyl]-2,3,6,7- Tetrahydro-1,1,7,7-tetramethyl-1H,5H,11H-[1]benzopyrano[6,7,8-ij]quinolidin-11-one, 10-(2-benzothiazolyl)-2, 3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H,5H,11H-[1]benzopyrano[6,7,8-ij]quinolidin-11-one and the like.

Among these coumarins, 3,3'-carbonylbis(7-diethylaminocoumarin) and 3,3'-carbonylbis(7-dibutylaminocoumarin) are preferred.

Examples of the anthraquinones include anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 1-bromoanthraquinone, 1,2-benzanthraquinone, 1-methylanthraquinone, 2-ethylanthraquinone, and 1-hydroxyanthraquinone. .

Examples of the benzoin alkyl ether compounds include benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

Examples of the α-aminoketone compound include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one.

Among these water-insoluble photopolymerization initiators (D-2), at least one selected from the group consisting of (bis)acylphosphine oxides, α-diketones and coumarins is preferred. As a result, it has excellent photocurability in the visible light region and near-ultraviolet light region. It becomes a composition.

The content of the water-insoluble photopolymerization initiator (D-2) is not particularly limited. From the viewpoint of preventing the precipitation of 2), it should be in the range of 0.01 to 10 parts by mass with respect to 100 parts by mass of all the polymerizable monomers contained in the non-solvent dental composition of the present invention. is preferred, more preferably in the range of 0.05 to 7 parts by mass, and even more preferably in the range of 0.1 to 5 parts by mass.

Further, when the water-soluble photopolymerization initiator (D-1) and the water-insoluble photopolymerization initiator (D-2) are used in combination, the mass ratio of the two [(D-1)/(D-2 )] is preferably in the range of 1/10 to 10/1, more preferably in the range of 1/7 to 7/1, and in the range of 1/5 to 5/1 is more preferred, and a range of 1/3 to 3/1 is particularly preferred. When the mass ratio is equal to or higher than the lower limit, polymerization at the adhesive interface is further promoted to improve adhesiveness. Further, when the mass ratio is equal to or less than the upper limit, the curability of the non-solvent-based dental composition is improved, and the adhesiveness is also improved.

・Chemical polymerization initiator (D-3)
As the chemical polymerization initiator (D-3), conventionally known ones can be used, and specific examples include organic peroxides and inorganic peroxides, with organic peroxides being preferred. Examples of the organic peroxides include ketone peroxides, hydroperoxides, diacyl peroxides, dialkyl peroxides, peroxyketals, peroxyesters and peroxydicarbonates. The chemical polymerization initiator (D-3) may be used alone or in combination of two or more.

[Polymerization accelerator (E)]
The non-solvent-based dental composition of the present invention preferably contains a polymerization accelerator (E). The polymerization accelerator (E) is used together with the polymerization initiator (D) such as the water-insoluble photopolymerization initiator (D-2) and the chemical polymerization initiator (D-3) to cure the non-solvent-based dental composition. can promote sexuality. As the polymerization accelerator (E), known polymerization accelerators can be used, for example, amines, sulfinic acids (including salts), borate compounds, barbituric acid derivatives, triazine compounds, copper compounds, tin compounds. , vanadium compounds, halogen compounds, aldehydes, thiol compounds, sulfites, hydrogen sulfites, thiourea compounds, and the like. The polymerization accelerator (E) may be used alone or in combination of two or more.

Said amines are divided into aliphatic amines and aromatic amines. Examples of the aliphatic amine include primary aliphatic amines such as n-butylamine, n-hexylamine and n-octylamine; secondary aliphatic amines such as diisopropylamine, dibutylamine and N-methylethanolamine. ; N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-lauryldiethanolamine, 2-(dimethylamino)ethyl methacrylate, N-methyldiethanolamine dimethacrylate, N-ethyldiethanolamine dimethacrylate, triethanolamine mono tertiary aliphatic amines such as methacrylate, triethanolamine dimethacrylate, triethanolamine trimethacrylate, triethanolamine, trimethylamine, triethylamine and tributylamine; Among these, tertiary aliphatic amines are preferred, and N-methyldiethanolamine and triethanolamine are more preferred, from the viewpoint of the curability and storage stability of the non-solvent-based dental composition.

Examples of the aromatic amine include N,N-bis(2-hydroxyethyl)-3,5-dimethylaniline, N,N-bis(2-hydroxyethyl)-p-toluidine, N,N-bis( 2-hydroxyethyl)-3,4-dimethylaniline, N,N-bis(2-hydroxyethyl)-4-ethylaniline, N,N-bis(2-hydroxyethyl)-4-isopropylaniline, N,N -bis(2-hydroxyethyl)-4-t-butylaniline, N,N-bis(2-hydroxyethyl)-3,5-diisopropylaniline, N,N-bis(2-hydroxyethyl)-3,5 -di-t-butylaniline, N,N-dimethylaniline, N,N-dimethyl-p-toluidine, N,N-dimethyl-m-toluidine, N,N-diethyl-p-toluidine, N,N-dimethyl -3,5-dimethylaniline, N,N-dimethyl-3,4-dimethylaniline, N,N-dimethyl-4-ethylaniline, N,N-dimethyl-4-isopropylaniline, N,N-dimethyl-4 -t-butylaniline, N,N-dimethyl-3,5-di-t-butylaniline, 4-(N,N-dimethylamino)ethyl benzoate, 4-(N,N-dimethylamino)methyl benzoate , 4-(N,N-dimethylamino)propyl benzoate, 4-(N,N-dimethylamino)n-butoxyethyl benzoate, 4-(N,N-dimethylamino)benzoate 2-((meth) acryloyloxy)ethyl, 4-(N,N-dimethylamino)benzophenone, 4-(N,N-dimethylamino)butyl benzoate and the like. Among these, N,N-bis(2-hydroxyethyl)-p-toluidine and 4-(N,N-dimethylamino)benzoic acid are used from the viewpoint of imparting excellent curability to non-solvent-based dental compositions. Ethyl, 4-(N,N-dimethylamino)n-butoxyethyl benzoate, 4-(N,N-dimethylamino)benzophenone are preferred.

Examples of the sulfinic acids, borate compounds, barbituric acid derivatives, triazine compounds, copper compounds, tin compounds, vanadium compounds, halogen compounds, aldehydes, thiol compounds, sulfites, hydrogen sulfites and thiourea compounds include: Those described in 2008/087977 and the like can be used.

The content of the polymerization accelerator (E) is not particularly limited, but from the viewpoint of adhesiveness, etc., 0 It is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, still more preferably 0.05 parts by mass or more, and particularly preferably 0.1 parts by mass or more, Also, it is preferably 30 parts by mass or less, more preferably 10 parts by mass or less, even more preferably 7 parts by mass or less, and particularly preferably 5 parts by mass or less.

[Filler (F)]
The non-solvent-based dental composition of the present invention preferably contains a filler (F). The filler (F) often has a higher thickening effect and specific gravity than the polymerizable monomers described above, and the inclusion of the filler (F) increases the viscosity and Specific gravity can be increased. In addition, the inclusion of the filler (F) improves the mechanical strength of the obtained cured product (cured layer) and improves the adhesiveness. Although it depends on the type of filler (F), the average primary particle size of the filler (F) is generally 0 because a non-solvent-based dental composition having desired viscosity and specific gravity can be obtained more easily. It is preferably 0.001 μm or more, more preferably 0.01 μm or more, still more preferably 0.1 μm or more, particularly preferably 0.2 μm or more, and 0.3 μm or more, 0.5 μm or more. It may be 0.8 μm or more, preferably 50 μm or less, more preferably 30 μm or less, further preferably 10 μm or less, and particularly preferably 5 μm or less. .

As the filler (F), conventionally known fillers used for dental purposes can be preferably used. Fillers can generally be broadly classified into organic fillers, inorganic fillers and organic-inorganic composite fillers (fillers containing an inorganic filler and a polymer of polymerizable monomers). 1 type or 2 types or more can be used. Examples of the case of using two or more types of fillers (F) include, for example, the case of using together fillers having different materials, particle size distributions, morphologies, and the like. A commercial item can be used as a filler (F). An inorganic filler is preferable as the filler (F).

Examples of organic filler materials include polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, crosslinked polymethyl methacrylate, crosslinked polyethyl methacrylate, polyamide, polyvinyl chloride, Polystyrene, chloroprene rubber, nitrile rubber, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, acrylonitrile-styrene copolymer, acrylonitrile-styrene-butadiene copolymer and the like. An organic filler may be used individually by 1 type, and may use 2 or more types together. The shape of the organic filler is not particularly limited. From the viewpoint of the operability of the resulting non-solvent-based dental composition and the mechanical strength of the cured product (cured layer), the average primary particle size of the organic filler is preferably 0.001 μm or more. It is more preferably 1 μm or more, further preferably 0.2 μm or more, particularly preferably 0.3 μm or more, and may be 0.5 μm or more, 0.8 μm or more, or even 1 μm or more. Also, it is preferably 50 μm or less, more preferably 30 μm or less, even more preferably 20 μm or less, and particularly preferably 10 μm or less.

Materials for the inorganic filler include, for example, various types of glasses [containing silica as a main component, and optionally containing oxides other than silica such as heavy metals, boron, and aluminum. For example, glass powder of general composition such as fused silica, quartz, soda lime silica glass, E glass, C glass, borosilicate glass (“Pyrex” glass); "8235", Esstech's "E2000", "E3000", etc.), strontium borosilicate glass (e.g., Esstech's "E4000", etc.), lanthanum glass ceramics (e.g., Schott's "GM31684") etc.), fluoroaluminosilicate glass (for example, dental glass powder such as “GM35429”, “G018-091”, “G018-117” manufactured by SCHOTT), etc.], alumina, various ceramics, various composite oxides (silica-titania, silica-zirconia, etc.), diatomaceous earth, kaolin, clay minerals (montmorillonite, etc.), activated clay, synthetic zeolite, mica, calcium fluoride, ytterbium fluoride, yttrium fluoride, silica-coated core shell structural calcium fluoride, silica-coated core-shell ytterbium fluoride, silica-coated core-shell yttrium fluoride, calcium phosphate, barium sulfate, zirconium dioxide (zirconia), titanium dioxide (titania) , hydroxyapatite, silica-coated core-shell calcium phosphate, silica-coated core-shell barium sulfate, silica-coated core-shell zirconium dioxide, silica-coated core-shell structural titanium dioxide, silica-coated core-shell structured hydroxyapatite, and the like. An inorganic filler may be used individually by 1 type, and may use 2 or more types together. Among these, from the viewpoint of workability, mechanical strength, etc., various glasses, various composite oxides, silica-coated core-shell calcium fluoride, silica-coated core-shell fluoride Ytterbium, silica-coated core-shell yttrium fluoride, silica-coated core-shell calcium phosphate, silica-coated core-shell barium sulfate, silica-coated core-shell structure zirconium dioxide, silica-coated core-shell titanium dioxide, and silica-coated core-shell hydroxyapatite.

The shape of the inorganic filler is not particularly limited, and it may be an amorphous filler or a spherical filler. Use of a spherical filler is preferable because it improves the dispersibility of the inorganic filler in the non-solvent-based dental composition. Here, the spherical filler is an electron microscope photograph of the inorganic filler, and the particles observed in the unit field of view are rounded. A filler having a degree of uniformity of 0.6 or more can be used.

The average primary particle size of the inorganic filler is not particularly limited. Considering the adhesiveness of the resulting non-solvent-based dental composition, the average primary particle size of the inorganic filler is preferably 0.001 μm or more, more preferably 0.01 μm or more, and more preferably 0.1 μm or more. is more preferably 0.2 μm or more, particularly preferably 0.3 μm or more, 0.5 μm or more, or even 0.8 μm or more, and preferably 50 μm or less, It is more preferably 30 µm or less, still more preferably 10 µm or less, and particularly preferably 5 µm or less.

For the purpose of adjusting the fluidity of the non-solvent-based dental composition, the inorganic filler may be used after surface treatment with a known surface treatment agent such as a silane coupling agent, if necessary. . Examples of the surface treatment agent include organic metal compounds such as organic silicon compounds, organic titanium compounds, organic zirconium compounds, and organic aluminum compounds. One of these surface treatment agents may be used alone, or two or more thereof may be used in combination. When two or more types of surface treatment agents are used in combination, the surface treatment layer formed by such surface treatment agents may be a surface treatment layer of a mixture of two or more surface treatment agents, or may have a multi-layer structure in which a plurality of surface treatment layers are laminated. It may be a surface treatment layer. The surface treatment method is not particularly limited, and known methods can be employed.

Examples of organosilicon compounds include compounds represented by (R ⁵ ) _n SiX _4-n (wherein R ⁵ is a substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms, and X is a C 1 4 alkoxy groups, hydroxyl groups, halogen atoms or hydrogen atoms, and n is an integer of 0 to 3. Provided that multiple R ⁵ and X may be the same or different from each other. Good.) and the like.

Specific examples of organosilicon compounds include methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, isobutyl trimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(β-methoxyethoxy)silane, 3,3,3-trifluoropropyltrimethoxysilane, methyl-3,3,3-trifluoropropyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-methacryloyloxy propylmethyldimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N -(2-aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane Silane, trimethylsilanol, methyltrichlorosilane, methyldichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, vinyltrichlorosilane, trimethylbromosilane, diethylsilane, vinyltriacetoxysilane, ω-(meth)acryloyl Oxyalkyltrimethoxysilane (number of carbon atoms between (meth)acryloyloxy group and silicon atom: 3 to 12, e.g., 3-methacryloyloxypropyltrimethoxysilane, etc.), ω-(meth)acryloyloxyalkyltriethoxysilane (Number of carbon atoms between (meth)acryloyloxy group and silicon atom: 3 to 12, e.g., 3-methacryloyloxypropyltriethoxysilane, etc.), hexaethyldisilazane, hexan-propyldisilazane, hexaisopropyldisilazane , 1,1,2,2-tetramethyl-3,3-diethyldisilazane, 1,1,3,3-tetramethyldisilazane, 1,1,1,3,3 ,3-hexamethyldisilazane and 1,1,1,3,3-pentamethyldisilazane. Among these, ω-(meth)acryloyloxyalkyltrimethoxysilane (the number of carbon atoms between the (meth)acryloyloxy group and the silicon atom: 3 to 12), ω-(meth)acryloyloxyalkyltriethoxysilane (( meth) Number of carbon atoms between acryloyloxy group and silicon atom: 3 to 12), hexaethyldisilazane, hexan-propyldisilazane, hexaisopropyldisilazane, 1,1,2,2-tetramethyl-3, 3-diethyldisilazane, 1,1,3,3-tetramethyldisilazane, 1,1,1,3,3,3-hexamethyldisilazane, 1,1,1,3,3-pentamethyldisilazane is preferred.

Examples of organic titanium compounds include tetramethyl titanate, tetraisopropyl titanate, tetra n-butyl titanate, butyl titanate dimer, and tetra(2-ethylhexyl) titanate.

Examples of organic zirconium compounds include zirconium isopropoxide, zirconium n-butoxide, zirconium acetylacetonate, zirconium acetate and the like.

Examples of organic aluminum compounds include aluminum acetylacetonate and aluminum organic acid salt chelate compounds.

As the organic-inorganic composite filler, for example, those obtained by previously adding a known polymerizable monomer to the inorganic filler described above, making it into a paste, polymerizing it, and pulverizing can be preferably used. Specific examples of the organic-inorganic composite filler include, for example, those described in International Publication No. 2011/115007, and TMPT filler (mixed with trimethylolpropane methacrylate and silica filler, polymerized and then pulverized). etc. The organic-inorganic composite filler may be used alone or in combination of two or more. The shape of the organic-inorganic composite filler is not particularly limited. The average primary particle size of the organic-inorganic composite filler is not particularly limited, but if it is too small, the thickening effect tends to increase, and if it is too large, it tends to be difficult to disperse in the non-solvent-based dental composition. Considering the adhesiveness of the obtained non-solvent-based dental composition, the average primary particle size of the organic-inorganic composite filler is preferably 0.001 μm or more, more preferably 0.1 μm or more, and 0.1 μm or more. It is more preferably 2 µm or more, particularly preferably 0.3 µm or more, and may be 0.5 µm or more, 0.8 µm or more, or even 1 µm or more, and preferably 50 µm or less. It is more preferably 30 μm or less, still more preferably 20 μm or less, and particularly preferably 10 μm or less.

The average primary particle size of the filler (F) can be determined by a laser diffraction scattering method or electron microscope observation of particles. Specifically, the laser diffraction scattering method is convenient for measuring the particle size of particles of 0.1 μm or more, and the electron microscope observation is convenient for measuring the particle size of ultrafine particles of less than 0.1 μm. A laser diffraction scattering method may be employed to determine whether or not the thickness is 0.1 μm or more.

In the laser diffraction scattering method, for example, a laser diffraction particle size distribution analyzer (e.g., "SALD-2300" manufactured by Shimadzu Corporation) is used to measure using a 0.2% sodium hexametaphosphate aqueous solution, ethanol, etc. as a dispersion medium. By doing so, the average primary particle size can be obtained.

In electron microscope observation, for example, a scanning electron microscope (for example, "SU3500" manufactured by Hitachi High-Technologies Co., Ltd.) photograph of particles is taken, and the particle diameter of particles (200 or more) observed in a unit field of view of the photograph. can be measured using image analysis type particle size distribution measurement software (such as “Mac-View” manufactured by Mountec Co., Ltd.) to determine the average primary particle size. At this time, the particle diameter of the particles is obtained as the arithmetic mean value of the longest length and the shortest length of the particles, and the average primary particle diameter is calculated from the number of particles and their particle diameters.

The content of the filler (F) is not particularly limited. It is preferably 1 part by mass or more, preferably 5 parts by mass or more, based on 100 parts by mass of the total polymerizable monomers contained in the non-solvent-based dental composition of the present invention, because it can be obtained more efficiently. More preferably, it is more preferably 20 parts by mass or more, particularly preferably 50 parts by mass or more, and may be 80 parts by mass or more, 100 parts by mass or more, or even 150 parts by mass or more. , Also, it is preferably 2,000 parts by mass or less, more preferably 900 parts by mass or less, even more preferably 500 parts by mass or less, particularly preferably 300 parts by mass or less, and 250 parts by mass parts or less, 200 parts by mass or less, or even 190 parts by mass or less. Note that the filler (F) may not be contained as long as the provisions of the present invention are satisfied.

[Fluoride ion-releasing substance (G)]
The non-solvent-based dental composition of the present invention may contain a fluoride ion-releasing substance (G). By containing the fluoride ion-releasing substance (G), acid resistance can be imparted to the dentin. Examples of the fluoride ion-releasing substance (G) include metal fluorides such as sodium fluoride, potassium fluoride, sodium monofluorophosphate, lithium fluoride, and ytterbium fluoride. The fluoride ion-releasing substance (G) may be used alone or in combination of two or more. The content of the fluoride ion-releasing substance (G) is not particularly limited. It can be 5 parts by mass or less, or even 3 parts by mass or less.

[Other ingredients]
The non-solvent-based dental composition of the present invention comprises the above polymerizable monomers (monomer having an acidic group (A), hydrophobic monomer having no acidic group (B), hydrophilic monomer (C), etc.), polymerization initiator (D), polymerization accelerator (E), filler (F), and one of other components other than fluoride ion releasing substance (G) Or it may further contain 2 or more types. Examples of other components include pH adjusters, polymerization inhibitors, ultraviolet absorbers, thickeners, colorants (dyes, pigments, etc.), fluorescent agents, perfumes, and the like. In addition, the non-solvent-based dental composition of the present invention contains other components such as cetylpyridinium chloride, benzalkonium chloride, (meth)acryloyloxide decylpyridinium bromide, (meth)acryloyloxyhexadecylpyridinium chloride, ( Antibacterial substances such as meth)acryloyloxydecylammonium chloride and triclosan may be included.

All polymerizable monomers, polymerization initiators (D), polymerization accelerators (E), fillers (F), and fluoride ion-releasing substances (G) contained in the non-solvent-based dental composition of the present invention The total content is not particularly limited, but since the effects of the present invention are exhibited more remarkably, it is preferably 50% by mass or more based on the mass of the non-solvent-based dental composition of the present invention. Preferably, it is 80% by mass or more, more preferably 90% by mass or more, particularly preferably 95% by mass or more, 98% by mass or more, 99% by mass or more, and further 100% by mass. may be

〔form〕
The form of the non-solvent-based dental composition of the present invention is not particularly limited, and various forms suitable for its use can be used. The non-solvent-based dental composition of the present invention may be either a one-component type or a divided package type (for example, a two-component type). preferable. In both the one-component type and the divided package type, each component can be stored and transported by storing each component in a suitable container.

<<Method for preparing non-solvent-based dental composition>>
There are no particular restrictions on the method for preparing the non-solvent-based dental composition of the present invention, and it can be obtained by blending the components described above. The order of blending is not particularly limited, and each component may be blended together or may be blended in two or more batches. In addition, if necessary, they may be mixed or kneaded or subjected to defoaming treatment such as vacuum defoaming treatment. When the non-solvent-based dental composition of the present invention has a divided package form, the target non-solvent-based dental composition can be obtained by appropriately blending the components to be included in each material. can.

《Application》
Applications of the non-solvent-based dental composition of the present invention are not particularly limited. The non-solvent-based dental composition of the present invention has high adhesiveness (initial adhesive strength and It is preferably used as a dental bonding material, a dental primer, or a dental coating material, and more preferably as a dental bonding material. Further, when the non-solvent-based dental composition of the present invention is used as a dental bonding material, a dental coating material, or the like, the non-solvent according to the present invention may be applied after pre-etching and/or priming the tooth structure. A solvent-based dental composition may be applied, but as described above, the non-solvent-based dental composition of the present invention exhibits high adhesiveness (initial adhesive strength and adhesive durability) even to wet tooth structure. Therefore, the use of directly applying the non-solvent-based dental composition of the present invention (typically, one-component dental It is particularly preferable to use it as a bonding material for dental use (one-step type dental bonding material, etc.). A dental bonding material, a dental primer, and a dental coating material, which are preferred uses of the present invention, are described below.

・Dental bonding material As a dental bonding material, for example, a so-called one-liquid type dental bonding material (one-step type dental bonding material ) and the like. The form of the dental bonding material includes a one-material type that can be used as it is, and a two-material type that is used by mixing two materials divided into material A and material B immediately before use, and the process is simple. A one-material type is preferable from the viewpoint of being made uniform. Specific examples of the dental bonding material include the monomer having an acidic group (A), the hydrophobic monomer having no acidic group (B), and the water-soluble photopolymerization initiator (D-1). and one or both of the water-insoluble photopolymerization initiator (D-2), polymerization accelerator (E), and filler (F).

・Dental Primer The dental primer is capable of modifying the surface of tooth substance. As a form of dental primer, there are a one-material type that can be used as it is, and a two-material type that is used by mixing two materials divided into material A and material B just before use, etc., simplifying the process. One material type is preferable from the viewpoint of being made. Specific examples of dental primers include the monomer (A) having an acidic group, the hydrophobic monomer (B) having no acidic group, and the hydrophilic monomer having no acidic group ( C), one or both of a water-soluble photopolymerization initiator (D-1) and a water-insoluble photopolymerization initiator (D-2), a polymerization accelerator (E), and at least a filler (F) Photopolymerization type, monomer (A) having an acidic group, hydrophobic monomer (B) having no acidic group, hydrophilic monomer (C) having no acidic group, chemical polymerization A chemical polymerization type containing at least an initiator (D-3), a polymerization accelerator (E), and a filler (F) can be mentioned.

·Dental Coating Material The dental coating material can protect the tooth substance or impart surface lubricity to the tooth substance. Forms of dental coating materials include a one-material type that can be used as it is, and a two-material type that uses two materials divided into A and B and mixed just before use, and the process is simple. A one-material type is preferable from the viewpoint of being made uniform. Specific examples of the dental coating material include the above-described monomer having an acidic group (A), the hydrophobic monomer having no acidic group (B), and the water-soluble photopolymerization initiator (D-1). and one or both of the water-insoluble photopolymerization initiator (D-2), and those containing at least a filler (F).

EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these Examples. Various components used in the following examples and comparative examples are shown below.

[Monomer (A) having an acidic group]
MDP: 10-methacryloyloxydecyl dihydrogen phosphate 2-MMPS: 2-methacrylamido-2-methylpropanesulfonic acid

[Hydrophobic monomer (B) having no acidic group]
DD: 1,10-decanediol dimethacrylate MAEA: N-methacryloyloxyethyl acrylamide D-2.6E: 2,2-bis(4-methacryloyloxypolyethoxyphenyl)propane (average added mole number of ethoxy groups is 2. 6)
Bis-GMA: 2,2-bis[4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane 3G: triethylene glycol dimethacrylate

[Hydrophilic monomer (C) having no acidic group]
HEMA: 2-hydroxyethyl methacrylate

[Polymerization initiator (D)]
- Water-soluble photopolymerization initiator (D-1)
BAPO-ONa: sodium salt of bis(2,4,6-trimethylbenzoyl)phosphinic acid (compound represented by the following formula (4); solubility in 1 L of water at 25°C: 60 g)

・ Water-insoluble photopolymerization initiator (D-2)
CQ: dl-camphorquinone (solubility in 1 L of water at 25° C.: 1.7 g)
BAPO: bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (solubility in 1 L of water at 25°C: less than 1 g)

[Polymerization accelerator (E)]
DMAB: 4-(N,N-dimethylamino)ethyl benzoate

[Filler (F)]
Inorganic filler 1: Admatechs Co., Ltd., true spherical fine particle silica "ADMAFINE", average primary particle size: 1.0 μm
Inorganic filler 2: Silane-treated quartz powder prepared by the following method Quartz (manufactured by MARUWA QUARTZ) was pulverized with a ball mill to obtain quartz powder having an average primary particle size of about 4.5 µm. 100 parts by mass of this quartz powder was surface-treated with 3 parts by mass of 3-methacryloyloxypropyltrimethoxysilane in a conventional manner to obtain silane-treated quartz powder.
Inorganic filler 3: Nippon Aerosil Co., Ltd., fine particle silica "AEROSIL (registered trademark) R 972", average primary particle size: 16 nm
Inorganic filler 4: sol-gel spherical silica-zirconia, average primary particle size: 0.15 μm
Organic-inorganic composite filler 1: Using inorganic filler 3 as inorganic particles and UDMA (2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl) dimethacrylate) as a polymerizable monomer, International Publication No. 2011 / Organic-inorganic composite filler prepared by the same method as described in Example 1 of No. 115007 (content of inorganic filler 3: 80% by mass, average primary particle size: 20 μm)

[Other ingredients]
- Polymerization inhibitor BHT: 2,6-di-t-butyl-4-methylphenol HQME: hydroquinone monomethyl ether

[Examples 1 to 10 and Comparative Examples 1 to 7]
Dental bonding materials according to Examples 1 to 10 and Comparative Examples 1 to 7 were prepared by mixing and dispersing the respective components shown in Tables 1 and 2 at room temperature. Using these dental bonding materials, the viscosity at 30° C., the specific gravity at 20° C., and the adhesiveness (initial adhesive strength and adhesive durability) to wet dentin were measured or evaluated according to the following methods. bottom. Results are shown in Tables 1 and 2.

[Viscosity at 30°C]
0.7 mL of the dental bonding material prepared in each of the above Examples or Comparative Examples was dropped onto a rotational viscometer (manufactured by Toki Sangyo Co., Ltd., "VISCOMETER TV-30"), measurement temperature: 30 ° C., rotation speed: 10 rpm. Stirring was started at , and the viscosity at 30°C was measured 3 minutes after the start of stirring. Three measurement samples were prepared for each dental bonding material, and the average value of the measured values was taken as the viscosity of the dental bonding material at 30°C.

[Specific gravity at 20°C]
0.05 g of the dental bonding material prepared in each of the above examples or comparative examples was added to the measurement cell of a dry automatic density meter (manufactured by Shimadzu Corporation, "AccuPyc 1330"), and the specific gravity was measured at a temperature of 20 ° C. was measured. Three measurement samples were prepared for each dental bonding material, and the average value of the measured values was taken as the specific gravity of the dental bonding material at 20°C.

[Adhesion to wet dentin (initial adhesive strength and adhesion durability)]
The lip surface of the bovine mandibular anterior tooth was polished with #80 silicon carbide paper (manufactured by Nihon Kenshi Co., Ltd.) under running water to obtain a sample in which the flat surface of the dentin was exposed. The obtained sample was further polished with #1000 silicon carbide paper (manufactured by Nihon Kenshi Co., Ltd.) under running water. After polishing, the water on the surface was dried by air blowing. An adhesive tape having a thickness of about 150 μm and having a round hole with a diameter of 3 mm was adhered to the smooth surface after drying to define the adhesion area. A glossy surface with water was formed by applying absorbent cotton soaked with water to the adherend surface in the round hole.

Next, the dental bonding material prepared in each of the above examples or comparative examples is applied to the inside of the round hole (the part where the glossy surface is formed) using a brush, and after leaving it for 10 seconds, a layer of the dental bonding material is applied. The surface was air blown to smooth the surface. Subsequently, the applied dental bonding material was cured by light irradiation for 10 seconds with a dental LED light irradiator (manufactured by Ultradent, trade name "VALO").

The surface of the cured dental bonding material obtained is filled with a dental filling composite resin (manufactured by Kuraray Noritake Dental Co., Ltd., trade name “Clearfill (registered trademark) AP-X”), and a release film (polyester ). Then, a slide glass was placed on the release film and pressed to smooth the coating surface of the dental filling composite resin. Subsequently, through the release film, the dental filling composite resin is irradiated with light for 20 seconds using the dental LED light irradiator (manufactured by Ultradent, trade name "VALO"). The dental filling composite resin was cured.

A stainless steel cylindrical rod ( 7 mm in diameter and 2.5 cm in length) was bonded at one end face (circular cross section). After adhesion, the sample was allowed to stand at room temperature for 30 minutes, and then immersed in distilled water to obtain an adhesion test sample. Twenty samples for the adhesion test were prepared for each example or comparative example, and immersed in distilled water were allowed to stand in a constant temperature vessel maintained at 37° C. for 24 hours.
Ten of the 20 samples were measured for tensile bond strength immediately after standing for 24 hours as described above to assess initial bond strength. The tensile bond strength was measured using a universal testing machine (manufactured by Shimadzu Corporation, Autograph "AG-I 100 kN") with a crosshead speed of 2 mm/min. The average value of the obtained tensile bond strength values was taken as the initial bond strength.
In addition, in order to evaluate the adhesion durability, the remaining 10 samples were further subjected to 4000 cycles of heat cycles, in which one cycle was alternately immersed in cold water at 4 ° C. and hot water at 60 ° C. for 1 minute. , the tensile bond strength was measured in the same manner as above. The average value of the obtained tensile bond strength values was defined as bond durability.

As is clear from the above results, the dental bonding materials according to the present invention (Examples 1 to 10) exhibit an initial adhesive strength of 10 MPa or more and an adhesive durability of 8 MPa or more to wet dentin. It was found to be a non-solvent-based dental composition that exhibits high adhesiveness (initial adhesive strength and adhesive durability) even to wet dentin.
On the other hand, in the dental bonding materials of Comparative Examples 1 to 7, which do not satisfy the constitution of the present invention, one or both of the initial adhesive strength and adhesive durability to wet dentin are lower than those of the above examples. was inferior in adhesion.

Claims (11)

a viscosity of 1 to 700 cP at 30°C and a specific gravity of 1.10 or more at 20°C ;
A non-solvent-based dental composition containing a monomer (A) having an acidic group and not containing a monomer having a sulfonic acid group . 2. The non-solvent-based dental composition according to claim 1 , comprising a hydrophobic monomer (B) having no acidic group. 3. The non-solvent-based dental composition according to claim 1, comprising a hydrophilic monomer (C) having no acidic group. Containing a hydrophobic monomer (B) having no acidic group, relative to the total mass of the hydrophobic monomer (B) having no acidic group and the hydrophilic monomer (C) having no acidic group 4. The non-solvent-based dental composition according to any one of claims 1 to 3 , wherein the content of the hydrophilic monomer (C) having no acidic group is 50% by mass or less. The non-solvent-based dental composition according to any one of claims 1 to 4 , comprising a polymerization initiator (D). The solvent-free dental composition according to any one of claims 1 to 5 , wherein the polymerization initiator (D) comprises a water-soluble photopolymerization initiator (D-1). The non-solvent-based dental composition according to any one of claims 1 to 6 , comprising a filler (F). 8. The non-solvent-based dental composition according to claim 7 , wherein the filler (F) has an average primary particle size of 0.001 to 50 μm. The non-solvent-based dental composition according to any one of claims 1 to 8 , which is a dental bonding material. The non-solvent-based dental composition according to any one of claims 1 to 8 , which is a dental primer. The non-solvent-based dental composition according to any one of claims 1 to 8 , which is a dental coating material.