JP6785153B2 - Dental adhesive composition - Google Patents

Description

The present invention has a specific viscosity, the contact angle with respect to the hydroxyapatite plate is a specific value, and the tensile adhesive strength to the hydroxyapatite plate measured without blowing air is a specific value for dentistry. Regarding adhesive compositions. More specifically, the present invention relates to a dental adhesive composition suitable for sealing microcracks in the dentin caused by aging, bruxism, or the like.

Microcracks in the field of dentistry are fine cracks and cracks in the tooth substance caused by aging, bruxism, etc., and may cause caries, hypersensitivity, root fracture, and the like. However, in the field of dentistry, no effective method for treating microcracks has been established, and no effective dental composition has been proposed.

As the dental composition used for sealing the microcracks, a dental adhesive composition can be considered. However, since the gap between microcracks is as small as several tens of micrometers, a dental adhesive composition that can penetrate into a small gap in the dentin is required. Further, since the gap between the microcracks is very small, it is difficult to blow air onto the permeated dental adhesive composition, so that excellent adhesion to the dentin is required even without blowing air.

Patent Documents 1 and 2 propose non-solvent-based dental adhesive compositions and non-solvent-based dental self-etching compositions that can omit the air blowing process. Further, Patent Document 3 proposes a dental one-component adhesive composition characterized by substantially containing no water.

However, as a result of studies by the present inventors, when the compositions described in Patent Documents 1 and 2 are applied, there is a problem that they do not sufficiently penetrate into microcracks due to their high viscosity and their adhesiveness to microcracks is low. It turned out that there is. Further, it was found that when the composition described in Patent Document 3 was applied, there was a problem that the microcracks penetrated, but the adhesiveness to the dentin was very low as measured without blowing air.

Japanese Unexamined Patent Publication No. 2016-56145 Japanese Unexamined Patent Publication No. 2016-69281 Japanese Unexamined Patent Publication No. 2003-342112

The present invention has excellent permeability to microcracks in the dentin and has good adhesiveness to the dentin as measured without blowing air. Dental adhesiveness suitable for sealing microcracks. It is an object of the present invention to provide a composition.

As a result of diligent research to solve the above problems, the present inventors have measured hydroxyapatite having a viscosity of 45 cP or less, a contact angle with a hydroxyapatite plate of 45 ° or less, and no air blowing. We have found that the above problems can be solved by using a dental adhesive composition having a tensile adhesive strength to a plate of 15 MPa or more, and have completed the present invention.

That is, the present invention relates to a total of 100 parts by weight of the content of the radically polymerizable monomer (a) having no acidic group, the radically polymerizable monomer (b) containing an acidic group, and the radically polymerizable monomer. Water (c) of 3.0 parts by weight or less, organic solvent (d) of 40.0 parts by weight or less with respect to 100 parts by weight of the total content of the radically polymerizable monomer, and the polymerization initiator (e). Dental adhesive composition having a viscosity of 45 cP or less, a contact angle with respect to the hydroxyapatite plate of 45 ° or less, and a tensile adhesive strength with respect to the hydroxyapatite plate of 15 MPa or more measured without blowing air. Providing things.

In a specific embodiment of the present invention, the radically polymerizable monomer (a) having no acidic group is a (meth) acrylamide-based polymerizable monomer (a1) and / or (meth) acrylate-based polymerization. It is a dental adhesive composition containing a sex monomer (a2).

Further, in a specific embodiment of the present invention, the (meth) acrylamide-based polymerizable monomer (a1) is a bifunctional or higher (meth) acrylamide-based polymerizable monomer (a1-1). It is a dental adhesive composition containing.

Further, in a specific embodiment of the present invention, the (meth) acrylate-based polymerizable monomer (a2) is a bifunctional or higher (meth) acrylate-based polymerizable monomer (a2-1). It is a dental adhesive composition containing.

In any one of the above-mentioned specific embodiments of the present invention, the radically polymerizable monomer (a) having no acidic group has a viscosity at 25 ° C. of 45 cP or less, which is a low viscosity radically polymerizable monomer. It is a dental adhesive composition containing (a3).

In the dental adhesive composition of any one of the above-mentioned specific embodiments of the present invention, the acidic group-containing radically polymerizable monomer (b) is a phosphate group-containing (meth) acrylic monomer. (B1).

In any one of the above-mentioned specific embodiments of the present invention, the content of the acidic group-containing radically polymerizable monomer (b) is the content of the radically polymerizable monomer. In a total of 100 parts by weight, it is 1 to 50 parts by weight.

In one particular embodiment of the invention, any of the above-mentioned dental adhesive compositions is for microcrack sealing.

The dental adhesive composition of the present invention exhibits excellent permeability to microcracks in the dentin and has good adhesion to the dentin measured without blowing air. The dental adhesive composition of the present invention has excellent permeability to microcracks in the dentin and has good adhesion to the dentin measured without blowing air, so that it is difficult to blow air. It can be used for dental treatment to block microcracks with gaps of several tens of micrometers.

The dental adhesive composition of the present invention is the total content of the radically polymerizable monomer (a) having no acidic group, the acidic group-containing radically polymerizable monomer (b), and the radically polymerizable monomer. 3.0 parts by weight or less of water (c) with respect to 100 parts by weight, 40.0 parts by weight or less of organic solvent (d) with respect to 100 parts by weight of the total content of the radically polymerizable monomer, and polymerization. It contains the initiator (e), has a viscosity of 45 cP or less, has a contact angle with respect to the hydroxyapatite plate of 45 ° or less, and has a tensile adhesion strength to the hydroxyapatite plate of 15 MPa or more as measured without blowing air. It is characterized by that.

Hereinafter, a radically polymerizable monomer (a) having no acidic group, a radically polymerizable monomer (b) containing an acidic group, and a radically polymerizable monomer, which are components of the dental adhesive composition of the present invention. 3.0 parts by weight or less of water (c) with respect to 100 parts by weight of the total content of the radical-polymerizable monomer, and 40.0 parts by weight or less of the organic solvent with respect to 100 parts by weight of the total content of the radically polymerizable monomer ( d) and the polymerization initiator (e) will be described.

The radically polymerizable monomer (a) having no acidic group does not have an acidic group such as a phosphoric acid group, a pyrophosphate group, a thiophosphate group, a phosphonic acid group, a sulfonic acid group or a carboxylic acid group. It is not particularly limited as long as it is a radically polymerizable monomer having a polymerizable group. Preferable examples of such compounds include those having an acryloyl group or a methacryloyl group, that is, (meth) acrylamide-based polymerizable monomer (a1) and / or (meth) acrylate-based polymerizable monomer (a2). Be done. The radically polymerizable monomer (a) having no acidic group may be blended alone or in combination of two or more. Further, in the present specification, the polymerizable monomer having a (meth) acrylamide group means a (meth) acrylamide-based polymerizable monomer even if it has a (meth) acrylate group. .. As used herein, (meth) acrylic means a generic term for acrylic and methacrylic.

Examples of the (meth) acrylamide-based polymerizable monomer (a1) include a bifunctional or higher (meth) acrylamide-based polymerizable monomer (a1-1) and a monofunctional (meth) acrylamide-based polymerizable monomer. The body (a1-2) is mentioned, and from the viewpoint of curability of the radically polymerizable monomer, a bifunctional or higher (meth) acrylamide-based polymerizable monomer (a1-1) is preferable.

Examples of the (meth) acrylate-based polymerizable monomer (a2) include a bifunctional or higher (meth) acrylate-based polymerizable monomer (a2-1) and a monofunctional (meth) acrylate-based polymerizable monomer. The body (a2-2) is mentioned, and from the viewpoint of curability of the radically polymerizable monomer, a bifunctional or higher (meth) acrylate-based polymerizable monomer (a2-1) is preferable.

Examples of the bifunctional or higher (meth) acrylamide-based polymerizable monomer (a1-1) include N, N'-ethylenebis (meth) acrylamide, N, N'-propylene bis (meth) acrylamide, and N. , N'-butylenebis (meth) acrylamide, N, N'-(dimethyl) ethylenebis (meth) acrylamide, N, N'-diethyl-1,3-propylene bis (meth) acrylamide, bis [2- (2- (2-) Methyl- (meth) acrylic amino) ethoxycarbonyl] hexamethylenediamine, 2,2,4-trimethylhexamethylene-1,6-bis (meth) acrylamide, N-methacryloxyethyl acrylamide, N-methacryloxypropylacrylamide, N Bifunctional (meth) acrylamide-based polymerization of −methacryloxybutylacrylamide, N- (1-ethyl- (2-methacryloyloxy) ethyl) acrylamide, N- (2- (2-methacryloyloxyethoxy) ethyl) acrylamide, etc. Sexual monomers; N, N', N'', N'''-tetraacrylloyltriethylenetetramine and other trifunctional or higher (meth) acrylamide-based polymerizable monomers include N-methacryloxypropyl. One or more selected from acrylamide, N-methacryloyloxybutyl acrylamide, N, N', N'', N'''-tetraacryloyltriethylenetetramine is preferable.

Examples of the monofunctional (meth) acrylamide-based polymerizable monomer (a1-2) include N, N-diethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, and N-methylol (meth). Examples thereof include acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N- (2,3-dihydroxypropyl) (meth) acrylamide, diacetone (meth) acrylamide, and 4- (meth) acryloylmorpholin.

Examples of the bifunctional or higher (meth) acrylate-based polymerizable monomer (a2-1) include 1,2-bis (3-methacryloyloxy-2-hydroxypropoxy) ethane and ethylene glycol di (meth) acrylate. , Diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, Elythritol di (meth) acrylate, sorbitol di (meth) acrylate, mannitol di (meth) acrylate, pentaerythritol di (meth) acrylate, dipentaerythritol di (meth) acrylate, glycerol di (meth) acrylate, 1,3-butane Didiol di (meth) acrylate, 1,5-pentanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, tricyclodecanedimethanol di ( Aliphalic bifunctional (meth) acrylate-based polymerizable monomer such as meta) acrylate; 2,2-bis [4- (3- (meth) acryloyloxy) -2-hydroxypropoxyphenyl] propane, 2 , 2-bis [4- (4- (meth) acryloyloxy) -3-hydroxybutoxyphenyl] propane, 2,2-bis [4- (4- (meth) acryloyloxy) -2-hydroxybutoxyphenyl] propane , 2,2-bis [4- (5- (meth) acryloyloxy) -4-hydroxypentoxyphenyl] propane, 2,2-bis ((meth) acryloyloxyphenyl) propane, 2,2-bis (4) -(Meta) acryloyloxyethoxyphenyl) 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- (4- (meth) acryloyloxydiethoxyphenyl) ) -2- (4- (Meta) acryloyloxyethoxyphenyl) propane, 2- (4- (meth) acryloyloxydiethoxyphenyl) -2- (4- (meth) acryloyloxytriethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxypolyethoxyphenyl) propane, 2- (4- (meth) acryloyloxydipropoxyphenyl) -2- (4- (meth) acryloyloxytriethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxypropoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxydipropoxy) Aromatic bifunctional (meth) acrylate-based polymerizable monomers such as phenyl) propane and 2,2-bis (4- (meth) acryloyloxyisopropoxyphenyl) propane; trimethylolpropane tri (meth) acrylate , Trimethylol ethanetri (meth) acrylate, trimethylolmethanthry (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) ) Acrylate, dipentaerythritol penta (meth) acrylate, N, N- (2,2,4-trimethylhexamethylene) bis [2- (aminocarboxy) propan-1,3-diol] tetramethacrylate, 1,7- Diacryloyloxy-2,2,6,6-tetraacryloyloxymethyl-4-oxyheptane, 1,7-diacryloyloxy-2,2,6,6-tetraacryloyloxymethyl-4-oxyheptane, 1, Trifunctional or higher (meth) acrylate-based polymerization such as 7-di (meth) acryloyloxy-2,2,6,6-tetra (meth) acryloyloxymethyl-4-oxaheptanedipentaerythritol hexa (meth) acrylate Sexual monomers include 1,2-bis (3-methacryloyloxy-2-hydroxypropoxy) ethane, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, neopentyl glycol di (meth). Acrylate, 2,2,4-trimethylhexamethylenebis (2-carbamoyloxyethyl) dimethacrylate, 2,2-bis (4-methacryloyloxypolyethoxyphenyl) propane (average number of moles of ethoxy group added: 2.6) ), And 2,2-bis [4- (3-methacryloyloxy-2-hydroxypropoxy) phenyl] propane. More preferably, one or more selected from the above group.

Examples of the monofunctional (meth) acrylate-based polymerizable monomer (a2-2) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and isobutyl (. Meta) acrylate, lauryl (meth) acrylate, 2,3-dibromopropyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) ) Acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate and other aliphatic monofunctional (meth) acrylate-based polymerizable monomers; benzyl (meth) acrylate, phenoxy. Ethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl-phthal Examples thereof include aromatic monofunctional (meth) acrylate-based polymerizable monomers such as acids, neopentyl glycol- (meth) acrylic acid-benzoic acid ester.

Among the radically polymerizable monomers (a) having no acidic group, the low viscosity radically polymerizable monomer (a3) having a viscosity at 25 ° C. of 45 cP or less from the viewpoint of the viscosity capable of penetrating microcracks. Is particularly preferably contained in the dental adhesive composition. Examples of the low-viscosity radical polymerizable monomer (a3) include a low-viscosity (meth) acrylamide-based polymerizable monomer (a3-1) and a low-viscosity (meth) acrylate-based polymerizable monomer (a3-2). Can be mentioned. Specific examples of the low-viscosity radical-polymerizable monomer (a3) include low-viscosity (meth) acrylamide-based polymerizable singles such as N, N-diethyl (meth) acrylamide and N, N-dimethyl (meth) acrylamide. Quantum (a3-1); methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, triethylene glycol di (meth) ) Low-viscosity (meth) acrylate-based polymerizable monomer (a3-2) such as acrylate is preferable, 2-hydroxyethyl (meth) acrylate, N, N-diethyl (meth) acrylamide, and triethylene glycol di (meth). ) One or more selected from the group consisting of acrylate is more preferable. The blending amount of the low-viscosity radically polymerizable monomer (a3) is preferably in the range of 10 to 99 parts by weight, preferably in the range of 20 to 90 parts by weight, based on 100 parts by weight of the total content of the radically polymerizable monomer. More preferably, the range of 30 to 85 parts by weight is further preferable, and the range of 35 to 80 parts by weight is most preferable. The blending amount of the low-viscosity radical-polymerizable monomer (a3) does not exceed the blending amount of the radical-polymerizable monomer (a) having no acidic group.

Among the radically polymerizable monomers (a) having no acidic group described above, the dental adhesive composition contains the hydrophilic radically polymerizable monomer (a4) from the viewpoint of the contact angle with the hydroxyapatite plate. Is particularly preferred. In this specification, the hydrophilic radically polymerizable monomer (a4) means a hydrophilic radically polymerizable monomer having a solubility in water at 25 ° C. of 5% by weight or more, and has a solubility of 10% by weight or more. Those having the same solubility of 15% by weight or more are preferable. Examples of the hydrophilic radically polymerizable monomer (a4) include a difunctional or higher hydrophilic (meth) acrylamide-based polymerizable monomer (a4-1) and a monofunctional hydrophilic (meth) acrylamide-based polymerizable monomer. Monomer (a4-2), bifunctional or higher hydrophilic (meth) acrylate-based polymerizable monomer (a4-3), monofunctional hydrophilic (meth) acrylate-based polymerizable monomer (a4) -4) can be mentioned. In the present specification, when the hydrophilic radical-polymerizable monomer (a4) overlaps with the low-viscosity radical-polymerizable monomer (a3), it is treated as the low-viscosity radical-polymerizable monomer (a3).

Examples of the hydrophilic radically polymerizable monomer (a4) include N, N'-ethylenebis (meth) acrylamide, N, N'-propylene bis (meth) acrylamide, and N, N'-butylenebis (meth) acrylamide. , N, N'-(dimethyl) ethylenebis (meth) acrylamide, N, N'-diethyl-1,3-propylene bis (meth) acrylamide, bis [2- (2-methyl- (meth) acrylicamino) ethoxy Carbonyl] Hexamethylenediamine, N-methacryloyloxyethylacrylamide, N-methacryloyloxypropylacrylamide, and other difunctional or higher hydrophilic (meth) acrylamide-based polymerizable monomers (a4-1); N-methylol (meth). ) Acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N- (2,3-dihydroxypropyl) (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, diacetone Simple acrylamide such as (meth) acrylamide, 4- (meth) acryloylmorpholin, N- (tris (hydroxymethyl) methyl) (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, etc. Functional hydrophilic (meth) acrylamide-based polymerizable monomer (a4-2); erythritol di (meth) acrylate, sorbitol di (meth) acrylate, mannitol di (meth) acrylate, pentaerythritol di (meth) acrylate, Dipentaerythritol di (meth) acrylate, glycerol di (meth) acrylate, polyethylene glycol di (meth) acrylate and other difunctional or higher hydrophilic (meth) acrylate-based polymerizable monomers (a4-3); 2- Hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,3-dihydroxypropyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, 2-trimethyl Examples thereof include monofunctional hydrophilic (meth) acrylate-based polymerizable monomers (a4-4) such as ammonium ethyl (meth) acrylic chloride. One or more selected from the group consisting of 2-hydroxyethyl (meth) acrylate, N, N-diethyl (meth) acrylamide, and N, N-dimethyl (meth) acrylamide is preferable, and N, N-diethyl (meth) acrylamide is preferable. Acrylamide is more preferred.

The radically polymerizable monomer (a) having no acidic group has a viscosity of 45 cP or less, a contact angle with respect to the hydroxyapatite plate of 45 ° or less, and the hydroxyapatite plate measured without blowing air. In order to satisfy the tensile adhesion strength to 15 MPa or more, one or more of each of the low-viscosity radical-polymerizable monomer (a3) and the hydrophilic radical-polymerizable monomer (a4) are used from the above three viewpoints. It is preferable to select and combine.

In a preferred embodiment, the radically polymerizable monomer (a) having no acidic group is a (meth) acrylamide-based polymerizable monomer (a1) and / or a (meth) acrylate-based polymerizable monomer (a2). ), The embodiment (X-1) in which the radically polymerizable monomer (a) having no acidic group contains a low-viscosity radically polymerizable monomer (a3) can be mentioned.

Further, in another preferred embodiment, the radically polymerizable monomer (a) having no acidic group is a (meth) acrylamide-based polymerizable monomer (a1) and / or a (meth) acrylate-based polymerizable simpler. It is a metric (a2), and the (meth) acrylamide-based polymerizable monomer (a1) is a bifunctional or higher (meth) acrylamide-based polymerizable monomer (a1-1) and a low-viscosity radical-polymerizable monomer. An embodiment (X-2) including a monomer (a3) can be mentioned.

Furthermore, in another preferred embodiment, the radically polymerizable monomer (a) having no acidic group is a (meth) acrylamide-based polymerizable monomer (a1) and / or a (meth) acrylate-based polymerizable simpler. It is a metric (a2), and the (meth) acrylate-based polymerizable monomer (a2) is a bifunctional or higher (meth) acrylate-based polymerizable monomer (a2-1) and a low-viscosity radical-polymerizable monomer. An embodiment (X-3) including a monomer (a3) can be mentioned.

Further, in another preferred embodiment, the radically polymerizable monomer (a) having no acidic group is a (meth) acrylamide-based polymerizable monomer (a1) and / or a (meth) acrylate-based polymerizable simpler. It is a metric (a2), and the (meth) acrylamide-based polymerizable monomer (a1) is a bifunctional or higher (meth) acrylamide-based polymerizable monomer (a1-1) and a bifunctional or higher (a1-1). Examples thereof include an embodiment (X-4) containing a meta) acrylate-based polymerizable monomer (a2-1) and a low-viscosity radical-polymerizable monomer (a3).

The radically polymerizable monomer (a) having no acidic group of the preferred embodiments (X-1), (X-2), (X-3) and (X-4) described above is further hydrophilic radical. It may contain a polymerizable monomer (a4) (a monomer other than the low-viscosity radically polymerizable monomer (a3)). Further, in the above-mentioned preferred embodiments (X-2), (X-3) and (X-4), the bifunctional or higher (meth) acrylamide-based polymerizable monomer (a1-1) and the bifunctional The (meth) acrylate-based polymerizable monomer (a2-1) having a sex or higher property is preferably a monomer different from the low-viscosity radical-polymerizable monomer (a3). In any of the preferred embodiments (X-1), (X-2), (X-3) and (X-4) described above, the type and amount of each component are determined based on the description of the present specification. It can be changed as appropriate, and any component can be added, deleted, or otherwise changed. Further, in any of the preferred embodiments (X-1), (X-2), (X-3) and (X-4) described above, the composition and the respective characteristics (viscosity) of each dental adhesive composition. , Contact angle, tensile adhesive strength, etc.) can be appropriately changed and combined.

If the amount of the radically polymerizable monomer (a) having no acidic group is too small, the curability of the dental adhesive composition may be lowered and the adhesive strength may be lowered, and if it is too large, the dental adhesive composition may be weakened. Permeability of the adhesive composition for dentin into microcracks may decrease. The amount of the radically polymerizable monomer (a) having no acidic group is not particularly limited as long as the effect of the present invention is obtained, but the total content of the radically polymerizable monomer is 50 to 99 parts by weight. The range of parts by weight is preferable, the range of 70 to 99 parts by weight is more preferable, the range of 85 to 99 parts by weight is further preferable, and the range of 92 to 98.5 parts by weight is most preferable.

Next, the acidic group-containing radically polymerizable monomer (b) used in the present invention will be described.

The acidic group-containing radically polymerizable monomer (b) permeates the tooth substance while decalcifying and binds to the tooth substance to improve the adhesiveness to the tooth substance. The acidic group-containing radical polymerizable monomer (b) has at least one acidic group such as a phosphoric acid group, a phosphonic acid group, a pyrophosphate group, a carboxylic acid group and a sulfonic acid group, and has an acryloyl group and a methacryloyl group. , A polymerizable monomer having at least one radically polymerizable group such as an acrylamide group and a methacrylicamide group. From the viewpoint of adhesiveness to enamel, the acidic group-containing radically polymerizable monomer (b) is preferably monofunctional having any one of an acryloyl group, a methacryloyl group, an acrylamide group and a methacrylamide group. .. Specific examples include the following.

Examples of the phosphoric acid group-containing (meth) acrylic monomer include 2- (meth) acryloyloxyethyl dihydrogen phosphate, 3- (meth) acryloyloxypropyl dihydrogen phosphate, and 4- (meth) acryloyloxy. Butyldihydrogen phosphate, 5- (meth) acryloyloxypentyl dihydrogen phosphate, 6- (meth) acryloyloxyhexyl dihydrogen phosphate, 7- (meth) acryloyloxyheptyl dihydrogen phosphate, 8- (meth) Acryloyloxyoctyldihydrogenphosphate, 9- (meth) acryloyloxynonyldihydrogenphosphate, 10- (meth) acryloyloxydecyldihydrogenphosphate, 11- (meth) acryloyloxyundecyldihydrogenphosphate, 12- (Meta) Acryloyl Oxide Decyl Dihydrogen Phosphate, 16- (Meta) Acryloyl Oxyhexadecyl Dihydrogen Phosphate, 20- (Meta) Acryloyl Oxycoyl Dihydrogen Phosphate, Bis [2- (Meta) Acryloyl Oxyethyl] Hydrogen phosphate, bis [4- (meth) acryloyloxybutyl] hydrogen phosphate, bis [6- (meth) acryloyloxyhexyl] hydrogen phosphate, bis [8- (meth) acryloyloxyoctyl] hydrogen phosphate, bis [9- (meth) acryloyloxynonyl] hydrogen phosphate, bis [10- (meth) acryloyloxydecyl] hydrogen phosphate, 1,3-di (meth) acryloyloxypropyl dihydrogen phosphate, 2- (meth) Acryloyloxyethyl phenylhydrogen phosphate, 2- (meth) acryloyloxyethyl-2-bromoethyl hydrogen phosphate, 2- (meth) acryloyloxyethyl- (4-methoxyphenyl) hydrogen phosphate, 2- (meth) chestnut Examples thereof include rhoyloxypropyl- (4-methoxyphenyl) hydrogen phosphate, acid salts thereof, alkali metal salts, ammonium salts, amine salts and the like.

Examples of the phosphonic acid group-containing (meth) acrylic monomer include 2- (meth) acryloyloxyethylphenylphosphonate, 5- (meth) acryloyloxypentyl-3-phosphonopropionate, and 6- (meth). Acryloyloxyhexyl-3-phosphonopropionate, 10- (meth) acryloyloxydecyl-3-phosphonopropionate, 6- (meth) acryloyloxyhexyl-phosphonoacetate, 10- (meth) acryloyloxydecyl − Phosphonoacetates, acid acid groups thereof, alkali metal salts, ammonium salts, amine salts and the like.

Examples of the pyrophosphate group-containing (meth) acrylic monomer include bis pyrophosphate [2- (meth) acryloyloxyethyl], bis pyrophosphate [4- (meth) acryloyloxybutyl], and bis pyrophosphate [6]. -(Meta) acryloyloxyhexyl], bis pyrophosphate [8- (meth) acryloyloxyoctyl], bis pyrophosphate [10- (meth) acryloyloxydecyl], tetra (meth) acryloyloxyethyl pyrophosphate, these acids Examples thereof include chlorides, alkali metal salts, ammonium salts and amine salts.

Examples of the carboxylic acid group-containing (meth) acrylic monomer include (meth) acrylic acid, 4- (meth) acryloyloxyethoxycarbonylphthalic acid; 4- (meth) acryloxyethyltrimellitic acid, 4-(. Meta) acryloyloxybutyloxycarbonylphthalic acid, 4- (meth) acryloyloxyhexyloxycarbonylphthalic acid, 4- (meth) acryloyloxyoctyloxycarbonylphthalic acid, 4- (meth) acryloyloxydecyloxycarbonylphthalic acid and these Acid anhydrides; 5- (meth) acryloylaminopentylcarboxylic acid, 6- (meth) acryloyloxy-1,1-hexanedicarboxylic acid, 8- (meth) acryloyloxy-1,1-octanedicarboxylic acid, 10- Examples thereof include (meth) acryloyloxy-1,1-decandycarboxylic acid, 11- (meth) acryloyloxy-1,1-undecandicarboxylic acid, acidified products thereof, alkali metal salts, ammonium salts, amine salts and the like.

Examples of the sulfonic acid group-containing (meth) acrylic monomer include 2- (meth) acrylamide-2-methylpropanesulfonic acid, 2-sulfoethyl (meth) acrylate, acidified products thereof, alkali metal salts, and ammonium. Examples thereof include salts and amine salts.

Among the above-mentioned acidic group-containing radically polymerizable monomers (b), a phosphoric acid group or a pyrophosphate group-containing (meth) acrylic monomer is preferable because it exhibits better adhesiveness to the dentin. In particular, a phosphate group-containing (meth) acrylic monomer is preferable. Among them, a divalent phosphate group-containing (meth) acrylic monomer having an alkyl group or an alkylene group having 6 to 20 carbon atoms as the main chain in the molecule is more preferable, and 10-methacryloyloxydecyldihydrogen. A divalent phosphate group-containing (meth) acrylic monomer having an alkylene group having 8 to 12 carbon atoms as a main chain in a molecule such as phosphate is most preferable.

The acidic group-containing radically polymerizable monomer (b) may be blended alone or in combination of two or more. If the amount of the acidic group-containing radically polymerizable monomer (b) is too small, the effect of the compounding of (b) may not be obtained, and if it is too large, the curability of the dental adhesive composition may be increased. It may decrease and the adhesive strength may decrease. The amount of the acidic group-containing radical polymerizable monomer (b) to be blended is not particularly limited as long as the effects of the present invention are exhibited, but is 1 to 50 parts by weight based on a total content of 100 parts by weight of the radically polymerizable monomer. The range of 1 to 30 parts by weight is more preferable, the range of 1 to 15 parts by weight is further preferable, and the range of 1.5 to 8.0 parts by weight is most preferable.

Weight ratio of the content of the acidic group-containing radical polymerizable monomer (b) to the content of the radical polymerizable monomer (a) having no acidic group (content of the polymerizable monomer (a)) / The content of the polymerizable monomer (b)) is excellent in the point of improving the permeability to microcracks when combined with other configurations and the adhesiveness to the dentin measured without blowing air. From the point of view, it is preferably in the range of 5.0 to 99, more preferably in the range of 7.0 to 70, and even more preferably in the range of 8.0 to 50. When the radically polymerizable monomer (a) having no acidic group contains a polymerizable monomer having bifunctionality or higher, the content of the acidic group-containing radically polymerizable monomer (b) and the bifunctionality The weight ratio to the content of the polymerizable monomer (a) having a sex or higher (the content of the polymerizable monomer (a) having a bifunctionality or higher / the content of the polymerizable monomer (b)) is It is preferably in the range of 5.0 to 99 from the viewpoint of improving the permeability to microcracks when combined with other configurations and the excellent adhesion to the dentin measured without blowing air. , 7.0 to 70, more preferably in the range of 8.0 to 50.

Next, water (c) used as needed in the present invention will be described.

When the dental adhesive composition of the present invention contains water (c), the decalcification action of the acidic group-containing (meth) acrylic monomer (b) on the dentin is promoted, but if it is too much, the dentistry The curability of the adhesive composition for use may decrease, and the adhesive strength may decrease. Further, it is necessary to use water that does not substantially contain impurities that adversely affect the adhesiveness, and distilled water or ion-exchanged water is preferable. The blending amount of water (c) is 3.0 parts by weight or less, preferably 1.5 parts by weight or less, and 0.5 parts by weight or less, based on 100 parts by weight of the total content of the radically polymerizable monomer. Is more preferable. The dental adhesive composition of the present invention does not have to contain water (c).

Subsequently, the organic solvent (d) used as needed in the present invention will be described.

When the dental adhesive composition of the present invention contains the organic solvent (d), the permeability to microcracks is improved, and various components are uniformly and stably dispersed. However, if the amount is too large, the dental adhesiveness The curability of the composition may decrease and the adhesive strength may decrease. The organic solvent (d) is not particularly limited as long as it does not affect the curability and adhesiveness of the dental adhesive composition, and examples thereof include methanol, ethanol, 1-propanol, 1-butanol, and acetone. The blending amount of the organic solvent (d) is 40.0 parts by weight or less, preferably 20.0 parts by weight or less, and 10.0 parts by weight with respect to 100 parts by weight of the total content of the radically polymerizable monomer. The following is more preferable. The dental adhesive composition of the present invention does not have to contain the organic solvent (d).

Subsequently, the polymerization initiator (e) used in the present invention will be described.

As the polymerization initiator (e) used in the present invention, a known polymerization initiator can be used. In particular, the photopolymerization initiator and the chemical polymerization initiator are used alone or in combination of two or more.

Examples of the photopolymerization initiator include (bis) acylphosphine oxides, water-soluble acylphosphine oxides, thioxanthones or quaternary ammonium salts of thioxanthones, ketals, α-diketones, coumarins, anthraquinones, and benzoin alkyl. Examples thereof include ether compounds and α-aminoketone compounds.

Among the (bis) acylphosphine oxides used as the photopolymerization initiator, the acylphosphine oxides include 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- Examples thereof include (2,6-dimethylphenyl) phosphonate. Examples of bisacylphosphine oxides include bis (2,6-dichlorobenzoyl) phenylphosphine oxide, bis (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, and 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 (2,5,6-trimethyl) Benzoyl) -2,4,4-trimethylpentylphosphine oxide and the like can be mentioned.

The water-soluble acylphosphine oxides used as the photopolymerization initiator preferably have an alkali metal ion, an alkaline earth metal ion, a pyridinium ion or an ammonium ion in the acylphosphine oxide molecule. For example, water-soluble acylphosphine oxides can be synthesized by the method disclosed in European Patent No. 0009348 or JP-A-57-197289.

Specific examples of the water-soluble acylphosphine oxides include monomethylacetylphosphonate / sodium salt, monomethyl (1-oxopropyl) phosphonate / sodium salt, monomethylbenzoylphosphonate / sodium salt, monomethyl (1-oxobutyl) phosphonate / sodium salt, and the like. Monomethyl (2-methyl-1-oxopropyl) phosphonate sodium salt, acetylphosphonate sodium salt, acetylmethylphosphonate sodium salt, methyl 4- (hydroxymethoxyphosphinyl) -4-oxobutanoate sodium salt, Methyl 4-oxophosphonobutanoate mononatriu salt, acetylphenylphosphinate sodium salt, (1-oxopropyl) pentylphosphinate sodium salt, methyl 4- (hydroxypentylphosphinyl) -4-oxobuta Noate sodium salt, acetylpentylphosphinate sodium salt, acetylethyl phosphinate sodium salt, methyl (1,1-dimethyl) methylphosphinate sodium, (1,1-dimethoxyethyl) methylphosphinate sodium salt , (1,1-diethoxyethyl) methylphosphinate sodium salt, methyl4- (hydroxymethylphosphinyl) -4-oxobutanoate lithium salt, 4- (hydroxymethylphosphinyl) -4- Oxobutanoic acid dilithium salt, methyl (2-methyl-1,3-dioxolan-2-yl) phosphinate sodium salt, methyl (2-methyl-1,3-thiazolidine-2-yl) phosphonite sodium salt , (2-Methylperhydro-1,3-diadin-2-yl) phosphonite sodium salt, acetylphosphinate sodium salt, (1,1-diethoxyethyl) phosphonite sodium salt, (1,1-di Ethoxyethyl) methylphosphonite sodium salt, methyl (2-methyloxathiolan-2-yl) phosphinate sodium salt, methyl (2,4,5-trimethyl-1,3-dioxolan-2-yl) phosphinate. Sodium salt, methyl (1,1-dipropoxyethyl) phosphinate / sodium salt, (1-methoxyvinyl) methylphosphinate / sodium salt, (1-ethylthiovinyl) methylphosphinate / sodium salt, methyl (2-methyl) Perhydro-1,3-diazine-2-yl) Phosphinate sodium salt, methyl (2-methylperhydro-1,3-thiazin-2-yl) phosphinate sodium salt, methyl (2-methyl-1,3-diazolidine-2-yl) phosphinate sodium salt, methyl (2-Methyl-1,3-thiazolidine-2-yl) phosphinate sodium salt, (2,2-dicyano-1-methylethynyl) phosphinate sodium salt, acetylmethylphosphinate oxime natriu salt, acetylmethylphosph Inate-O-benzyloxime sodium salt, 1-[(N-ethoxyimino) ethyl] methylphosphinate sodium salt, methyl (1-phenyliminoethyl) phosphinate sodium salt, methyl (1-phenylhydrazone ethyl) phosphinate -Sodium salt, [1- (2,4-dinitrophenylhydrazono) ethyl] methylphosphinate-sodium salt, acetylmethylphosphinate semicarbazone-sodium salt, (1-cyano-1-hydroxyethyl) methylphosphinate -Sodium salt, (dimethoxymethyl) methylphosphinate-sodium salt, formylmethylphosphinate-sodium salt, (1,1-dimethoxypropyl) methylphosphinate-sodium salt, methyl (1-oxopropyl) phosphinate-sodium salt, (1,1-dimethoxypropyl) methylphosphinate dodecylguanidine salt, (1,1-dimethoxypropyl) methylphosphinate isopropylamine salt, acetylmethylphosphinate thiosemicarbazone sodium salt, (1,1-dimethoxypropyl) Ethyl) Methylphosphinate 1,3,5-tributyl-4-methylamino-1,2,4-triazolium salt, (1,1-dimethoxyethyl) methylphosphinate 1-butyl-4-butylaminomethylamino -3,5-dipropyl-1,2,4-triazolium salt, 2,4,6-trimethylbenzoylphenylphosphine oxide sodium salt, 2,4,6-trimethylbenzoylphenylphosphine oxide potassium salt, 2,4,6- Examples thereof include an ammonium salt of trimethylbenzoylphenylphosphine oxide. Further, the compounds described in JP-A-2000-159621 are also mentioned.

Among these (bis) acylphosphine oxides and water-soluble acylphosphine oxides, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, bis (2,4,6) -Trimethylbenzoyl) phenylphosphine oxide and 2,4,6-trimethylbenzoylphenylphosphine oxide sodium salt are particularly preferred.

Examples of the thioxanthones or the quaternary ammonium salt of the thioxanthones used as the photopolymerization initiator include thioxanthone, 2-chlorothioxanthene-9-one, and 2-hydroxy-3- (9-oxo-9H-thio). Xanthene-4-yloxy) -N, N, N-trimethyl-1-propaneaminium chloride, 2-hydroxy-3- (1-methyl-9-oxo-9H-thioxanthene-4-yloxy) -N, N , N-trimethyl-1-propaneaminium chloride, 2-hydroxy-3- (9-oxo-9H-thioxanthene-2-yloxy) -N, N, N-trimethyl-1-propaneaminium chloride, 2- Hydroxy-3- (3,4-dimethyl-9-oxo-9H-thioxanthene-2-yloxy) -N, N, N-trimethyl-1-propaneaminium chloride, 2-hydroxy-3- (3,4) -Dimethyl-9H-thioxanthene-2-yloxy) -N, N, N-trimethyl-1-propaneaminium chloride, 2-hydroxy-3- (1,3,4-trimethyl-9-oxo-9H-thio) Xanthene-2-yloxy) -N, N, N-trimethyl-1-propaneaminium chloride and the like can be used.

Among these thioxanthones or quaternary ammonium salts of thioxanthones, a particularly suitable thioxanthone is 2-chlorothioxanthene-9-one, and a particularly suitable quaternary ammonium salt of thioxanthones is 2. -Hydroxy-3- (3,4-dimethyl-9H-thioxanthene-2-yloxy) -N, N, N-trimethyl-1-propaneammonium chloride.

Examples of the ketals used as the photopolymerization initiator include benzyldimethyl ketal and benzyldiethyl ketal.

Examples of the α-diketones used as the photopolymerization initiator include diacetyl, dibenzyl, camphorquinone, 2,3-pentadione, 2,3-octadione, 9,10-phenanthrene quinone, and 4,4'-. Examples thereof include oxybenzyl and acenaphthenquinone. Of these, camphorquinone is particularly preferable from the viewpoint of having a maximum absorption wavelength in the visible light region.

Examples of the coumarin compound used as the photopolymerization initiator include 3,3'-carbonylbis (7-diethylamino kumarin), 3- (4-methoxybenzoyl) coumarin, 3-thienoyl coumarin, and 3-benzoyl-5. , 7-Dimethoxykumarin, 3-benzoyl-7-methoxykumarin, 3-benzoyl-6-methoxykumarin, 3-benzoyl-8-methoxykumarin, 3-benzoyl kumarin, 7-methoxy-3- (p-nitrobenzoyl) Kumarin, 3- (p-nitrobenzoyl) coumarin, 3,5-carbonylbis (7-methoxykumarin), 3-benzoyl-6-bromokumarin, 3,3'-carbonylbis cumarin, 3-benzoyl-7-dimethyl Amino kumarin, 3-benzoylbenzo [f] kumarin, 3-carboxy kumarin, 3-carboxy-7-methoxy kumarin, 3-ethoxycarbonyl-6-methoxy kumarin, 3-ethoxycarbonyl-8-methoxy kumarin, 3-acetyl benzo [F] Kumarin, 3-benzoyl-6-nitrocoumarin, 3-benzoyl-7-diethylaminocoumarin, 7-dimethylamino-3- (4-methoxybenzoyl) coumarin, 7-diethylamino-3- (4-methoxybenzoyl) Kumarin, 7-diethylamino-3- (4-diethylamino) coumarin, 7-methoxy-3- (4-methoxybenzoyl) coumarin, 3- (4-nitrobenzoyl) benzo [f] coumarin, 3- (4-ethoxycinna) Moyle) -7-methoxycoumarin, 3- (4-dimethylaminocinnamoyl) coumarin, 3- (4-diphenylaminocinnamoyle) coumarin, 3-[(3-dimethylbenzothiazole-2-ylidene) acetyl] coumarin, 3-[(1-Methylnaphtho [1,2-d] thiazole-2-ylidene) acetyl] coumarin, 3,3'-carbonylbis (6-methoxycumarin), 3,3'-carbonylbis (7-acetoxycmarin) ), 3,3'-carbonylbis (7-dimethylaminocoumarin), 3- (2-benzothiazoyl) -7- (diethylamino) coumarin, 3- (2-benzothiazoyl) -7- (dibutylamino) Kumarin, 3- (2-benzoimidazole) -7- (diethylamino) coumarin, 3- (2-benzothiazoyl) -7- (dioctylamino) coumarin, 3-acetyl-7- (dimethylamino) coumarin, 3 , 3'-carbonylbis (7-di) Butylaminocoumarin), 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] quinolidine-11-one, 10-( 2-Benzothiazoyl) -2,3,6,7-tetrahydro-1,1,7,7-tetramethyl 1H, 5H, 11H- [1] benzopyrano [6,7,8-ij] quinolidine-11- Examples thereof include compounds described in JP-A-9-3109 and JP-A-10-245525, such as ON.

Among the above-mentioned coumarin compounds, 3,3'-carbonylbis (7-diethylaminocoumarin) and 3,3'-carbonylbis (7-dibutylaminocoumarin) are particularly preferable.

Examples of anthraquinones used as the photopolymerization initiator include anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 1-bromoanthraquinone, 1,2-benzanthraquinone, 1-methylanthraquinone, 2-ethylanthraquinone, 1 -Hydroxyanthraquinone and the like can be mentioned.

Examples of benzoin alkyl ethers used as the photopolymerization initiator include benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether and the like.

Examples of α-aminoketones used as the photopolymerization initiator include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one.

Among these photopolymerization initiators, it is preferable to use at least one selected from the group consisting of (bis) acylphosphine oxides, α-diketones, and coumarin compounds. As a result, a dental adhesive composition having excellent photocurability in the visible and near-ultraviolet regions and exhibiting sufficient photocurability regardless of the light source of a halogen lamp, a light emitting diode (LED), or a xenon lamp can be obtained. Be done.

Of the polymerization initiators (e) used in the present invention, organic peroxides are preferably used as the chemical polymerization initiator. The organic peroxide used in the above-mentioned chemical polymerization initiator is not particularly limited, and known ones can be used. Typical organic peroxides include ketone peroxides, hydroperoxides, diacyl peroxides, dialkyl peroxides, peroxyketals, peroxyesters, peroxydicarbonates and the like.

Examples of the ketone peroxide used as the chemical polymerization initiator include methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, methylcyclohexanone peroxide, cyclohexanone peroxide and the like.

Hydroperoxides used as the above-mentioned chemical polymerization initiator include 2,5-dimethylhexane-2,5-dihydroperoxide, diisopropylbenzenehydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide and 1, Examples thereof include 1,3,3-tetramethylbutylhydroperoxide.

Examples of the diacyl peroxide used as the above-mentioned chemical polymerization initiator include acetyl peroxide, isobutyryl peroxide, benzoyl peroxide, decanoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, and 2,4-dichlorobenzoyl. Examples thereof include peroxide and lauroyl peroxide.

Examples of the dialkyl peroxide used as the above-mentioned chemical polymerization initiator include di-t-butyl peroxide, dicumyl peroxide, t-butyl cumyl peroxide, and 2,5-dimethyl-2,5-di (t-butyl peroxide). Examples thereof include oxy) hexane, 1,3-bis (t-butylperoxyisopropyl) benzene and 2,5-dimethyl-2,5-di (t-butylperoxy) -3-hexine.

Examples of the peroxyketal used as the chemical polymerization initiator include 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane and 1,1-bis (t-butylperoxy) cyclohexane. 2,2-bis (t-butylperoxy) butane, 2,2-bis (t-butylperoxy) octane and 4,4-bis (t-butylperoxy) balleric acid-n-butyl ester, etc. Can be mentioned.

Examples of the peroxy ester used as the chemical polymerization initiator include α-cumylperoxyneodecanoate, t-butylperoxyneodecanoate, t-butylperoxypivalate, and 2,2,4-trimethylpentyl. Peroxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, di-t-butylperoxyisophthalate, di-t- Butyl peroxyhexahydroterephthalate, t-butylperoxy-3,3,5-trimethylhexanoate, t-butylperoxyacetate, t-butylperoxybenzoate, t-butylperoxymaleic acid and the like. Be done.

Examples of the peroxydicarbonate used as the above-mentioned chemical polymerization initiator include di-3-methoxyperoxydicarbonate, di-2-ethylhexyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, and diisopropyl. Examples thereof include peroxydicarbonate, di-n-propylperoxydicarbonate, di-2-ethoxyethylperoxydicarbonate and diallyl peroxydicarbonate.

The polymerization initiator (e) may be blended alone or in combination of two or more. The blending amount of the polymerization initiator (e) used in the present invention is not particularly limited, but from the viewpoint of curability and the like of the obtained composition, the blending amount of the polymerization initiator (e) is a radically polymerizable monomer. With respect to the total content of 100 parts by weight, the range of 0.01 to 10 parts by weight is preferable, the range of 0.05 to 5 parts by weight is more preferable, and the range of 0.2 to 2 parts by weight is most preferable. If the amount of the polymerization initiator (e) to be blended exceeds 10 parts by weight with respect to the total content of the radically polymerizable monomer of 100 parts by weight, or if the polymerization performance of the polymerization initiator itself is low, it is sufficient. There is a risk that a good adhesive strength cannot be obtained, and further, there is a risk of causing precipitation from the composition.

In a preferred embodiment, the above-mentioned polymerization initiator (e) is used together with a polymerization accelerator (f). Examples of the polymerization accelerator (f) used in the present invention include amines, sulfinic acid and salts thereof, borate compounds, barbituric acid derivatives, triazine compounds, copper compounds, tin compounds, vanadium compounds, halogen compounds, aldehydes and thiols. Examples thereof include compounds, sulfites, hydrogen sulfites, thiourea compounds and the like.

The amines used as the polymerization accelerator (f) 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; and secondary aliphatic amines such as diisopropylamine, dibutylamine and N-methylethanolamine; N-Methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-lauryldiethanolamine, 2- (dimethylamino) ethylmethacrylate, N-methyldiethanolaminedimethacrylate, N-ethyldiethanolaminedimethacrylate, triethanolamine monomethacrylate , Triethanolamine dimethacrylate, triethanolamine trimethacrylate, triethanolamine, trimethylamine, triethylamine, tributylamine and other tertiary aliphatic amines. Among these, tertiary aliphatic amines are preferable from the viewpoint of curability and storage stability of the composition, and among them, N-methyldiethanolamine and triethanolamine are more preferably used.

Examples of the aromatic amine include N, N-bis (2-hydroxyethyl) -3,5-dimethylaniline, N, N-bis (2-hydroxyethyl) -p-toluidine, and 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-di-isopropylaniline, 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, ethyl 4- (N, N-dimethylamino) benzoate, 4- (N, N-dimethylamino) Methyl benzoate, propyl 4- (N, N-dimethylamino) benzoate, n-butoxyethyl 4- (N, N-dimethylamino) benzoate, 2- [N, N-dimethylamino) benzoate 2-[ Examples thereof include (meth) acryloyloxy] ethyl, 4- (N, N-dimethylamino) benzophenone, and butyl 4-dimethylaminobenzoate. Among these, from the viewpoint of imparting excellent curability to the composition, N, N-bis (2-hydroxyethyl) -p-toluidine, 4- (N, N-dimethylamino) ethyl benzoate, 4- ( At least one selected from the group consisting of n-butoxyethyl benzoate (N, N-dimethylamino) and 4- (N, N-dimethylamino) benzophenone is preferably used.

Examples of sulfinic acid and a salt thereof used as the polymerization accelerator (f) include p-tolusinulfinic acid, sodium p-toluenesulfinate, potassium p-toluenesulfinate, lithium p-toluenesulfinate, and p-toluenesulfin. Calcium acid, benzenesulfinic acid, sodium benzenesulfinate, potassium benzenesulfinate, lithium benzenesulfinate, calcium benzenesulfinate, 2,4,6-trimethylbenzenesulfinic acid, sodium 2,4,6-trimethylbenzenesulfinate, Potassium 2,4,6-trimethylbenzenesulfinate, lithium 2,4,6-trimethylbenzenesulfinate, calcium 2,4,6-trimethylbenzenesulfinate, 2,4,6-triethylbenzenesulfinate, 2,4 , Sodium 6-triethylbenzenesulfinate, potassium 2,4,6-triethylbenzenesulfinate, lithium 2,4,6-triethylbenzenesulfinate, calcium 2,4,6-triethylbenzenesulfinate, 2,4,6 -Triisopropylbenzenesulfinic acid, sodium 2,4,6-triisopropylbenzenesulfinate, potassium 2,4,6-triisopropylbenzenesulfinate, lithium 2,4,6-triisopropylbenzenesulfinate, 2,4 Examples thereof include calcium 6-triisopropylbenzenesulfinate, and sodium benzenesulfinate, sodium p-toluenesulfinate, and sodium 2,4,6-triisopropylbenzenesulfinate are particularly preferable.

The borate compound used as the polymerization accelerator (f) is preferably an aryl borate compound. Specific examples of preferably used arylborate compounds include trialkylphenylboron, trialkyl (p-chlorophenyl) boron, and trialkyl (p-fluoro) as borate compounds having one aryl group in one molecule. Phenyl) boron, trialkyl [3,5-bis (trifluoromethyl) phenyl] boron, trialkyl [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2) -Propyl) phenyl] boron, trialkyl (p-nitrophenyl) boron, trialkyl (m-nitrophenyl) boron, trialkyl (p-butylphenyl) boron, trialkyl (m-butylphenyl) boron, trialkyl ( p-Butyloxyphenyl) boron, trialkyl (m-butyloxyphenyl) boron, trialkyl (p-octyloxyphenyl) boron and trialkyl (m-octyloxyphenyl) boron (alkyl groups are n-butyl group, n -At least one selected from the group consisting of an octyl group, an n-dodecyl group, etc.) and their sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, etc. , Methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt, butylquinolinium salt and the like.

Examples of the borate compound having two aryl groups in one molecule include dialkyldiphenylboron, dialkyldi (p-chlorophenyl) boron, dialkyldi (p-fluorophenyl) boron, and dialkyldi [3,5-bis (trifluoromethyl). ) Phenyl] boron, dialkyldi [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, dialkyldi (p-nitrophenyl) boron, dialkyldi (M-Nitrophenyl) boron, dialkyldi (p-butylphenyl) boron, dialkyldi (m-butylphenyl) boron, dialkyldi (p-butyloxyphenyl) boron, dialkyldi (m-butyloxyphenyl) boron, dialkyldi (p-) Octyloxyphenyl) boron and dialkyldi (m-octyloxyphenyl) boron (alkyl group is at least one selected from the group consisting of n-butyl group, n-octyl group, n-dodecyl group, etc.) and theirs. Sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt butyl Examples include quinolinium salt and the like.

Further, examples of the borate compound having three aryl groups in one molecule include monoalkyltriphenylboron, monoalkyltri (p-chlorophenyl) boron, monoalkyltri (p-fluorophenyl) boron, and monoalkyltri [3]. , 5-bis (trifluoromethyl) phenyl] boron, monoalkyltri [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, Monoalkyltri (p-nitrophenyl) boron, monoalkyltri (m-nitrophenyl) boron, monoalkyltri (p-butylphenyl) boron, monoalkyltri (m-butylphenyl) boron, monoalkyltri (p-) Butyloxyphenyl) boron, monoalkyltri (m-butyloxyphenyl) boron, monoalkyltri (p-octyloxyphenyl) boron and monoalkyltri (m-octyloxyphenyl) boron (alkyl group is n-butyl group, (It is one selected from n-octyl group, n-dodecyl group, etc.) and their sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium. Examples thereof include salts, ethylpyridinium salts, butylpyridinium salts, methylquinolinium salts, ethylquinolinium salts, butylquinolinium salts and the like.

Further, examples of the borate compound having four aryl groups in one molecule include tetraphenylboron, tetrakis (p-chlorophenyl) boron, tetrakis (p-fluorophenyl) boron, and tetrakis [3,5-bis (trifluoromethyl)). Phenyl] boron, tetrakis [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, tetrakis (p-nitrophenyl) boron, tetrakis (m) -Nitrophenyl) boron, tetrakis (p-butylphenyl) boron, tetrakis (m-butylphenyl) boron, tetrakis (p-butyloxyphenyl) boron, tetrakis (m-butyloxyphenyl) boron, tetrakis (p-octyloxy) Boron (phenyl), tetrakis (m-octyloxyphenyl) boron, (p-fluorophenyl) triphenylboron, [3,5-bis (trifluoromethyl) phenyl] triphenylboron, (p-nitrophenyl) triphenylboron , (M-Butyloxyphenyl) triphenylboron, (p-butyloxyphenyl) triphenylboron, (m-octyloxyphenyl) triphenylboron and (p-octyloxyphenyl) triphenylboron and their sodium salts, Lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt, butylquinoli Nium salt and the like can be mentioned.

Among these aryl borate compounds, it is more preferable to use a borate compound having 3 or 4 aryl groups in one molecule from the viewpoint of storage stability. Further, these aryl borate compounds can be used alone or in admixture of two or more.

Examples of the barbituric acid derivative used as the polymerization accelerator (f) include barbituric acid, 1,3-dimethylbarbituric acid, 1,3-diphenylbarbituric acid, 1,5-dimethylbarbituric acid and 5-butyl. Barbituric acid, 5-ethylbarbituric acid, 5-isopropylbarbituric acid, 5-cyclohexylbarbituric acid, 1,3,5-trimethylbarbituric acid, 1,3-dimethyl-5-ethylbarbituric acid, 1 , 3-Dimethyl-5-n-butylbarbituric acid, 1,3-dimethyl-5-isobutylbarbituric acid, 1,3-dimethyl-5-cyclopentyl barbituric acid, 1,3-dimethyl-5-cyclohexylbarbituric acid Tool acid, 1,3-dimethyl-5-phenylbarbituric acid, 1-cyclohexyl-1-ethylbarbituric acid, 1-benzyl-5-phenylbarbituric acid, 5-methylbarbituric acid, 5-propylbarbituric Acids, 1,5-diethylbarbituric acid, 1-ethyl-5-methylbarbituric acid, 1-ethyl-5-isobutylbarbituric acid, 1,3-diethyl-5-butylbarbituric acid, 1-cyclohexyl- 5-Methylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, 1-cyclohexyl-5-octylbarbituric acid, 1-cyclohexyl-5-hexylbarbituric acid, 5-butyl-1-cyclohexylbarbituric acid , 1-benzyl-5-phenylbarbituric acid and thiobarbituric acid, and salts thereof (particularly alkali metals or alkaline earth metals are preferable), and examples of the salts of these barbituric acids include 5. Examples thereof include sodium butyl barbiturate, sodium 1,3,5-trimethylbarbiturate and sodium 1-cyclohexyl-5-ethyl barbiturate.

Particularly suitable barbituric acid derivatives include 5-butylbarbituric acid, 1,3,5-trimethylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, 1-benzyl-5-phenylbarbituric acid, and the like. And sodium salts of these barbituric acids and the like.

Examples of the triazine compound used as the polymerization accelerator (f) include 2,4,6-tris (trichloromethyl) -s-triazine, 2,4,6-tris (tribromomethyl) -s-triazine, 2 -Methyl-4,6-bis (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl)- s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methylthiophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2,4-dichlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p) -Bromophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-n-propyl-4,6 -Bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) ) -S-Triazine, 2- [2- (p-methoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (o-methoxyphenyl) ethenyl] -4, 6-bis (trichloromethyl) -s-triazine, 2- [2- (p-butoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-) Dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4,5-trimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s -Triazine, 2- (1-naphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-biphenylyl) -4,6-bis (trichloromethyl) -s-triazine, 2-[ 2- {N, N-bis (2-hydroxyethyl) amino} ethoxy] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- {N-hydroxyethyl-N-ethylamino} ethoxy] ] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- {N-hydroxyethyl-N-methylamino} ethoxy]- Examples thereof include 4,6-bis (trichloromethyl) -s-triazine and 2- [2- {N, N-diallylamino} ethoxy] -4,6-bis (trichloromethyl) -s-triazine.

Of the triazine compounds exemplified above, particularly preferred are 2,4,6-tris (trichloromethyl) -s-triazine in terms of polymerization activity and 2-phenyl-4 in terms of storage stability. , 6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, and 2- (4-biphenylyl) -4,6-bis ( It is trichloromethyl) -s-triazine. The above triazine compound may be used alone or in combination of two or more.

As the copper compound used as the polymerization accelerator (f), for example, acetylacetone copper, cupric acetate, copper oleate, cupric chloride, cupric bromide and the like are preferably used.

Examples of the tin compound used as the polymerization accelerator (f) include di-n-butyl tin dilaurate, di-n-octyl tin dilaurate, di-n-octyl tin dilaurate, di-n-butyl tin dilaurate and the like. Be done. Particularly suitable tin compounds are di-n-octyl tin dilaurate and di-n-butyl tin dilaurate.

The vanadium compound used as the polymerization accelerator (f) is preferably an IV-valent and / or V-valent vanadium compound. Examples of the IV-valent and / or V-valent vanadium compounds include divanadium tetraoxide (IV), vanadium oxide acetylacetonate (IV), vanadil oxalate (IV), vanadil sulfate (IV), and oxobis (1-). Ph.D. 2003 Examples include the compounds described in JP-96122.

Examples of the halogen compound used as the polymerization accelerator (f) include dilauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride, benzyltrimethylammonium chloride, tetramethylammonium chloride, benzyldimethylcetylammonium chloride, dilauryldimethylammonium bromide and the like. Is preferably used.

Examples of aldehydes used as the polymerization accelerator (f) include terephthalaldehyde and benzaldehyde derivatives. Examples of the benzaldehyde derivative include dimethylaminobenzaldehyde, p-methyloxybenzaldehyde, p-ethyloxybenzaldehyde, pn-octyloxybenzaldehyde and the like. Among these, pn-octyloxybenzaldehyde is preferably used from the viewpoint of curability.

Examples of the thiol compound used as the polymerization accelerator (f) include 3-mercaptopropyltrimethoxysilane, 2-mercaptobenzoxazole, decanethiol, and thiobenzoic acid.

Examples of the sulfite salt used as the polymerization accelerator (f) include sodium sulfite, potassium sulfite, calcium sulfite, ammonium sulfite and the like.

Examples of the hydrogen sulfite used as the polymerization accelerator (f) include sodium bisulfite, potassium bisulfite and the like.

Examples of the thiourea compound used as the polymerization accelerator (f) include 1- (2-pyridyl) -2-thiourea, thiourea, methylthiourea, ethylthiourea, N, N'-dimethylthiourea, N, N'-. Diethylthiourea, N, N'-di-n-propylthiourea, N, N'-dicyclohexylthiourea, trimethylthiourea, triethylthiourea, tri-n-propylthiourea, tricyclohexylthiourea, tetramethylthiourea, tetraethylthiourea Examples thereof include urea, tetra-n-propylthiourea and tetracyclohexylthiourea.

The polymerization accelerator (f) may be used alone or in combination of two or more. The amount of the polymerization accelerator (f) used in the present invention is not particularly limited, but from the viewpoint of curability and the like of the obtained composition, the total content of the radically polymerizable monomer is 100 parts by weight. , 0.01 to 10% by weight, more preferably 0.05 to 5% by weight, and most preferably 0.2 to 2% by weight. If the amount of the polymerization accelerator (f) is more than 10% by weight, or if the polymerization performance of the polymerization initiator itself is low, sufficient adhesive strength may not be obtained.

In addition, the dental adhesive composition of the present invention contains fillers, fluorine ion-releasing substances, pH adjusters, polymerization inhibitors (for example, BHT, MEHQ), and ultraviolet absorption as long as the effects of the present invention are not impaired. Agents, thickeners, colorants, fluorescent agents, fragrances and the like may be blended. In addition, antibacterial substances such as cetylpyridinium chloride, benzalkonium chloride, (meth) acryloyloxidedecylpyridinium bromide, (meth) acryloyloxyhexadecylpyridinium chloride, (meth) acryloyloxydecylammonium chloride, and triclosan may be blended. Good.

The dental adhesive composition in the present invention has a viscosity at 25 ° C. of 45 cP or less, preferably 30 cP or less, more preferably 25 cP or less, still more preferably 20 cP or less, from the viewpoint of viscosity that allows penetration into microcracks. When the viscosity at 25 ° C. exceeds 45 cP, the permeability to microcracks is lowered, and the sealing property to microcracks is lowered. The method for measuring the viscosity is as described in Examples described later.

The dental adhesive composition in the present invention has a contact angle with respect to the hydroxyapatite plate of 45 ° or less, preferably 40 ° or less, more preferably 36 ° or less, from the viewpoint of permeability to microcracks and affinity. .. When the contact angle with respect to the hydroxyapatite plate exceeds 45 °, the permeability and affinity for microcracks are lowered, and the sealing property and adhesiveness to microcracks are lowered. The method for measuring the contact angle with respect to the hydroxyapatite plate is as described in Examples described later.

From the viewpoint of adhesiveness to microcracks, the dental adhesive composition in the present invention has a tensile adhesive strength to a hydroxyapatite plate of 15 MPa or more, preferably 17 MPa or more, preferably 20 MPa or more, as measured without blowing air. Is more preferable. When the tensile adhesive strength to the hydroxyapatite plate measured without blowing air is smaller than 15 MPa, the adhesiveness to microcracks decreases. The method for measuring the tensile adhesive strength to the hydroxyapatite plate, which was measured without blowing air, is as described in Examples described later.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples. The abbreviations used below are as follows.

ＤＥＡＡ：Ｎ，Ｎ−ジエチルアクリルアミド
ＴＡＣ４：Ｎ，Ｎ’，Ｎ’’，Ｎ’’’−テトラアクリロイルトリエチレンテトラミン

ＨＥＭＡ：２−ヒドロキシエチルメタクリレート
３Ｇ：トリエチレングリコールジメタクリレート
ＵＤＭＡ：２，２，４−トリメチルヘキサメチレンビス（２−カルバモイルオキシエチル）ジメタクリレート
Ｂｉｓ−ＧＭＡ：２，２−ビス〔４−（３−メタクリロイルオキシ−２−ヒドロキシプロポキシ）フェニル〕プロパン
Ｄ−２，６Ｅ：２，２−ビス（４−メタアクリロイルオキシポリエトキシフェニル）プロパン（エトキシ基の平均付加モル数が２．６である化合物）
ＰＰＺ：（２，２，４，４，６，６−ヘキサ｛２−（メタクロイルオキシ）−エトキシ｝−１，３，５−トリアザ−２，４，６−トリホスホリン） [Radical polymerizable monomer having no acidic group (a)]
MAEA: N-methacryloyloxyethyl acrylamide (asymmetric acrylamide / methacrylic acid ester compound represented by the following formula)

DEAA: N, N-diethylacrylamide TAC4: N, N', N'', N'''-tetraacryloyltriethylenetetramine

HEMA: 2-Hydroxyethyl methacrylate 3G: Triethylene glycol dimethacrylate UDMA: 2,2,4-trimethylhexamethylene bis (2-carbamoyloxyethyl) Dimethacrylate Bis-GMA: 2,2-bis [4- (3- (3- (3-) Methacryloyloxy-2-hydroxypropoxy) phenyl] Propane D-2,6E: 2,2-bis (4-methacryloyloxypolyethoxyphenyl) propane (compound with an average added molar number of ethoxy groups of 2.6)
PPZ: (2,2,4,4,6,6-hexa {2- (metacloyloxy) -ethoxy} -1,3,5-triaza-2,4,6-triphosphorin)

[Acid group-containing radical polymerizable monomer (b)]
MDP: 10-methacryloyloxydecyldihydrogen phosphate 2MMPS: 2-methyl-2-methacrylamide propanesulfonic acid TMEPA: tetramethacryloxyethyl pyrophosphate

[Organic solvent (d)]
EtOH: Ethanol1-BuOH: 1-Butanol

[Polymerization initiator (e)]
CQ: dl-camphorquinone BAPO: bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide TMDPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide

[Polymerization accelerator (f)]
DABE: 4- (N, N-dimethylamino) ethyl benzoate DEPT: N, N-bis (2-hydroxyethyl) -p-toluidine

[Other]
R972: Fine particle silica "Aerosil (registered trademark) R972" manufactured by Nippon Aerosil Co., Ltd.
R974: Fine particle silica "Aerosil (registered trademark) R 974" manufactured by Nippon Aerosil Co., Ltd.
BHT: 2,6-di-t-butyl-4-methylphenol MEHQ: 4-methoxyphenol

(Synthesis Example 1)
Synthesis of TAC4 Triethylenetetramine (manufactured by Tokyo Chemical Industry Co., Ltd., 21.9 g, 0.15 mol), triethylamine (75.9 g, 0.75 mol), p-methoxyphenol (3.7 mg, 0.03 mmol) in a 1 L 4-neck flask. ), 250 mL of dichloromethane was charged, stirred, and cooled to an internal temperature of 2 ° C. A 100 mL solution of chloride (67.9 g, 0.75 mol) in dichloromethane was added dropwise at 5 ° C. or lower over 2 hours. After the dropping, the mixture was stirred under room temperature conditions for 24 hours. The reaction mixture was filtered, the insoluble material was washed with dichloromethane, and concentrated under reduced pressure at 35 ° C. or lower. The obtained concentrated residue was purified by silica gel column chromatography (developing solvent: ethyl acetate: methanol = 4: 1). After column purification, the solvent was distilled off under reduced pressure using a rotary evaporator to obtain a white solid. LC / MS analysis and ¹ H-NMR measurement were performed, and it was confirmed from the signal position and integrated value that the obtained white individual was the target compound. The yield was 12.7 g and the yield was 23.3%.

MS m / z: 363 (M + H) ^{+
1 1} H-NMR (270 MHz D ₂ O): δ3.37 (m, 6H), 3.57 (m, 6H), 5.66 (m, 4H), 6.07 (m, 6H), 6.56 (M, 2H) (ppm)

[Examples 1 to 25 and Comparative Examples 1 to 13]
As an example and a comparative example, a dental adhesive composition was prepared as follows.

[Preparation of dental adhesive composition]
Each component shown in Tables 1 to 3 below was mixed at a weight ratio shown in Tables 1 to 3 at room temperature to prepare a pretreatment material for adhesion. The obtained pretreatment material for adhesion was used by filling it in a container of "Clearfill (registered trademark) Megabond (registered trademark) primer" (manufactured by Kuraray Noritake Dental Co., Ltd.).

The dental adhesive compositions of Examples and Comparative Examples were evaluated by the following methods. The evaluation results are shown in Tables 1 to 3.

[Viscosity measurement method]
The viscosity of 700 μl of the dental adhesive composition was measured with a viscometer (manufactured by Toki Sangyo Co., Ltd.) under the conditions of 30 ° C. and 100 rpm.

[Measurement method of contact angle with hydroxyapatite plate]
After dropping 1 drop (5 μl) of a dental adhesive composition onto a hydroxyapatite plate (trade name: apatite pellet APP-100, size: 10 mm × 10 mm × 2 mm, manufactured by HOYATechnosurgical Co., Ltd.) and allowing it to stand for 5 seconds. The contact angle was measured with a contact angle meter (manufactured by Cruz Co., Ltd.).

[Measurement method of tensile adhesive strength to hydroxyapatite plate measured without blowing air]
Hydroxyapatite plate (trade name: apatite pellet APP-100, size: 10 mm x 10 mm x 2 mm, manufactured by HOYATechnosurgical Co., Ltd.) is polished with # 1000 silicon carbide paper (manufactured by Nihon Kenshi Co., Ltd.) to form a flat surface. Was obtained as an exposed sample. The obtained sample was washed with an ultrasonic cleaner (manufactured by Yamato Scientific Co., Ltd.) for 5 minutes, and then the water on the surface was dried. An adhesive tape having a diameter of 3 mm and a thickness of about 150 μm was attached to the smooth surface after drying to define the adhesive area.

The dental adhesive compositions of each Example and Comparative Example were placed in a round hole having a diameter of 3 mm of the adhesive tape attached to the above-mentioned hydroxyapatite plate, and the composition was not blown with air. , After covering with a release film (trade name "Eval", manufactured by Kuraray Co., Ltd.), irradiate for 10 seconds in the normal mode of a dental polymerization light irradiator (trade name "Pencure 2000", manufactured by Morita Co., Ltd.). And cured to obtain a cured product. Next, this cured product was sandblasted with an alumina abrasive of 50 microns (manufactured by Morita Co., Ltd.), and on the cured product subjected to the sandblasting treatment, a dental resin cement (manufactured by Clarenoritake Dental Co., Ltd.) A composition obtained by kneading the trade name "Panavia 21" at a volume ratio of 1: 1) is placed on the resin cement, and sandblasting is performed on the resin cement with an alumina abrasive of 50 microns (manufactured by Morita Co., Ltd.). One end face (circular cross section) of the provided stainless steel columnar rod (diameter 7 mm, length 2.5 cm) was placed, and the stainless steel columnar rod and the above-mentioned cured product were adhered to each other. After adhesion, the sample was allowed to stand at room temperature for 30 minutes. Then, after removing the excess cement composition protruding from the periphery of the stainless steel columnar rod, the sample was immersed in distilled water. The sample immersed in distilled water was allowed to stand in an incubator kept at 37 ° C. for 24 hours to prepare a sample for adhesion test. Adhesion test A total of 5 test samples were prepared.

The tensile adhesive strength of the above 5 adhesive test samples was set to 2 mm / min by a universal testing machine (trade name: Autograph AG-1 / 100 kN, manufactured by Shimadzu Corporation). The average value was taken as the tensile adhesive strength.

[Measurement of penetration into simulated microcracks]
A gap obtained by bringing two 2 mm-thick hydroxyapatite plates (trade name: apatite pellet APP-100, size: 10 mm x 10 mm x 2 mm, manufactured by HOYA Technical Co., Ltd.) into close contact with each other under a load of 20 N. It was confirmed to be 10 μm with a 3D laser microscope (manufactured by KEYENCE CORPORATION), and a simulated microcrack was used. After applying the dental adhesive compositions of each example and comparative example to the simulated microcracks and allowing them to stand for 10 seconds, a light irradiator for dental polymerization (trade name "Pencure 2000", manufactured by Morita Co., Ltd.) Was irradiated for 10 seconds in the normal mode of No. 1 and cured to prepare a measurement sample. Then, the measurement sample was peeled off from the adhesive surface, and the length of penetration of the dental adhesive composition into the hydroxyapatite plate with a 3D laser microscope (manufactured by KEYENCE CORPORATION) was measured as the degree of penetration. Penetrance of 2.0 mm or more was accepted.

[Tensile adhesion test with simulated microcracks]
A gap obtained by bringing two 2 mm-thick hydroxyapatite plates (trade name: apatite pellet APP-100, size: 10 mm x 10 mm x 2 mm, manufactured by HOYA Technical Co., Ltd.) into close contact with each other under a load of 20 N. It was confirmed to be 10 μm with a 3D laser microscope (manufactured by KEYENCE CORPORATION), and a simulated microcrack was used. After applying the dental adhesive compositions of the respective examples and comparative examples to the simulated microcracks and allowing them to stand for 10 seconds, a light irradiator for dental polymerization (commodity) without blowing air on the compositions. The simulated microcracks were irradiated for 10 seconds in the normal mode of the name "Pencure 2000" (manufactured by Morita Co., Ltd.) and cured. Then, it was immersed in distilled water and allowed to stand in an incubator kept at 37 ° C. for 24 hours to prepare an adhesion test test sample. Adhesion test A total of 5 test samples were prepared.

After fixing the above five adhesive test test samples to a tensile test jig with a high-viscosity instant curing model restoration material (trade name "Model Repair-II Blue", manufactured by DENTSPLY-Sankin Co., Ltd.) The tensile adhesive strength was measured with a desktop tester (trade name: EZ tester, manufactured by Shimadzu Corporation) at a cross head speed of 1.0 mm / min, and the average value was taken as the tensile adhesive strength.

As shown in Tables 1 and 2, the dental adhesive composition according to the present invention has a viscosity of 45 cP or less, a contact angle with respect to a hydroxyapatite plate of 45 ° or less, and is measured without blowing air. When the tensile adhesive strength to the hydroxyapatite plate was 15 MPa or more, excellent permeability of 2 mm or more to simulated microcracks and excellent adhesiveness of 100 N or more to simulated microcracks were exhibited. On the other hand, as shown in Table 3, the viscosities of the compositions of Comparative Examples 6, 7, 8 and 10 to 12 exceeded 45 cP, and in Comparative Examples 8 and 10, the contact angle with respect to the hydroxyapatite plate was 45. It exceeded °, had a low permeability of 1.2 mm or less with respect to simulated microcracks, and had a low adhesiveness of 58.2 N or less with respect to simulated microcracks. Further, in the compositions of Comparative Examples 1 to 5 and 9, the tensile adhesive strength to the hydroxyapatite plate was 12.3 MPa or less, and the adhesiveness to the simulated microcracks was 71.2 N or less.

The dental adhesive composition according to the present invention can be used for sealing microcracks.

Claims (7)

3.0 parts by weight based on 100 parts by weight of the total content of the radically polymerizable monomer (a) having no acidic group, the radically polymerizable monomer (b) containing an acidic group, and the radically polymerizable monomer. It contains the following water (c), an organic solvent (d) of 40.0 parts by weight or less with respect to a total content of 100 parts by weight of the radically polymerizable monomer, and a polymerization initiator (e).
Viscosity below 45 cP, and not more than the contact angle of 45 ° with respect to hydroxyapatite plate, and was measured without blowing air, bond strength tensile for hydroxyapatite plate Ri der least 15 MPa, is for microcracks blockade , Dental adhesive composition. Claimed that the radically polymerizable monomer (a) having no acidic group is a (meth) acrylamide-based polymerizable monomer (a1) and / or a (meth) acrylate-based polymerizable monomer (a2). Item 2. The dental adhesive composition according to Item 1. The dental adhesive composition according to claim 2, wherein the (meth) acrylamide-based polymerizable monomer (a1) contains a bifunctional or higher (meth) acrylamide-based polymerizable monomer (a1-1). Stuff. The dental adhesive composition according to claim 2, wherein the (meth) acrylate-based polymerizable monomer (a2) contains a bifunctional or higher (meth) acrylate-based polymerizable monomer (a2-1). Stuff. The invention according to any one of claims 1 to 4, wherein the radically polymerizable monomer (a) having no acidic group contains a low viscosity radically polymerizable monomer (a3) having a viscosity at 25 ° C. of 45 cP or less. Dental adhesive composition. The dental adhesive composition according to any one of claims 1 to 5, wherein the acidic group-containing radical polymerizable monomer (b) is a phosphoric acid group-containing (meth) acrylic monomer (b1). .. Any of claims 1 to 6, wherein the content of the acidic group-containing radically polymerizable monomer (b) is 1 to 50 parts by weight based on 100 parts by weight of the total content of the radically polymerizable monomer. The dental adhesive composition according to.