JP4818591B2 - 1-step dental adhesive composition - Google Patents

Description

The present invention relates to a one-step dental adhesive composition characterized in that the composition comprising a radically polymerizable monomer, a polymerization initiator, and water consists essentially of a heterogeneous solution at room temperature. More specifically, the present invention is a step in which a composition containing a radical polymerizable monomer, a polymerization initiator, and water and to which an organic solvent may be added may be further divided into two and used. It is possible to improve the adhesion to enamel and dentin with an extremely simple tooth surface treatment in a composition region that is essentially a heterogeneous solution at room temperature. The present invention relates to a one-step dental adhesive composition that exhibits excellent photocuring and tooth adhesion even with an irradiator having various wavelength ranges, such as a halogen lamp, LED, and xenon lamp.

In the dental field, a method using a dental adhesive comprising a two-step type self-etching primer and a photopolymerization type bonding agent has attracted attention. This method is widely used in dental clinics as an adhesive system that is gentle to the dental pulp because the dentin is imparted with strong adhesiveness without being treated with a strong acid such as phosphoric acid. The self-etching primer is an acidic aqueous solution having a basic composition, usually pH 1.3 to 3.0, containing a radically polymerizable monomer containing an acidic group and water, and the effectiveness of the adhesiveness has been clarified. Recently, a water-soluble polymerization initiator is added to the self-etching primer, and an adhesion effect of a polymerization initiator that can penetrate into the dentin structure has been proposed.

On the other hand, regarding the water-soluble polymerization initiator, for example, European Patent No. No. 0009348 or JP-A-57-197289 discloses that a water-soluble acyl phosphine oxide compound having improved solubility in water by introducing an ionic group into the acyl phosphine oxide compound is used as a printing ink or unsaturated polyester. A technique effective for photopolymerization of a water-soluble polymerization composition such as a molding material or a recording material is disclosed.

In JP 2000-159621 A, a composition comprising a (meth) acrylate monomer having an acidic group, a water-soluble acylphosphine oxide compound, and water forms a uniform solution at room temperature. The adhesive composition is proposed to improve when the adhesive composition is used as a self-etching primer and used in combination with a one-part photopolymerizable bonding agent. In this system, the primer is one liquid or two liquid, and after the primer treatment, a photopolymerization type bonding agent is applied and photopolymerization is performed. However, it has been found that the adhesion is remarkably low when the uniform aqueous solution is used as a one-step bonding agent.

Recently, the development of a one-component, one-step dental bonding agent that does not require pretreatment such as etching treatment or primer treatment has been progressing. In Japanese Patent No. 3158422, a water-soluble thioxanthone derivative having a quaternary ammonium base, a primer for a uniform aqueous solution of a water-based photocurable adhesive composition containing a hydrophilic group-containing radical polymerizable (meth) acrylate monomer and water. It has been reported that the adhesion to the tooth is improved only by the treatment, but the adhesive strength is insufficient.

On the other hand, JP-A-2003-73218 proposes a one-part dental adhesive composition comprising a polymerizable monomer containing a phosphate group or a carboxylic acid group, water, a photopolymerization initiator, and a viscosity modifier. The bond strength is not enough. In Japanese Patent Application Laid-Open No. 2003-342112, (A) a radical polymerizable monomer having an acidic group in the molecule, (B) a radical polymerizable monomer other than those described above, (C) a photopolymerization initiator, and (D) an aqueous solution. A dental one-component adhesive composition characterized in that it contains a basic organic solvent and is substantially free of water is disclosed. However, sufficient adhesive strength is not obtained with this adhesive composition. These one-part dental adhesive compositions use a hydrophobic polymerization initiator such as conventional D, L-camphorquinone, so that the adhesive effect is insufficient regardless of whether water is contained or not. The fact is.

On the other hand, in the dental clinic, there has been development of a dental resin material that has excellent photocurability in the visible and near-ultraviolet regions and exhibits sufficient photocurability when irradiated with any light from halogen lamps, light-emitting diodes (LEDs), and xenon lamps. It is requested. So far, Japanese Patent Publication No. 54-10986 has so-called α-diketone and N, N-dimethylaminoethyl methacrylate, Japanese Patent Publication No. 60-26002 has so-called α-diketone and N, N-dimethylaminobenzoic acid ethyl ester, etc. A photoinitiator effective for visible light polymerization passing through an exciplex by a photosensitizer and a photoreducing agent as a hydrogen donor is disclosed. However, these photopolymerization initiators have a problem that the photocurability is lowered when an adhesive monomer having an acid group coexists or when the initiator concentration is extremely low.

Further, in JP-A-9-3109, a polymerizable composition comprising a visible light polymerization initiator comprising (A) a coumarin dye, (B) a photoacid generator, and (C) an aryl borate compound. Have been reported to develop high adhesive strength in dentin adhesion. However, photocuring with LEDs and xenon lamps is unclear.

The bonding agents in the techniques disclosed so far are unclear about the adhesion of LEDs, xenon lamps, etc., and no one-step type bonding agents that can be used for various light irradiators used in dental clinics have been provided.

European patent no. 0009348 JP 57-197289 A Japanese Patent No. 3158422 JP 2003-73218 A JP 2003-342112 A Japanese Patent Publication No.54-10986 Japanese Patent Publication No. 60-26002 JP-A-9-3109

Conventionally, an adhesive composition containing a radical polymerizable monomer, a polymerization initiator, and water has been disclosed, but a proposal of an adhesive effect in a composition region in which these components are essentially a heterogeneous solution at room temperature. There was no such one-step dental adhesive composition.
In particular, in an adhesive composition composed of an adhesive monomer having an acidic group, a water-soluble acylphosphine oxide compound and water, the adhesive effect of the self-etching primer which is essentially a homogeneous solution at room temperature is in a two-step adhesive system. Although exhibited, the adhesion as a one-step type bonding agent was insufficient.
Conventionally, in a one-step dental adhesive composition, a composition containing no water has not imparted high tooth adhesion.
Conventionally, in a one-step dental adhesive composition, a composition containing water and a composition made of a uniform solution have not yet provided high tooth adhesion.
Conventionally, a composition containing a radical polymerizable monomer, a polymerization initiator, and water and to which an organic solvent can be added is a one-step adhesive composition that may be further divided into two and used. Thus, there has been no provision of a one-step dental adhesive composition that exhibits excellent adhesion to enamel and dentin in a composition region that is essentially a heterogeneous solution at room temperature.
Furthermore, a one-step dental adhesive composition, characterized in that, conventionally, a composition comprising a radical polymerizable monomer, a polymerization initiator, and water consists essentially of a heterogeneous solution at room temperature, There has been no provision of a one-step dental adhesive composition that can cope with various light irradiators used in dental clinics such as halogen lamps, LEDs, and xenon lamps, and that improves adhesion to the tooth.

The present invention provides a one-step dental adhesive composition characterized in that the composition comprising a radical polymerizable monomer, a polymerization initiator, and water consists essentially of a heterogeneous solution at room temperature. More specifically, the present invention is a step in which a composition containing a radical polymerizable monomer, a polymerization initiator, and water and to which an organic solvent may be added may be further divided into two and used. In the dental adhesive composition of the above, in a composition region that is essentially a heterogeneous solution at room temperature, it exhibits excellent adhesion to enamel and dentin, and at the same time, dental halogen lamp, LED, xenon lamp, etc. The present invention provides a one-step dental adhesive composition that exhibits excellent photocurability and tooth adhesion even with an irradiator in various wavelength ranges.

The present invention is a one-step dental adhesive composition in which the radical polymerizable monomer is a radical polymerizable monomer containing an acidic group and a radical polymerizable monomer not containing an acidic group.
In the present invention, the polymerization initiator is (bis) acylphosphine oxides, α-diketones, coumarin compounds, thioxanthone derivatives, and the water-soluble polymerization initiator is a metal salt and / or a quaternary ammonium salt of the polymerization initiator. A one-step dental adhesive composition characterized in that it is a metal salt and quaternary ammonium salt of acylphosphine oxides, a metal salt of sulfinic acids, and a quaternary ammonium salt of thioxanthones. .
The present invention is a one-step dental adhesive composition characterized in that the polymerization accelerator is a barbituric acid derivative and a metal salt thereof, an amine, and a tin compound.
In the present invention, the curable composition is excellent in photocurability in the visible and near-ultraviolet region, and is photopolymerized that can exhibit sufficient photocurability when irradiated with any light from a halogen lamp, a light emitting diode (LED), or a xenon lamp. It is a one-step dental adhesive composition in which (bis) acylphosphine oxides and salts thereof, α-diketones, and coumarin compounds may be used in combination as an initiator.
The present invention is a one-step dental adhesive composition to which an organic solvent, an organic or inorganic filler, and a polymerization inhibitor may be appropriately added.
The present invention is a one-step dental adhesive composition to which an acid-reactive filler and / or an electrolyte polymer and an electrolyte polymer aqueous solution may be added as appropriate.

In the present invention, the radical polymerizable monomer containing an acidic group is 4- (meth) acryloxyethyl trimellitic acid, 4- (meth) acryloxyethyl trimellitic anhydride, 6- (meth) acryloxy. It is a one-step dental adhesive composition such as hexylphosphonoacetate, 6- (meth) acryloxyhexylphosphonopropionate, 10- (meth) acryloxydecyl hydrogen phosphate, and the like.

In the present invention, the radical polymerizable monomer containing no acidic group is selected from ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 2-hydroxyethyl methacrylate, 2,3-dihydroxypropyl methacrylate, 2- Hydroxypropyl-1,3-di (meth) acrylate (= glycerol di (meth) acrylate, 2,2-methylhydroxypropyl (meth) acrylate, hexamethylene glycol di (meth) acrylate, 2,2-bis {4- (Meth) acryloxypropoxyphenyl} propane; bisphenol A-diglycidyl (meth) acrylate, di (meth) acryloxyethyl-2,2,4-trimethylhexamethylenediurethane, 6- (meth) acryloyloxyhexyl 6,8 -Dithio Taneto, 10- (meth) acryloyloxydecyl 6,8 Jichiokutaneto, a dental adhesive composition of one step, and the like.

The present invention provides a one-step dental method in which (bis) acylphosphine oxides are 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) acylphosphine oxide, and the like. Adhesive composition for use.

The present invention is a one-step dental adhesive composition in which the polymerization initiator for α-diketones is D, L-camphorquinone, and the like.

The present invention is a one-step dental adhesive composition in which the coumarin compounds are 3,3′-carbonylbis (7-diethylaminocoumarin) and 3,3′-carbonylbis (7-dibutylaminocoumarin). .

The present invention is a one-step dental adhesive composition in which the thioxanthone derivative is 2-chlorothioxanthen-9-one, and the like.

In the present invention, the water-soluble polymerization initiator is a salt of aromatic sulfinic acid such as sodium 2,4,6-trimethylbenzoylphenylphosphine oxide / sodium benzenesulfinate and sodium p-toluenesulfinate, 2-hydroxy-3 A one-step dental adhesive composition that is-(3,4-dimethyl-9H-thioxanthen-2-yloxy) -N, N, N-trimethyl-1-propanaminium chloride.

The present invention provides a polymerization accelerator comprising 5-butyl barbituric acid, 1,3,5-trimethylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, and 1-benzyl-5-phenylbarbituric acid and Sodium salts of these barbituric acids, amines such as N, N-di (2-hydroxyethyl) -p-toluidine, 4-N, N-dimethylaminobenzoic acid ethyl ester, and di-n-octyltin dilaurate and A one-step dental adhesive composition that is a tin compound such as di-n-butyltin dilaurate.

In the present invention, an organic solvent, a filler and a polymerization inhibitor are preferably added as appropriate. The solvent is acetone, ethanol or isopropyl alcohol, the filler is a polymer, an inorganic filler or an organic composite filler, and the polymerization inhibitor is hydroquinone monomethyl. A one-step dental adhesive composition such as ether, butylated hydroxytoluene and the like.

The present invention is a one-step dental adhesive composition in which an acid-reactive filler may be added as appropriate, and the acid-reactive filler is fluoroaluminosilicate glass.
The present invention provides a one-step process wherein the electrolyte polymer and the electrolyte polymer aqueous solution are homopolymers and copolymers of unsaturated mono-, di-, and tricarboxylic acids, particularly those having a carboxyl group in the side chain, and aqueous solutions thereof. It is a dental adhesive composition.

In order to solve the problems of the prior art, the present inventors have intensively searched for a one-step dental adhesive composition that exhibits excellent tooth adhesion, and as a result, radical polymerizable monomers, polymerization initiators, And a conventionally known adhesive composition consisting essentially of a “homogeneous solution” at room temperature containing water and water has an adhesive effect as a two-step self-etching primer, but when used with a one-step adhesive, it adheres to teeth The result was low. However, as a composition region composed of the above-described constituents and conventionally excluded from the range, an adhesive composition consisting essentially of a “heterogeneous solution” at room temperature was studied in one step, and it was surprising. In particular, they have found that they exhibit excellent adhesion to enamel and dentin, and have reached the present invention.

That is, the present inventors provide a one-step dental adhesive composition that includes a radical polymerizable monomer, a polymerization initiator, and water, and may be added in an organic solvent or may be used in two parts. It has been found that a composition region that is essentially a “heterogeneous solution” at room temperature exhibits high adhesion strength to enamel and dentin with a simple tooth surface treatment. Furthermore, the present inventors are excellent even when various irradiators such as dental halogen lamps, LEDs, and xenon lamps are used together with a specific photopolymerization initiator in the dental adhesive. The present invention was completed by finding that the adhesiveness to the tooth was imparted.

The novel one-step dental adhesive composition of the present invention is characterized in that the composition comprising a radical polymerizable monomer, a polymerization initiator, and water consists essentially of a heterogeneous solution at room temperature. In a one-step dental adhesive composition that may be added into an organic solvent or may be used in two parts, it is a composition region that is essentially a heterogeneous solution at room temperature, and in one step on enamel and dentin. By applying and photopolymerizing, it exhibits excellent adhesion to the tooth structure with a very simple tooth surface treatment, and at the same time, irradiators of various wavelength ranges such as dental halogen lamps, LEDs and xenon lamps were used. Even in this case, it became clear that excellent tooth adhesion was imparted.

The best mode for carrying out the present invention is a one-step photopolymerizable dental adhesive, an adhesive resin cement, a resin modified glass ionomer cement, and the like. In particular, in the embodiment as a one-step photopolymerizable dental adhesive, even when using an irradiator having various wavelength ranges such as a dental halogen lamp, an LED, and a xenon lamp, the tooth surface treatment is extremely simple. A one-step dental adhesive composition characterized by exhibiting adhesiveness to teeth.

The dental adhesive composition of the present invention includes a dental bonding agent, an (adhesive) composite resin, a fisher sealant, an orthodontic adhesive, a teeth coating agent, a dual cure resin cement, a resin cement, as an embodiment thereof. It can be used for resin-modified glass ionomer cement, opaque agent, compomer, resin core, crowning material.
Further, since the operability is simple and the adhesive performance is high, it can be used not only in the dental field but also in the fields of plastic surgery, general industrial fields such as paints, lacquers, adhesives, and semiconductor substrate materials.

The radical polymerizable monomer of the dental adhesive composition of the present invention is selected from monomers, oligomers, prepolymers and the like having a radical polymerizable unsaturated double bond used in the dental field and general industry. Can be used. Furthermore, a radical polymerizable monomer containing an acidic group in the molecule of the radical polymerizable monomer, a radical polymerizable monomer not containing an acidic group, a polymerizable monomer having a sulfur atom in the molecule, a fluoroalkyl A polymerizable monomer having a group in the molecule, a polymerizable monomer having a fluorine ion releasing ability, and the like can be selected and used. As an abbreviation in the present invention, for example, methyl (meth) acrylate means methyl methacrylate and methyl acrylate.

As the radical polymerizable monomer containing an acidic group of the dental adhesive composition of the present invention, all monomers conventionally used as dental adhesive monomers can be used, and in particular, a carboxyl group and phosphoric acid in the molecule. A radical polymerizable monomer having an ester group, a phosphonic acid group, a pyrophosphoric acid group, a sulfonic acid group or the like can be selected and used.

Among the radical polymerizable monomers containing an acidic group of the present invention, examples of the monomer containing a carboxyl group in the molecule include methacrylic acid, 4- (meth) acryloxyethyl trimellitic acid, 4- (Meth) acryloyloxyethoxycarbonylphthalic acid, 4- (meth) acryloyloxybutyloxycarbonylphthalic acid, 4- (meth) acryloyloxyhexyloxycarbonylphthalic acid, 4- (meth) acryloyloxyoctyloxycarbonylphthalic acid, 4 -(Meth) acryloyloxydecyloxycarbonylphthalic acid, maleic acid, and acid anhydrides thereof, 5- (meth) acryloylaminopentylcarboxylic acid, 6- (meth) acryloyloxy-1,1-hexanedicarboxylic acid, 7 -(Meth) acryloyloxy-1,1 Heptanedicarboxylic acid, 8- (meth) acryloyloxy-1,1-octanedicarboxylic acid, 10- (meth) acryloyloxy-1,1-decanedicarboxylic acid, 11- (meth) acryloyloxy-1,1-undecanedicarboxylic acid Acids and the like can be mentioned, and furthermore, acid chlorides, alkali metal salts, alkaline earth metal salts, ammonium salts and the like of these can also be mentioned.

Among the radical polymerizable monomers containing an acidic group of the present invention, examples of the monomer containing a phosphate group, phosphonic acid group, or pyrophosphoric acid group in the molecule include 3- (meth) Acryloxypropyl-3-phosphonopropionate, 3- (meth) acryloxypropyl-3-phosphonoacetate, 4- (meth) acryloxybutyl-3-phosphonopropionate, 4- (meth) acrylate Loxybutylphosphonoacetate, 5- (meth) acryloxypentylphos-3-phonopropionate, 5- (meth) acryloxypentyl-3-phosphonoacetate, 6- (meth) acryloxyhexyl-3-phospho Nopropionate, 6- (meth) acryloxyhexyl-3-phosphonoacetate, 10- (meth) acryloxydecyl-3-phosphine Nopropionate, 10- (meth) acryloxydecyl-3-phosphonoacetate, bis [2- (meth) acryloxyethyl] phosphate, 2- (meth) acryloyloxyethyl dihydrogen phosphate, 3- (meth) acryloyl Oxypropyl dihydrogen phosphate, 4- (meth) acryloyloxybutyl dihydrogen phosphate, 5- (meth) acryloyloxypentyl dihydrogen phosphate, 6- (meth) acryloyloxyhexyl dihydrogen phosphate, 7- (meta ) Acryloyloxyheptyl dihydrogen phosphate, 8- (meth) acryloyloxyoctyl dihydrogen phosphate, 9- (meth) acryloyloxynonyl dihydrogen phosphate 10- (meth) acryloyloxydecyl dihydrogen phosphate, 11- (meth) acryloyloxyundecyl dihydrogen phosphate, 12- (meth) acryloyl oxide decyl dihydrogen phosphate, 16- (meth) acryloyloxyhexadecyl Dihydrogen phosphate, 20- (meth) acryloyloxyeicosyl dihydrogen phosphate, di [2- (meth) acryloyloxyethyl] hydrogen phosphate, di [4- (meth) acryloyloxybutyl] hydrogen phosphate, di [6- (Meth) acryloyloxyhexyl] hydrogen phosphate, di [8- (meth) acryloyloxyoctyl] hydrogen phosphate, di [9- (meth) acrylo Yloxynonyl] hydrogen phosphate, di [10- (meth) acryloyloxydecyl] hydrogen phosphate, 1,3-di (meth) acryloyloxypropyl-2-dihydrogen phosphate, 2- (meth) acryloyloxyethyl Phenyl hydrogen phosphate, 2- (meth) acryloyloxyethyl 2-bromoethyl hydrogen phosphate, 2- (meth) acryloyloxyethyl phenylphosphonate, 10- (meth) acryloyloxydecylphosphonic acid, vinylphosphonic acid, p- Vinyl benzyl phosphonic acid, 2-methacryloyloxyethyl (4-methoxyphenyl) hydrogen phosphate, 2-methacrylo described in JP-A-62-281885 Ruoxypropyl (4-methoxyphenyl) hydrogen phosphate, di [2- (meth) acryloyloxyethyl pyrophosphate], di [4- (meth) acryloyloxybutyl] pyrophosphate, di [6- (meth) pyrophosphate Examples thereof include polymerizable monomers such as acryloyloxyhexyl], di [8- (meth) acryloyloxyoctyl] pyrophosphate, and di [10- (meth) acryloyloxydecyl] pyrophosphate. Also included are chlorides, alkali metal salts, alkaline earth metal salts and ammonium salts.

Among the radical polymerizable monomers containing an acidic group of the present invention, examples of the monomer containing a sulfonic acid group in the molecule include styrene sulfonic acid, 2-sulfoethyl (meth) acrylate, and 6-sulfohexyl. (Meth) acrylate, 10-sulfodecyl (meth) acrylate, 2- (meth) acrylamido-2-methylpropanesulfonic acid, and the like, and further, acid chlorides, alkali metal salts, and alkaline earth metal salts thereof. And ammonium salts.

Examples of the radical polymerizable monomer containing no acidic group of the present invention include (meth) acrylic acid ester derivatives, alkylene glycol di (meth) acrylates, alkyl di (meth) acrylates, epoxy di (meth) acrylates, bisphenol A -Alkyl di (meth) acrylates, urethane di (meth) acrylates, urethane tri (meth) acrylates, urethane tetra (meth) acrylates, hydroxyalkyl (meth) acrylates, (meth) acrylates having Si groups and Ti groups And styrene derivatives. Specifically, a monomer having one olefinic double bond is a monofunctional monomer, and a bifunctional crosslinkable monomer or trifunctional crosslinkable according to the number of olefinic double bonds. Expressed as a monomer.

Monofunctional monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, benzyl (meth) acrylate , Lauryl (meth) acrylate, 2,3-dibromopropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl ( (Meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 1,3-dihydroxypropyl (meth) acrylate, 2 3-dihydroxypropyl (meth) acrylate, 2,2-methylhydroxypropyl (meth) acrylate, (meth) acrylamide, 2-hydroxyethyl (meth) acrylamide, 1,2-dihydroxypropyl (meth) acrylate, styrene, 3- (Meth) acryloyloxypropylpentamethyldisiloxane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 6- (meth) acryloyloxyhexyltrimethoxysilane, 6- ( (Meth) acryloyloxyhexyltriethoxysilane, 10- (meth) acryloyloxydecyltrimethoxysilane, 10- (meth) acryloyloxydecyltriethoxysilane, 11- (meth) acryloyl Oxy undecyl trimethoxysilane, 11- (meth) acryloyloxy undecyl triethoxysilane and the like.

As bifunctional crosslinkable monomers, 2-hydroxypropyl-1,3-di (meth) acrylate (= glycerol di (meth) acrylate), 2,2-bis {4- (meth) acryloxypropoxyphenyl} Propane; bisphenol A diglycidyl (meth) acrylate; Bis-GMA, [2,2,4-trimethylhexamethylenebis (2-carbamoyloxyethyl)] di (meth) acrylate; UDMA, ethylene glycol di (meth) acrylate, tri Ethylene glycol di (meth) acrylate, dipentaerythritol di (meth) acrylate, polyethylene glycol di (meth) acrylate (number of oxyethylene groups 9, 14, and 23), propylene glycol di (meth) acrylate, neopentyl glycol Di (Meta Acrylate, 1,6-hexanediol di (meth) acrylate, 1,6-hexanedi (meth) acrylate, 1,10-decanediol di (meth) acrylate, 2,2-bis [4- (meth) acryloyloxypoly Ethoxyphenyl] propane, 2,2-bis [4- (meth) acryloyloxyethoxyphenyl] propane, 2,2-bis [4- [3- (meth) acryloyloxy-2-hydroxypropoxy] phenyl] propane, penta Erythritol di (meth) acrylate, 1,2-bis [3- (meth) acryloyloxy-2-hydroxypropoxy] ethane, 1,2-bis (3-methacryloyloxy-2-hydroxypropoxy) ethane, 1,3- Di (meth) acryloyloxy-2-hydroxypropane, di (meth) Acryloxy isophorone diurethane, di (meth) acryloxyethyl-2,2,4-trimethylhexamethylene diurethane, glycerol di (meth) acrylate, isopropyl dimethacryloyl Louis isostearoyl titanate, and the like.

Examples of the trifunctional or more crosslinkable monomers include pentaerythritol tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, 1,7 -Diacryloyloxy-2,2,6,6-tetraacryloyloxymethyl-4-oxyheptane N, N '-(2,2,4-trimethylhexamethylene) bis [2- (aminocarboxy) propane-1,3 -Diol] tetramethacrylate, and the like. Particularly suitable monomers are ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate hexamethylene glycol di (meth) acrylate, 1,6-hexanedi (meth) acrylate, 2,2-bis {4- ( (Meth) acryloxypropoxyphenyl} propane = bisphenol A-diglycidyl (meth) acrylate, di (meth) acryloxyethyl-2,2,4 □ trimethylhexamethylene diurethane, di (meth) acryloxyisophorone diurethane, 2 -Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycerol di (meth) acrylate, γ- (meth) acryloxypropyltrimethoxysilane and the like.

In order to improve the adhesion of the composition of the present invention to a noble metal, a radical polymerizable monomer having a sulfur atom in the molecule may be used. Examples of the radical polymerizable monomer include mercapto group, disulfide group, polysulfide group, cyclic disulfide group, hydropolysulfide group, sulfide group, thioketone group, thioaldehyde group, thioacetal group, thiocarboxylic acid group, and thiocarboxylic acid anhydride. Group, thiocarboxylic acid ester group, thiophene carboxylic acid group, thiouracil group, triazine dithione group, mercaptothiadiazole group, triazine monothione group, thiirane group, thiophosphoric acid group, thiophosphoric acid ester group, thiopyrophosphoric acid group, thiopyrophosphoric acid ester group, thiophosphorus A polymerizable monomer having one or more acid halide groups can be used. In addition, alkali metal salts, alkaline earth metal salts, ammonium salts and the like of these sulfur group-containing polymerizable monomers are also preferably used. Specifically, 2- (meth) acryloyloxyethyl 6,8-dithiooctanoate, 6- (meth) acryloyloxyhexyl 6,8-dithiooctanoate, and 10- (as esterification reaction products of thioctic acid and hydroxyalkyl (meth) acrylate (Meth) acryloyloxydecyl 6,8-dithiooctanate, compounds described in JP-A-2003-105272

Chemical 3

~

17

Etc. Compounds are listed at the end.

The radical polymerizable monomer having a fluoroalkyl group composed of at least one fluorocarbon of the present invention contains one or more polymerizable groups such as a methacryloyl group, an acryloyl group, a vinyl group or a vinylbenzyl group (meta ) Acrylate compounds can be used, for example, compounds 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) described in JP-A-2003-095838 ) Acrylate, 2- (perfluoroptyl) ethyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 2- (perfluorooctyl) ethyl (meth) acrylate, etc. Also described in JP-A-2003-105272 Compound

18

and

19

Etc.

Examples of the radical polymerizable monomer having fluorine ion releasing ability of the present invention include cyclic phosphazene compounds described in JP-A-2003-342112. Specifically, a 6-membered ring compound of P ₃ N ₃ (F) n [O (CH ₂ ) ₂ OOC (CH ₃ ) C═CH ₂ ] _6-n (n is an integer of 1 to 5) Or an 8-membered ring compound of P ₄ N ₄ (F) m [O (CH ₂ ) ₂ OOC (CH ₃ ) C═CH ₂ ] _8-m (where m is an integer from 1 to 7), and the like. It is done.

These radically polymerizable monomers are used alone or in appropriate combination. Among them, 4- (meth) acryloxyethyl trimellitic acid, 4- (meth) acryloxyethyl trimellitic anhydride, 6- Radical polymerization having acidic groups such as (meth) acryloxyhexyl-3-phosphonoacetate, 6- (meth) acryloxyhexyl-3-phosphonopropionate, 10- (meth) acryloxydecylhydrogenphosphate Monomer and triethylene glycol di (meth) acrylate, 2-hydroxyethyl methacrylate, 2,3-dihydroxypropyl methacrylate, glycerol dimethacrylate, hexamethylene glycol di (meth) acrylate, 2,2-bis {4- ( (Meth) acryloxypropoxyphenyl} Lopan: Bisphenol A-diglycidyl (meth) acrylate, di (meth) acryloxyethyl-2,2,4-trimethylhexamethylene diurethane, 6- (meth) acryloyloxyhexyl 6,8-dithiooctanoate, 10- (meth) A combination with a radical polymerizable monomer that does not contain an acidic group such as acryloyloxydecyl 6,8-dithiooctanate is preferred.

These radical polymerizable monomers may be used alone or in combination of two or more compounds. The amount of these radically polymerizable monomers is 1% to 99.8% by weight, preferably 10% to 95%, based on the total amount of the curable composition of the present invention other than the organic solvent. % By weight, particularly preferably 15% by weight to 70% by weight.

In the dental adhesive composition of the present invention, the polymerization initiator can be selected from polymerization initiators used in the dental field and general industry. In particular, polymerization initiators for photopolymerization and chemical polymerization are used alone or in combination of two or more.

Among the polymerization initiators used in the present invention, examples of the photopolymerization initiator include (bis) acylphosphine oxides, water-soluble acylphosphine oxides, thioxanthones or quaternary ammonium salts of thioxanthones, ketals, and α-diketones. , Coumarins, anthraquinones, benzoin alkyl ether compounds, α-aminoketone compounds and the like.

Examples of (bis) acylphosphine oxides contained in the photopolymerization initiator of the present invention include (bis) acylphosphine oxides and water-soluble acylphosphine oxides. Acylphosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenyl Examples include phosphine oxide, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, and benzoyldi- (2,6-dimethylphenyl) phosphonate. Examples of bisacylphosphine oxides include bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine 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) phenyl phosphite Oxide, and (2,5,6-trimethylbenzoyl) -2,4,4-trimethylpentyl phosphine oxide.

（ここで、ＲａはＲ２基または−ＯＲ２基であり、Ｅは酸素原子またはイオウ原子であり、Ｒｍは−Ｏ⁻Ｍ^＋または−ＮＲｙＲｚであり、Ｍ^＋は水素イオン、アルカリ金属イオン、アルカリ土類金属イオンの等量、ピリジニウムイオン（芳香環が有機基で置換されていても良い）、または、ＨＮ＋Ｒ３Ｒ４Ｒ５（式中、Ｒ３、Ｒ４、Ｒ５は同一または異なる有機基または水素原子）で示されるアンモニウムイオンで示されるなど医療的に受容できるカチオンであり、Ｒ１およびＲ２は同じか異なっていても良く、それぞれ水素原子、アルキル、アルケニル、アルキニルまたはアリール；１つまたは２以上のハロゲン、アルコキシ、ニトロ、アルキル、−ＣＦ３，ニトリルまたはカルボン酸または塩、エステルまたはアミドによって置換されたアルキル、アルケニル、アルキニルまたはアリールのそれぞれ全てであり、およびＲｙおよびＲｚは、同じか異なっていても良く、それぞれ水素原子、アルキルまたは医療的に受容できる誘導体のそれぞれ全てである。）Water-soluble acyl phosphine oxides contained in the photopolymerization initiator of the present invention are those having an alkali metal ion, an alkaline earth metal ion, a pyridinium ion or an ammonium ion in the acyl phosphine oxide molecule, for example, Water-soluble acylphosphine oxides represented by the general formula [1] are disclosed in European Patent No. It can be synthesized by the method disclosed in Japanese Patent No. 0009348 or JP-A-57-197286.

(Where Ra is an R 2 group or —OR 2 group, E is an oxygen atom or a sulfur atom, R m is —O ⁻ M ⁺ or —NRyRz, and M ⁺ is a hydrogen ion, an alkali metal ion, an alkaline earth, Ammonium represented by an equivalent amount of metal ion, pyridinium ion (the aromatic ring may be substituted with an organic group), or HN + R3R4R5 (wherein R3, R4 and R5 are the same or different organic groups or hydrogen atoms) A medically acceptable cation such as represented by an ion, wherein R 1 and R 2 may be the same or different and each is a hydrogen atom, alkyl, alkenyl, alkynyl or aryl; one or more halogen, alkoxy, nitro, Substituted by alkyl, -CF3, nitrile or carboxylic acid or salt, ester or amide And all of alkyl, alkenyl, alkynyl or aryl, and Ry and Rz may be the same or different, and are each a hydrogen atom, alkyl or a medically acceptable derivative, respectively.)

Such water-soluble acyl phosphine oxides include monomethyl acetyl phosphonate sodium, monomethyl (1-oxopropyl) phosphonate sodium, monomethyl benzoyl phosphonate sodium, monomethyl (1-oxobutyl) phosphonate. Sodium, monomethyl (2-methyl-1-oxopropyl) phosphonate Sodium, acetyl phosphonate Sodium, monomethyl acetyl phosphonate sodium, acetyl methyl phosphonate sodium, methyl 4- (hydroxymethoxyphos Finyl) -4-oxobutanoate sodium salt, methyl 4-oxo-phosphonobutanoate mononatrium salt, acetyl phenylphosphinate sodium Salt, (1-oxopropyl) pentylphosphinate sodium, methyl 4- (hydroxypentylphosphinyl) -4-oxobutanoate sodium salt, acetylpentylphosphinate sodium, acetylethylphosphinate Sodium, methyl (1,1-dimethyl) methyl phosphinate / sodium, (1,1-diethoxyethyl) methyl phosphinate / sodium, (1,1-dioxyethyl) methyl phosphinate / sodium, methyl 4- (hydroxy Methylphosphinyl) -4-oxobutanoate lithium salt, 4- (hydroxymethylphosphinyl) -4-oxobutanoic acid dilithium salt, methyl (2-methyl-1,3-dioxolane-2) -Il) Phosphinate Thorium salt, methyl (2-methyl-1,3-thiazolidin-2-yl) phosphonite sodium salt, (2-methylperhydro-1,3-diazin-2-yl) phosphonite sodium salt, Acetyl phosphinate sodium salt, (1,1-diethoxyethyl) phosphonite sodium salt, (1,1-diethoxyethyl) methyl phosphonite sodium salt, methyl (2-methyloxathiolane- 2-yl) phosphinate sodium salt, methyl (2,4,5-trimethyl-1,3-dioxolan-2-yl) phosphinate sodium salt, methyl (1,1-propoxyethyl) phosphinate Sodium salt, (1-methoxyvinyl) methyl phosphinate Sodium salt, (1-ethylthiobi Nyl) methyl phosphinate sodium salt, methyl (2-methylperhydro-1,3-diazin-2-yl) phosphinate sodium salt, methyl (2-methylperhydro-1,3-thiazine-2) -Yl) phosphinate sodium salt, methyl (2-methyl-1,3-diazolidin-2-yl) phosphinate sodium salt, methyl (2-methyl-1,3-thiazolidin-2-yl) phos Finate sodium salt, (2,2-dicyano-1-methylethynyl) phosphinate sodium salt, acetyl methyl phosphinate oxime natriu salt, acetyl methyl phosphinate O-benzyl oxime sodium salt, 1 -[(N-ethoxyimino) ethyl] methyl phosphinate sodium salt, methyl ( -Phenyliminoethyl) phosphinate sodium salt, methyl (1-phenyl hydrazone ethyl) phosphinate sodium salt, [-(2,4-dinitrophenyl hydrazono) ethyl] methyl phosphinate sodium salt , Acetyl methyl phosphinate semicarbazone sodium salt, (1-cyano-1-hydroxyethyl) methyl phosphinate sodium salt, (dimethoxymethyl) methyl phosphinate sodium salt, formyl methyl phosphinate Sodium salt, (1,1-dimethoxypropyl) methyl phosphinate sodium salt, methyl (1-oxopropyl) phosphinate sodium salt, (1,1-dimethoxypropyl) methyl phosphinate dodecylguanidine salt, ( , 1-dimethoxypropyl) methyl phosphinate isopropylamine salt, acetyl methyl phosphinate thiosemicarbazone sodium salt, 1,3,5-tributyl-4-methylamino-1,2,4-triazolium (1 , 1-dimethoxyethyl) -methyl phosphinate, 1-butyl-4-butylaminomethylamino-3,5-dipropyl-1,2,4-triazolium (1,1-dimethoxyethyl) -methyl phosphinate, 2,4,6-trimethylbenzoylphenylphosphine oxide sodium salt, 2,4,6-trimethylbenzoylphenylphosphine oxide potassium salt, 2,4,6-trimethylbenzoylphenylphosphine oxide ammonium salt, and the like. Further, compounds described in JP 2000-159621 A

20

Also mentioned.

These (bis) acylphosphine oxides and water-soluble acylphosphine oxides are 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, bis (2, 4,6-trimethylbenzoyl) acylphosphine oxide and 2,4,6-trimethylbenzoylphenylphosphine oxide sodium salt are particularly preferred.

The blending amount of these (bis) acylphosphine oxides and water-soluble acylphosphine oxides is 0.001% by weight to 15% by weight with respect to the total amount other than the organic solvent of the dental adhesive composition of the present invention. %, Preferably 0.01% to 10% by weight, particularly preferably 0.1% to 5% by weight.

Examples of thioxanthones or quaternary ammonium salts of thioxanthones contained in the photopolymerization initiator of the present invention include thioxanthone, 2-chlorothioxanthen-9-one, 2-hydroxy-3- (9-oxy- 9H-thioxanthen-4-yloxy) -N, N, N-trimethyl-propanaminium chloride, 2-hydroxy-3- (1-methyl-9-oxy-9H-thioxanthen-4-yloxy) -N, N, N-trimethyl-propanaminium chloride, 2-hydroxy-3- (9-oxo-9H-thioxanthen-2-yloxy) -N, N, N-trimethyl-propanaminium chloride, 2-hydroxy-3 -(3,4-Dimethyl-9-oxo-9H-thioxanthen-2-yloxy) -N, N, N-trime Ru-1-propaneaminium 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 can be used.

A particularly preferred thioxanthone is 2-chlorothioxanthen-9-one, and the quaternary ammonium salt of thioxanthone is 2-hydroxy-3- (3,4-dimethyl-9H-thioxanthen-2- Iloxy) -N, N, N-trimethyl-1-propanaminium chloride.

Examples of ketals contained in the photopolymerization initiator of the present invention include benzyl dimethyl ketal and benzyl diethyl ketal.

Examples of the α-diketone contained in the photopolymerization initiator of the present invention include diacetyl, dibenzyl, D, L-camphorquinone, 2,3-pentadione, 2,3-octadione, and 9,10-phenanthrenequinone. 4,4′-oxybenzyl, acenaphthenequinone and the like.

The dental adhesive composition of the present invention is excellent in photocurability in the visible and near-ultraviolet region, and exhibits sufficient photocurability even with dental light irradiation of any of halogen lamps, light emitting diodes (LEDs), and xenon lamps. (Bis) acylphosphine oxides and salts thereof, α-diketones, and coumarin compounds can be used in combination as photopolymerization initiators that can be used as agent compositions.

Examples of the coumarin compound contained in the photopolymerization initiator of the present invention include 3,3′-carbonylbis (7-diethylamino) coumarin, 3- (4-methoxybenzoyl) coumarin, 3-chenoylcoumarin, and 3-benzoyl. -5,7-dimethoxycoumarin, 3-benzoyl-7-methoxycoumarin, 3-benzoyl-6-methoxycoumarin, 3-benzoyl-8-methoxycoumarin, 3-benzoylcoumarin, 7-methoxy-3- (p-nitro Benzoyl) coumarin, 3- (p-nitrobenzoyl) coumarin, 3-benzoyl-8-methoxycoumarin, 3,5-carbonylbis (7-methoxycoumarin), 3-benzoyl-6-bromocoumarin, 3,3′- Carbonyl biscoumarin, 3-benzoyl-7-dimethylaminomarin, 3-benzoylben [F] Coumarin, 3-carboxycoumarin, 3-carboxy-7-methoxycoumarin, 3-ethoxycarbonyl-6-methoxycoumarin, 3-ethoxycarbonyl-8-methoxycoumarin, 3-acetylbenzo [f] coumarin, 7- Methoxy-3- (p-nitrobenzoyl) coumarin, 3- (p-nitrobenzoyl) coumarin, 3-benzoyl-8-methoxycoumarin, 3-benzoyl-6-nitrocoumarin, 3-benzoyl-7-diethylaminomarine, 7 -Dimethylamino-3- (4-iobenzoyl) coumarin, 7-diethylamino-3- (4-iobenzoyl) coumarin, 7-diethylamino-3- (4-diethylamino) coumarin, 7-methoxy-3- (4- Methoxybenzoyl) coumarin, 3- (4-nitrobenzoyl) ben [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′-carbonylbis (7-dimethylaminocoumarin), 3- (2-benzothiazoyl) -7- (diethylamino) coumarin, 3- (2 -Benzothiazoyl) -7- (dibutylamino) coumarin, 3- (2-benzimidazolyl) -7- (diethylamino) bear Phosphorus, 3- (2-benzothiazoyl) -7- (dioctylamino) coumarin, 3-cabetoxy-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 -1,1,7,7-tetramethyl 1H, 5H, 11H- [1] benzopyrano [6,7,8-ij] quinolizin-11-one, 10- (2-benzothiazoyl) -2,3 JP-A-9-3109 such as 6,7-tetrahydro-1,1,7,7-tetramethyl 1H, 5H, 11H- [1] benzopyrano [6,7,8-ij] quinolidin-11-one , Compounds described in JP-A-10-245525 can be cited.

As the coumarin compound contained in the dental adhesive composition of the present invention, 3,3′-carbonylbis (7-diethylaminocoumarin) and 3,3′-carbonylbis (7-dibutylaminocoumarin) are particularly suitable. .

Examples of anthraquinones contained in the photopolymerization initiator of the present invention include anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 1-bromoanthraquinone, 1,2-benzanthraquinone, 1-methylanthraquinone, 2-ethylanthraquinone. 1-hydroxyanthraquinone and the like.

Examples of benzoin alkyl ethers contained in the photopolymerization initiator of the present invention include benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

Examples of α-aminoketones contained in the photopolymerization initiator of the present invention include 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one.

Among the polymerization initiators used in the present invention, examples of the chemical polymerization initiator include organic peroxides, sulfinic acid (salts), and borate compounds.

Examples of the organic peroxide contained in the chemical polymerization initiator of the present invention include diacyl peroxides, peroxyesters, dialkyl peroxides, peroxyketals, ketone peroxides, hydroperoxides and the like. can give. Specific examples of diacyl peroxides include benzoyl peroxide, m-toluoyl peroxide, and 2,4-dichlorobenzoyl peroxide. Examples of peroxyesters include t-butyl peroxybenzoate, bis-t-butylperoxyisophthalate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxy- Examples include 2-ethylhexanoate, t-butyl peroxymaleic acid, t-butyl peroxyisopropyl carbonate, and the like. Examples of the dialkyl peroxides include dicumyl peroxide, di-t-butyl peroxide, lauroyl peroxide, and the like. Examples of peroxyketals include 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane and the like. Examples of ketone peroxides include cyclohexanone peroxide, methyl ethyl ketone peroxide, and methyl acetoacetate peroxide. Examples of hydroperoxides include t-butyl hydroperoxide, p-diinpropylbenzene peroxide, cumene hydroperoxide, and the like.

Examples of the sulfinic acid or salt thereof contained in the dental adhesive composition of the present invention include p-position toluene sulfinic acid, sodium toluene sulfinate, potassium toluene sulfinate, lithium toluene sulfinate, calcium toluene sulfinate, and benzene. Sulfinic acid, sodium benzenesulfinate, potassium benzenesulfinate, lithium benzenesulfinate, calcium benzenesulfinate, 2,4,6-trimethylbenzenesulfinate, sodium 2,4,6-trimethylbenzenesulfate, 2,4, Potassium 6-trimethylbenzenesulfinate, lithium 2,4,6-trimethylbenzenesulfinate, calcium 2,4,6-trimethylbenzenesulfinate, 2,4,6-triethylbenzenesulfate Acid, sodium 2,4,6-triethylbenzenesulfinate, potassium 2,4,6-triethylbenzenesulfinate, lithium 2,4,6-triethylbenzenesulfinate, calcium 2,4,6-triethylbenzenesulfinate 2,4,6-isopropylbenzenesulfinic acid, sodium 2,4,6-isopropylbenzenesulfinate, potassium 2,4,6-isopropylbenzenesulfinate, lithium 2,4,6-isopropylbenzenesulfinate, 2, Examples include calcium 4,6-isopropylbenzenesulfinate, and sodium benzenesulfinate and sodium p-toluenesulfinate are particularly preferable.

Specific examples of the boron borate compound preferably used as the boron compound contained in the dental adhesive composition of the present invention include, for example, compounds described in JP-A No. 2003-342112, As borate compounds having one aryl group in one molecule, trialkylphenyl boron, trialkyl (p-chlorophenyl) boron, trialkyl (p-fluorophenyl) boron, trialkyl (3,5-bistrifluoromethyl) Phenylboron, 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, tria Kill (m-butylphenyl) boron, trialkyl (p-butyloxyphenyl) boron, trialkyl (m-butyloxyphenyl) boron, trialkyl (p-octyloxyphenyl) boron, trialkyl (m-octyloxyphenyl) ) Sodium salt of lithium (alkyl group is n-butyl group, n-octyl group, n-dodecyl group, etc.), lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methyl Examples thereof include pyridinium 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 dialkyldiphenyl boron, dialkyldi (p-chlorophenyl) boron, dialkyldi (p-fluorophenyl) boron, and dialkyldi (3,5-bistrifluoromethyl) 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-nitro Phenyl) boron, dialkyldi (p-butylphenyl) boron, dialkyldi (m-butylphenyl) boron, dialkyldi (p-butyloxyphenyl) boron, dialkyldi (m-butyloxyphenyl) boron, dialkyldi (p-octyloxyphenyl) Boron, dia Sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium of killi (m-octyloxyphenyl) boron (alkyl group is the same as above) Salts, butylpyridinium salts, methylquinolinium salts, ethylquinolinium salts, butylquinolinium salts and the like.

Further, borate compounds having three aryl groups in one molecule include monoalkyltriphenylboron, monoalkyltri (p-chlorophenyl) boron, monoalkyltri (p-fluorophenyl) boron, monoalkyltri (3 , 5-Bistrifluoromethyl) 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, monoal Sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt of rutri (p-octyloxyphenyl) boron, monoalkyltri (m-octyloxyphenyl) boron (alkyl group is the same as above) Examples thereof include salts, tetraethylammonium salts, methylpyridinium salts, ethylpyridinium salts, butylpyridinium salts, methylquinolinium salts, ethylquinolinium salts, and butylquinolinium salts.

Further, borate compounds having four aryl groups in one molecule include tetraphenyl boron, tetrakis (p-chlorophenyl) boron, tetrakis (p-fluorophenyl) boron, tetrakis (3,5-bistrifluoromethyl) phenylboron. 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-octyloxyphenyl) boron , Tetrakis (m-octyloxyf Nyl) boron, (p-fluorophenyl) triphenylboron, (3,5-bistrifluoromethyl) phenyltriphenylboron, (p-nitrophenyl) triphenylboron, (m-butyloxyphenyl) triphenylboron, ( p-butyloxyphenyl) triphenylboron, (m-octyloxyphenyl) triphenylboron, (p-octyloxyphenyl) triphenylboron, sodium salt (alkyl group is the same as above), lithium salt, potassium salt, Examples include magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt, and butylquinolinium salt.

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.

These aryl borate compounds can be used alone or in combination.

These polymerization initiators may be used alone or in combination of two or more compounds. The blending amount of these polymerization initiators is 0.001% by weight to 20% by weight, preferably 0.01% by weight to 15% by weight based on the total amount of the curable composition of the present invention other than the organic solvent. % By weight, particularly preferably 0.01% by weight to 7% by weight.

As the polymerization accelerator used in combination with the polymerization initiator contained in the dental adhesive composition of the present invention, a compound conventionally used as a photopolymerization accelerator or a room temperature polymerization accelerator can be used. Derivatives, aromatic amines, aliphatic amines, tin compounds, aldehydes and compounds having a thiol group, halomethyl group-substituted s-triazine derivatives, diphenyliodonium salt compounds, IV and / or V valent Vanadium compounds are preferred.

（Ｒ１、Ｒ２およびＲ３は同一もしくは異なっていてもよく、それぞれハロゲン原子、アルキル基、アルコキシ基、アリル基またはシクロヘキシル基等の置換基を有してもよい脂肪族、芳香族、脂環式または複素環式残基もしくは水素元素を表す。）で表される。The babituric acid derivative of the polymerization accelerator used in combination with the polymerization initiator of the present invention includes the following general formula [2]

(R1, R2 and R3 may be the same or different and each may have a substituent such as a halogen atom, an alkyl group, an alkoxy group, an allyl group or a cyclohexyl group, an aliphatic, aromatic, alicyclic or Represents a heterocyclic residue or a hydrogen element).

Specifically, barbituric acid, 1,3-dimethylbarbituric acid, 1,3-diphenylbarbituric acid, 1,5-dimethylbarbituric acid, 5-butylbarbituric acid, 5-ethylbarbituric acid, 5-isopropyl barbituric acid, 5-cyclohexyl barbituric acid, 1,3,5-trimethylbarbituric acid, 1,3-dimethyl-5-ethylbarbituric acid, 1,3-dimethyl-n-butylbarbituric acid 1,3-dimethyl-5-isobutylbarbituric acid, 1,3-dimethylbarbituric acid, 1,3-dimethyl-5-cyclopentylbarbituric acid, 1,3-dimethyl-5-cyclohexylbarbituric acid, , 3-Dimethyl-5-phenylbarbituric acid, 1-cyclohexyl-1-ethylbarbituric acid, 1-benzyl-5-phenyl Rubarbituric acid, 5-methylbarbituric acid, 5-propylbarbituric acid, 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 Hexyl barbituric acid, 5-butyl-1-cyclohexyl barbituric acid, 1-benzyl-5-phenylbarbituric acid and thiobarbituric acids, and salts thereof (especially preferred are alkali metals or alkaline earth metals), For example, sodium 5-butyl barbiturate, 1,3,5-trimethyl Sodium Rubitsuru acid and 1-cyclohexyl-5-ethyl barbituric sodium tools acids and the like.

Particularly suitable barbituric acid derivatives are 5-butyl barbituric acid, 1,3,5-trimethylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, and 1-benzyl-5-phenylbarbituric acid and These are the sodium salts of barbituric acids.

Examples of the aromatic amine of the polymerization accelerator used in combination with the polymerization initiator of the present invention include N, N-bis (2-hydroxyethyl) -3,5-dimethylaniline, N, N-di (2-hydroxy). Ethyl) -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-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, 4-N, N-dimethylaminobenzoic acid Ethyl ester, 4-N, N-dimethylaminobenzoic acid methyl ester, N, N-dimethylaminobenzoic acid n-butoxyethyl ester, 4-N, N-dimethylaminobenzoic acid 2- (methacryloyloxy) ethyl ester, 4 -N, N-dimethylaminobenzophenone, butyl 4-dimethylaminobenzoate and the like.

As the aliphatic amine of the polymerization accelerator used in combination with the polymerization initiator of the present invention, for example, N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-lauryldiethanolamine, 2- (dimethylamino) Examples include ethyl methacrylate, N-methyldiethanolamine dimethacrylate, N-ethyldiethanolamine dimethacrylate, triethanolamine monomethacrylate, triethanolamine dimethacrylate, triethanolamine trimethacrylate, triethanolamine, trimethylamine, and triethylamine.

Particularly preferred amines are N, N-di (2-hydroxyethyl) -p-toluidine, 4-N, N-dimethylaminobenzoic acid ethyl ester.

Examples of the tin compound of the polymerization accelerator used in combination with the polymerization initiator of the present invention include di-n-butyltin dimaleate, di-n-octyltin dimaleate, di-n-octyltin dilaurate, and di-n-butyltin dilaurate. Or a mixture thereof. Particularly suitable tin compounds are di-n-octyltin dilaurate and di-n-butyltin dilaurate.

Examples of aldehydes among aldehydes and compounds having a thiol group as polymerization accelerators used in combination with the polymerization initiator of the present invention include terephthalaldehyde and dimethylaminobenzaldehyde. Examples of the compound having a thiol group include 3-mercaptopropyltrimethoxysilane, 2-mercaptobenzoxazole, decanethiol, and thiobenzoic acid.

As the halomethyl group-substituted s-triazine derivative of the polymerization accelerator used in combination with the polymerization initiator of the present invention,

19

Or 2,4,6-tris (trichloromethyl) -s-triazine, 2,4,6-tris (tribromomethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) ) -S-triazine and the compounds described in JP-A-10-245525.

Examples of the polymerization accelerator diphenyliodonium salt compounds used in combination with the polymerization initiator of the present invention include bromides such as diphenyliodonium and p-octyloxyphenyliodonium, tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, and trifluoride. Examples thereof include compounds described in JP-A-9-3109 such as lomethanesulfonate salt.

Specific examples of the IV and / or V vanadium compounds used in combination with the polymerization initiator of the present invention include divanadium tetroxide (IV), vanadium acetylacetonate (IV), Vanadyl oxalate (IV), vanadyl sulfate (IV), oxobis (1-phenyl-1,3-butanedionate) vanadium (IV), bis (maltolate) oxovanadium (IV), vanadium pentoxide (V), metavanadium Examples thereof include compounds described in JP-A No. 2003-96122, such as vanadium compounds such as sodium acid (V) and ammonium metavanadate (V).

These polymerization accelerators may be used alone or in combination of two or more compounds.

In particular, as a polymerization initiator of the dental adhesive composition of the present invention, coumarin as a photopolymerization initiator, a borate compound as a chemical polymerization initiator, and a halomethyl group-substituted s-triazine derivative or diphenyliodonium salt as a polymerization accelerator. A ternary polymerization initiator mixed with a series compound, or a ternary polymerization initiator of a halomethyl group-substituted s-triazine derivative or a diphenyliodonium salt compound, an IV-valent and / or a V-valent vanadium compound is combined. It can be suitably used.

The water used in the dental adhesive composition of the present invention is water that is acceptable for medical use, and ion-exchanged water, purified water, and the like are used. These waters can be expected to increase the penetration of the components of the present invention into the dentin, but the blending amount is 0.1% by weight to 99% with respect to the total amount of the adhesive composition of the present invention. 0.5 wt%, preferably 5 wt% to 80 wt%, particularly preferably 10 wt% to 70 wt%.

The dental adhesive composition of the present invention comprises an inclusion compound, a radical polymerizable monomer, a polymerization initiator, and water as essential components, fillers such as organic solvents, coupling agents, inorganic and organic fillers, modifiers, Thickeners, dyes, pigments, polymerization regulators, polymerization inhibitors and the like may be appropriately blended.

Examples of the organic solvent include alcohols such as ethanol, methanol, 1-propanol, and isopropyl alcohol, ketones such as acetone, methyl ethyl ketone, pentanone, and hexanone, esters such as ethyl acetate, methyl acetate, and ethyl propionate, Ethers such as 2-dimethoxyethane, 1,2-diethoxyethane and tetrahydrofuran, hydrocarbons such as heptane, hexane, octane and toluene, and halogenated hydrocarbons such as chloroform and dichloromethane are preferably used. Of these, acetone, ethanol, isopropyl alcohol, and the like are preferably used.

These organic solvents may be used alone or in combination of two or more compounds. The compounding amount of these organic solvents is 1% by weight to 99.5% by weight, preferably 5% by weight to 80% by weight, particularly with respect to the total amount of the dental adhesive composition of the present invention. It is preferably 10% by weight to 70% by weight.

Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, butylated hydroxytoluene and the like, which are suitable for stabilizing the shelf life of the composition.

The dental adhesive composition of the present invention can be used as a one-component one-step bonding agent as an embodiment, but a two-component one-step bonding agent and a one-paste adhesive low-viscosity composite resin. It can also be used in an embodiment such as a one-paste adhesive composite resin.

The dental adhesive composition according to the present invention includes, as an embodiment, a dental photopolymerization type bonding agent, a resin cement, a paste-paste resin modified glass ionomer cement, a composite resin, a fisher sealant, and an orthodontic appliance. It may also be used in adhesives, teeth coating agents, crown and bridge composite resins, opaque agents, and the like.

Next, the present invention will be specifically described with reference to examples and comparative examples. In addition, this invention is not limited to these Examples at all.

Examples 1-16 and Comparative Examples 1-4
The dental adhesive composition of the present invention was examined in the form as a photopolymerizable bonding agent. As a radical polymerizable monomer, 6-methacryloxyhexyl-3-phosphonoacetate (6-MHPA), 4-methacryloxyethyl trimellitic acid (4-MET), bisphenol A-diglycidyl methacrylate (Bis-GMA) , And triethylene glycol dimethacrylate (TEGDMA), 2,4,6-trimethylbenzoyldiphenylphosphine oxide (TBPO) as a polymerization initiator, and acetone are mixed in the composition shown in Table 1 to perform one-step photopolymerization bonding An agent was prepared. Furthermore, distilled water (α solution) and 3% sodium p-toluenesulfinate (p-TS-Na) aqueous solution (β solution) were prepared. The non-aqueous photopolymerizable bonding agent and α liquid or β liquid were mixed at a ratio of 1: 2, 1: 1, and 2: 1, and a shear adhesion test to enamel and dentin was performed in one step.

[Shear adhesion test]
The tooth quality was changed to human teeth using freshly extracted bovine anterior teeth, the roots were deleted and the pulp removed, and then embedded in epoxy resin. The lip enamel and dentin of the bovine teeth were polished with water-resistant polishing paper No. 80 under water injection and then polished with No. 600 under water injection. In the adhesion test body, the polished tooth surface was first dried with compressed air containing no oil, and a double-sided tape with a hole having a diameter of 4 mm was attached to define the adhesion surface. Next, the prepared photopolymerizable bonding agent and distilled water (α solution) or 3% sodium p-toluenesulfinate (p-TS-Na) aqueous solution (β solution) were collected in an arbitrary ratio in a microbrush. After being applied to the enamel or dentin bond surface in one step using rubbing treatment or active treatment by rubbing or active treatment to rub for 20 seconds, water and organic solvent are evaporated with compressed air without oil. It was. Subsequently, light was irradiated for 20 seconds with Shofu Grip Light II [manufactured by Shofu Co., Ltd.]. Thereafter, a plastic mold having a diameter of 4 mm and a height of 2 mm was fixed to the adhesion regulating surface, and a photopolymerizable composite resin “Beauty Fill” [manufactured by Matsukaze Co., Ltd.] was filled in the mold. Next, the cover glass was shielded from air, and the composite resin was cured by irradiating light with a pine wind grip light II for 30 seconds, and the mold was removed to obtain an adhesion test specimen. Here, the illuminance of the bonding agent and composite resin light irradiator was Matsukaze Grip Light II: 650 mW / cm ² . In the shear adhesion test, the specimen was immersed in distilled water at 37 ° C. for 24 hours and then measured using an Instron universal testing machine (Instron 5567, Instron) at a crosshead speed of 1 mm / min. The value was determined. Table 1 shows the composition of the two-component one-step photopolymerization type bonding agent and the results of the adhesion test.

（ 注） ： 単位＝ 重量部、Ａ ： ラジカル重合性単量体、Ｂ ： 重合開始剤、Ｃ ： 有機溶媒、Ｄ： 蒸留水（ α 液） または３ ％ ｐ − トルエンスルフィン酸ナトリウム（
ｐ − Ｔ Ｓ − Ｎ ａ ） 水溶液（ β 液） とＡ 〜 Ｃ から成る光重合性ボンディング剤との混合比、ａ ： ６ − （ メタ） アクリロキシヘキシル−
３ − ホスホノアセテート（ ６ − Ｍ Ｈ Ｐ Ａ ） 、ｂ ： ４ − メタクリロキシエチルトリメリット酸（ ４ − Ｍ Ｅ Ｔ ） 、ｃ ： ビスフェノールＡ
− ジグリシジルメタクリレート（ Ｂ ｉ ｓ − Ｇ Ｍ Ａ ） ／ トリエチレングリコールジメタクリレート（ Ｔ Ｅ Ｇ Ｄ Ｍ Ａ ）＝ ６ ０ ／ ４ ０
（ 重量％ ） 、ｄ ： ２ ， ４ ， ６ − トリメチルベンゾイルジフェニルホスフィンオキサイド（ Ｔ Ｂ Ｐ Ｏ ） 、ｅ ： アセトン

(Note): Unit = part by weight, A: radical polymerizable monomer, B: polymerization initiator, C: organic solvent, D: distilled water (α liquid) or 3% sodium p-toluenesulfinate (
p-TS-Na) Mixing ratio of aqueous solution (β solution) to photopolymerizable bonding agent comprising A to C, a: 6- (meth) acryloxyhexyl-
3-phosphonoacetate (6-MHPA), b: 4-methacryloxyethyl trimellitic acid (4-MET), c: bisphenol A
-Diglycidyl methacrylate (Bis-GMA) / triethyleneglycol dimethacrylate (TEGDMA) = 60/40
(% By weight), d: 2,4,6-trimethylbenzoyldiphenylphosphine oxide (TBPO), e: acetone

As is clear from the results in Table 1, Comparative Examples 1 to 4 containing no water showed extremely low tooth adhesion strength. In contrast to these comparative examples, in the one-step photopolymerization type bonding agent comprising the radical polymerizable monomer, polymerization initiator, water and organic solvent of the present invention, the mixed liquid with water or 3% p-TS-Na aqueous solution is All became “heterogeneous solutions” and showed a result that the adhesion strength to enamel and dentin was significantly high by a simple operation.

Examples 17-32
The dental adhesive composition of the present invention is used in the form of a photopolymerizable bonding agent, and all the components a to e used in Example 1 are used. The adhesion was examined. The results are shown in Table 2.

（注）：単位＝重量部、Ａ：ラジカル重合性単量体、Ｂ：重合開始剤、Ｃ：有機溶媒、Ｄ：蒸留水（α液）または３％ｐ−トルエンスルフィン酸ナトリウム（ｐ−ＴＳ−Ｎａ）水溶液（β液）とＡ〜Ｃから成る光重合性ボンディング剤との混合比。ａ〜ｅ：表１に示した成分と同じ。

(Note): Unit = part by weight, A: radical polymerizable monomer, B: polymerization initiator, C: organic solvent, D: distilled water (α liquid) or 3% sodium p-toluenesulfinate (p-TS) -Na) Mixing ratio of aqueous solution (beta liquid) and the photopolymerizable bonding agent which consists of AC. a to e: the same as the components shown in Table 1.

As is clear from the results in Table 2, the one-step light in which the mixed solution of the radical polymerizable monomer of the present invention, the polymerization initiator, the organic solvent and water or 3% p-TS-Na aqueous solution is a heterogeneous solution. The polymerized bonding agent showed high adhesion strength to enamel and dentin with a simple operation.

Examples 35-46
The dental adhesive composition of the present invention was examined in the form of a one-step type photopolymerizable bonding agent. As radical polymerizable monomers, 6-MHPA, 6- (meth) acryloxyhexyl-3-phosphonopropionate (6-MHPP), 4-methacryloxyethyl trimellitic anhydride (4-META), 4 -MET, Bis-GMA, dimethacryloxyethyl-2,2,4-trimethylhexamethylene diurethane (UDMA), TEGDMA, 2-hydroxyethyl methacrylate (HEMA), TBPO, DL-camphorquinone as polymerization initiator (CQ), di-n-butyltin dilaurate (Butyl-Tin) and 4-N, N-dimethylaminobenzoic acid ethyl ester (4-MABE), acetone, ethanol, and ultrafine filler (Aerosil) R-972: manufactured by Nippon Aerosil Co., Ltd.) with the composition shown in Table 3 The adhesive composition was prepared. Further, water, 3% p-TS-Na aqueous solution, 3% 1-benzyl-5-phenylbarbituric acid / sodium salt aqueous solution (3% BPBA-Na), 3% 2,4,6-trimethylbenzoylphenylphosphine oxide -An aqueous sodium salt solution (3% TBPO-Na) was prepared. The adhesive composition and the aqueous solution were mixed and used as a one-step photopolymerizable bonding agent, and a shear adhesion test was conducted according to Example 1. The results are shown in Table 3.

（ 注） ： 単位＝ 重量部、A：ラジカル重合性単量体、B：
重合開始剤、C： 有機溶媒、、Ｂｉｓ−ＧＭＡｓｏｌ．：Ｂｉｓ−ＧＭＡ／ＴＥＧＤＭＡ＝６０／４０（ｗｔ％）、ＵＤＭＡｓｏｌ．：ＵＤＭＡ／ＴＥＧＤＭＡ＝６０／４０（ｗｔ％）

(Note): Unit = parts by weight, A: radical polymerizable monomer, B:
Polymerization initiator, C: organic solvent, Bis-GMAsol. : Bis-GMA / TEGDMA = 60/40 (wt%), UDMAsol. : UDMA / TEGDMA = 60/40 (wt%)

As is apparent from the results in Table 3, in Comparative Examples 5 and 6, the photopolymerizable bonding agent that is a “homogeneous solution” composed of a radical polymerizable monomer, a polymerization initiator, water, and an organic solvent is 1 Insufficient adhesion strength as a step bond. On the other hand, a one-step photopolymerization type bonding agent comprising a radically polymerizable monomer, a polymerization initiator, water, and an organic solvent of the present invention, which is a “heterogeneous solution”, has an enamel and an enamel Stable and high bond strength in dentin.

Example 40
Using the composition of Example 16 of the dental adhesive composition of the present invention, an adhesive treatment was carried out by applying photopolymerization to the enamel or dentin adhesion surface according to Example 1. Further, an aluminum oxide powder was sprayed on the adhesive surface of a stainless steel rod (diameter 5 mm, length 12 mm) to perform sandblasting. Subsequently, impregnated dental resin cement (made by Matsumatsu Matsukaze Co., Ltd.) is kneaded with a spatula according to the instructions, and the adhering treatment is performed by interposing the kneaded mud. A stainless steel rod was joined to the tooth surface, a load of 200 g was applied, and the kneaded mud protruding from the adhesion interface was removed with a blade. Subsequently, the adhesion interface was irradiated with light for 20 seconds from an oblique direction using the Matsukaze Grip Light II [manufactured by Matsukaze Co., Ltd.]. Thereafter, the shear bond strength test was performed by immersing the specimen for 24 hours in distilled water at 37 ° C., and using an Instron universal testing machine (Instron 5567, Instron) at a crosshead speed of 1 mm / min. An average value of 7 was obtained. As a result, the bond strength of the enamel-stainless steel rod was 23.5 MPa, and the bond strength of the dentin-stainless steel rod was 18.7 MPa.

Examples 41-44
The dental adhesive composition of the present invention was examined in the form of a one-step type photopolymerizable bonding agent. As radical polymerizable monomers, 6-MHPA (20 parts by weight), 4-MET (15 parts by weight), HEMA (1 part by weight), Bis-GMA / TEGDMA (= 60/40, wt%) (35 parts by weight) ), TBPO (1 part by weight), CQ (1 part by weight) as a polymerization initiator, 3,3′-carbonylbis (7-diethylaminocoumarin) (0.005 part by weight) as a coumarin compound, and a polymerization accelerator 4-MABE (1 part by weight), acetone (26 parts by weight), and Aerosil R-972 (3 parts by weight) were mixed to prepare “Bond 1”. “Bond 2” was prepared by replacing only the coumarin compound of “Bond 1” with 3,3′-carbonylbis (7-dibutylaminocoumarin) (0.005 parts by weight). Furthermore, the case where 6-MHPA of these bonds 1 and 2 was substituted with 6-MHPP was prepared as “bond 3” and “bond 4”. Furthermore, 3% p-toluenesulfinic acid sodium salt (3% p-TS-Na) aqueous solution was prepared. Each of the bonds 1 to 4 and a 3% p-TS-Na aqueous solution were mixed at a ratio of 1: 1 and used as a one-step photopolymerizable bonding agent, and a shear adhesion test was performed according to Example 1. The results are shown in Table 4.

Here, the light irradiator is a Matsukaze Grip Light II (Hal) using a halogen lamp (manufactured by (Matsu) Matsukaze Co., Ltd.), and a light emitting diode (LED) irradiator Eliper Free Light 2 (LED) (3M manufactured by Esper And Xenon lamp Apollo Elite 95E (Xe) (manufactured by DMD). The illumination intensity of each light irradiator was used at Matsukaze Grip Light II: 650 mW / cm ² , Eliper Free Light 2: 635 mW / cm ² and APPOLLO ELITE 95E: 1330 mW / cm ² . The illuminance measurement wavelength region of these irradiators was set to 400 to 515 nm.

Each of the liquids of Bonds 1 to 4 and 3% p-TS-Na aqueous solution were 1: 1, and the properties of the mixed solution were all “non-uniform solutions”. As is clear from the results in Table 4, the dental adhesive composition of the present invention is a heterogeneous solution comprising a radical polymerizable monomer, a polymerization initiator, water, and an organic solvent. As a photopolymerization initiator of the photopolymerization type bonding agent, a photopolymerizable composition containing acylphosphine oxide, α-diketone, coumarin compound, and polymerization accelerator can be used in any light irradiation of halogen light, LED, or xenon lamp. Also showed high photocuring properties, and as a result, showed high enamel adhesion and dentin adhesion. High cohesion even when three types of light irradiators are used by coexisting the visible light sensitization effect of coumarin compounds and visible light initiators such as acylphosphine oxide and α-diketone. It is thought that it showed strength.

Example 45
The dental adhesive composition of the present invention was examined in the form of a one-step dental adhesive. As a two-component type bonding agent, as a radical polymerizable monomer of the A solution, 6-MHPP (15 parts by weight), 4-MET (20 parts by weight), 4-acryloxyethyl trimellitic acid (1 part by weight), HEMA (2 parts by weight), Bis-GMA / TEGDMA (= 60/40 parts by weight) (35 parts by weight), TBPO (1 part by weight), DL-camphorquinone (CQ) (1 part by weight) as a polymerization initiator , Ultrafine filler (R-972) (2 parts by weight), acetone (20 parts by weight), and B liquid, p-TS-Na (3 parts by weight), 1,3,5-trimethylbarbituric acid / sodium Salt (TMBA-Na) (3 parts by weight), fluoroaluminosilicate glass (average particle size: 5 μm) (40 parts by weight), acetone (10 parts by weight), and distilled water (44 parts by weight) It was developed a liquid type of bonding agent. Equivalent amounts of A liquid and B liquid of a two-component type bonding agent were mixed with an eye plate, collected with a microbrush, and applied to enamel or dentin, all in accordance with Example 1. As a result, the bond strength to the enamel was 18.3 MPa, and the bond strength to the dentin was 15.8 MPa.

Example 46
The dental adhesive composition of the present invention was examined in the form of a one-step type photopolymerizable bonding agent. 6-MHPP (12.5 parts by weight), 4-MET (20 parts by weight), HEMA (2 parts by weight), Bis-GMA / TEGDMA (= 60/40 parts by weight) as radical polymerizable monomers for the bonding agent (35 parts by weight), as a polymerization initiator, TBPO (0.5 parts by weight), DL-camphorquinone (CQ) (0.5 parts by weight), ultrafine filler (R-972) (3 parts by weight), and As polymerization initiators for acetone (30 parts by weight) and bonding agent B solution, p-TS-Na (2 parts by weight), TBPO-Na (2 parts by weight), water (50 parts by weight), and acetone (46 parts by weight) Part), a two-liquid one-step type photopolymerizable bonding agent was dropped in an equal amount on a mixing pan and mixed with a microbrush, and the mixed liquid was non-uniform. Using the mixed solution, a shear adhesion test was conducted according to Example 1. As a result, the enamel bond strength was 22.4 MPa, and the dentin bond strength was 19.7 MPa.

Claims (2)

A two-liquid mixed type one-step photopolymerization type dental adhesive composition composed of liquid A and liquid B,
Liquid A is (a) 20-40 parts by weight of a radically polymerizable monomer containing an acidic group, (b) 30-45 parts by weight of a radically polymerizable monomer containing no acidic group, and (c) photopolymerization is initiated. Consisting of only 0.25 to 3.0 parts by weight of an agent and / or photopolymerization accelerator, and (d) 20 to 45 parts by weight of an organic solvent,
Liquid B consists of (e) 97-100 parts by weight of water, and (f) 0-3 parts by weight of a metal salt of sulfinic acid or a water-soluble photopolymerization initiator,
A one-step photopolymerization type dental adhesive composition characterized in that the properties of the mixed solution of liquid A: liquid B of 1: 2, 1: 1, and 2: 1 are not compatible and non-uniform. . (a) radical polymerizable monomers containing acidic groups are 6- (meth) acryloxyhexyl-3-phosphonoacetate and 6- (meth) acryloxyhexyl-3-phosphonopropionate, 4 -Methacryloxyethyl trimellitic acid, 4-acryloxyethyl trimellitic acid,
(b) The radical polymerizable monomer containing no acidic group is bisphenol A-diglycidyl methacrylate, triethylene glycol dimethacrylate, di (meth) acryloxyethyl-2,2,4-trimethylhexamethylene diurethane. ,
(c) The photopolymerization initiator is 2,4,6-trimethylbenzoyldiphenylphosphine oxide, which is a (bis) acylphosphine oxide, D, L-camphorquinone, which is an α-diketone, and a coumarin compound, 3'-carbonylbis (7-diethylaminocoumarin) and 3,3'-carbonylbis (7-dibutylaminocoumarin),
The photopolymerization accelerator is 1,3,5-trimethylbarbituric acid which is a barbituric acid derivative, the amines are 4-N, N-dimethylaminobenzoic acid ethyl ester, and the tin compound is di-n-octyltin dilaurate And di-n-butyltin dilaurate, and
(d) the organic solvent is acetone, ethanol,
(f) The metal salt of sulfinic acid or the water-soluble photopolymerization initiator is sodium benzenesulfinate, sodium p-toluenesulfinate, sodium salt of 2,4,6-trimethylbenzoylphenylphosphine oxide. Item 1. A one-step photopolymerizable dental adhesive composition according to item 1.