JP4606874B2 - Phase separation one-component adhesive composition - Google Patents

Description

The present invention relates to a one-component adhesive composition, and in particular, a one-step type having three functions (all-in-one) of etching, priming, and bonding in adhesion between a tooth structure and a dental restorative material. The present invention relates to a one-component adhesive composition.

In dental practice, caries treatment is carried out by removing a carious portion of a tooth to form a cavity and filling a dental restoration such as a composite resin after treatment with a dental adhesive. However, due to insufficient adhesiveness to the teeth, there are problems such as postoperative discomfort such as pulp stimulation and secondary caries and loss of the composite. In the conventional three-step type dental adhesive, after the cavity formation, (1) acid etching treatment, (2) primer treatment, (3) complicated operation of bonding treatment, and low bond strength to dentin Therefore, it is desired to develop a dental adhesive having a strong adhesive strength with a simple operation.

Japanese Patent Laid-Open No. 2000-159621 consists of a (meth) acrylate monomer having an acidic group in the molecule, a water-soluble acylphosphine oxide compound and water, and forms a uniform solution at room temperature. It has been proposed that when the polymerizable composition is used as a self-etching primer for a two-step adhesive system and a photopolymerization bonding agent is used in combination, the adhesion to the tooth is improved. However, it has been found that if the dental polymerizable composition of the uniform aqueous solution is used as a one-step type bonding agent, the adhesiveness is remarkably low.

In Japanese Patent No. 3158422, a one-part photocurable adhesive composition comprising a water-soluble thioxanthone derivative having a quaternary ammonium base, a hydrophilic group-containing radically polymerizable (meth) acrylate monomer and water is uniform. Although it has been reported that the adhesion to the dentin is improved only by the one-step treatment of the aqueous solution, the adhesive strength is insufficient.

Japanese Patent Application Laid-Open No. 11-140383 proposes a one-step type adhesive composition containing an allyl borate compound or a monomer having an acidic group. The allyl borate compound and an acidic compound are used as a chemical polymerization catalyst. The one-part composition does not hold. Japanese Patent Application Laid-Open Nos. 10-245525 and 2001-72523 relate to a one-step type adhesive, but the operability is complicated because two divided adhesives are used.

Japanese Patent Application Laid-Open Nos. 11-240815 and 2003-238325 propose a one-step type adhesive composition that only requires a bonding agent application that does not require etching treatment and primer treatment. In particular, in the composition disclosed in Japanese Patent Application Laid-Open No. 2003-238325, the water-soluble reducing agent sulfinate and N-aromatic group-substituted glycine salt react with the acidic group acidic group to form an adhesive composition. Since it gels within several days, a one-component adhesive composition does not hold. Therefore, we have proposed a method in which these water-soluble reducing agents are impregnated in advance in a brush or sponge used for coating, but the disadvantage is that the mixing operation for compatibilizing each component at the time of use becomes complicated and the adhesive strength is extremely low. There is.

Furthermore, in the specification of JP-A-2003-238325, it is preferable that a one-component adhesive composition containing water undergoes phase separation at 37 ° C., and a water-soluble organic solvent is added to the adhesive composition. It is described that a transparent solution that is uniform at room temperature is preferred. It is also described that this uniform transparent solution has an advantage that the liquid can be collected at a constant ratio at all times. However, it has been found that both the adhesive composition that undergoes phase separation and the uniform transparent solution obtained by adding a water-soluble organic solvent to the composition exhibit a significantly low bond strength to the tooth.

Conventionally, as a result of many studies on so-called self-etching primers in which 2-hydroxyethyl methacrylate, water and a radical polymerizable monomer having an acidic group are blended, dentin bond strength has been remarkably improved. However, a one-step one-component adhesive composition in which a hydrophobic monomer or an acidic monomer is uniformly mixed with water using 2-hydroxyethyl methacrylate or a water-soluble organic solvent has high adhesive strength as expected at this stage. Not expressed.

In JP-A-2001-26511, as an adhesive composition composed of a polymerizable compound having an acidic group, a water-soluble film forming agent, water and a curing agent, a one-step type in which only a bonding agent application requiring no etching treatment and primer treatment is required. It is proposed that the calcium salt of a polymerizable compound having an acidic group is insoluble in water, which is important in terms of adhesion durability. However, the water-soluble film-forming agent that is miscible with physiological saline is used at 50% by weight or more, and 2-hydroxyethyl methacrylate is particularly preferable. There is a major contradiction in this proposal. That is, even if the calcium salt of the polymerizable compound having an acidic group is insoluble in water, HEMA, which is the main component of the adhesive layer, or a water-soluble polymer with insufficient polymerization [poly (2-hydroxy Ethyl methacrylate) = poly-HEMA)] elutes or swells due to water absorption and has a serious problem in adhesion durability.

Furthermore, in Japanese Patent Application Laid-Open No. 2003-73218, a hydrophilic polymerizable monomer such as 2-hydroxyethyl methacrylate or 2-hydroxy-1,3-dimethacryloyloxypropane is added to triethylene glycol dimethacrylate or di-2-methacrylate. It is preferable that a polymerizable monomer having good polymerizability such as loxyethyl-2,2,4-trimethylhexamethylene dicarbamate is mixed and used so that the solubility of water at 25 ° C. is 25% by weight or less. Although described, adhesion is insufficient.

In addition, in the specification of Japanese Patent Application Laid-Open No. 2003-73218, there is a description that “it may be in an emulsified state”, but there is also a description and concept of a difference from an aggressive uniform solution that the heterogeneous solution improves the adhesive strength. Not presented at all. In addition, the specification of this publication mentions that it is used in a small amount because of the problem of skin sensitization of 2-hydroxyethyl methacrylate. Originally, skin sensitization is not a matter of quantity and needs to be completely removed, but it has not been completely removed from the composition and is still a biomaterial in the sense that there is a possibility of skin sensitization. There's a problem.

Japanese Patent Application Laid-Open No. 2003-342112 discloses a dental one-component adhesive composition characterized by being substantially free of water. The tooth surface treatment is performed using water on the tooth surface. For this reason, adhesion is influenced by the water on the tooth surface, and it becomes a technique centric.

In short, the conventional one-part adhesive composition uses a water-soluble film-forming agent such as 2-hydroxyethyl methacrylate as a technique for extending the self-etching primer, and is composed of a uniform solution. The current situation is that the adhesive strength is not obtained. In other words, it has a simple operability of 1 liquid 1 step and exhibits strong tooth bonding strength equal to or better than that of 2 step type adhesives. The composition is not yet present.

JP 2000-159621 A Japanese Patent No. 3158422 JP-A-11-140383 Japanese Patent Laid-Open No. 10-245525 JP 2001-72523 A JP-A-11-240815, JP 2003-238325 A JP 2001-26511 A Japanese Patent Laid-Open No. 2003-73218 JP 2003-342112 A

Conventionally, its constituent components consisted of a radical polymerizable monomer having an acidic group in the molecule, a radical polymerizable monomer not containing an acidic group in the molecule, a photopolymerization initiator, water, and an organic solvent. A one-component adhesive composition consisting essentially of a heterogeneous solution, wherein the composition consists essentially of a heterogeneous solution characterized in that it contains substantially no water-soluble film-forming agent that does not contain acidic groups in the molecule. There is no proposal of an adhesive technique in which the liquid adhesive composition exerts strong adhesion strength to the enamel or dentin of the tooth, and such a one-step one-liquid adhesive composition exists. I did not.
Conventionally, a uniform solution comprising an adhesive monomer having an acidic group, a water-soluble polymerization initiator, and water is a one-step one-component adhesive composition although the adhesive effect of the self-etching primer of the two-step adhesive system is high. When used in, there is a problem that the adhesion to the tooth is low.

Conventionally, a one-component adhesive composition containing no water has low adhesiveness to teeth, and further, there is a problem that the adhesive strength varies depending on the wet state or dry state of the tooth surface, resulting in a technique sensitive. .
Conventionally, a one-part adhesive composition containing water and consisting of a uniform solution is a uniform solution, so it is difficult to separate and remove water and water-soluble organic solvents by air blow, and the adhesive strength to the tooth is reduced. To do.
Conventionally, an adhesive composition comprising a radically polymerizable monomer having an acidic group in the molecule, a water-soluble film forming agent, water and a curing agent, and a uniform solution, 2-hydroxyethyl methacrylate which is a water-soluble film forming agent The polymer has a low photopolymerizability and elution from the adhesive layer, and even when polymerized, the polymer has a large amount of water absorption, so that the cohesive force of the adhesive layer is lowered and the adhesive strength is low.
Furthermore, since 2-hydroxyethyl methacrylate has a skin sensitization property, there is a problem that it is not suitable as a component of a biomaterial.
Conventionally, it is a uniform solution containing a one-component adhesive composition containing a radical polymerizable monomer having an acidic group in the molecule, a radical polymerizable monomer not containing an acidic group, a photopolymerization initiator, and water. In a one-part adhesive composition comprising a water-soluble film-forming agent such as 2-hydroxyethyl methacrylate and / or 2-hydroxy-1,3-dimethacryloyloxypropane, There is a problem that the cohesive force is reduced and the adhesive layer swells and absorbs water over a long period of time, resulting in a low adhesive strength. Conventionally, when a composition containing a radically polymerizable monomer having an acidic group in the molecule, a polymerization initiator, a reducing agent and water is used as a uniform emulsion, a water-soluble organic solvent is added to the composition. In the adhesive composition used in a uniform and transparent solution, the reducing agent, particularly the water-soluble reducing agent N-phenylglycine sodium or sodium p-toluenesulfinate, reacts with the radical polymerizable monomer having an acidic group. Since the water-soluble reducing agent is divided and impregnated in advance in a coating sponge and mixed before use, there is a problem that the operation is complicated and the adhesive strength is extremely low.

An object of the present invention is to solve the problems of the prior art as described above. That is, the present invention does not require a complicated operation as in the conventional two-step type dental adhesive in the adhesion between the tooth enamel and dentin and the dental restorative material, and includes etching, priming and bonding. It is a one-component adhesive composition that has a function (all-in-one) and simplifies the bonding operation by a one-step operation, and is concerned with 2-hydroxyethyl methacrylate or 2-hydroxy- It does not contain any water-soluble film forming agent such as 1,3-dimethacryloyloxypropane, and unnecessary elution from the cured adhesive layer at the adhesive interface can be avoided. An object is to provide a one-component adhesive composition.

As a result of intensive studies on the above-mentioned problems of the prior art, the inventors have (A) a radical polymerizable monomer having an acidic group in the molecule, and (B) a radical polymerization not containing an acidic group in the molecule. A one-component adhesive composition comprising an organic monomer, (C) a photopolymerization initiator, (D) water, and (E) an organic solvent, and consisting essentially of a heterogeneous solution at room temperature. A one-component adhesive composition characterized by substantially not containing a water-soluble film-forming agent that does not contain an acidic group in the one-component one-step, one-step, one-step, strong tooth adhesion It was revealed that it was expressed. More specifically, the present inventors have a phosphate group in the molecule that exhibits high adhesion strength to enamel as a radical polymerizable monomer having an acidic group in the molecule (A) as a constituent component. Radical polymerizable monomer and radical polymerizable monomer having carboxyl group or anhydride group of carboxyl group in molecule showing high adhesive strength to dentin, (B) No acidic group in molecule It consists of a radically polymerizable monomer, (C) a photopolymerization initiator alone or a photopolymerization initiator and a polymerization accelerator, (D) water, and (E) an organic solvent, and consists essentially of a heterogeneous solution at room temperature. It is a one-component adhesive composition that is substantially free of a water-soluble film forming agent that does not contain acidic groups such as 2-hydroxyethyl methacrylate or 2-hydroxy-1,3-dimethacryloyloxypropane. A one-part adhesive composition of a heterogeneous solution characterized by the following three functions (all-in-one): etching, priming, and bonding, completing the bonding operation in one step, and enamel of the tooth It was also found that it can adhere firmly to dentin. Furthermore, since the one-component adhesive composition of the present invention does not contain a water-soluble film-forming agent that can cause skin sensitization, such as 2-hydroxyethyl methacrylate, it solves the above problems, It is useful as a dental / medical adhesive.

The reason why the water-soluble film forming agent that is not substantially contained in the one-component adhesive composition of the present invention is not contained will be described below. Water-soluble film forming agents such as 2-hydroxyethyl methacrylate have a tremendous effect as an essential component of a self-etching primer of a two-step adhesive, but because of their poor photopolymerizability, they are bonding agents that require high cohesive strength. Not suitable for ingredients. Therefore, as a result of intensive studies, the present inventors have made it possible to integrate the functions of a two-step type adhesive into a one-step type one-part adhesive composition. A one-part adhesive composition in a non-uniform, micellar, or emulsion state is effectively self-etched without adding any water-soluble film-forming agent that can be expected to be compatible with water and resin such as methacryloyloxypropane. The present inventors have found that a bonding layer having a high cohesive force is formed and that a strong adhesiveness is expressed in the tooth structure, and the present invention has been achieved.

The present invention does not add any water-soluble film-forming agent that can be expected to be compatible with water and resin, such as 2-hydroxyethyl methacrylate and 2-hydroxy-1,3-dimethacryloyloxypropane, thereby, The adhesive adhesive composition is characterized by being in a non-uniform state, a micelle state, or an emulsion state. Here, in the specification of Japanese Patent Application Laid-Open No. 2003-73218, there is a description that it may be in an emulsified state, but there is absolutely no description or concept about the difference from the aggressive uniform solution that the heterogeneous solution improves the adhesive strength. It is not presented and water-soluble film formers are essential for its composition. The present inventors have determined that a one-part adhesive composition that is a heterogeneous solution and does not contain a water-soluble film-forming agent exhibits strong tooth adhesion.

In the specification of JP-A No. 2003-238325, it is preferable that a one-component adhesive composition containing water undergoes phase separation at 37 ° C., and a water-soluble organic solvent is added to the adhesive composition at room temperature. It is described that a uniform transparent solution is preferred. It is also described that this uniform transparent solution has an advantage that the liquid can be collected at a constant ratio at all times. However, the present inventors show that the adhesive strength is extremely low in a uniform transparent solution obtained by adding a water-soluble organic solvent to the phase-separating adhesive composition, and conversely, an adhesive composition obtained by adding a water-soluble organic solvent. It was found that a high adhesion strength comparable to a two-step bond was reached by using a non-uniform solution.

In other words, the present inventors have heretofore described a “non-uniform solution” that is completely opposite to the concept of the prior art that a single-component adhesive composition containing water as a constituent component must be a “uniform solution”. A one-component adhesive composition comprising a radical polymerizable monomer having an acidic group in the molecule, a radical polymerizable monomer having no acidic group in the molecule, a photopolymerization initiator, water, and an organic solvent It was confirmed that the product exhibited a surprisingly strong adhesive strength by a simple operation of one step, and the present invention was reached.

That is, the one-component adhesive composition of the present invention comprises (A) a radical polymerizable monomer having an acidic group in the molecule and (B) a radical polymerizable monomer having no acidic group in the molecule. A one-part adhesive composition comprising a monomer, (C) a photopolymerization initiator, (D) water, and (E) an organic solvent, wherein the one-part adhesive consists essentially of a heterogeneous solution at room temperature It is a one-component adhesive composition characterized in that the one-component adhesive composition does not substantially contain a water-soluble film forming agent that does not contain an acidic group in the molecule. More specifically, the one-component adhesive composition of the present invention is a one-component adhesive composition consisting essentially of a heterogeneous solution at room temperature, and the component (A) has an acidic group in the molecule. As a radical polymerizable monomer, a radical polymerizable monomer having a phosphate group in the molecule showing high adhesive strength to enamel and a carboxyl in the molecule showing high adhesive strength to dentin Radical polymerizable monomer having a group or carboxyl anhydride group, (B) a radical polymerizable monomer not containing an acidic group in the molecule, (C) a photopolymerization initiator alone or a photopolymerization initiator, and A one-component adhesive composition comprising a polymerization accelerator, (D) water, and (E) an organic solvent, and an acidic group such as 2-hydroxyethyl methacrylate or 2-hydroxy-1,3-dimethacryloyloxypropane Have It is a one-part adhesive composition of a heterogeneous solution characterized by substantially not containing a high water-soluble film forming agent, and has three functions (all-in-one) of etching, priming, and bonding. The bonding operation is completed by a step operation and can be firmly bonded to the enamel and dentin of the tooth.

In the present invention, (A) the radical polymerizable monomer having an acidic group in the molecule is one or more radical polymerizable monomers having a phosphate group, a carboxyl group or an anhydride group of a carboxyl group in the molecule. It is a one-component adhesive composition comprising a mixed system.

In the present invention, (A) the radical polymerizable monomer having an acidic group in the molecule is 4- (meth) acryloxyethyl trimellitic acid, 4- (meth) acryloxyethyl trimellitic anhydride, 6- It is a one-component adhesive composition that is (meth) acryloxyhexylphosphonoacetate, 6- (meth) acryloxyhexylphosphonopropionate, 10- (meth) acryloxydecylhydrogenphosphate.

In the present invention, (B) a radically polymerizable monomer that does not contain an acidic group in the molecule does not have an acidic group in the molecule, and an aliphatic and aromatic monofunctional or polyfunctional radically polymerizable monomer It is a one-component adhesive composition that is a body and is arbitrarily selected from these.

In the present invention, (B) the radical polymerizable monomer containing no acidic group in the molecule is ethylene glycol di (meth) acrylate, triethylene glycol di (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 Adhesive composition.

The present invention is a one-component adhesive composition in which (C) the photopolymerization initiator is a photopolymerization initiator alone or a mixed system of a photopolymerization initiator and a polymerization accelerator.

In the present invention, (C) the photopolymerization initiator is arbitrarily selected from among α-diketones, (bis) acylphosphine oxides, coumarin compounds, thioxanthone derivatives, and photopolymerization accelerators. This is a one-component adhesive composition.

The present invention is a one-component adhesive composition in which the α-diketone is D, L-camphorquinone.

The present invention provides a one-component adhesive composition in which (bis) acylphosphine oxides are 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) acylphosphine oxide. It is a thing.

The present invention is a one-component 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 one-component adhesive composition in which the thioxanthone derivative is 2-chlorothioxanthen-9-one.

In the present invention, the polymerization accelerator is an amine such as N, N-di (2-hydroxyethyl) -p-toluidine, 4-N, N-dimethylaminobenzoic acid ethyl ester, 5-butyl barbituric acid, , 3,5-trimethylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, barbituric acids such as 1-benzyl-5-phenylbarbituric acid, and di-n-octyltin dilaurate and di-n- It is a one-component adhesive composition that is an organic tin compound such as butyltin dilaurate.

The present invention is a photopolymerization in which the adhesive composition is excellent in photocurability in the visible and near-ultraviolet regions, and 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-component adhesive composition in which (bis) acylphosphine oxides and salts thereof, α-diketones, and coumarin compounds may be used in combination as initiators.

The present invention is a one-component adhesive composition in which the organic solvent of component (E) of the adhesive composition is acetone and ethyl alcohol.

In the present invention, the polymerization inhibitor added within the range in which the adhesive composition is essentially a heterogeneous solution at room temperature is hydroquinone monomethyl ether and butylated hydroxytoluene, and the filler is an ultrafine filler, fluorine sustained-release filler, It is a one-component adhesive composition that is a polymer and a silica filler.

In the present invention, the water-soluble film forming agent which does not contain an acidic group in the molecule, which the adhesive composition substantially does not contain, is 2-hydroxyethyl methacrylate and 2-hydroxy-1,3-dimethacryloyloxy. It is a one-component adhesive composition that is propane.

The present invention further provides a one-component adhesive composition that does not contain a sulfinate and an N-aromatic group-substituted glycine salt that can react with a radically polymerizable monomer having an acidic group in the molecule.

In the present invention, the water-soluble polymerization initiator contains 2,4,6-trimethylbenzoylphenylphosphine oxide sodium and 2-hydroxy-3- (3,4-dimethyl-9H-thioxanthen-2-yloxy) -N, This is a one-step one-component adhesive composition which is N, N-trimethyl-1-propaneaminium chloride.

As the radically polymerizable monomer having an acidic group in the molecule (A) of the one-part adhesive composition of the present invention, all the monomers conventionally used as dental adhesive monomers can be used. Have at least one phosphoric acid group such as a phosphoric acid ester group, a phosphonic acid group, and a pyrophosphoric acid group, a carboxyl group, an acid anhydride group of a carboxyl group, a sulfonic acid group, and the like, a (meth) acryloyl group and N- ( A radically polymerizable monomer containing a polymerizable group such as a (meth) acryloylamide group can be selected and used. As an abbreviation of the compound in the present invention, for example, methyl (meth) acrylate means methyl methacrylate and methyl acrylate.

Examples of the radical polymerizable monomer having a phosphate group such as a phosphate group, a phosphonate group, or a pyrophosphate group in the molecule of the present invention include 3- (meth) acryloxypropyl-3-phospho Nopropionate, 3- (meth) acryloxypropylphosphonoacetate, 4- (meth) acryloxybutyl-3-phosphonopropionate, 4- (meth) acryloxybutylphosphonoacetate, 5- (meta ) Acryloxypentyl-3-phosphonopropionate, 5- (meth) acryloxypentylphosphonoacetate, 6- (meth) acryloxyhexyl-3-phosphonopropionate, 6- (meth) acryloxyhexyl Phosphonoacetate, 10- (meth) acryloxydecyl-3-phosphonopropionate, 10- (meth) actone Roxydecylphosphonoacetate, bis [2- (meth) acryloxyethyl] hydrogen phosphate, 2- (meth) acryloyloxyethyl dihydrogen phosphate, 3- (meth) acryloyloxypropyl dihydrogen phosphate, 4- (Meth) acryloyloxybutyl dihydrogen phosphate, 5- (meth) acryloyloxypentyl dihydrogen phosphate, 6- (meth) acryloyloxyhexyl dihydrogen phosphate, 7- (meth) acryloyloxyheptyl dihydrogen phosphate, 8- (meth) acryloyloxyoctyl dihydrogen phosphate, 9- (meth) acryloyloxynonyl dihydrogen phosphate, 10- (meth) acryloyl Xyldecyl 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) acryloyloxynonyl] hydrogen phosphate, di [10- (meth) acryloyloxydecyl] hydrogen phosphate, 2- ( (Meth) acryloyloxyethyl phenylphosphonate, 10- (meth) acryloyloxydecylphosphonic acid, vinylphosphonic acid, p-vinylbenzylphosphonic acid, JP-A-62-281885 2-methacryloyloxyethyl (4-methoxyphenyl) hydrogen phosphate, 2-methacryloyloxypropyl (4-methoxyphenyl) hydrogen phosphate, di [2- (meth) acryloyloxyethyl] pyrophosphate, Di [4- (meth) acryloyloxybutyl] pyrophosphate, di [6- (meth) acryloyloxyhexyl] pyrophosphate, di [8- (meth) acryloyloxyoctyl] pyrophosphate, di [10- (meta ) Acryloyloxydecyl], N- (meth) acryloyl-ω-aminopropylphosphonic acid, and the like.

Examples of the radical polymerizable monomer having a carboxyl group and an acid anhydride group in the molecule of the present invention include methacrylic acid, 4- (meth) acryloxyethyl trimellitic acid, 4- (meth) acryloyloxyethoxy. Carbonylphthalic acid, 4- (meth) acryloyloxybutyloxycarbonylphthalic acid, 4- (meth) acryloyloxyhexyloxycarbonylphthalic acid, 4- (meth) acryloyloxyoctyloxycarbonylphthalic acid, 4- (meth) acryloyloxy Decyloxycarbonylphthalic acid and anhydrides thereof, 2- (meth) acryloyloxyethylmaleic acid, 5- (meth) acryloylaminopentylcarboxylic acid, 6- (meth) acryloyloxy-1,1-hexanedicarboxylic acid , 7- (Meta) Ac Royloxy-1,1-heptanedicarboxylic acid, 8- (meth) acryloyloxy-1,1-octanedicarboxylic acid, 10- (meth) acryloyloxy-1,1-decanedicarboxylic acid, 11- (meth) acryloyloxy- Examples include N- (meth) acryloyl amino acids such as 1,1-undecanedicarboxylic acid, N- (meth) acryloylalanine, N- (meth) acryloylglycine, N- (meth) acryloylaspartic acid, and the like.

Examples of the radical polymerizable monomer having a sulfonic acid group in the molecule of the present invention include styrene sulfonic acid, 2-sulfoethyl (meth) acrylate, 6-sulfohexyl (meth) acrylate, and 10-sulfodecyl (meth) acrylate. , 2- (meth) acrylamide-2-methylpropanesulfonic acid and the like.

These radically polymerizable monomers having an acidic group in the molecule are used alone or in appropriate combination. Among them, 6- (meth) acryloxyhexyl-3-phosphonoacetate, 6- (meth) acrylic acid are used. Roxyhexyl-3-phosphonopropionate, 10- (meth) acryloxydecyl hydrogen phosphate, 4- (meth) acryloxyethyl trimellitic acid, 4- (meth) acryloxyethyl trimellitic anhydride, etc. Is preferred.

One or more radically polymerizable monomers having an acidic group in these molecules can be arbitrarily selected and used, and the one-part adhesive composition of the present invention can be used in combination within the range of a heterogeneous solution. The compounding amount of the radical polymerizable monomer having an acidic group in the molecule is 1% by weight to 80% by weight, preferably 3%, based on the total amount of the one-component adhesive composition of the present invention. % By weight to 60% by weight, particularly preferably 5% by weight to 30% by weight. If it is less than 1% by weight or more than 80% by weight, the adhesiveness is lowered.

The radically polymerizable monomer that does not contain an acidic group in the molecule (B) of the one-component adhesive composition of the present invention is an aliphatic and aromatic monofunctional or polyfunctional that does not contain an acidic group in the molecule. It is a radically polymerizable monomer and can be selected from monomers, oligomers and prepolymers having radically polymerizable unsaturated double bonds used in the dental field and general industry. Moreover, the polymerizable monomer which has a sulfur atom in a molecule | numerator, the polymerizable monomer which has a fluoroalkyl group in a molecule | numerator, and the radically polymerizable monomer containing the functional group which has a fluorine ion discharge | release capability can also be used.

Specific examples of the radical polymerizable monomer that does not contain an acidic group in the molecule of the one-part adhesive composition of the present invention include methyl (meth) acrylate, ethyl (meth) acrylate, styrene, and 5-hydroxy. Pentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 3- (meth) acryloyloxyhexyltriethoxysilane, 10- (meth) acryloyloxypropylmethoxysilane, 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 Cold di (meth) acrylate, triethylene glycol di (meth) acrylate, dipentaerythritol di (meth) acrylate, 1,6-hexanedi (meth) acrylate, 1,10-decanediol di (meth) acrylate, pentaerythritol tetra ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, 1,7-diaacryloyloxy-2,2,6,6-tetraacryloyloxy Methyl-4-oxyheptane N, N ′-(2,2,4-trimethylhexamethylene) bis [2- (aminocarboxy) propane-1,3-diol] tetramethacrylate, and urethane tetramethacrylates 2: 1 addition reaction product of 1,3-dimethacryloyloxy-2-hydroxypropane and 2,2,4-trimethyl diisocyanate, 6- (meth) acryloyloxyhexyl 6,8-dithiooctanoate, 10- (meta ) Acrylyloxydecyl 6,8-dithiooctanoate and the like.

The radical polymerizable monomer having a fluoroalkyl group composed of at least one fluorocarbon of the present invention has one or more polymerizable groups such as a methacryloyl group, an acryloyl group, a vinyl group or a vinylbenzyl group (meth). An acrylate compound can be used, and examples thereof include compounds described in JP-A-2003-095838 and compounds described in JP-A-2003-105272.

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.

These radically polymerizable monomers that do not contain an acidic group in the molecule are used singly or in appropriate combination, but 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 and the like are particularly preferable.

These radically polymerizable monomers that do not contain an acidic group in the molecule may be used alone or in combination of two or more compounds, and the one-component adhesive composition of the present invention is a heterogeneous solution. Can be used in combination. The blending amount of the radical polymerizable monomer not containing these acidic groups is 5% by weight to 80% by weight with respect to the total amount of the radical polymerizable monomer of the one-part adhesive composition of the present invention. It is preferably 10% by weight to 70% by weight, and particularly preferably 15% by weight to 50% by weight. If it is less than 5% by weight or more than 80% by weight, the adhesiveness is lowered.

The (C) photopolymerization initiator contained in the one-component adhesive composition of the present invention is a photopolymerization initiator used in the dental field and general industry, for example, α-diketones, (bis) One or more selected from acylphosphine oxides, coumarin compounds, thioxanthone derivatives and the like can be used.

Examples of the α-diketone contained in the photopolymerization initiator of the present invention include diacetyl, benzyl, 4,4′-dimethoxybenzyl, 4,4′-dimethoxybenzyl, 4,4′-oxybenzyl, and 4,4. '-Chlorobenzyl, D, L-camphorquinone, 2,3-pentadione, 2,3-octadione, 9,10-phenanthrenequinone, acenaphthenequinone and the like can be mentioned. Is preferred.

Examples of the acylphosphine oxides (bis) acylphosphine oxides contained in the photopolymerization initiator of the present invention include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 2,6-dimethoxybenzoyldiphenylphosphine oxide. 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine Examples thereof include 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.

These (bis) acylphosphine oxides are 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, and bis (2,4,6-trimethylbenzoyl). Acylphosphine oxide is particularly preferred.

As the photopolymerization initiator of the present invention, water-soluble acylphosphine oxides may be added and used within the range where the one-component adhesive composition of the present invention becomes a heterogeneous solution. Examples of water-soluble acyl phosphine oxides include those having an alkali metal ion, an alkaline earth metal ion, a pyridinium ion, or an ammonium ion in the acyl phosphine oxide molecule. And water-soluble acylphosphine oxides disclosed in JP-A-0009348 or JP-A-57-197286. Specifically, 2,4,6-trimethylbenzoylphenylphosphine oxide sodium salt, 2,4,6-trimethylbenzoylphenylphosphine oxide potassium salt, 2,4,6-trimethylbenzoylphenylphosphine oxide ammonium salt Etc. Furthermore, water-soluble acyl phosphine oxides described in JP-A No. 2000-159621 are also included.

Examples of the coumarin compound contained in the photopolymerization initiator of the present invention include 3,3'-carbonylbis (7-diethylaminocoumarin) and 3,3'-carbonylbis (7-dibutylaminocoumarin).

Examples of the thioxanthone derivative contained in the photopolymerization initiator of the present invention include 2-chlorothioxanthen-9-one and 2-hydroxy-3- (3,4-dimethyl-9H-thioxanthen-2-yloxy). -N, N, N-trimethyl-1-propanaminium chloride.

As the photopolymerization initiator of the present invention, anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 1-bromoanthraquinone, 1,2-benzanthraquinone, 1-methylanthraquinone, 2-ethylanthraquinone, 1-hydroxyanthraquinone, etc. Anthraquinones, and benzoin alkyl ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropane-1- Α-amino ketones such as ON may be appropriately selected and added.

These photopolymerization initiators may be used alone or in combination of two or more compounds. The blending amount of these photopolymerization initiators is 0.01% by weight to 10% by weight with respect to the total amount of radically polymerizable monomers of the one-component adhesive composition of the present invention, preferably It is 0.1 to 5% by weight, particularly preferably 0.2 to 3% by weight. If it is 0.01% by weight, curing is insufficient, and if it exceeds 10% by weight, the adhesiveness is lowered.

As the polymerization accelerator used in combination with the photopolymerization initiator contained in the one-component adhesive composition of the present invention as needed, compounds conventionally used as a photopolymerization accelerator or a room temperature polymerization accelerator can be used. However, aromatic amines, aliphatic amines, barbituric acids, and organotin compounds are particularly suitable.

As an aromatic amine of a polymerization accelerator used in combination with the photopolymerization initiator of the present invention, for example, 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, N, N-bis (2-hydroxyethyl)- 3,5-dimethylaniline, N, N-di (2-hydroxyethyl) -p-toluidine, N, N-bis (2-hydroxyethyl) -3,4-dimethylaniline, N, N-bis (2- Hide Xylethyl) -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, methyl 4-dimethylaminobenzoate, 4-dimethylamino Ethyl benzoate, n-butoxyethyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate (2-methacryloyloxy), dimethylamyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4-dimethylamino Examples include benzophenone and butyl 4-dimethylaminobenzoate.

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

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

Examples of the polymerization accelerator used in combination with the photopolymerization initiator of the present invention include bibutyl acid, 5-butyl barbituric acid, 1,3,5-trimethylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, and 1-benzyl-5-phenylbarbituric acid, and the like include 5-butylbarbituric acid, 1,3,5-trimethylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, 1-benzyl-5 Barbituric acids such as phenyl barbituric acid are particularly preferred.

Examples of the organic tin compound as a polymerization accelerator used in combination with the photopolymerization initiator of the present invention include di-n-butyltin dimaleate, di-n-octyltin dimaleate, di-n-octyltin dilaurate, and di-n-butyl. Tin dilaurate and the like can be mentioned, and di-n-octyltin dilaurate and di-n-butyltin dilaurate are particularly suitable.

The present invention is a photopolymerization in which the adhesive composition is excellent in photocurability in the visible and near-ultraviolet regions, and 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-component adhesive composition in which (bis) acylphosphine oxides and salts thereof, α-diketones, and coumarin compounds may be used in combination as initiators.

These polymerization accelerators may be used alone or in combination of two or more compounds. The blending amount of these polymerization accelerators is 0.01% by weight to 20% by weight, preferably 0%, based on the total amount of radical polymerizable monomers of the one-component adhesive composition of the present invention. 0.1 wt% to 10 wt%, particularly preferably 0.2 wt% to 3 wt%. If it is less than 0.01% by weight, curing is insufficient, and if it exceeds 20% by weight, the adhesiveness is lowered.

The water (D) used in the one-component 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 promote the ion dissociation of the acid group of the radical polymerizable monomer having an acidic group in the molecule of the present invention, and can be expected to have an effect of enhancing the demineralization of the tooth and the penetration into the dentin. The blending amount is 3% by weight to 90% by weight, preferably 15% by weight to 70% by weight, particularly preferably 20% by weight, based on the total amount of the one-component adhesive composition of the present invention. % To 60% by weight. If it is less than 3% by weight or more than 90% by weight, the adhesiveness is lowered.

In the one-component adhesive composition of the present invention, the organic solvent as the component (E) can be added within a range where the adhesive composition is essentially a heterogeneous solution at room temperature. Organic solvents are water-soluble organic solvents and hydrophobic organic solvents, for example, alcohols such as ethanol, methanol, 1-propanol, isopropyl alcohol, ketones such as acetone, methyl ethyl ketone, pentanone, hexanone, ethyl acetate, methyl acetate Esters such as ethyl propionate, ethers such as 1,2-dimethoxyethane, 1,2-diethoxyethane and tetrahydrofuran, hydrocarbons such as heptane, hexane, octane and toluene, and halogenation such as chloroform and dichloromethane Hydrocarbons and the like are preferably used. Among these, acetone, ethanol, isopropyl alcohol and the like that can be applied to a living body 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 80% by weight, preferably 5% by weight to 60% by weight, particularly preferably, based on the total amount of the one-component adhesive composition of the present invention. Is 5 to 30% by weight. If it is less than 1% by weight or more than 80% by weight, the adhesiveness is lowered.

In order to adjust the mechanical strength, operability, applicability, and fluidity of the one-component adhesive composition of the present invention, a filler may be appropriately blended. Suitable fillers are ultrafine fillers, silica fillers, polymers, and pre-reactions described in the Applicant's Patent No. 3497508 (2003) and US Patent Application No. 08 / 892,766 (2000). Glass ionomer filler (= PRG filler: preformed glass ionomer filler = filler produced by drying a glass ionomer reaction gel produced by acid-base reaction in fluoroaluminosilicate glass, polyalkenoic acid and water). Moreover, you may use these fillers after surface-treating beforehand with well-known surface treating agents, such as a silane coupling agent, as needed. Examples of such a surface treatment agent include vinyltrichlorosilane, γ-methacryloyloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and the like.

Among these fillers, ultrafine particle fillers, fluorine sustained-release fillers, polymers and silica fillers are particularly suitable.

Examples of the polymerization inhibitor contained for stabilizing the shelf life of the one-component adhesive composition of the present invention include hydroquinone, hydroquinone monomethyl ether, butylated hydroxytoluene, and the like. Hydroquinone monomethyl ether and butylated hydroxytoluene Is suitable.

Depending on the purpose of use of the one-component adhesive composition of the present invention, a modifier, a thickener, a dye, a pigment, a polymerization regulator, and the like may be appropriately blended.

The one-component adhesive composition of the present invention can be used as a one-component one-step type bonding agent as an embodiment, but one paste adhesive low-viscosity composite resin, one paste adhesive composite You may use for resin cement, a fisher sealant, an orthodontic adhesive, a teeth coating agent, an opaque agent, etc.

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.

Abbreviations of the compounds used in the examples of the present invention are shown below.
6-MHPA: 6-methacryloxyhexylphosphonoacetate 6-MHPP: 6-methacryloxyhexyl-3-phosphonopropionate 4-MET: 4-methacryloxyethyl trimellitic acid 4-META: 4-methacryloxyethyl Trimellitic anhydride 4-AET: 4-acryloxyethyl trimellitic acid 4-AETA: 4-acryloxyethyl trimellitic anhydride Bis-GMA: bisphenol A-diglycidyl methacrylate,
UDMA: dimethacryloxyethyl-2,2,4-trimethylhexamethylene diurethane TEGDMA: triethylene glycol dimethacrylate HEMA: 2-hydroxyethyl methacrylate GDMA: 2-hydroxy-1,3-dimethacryloyloxypropane CQ: camphorquinone TBPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide BTBPO: bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide 4-MABE: ethyl 4-dimethylaminobenzoate BPBA: 1-benzyl-5-phenylbarbi Tool acid TMBA: 1,3,5-trimethylbarbituric acid Butyl-Tin: di-n-butyltin dilaurate NPG-Na: N-phenylglycine sodium p-TSNa: p Toluene sulfinic acid sodium R-972: ultrafine silica filler (average particle size: 0.18 .mu.m)
OX-50: Ultrafine silica filler (average particle size: 0.4 μm)
PRG filler: preformed glass ionomer filler = filler produced by drying glass ionomer reaction gel produced by acid-base reaction of fluoroaluminosilicate glass, polyalkenoic acid and water in water MeHQ: hydroquinone monomethyl ether BHT: butylated hydroxytoluene

Examples 1-6 and Comparative Examples 1-3
In carrying out the one-component adhesive composition of the present invention in the form of a one-step one-component dental bonding agent, among the radical polymerizable monomers, (A) a radical polymerizable monomer having a phosphate group 6-MHPA and 6-MHPP as a body, 4-MET as a radical polymerizable monomer having a carboxyl group in the molecule, 4-META as a radical polymerizable monomer having a carboxyl group anhydride in the molecule, ( B) Bis-GMA, UDMA, and TEGDMA as radical polymerizable monomers that do not contain an acidic group in the molecule, (C) CQ as a photopolymerization initiator, 4-MABE as a photopolymerization accelerator, (D) as water Distilled water, (E) acetone as an organic solvent, HEMA as a water-soluble film forming agent, and MeHQ as a polymerization inhibitor in all compositions And 1000ppm added to the body the total amount, was prepared by mixing the compositions shown in Table 1. Here, the liquid was prepared by measuring the required amount of each component in Table 1 in a dark room and mixing with a mixer. A compound having low solubility was prepared by mixing in a composition liquid containing components other than water and, if necessary, leaving it in a constant temperature bath at 40 to 50 ° C. for 5 to 24 hours, followed by mixing with a mixer.

[Properties of the mixed solution]
After mixing and preparing the solution, the one-component adhesive composition was put in a glass bottle, and the property of the mixed solution was visually judged with an infrared lamp in a dark room. The whole solution was judged to be non-uniform except for a uniform and transparent liquid. When the filler was included, the determination was made based on the properties of the liquid before mixing the filler.

[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. The polished tooth surface was dried with compressed air containing no oil, and a double-sided tape with a hole having a diameter of 4 mm was attached thereto to define an adhesive surface. Next, after a bottle containing the one-component one-step dental one-component adhesive composition is lightly shaken, it is dropped on the eye plate, applied to the adhesion regulating surface with a microbrush, and then treated to rub for 10 seconds. Then, weak compressed air without oil was blown for 5 seconds to evaporate volatile components, and the bonding agent was spread thinly on the tooth surface. Subsequently, the sample was irradiated for 10 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 frame, and a photopolymerizable composite resin “Beauty Fill” [manufactured by Matsukaze Co., Ltd.] was filled in the mold. Next, air was shut off with a cover glass, and light irradiation was performed with a pine wind grip light II for 30 seconds to photocur the composite resin, and then the mold was removed to prepare an adhesion test body. After immersion in distilled water at 37 ° C. for 24 hours, the specimen is set on a jig for shear bond strength and shear bonded at a crosshead speed of 1 mm / min using an Instron universal testing machine (Instron 5567, Instron). The strength was measured and the average value of n = 5 was obtained. Table 1 shows the composition of the one-step photopolymerization type bonding agent and the result of the adhesion test.

（注）：単位：重量部、Ａ：分子内に酸性基を有するラジカル重合性単量体、Ｂ：分子内に酸性基を含有しないラジカル重合性単量体、Ｃ：光重合開始剤、Ｄ：水、Ｅ：有機溶剤

(Note): Unit: part by weight, A: radical polymerizable monomer having an acidic group in the molecule, B: radical polymerizable monomer having no acidic group in the molecule, C: photopolymerization initiator, D : Water, E: Organic solvent

As is apparent from the results in Table 1, (A) the radical polymerizable monomer having an acidic group in the molecule, (B) the radical polymerizable monomer having no acidic group in the molecule, (C In the one-step one-part photopolymerization type bonding agent comprising a photopolymerization initiator, (D) water, and (E) an organic solvent, the mixed solutions are all “heterogeneous solutions” and can be easily operated with enamel. And strong bond strength to dentin. On the other hand, in the case of a “homogeneous solution” consisting of (A), (B), (C) and (E) and not containing water as component (D) (Comparative Example 1), and (A), (B ), (C), (D), and the “homogeneous solution” with the water-soluble film former 2-hydroxyethyl methacrylate (HEMA) (Comparative Examples 2 and 3) has significantly lower tooth adhesion strength. Indicated.

Examples 7-12 and Comparative Examples 4-6
The one-component adhesive composition of the present invention was implemented in the form of a one-step one-component dental bonding agent. Radical polymerizable monomer having an acidic group in the molecule, radical polymerizable monomer not containing an acidic group in the molecule, photopolymerization initiator, water, acetone, ultrafine filler (Aerosil R-972: Nippon Aerosil Co., Ltd.) Made of water-soluble film forming agent HEMA, and water-soluble reducing agents N-phenylglycine sodium (NPG-Na) and sodium p-toluenesulfinate (p-TSNa). As a polymerization inhibitor, MeHQ was added at 1000 ppm with respect to the total amount of radical polymerizable monomers, and mixed in the composition shown in Table 2 according to Example 1 to prepare a one-part adhesive composition, and an adhesion test was conducted. went. The properties of the mixed solution were determined according to Example 1. The results are shown in Table 2.

（注）：単位：重量部、Ａ：分子内に酸性基を有するラジカル重合性単量体、Ｂ：分子内に酸性基を含有しないラジカル重合性単量体、Ｃ：光重合開始剤、Ｄ：水、Ｅ：有機溶剤および微粒子フィラー

(Note): Unit: part by weight, A: radical polymerizable monomer having an acidic group in the molecule, B: radical polymerizable monomer having no acidic group in the molecule, C: photopolymerization initiator, D : Water, E: Organic solvent and fine particle filler

As is apparent from the results of Table 2, the radical polymerizable monomer having an acidic group in the molecule of the present invention, the radical polymerizable monomer having no acidic group in the molecule, a photopolymerization initiator, and water. A one-step one-part photopolymerization type bonding agent consisting of a “heterogeneous solution” containing a fine particle filler and / or an organic solvent exhibits high adhesion strength to enamel and dentin with a simple operation. It was. On the other hand, these radical polymerizable monomers, a polymerization initiator, water and an organic solvent, which is a “heterogeneous solution” but having a water-soluble film forming agent HEMA (Comparative Example 4), and “nonuniform "Solution" but without an organic solvent and having water-soluble reducing agent N-phenylglycine sodium (NPG-Na) (Comparative Example 5), or "Homogeneous solution" and water-soluble reducing agent In the case of containing sodium p-toluenesulfinate (p-TSNa) (Comparative Example 5), the tooth adhesion strength was remarkably low. Further, the mixed solution containing NPG-Na and p-TSNa, which are water-soluble reducing agents, showed a significant increase in viscosity within 7 days after preparation.

Examples 13-19
The composition shown in Table 3 was prepared using the one-component adhesive composition of the present invention as a one-step one-component photopolymerizable bonding agent, and an adhesion test was conducted in accordance with Example 1. The properties of the mixed solution were determined according to Example 1. The results are shown in Table 3.

（注）：単位：重量部、Ａ：分子内に酸性基を有するラジカル重合性単量体、Ｂ：分子内に酸性基を含有しないラジカル重合性単量体、Ｃ：光重合開始剤、Ｄ：水、Ｅ：有機溶剤

(Note): Unit: part by weight, A: radical polymerizable monomer having an acidic group in the molecule, B: radical polymerizable monomer having no acidic group in the molecule, C: photopolymerization initiator, D : Water, E: Organic solvent

As is apparent from the results of Table 3, a radical polymerizable monomer having an acidic group in the molecule, a radical polymerizable monomer having no acidic group in the molecule, a polymerization initiator, water, and an organic solvent are included. In the one-component adhesive composition of the present invention (Examples 14 to 20), since it does not have a water-soluble film forming agent or a water-soluble reducing agent, and all the mixed solutions are “heterogeneous solutions”, Showed a strong bond strength to enamel and dentin.

Examples 20-26
Using the one-part adhesive composition of the present invention as a one-step one-part photopolymerizable bonding agent, the compositions shown in Table 4 were prepared according to Example 1, and adhered according to Example 1. A test was conducted. The properties of the mixed solution were determined according to Example 1. The results are shown in Table 4.

（注）：単位：重量部、Ａ：分子内に酸性基を有するラジカル重合性単量体、Ｂ：分子内に酸性基を含有しないラジカル重合性単量体、Ｃ：光重合開始剤、Ｄ：水、Ｅ：有機溶剤および微粒子フィラー

(Note): Unit: part by weight, A: radical polymerizable monomer having an acidic group in the molecule, B: radical polymerizable monomer having no acidic group in the molecule, C: photopolymerization initiator, D : Water, E: Organic solvent and fine particle filler

Examples 27 to 32 and Comparative Example 7
Using the one-component adhesive composition of the present invention as a one-step one-component photopolymerizable bonding agent, the compositions shown in Table 5 were prepared according to Example 1 and adhered according to Example 1. A test was conducted. As the polymerization inhibitor, 1500 ppm of MeHQ was added. The properties of the mixed solution were determined according to Example 1. The results are shown in Table 5.

（注）：単位：重量部、Ａ：分子内に酸性基を有するラジカル重合性単量体、Ｂ：分子内に酸性基を含有しないラジカル重合性単量体、Ｃ：光重合開始剤、Ｄ：水、Ｅ：有機溶剤および微粒子フィラー

(Note): Unit: part by weight, A: radical polymerizable monomer having an acidic group in the molecule, B: radical polymerizable monomer having no acidic group in the molecule, C: photopolymerization initiator, D : Water, E: Organic solvent and fine particle filler

Examples 34 to 40 and Comparative Examples 7 to 8
In examining the one-component adhesive composition of the present invention in the form of a one-step one-component photopolymerizable bonding agent, the compositions shown in Table 6 were prepared according to Example 1, and the Examples The adhesion test was conducted according to 1. As a polymerization inhibitor, 1500 ppm of butylated hydroxytoluene (BHT) was added. The properties of the mixed solution were determined according to Example 1. The results are shown in Table 6.

（注）：単位：重量部、Ａ：分子内に酸性基を有するラジカル重合性単量体、Ｂ：分子内に酸性基を含有しないラジカル重合性単量体、Ｃ：光重合開始剤、Ｄ：水、Ｅ：有機溶剤および微粒子フィラー

(Note): Unit: part by weight, A: radical polymerizable monomer having an acidic group in the molecule, B: radical polymerizable monomer having no acidic group in the molecule, C: photopolymerization initiator, D : Water, E: Organic solvent and fine particle filler

As is apparent from the results in Table 6, it consists of a radical polymerizable monomer having an acidic group in the molecule, a radical polymerizable monomer having no acidic group in the molecule, a polymerization initiator, water, and an organic solvent. The one-step one-component photopolymerizable bonding agent of the present invention, which is a heterogeneous solution, showed a stable and high adhesive strength to enamel and dentin. On the other hand, a water-soluble film comprising 2-hydroxyethyl methacrylate and 2-hydroxy-1,3-dimethacryloyloxypropane, comprising a radical polymerizable monomer, a polymerization initiator, water, an organic solvent and a fine particle filler. Comparative Examples 7 and 8, which are “homogeneous solutions” containing a forming agent, showed insufficient adhesion strength when used as a one-step one-component bonding agent.

Examples 41-56 and Comparative Examples 9-12
Using the one-component adhesive composition of the present invention as a one-step one-component photopolymerizable bonding agent, the compositions shown in Table 7 were prepared according to Example 1 and adhered according to Example 1. A test was conducted. As a polymerization inhibitor, 1500 ppm of BHT was added. The properties of the mixed solution were determined according to Example 1. The results are shown in Table 7.

（注）：単位：重量部、Ａ：分子内に酸性基を有するラジカル重合性単量体、Ｂ：分子内に酸性基を含有しないラジカル重合性単量体、Ｃ：光重合開始剤、Ｄ：水、Ｅ：有機溶剤および微粒子フィラー、
ａ：６−ＭＨＰＡ、ｂ：６−ＭＨＰＰ、ｃ：４−ＭＥＴ、ｄ：Ｂｉｓ−ＧＭＡ／ＴＥＧＤＭＡ＝６０／４０（重量％）、ｅ：ＴＢＰＯ、ｆ：蒸留水、ｇ：アセトン、ｈ：アエロジルＲ−９７２

(Note): Unit: part by weight, A: radical polymerizable monomer having an acidic group in the molecule, B: radical polymerizable monomer having no acidic group in the molecule, C: photopolymerization initiator, D : Water, E: organic solvent and fine particle filler,
a: 6-MHPA, b: 6-MHPP, c: 4-MET, d: Bis-GMA / TEGDMA = 60/40 (% by weight), e: TBPO, f: distilled water, g: acetone, h: aerosil R-972

As is clear from the results of Table 7, Comparative Example 9 containing no water and no homogeneous solution, Comparative Example 10 containing a heterogeneous solution containing no organic solvent, and no radical polymerizable monomer having an acidic group in the molecule. Comparative Example 11 of heterogeneous solution, radical polymerizable monomer having acidic group in molecule, radical polymerizable monomer not containing acidic group in molecule, photopolymerization initiator, water, organic solvent and fine particle filler In Comparative Example 12 consisting of a uniform solution, the adhesive strength of the tooth was remarkably low. In contrast to these comparative examples, in the one-component one-step photopolymerization bonding agent comprising the radically polymerizable monomer, the polymerization initiator, and water of the present invention, and further an organic solvent and fine particle filler, It was a “solution” and showed high adhesion strength to enamel and dentin with a simple operation.

Examples 57-72
The dental one-part adhesive composition of the present invention was used in the form of a photopolymerizable bonding agent, and the compositions shown in Table 8 were prepared according to Example 1 and applied to the adhesion test method of Example 1. Similarly, the adhesion to the tooth was examined. As the polymerization inhibitor, 1500 ppm of MeHQ was added. The properties of the mixed solution were determined according to Example 1. The results are shown in Table 8.

（注）：単位：重量部、Ａ：分子内に酸性基を有するラジカル重合性単量体、Ｂ：分子内に酸性基を含有しないラジカル重合性単量体、Ｃ：光重合開始剤、Ｄ：水、Ｅ：有機溶剤および微粒子フィラー、ａ：６−ＭＨＰＡ、ｂ：４−ＭＥＴ、ｃ：Ｂｉｓ−ＧＭＡ／ＴＥＧＤＭＡ＝６０／４０（重量％）、ｄ：ＴＢＰＯ、ｅ：蒸留水、ｆ：アセトン、ｇ：アエロジルＲ−９７２

(Note): Unit: part by weight, A: radical polymerizable monomer having an acidic group in the molecule, B: radical polymerizable monomer having no acidic group in the molecule, C: photopolymerization initiator, D : Water, E: organic solvent and fine particle filler, a: 6-MHPA, b: 4-MET, c: Bis-GMA / TEGDMA = 60/40 (% by weight), d: TBPO, e: distilled water, f: Acetone, g: Aerosil R-972

Example 73
A one-component adhesive composition was prepared according to Example 1 by substituting Aerosil R-972 in the ultrafine particle filler of the composition of Example 12 with Aerosil OX-50. As the polymerization inhibitor, 1500 ppm of MeHQ was added. The property of the mixed solution was determined to be in accordance with Example 1 and was “non-uniform”. The adhesive composition was applied to an enamel or dentin adhesive surface according to Example 12 and then photopolymerized to perform an adhesion treatment. 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. Next, impregnating the dental resin cement Impervual [manufactured by Matsukaze Co., Ltd.] in accordance with the instructions, knead the powder and liquid material with a spatula, and interpose the kneaded mud as described above. A stainless steel rod was joined to the finished tooth surface, a load 2009 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 test specimen in 37 ° C. distilled water for 24 hours, 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 20.3 MPa, and the bond strength of the dentin-stainless steel rod was 19.6 MPa.

Example 74 and Comparative Example 13
Substituting Aerosil R-972 of the ultrafine particle filler of the composition of Example 12 with Aerosil OX-50, and further adding 1 part by weight of PRG filler (= preformed glass ionomer filler: particle size 5 μm), one-component adhesion An agent composition was prepared according to Example 1. As the polymerization inhibitor, 1500 ppm of MeHQ was added. The property of the mixed solution was determined to be in accordance with Example 1 and was “non-uniform”. Using the adhesive composition, an adhesion test to enamel and dentin was conducted according to Example 12. On the other hand, as a comparison, an adhesion test was performed using a two-step dental adhesive “Impervafluorobond” [manufactured by Matsukaze Co., Ltd.] according to the instruction manual.
As a result, Impervafluorobond has two steps consisting of a two-component self-etching plummer treatment and a photopolymerization bonding agent, so that the operation is complicated and the tooth surface treatment time is 45 seconds. In the one-part adhesive composition of No. 1, the operation was extremely simple and the tooth surface treatment time was shortened to 26 seconds in one part per step. In addition, the Impervafluorobond showed an enamel bond strength of 17.4 MPa and a dentin bond strength of 20.1 MPa. In contrast, the one-component adhesive composition of the present invention has an enamel bond strength of 21.5 MPa and a dentin bond strength of 20.3 MPa, in addition to the simple operability of one liquid one step. Strong adhesion strength equal to or better than that of 2-step bond was exhibited.

The invention's effect

As described above, the one-component adhesive composition of the present invention is a one-component adhesive composition consisting essentially of a heterogeneous solution at room temperature, and its constituent components have acidic groups in the molecule. It consists of a radically polymerizable monomer, a radically polymerizable monomer that does not contain an acidic group in the molecule, a photopolymerization initiator, water, and an organic solvent. An acidic group is added to the one-component adhesive composition in the molecule. It is characterized in that it contains substantially no water-soluble film-forming agent. As a result, the one-component adhesive composition of the present invention has three functions (all-in-one) of etching, priming, and bonding, so that it can be used for dental composite resins, compomers, etc. when treating dental caries. Without applying etching treatment or primer treatment to the enamel and dentin of the tooth when the dental restorative material is bonded, or to the abutment tooth when the crown is bonded and repaired with resin cement, 1 Even in step processing, it is possible to simplify adhesion treatment operability without mixing two or more types as in the past, or by having some of the constituent components in an applicator or the like to perform mixing operations. Because both the dental restoration material and the dental restoration material can be firmly bonded and held for a long time, the treatment time of the dentist can be shortened and speedy treatment is possible. And then, simultaneously to the storage of the treatment and the patient's teeth caries and more reliable, it can contribute greatly to dentistry, but valuable as a dental adhesive. As described above, the one-component adhesive composition of the present invention exhibits strong adhesiveness with a dental hard tissue or a bone hard tissue by a simple operation of one step. It can be applied in the field of dentistry and orthopedics.

It can be used not only in the dental field and orthopedics but also in general industrial fields such as adhesives, paints and lacquers.

Claims (2)

In the adhesive agent composition having the three functions of etching, priming and bonding in the adhesion between the tooth substance and the dental restorative material,
The constituent components are (A) a radical polymerizable monomer having an acidic group in the molecule, (B) a radical polymerizable monomer not containing an acidic group in the molecule, (C) a photopolymerization initiator, and (D) water. , (E) consisting only of organic solvent,
(A) The radical polymerizable monomer having an acidic group in the molecule is 6- (meth) acryloxyhexyl-3-phosphonoacetate, 6- (meth) acryloxyhexyl-3-phosphonopropionate, 10 -Containing one or more of (meth) acryloxydecyl hydrogen phosphate, 4- (meth) acryloxyethyl trimellitic acid, 4- (meth) acryloxyethyl trimellitic anhydride,
(B) A radical polymerizable monomer that does not contain an acidic group in the molecule is 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, Including one or more of di (meth) acryloxyethyl-2,2,4-trimethylhexamethylenediurethane,
(C) the photopolymerization initiator is arbitrarily selected from one or more of α-diketones, (bis) acylphosphine oxides, coumarin compounds, and thioxanthone derivatives,
(E) the organic solvent contains one or more of acetone, ethanol, isopropyl alcohol,
(A) The radically polymerizable monomer having an acidic group in the molecule is 5% by weight to 30% by weight with respect to the total amount of the adhesive composition,
(B) The radically polymerizable monomer containing no acidic group in the molecule is 15% by weight to 50% by weight with respect to the total amount of the radically polymerizable monomer,
(C) 0.01% by weight to 10% by weight of the photopolymerization initiator based on the total amount of the radical polymerizable monomer, and 0.01% by weight of the polymerization accelerator based on the total amount of the radical polymerizable monomer. % To 20% by weight,
(D) 15% to 70% by weight of water based on the total amount of the adhesive composition;
(E) The dental adhesive composition, wherein the organic solvent is 5% by weight to 60% by weight with respect to the total amount of the adhesive composition. The dental adhesive composition according to claim 1.
A dental adhesive composition, wherein the polymerization accelerator contains one or more of aromatic amines, aliphatic amines, barbituric acids, and organotin compounds.