JP2000212015A - Adhesive system - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a dental adhesive system capable of photocuring not only bonding composition but also a primer composition simultaneously in a short time firmly, having extremely excellent adhesiveness to dentine. SOLUTION: This dental adhesive system characteristically comprises a primer composition composed of (a) an acidic group-containing polymerizable monomer, (b) a hydroxyl group-containing polymerizable monomer and (c) water and a bonding composition composed of (d) a polymer monomer, (e) an acylphosphine oxide compound as a photopolymerization initiator and (f) an α-diketone compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a dental adhesive system. More specifically, the present invention relates to a dental adhesive system comprising a primer composition and a bonding composition used for obtaining a high adhesive strength between a filling material and a tooth material during filling restoration in dental treatment.

[0002]

2. Description of the Related Art For restoring tooth material damaged by dental caries or the like, a filling restoration material called a filling composite resin or a filling compomer is usually used. For this reason, conventionally, the tooth surface has been treated with a strong acid etching agent such as phosphoric acid, and then a bonding material has been applied to adhere the tooth material to the filling material. However, such a treatment method using an acid etching agent has a drawback in that a water washing operation is required to sufficiently remove the acid after the treatment, and the operation such as drying again is complicated. Further, it is said that an adhesive system using an acid etching agent has excellent adhesive strength to enamel, but it is difficult to obtain high adhesive strength to dentin.

As a countermeasure, Japanese Patent Application Laid-Open No. 62-22328
No. 9, JP-A-3-240712 discloses that after a tooth composition is treated with a primer composition comprising an acid or an acidic monomer and a hydrophilic monomer instead of an acid etching agent, the bonding material is not washed with water. An adhesive system using a so-called self-etching type primer has been proposed, and the simplification of the bonding operation has been attempted. However, such a self-etching type primer that does not require a water washing operation, although most of the solvent such as water is removed by drying with a dental air syringe after coating, the polymerizable monomer in the primer component is removed. The component remains more in the surface layer of the tooth. The remaining monomer is then polymerized and cured by light irradiation simultaneously with the bonding material coated thereon, but the primer component contains many poorly polymerizable monomers such as hydrophilic monomers and acidic monomers. Therefore, polymerization cannot be driven instantaneously. Therefore,
Attempts have been made to improve the polymerizability by adding a photopolymerization initiator to the primer, but no effect has been obtained at present. As a result, the polymerization of the polymerizable monomer of the bonding material (including the primer) applied to the tooth surface becomes insufficient, and after a fixed period of time after the restoration, a gap between the tooth material and the restoration material is formed, and the side surface is damaged. Problems such as edge leaks and loss of restorations have often been pointed out. In particular, it is said that such inconvenience often occurs when the light irradiation time is short when the bonding material is irradiated with light.

[0004] In order to improve the polymerization curability of the primer composition and the bonding composition, a certain improvement can be achieved by increasing the blending amount of the photopolymerization initiator in each composition. However, when the amount of the photopolymerization initiator is extremely increased, since the initiator itself does not have a polymerizable group, not only the amount of the polymerization initiator component remaining from the cured product of each composition leaks but also the cured product becomes larger. This is not practical because there are problems such as a decrease in the mechanical strength of the cured product and the discoloration of the cured product over time, making it impossible to perform aesthetic restoration of the crown.

[0005]

The problem to be solved by the present invention is that not only the bonding composition but also the primer composition can be simultaneously and strongly photo-cured in a short period of time, and the adhesiveness to the tooth is reduced. An object of the present invention is to provide a new dental adhesive system which is extremely excellent.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to solve the above technical problems, and as a result, have found that a self-etching type primer composition in which an acidic monomer and a hydrophilic monomer are dissolved in water; In an adhesive system comprising a bonding composition used in combination therewith, a bonding composition containing both a photopolymerization initiator of an acylphosphine oxide compound and an α-diketone compound improves the photocurability of the adhesive system. It has been found that the adhesion durability in water can be improved thereby. Even more surprisingly, the bonding composition containing both the photoinitiator of the acylphosphine oxide compound and the α-diketone compound can be used even if the previously applied primer composition does not contain a polymerization initiator. It has been found that both the primer composition and the bonding composition are hardened firmly in a short period of time, and a high adhesive strength to the tooth material is obtained, and that the adhesive durability is further improved, thereby completing the present invention. Reached.

That is, the present invention provides a primer composition comprising (a) a polymerizable monomer having an acidic group, (b) a polymerizable monomer having a hydroxyl group, and (c) water; A dental adhesive system comprising a bonding composition containing a polymerizable monomer, (e) an acylphosphine oxide compound as a photopolymerization initiator, and (f) an α-diketone compound. .

[0008] In the present invention, the polymerizable monomer having an acidic group used in the primer composition is blended for the purpose of ensuring adhesiveness to the dentin and the restoration.
Acidic groups such as phosphoric acid residues, pyrophosphoric acid residues, thiophosphoric acid residues, carboxylic acid residues or sulfonic acid residues, and polymerizable unsaturated groups such as acryloyl, methacryloyl, vinyl and styrene groups. The following are specific examples of the polymerizable monomer. In the present invention, both (meth) acryl and acryl are comprehensively represented by (meth) acryl.

Examples of the polymerizable monomer having a phosphoric acid residue include 2- (meth) acryloyloxyethyl dihydrogen phosphate, 4- (meth) acryloyloxybutyl dihydrogen phosphate,
(Meth) acryloyloxyhexyl dihydrogen phosphate, 8- (meth) acryloyloxyoctyl dihydrogen phosphate, 9- (meth) acryloyloxynonyl dihydrogen phosphate,
0- (meth) acryloyloxydecyl dihydrogen phosphate, 11- (meth) acryloyloxyundecyl dihydrogen phosphate, 12- (meth) acryloyloxydecyl dihydrogen phosphate, 20- (meth) acryloyloxy eicosyldi Hydrogen phosphate, 1,3-di (meth)
Acryloyloxypropyl-2-dihydrogenphosphate, 2- (meth) acryloyloxyethylphenylhydrogenphosphate, 2- (meth) acryloyloxyethyl 2′-bromoethylhydrogenphosphate, (meth) acryloyloxyethylphenylphosphonate, etc. , And their acid chlorides.

[0010] Examples of the polymerizable monomer having a pyrophosphate residue include di (2- (meth) acryloyloxyethyl) pyrophosphate and the like, and acid chlorides thereof.
Examples of the polymerizable monomer having a thiophosphoric acid residue include 2- (meth) acryloyloxyethyl dihydrogen dithiophosphate, 10- (meth) acryloyloxydecyl dihydrogen thiophosphate, and the like.
And their acid chlorides.

Examples of the polymerizable monomer having a carboxylic acid residue include maleic acid, maleic anhydride,
(Meth) acryloyloxyethoxycarbonylphthalic acid, 4- (meth) acryloyloxyethoxycarbonylphthalic anhydride, 5- (meth) acryloylaminopentylcarboxylic acid, N- (meth) acryloyl-5-aminosalicylic acid, 11- ( (Meth) acryloyloxy-
1,1-undecanedicarboxylic acid and the like and their acid chlorides.

Examples of the polymerizable monomer having a sulfonic acid residue include sulfonic acid groups such as 2- (meth) acrylamido-2-methylpropanesulfonic acid, styrenesulfonic acid and 2-sulfoethyl (meth) acrylate. Compounds contained therein can be exemplified. Among them, when a polymerizable monomer having a phosphate group is blended into the primer composition, a higher adhesive strength to teeth is obtained as compared with a case where a polymerizable monomer having another acidic group is blended. ,
A polymerizable monomer having a phosphate group is preferably used. These polymerizable monomers having an acidic group are used singly or in combination. The mixing amount of these acidic monomers is usually from 0.1% by weight to the entire primer composition.
It is used in the range of 80% by weight, preferably in the range of 1% to 50% by weight, more preferably in the range of 5% to 30% by weight.

In the present invention, the polymerizable monomer having a hydroxyl group used in the primer composition includes a polymerizable monomer having a hydroxyl group and a polymerizable unsaturated group such as an acryloyl group, a methacryloyl group, a vinyl group or a styrene group. It is a monomer, an oligomer or a polymer, and among them, a monomer is particularly preferred. Compounds of this type include, for example, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and 10-hydroxydecyl (meth) ) Acrylate, propylene glycol mono (meth) acrylate, glycerin mono (meth) acrylate, glycerin-1,3-di (meth) acrylate, erythritol mono (meth) acrylate, pentaerythritol di (meth) acrylate, 1,2-bis (3-methacryloyloxy-2-hydroxypropoxy) ethane, N-
Methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N, N- (dihydroxyethyl) (meth) acrylamide and the like can be mentioned. The amount of the polymerizable monomer having a hydroxyl group is usually from 0.1% by weight to the total amount of the primer composition.
It is used in the range of 95% by weight, preferably in the range of 1% to 70% by weight, more preferably in the range of 10% to 50% by weight.

In the present invention, the water used for the primer composition must be substantially free of impurities which adversely affect the adhesive strength between the tooth and the restorative material. Alternatively, ion-exchanged water is suitable. The amount of water, based on the entire primer composition,
Usually in the range of 0.01% to 90% by weight, preferably in the range of 0.1% to 70% by weight, more preferably 10% by weight.
It is used in the range of 60% by weight to 60% by weight.

In the present invention, the primer composition is applied to a tooth surface and then dried with a dental air syringe to form an extremely thin layer. Therefore, a polymerization initiator is not necessarily required in the primer. When drying the primer composition, for example, when the operator has left an extremely large amount of the primer composition, the curability is reduced, and the adhesive strength may be reduced. It is more desirable to mix them. As the polymerization initiator, a known photopolymerization initiator and / or chemical polymerization initiator can be blended. As the photopolymerization initiator, for example, an acylphosphine oxide-based photopolymerization initiator and / or an α-diketone-based photopolymerization initiator essential for the bonding material composition of the present invention are preferably used.
It is also possible to use photopolymerization initiators such as ketals and thioxanthones.

Examples of the acylphosphine oxide include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-diethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, and 2,6-dichlorobenzoyldiphenyl. Phosphine oxide, 2,
3,5,6-Tetramethylbenzoyldiphenylphosphine oxide, benzoyldi- (2,6-dimethylphenyl) phosphonate, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide and Japanese Patent Publication No. 3-57916. And water-soluble acylphosphine oxide compounds.

Examples of the α-diketone include camphorquinone, benzyl, 2,3-pentanedione and the like. Examples of ketals include benzyl dimethyl ketal, benzyl diethyl ketal, and the like. Examples of thioxanthone include 2-chlorothioxanthone,
2,4-diethylthioxanthone and the like. These photopolymerization initiators may be used alone,
Usually, for the purpose of further promoting photocurability, it is used in combination with a reducing agent such as various amines, aldehydes, mercaptans or sulfinates.

Examples of the amines include 2-dimethylaminoethyl methacrylate, N, N-bis [(meth) acryloyloxyethyl] -N-methylamine, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, Butoxyethyl 4-dimethylaminobenzoate,
Tertiary amines such as N, N-di (2-hydroxyethyl) -p-toluidine, N-methyldiethanolamine, 4-dimethylaminobenzophenone, and dimethylaminophenanthol; Aldehydes include dimethylaminobenzaldehyde, terephthalaldehyde, p
-N-octyloxybenzaldehyde and the like. Examples of mercaptans include 2-mercaptobenzoxazole, decanethiol, 3-mercaptopropyltrimethoxysilane, and thiobenzoic acid. Examples of sulfinates include sodium benzenesulfinate, 2,4-
Sodium dimethylbenzenesulfinate, sodium 2,4-dimethoxybenzenesulfinate, 2,4,6
Sodium trimethylbenzenesulfinate, 2,
Potassium 4,6-triethylbenzenesulfinate,
And sodium 2,4,6-triisopropylbenzenesulfinate. When photopolymerization by ultraviolet irradiation is performed, benzoin alkyl ether, benzyl dimethyl ketal, and the like are preferable.

As the chemical polymerization initiator, for example, a redox polymerization initiator composed of an oxidizing agent and a reducing agent is suitably used. When using a redox polymerization initiator,
The primer composition of the present invention needs to be divided into two or more packaging forms so as to contain each component separately. Further, in the adhesive system of the present invention, since the primer composition and the bonding composition are always used in combination, if the bonding composition contains an oxidizing agent or a reducing agent, the primer composition may be oxidized or reduced. By mixing only one of the agents, the primer composition can take one package form.

As the oxidizing agent, for example, organic peroxides such as diacyl peroxides, peroxyesters, dialkyl peroxides, peroxyketals, ketone peroxides and hydroperoxides may be added. It is possible, specifically, benzoyl peroxide as the diacyl peroxides,
2,4-dichlorobenzoyl peroxide, m-toluoyl peroxide and the like. Examples of peroxyesters include t-butyl peroxybenzoate, bis-t-butyl peroxyisophthalate,
Examples thereof include 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxy-2-ethylhexanoate, and t-butylperoxyisopropyl carbonate. Examples of the dialkyl peroxides include dicumyl peroxide, di-t-butyl peroxide, lauroyl peroxide, and the like. As peroxyketals, for example,
Examples thereof include 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane. Examples of the ketone peroxides include methyl ethyl ketone peroxide, cyclohexanone peroxide, methyl acetoacetate peroxide, and the like. Examples of hydroperoxides include t-butyl hydroperoxide, cumene hydroperoxide,
p-Diisopropylopybenzenebenzene peroxide and the like.

As the reducing agent, aromatic tertiary amines, aliphatic tertiary amines and sulfinic acid or salts thereof are used as suitable reducing agents. As the aromatic tertiary amine, 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-i-propylaniline, 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-hydroxyethyl) -4-ethylaniline, N,
N-bis (2-hydroxyethyl) -4-i-propylaniline, N, N-bis (2-hydroxyethyl) -4
-T-butylaniline, N, N-bis (2-hydroxyethyl) -3,5-di-i-propylaniline, N, N
-Bis (2-hydroxyethyl) -3,5-di-t-butylaniline, ethyl 4-dimethylaminobenzoate, 4
N-butoxyethyl dimethylaminobenzoate, (2-methacryloyloxy) ethyl 4-dimethylaminobenzoate, and the like.

Examples of the aliphatic tertiary amine include trimethylamine, triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, Nn
-Butyldiethanolamine, N-lauryldiethanolamine, triethanolamine, (2-dimethylamino) ethyl methacrylate, N-methyldiethanolamine dimethacrylate, N-ethyldiethanolamine dimethacrylate, triethanolamine monomethacrylate, triethanolamine dimethacrylate, triethanol Amine trimethacrylate and the like.

Examples of the sulfinic acid or a salt thereof include benzenesulfinic acid, sodium benzenesulfinate, potassium benzenesulfinate, calcium benzenesulfinate, lithium benzenesulfinate,
Toluenesulfinic acid, sodium toluenesulfinate, potassium toluenesulfinate, calcium toluenesulfinate, lithium toluenesulfinate, 2,
4,6-trimethylbenzenesulfinic acid, 2,4,6
Sodium trimethylbenzenesulfinate, 2,
Potassium 4,6-trimethylbenzenesulfinate,
Calcium 2,4,6-trimethylbenzenesulfinate, lithium 2,4,6-trimethylbenzenesulfinate, 2,4,6-triethylbenzenesulfinic acid,
Sodium 2,4,6-triethylbenzenesulfinate, potassium 2,4,6-triethylbenzenesulfinate, calcium 2,4,6-triethylbenzenesulfinate, 2,4,6-triisopropylbenzenesulfinic acid, 2, Sodium 4,6-triisopropylbenzenesulfinate, potassium 2,4,6-triisopropylbenzenesulfinate, calcium 2,4,6-triisopropylbenzenesulfinate and the like. These polymerization initiators are used alone or in combination. The amount of these polymerization initiators is
It is usually used in the range of 0.01% by weight to 20% by weight, preferably in the range of 0.05% by weight to 10% by weight, more preferably in the range of 0.1 to 5% by weight, based on the primer composition.

The primer composition of the present invention may contain, if desired, a (meth) acrylate polymerizable monomer having no hydroxyl group or acidic group, a volatile solvent such as ethanol or acetone, a polymerization inhibitor, and a coloring agent. Agents, fluorescent agents, ultraviolet absorbers and the like may be added. Also, for the purpose of imparting antibacterial properties,
An antibacterial polymerizable monomer having a cationic group such as (meth) acryloyloxidedecylpyridinium bromide, (meth) acryloyloxyhexadecylpyridinium chloride and (meth) acryloyloxydecylammonium chloride may be blended, For the purpose of imparting an effect, a metal fluoride salt such as sodium fluoride may be blended. Further, the filler can be blended in an amount that does not impair the fluidity of the primer composition.

As the filler, an inorganic or organic substance and a composite thereof are used. As the inorganic filler, silica or kaolin, clay, mica,
Minerals based on silica such as mica, silica based, Al ₂ O ₃ , B ₂ O ₃ , TiO ₂ , ZrO ₂ , BaO, L
Ceramics and glasses containing a ₂ O ₃ , SrO ₂ , CaO, P ₂ O _5, etc., especially lanthanum glass, barium glass, strontium glass, soda glass, lithium borosilicate glass, zinc glass, fluoroaluminum borosilicate glass , Borosilicate glass, bioglass and the like. Further, crystal quartz, hydroxyapatite, alumina, titanium oxide, yttrium oxide, zirconia, calcium phosphate, barium sulfate, aluminum hydroxide and the like are also preferably used. Examples of the organic filler include organic resins such as polymethyl methacrylate, polyfunctional methacrylate polymers, polyamide, polystyrene, polyvinyl chloride, chloroprene rubber, nitrile rubber, and styrene-butadiene rubber. Further, an inorganic filler is dispersed in these organic resins, or an inorganic / organic composite filler obtained by coating the inorganic filler with the organic resin.

These fillers may be used after a surface treatment with a known surface treatment agent such as a silane coupling agent, if necessary, in order to adjust the fluidity of the primer composition. Examples of such a surface treatment agent include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltri (β-methoxyethoxy) silane, γ-methacryloyloxypropyltrimethoxysilane, and 11-methacryloyloxyundecyltrimethoxysilane. , Γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane and the like. These fillers are compounded alone or in combination of several kinds, and 3 parts with respect to the entire primer composition.
0% by weight or less, preferably 10% by weight or less. More preferably, the following colloidal silica having an average particle size of 0.1 μm is used.

In the bonding agent composition of the present invention,
The following are specific examples of the acylphosphine oxide compound and the α-diketone compound used as the photopolymerization initiator. Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-diethylbenzoyldiphenylphosphine oxide,
6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, benzoyldi-
(2,6-dimethylphenyl) phosphonate, 2,4
Examples thereof include 6-trimethylbenzoylethoxyphenylphosphine oxide and water-soluble acylphosphine oxide compounds disclosed in Japanese Patent Publication No. 57916/1991. Examples of the α-diketone include camphorquinone, benzyl, and 2,3-pentanedione.

The amount of each of the acylphosphine oxide-based photopolymerization initiator and the α-diketone-based photopolymerization initiator is usually in the range of 0.05% by weight to 15% by weight based on the whole bonding composition. , Preferably 0.1
It is used in the range of 5% by weight to 5% by weight. Further, these acylphosphine oxide-based photopolymerization initiators and α-
Diketone photopolymerization initiators are used in combination with reducing agents such as amines, aldehydes, mercaptans or sulfinates, since photocurability is promoted. You. As the specific reducing agent, the same one as described above is suitably used. The amount of these reducing agents is usually in the range of 0.05% by weight to 10% by weight, preferably in the range of 0.1% by weight to 5% by weight, based on the whole bonding composition.
In addition, during clinical use, to avoid the danger of the bonding composition becoming thickened, gelled or cured in a short time due to ambient light due to ambient light, the acyl phosphine oxide compound and the α-diketone compound may be used. The total amount is preferably in the range of 1% by weight to 5% by weight based on the entire bonding composition. More preferably, when the compounding amount of α-diketone is mixed in a ratio of 0.01 part by weight to 0.5 part by weight with respect to 1 part by weight of the acylphosphine oxide compound, the compound is stable to light of the surrounding environment, It is also good because it has excellent photocurability.

In addition to these acylphosphine oxide compounds, known photopolymerization initiators and / or chemical polymerization initiators can be added, if necessary. The photopolymerization initiator and the chemical polymerization initiator are the same as those described above. These photopolymerization initiators are usually in the range of 0.05% by weight to 15% by weight, preferably in the range of 0.1% by weight to 5% by weight, more preferably 0.5% by weight, based on the whole bonding composition. It is used in the range of 3% by weight to 3% by weight.

As a chemical polymerization initiator, for example, when a redox-based polymerization initiator comprising an oxidizing agent and a reducing agent is blended into the bonding composition, the bonding composition of the present invention is prepared so that each component is blended separately. It is necessary to take two or more divided packaging forms. Further, in the adhesive system of the present invention, since the bonding composition is always used in combination with the primer composition, the oxidizing agent and the reducing agent can be separately added to the primer composition and the bonding composition. The chemical polymerization initiator is divided into one or both of the primer composition and the bonding composition, and can be contained in various packaging forms so that both components coexist at the time of use. These oxidizing and reducing agents are the same as those described above.

The oxidizing agent and the reducing agent may be used alone or in combination of several kinds. The oxidizing agent and the reducing agent are used in an amount of usually 0.01% by weight to 20% by weight, preferably 0.1% by weight to 10% by weight, based on the whole bonding composition. Is done.

The polymerizable monomer used in the bonding composition of the present invention is usually α-cyanoacrylic acid,
Esters such as (meth) acrylic acid, α-halogenated acrylic acid, crotonic acid, cinnamic acid, sorbic acid, maleic acid, and itaconic acid, (meth) acrylamide, and (meth) acrylamide derivatives, vinyl esters, and vinyl ethers , A mono-N-vinyl derivative, a styrene derivative and the like. Among them, (meth) acrylate is preferably used, and examples of such a polymerizable monomer are shown below.

In the present invention, a monomer having one unsaturated group is defined as a monofunctional monomer. (A) Monofunctional monomer methyl (meth) acrylate, iso-butyl (meth)
Acrylate, benzyl (meth) acrylate, lauryl (meth) acrylate, 2- (N, N-dimethylamino) ethyl (meth) acrylate, 2,3-dibromopropyl (meth) acrylate, 3-methacryloyloxypropyltrimethoxysilane, 11-methacryloyloxyundecyltrimethoxysilane, 2-hydroxyethyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, propylene glycol mono (meth)
Acrylate, glycerin mono (meth) acrylate,
Erythritol mono (meth) acrylate, N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N, N- (dihydroxyethyl) (meth) acrylamide, γ- (meth) acryloyloxypropyltrimethoxysilane, ( (Meth) acryloyloxidedecylpyridinium bromide, (meth) acryloyloxidedecylpyridinium chloride, (meth) acryloyloxidedecylpyridiniumbromide, (meth) acryloyloxyhexadecylpyridinium chloride and the like.

(B) Bifunctional monomers: ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6- Hexanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, bisphenol A diglycidyl (meth) acrylate, 2,2-bis [4- (meth)
Acryloyloxyethoxyphenyl] propane, 2,
2-bis [4- (meth) acryloyloxypolyethoxyphenyl] propane, 2,2-bis [4- [3-
((Meth) acryloyloxy-2-hydroxypropoxy] phenyl] propane, 1,2-bis [3- (meth) acryloyloxy-2-hydroxypropoxy]
Ethane, pentaerythritol di (meth) acrylate, 1,2-bis (3-methacryloyloxy-2-hydroxypropoxy) ethane, [2,2,4-trimethylhexamethylenebis (2-carbamoyloxyethyl)] dimethacrylate and the like .

(C) Multifunctional group monomer Trimethylolpropane tri (meth) acrylate, trimethylolethanetri (meth) acrylate, tetramethylolmethanetri (meth) acrylate, pentaerythritol tetra (meth) acrylate, N, N-
(2,2,4-trimethylhexamethylene) bis [2-
(Aminocarboxy) propane-1,3-diol] tetramethacrylate, 1,7-diacryloyloxy-
2,2,6,6-tetraacryloyloxymethyl-4
-Oxyheptane and the like. These polymerizable monomers are used singly or in combination. The compounding amount of these polymerizable monomers is usually in the range of 60% by weight to 99% by weight, preferably 80% by weight, based on the whole bonding composition.
It is used in the range of ９５95% by weight.

In the present invention, the polymerizable monomer having an acidic group used in the bonding material composition is not an essential component for ensuring the adhesion to the dentin and the restoration, but it is necessary to further enhance the adhesion. It is more desirable to mix them. The polymerizable monomer having such an acidic group corresponds to the same acidic monomer used in the primer composition of the present invention. Above all, a bonding composition containing a polymerizable monomer having a phosphoric acid group is preferable since it has excellent adhesive strength to tooth materials or restorative materials such as metal, resin and porcelain. The amount of the polymerizable monomer having an acidic group is usually in the range of 0.1% by weight to 50% by weight, preferably 1% by weight, based on the whole bonding composition.
It is used in the range of ３０30% by weight.

The bonding agent composition of the present invention may contain a filler in order to improve operability, applicability and mechanical strength. Such fillers are the same as the fillers incorporated in the primer composition. These fillers are compounded alone or in combination of several kinds, and are added in a range of 40% by weight or less, preferably 20% by weight or less based on the whole bonding composition. More preferably, the following colloidal silica having an average particle size of 0.1 μm is used.

The bonding composition of the present invention may contain, in addition to the components described above, organic solvents such as ethanol and acetone, a polymerization inhibitor, an antioxidant, an ultraviolet absorber, a pigment and a dye, if necessary for practical use. Etc. can be added. Also,
Fluorine compounds such as sodium fluoride can be blended in anticipation of anti-caries effects.

The bonding system of the present invention is a dental adhesive system for bonding tooth material and a filling restoration material such as a filling compomer and a filling composite resin.
It can also be used in combination with a luting material such as resin cement, glass ionomer cement, zinc phosphate cement, polycarboxylate cement, silicate cement, zinc oxide eugenol cement and the like. Moreover,
It can be used as a fissure sealant, a coating material for root surfaces and adjacent teeth, and a dentinal tubule sealing material for suppressing hyperesthesia by directly applying to the pit and fissure without using a filling restoration material.

Further, for example, when the restoration material is broken in the oral cavity, it can be used for materials other than teeth, such as metal, porcelain, and composite hardened material. Metal adhesive primer, dental porcelain adhesive primer, acid etchant, hypochlorite-containing tooth surface cleaner.

[0041]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The abbreviations and abbreviations shown in the present invention and the examples are as follows.

Abbreviations and abbreviations Polymerizable monomer having an acidic group MNP: 9-methacryloyloxynonyl dihydrogen phosphate MDP: 10-methacryloyloxydecyl dihydrogen phosphate MUP: 11-methacryloyloxyundecyl dihydrogen phosphate hydroxyl group HEMA: 2-hydroxyethyl methacrylate Other polymerizable monomer Bis-GMA: bisphenol A diglycidyl methacrylate UDMA: [2,2,4-trimethylhexamethylenebis (2-carbamoyloxyethyl) Dimethacrylate HD: 1,6-hexanediol dimethacrylate Photopolymerization initiator TMDPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide DEDPO: 2,6-di Tylbenzoyldiphenylphosphine oxide DCDPO: 2,6-dichlorobenzoyldiphenylphosphine oxide CQ: camphorquinone Oxidizing and reducing agents DMAB: 4-dimethylaminobenzophenone EDMABA: ethyl 4-dimethylaminobenzoate DMAEMA: 2-dimethylaminoethyl methacrylate DEPT : N, N-di (2-hydroxyethyl) -p
-Toluidine

Example 1 A primer composition was prepared by mixing MUP, HEMA and distilled water at the weight ratio shown in Table 1. In addition, UDM
A, HEMA, TMDPO, CQ, EDMABA and DEPT were mixed at a weight ratio shown in Table 1 to prepare a bonding composition. Using this primer composition and the bonding composition, the photocuring completion time and the photocuring depth were measured according to the photocurability test method described below, and the measurement results are also shown in Table 1. Further, using the same primer composition and bonding composition, the adhesive strength was measured according to the adhesive strength test method described later, and the measurement results are shown in Table 1.

(1) Method of Measuring Photocuring Time The front teeth of a bovine were smooth and wet-polished with # 1000 silicon carbide paper (manufactured by Nippon Kenshi Co., Ltd.) to expose the dentin surface, and then water on the surface was exposed. Was blown off with a dental air syringe. The primer composition was applied to the exposed dentin surface with a brush, left as it was for 30 seconds, and dried with an air syringe. A washer having a hole with a thickness of 0.8 mm and a diameter of 4 mm was placed thereon, and after filling the bonding composition in the hole, the tip of a thermocouple was inserted into the hole. II "(Gunma Ushio Electric Co., Ltd.). The temperature change was recorded by a thermocouple, and the time from the start of irradiation to the peak of the exothermic peak was determined, and this was defined as the photopolymerization curing completion time.

(2) Method of Measuring Depth of Light Curing After filling a bonding composition in a mold having a diameter of 4 mm and a depth of 5 mm, a dental light irradiator “Lightel” (Gunma Ushio Electric Co., Ltd.) was placed 1 cm away from the top. ) For 10 seconds. Thereafter, the mold was removed, the uncured portion was removed with tissue paper, and a low-polymerized portion was compressed by applying a load of 1 kg and the depth of the hardened portion was measured using a caliper. .

(3) Test Method for Adhesive Strength The front teeth of bovine were smooth and wet-polished with # 1000 silicon carbide paper (manufactured by Nippon Kenshi Co., Ltd.) to obtain an enamel surface.
Alternatively, after exposing the dentin surface, water on the surface was blown off with a dental air syringe. Stick a tape of about 150 microns thick with a hole of 3 mmφ on the exposed enamel surface or dentin surface, apply the primer composition to the hole part with a brush, leave it for 30 seconds as it is, and use an air syringe Let dry. The bonding composition was applied thereon to a thickness of about 100 μm with a brush, and irradiated with light for 10 seconds using a dental light irradiator “Lightel II” (manufactured by Gunma Ushio Electric Co., Ltd.) to cure. . Further, a commercially available light-curable dental composite resin "Clearfill AP"
-X "(manufactured by Kuraray Co., Ltd.) and covered with a film made of EVAL (registered trademark, manufactured by Kuraray Co., Ltd.)
The slide glass was pressed from above, and in this state, light irradiation was performed for 40 seconds with the light irradiation device to cure the slide glass. For this hardened surface, a commercially available dental resin cement “Panavia 2”
A stainless steel rod was adhered using "1" (manufactured by Kuraray Co., Ltd.), and after 30 minutes, all 16 test pieces were immersed in water at 37 ° C. Eight of them were 24 in 37 ° C water.
After immersion for a time, the adhesive strength was measured. The remaining eight test pieces were immersed in water at 37 ° C. for 24 hours, and then subjected to 10,000 thermal cycles of immersion in cold water at 4 ° C. and warm water at 60 ° C. for 1 minute each. The adhesive strength was measured. To measure the adhesive strength, use a universal testing machine (manufactured by Instron) with a cross head speed of 2 mm / m.
The tensile adhesive strength was measured under the conditions of “in”. The average of each measurement was determined.

Examples 2 to 4 and Comparative Examples 1 to 4 As shown in Table 1, the same primer composition as in Example 1 was prepared, and further, UDMA or Bis-GMA, H
D, HEMA, TMDPO, CQ, EDMABA, DE
A bonding composition was prepared by mixing PT and the like at the weight ratio shown in Table 1. Using each primer composition and bonding composition, the photocuring completion time, photocuring depth and adhesive strength were measured by the same photocurability test method and adhesive strength test method as in Example 1, and measured in Table 1, respectively. The results are also shown.

As is clear from Table 1, the adhesive systems of Examples 1 to 4 in which both an acylphosphine oxide compound and CQ were compounded as a photopolymerization initiator in the bonding composition, the photocuring was completed within 10 seconds. It was completed, and a curing depth of about 2 mm was obtained by irradiating with light for 10 seconds, which proved to be excellent in photocurability. Furthermore, in the adhesion test,
Even after the heat cycle load, there was almost no decrease in the adhesive strength.
On the other hand, in the adhesive systems of Comparative Examples 1 and 2 in which only TMDPO was added to the bonding composition as the photopolymerization initiator, although the photopolymerization was completed in 10 seconds,
The photocuring depth was about 0.5 mm, and sufficient photocurability could not be obtained. Furthermore, the adhesive strength decreased due to the heat cycle load. Further, the adhesive systems of Comparative Examples 3 and 4 in which only CQ was blended as a photopolymerization initiator into the bonding composition could not complete photocuring in 10 seconds, and the photocuring depth was only about 1 mm, which was sufficient. Light curability could not be obtained. Furthermore, the adhesive strength was significantly reduced due to the heat cycle load.

[0049]

[Table 1]

Examples 5 to 8 and Comparative Examples 5 to 8 A primer composition was prepared by mixing MUP, HEMA, TMDPO, DMAB and distilled water in the weight ratio shown in Table 2. In addition, UDMA or Bis-GMA, HD,
HEMA, TMDPO, CQ, DMAB and DEPT
And the like were mixed at the weight ratio shown in Table 2 to prepare a bonding composition. Using each primer composition and the bonding composition, the photocuring completion time, the photocuring depth and the adhesive strength were measured by the same photocurability test method and adhesive strength test method as in Example 1, and measured in Table 2, respectively. The results are also shown.

As is clear from Table 2, the adhesive systems of Examples 5 to 8 in which both the acylphosphine oxide compound and CQ were blended as the photopolymerization initiator in the bonding composition, the photocuring was completed within 10 seconds. It was completed, and a curing depth of about 2 mm was obtained by irradiating with light for 10 seconds, which proved to be excellent in photocurability. Furthermore, in the adhesion test,
Even after the heat cycle load, there was almost no decrease in the adhesive strength.
On the other hand, in the adhesive systems of Comparative Examples 5 and 6 in which only TMDPO was blended as the photopolymerization initiator into the bonding composition, although the photopolymerization was completed in 10 seconds,
The photocuring depth was about 0.5 mm, and sufficient photocurability could not be obtained. Furthermore, the adhesive strength decreased due to the heat cycle load. In addition, the adhesive systems of Comparative Examples 7 and 8 in which only CQ was blended into the bonding composition as a photopolymerization initiator could not complete photocuring in 10 seconds, and the photocuring depth was only about 1 mm, which was sufficient. Light curability could not be obtained. Furthermore, the adhesive strength was significantly reduced due to the heat cycle load.

[0052]

[Table 2]

Examples 9 to 12 and Comparative Examples 9 to 12 Primer compositions were prepared by mixing MNP, HEMA and distilled water at the weight ratios shown in Table 3. In addition, UDMA
Or Bis-GMA, HD, HEMA, MUP, TM
A bonding composition was prepared by mixing DPO, CQ, EDMABA, and the like at the weight ratio shown in Table 3. Using each primer composition and the bonding composition, the photocuring completion time, the photocuring depth and the adhesive strength were measured by the same photocurability test method and adhesive strength test method as in Example 1, and measured in Table 3, respectively. The results are also shown.

As is clear from Table 3, the adhesive systems of Examples 9 to 12 in which both the acylphosphine oxide compound and CQ were blended as the photopolymerization initiator in the bonding composition, the photocuring was completed within 10 seconds. Complete and 10
A light-curing depth of about 2 mm was obtained by light irradiation for seconds, and it was found that the photocurability was excellent. Furthermore, in the adhesive strength test, there was almost no decrease in the adhesive strength even after the heat cycle load. On the other hand, Comparative Example 9 and Comparative Example 1 in which only TMDPO was blended as a photopolymerization initiator into the bonding composition.
In the adhesive system of No. 0, although photopolymerization was completed in 10 seconds, the photocuring depth was about 0.5 mm, and sufficient photocurability could not be obtained. Furthermore, the adhesive strength decreased due to the heat cycle load. Comparative Example 11 in which only CQ was compounded as a photopolymerization initiator in the bonding composition
In the adhesive system of Comparative Example 12, photocuring could not be completed in 10 seconds, the photocuring depth was only about 1.5 mm, and sufficient photocurability could not be obtained. Furthermore, the adhesive strength was significantly reduced due to the heat cycle load.

[0055]

[Table 3]

Examples 13 to 16 and Comparative Examples 13 to 16 A primer composition was prepared by mixing MDP, HEMA, CQ, DMAEMA and distilled water at the weight ratio shown in Table 4. Further, UDMA or Bis-GMA, HD, H
EMA, MDP, TMDPO, CQ and EDMABA
And the like were mixed at the weight ratio shown in Table 4 to prepare a bonding composition. Using each primer composition and the bonding composition, the photocuring completion time, the photocuring depth and the adhesive strength were measured by the same photocurability test method and adhesive strength test method as in Example 1, and measured in Table 4, respectively. The results are also shown.

As is clear from Table 4, the adhesive systems of Examples 13 to 16 in which both an acylphosphine oxide compound and CQ were blended as a photopolymerization initiator in the bonding composition, the photocuring was completed within 10 seconds. Complete and 1
A curing depth of about 2 mm was obtained by irradiating with light for 0 seconds, which proved to be excellent in photocurability. Furthermore, in the adhesive strength test, there was almost no decrease in the adhesive strength even after the heat cycle load. In contrast, the adhesive systems of Comparative Examples 13 and 14 in which only TMDPO was blended into the bonding composition as the photopolymerization initiator, although the photopolymerization was completed in 10 seconds, but the photocuring depth was about 0.5 mm. And sufficient photocurability could not be obtained. Furthermore, the adhesive strength decreased due to the heat cycle load. Comparative Example 1 in which only CQ was compounded as a photopolymerization initiator in the bonding composition
The adhesive systems of Comparative Example 5 and Comparative Example 16 could not complete photocuring in 10 seconds, had a photocuring depth of only about 1.5 mm, and could not obtain sufficient photocurability. Furthermore, the adhesive strength was significantly reduced due to the heat cycle load.

[0058]

[Table 4]

[0059]

According to the present invention, in a dental adhesive system composed of a primer composition and a bonding composition, by blending both an acylphosphine oxide compound and an α-diketone compound as a photopolymerization initiator in the bonding composition. Not only the bonding composition but also the primer composition can be simultaneously photo-hardened strongly in a short period of time, and the adhesion durability to the tooth can be significantly improved.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4C089 AA10 BC11 BC12 BD03 BD07 BD20 4J040 FA041 FA061 FA091 FA101 FA121 FA141 FA161 FA171 FA181 FA201 GA02 HB20 HB21 HD24 HD27 KA13 KA21 LA06 MA15 NA03 PA04 PA05 PA06 PA10

Claims (4)

[Claims] (A) a polymerizable monomer having an acidic group,
(B) a primer composition containing a polymerizable monomer having a hydroxyl group and (c) water; (d) a polymerizable monomer; (e) an acylphosphine oxide compound as a photopolymerization initiator; A) a dental adhesive system comprising a bonding composition comprising an α-diketone compound; 2. The dental adhesive system according to claim 1, wherein said primer composition further comprises (g) a polymerization initiator. 3. The dental adhesive system according to claim 1, wherein the bonding composition further comprises (h) a polymerizable monomer having an acidic group. 4. The bonding composition according to claim 1, further comprising (i) an oxidizing agent and / or (j) a reducing agent.
4. The dental adhesive system according to any one of 3.