JP2000016911A - Dental adhesive system - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject system with high adhesivity to the dentin by combining a specific primer composition prepared by dissolving an acidic monomer and a hydrophilic monomer in water with a bonding composition containing an acylphosphine oxide compounds so as to effect firmly photocuring of both the composition in a short time. SOLUTION: This dental adhesive system is obtained by combining (A) a primer composition comprising (i) pref. 0.1-80 wt.% of an acidic group-bearing polymerizable monomer [e.g. 2-(meth)acryloyloxyethyl dihydrogenphosphate], (ii) pref. 0.1-95 wt.% of a hydroxyl-bearing polymerizable monomer [e.g. 2- hydroxyethyl (meth)acrylate] and (iii) pref. 0.01-90 wt.% of water with (B) a bonding composition comprising (i) pref. 0.05-15 wt.% of an acylphosphine oxide compound (e.g. 2,4,6-trimethylbenzoyl diphenylphosphine oxide) and (ii) a polymerizable monomer.

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 providing 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. Conventionally, a tooth material surface is treated with a strong acid etching material such as phosphoric acid, and then a bonding material is applied to bond the tooth material and the filling material. However, such a processing method using an acid etching material is disadvantageous 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 material has an excellent adhesive force to enamel, but it is difficult to obtain a high adhesive force 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 in place of an acid etching material, 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 monomers are then polymerized and cured by light irradiation simultaneously with the bonding material coated thereon, but the primer component contains a large amount of monomers having poor polymerizability such as hydrophilic monomers and acidic monomers. Therefore, polymerization cannot be driven instantaneously. Therefore,
Attempts have been made to improve the polymerizability, for example, by adding a photopolymerization initiator to the primer. However, at present, sufficient effects have not been obtained. as a result,
The polymerization of the polymerizable monomer in the bonding material (including the primer) applied to the tooth surface became insufficient, and after a certain period of time after the restoration, unfortunately, a gap between the tooth material and the restoration material was formed, 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 material composition used in combination with the above, when an acylphosphine oxide compound is blended as a photopolymerization initiator in the bonding composition, photocurability is improved, and thereby, adhesion durability in water is improved. It has been found that the properties can be improved. Even more surprisingly, when the acylphosphine oxide compound is blended in the bonding composition as a photopolymerization initiator, even when the photopolymerization initiator is not blended in the primer composition to be treated first, it is hardened in a short time. However, it has been found that a high adhesive strength can be obtained with respect to the tooth material, and that the adhesive durability is further improved, and the present invention has been completed.

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 comprising a phosphine oxide compound and (e) a polymerizable monomer.

[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, 9- (meth) acryloyloxynonyl dihydrogen phosphate, and 10- (meth) acryloyloxynonyl dihydrogen phosphate.
(Meth) acryloyloxydecyl dihydrogen phosphate, 11- (meth) acryloyloxyundecyl dihydrogen phosphate, 20- (meth) acryloyloxyeicosyl dihydrogen phosphate, 1,3-di (meth) acryloyloxypropyl -2-dihydrogen phosphate, 2- (meth) acryloyloxyethyl phenyl hydrogen phosphate, 2- (meth) acryloyloxyethyl 2 ′
-Bromoethyl hydrogen phosphate, (meth)
Acryloyloxyethyl phenylphosphonate, etc.
And their acid chlorides.

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, for example, 2-
(Meth) acryloyloxyethyl dihydrogen dithiophosphate, 10- (meth) acryloyloxydecyl dihydrogen thiophosphate and the like, and acid chlorides thereof.

Examples of the polymerizable monomer having a carboxylic acid residue include 4- (meth) acryloyloxyethoxycarbonylphthalic acid, 4- (meth) acryloyloxyethoxycarbonylphthalic anhydride, and 5- (meth) Acryloylaminopentyl carboxylic acid, 11- (meth)
Acryloyloxy-1,1-undecanedicarboxylic acid and the like and acid chlorides thereof.

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. And the like. These polymerizable monomers having an acidic group are used singly or in combination. The compounding amount of these acidic monomers is usually in the range of 0.1% by weight to 80% by weight, preferably in the range of 1% by weight to 50% by weight, based on the entire primer composition.

In the present invention, the polymerizable monomer containing a hydroxyl group used in the primer composition includes a hydroxyl group and a polymerizable monomer having a polymerizable unsaturated group such as an acryloyl group, a methacryloyl group, a vinyl group and a styrene group. It can be a monomer, oligomer or polymer, with monomers being particularly preferred. Such compounds include, for example, 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, 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 in the range of 0.1% to 95% by weight, preferably 1% by weight, based on the entire primer composition.
Used in the range of ~ 70 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, it is used in the range of 0.01% by weight to 90% by weight, preferably in the range of 0.1% by weight to 70% by weight.

In the present invention, the primer composition is extremely thin by being applied to the tooth surface and then dried with a dental air syringe. Therefore, a polymerization initiator is not necessarily required in the primer. However, when the primer composition is dried, for example, when the operator leaves an extremely large amount of the primer composition, the photocurability is reduced, and the adhesive strength may be reduced. It is more desirable to incorporate an initiator. As the polymerization initiator, a known photopolymerization initiator and / or chemical polymerization initiator can be blended.

Examples of the photopolymerization initiator include α-diketone / reducing agent, ketal / reducing agent, thioxanthone / reducing agent and the like. Examples of α-diketones 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.

Examples of the reducing agent include 2-dimethylaminoethyl methacrylate, N, N-bis [(meth) acryloyloxyethyl] -N-methylamine, ethyl 4-dimethylaminobenzoate, and 4-dimethylaminobenzoic acid. Butyl, butoxyethyl 4-dimethylaminobenzoate,
Tertiary amines such as N, N-di (2-hydroxyethyl) -p-toluidine, N-methyldiethanolamine, 4-dimethylaminobenzophenone, and dimethylaminophenanthol; aldehydes such as dimethylaminobenzaldehyde and terephthalaldehyde; Examples thereof include compounds having a thiol group such as 2-mercaptobenzoxazole, decanethiol, 3-mercaptopropyltrimethoxysilane, and thiobenzoic acid. When photopolymerization by ultraviolet irradiation is performed, benzoin alkyl ether, benzyl dimethyl ketal, and the like are preferable.
Further, various acylphosphine oxide-based photopolymerization initiators essential for the bonding material composition of the present invention are also preferably used.

Examples of the acylphosphine oxide include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide,
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. These acylphosphine oxide-based photopolymerization initiators may be used alone or in combination with various amines, aldehydes or mercaptans, sulfinic acid salts and other reducing agents.

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 contains 2
It is necessary to take a packaging form that is more than divided. On the other hand, in the adhesive system of the present invention, since the primer composition is always used in combination with the bonding composition, the oxidizing agent and the reducing agent can be separately added to the primer composition and the bonding composition.

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.

As peroxyesters, for example,
t-butylperoxybenzoate, bis-t-butylperoxyisophthalate, 2,5-dimethyl-2,5
-Bis (benzoylperoxy) hexane, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisopropyl carbonate and the like. 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. Ketone peroxides include, for example, methyl ethyl ketone peroxide and the like. Examples of the hydroperoxides include t-butyl hydroperoxide 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-dii-propylaniline, N, N-
Bis (2-hydroxyethyl) -3,5-di-t-butylaniline, ethyl 4-dimethylaminobenzoate, n-butoxyethyl 4-dimethylaminobenzoate, (2-methacryloyloxy) ethyl 4-dimethylaminobenzoate And the like.

As the aliphatic tertiary amine, for example, 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-i-propylbenzenesulfinic acid, Sodium 4,4,6-i-propylbenzenesulfinate, potassium 2,4,6-i-propylbenzenesulfinate, calcium 2,4,6-i-propylbenzenesulfinate and the like. These polymerization initiators are used alone or in combination. The amount of these polymerization initiators is usually in the range of 0.01% by weight to 20% by weight, and preferably in the range of 0.1% by weight to 10% 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. Furthermore, the filler can be added 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, examples thereof include those in which an inorganic filler is dispersed in these organic resins, and an inorganic / organic composite filler which is a composite obtained by coating an inorganic filler with the organic resin.

These fillers may be used after being subjected to 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 γ-glycidoxypropyltrimethoxysilane. , Γ-mercaptopropyltrimethoxysilane,
γ-aminopropyltriethoxysilane and the like. These fillers are blended alone or in combination of several types, and are added in an amount of 30% by weight or less, preferably 10% by weight or less, based on the entire primer composition. More preferably, the following colloidal silica having an average particle size of 0.1 μm is used.

The acylphosphine oxide compound used as a photopolymerization initiator in the bonding agent composition of the present invention includes, for example, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, , 6
-Dichlorobenzoyldiphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, benzoyldi- (2,6-dimethylphenyl) phosphonate, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide and JP-B-3 And water-soluble acylphosphine oxide compounds disclosed in JP-A-57916. These acylphosphine oxide-based photopolymerization initiators may be used alone or in combination with various amines, aldehydes or mercaptans, sulfinic acid salts and other reducing agents. The amount of the acylphosphine-based photopolymerization initiator is usually in the range of 0.05% by weight to 15% by weight, preferably 0.1% by weight, based on the whole bonding composition.
It is used in the range of 1% by weight to 5% by weight.

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 used in an amount of from 0.05% by weight to the entire bonding composition.
15% by weight, preferably 0.1% to 5% by weight
Used in the range.

When a redox-based polymerization initiator is used as the chemical polymerization initiator, the bonding composition of the present invention must be packaged in two or more parts. Since the product is always used in combination with the bonding composition, the oxidizing agent and the reducing agent can be separately blended into the primer composition and the bonding composition. Known photopolymerization initiators and chemical polymerization initiators to be incorporated into the bonding composition are the same as those described above.

The oxidizing agent and the reducing agent are used alone or in combination of several kinds. The amount of these components is usually in the range of 0.01% by weight to 20% by weight, preferably 0.1% by weight to 10% by weight, based on the bonding composition.
Used in the range of weight percent.

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) Polyfunctional group monomers trimethylolpropane tri (meth) acrylate, trimethylolethanetri (meth) acrylate, tetramethylolmethanetri (meth) acrylate, pentaerythritol tetra (meth) acrylate, urethane tetra Methacrylate, 1,7-diacryloyloxy-
2,2,6,6-tetraacryloyloxymethyl-4
-Oxyheptane and the like. These polymerizable monomers are used singly or in combination.

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 adhesiveness to the dentin and the restoration, but when the adhesiveness is further improved. Is desirably compounded. The polymerizable monomer having such an acidic group corresponds to the same acidic monomer used in the primer composition of the present invention. The amount of these acidic monomers is usually 0.1% by weight to 80% by weight based on the whole bonding composition.
%, Preferably in the range 1% to 50% 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 used 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 agent composition. More preferably, the following colloidal silica having an average particle size of 0.1 μm is used.

In the bonding material composition of the present invention, in addition to the components described above, ethanol, if necessary for practical use,
Organic solvents such as acetone, polymerization inhibitors, antioxidants, ultraviolet absorbers, pigments, dyes and the like can be added. In addition, a fluorine compound such as sodium fluoride can be blended in order to impart an anti-caries effect.

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 applied to pits and fissures as it is without using a filling restoration material, and it can also be used as a coating material for a Fischer sealant, root surface and adjacent teeth.

When the restorative material is broken in the oral cavity, it can be used for materials other than teeth, such as metals, porcelains, and cured composites. It may be used in combination with a primer, a primer for porcelain adhesive, an acid etching agent, a tooth surface cleaning agent such as hypochlorite.

[0043]

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 Polymerizable monomer having a HEMA: 2-hydroxyethyl methacrylate

Other polymerizable monomers Bis-GMA: bisphenol A diglycidyl methacrylate UDMA: [2,2,4-trimethylhexamethylenebis (2-carbamoyloxyethyl)] dimethacrylate Photopolymerization initiator TMDPO: 2, 4,6-trimethylbenzoyldiphenylphosphine oxide DEDPO: 2,6-diethylbenzoyldiphenylphosphine oxide DCDPO: 2,6-dichlorobenzoyldiphenylphosphine oxide CQ: camphorquinone

Oxidizing and reducing agents BPO: benzoyl peroxide DMAB: 4-dimethylaminobenzophenone DMAPH: dimethylaminophenanthol DMAEMA: 2-dimethylaminoethyl methacrylate DEPT: N, N-di (2-hydroxyethyl) -p
-Toluidine, BSS: sodium benzenesulfinate

Example 1 A primer composition was prepared by mixing MDP, HEMA, and distilled water at the weight ratio shown in Table 1. Furthermore, Bis
-A bonding composition was prepared by mixing GMA, HEMA and TMDPO in the weight ratio shown in Table 1. Using this primer composition and the bonding composition, the photocuring completion time was measured in accordance with the photocurability test method described below. Table 1 also shows the measurement results. 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) Photo-curing test method The bovine front teeth were smooth and wet-polished with # 1000 silicon carbide paper (manufactured by Nippon Kenshi Co., Ltd.), and the dentin 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. On top of that, thickness 0.8mm, diameter 4m
After placing a washer with a hole of m, filling the hole with the bonding composition, put the tip of the thermocouple into it,
Dental light irradiator "Lightel 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) Test Method of Adhesive Strength After bovine anterior teeth were smooth and wet-polished with # 1000 silicon carbide paper (manufactured by Nippon Kenshi Co., Ltd.), after exposing the enamel surface or dentin surface The water on the surface was blown off with a dental air syringe. Approximately 15 with a 3mmφ hole in the exposed enamel surface or dentin surface
A 0-micron adhesive tape was applied, and the primer composition was applied to the holes with a brush, left as it was for 30 seconds, and dried with an air syringe. Then, the bonding composition was applied with a brush to a thickness of about 100 μm, and the light was applied to a dental light irradiator “Lightel II” (manufactured by Gunma Ushio Electric Co., Ltd.).
Light irradiation was performed for 0 seconds to cure. Further, a commercially available light-curable dental composite resin “Clearfill AP-X” (manufactured by Kuraray Co., Ltd.) is placed thereon, and after covering 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. A stainless steel rod was bonded to the cured surface using a commercially available dental resin cement “Panavia 21” (manufactured by Kuraray Co., Ltd.), and after 30 minutes, all 16 test pieces were immersed in water at 37 ° C.

Of the eight test pieces, the adhesive strength was measured after immersion in water at 37 ° C. for 24 hours. The remaining eight test pieces were immersed in water at 37 ° C. for 24 hours, and then subjected to 8000 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
The tensile adhesive strength was measured under the condition of mm / min. Each measurement was averaged.

Examples 2 to 6 and Comparative Examples 1 to 4 Using the components shown in Table 1, a primer composition and a bonding composition were prepared in the same manner as in Example 1. For each of the primer composition and the bonding composition, the photocuring completion time and the adhesive strength were measured by the same photocurability test method and adhesive force test method as in Example 1, and the measurement results are shown in Table 1, respectively.

As is clear from Table 1, in the case of the adhesive systems of Examples 1 to 6 in which an acylphosphine oxide compound was blended as a photopolymerization initiator into the bonding composition, the photopolymerization was completed within 10 seconds and the photopolymerization was completed. It turned out to be excellent in curability. 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, in the case of the adhesive systems of Comparative Examples 1 to 4 in which a photopolymerization initiator composed of CQ and a reducing agent was added to the bonding composition, photopolymerization could not be completed in 10 seconds. In addition, the adhesive strength was significantly reduced due to the heat cycle load.

[0053]

[Table 1]

Examples 7 to 12 and Comparative Examples 5 to 8 As shown in Table 2, the same primer composition as in Example 1 or Example 4 was prepared.
And a component such as TMDPO was mixed at a weight ratio shown in Table 2 to prepare a bonding composition. For each of the primer composition and the bonding composition, the photocuring completion time and the adhesive strength were measured by the same photocurability test method and adhesive force test method as in Example 1, and the measurement results are shown in Table 2, respectively.

As is clear from Table 2, in the case of the adhesive systems of Examples 7 to 12 in which the bonding composition was mixed with an acylphosphine oxide compound as a photopolymerization initiator, the photopolymerization was completed within 10 seconds and the photopolymerization was completed. It turned out to be excellent in curability. 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, in the case of the adhesive systems of Comparative Examples 5 to 8 in which a photopolymerization initiator composed of CQ and a reducing agent was added to the bonding composition, photopolymerization could not be completed in 10 seconds. In addition, the adhesive strength was significantly reduced due to the heat cycle load.

[0056]

[Table 2]

Examples 13 to 18 and Comparative Examples 9 to 10 MDP or MUP, HEMA, distilled water, CQ and DM
A primer composition was prepared by mixing AEMA at a weight ratio shown in Table 3. Further, Bis-GMA, HEMA, M
A bonding composition was prepared by mixing components such as DP, TMDPO and DMAB at the weight ratios shown in Table 3. For each of the primer composition and the bonding composition, the photocuring completion time and the adhesive strength were measured by the same photocurability test method and adhesive strength test method as in Example 1, and the measurement results are shown in Table 3, respectively.

As is clear from Table 3, in the case of the adhesive systems of Examples 13 to 18 in which the bonding composition was blended with an acylphosphine oxide compound as a photopolymerization initiator, the photopolymerization was completed within 10 seconds and the photopolymerization was completed. It turned out to be excellent in curability. 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, in the case of the adhesive systems of Comparative Examples 9 and 10 in which a photopolymerization initiator composed of CQ and a reducing agent was added to the bonding composition, photopolymerization could not be completed in 10 seconds. In addition, the adhesive strength was significantly reduced due to the heat cycle load.

[0059]

[Table 3]

Examples 19 to 24 and Comparative Examples 11 to 12 As shown in Table 4, the same primer compositions as those of Example 13 or Example 16 were prepared.
A bonding composition was prepared by mixing components such as MA, MDP, TMDPO and DMAB at the weight ratios shown in Table 4. For each of the primer composition and the bonding composition, the photocuring completion time and the adhesive strength were measured by the same photocurability test method and adhesive strength test method as in Example 1, and the measurement results are shown in Table 4, respectively.

As is clear from Table 4, in the case of the adhesive systems of Examples 19 to 24 in which the bonding composition was mixed with an acylphosphine oxide compound as a photopolymerization initiator, the photopolymerization was completed within 10 seconds and the photopolymerization was completed. It turned out to be excellent in curability. 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, in the case of the adhesive systems of Comparative Examples 11 and 12 in which a photopolymerization initiator composed of CQ and a reducing agent was added to the bonding composition, photopolymerization could not be completed in 10 seconds.
In addition, the adhesive strength was significantly reduced due to the heat cycle load.

[0062]

[Table 4]

Examples 25 to 26 and Comparative Examples 13 to 14 A primer composition was prepared by mixing components such as MDP, HEMA, distilled water, CQ, DMAEMA and DEPT in the weight ratios shown in Table 5. UDMA, HEM
Table 5 shows components such as A, MDP, TMDPO and BPO.
The bonding compositions mixed at the weight ratios shown in Table 1 were prepared. For each of the primer composition and the bonding composition, the photocuring completion time and the adhesive strength were measured by the same photocurability test method and adhesive strength test method as in Example 1, and the measurement results are shown in Table 5, respectively.

[0064]

[Table 5]

As is clear from Table 5, in the case of the adhesive systems of Examples 25 and 26 in which the bonding composition was blended with an acylphosphine oxide compound as a photopolymerization initiator, the photopolymerization was completed within 10 seconds and the photopolymerization was completed. It turned out to be excellent in curability. 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 Examples 13 and 14 in which CQ was blended in the bonding composition and a reducing agent was blended in the primer composition
In the case of the adhesive system, the photopolymerization could not be completed in 10 seconds. In addition, the adhesive strength showed a remarkably low value.

Examples 27 to 35 and Comparative Examples 15 to 23 Using the components shown in Tables 6 and 7, a primer composition and a bonding composition were prepared in the same manner as in Example 1. Each primer composition and bonding composition is 2
In the case of liquids, take an equal amount of each, use the mixed liquid, and use the same photocurability test method and adhesive strength test method as in Example 1 as in Example 1 to complete the photocuring completion time and adhesive strength. Was measured, and the measurement results are shown in Tables 6 and 7, respectively.

[0067]

[Table 6]

[0068]

[Table 7]

As is clear from Table 6, in the case of the adhesive systems of Examples 27 to 35 in which the bonding composition was blended with an acylphosphine oxide compound as a photopolymerization initiator, the photopolymerization was completed within 10 seconds and the photopolymerization was completed. It turned out to be excellent in curability. 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, as is clear from Table 7, CQ was added to the bonding composition.
Comparative Examples 15 to 15 in which a photopolymerization initiator consisting of and a reducing agent was blended
In the case of the adhesive system of No. 23, photopolymerization could not be completed in 10 seconds. In addition, the adhesive strength was significantly reduced due to the heat cycle load.

[0070]

Industrial Applicability In a dental adhesive system composed of a primer composition and a bonding composition, an acylphosphine oxide compound is compounded as a photopolymerization initiator in the bonding composition, so that not only the bonding composition but also the primer composition can be obtained. The object can also be lightly hardened at the same time in a short period of time, and the durability to adhesion to the tooth can be significantly improved.

Claims (4)

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