JP2001322908A - Composition for dentistry - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition for dentistry, capable of gradually releasing a fluorine ion capable of fortifying the dentin without releasing a large amount thereof, and having excellent adhesion to a tooth especially the dentin. SOLUTION: This composition for the dentistry comprises (a) a hydrophilic polymerizable monomer, (b) a hydrophobic polymerizable monomer, (c) a metal fluoride, (d) a polymerization initiator and (e) a filler regulated so that the formulated amount of the hydrophilic polymerizable monomer (a) may be 20-40 wt.% based on the whole composition, and the formulated amount of the metal fluoride (c) may be 0.1-1 wt.% based on the whole composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a dental composition comprising a specific amount of a hydrophilic polymerizable monomer, a hydrophobic polymerizable monomer, a specific amount of a metal fluoride, a polymerization initiator and a filler. . More specifically, the present invention relates to a dental adhesive for bonding a filling material such as a composite resin by coating the surface thereof directly or after applying an acid etching agent or a primer to the tooth material. ADVANTAGE OF THE INVENTION The dental composition of this invention has a preventive action of dental caries by strengthening the tooth by gradually releasing fluoride ions in the oral cavity, and shows excellent adhesion to teeth.

[0002]

2. Description of the Related Art In dental care, it is already well known that fluorine ions act on the tooth material to strengthen the tooth material. For the purpose of preventing and / or suppressing dental caries, the dental material is treated with fluorine ion. May be treated. Recently, a fluoride capable of releasing fluoride ions has been added to a dental adhesive in advance, and the fluoride ions eluted from the adhesive have been used to fluorinate the cavity wall of the cavity, thereby strengthening the tooth material and secondary dental caries. Some dental adhesives have been put on the market to prevent this.

[0003] As the fluoride used for such purpose, fluorine-containing glass represented by fluoroaluminosilicate glass and the like, and metal fluoride represented by sodium fluoride and the like are known. Fluorine-containing glass has the feature of gradually releasing fluoride ions, and although it is unlikely to cause significant deterioration in mechanical strength, due to the small amount of fluoride ion released, it is not possible to sufficiently strengthen tooth quality to prevent caries There is a problem.

[0004] On the other hand, although metal fluorides release a large amount of fluorine ions, they release fluorine ions in a short period of time, making it difficult to supply fluorine ions to the tooth material over a long period of time. Further, although the reason is not clear, when a large amount of fluorine ions is supplied to the bonding portion between the dentin and the adhesive in a short period of time, it becomes difficult to obtain excellent adhesiveness, particularly excellent adhesive durability.

[0005] Specific examples of adhesives containing a metal fluoride include, for example, JP-A-62-201806, JP-A-2-115108 and JP-A-2-25860.
An adhesive described in Japanese Patent Publication No. 2 (Kokai) No. 2 is cited. Adhesives described in these publications, by blending a metal fluoride such as sodium fluoride in the dental composition,
After the composition is cured, fluorine ions are released, strengthening the tooth quality and exerting a caries preventive effect. However, in the examples of any of the publications, none of the compositions contains a hydrophilic polymerizable monomer, and is useful as an adhesive for enamel, but for dentin containing a large amount of water. Has an extremely low adhesive strength. That is, the composition is not always satisfactory for use as a bonding material for bonding dentin and a filler material such as a composite resin or a compomer.

[0006] Also, Japanese Patent Application Laid-Open No. 5-85912 discloses that
An orthodontic dental adhesive containing 1% to 50% by weight of a hydrophilic polymerizable monomer and 0.1 to 20% by weight of a metal fluoride is disclosed. Thus, in orthodontic treatment, it is necessary to remove the orthodontic bracket (debonding). In other words, the orthodontic adhesive requires high adhesive strength when mounting the bracket, but when debonding, if the adhesive remains on the tooth surface, the adhesive is removed and the tooth material is scraped off at the same time Because of the high possibility, an adhesive excellent in adhesive durability is not preferable.

[0007] The technique disclosed in the publication is to promote the release of fluorine ions by incorporating a large amount of a hydrophilic polymerizable monomer into the composition, and to reduce the strength over time due to water absorption of the cured product. And is a useful technique that facilitates removal of brackets and adhesive. However, the adhesive described in the examples of the publication has an appropriate adhesive durability to enamel containing almost no water, and thus is useful as a correction adhesive,
Adhesion to water-rich dentin releases a large amount of fluorine ions in a short period of time and significantly lowers the adhesive strength, particularly the adhesive durability, and is therefore unsuitable as an adhesive for filling and restoring.

Furthermore, Japanese Patent Application Laid-Open No. 11-209213 discloses that if a fluoride obtained by coating the surface of a metal fluoride with polysiloxane is mixed with an adhesive, sufficient adhesion can be achieved while releasing fluorine ions from the adhesive. It is stated that performance is obtained. However, dental adhesives that release fluorine ions do not always have sufficient adhesiveness to dentin, especially dentin, and further improvement in adhesive strength is desired.

[0009]

The problem to be solved by the present invention is to gradually release fluorine ions capable of strengthening the dentin without releasing a large amount thereof, and to improve the dentin, particularly the dentin. Another object of the present invention is to provide a dental composition capable of obtaining improved adhesiveness, especially adhesive durability.

[0010]

The present inventors believe that the above object can be achieved if the amount and rate of release of fluorine ions from the cured composition can be adjusted. As a result of intensive studies on the amounts of monomers and metal fluorides, when these are blended in a specific amount range, the acid resistance of the dentin is improved more than expected, and especially excellent adhesion to dentin They found that durability was obtained, and completed the present invention.

That is, the present invention provides (a) a hydrophilic polymerizable monomer, (b) a hydrophobic polymerizable monomer, (c) a metal fluoride,
(D) a composition comprising a polymerization initiator and (e) a filler, wherein the compounding amount of the hydrophilic polymerizable monomer (a) is 20% by weight to 40% by weight based on the whole composition; And the compounding amount of the metal fluoride (c) is 0.1 to the whole composition.
It is a dental composition characterized in that it is from 1% by weight to 1% by weight.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The hydrophilic polymerizable monomer used in the present invention is not only necessary for obtaining excellent adhesiveness, but also for the fluorine ion released from metal fluoride after polymerization and curing. Required to control release rate. Such a hydrophilic polymerizable monomer has a solubility in water at 25 ° C. of 5% by weight or more, more preferably 1% by weight.
Those showing 0% by weight or more are preferably used. Specifically, 2-hydroxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate,
Hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 1,3-dihydroxypropyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, 2-trimethylammoniumethyl (meth) acryl chloride, ( (Meth) acrylamide, 2-hydroxyethyl (meth) acrylamide, polyethylene glycol di (meth) acrylate (having 9 or more oxyethylene groups) and the like. These hydrophilic polymerizable monomers are used alone or in combination of two or more. In the present invention, both (meth) acryl and acryl are comprehensively represented by (meth) acryl.

The amounts of these hydrophilic polymerizable monomers are as follows:
If the amount is too small, the release rate of fluorine ions will be slow, and the dentin cannot be sufficiently strengthened, and the adhesive performance will also be reduced. 20% by weight to 40% by weight, based on the total weight of the dental composition, since the adhesive durability may be reduced.
Wt% range, more preferably 25 wt% to 35 wt%
It is blended and used in the range.

[0014] The hydrophobic polymerizable monomer used in the present invention is necessary for improving excellent adhesiveness, curability, mechanical strength and coatability. Such a hydrophobic polymerizable monomer has a solubility in water at 25 ° C. of 5% by weight.
It is smaller, more preferably 1% by weight or less. Such hydrophobic polymerizable monomers include esters such as α-cyanoacrylic acid, (meth) acrylic acid, α-halogenated acrylic acid, crotonic acid, cinnamic acid, sorbic acid, maleic acid, itaconic acid and ( (Meth) acrylamide derivatives, vinyl esters, vinyl ethers, mono-N-vinyl derivatives, styrene derivatives and the like. Among them, (meth) acrylate is preferably used.

Examples of (meth) acrylates include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, isobutyl (meth) acrylate, benzyl (meth) acrylate, lauryl (meth) Acrylate,
2,3-dibromopropyl (meth) acrylate, 3-
Methacryloyloxypropyltrimethoxysilane, 1
1-methacryloyloxyundecyltrimethoxysilane, 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, 1,2-bis (3-methacryloyloxy-2
-Hydroxypropoxy) ethane, [2,2,4-trimethylhexamethylenebis (2-carbamoyloxyethyl)] dimethacrylate, trimethylolpropanetri (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-
Examples include tetraacryloyloxymethyl-4-oxyheptane, 2-hydroxypropyl-1,3-di (meth) acrylate, 3-hydroxypropyl-1,2-di (meth) acrylate, and pentaerythritol di (meth) acrylate. Can be

These hydrophobic polymerizable monomers are used alone or in combination of two or more. The amount of these hydrophobic polymerizable monomers, even if too large or too small, the adhesive strength to dentin may be reduced, so that the total amount of the dental composition of the present invention is usually , 3
It is used in the range of 0 to 80% by weight, preferably 40 to 70% by weight.

As the metal fluoride used in the present invention, any metal fluoride capable of dissolving in water and releasing fluorine ions can be used. Specifically, lithium fluoride, sodium fluoride, potassium fluoride, rubidium fluoride, cesium fluoride, beryllium fluoride, magnesium fluoride, calcium fluoride, strontium fluoride,
Barium fluoride, aluminum fluoride, manganese (II) fluoride, iron (II) fluoride, iron (III), cobalt (II) fluoride, copper (II) fluoride, copper (III) fluoride, Zinc fluoride, antimony fluoride, lead (II) fluoride, silver (I) fluoride, cadmium fluoride, tin (II) fluoride, tin (IV) fluoride, silver diamine fluoride, sodium monofluorophosphate , Potassium hexafluorotitanate, hexafluorotin (IV), potassium hexafluorozirconate, and the like. Among them, lithium fluoride, sodium fluoride, potassium fluoride and sodium monofluorophosphate are preferably used. Further, as the metal fluoride, those having fine particles of 1 μm or less are preferably used. As a method for producing the metal fluoride of these fine particles, generally, after dissolving or uniformly dispersing in distilled water or a polar organic solvent, the solvent is cooled and solidified using, for example, a freeze dryer, and the solvent is further sublimated. Can be obtained.

These metal fluorides are used in one kind or in combination of plural kinds. The compounding amount of these metal fluorides is 0.1% based on the whole dental composition of the present invention.
It is necessary to mix in a range of 1% by weight to 1% by weight, preferably in a range of 0.15% by weight to 0.7% by weight, more preferably in a range of 0.2% to 0.5% by weight. You.
If the amount is less than 0.1% by weight, the release rate of fluorine ions becomes extremely slow, and it is not possible to sufficiently strengthen the dentin. If the amount is more than 1% by weight, a large amount of fluorine ions are released in a short time, and the adhesiveness, particularly the adhesive durability, is reduced.

It is preferable to use these metal fluorides by coating their surfaces in advance with various polymerizable monomers and silane coupling agents. As described above, the amount of the metal fluoride in the fluoride whose surface is coated is 0.1 to 1% by weight based on the whole composition. Fluoride coated on these surfaces is
Those having an average particle size of 1 to 30 μm are preferably used.

Among such coated metal fluorides, the use of a polysiloxane-coated metal fluoride obtained by coating the surface of the metal fluoride with a polysiloxane is particularly preferred because the adhesion durability is more excellent. You. The “polysiloxane” used in the present invention is represented by-
It means a silicon compound having a molecular structure in which Si—O— bonds are linked in a network, and includes an organopolysiloxane in which one bond of a silicon atom is bonded to an organic group instead of an oxygen atom. As the polysiloxane, a compound obtained by dehydrating and condensing a silane compound that produces a silane compound having a silanol group is preferably used.
The polysiloxane is obtained by dehydrating and condensing the silanol groups of the obtained silanol compound by hydrolysis or partial hydrolysis. In order to coat the surface of the metal fluoride with polysiloxane, for example, a method of hydrolyzing a silane compound and further dehydrating and condensing it into a polymer as described in JP-A-11-209213 is used. it can.

The polymerization initiator used in the present invention is necessary for hardening the dental composition firmly, and known photopolymerization initiators and / or chemical polymerization initiators can be used. Examples of the photopolymerization initiator include α-diketones, ketals, thioxanthones, acylphosphine oxides, coumarins, and halomethyl-substituted -s-.
And triazine derivatives.

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 thioxanthones include 2-chlorothioxanthone, 2,4-diethylthioxanthone, and the like.
Examples of acylphosphine oxides include, for example,
2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, bis (2 , 4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,6-dimethylbenzoyl) phenylphosphine oxide, bis (2,6
-Dimethoxybenzoyl) phenylphosphine oxide, tris (2,4,6-trimethylbenzoyl) phosphine 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.

Coumarins are described in JP-A-10-245525 such as 3,3'-carbonylbis (7-diethylamino) coumarin, 3- (4-methoxybenzoyl) coumarin and 3-chenoylcoumarin. Compounds. Examples of the halomethyl group-substituted -s-triazine derivatives include 2,4,6-tris (trichloromethyl) -s-triazine, 2,4,6-tris (tribromomethyl) -s-triazine, 2-methyl-4, 6-
Compounds described in JP-A-10-245525 such as bis (trichloromethyl) -s-triazine are exemplified. When photopolymerization by ultraviolet irradiation is performed, benzoin alkyl ether, benzyl dimethyl ketal, and the like are preferable. These photopolymerization initiators are used alone or in combination of two or more. The compounding amount of these photopolymerization initiators is usually in the range of 0.01 to 10% by weight, more preferably 0.1 to 5% by weight, based on the whole dental composition of the present invention. Is done.

These photopolymerization initiators may be used alone, but are generally used in combination with a reducing agent for the purpose of promoting photocurability. Examples of such a reducing agent include tertiary amines, aldehydes, and compounds having a thiol group. Examples of the tertiary amine include 2- (dimethylamino) ethyl methacrylate, N, N-bis [(meth) acryloyloxyethyl] -N-methylamine, ethyl 4-dimethylaminobenzoate, and 4-dimethylaminobenzoate. Butyl acid, butoxyethyl 4-dimethylaminobenzoate, N-methyldiethanolamine, 4-dimethylaminobenzophenone,
N, N-di (2-hydroxyethyl) -p-toluidine and the like can be mentioned.

Examples of aldehydes include dimethylaminobenzaldehyde, terephthalaldehyde and the like. Examples of the compound having a thiol group include 2-mercaptobenzoxazole, decanethiol, 3-mercaptopropyltrimethoxysilane, and thiobenzoic acid. These reducing agents are used in one kind or in combination of plural kinds. The compounding amount of these reducing agents is usually in the range of 0.01% by weight to 10% by weight, more preferably 0.05% by weight to 7% by weight, based on the dental composition of the present invention.
And more preferably in the range of 0.1% by weight to 5% by weight.

As the chemical polymerization initiator, for example, a redox polymerization initiator composed of an oxidizing agent and a reducing agent is suitably used. As the oxidizing agent, for example, organic peroxides such as diacyl peroxides, peroxy esters, dialkyl peroxides, peroxy ketals, ketone peroxides, and hydroperoxides can also be blended. Specifically, diacyl peroxides include benzoyl peroxide, 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,
1,1-bis (t-butylperoxy) -3,3,5-
Examples include trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, and the like. Examples of the ketone peroxides include methyl ethyl ketone peroxide, cyclohexanone peroxide, methyl acetoacetate peroxide, and the like. Examples of hydroperoxides include, for example, t
-Butyl hydroperoxide, cumene hydroperoxide, p-diisopropylbenzene peroxide and the like.

As the reducing agent, aromatic tertiary amines, aliphatic tertiary amines, sulfinic acid or salts thereof are preferably used. 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, N-dimethyl-4-t-butylaniline,
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-isopropylaniline, N, N-bis (2- Hydroxyethyl) -4-t-
Butylaniline, N, N-bis (2-hydroxyethyl) -3,5-diisopropylaniline, N, N-bis (2-hydroxyethyl) -3,5-dibutylaniline, n-butoxy 4-dimethylaminobenzoate ethyl,
(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-triisopropylbenzenesulfinic acid, 2, Sodium 4,6-triisopropylbenzenesulfinate, potassium 2,4,6-triisopropylbenzenesulfinate, calcium 2,4,6-triisopropylbenzenesulfinate and the like. These oxidizing agents and reducing agents are used in one kind or in combination of plural kinds. The amount of these chemical polymerization initiators is usually in the range of 0.01% by weight to 10% by weight, more preferably in the range of 0.05 to 7% by weight, and more preferably in the range of 0.01 to 7% by weight, based on the dental composition of the present invention. Preferably 0.1 to
Used in the range of 5% by weight.

The filler used in the present invention is required to suppress the sedimentation of the metal fluoride, and is also required to adjust the coatability, fluidity, mechanical strength, etc. of the composition. There is. As such a filler, an inorganic filler or an organic filler and a composite thereof are used. Examples of the inorganic filler include silica or a silica-based mineral such as kaolin, clay, mica, and mica; silica-based mineral; Al ₂ O ₃ , B ₂ O ₃ , TiO _2
2 , ZrO ₂ , BaO, La ₂ O ₃ , SrO ₂ , CaO, P ₂
Ceramics and glasses containing O _{5 and the} like, particularly lanthanum glass, barium glass, strontium glass,
Examples include soda glass, lithium borosilicate glass, zinc glass, fluoroaluminum borosilicate glass, borosilicate glass, and bioglass. 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. In addition, an inorganic / organic composite filler obtained by dispersing an inorganic filler in these organic fillers, or coating the inorganic filler with various organic resins may also be used.

As described above, these fillers are known surface treatment agents such as silane coupling agents in order to suppress sedimentation of metal fluorides and adjust the coating properties, fluidity, mechanical strength, etc. of the composition. May be used after surface treatment in advance. 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 can be mentioned.

These fillers are compounded alone or in combination of two or more kinds, and are usually in the range of 1 to 40% by weight, preferably 5 to 40% by weight, based on the whole dental composition of the present invention.
A range of 30% by weight is preferred. The average particle diameter of the filler is usually in the range of 0.001 to 50 μm. In order to exhibit the effect of suppressing the sedimentation of the metal fluoride, an ultrafine filler of 1 μm or less is preferably blended. Among them, colloidal silica such as Aerosil is preferably used, and the viscosity of the composition is preferably adjusted to 0.1 to 2.0 Pa · s at 30 ° C. and 10 rpm.

In the dental composition of the present invention, by further compounding a polymerizable monomer having an acidic group, not only the adhesion to the tooth material is further improved, but also the release rate of fluorine ions can be easily controlled. can do. Examples of such acidic group-containing polymerizable monomers include, for example, a phosphoric acid residue, a pyrophosphoric acid residue, at least one acidic group such as a carboxylic acid residue or a sulfonic acid residue, and an acryloyl group, Examples include a polymerizable monomer having a polymerizable unsaturated group such as a methacryloyl group, a vinyl group, and a styrene group. Specific examples of the compound include the following.

Examples of the phosphoric acid group-containing polymerizable monomer include 2- (meth) acryloyloxyethyl dihydrogen phosphate, 3- (meth) acryloyloxypropyl dihydrogen phosphate and 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) acryloyloxydecyl dihydrogen phosphate, 11- (meth) acryloyloxyundecyl dihydrogen phosphate, 12- (meth) acryloyl oxide decyl dihydrogen phosphate, 16- (meth) acryloyloxyhexadecyl dihydrogen Phosphate, 20- (meth) acryloyloxyeicosyl dihydrogen phosphate,
Di [2- (meth) acryloyloxyethyl] hydrogen phosphate, di [4- (meth) acryloyloxybutyl] hydrogen phosphate, di [6-
(Meth) acryloyloxyhexyl] hydrogen phosphate, di [8- (meth) acryloyloxyoctyl] hydrogen phosphate, di [9- (meth) acryloyloxynonyl] hydrogen phosphate, di [10- (meth) acryloyloxy Decyl] hydrogen phosphate, 1,3-di (meth)
Acryloyloxypropyl-2-dihydrogenphosphate, 2- (meth) acryloyloxyethylphenylhydrogenphosphate, 2- (meth) acryloyloxyethyl 2′-bromoethylhydrogenphosphate, (meth) acryloyloxyethyl phenylphosphonate, etc. . (5-methacryloxy) pentyl-3-phosphonopropionate, (6-methacryloxy) hexyl-3-phosphonopropionate, and (10-) described in JP-A-3-294286.
(Methacryloxy) decyl-3-phosphonopropionate, (6-methacryloxy) hexyl-3-phosphonoacetate, (10-methacryloxy) decyl-3-phosphonoacetate and the like. 2-methacryloyloxyethyl (4-) described in JP-A-62-281885.
Methoxyphenyl) hydrogen phosphate, 2-
Methacryloyloxypropyl (4-methoxyphenyl) hydrogen phosphate and the like. Further, Japanese Unexamined Patent Publication No.
JP-A-2-113089, JP-A-53-67740, JP-A-53-69494, JP-A-53-14
No. 4,939, JP-A-58-128393, and phosphate-group-containing polymerizable monomers exemplified in JP-A-58-192891. Further, there may be mentioned acid chlorides, alkali metal salts and ammonium salts thereof.

The polymerizable monomers containing a pyrophosphate group include:
For example, di [2- (meth) acryloyloxyethyl pyrophosphate], di [4- (meth) acryloyloxybutyl] pyrophosphate, di [6- (meth) acryloyloxyhexyl] pyrophosphate, di [8-pyrophosphate] (Meth) acryloyloxyoctyl], dipyrophosphate di [10-
(Meth) acryloyloxydecyl].
Further, there may be mentioned acid chlorides, alkali metal salts and ammonium salts thereof.

As the carboxylic acid group-containing polymerizable monomer,
For example, 4- (meth) acryloyloxyethoxycarbonylphthalic acid, 4- (meth) acryloyloxybutyloxycarbonylphthalic acid, 4- (meth) acryloyloxyhexyloxycarbonylphthalic acid, 4- (meth) acryloyloxyoctyloxycarbonyl Phthalic acid, 4- (meth) acryloyloxydecyloxycarbonylphthalic acid, and their acid anhydrides, 5- (meth) acryloylaminopentylcarboxylic acid, 6- (meth) acryloyloxy-1,1-hexanedicarboxylic acid, 8- (meth) acryloyloxy-1,1-octanedicarboxylic acid, 10- (meth) acryloyloxy-
Examples thereof include 1,1-decanedicarboxylic acid, 11- (meth) acryloyloxy-1,1-undecanedicarboxylic acid, methacrylic acid, and maleic acid. Further, there may be mentioned acid chlorides, alkali metal salts and ammonium salts thereof.

As the sulfonic acid group-containing polymerizable monomer,
For example, 2- (meth) acrylamide-2-methylpropanesulfonic acid, styrenesulfonic acid, 2-sulfoethyl (meth) acrylate, and the like can be given. Above all, when a phosphoric acid group-containing polymerizable monomer is used, it is preferably used because it has extremely excellent adhesion to tooth material. The use of a divalent phosphoric acid group-containing polymerizable monomer such as 10-methacryloyloxydecyl dihydrogen phosphate is preferred because the fluorine ion release rate can be more easily controlled.

These acidic group-containing polymerizable monomers are used alone or in combination of two or more. If the compounding amount of these acidic group-containing polymerizable monomers is too large, the adhesive performance may be deteriorated. Therefore, the amount is usually 0.1 to 30% by weight based on the whole dental composition of the present invention. It is desirable to use it in the range, more preferably in the range of 0.5% to 20% by weight, even more preferably in the range of 1% to 10% by weight.

In the dental composition of the present invention, a calcium ion-releasing substance is further added to
The formation of the acid-resistant layer of the tooth can be promoted. Such calcium ion releasing substances include, for example, calcium hydroxide, calcium oxide, monobasic calcium phosphate,
Inorganic compounds such as calcium metaphosphate, dibasic calcium phosphate, calcium pyrophosphate, tribasic calcium phosphate, tetracalcium phosphate, octacalcium phosphate, hydroxyapatite, and calcium fluoride are preferred. Glasses containing these inorganic compounds in the composition are also suitable. These calcium ion releasing substances are used in one kind or in combination of plural kinds.

The optimum amount of the calcium ion-releasing substance is different between the case where the inorganic compound is compounded and the case where the compound is used as glass. Usually 0.01 weight to 1
It is desirable to use it in the range of 0% by weight, more preferably in the range of 0.1% to 5% by weight, and even more preferably in the range of 0.5% to 3% by weight. If the amount is less than 0.01% by weight, the effect of promoting the strengthening of the tooth may not be recognized,
If the amount is more than 10% by weight, the mechanical strength and the tooth adhesion may be reduced.

When compounded as glass, it is usually in the range of 0.1% to 30% by weight, more preferably 0.5% to 20% by weight, and still more preferably 1% to 30% by weight, based on the whole composition. It is desirable to use it in the range of 10% by weight.
If the amount is less than 0.1% by weight, the effect of promoting the strengthening of the tooth may not be recognized, and if it is more than 30% by weight, the mechanical strength and the adhesiveness of the tooth may decrease. In addition,
These calcium ion releasing substances are used as the above-mentioned filler.

Further, water, a volatile organic solvent and a mixture thereof can be blended for the purpose of improving the coating property or assisting the solubility in the polymerization initiator. As such a volatile organic solvent, a volatile organic solvent having a boiling point at normal pressure of 150 ° C. or lower, more preferably 100 ° C. or lower is usually used. For example, alcohols such as ethanol, methanol, 1-propanol, and isopropyl alcohol are used. Kind,
Acetones such as acetone and methyl ethyl ketone, ester compounds such as ethyl acetate, methyl acetate and ethyl propionate, ethers such as 1,2-dimethoxyethane, 1,2-diethoxyethane and tetrahydrofuran, heptane,
Hydrocarbon compounds such as hexane and toluene, and halogenated hydrocarbon compounds such as chloroform and dichloromethane are preferably used. Among them, water-soluble volatile solvents such as ethanol and acetone are preferably used. The amount of the water and / or volatile organic solvent is usually 30% by weight or less, preferably 10% by weight, based on the whole composition of the present invention.
It is desirable to use it in the range of not more than weight%. In addition, these water and / or volatile solvent blended in the dental composition of the present invention are applied to the dentin so that the adhesiveness is not impaired, and then, using a dental air syringe or the like. It is desirable to evaporate.

Further, a polymerization inhibitor, a coloring agent, a fluorescent agent, an ultraviolet absorber, and the like may be added to the dental composition of the present invention, if desired. Also, for the purpose of providing antibacterial properties,
Contains cationic antibacterial compounds such as cetylpyridinium chloride, chlorhexidine hydrochloride, benzalkonium chloride, (meth) acryloyloxidedecylpyridinium bromide, (meth) acryloyloxyhexadecylpyridinium chloride and (meth) acryloyloxydecylammonium chloride. You may.

Further, the dental composition of the present invention can be used not only for hard tissues such as teeth, but also for crown restorative materials such as metals, porcelains, and cured composites. It may be used in combination with a commercially available dental metal primer, a primer for bonding porcelain, a tooth surface cleaning agent such as hypochlorate, and the like. Hereinafter, preferred embodiments of the present invention will be described, but the present invention is not limited to the following embodiments. The abbreviations and abbreviations are as follows.

Hydrophilic polymerizable monomer: HEMA: 2-hydroxyethyl methacrylate 9G: polyethylene glycol dimethacrylate (the number of oxyethylene groups is 9)

Hydrophobic polymerizable monomer: Bis-GMA: bisphenol A diglycidyl methacrylate UDMA: [2,2,4-trimethylhexamethylenebis (2-carbamoyloxyethyl)] dimethacrylate HD: hexanediol dimethacrylate

Metal fluoride (fine particles of 1 μm or less): NaF: sodium fluoride KF: potassium fluoride PFNa: sodium monofluorophosphate

Polymerization initiator, reducing agent: CQ: camphorquinone TMDPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide DEPT: N, N-di (2-hydroxyethyl) -p-
Toluidine DMAB: 4-N, N-dimethylaminobenzophenone

Acidic group-containing polymerizable monomer: MDP: 10-methacryloyloxydecyl dihydrogen phosphate

Polymerization inhibitors and others: BHT: t-butylhydroxytoluene MDPB: 12-methacryloyloxidedecylpyridinium bromide

[0054]

EXAMPLES Example 1 MDP (15 parts by weight), HEMA (40 parts by weight), distilled water (40 parts by weight), MDPB (5 parts by weight), TMDPO
(0.5 parts by weight), DEPT (3.4 parts by weight), BHT
(0.1 parts by weight) was prepared. Subsequently, as shown in Table 1, HEMA, Bis-GMA,
A bonding material composed of HD, NaF, CQ, TMDPO, DMAB, and ultrafine silica was prepared. Using this primer A and the bonding material, the adhesion strength was measured according to the adhesion test method described later, and the measurement results are shown in Table 1. Further, the acid resistance effect of the tooth material was evaluated according to the test method for confirming the tooth material strengthening described below, and the evaluation results are shown in Table 1.

[0055]

[Table 1]

Adhesion test method: Bovine front teeth # 1000
After smooth wet polishing with silicon carbide paper (manufactured by Nippon Kenshi Co., Ltd.), the enamel surface or the dentin surface was exposed, and the water on the surface was blown off with a dental air syringe. Adhesive tape of about 150 microns thick with a hole of 3 mm in diameter is applied to the exposed enamel surface or dentin surface, primer A is applied to the hole portion with a brush, left as it is for 30 seconds, and then air syringe The primer A was dried until the fluidity of the primer A was lost.

On top of that, the bonding material is
Dental light irradiator "Lightel I"
I "(trade name, manufactured by Gunma Ushio Electric Co., Ltd.) for 20 seconds to cure by light irradiation. Further, a commercially available light-curable dental composite resin “Clearfill AP-
X "(trade name, manufactured by Kuraray Co., Ltd.), and a film made of EVAL (registered trademark, trade name, manufactured by Kuraray Co., Ltd.) is applied. A slide glass is pressed from above, and the light irradiation is performed in this state. Light irradiation was carried out for 40 seconds in a vessel to cure the composition.

For this hardened surface, a commercially available dental resin cement “Panavia 21” (trade name, manufactured by Kuraray Co., Ltd.)
After 30 minutes, the test piece was immersed in water at 37 ° C. for 24 hours, and further immersed in cold water at 4 ° C. and warm water at 60 ° C. for 1 minute each. After being loaded twice, the adhesive strength was measured. For the measurement of the adhesive strength, a universal testing machine (manufactured by Instron) was used to measure the tensile adhesive strength at a cross head speed of 2 mm / min. The measured value of each adhesive strength was represented by an average value of the measured values of eight test pieces.

Test method for confirming the strengthening of tooth quality: Human molars were replaced with # 8
After removing the crown portion by wet polishing with silicon carbide paper (manufactured by Nippon Kenshi Co., Ltd.) and then wet smooth polishing with # 1000 silicon carbide paper to expose the dentin surface, The water on the surface was blown off with a dental air syringe. Apply primer A to the exposed dentin surface with a brush,
After allowing the mixture to stand for 30 seconds, it was dried with an air syringe until the fluidity of the primer A disappeared.

On top of this, the bonding material is
Dental light irradiator "Lightel I"
I "(trade name, manufactured by Gunma Ushio Electric Co., Ltd.) for 20 seconds to cure by light irradiation. Further, a commercially available light-curable dental composite resin “Clearfill AP-
X "(manufactured by Kuraray Co., Ltd., trade name), and in this state, light irradiation was carried out for 40 seconds with the above light irradiation device to cure.

Thereafter, the prepared sample was placed in a container containing distilled water and stored in a thermostat at 37 ° C. for 6 months. 6
The sample immersed in water for months was cut using a low-speed diamond cutter so that a joint between the tooth material and the bonding material appeared. The fractured surface was further wet-polished with # 1500 silicon carbide paper, and then immersed in a citrate buffer (pH 5.6) so that the fractured surface was upward. Then, it was stored in a thermostat at 37 ° C. for 24 hours to demineralize the tooth substance (fractionated section). The degree of the demineralization was observed with a scanning electron microscope, and evaluated by the score described below.

-: Dentin immediately below the bonding material was also demineralized, and no acid resistance of the dentin was observed. +: 1 μm or more to 5 in the downward direction from immediately below the bonding material
In the range of less than μm, an acid-resistant layer was observed in the dentin. ++: An acid-resistant layer was observed in the dentin in a range of 5 μm or more from directly below the bonding material to below.

Examples 2 to 7, Comparative Examples 1 to 3 As shown in Table 1, HEMA, Bis-GMA, UDM
A, HD, NaF, CQ, TMDPO, DMAB, ultrafine silica, MDP, etc.
Bonding materials having different amounts of F were prepared. Using these bonding materials and the primer A used in Example 1, the adhesion strength was measured in accordance with the same adhesion test method as in Example 1, and the measurement results are shown in Table 1.
In addition, the acid resistance effect of the tooth substance was evaluated according to the test method for confirming the reinforcement of the tooth substance in Example 1, and the evaluation results are shown in Table 1.

As is clear from Table 1, NaF was 0.1%.
When the bonding material blended in the range of 1% by weight to 1% by weight was used, the adhesiveness to the tooth was excellent, the acid resistant layer was formed on the tooth, and the tooth was reinforced (Example 1). ~ 7). Among them, NaF is particularly 0.15% by weight to 0.1% by weight.
When the bonding material blended in the range of 7% by weight was used, both the tooth adhesion and the acid resistance of the tooth were more excellent (Example 1, Examples 3 to 6). On the other hand, NaF
When a bonding material containing no was used, the adhesiveness was excellent, but the tooth quality was not reinforced at all (Comparative Example 1). When a bonding material containing 5% by weight of NaF was used, the dentin was reinforced, but the adhesion to the tooth, particularly the adhesion to dentin, was very poor (Comparative Example 2, Comparative Example 2). 3).

Examples 8 to 14, Comparative Examples 4 to 6 As shown in Table 2, HEMA, Bis-GMA, HD,
In a composition comprising NaF, CQ, TMDPO, DMAB, ultrafine silica, MDP and the like, bonding materials having different amounts of HEMA were prepared. These bonding materials and the primer A used in Example 1
Was used to measure the adhesion strength in accordance with the same adhesion test method as in Example 1, and the measurement results are shown in Table 2. Further, the acid resistance effect of the tooth material was evaluated in accordance with the test method for confirming the reinforcement of the tooth material in Example 2, and the evaluation results are shown in Table 2.

[0066]

[Table 2]

As is clear from Table 2, HEMA was 20
When the bonding material blended in the range of 40% by weight to 40% by weight is used, the adhesiveness to the tooth is excellent, and an acid-resistant layer is formed on the tooth, and the tooth is reinforced (Example). 8-14). Among them, particularly, HEMA is 25% by weight or more.
When the bonding material blended in the range of 35% by weight was used, both the tooth adhesion and the acid resistance of the tooth were more excellent (Examples 10 to 12). In contrast, HEMA
When a bonding material containing 10% by weight is used,
The adhesiveness was reduced, and the tooth quality was not further strengthened (Comparative Examples 4 and 5). When a bonding material containing 50% by weight of HEMA was used, the dentin was reinforced, but the adhesion to the tooth, particularly the adhesion to dentin, was very poor (Comparative Example 6).

Examples 15 to 22, Comparative Examples 7 and 8 As shown in Table 3, hydrophilic polymerizable monomers, hydrophobic polymerizable monomers, metal fluorides, polymerization initiators, ultrafine silica and MDP And the like. Using these bonding materials and the primer A used in Example 1, the adhesion strength was measured according to the same adhesion test method as in Example 1, and the measurement results are also shown in Table 3.
Further, the acid resistance effect of the tooth material was evaluated according to the test method for confirming the reinforcement of the tooth material of Example 1, and the evaluation results are shown in Table 3. In addition, MC-NaF is obtained by coating the surface of NaF of fine particles of 1 μm or less with polysiloxane.
An aF having an NaF content of 50% by weight was used.

Method for producing MC-NaF 100 g of vinyltriethoxysilane was added to 40 m of 4 mN hydrochloric acid.
and stirred at room temperature until the system became homogeneous. 55 g of fine particles of NaF having a particle size of 1 μm or less, 40 g of ethanol and 3-aminopropyltriethoxysilane
After stirring for 24 hours, volatile components are removed by distillation under reduced pressure, and a heat treatment at 120 ° C. is further performed for 1 hour, and MC-NaF having an average particle size of 10 μm is obtained by grinding.
0 g was obtained.

[0070]

[Table 3]

As is clear from Table 3, even when a bonding material containing 0.5% by weight of KF, PFNa or MC-NaF is used instead of NaF, the adhesiveness to the tooth material is excellent, and the tooth material is further improved. Had an acid-resistant layer formed thereon, and had enhanced tooth quality (Examples 15 to 22). Further, even when a bonding material containing 9G as a hydrophilic polymerizable monomer was used, the adhesiveness to the tooth was excellent, and an acid-resistant layer was formed on the tooth, and the tooth was reinforced. (Example 21, Example 22). On the other hand, MC-N
When a bonding material containing 5% by weight of aF was used, the dentin was reinforced, but the adhesion to the tooth, particularly the adhesion to dentin, was very poor (Comparative Example 7). When a bonding material containing no hydrophilic polymerizable monomer was used, the dentin was not strengthened, and the adhesion to the tooth, particularly the adhesion to dentin, was very poor (Comparative Example 8).

Examples 23 to 28 and Comparative Examples 9 to 12 Measurement of Fluoride Ion Release A Teflon mold was placed on a polyester film, and Examples 1, 2, 7, and 7 were placed in the mold. 9, Example 13, Example 20, Comparative Example 3, Comparative Example 5, Comparative Example 6, or the filling material prepared in Comparative Example 8 or Comparative Example 8 was filled, a polyester film was placed thereon, and pressed with a glass plate. Irradiate with α-light (trade name, manufactured by Morita Tokyo Mfg. Co., Ltd.) for 3 minutes, diameter 1.5 cm, thickness 1 m
m of a disk-shaped cured product was prepared. 37.
It was immersed in 4 ml of a phosphate buffer solution (pH 7) at 4 ° C., and the amount of fluoride ion eluted from the disk-shaped cured product was determined. The quantification was performed using a fluorine ion electrode (manufactured by Orion Research). FIG. 1 shows the measurement results of the amount of released fluorine ions. The bonding materials used in Examples 23 to 28 and Comparative Examples 9 to 12 are shown in Table 4.

[0073]

[Table 4]

FIG. 1 is a graph showing the cumulative amount of fluorine ions released from the cured product.
In Examples 25, 26, 27 and 28, a large amount of fluorine ions was not released in a short period of time, and the cumulative amount of fluorine ions for at least 30 days of immersion was 20%.
It was 0 μg / g or more. When the bonding material used in these examples was used, it was confirmed that the dental adhesiveness and the tooth reinforcement were excellent as described above. On the other hand, in Comparative Examples 9 and 11, a large amount of fluorine ions were released in a short period of time, and when the bonding material used in these Comparative Examples was used, as described above, the dentin adhesiveness, particularly Adhesion durability to quality was poor. Comparative Example 10
In Comparative Example 12, the release rate of fluorine ions was extremely low. Therefore, when the bonding material used in these Comparative Examples was used, the dentin could not be sufficiently strengthened as described above, and the adhesion to dentin was further reduced. The sex was also clearly inferior.

Example 29 A bonding material was further prepared by further adding 0.5% by weight of calcium hydroxide to the whole bonding material of Example 1. Using this bonding material and the primer A used in Example 1, the adhesion strength was measured in accordance with the same adhesion test method as in Example 1. As a result, 17.0 MPa for bovine enamel and 17.0 MPa for bovine dentin. 17.3MPa
As in the case of using the bonding material of Example 1, excellent adhesive strength was exhibited. Further, according to the test method for confirming the strengthening of the tooth material of Example 1 (however, the period during which the sample was immersed in distilled water was shortened to three months), the acid resistance effect of the tooth material was evaluated. As a result, the acid-resistant layer was about 6 μm. (Score: +
On the other hand, the bonding material of Example 1 had a thickness of about 3 μm (score: +) under the same conditions, and the addition of calcium hydroxide promoted the speed of strengthening the tooth material.

Example 30 A bonding material was further prepared by further adding 0.5% by weight of calcium hydroxide to the whole bonding material of Example 17. Using this bonding material and the primer A used in Example 1, the adhesion strength was measured in accordance with the same adhesion test method as in Example 1, and as a result, 19.5 MPa for bovine enamel and 19.5 MPa for bovine dentin. 19.4MP
a, showing excellent adhesive strength as in the case of using the bonding material of Example 17. Example 29
As a result of evaluating the effect of acid resistance of the tooth substance according to the test method for confirming the reinforcement of the tooth substance, the acid-resistant layer was about 10 μm (score: +
On the other hand, the bonding material of Example 17 had a thickness of about 4 μm (score: +) under the same conditions, and the addition of calcium hydroxide promoted the speed of tooth reinforcement.

[0077]

Industrial Applicability The dental composition of the present invention exhibits excellent adhesiveness to dentin, particularly dentin, and gradually releases fluoride ions capable of strengthening the tooth without releasing a large amount of fluoride ions. Therefore, it is very useful for preventing dental caries, and is particularly suitably used in the field of dentistry as a dental adhesive for the purpose of bonding tooth material to a filling material such as a filling composite resin.

[Brief description of the drawings]

FIG. 1 is a graph showing the amount of fluorine ions released from a cured product.

Claims (5)

[Claims] 1. A composition comprising (a) a hydrophilic polymerizable monomer, (b) a hydrophobic polymerizable monomer, (c) a metal fluoride, (d) a polymerization initiator, and (e) a filler. The compounding amount of the hydrophilic polymerizable monomer (a) is 2 to the whole composition.
0% by weight to 40% by weight, and the compounding amount of the metal fluoride (c) is 0.1% by weight to 1% by weight based on the whole composition.
% By weight of the dental composition. 2. A dental composition according to claim 1, further comprising (f) an acidic group-containing polymerizable monomer. 3. The dental composition according to claim 2, wherein the acidic group-containing polymerizable monomer is a phosphate group-containing polymerizable monomer. 4. The dental composition according to claim 1, wherein the surface of the metal fluoride is coated with a polysiloxane. 5. A dental composition according to claim 1, further comprising (g) a calcium ion releasing substance.