JP3489601B2 - Dental composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dental composition suitable as a pretreatment material for the surface of a tooth in order to achieve high adhesive strength between the filling material and the tooth when the tooth is filled and restored in the field of dentistry. .

[0002]

2. Description of the Related Art A filling material called a composite resin is mainly used for repairing a tooth damaged by caries or the like. This composite resin is generally used by filling the cavity of the tooth and then polymerizing and hardening. However, since this material itself does not have adhesiveness to tooth structure, a dental adhesive is used together. This adhesive material is required to have an adhesive strength sufficient to overcome internal stress generated during curing of the composite resin, that is, tensile stress generated at the interface between the composite resin and the tooth structure. Otherwise, it may fall off due to long-term use in a harsh oral environment, and there may be a gap at the interface between the composite resin and the dentin, from which bacteria may invade and adversely affect the pulp. This is because.

The hard tissue of teeth consists of enamel and dentin, and clinically requires adhesion to both. Conventionally, for the purpose of improving the adhesiveness, a method of pretreating the surface of the tooth before applying the adhesive has been used. As such a pretreatment material, an acid aqueous solution that decalcifies the tooth surface is generally used, and an acid aqueous solution of phosphoric acid, citric acid, maleic acid, etc. has been used. In the case of enamel, the mechanism of adhesion to the treated surface is macro mechanical fitting in which the adhesive penetrates and hardens on the rough surface by decalcification of the acid aqueous solution, whereas in the case of dentin Is said to be micro mechanical fitting in which the adhesive penetrates into the minute voids of the sponge-like collagen fiber exposed on the tooth surface after decalcification and hardens. However, permeation into collagen fibers is not so easy as that on the surface of enamel, and a permeation enhancer called a primer is generally used after the treatment with an aqueous acid solution, resulting in complicated operation. In order to reduce this complexity, Inoue et al. Have proposed a primer composition using 2-acryloyloxyethyl hydrogen malate (40th JADR General Assembly and 24th Annual Meeting of the Japan Society for Dental Science and Engineering). Meeting). However, the treatment with this composition requires a long time, and the simplification of the operation was not sufficient.

[0004]

From the above points, pretreatment,
Simplifies the complicated operation of applying both acid solution and primer as pretreatment in the cavity repair procedures such as adhesive application and composite resin filling, and high adhesion to both enamel and dentin with one pretreatment It has been desired to develop a material that gives strength.

[0005]

Means for Solving the Problems As a result of intensive studies conducted by the present inventors to overcome the above technical problems, a composition containing a phosphoric acid group-containing polymerizable monomer, water and an aryl borate compound as main effect components It was found that the product does not need to be pretreated with an acid aqueous solution and can serve as a primer that gives high adhesive strength to enamel and dentin.

That is, the present invention provides (A) a phosphoric acid group-containing polymerizable monomer, (B) an aryl borate compound, and (C).
Water as the main component, based on 100% by weight of all components,
5 to 50% by weight of component (A), 0.01 to 10% by weight of (B) aryl borate compound, and 5 to 5% of component (C).
The dental composition is characterized by containing 90% by weight.

Still another invention mainly comprises (A) a phosphoric acid group-containing polymerizable monomer, (B) an aryl borate compound, (C) water and (D) a polyvalent carboxylic acid group-containing polymerizable monomer. 5% of component (A) based on 100% by weight of all constituents
˜50% by weight, component (B) 0.01 to 10% by weight,
A dental composition comprising (C) component in an amount of 5 to 90% by weight and (D) component in an amount of 1 to 50% by weight.

In the present invention, the weight content of each of the above-mentioned components is a value when all the components constituting the dental composition, and thus when the optional components are contained, all the components including them are taken as 100% by weight. is there.

The phosphoric acid group-containing polymerizable monomer used in the present invention has at least one ═P (O) —OH in one molecule.
Group, or a functional group capable of easily reacting with water, which is an essential component in the present invention, to generate at least one = P (O) -OH group, and a polymerizable ester group having a polymerizable unsaturated group. There is no particular limitation as long as it is a monomer, and known compounds can be used. Further, it may be a thiophosphoric acid group in which 1 to 2 of the oxygen atoms bonded to the phosphorus atom are replaced with a sulfur atom, or a derivative thereof.

Typical examples of the phosphoric acid group-containing polymerizable monomer include phosphoric acid monoesters represented by the following general formula (1) and diesters represented by the general formulas (2) and (3). Further, two of these compounds may be a pyrophosphate derivative in which two of these compounds are condensed in the form of -P-O-P- via an oxygen atom.

[0011]

[Chemical 1]

(However, R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group, and R ₃ and R ₄ each independently represent the number of carbon atoms which may have an ether bond and / or an ester bond. 1 to 30 divalent to 6-valent organic residue, R ₅ is a hydrogen atom or an alkyl group or an alkoxy group having 1 to 5 carbon atoms, Z is an oxygen atom or a sulfur atom, and X ₁ and X ₂ are each independently. Represents a hydroxyl group, a mercapto group, and a halogen atom, and n ₁ , n ₂
Is an integer from 1 to 5). General formula (1) (2) (3)
In the above, R ₃ R ₄ is a divalent to hexavalent organic residue having 1 to 30 carbon atoms, which may have an ether bond and / or an ester bond. The structure is not particularly limited, but specific examples are as follows.

[0013]

[Chemical 2]

(In the formula, m ₁ , m ₂ and m ₃ each represent an integer of 1 or 2.) Preferred specific examples of the phosphoric acid group-containing polymerizable monomer represented by the general formula (1) will be given. And as follows.

[0015]

[Chemical 3]

[0016]

[Chemical 4]

Specific preferred examples of the phosphoric acid group-containing polymerizable monomer represented by the general formula (2) are as follows.

[0018]

[Chemical 5]

In the general formula (3), R ₅ is a hydrogen atom, or an alkyl group or an alkoxy group having 1 to 5 carbon atoms, specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group. , A pentyl group, a methoxy group, an ethoxy group, a propoxy group and the like.

Preferred specific examples of the phosphoric acid group-containing polymerizable monomer represented by the general formula (3) are as follows.

[0021]

[Chemical 6]

[0022]

[Chemical 7]

Specific examples of the pyrophosphate type derivative in which two of the compounds represented by the general formulas (1), (2) and (3) are condensed in the form of -P-O-P- via an oxygen atom. An example is as follows.

[0024]

[Chemical 8]

Among the above phosphoric acid group-containing polymerizable monomers,
From the viewpoint of adhesiveness to the tooth structure, the phosphoric acid group-containing polymerizable monomer represented by the general formulas (2) and (3), particularly, one of the esters represented by the general formula (3) is an aromatic ester. Certain phosphoric acid group-containing polymerizable monomers are preferred.

If desired, a plurality of these phosphoric acid group-containing polymerizable monomers can be mixed and used.

The compounding amount of the phosphoric acid group-containing polymerizable monomer is 5 to 50% by weight, preferably 7 to 40% by weight based on all the constituent components.
% By weight. If it is less than 5% by weight, the adhesive strength to enamel tends to be insufficient, and the adhesive strength to dentin tends to decrease. If it exceeds 50% by weight, the adhesive strength of both dentin and enamel will decrease.

The water used in the present invention is necessary to decalcify dentin. This water preferably contains substantially no impurities harmful to storage stability, biocompatibility and adhesiveness, and examples thereof include deionized water and distilled water. The amount of water added is preferably 5 to 90% by weight of all the components,
20-80% by weight is more preferred. If it is less than 5% by weight, demineralization of the tooth becomes insufficient, resulting in insufficient adhesive strength for both enamel and dentin. If it exceeds 90% by weight, the adhesive strength tends to decrease in both dentin and enamel.

The aryl borate compound used in the present invention is used as a polymerization initiator. The aryl borate compound is decomposed by an acidic monomer which is an essential component in the present invention, that is, a phosphoric acid group-containing or polyvalent carboxylic acid group-containing polymerizable monomer to form a polymerizable radical species.

A typical one of the aryl borate compounds is represented by the following general formula (4).

[0031]

[Chemical 9]

(Wherein R ₆ , R ₇ and R ₈ are the same or different and optionally substituted alkyl, aryl, aralkyl and alkenyl groups, and R ₉ or R ₁₀ is a hydrogen atom or halogen. An atom, an optionally substituted alkyl group and a phenyl group, and L ⁺ is a metal cation, a quaternary ammonium ion, a quaternary pyridinium ion, a quaternary quinolinium ion and a phosphonium ion. Those having at least one boron-aryl bond in one molecule are mentioned.

An aryl borate compound having no boron-aryl bond is not preferable because it has extremely poor storage stability and easily reacts with oxygen in the air to decompose.

Specific examples of the aryl borate compounds that are preferably used include trialkylphenylboron, trialkyl (p-chlorophenyl) boron and trialkyl as arylborate compounds having one aryl group in one molecule. (P-Fluorophenyl) boron, trialkyl (3,5-bistrifluoromethyl) phenylboron, trialkyl [3,5-bis (1,1,1,1)
3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron (wherein the alkyl group is n-butyl group, n
-Octyl group, n-dodecyl group, etc.), lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methyl Examples thereof include quinolinium salt, ethylquinolinium salt, butylquinolinium salt and the like.

Examples of the aryl borate compound having two aryl groups in one molecule include dialkyldiphenylboron, dialkyldi (p-chlorophenyl) boron, dialkyldi (p-fluorophenyl) boron and dialkyldi (3,5-bistritriene). Fluoromethyl) phenylboron, dialkyldi [3,5-bis (1,1,1,3,3)
3,3-hexafluoro-2-methoxy-2-propyl)
Phenyl] boron (alkyl group is the same as above) sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, Methyl quinolinium salt, ethyl quinolinium salt, butyl quinolinium salt, etc. are mentioned.

Further, as the aryl borate compound having three aryl groups in one molecule, monoalkyltriphenylboron, monoalkyltri (p-chlorophenyl) boron, monoalkyltri (p-fluorophenyl) are used.
Boron, monoalkyltri (3,5-bistrifluoromethyl) phenyl Boron, monoalkyltri [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl ] Boron (alkyl group is the same as above) sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methyl Examples thereof include quinolinium salt, ethylquinolinium salt and butylquinolinium salt.

Furthermore, as aryl borate compounds having four aryl groups in one molecule, tetraphenylboron, tetrakis (p-chlorophenyl) boron,
Tetrakis (p-fluorophenyl) boron, tetrakis (3,5-bistrifluoromethyl) phenylboron, tetrakis [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-) Propyl) phenyl]
Boron (alkyl group is the same as above) sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinone. Examples thereof include a norinium salt, an ethylquinolinium salt, and a butylquinolinium salt.

The aryl borate compounds may be used alone or in combination of two or more.

The amount of the above aryl borate compound added for exhibiting the effect as a polymerization initiator is 0.01 to 10% by weight, preferably 0.05 to 8% by weight, based on all the constituent components.
%, Most preferably 0.5-5% by weight.

The polyvalent carboxylic acid group-containing polymerizable monomer used in the present invention is easily combined with water, which is an essential component in the present invention, such as a carboxyl group in one molecule, or an anhydride or acid halide thereof. 2 groups that react to form a carboxyl group
There is no particular limitation as long as it is a polymerizable monomer having one or more compounds, and known compounds can be used.

Examples of such compounds include trimellitic acid derivatives or pyromellitic acid derivatives represented by the following general formulas (5) and (6), their anhydrides and halides, and the following general formula (7). Examples thereof include malonic acid derivatives and anhydrides thereof, halides, 6- (meth) acryloxyethylnaphthalene 1,2,6-tricarboxylic acid, N- (meth) acryloyl aspartic acid.

[0042]

[Chemical 10]

(However, R ₁ represents a hydrogen atom or a methyl group, and R ₃ represents a divalent to hexavalent organic residue having 1 to 30 carbon atoms which may have an ether bond and / or an ester bond. , R ₆
Represents a hydrogen atom or a carboxyl group, n ₁ represents an integer of ₁ to 5, and n ₃ represents 1 or 2. The preferred specific examples of the polyvalent carboxylic acid group-containing polymerizable monomer represented by the general formula (5) are as follows.

[0044]

[Chemical 11]

[0045]

[Chemical 12]

[0046]

[Chemical 13]

[0047]

[Chemical 14]

[0048]

[Chemical 15]

Specific preferred examples of the polyvalent carboxylic acid group-containing polymerizable monomer represented by the general formula (6) are as follows.

[0050]

[Chemical 16]

Specific preferred examples of the polyvalent carboxylic acid group-containing polymerizable monomer represented by the general formula (7) are as follows.

[0052]

[Chemical 17]

[0053]

[Chemical 18]

Among the above-mentioned polyvalent carboxylic acid group-containing polymerizable monomers, trimellitic acid derivatives represented by the general formula (5) and general formula (7) are particularly preferable from the viewpoint of adhesiveness to teeth. A polyvalent carboxylic acid group-containing polymerizable monomer of a malonic acid derivative is preferably used.

If necessary, a plurality of these polyvalent carboxylic acid group-containing polymerizable monomers may be mixed and used.

The compounding amount of the polyvalent carboxylic acid group-containing polymerizable monomer in the present invention is 1 to 50% by weight, preferably 3 to 30% by weight based on all the constituent components. If it is less than 1% by weight, the adhesive strength to dentin is insufficient. If it exceeds 50% by weight, the adhesive strength of both dentin and enamel will decrease.

When the dental composition of the present invention is used as a pretreatment material for a tooth surface, the components (A), (B) and (C), that is, the phosphoric acid group-containing polymerizable monomer and the aryl borate are used. If a composition comprising a compound and water is used, a sufficiently high adhesive strength can be obtained, but by further adding a polyvalent carboxylic acid group-containing polymerizable monomer as the component (D), it is possible to obtain dentin. It is possible to realize higher adhesive strength with less variation in adhesive strength.

The total amount of the above-mentioned phosphoric acid group-containing polymerizable monomer and polyvalent carboxylic acid group-containing polymerizable monomer is 1 in all the constituent components.
It is preferable to contain 0% by weight or more, and 15% by weight
More preferably, it is included.

The dental composition of the present invention contains a phosphoric acid group-containing polymerizable monomer, a polyvalent carboxylic acid group-containing polymerizable monomer, water,
In addition to the aryl borate compound, various optional components described later can be contained within a range that does not impair the effects of the present invention. In that case, the content rate of each of the above components is 10 in total of the essential components and all other optional components.
It is the weight content of each component when it is 0% by weight.

When the phosphoric acid group-containing polymerizable monomer and / or polyvalent carboxylic acid group-containing polymerizable monomer used in the present invention is difficult to dissolve in water, a water-soluble organic solvent is used. It is preferable that each component is dissolved to form a uniform solution or an emulsion that is stable for a long time so that there is no problem in use.

Specific examples of such a water-soluble organic solvent include methanol, ethanol, propanol, butanol, ethylene glycol, propanediol, butanediol, pentanediol, butenediol, glycerin, trimethylolpropane, hexanetriol, allyl alcohol, Diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol, triethylene glycol monomethyl ether, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 2-methoxyethanol, 2-ethoxyethanol, 2- (methoxy Ethoxy) ethanol, 2-isopropoxy ethanol, 2-
Alcohols or ethers such as butoxyethanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, glycerin ether, acetone, methyl ethyl ketone, etc. Examples thereof include ketones, acetic acid, acetic anhydride, carboxylic acids such as propionic acid, and the like.
Further, those having a polymerizable functional group such as acrylic acid, methacrylic acid, and 2-hydroxyethyl methacrylate may be used.

Among them, those which are less harmful to the living body are desirable, and ethanol, propanol, ethylene glycol, propanediol, butanediol, pentanediol, glycerin, trimethylolpropane, hexanetriol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether. , Triethylene glycol, triethylene glycol monomethyl ether, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, dipropylene glycol, dipropylene glycol monomethyl ether,
Tripropylene glycol monomethyl ether, glycerin ether, acetone, 2-hydroxyethyl methacrylate and the like are preferable, and particularly alcohols such as ethanol, propanol, ethylene glycol, propanediol and 2-hydroxyethyl methacrylate are most preferably used.

If desired, a plurality of water-soluble organic solvents can be mixed and used. The blending amount of the water-soluble organic solvent is preferably 80% by weight or less based on all the constituent components.

The composition of the present invention contains other polymerizable monomers, water-insoluble organic solvents,
It is possible to add a polymerization catalyst other than the aryl borate compound, a strong inorganic acid, or a metal salt.

As the polymerizable monomer, methacrylic acid, methyl methacrylate, ethyl methacrylate, tetrahydrofurfuryl methacrylate, 2-hydroxyethyl methacrylate, N-methylol methacrylamide and monofunctional monomers such as acrylates thereof, Two
2-bis (4-methacryloyloxyphenyl) propane, 2,2-bis (4- (2-hydroxy-3-methacryloyloxypropoxy) phenyl) propane, 2,
2-bis (4-methacryloyloxyethoxyphenyl) propane, 2,2-bis (4-methacryloyloxydiethoxyphenyl) propane, 2,2-bis (4-
Methacryloyloxytetraethoxyphenyl) propane, 2,2-bis (4-methacryloyloxypentaethoxyphenyl) propane, 2,2-bis (4-methacryloyloxydipropoxyphenyl) propane, 2
(4-methacryloyloxyethoxyphenyl) -2
(4-methacryloyloxydiethoxyphenyl) propane, 2 (4-methacryloyloxydiethoxyphenyl) -2 (4-methacryloyloxytriethoxyphenyl) propane, 2 (4-methacryloyloxydipropoxyphenyl) -2 (4-methacryloyl Oxytriethoxyphenyl) propane, 2,2-bis (4-methacryloyloxydipropoxyphenyl) propane,
Aromatic bifunctional monomers such as 2,2-bis (4-methacryloyloxyisopropoxyphenyl) propane and acrylates thereof, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, butylene glycol dimethacrylate, Neopentyl glycol dimethacrylate, propylene glycol dimethacrylate,
Aliphatic bifunctional monomers such as 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate and their acrylates, trimethylolpropane trimethacrylate, trimethylolethane Examples thereof include trifunctional monomers such as trimethacrylate, trimethylolpropane trimethacrylate and acrylates thereof, and tetrafunctional monomers such as pentaerythritol tetramethacrylate and pentaerythritol tetraacrylate.

The non-water-soluble organic solvent includes hexane, heptane, octane, toluene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, methyl ethyl ketone, pentanone, hexanone, ethyl formate, propyl formate, butyl formate, ethyl acetate, acetic acid. Examples include propyl and butyl acetate.

Polymerization catalysts other than aryl borates include α-diketones such as camphorquinone, benzyl, α-naphthyl, acetonaphthene and naphthoquinone, and 2,4
Photosensitizers such as diethylthioxanthone, barbituric acids such as 5-butylbarbituric acid, 1-benzyl-5-phenylbarbituric acid, N, N-dimethylaniline, N, N-diethylaniline, N, N -Dimethyl-p
-Toluidine, N, N-diethyl-p-toluidine, p
-Photopolymerization such as tertiary amines such as dimethylaminobenzaldehyde, N, N-dimethylamino-p-ethyl benzoate and N, N-diethylamino-p-ethyl benzoate, and amino acids such as N-phenylglycine Accelerator, di-t-butyl peroxide, dicumyl peroxide, lauroyl peroxide,
Organic peroxides such as benzoyl peroxide, sodium benzenesulfinate, sodium p-toluenesulfinate, sodium m-nitrobenzenesulfinate, p-
Sulfinic acids such as sodium fluorobenzenesulfinate can be used.

Examples of the metal salt include polyvalent metals such as magnesium, aluminum, calcium, iron, cobalt, nickel, copper, zinc, strontium, tin and barium.
Hydrochloride, hydrofluoric acid salt, sulfate, nitrate, phosphate, acetate, citrate, oxalate, EDTA salt and the like can be mentioned.

Examples of strong inorganic acids include hydrochloric acid, sulfuric acid, nitric acid and the like. Further, a coloring matter may be blended as a coloring material.

The method for preparing the composition of the present invention is not particularly limited, and the above-mentioned phosphoric acid group-containing polymerizable monomer, polyvalent carboxylic acid group-containing polymerizable monomer, water and, if necessary, blended. The optional components may be weighed in a desired ratio in a container and mixed with stirring to form a uniform solution or emulsion.

The dental composition of the present invention is generally used in a filling and repairing procedure of applying a pretreatment material to a tooth surface, drying, applying an adhesive, curing an adhesive, filling a filling material, and curing a filling material. Used as a pretreatment material. The pretreatment material forms a uniform coating on the tooth surface after drying. Assuming an adhesion mechanism in which a layer suitable for adhesion to the tooth substance is formed by diffusing the adhesive component that is applied later in the film on the tooth substance, uniform adhesion is preferable. It can be inferred that it is advantageous for layer formation.

The packaging form of the composition of the present invention can be appropriately determined under the condition that the storage stability is not impaired. For example, a liquid containing a phosphoric acid group-containing polymerizable monomer and a polyvalent carboxylic acid group-containing polymerizable monomer as the main components, and a liquid containing water and an aryl borate compound as the main components are separately packaged, and at the time of use. It is possible to mix.

When the composition of the present invention is used as a pretreatment material for filling and repairing, the adhesive is an adhesive containing a polyfunctional carboxylic acid group-containing polyfunctional polymerizable monomer and a polymerization initiator. , Or in combination with an adhesive comprising a polyfunctional carboxylic acid group-containing monofunctional polymerizable monomer, a water-soluble hydroxyl group-containing polymerizable monomer, a polyfunctional polymerizable monomer and a polymerization initiator. It is preferable to use.

The polyfunctional carboxylic acid group-containing polyfunctional polymerizable monomer used in the above adhesive is an essential component in the present invention such as a carboxyl group in one molecule, or an anhydride or acid halide thereof. There is no particular limitation as long as it is a polyfunctional polymerizable monomer having two or more groups capable of easily reacting with water to generate a carboxyl group, and known compounds can be used. Among them, having two carboxyl groups in one molecule, or a group thereof which easily reacts with water such as an anhydride or acid halide thereof to form a carboxyl group on the same carbon or adjacent carbon, and two The above-mentioned polymerizable monomers having a polymerizable unsaturated group are preferable. It should be noted that a plurality of sites having two carboxyl groups or groups that generate a carboxyl group on the same carbon or adjacent carbons may exist in one molecule. Further, in addition to the above-mentioned site having two carboxyl groups or groups forming a carboxyl group on the same carbon or adjacent carbons, it may have a carboxyl group or a group forming a carboxyl group by itself.

Examples of such polyfunctional carboxylic acid group-containing polyfunctional polymerizable monomer compounds include the polyvalent carboxylic acid group-containing polymerizable monomers specifically exemplified in the section of the dental composition. Those having two or more polymerizable unsaturated groups can be used.

Among the polyfunctional carboxylic acid group-containing polyfunctional polymerizable monomers, a trimellitic acid derivative is particularly preferably used from the viewpoint of tooth adhesion.

If necessary, a plurality of these polyfunctional carboxylic acid group-containing polyfunctional polymerizable monomers can be mixed and used.

The polyfunctional carboxylic acid group-containing monofunctional polymerizable monomer contained in the adhesive is an essential component in the present invention such as a carboxyl group in one molecule, or an anhydride or acid halide thereof. The polymerizable monomer is not particularly limited as long as it is a polymerizable monomer having two or more groups capable of easily reacting with certain water to generate a carboxyl group, and known compounds can be used. Among them, it has two carboxyl groups in one molecule, or a group such as an anhydride or acid halide thereof, which easily reacts with water to form a carboxyl group, on the same carbon or adjacent carbon, and one The polymerizable monomer having a polymerizable unsaturated group of is preferable. In addition, 2 on the same carbon or adjacent carbon
A plurality of sites each having one carboxyl group or a group generating a carboxyl group may exist in one molecule. Also,
In addition to the above-mentioned moiety having two carboxyl groups or groups forming a carboxyl group on the same carbon or adjacent carbon atoms, it may have a carboxyl group or a group forming a carboxyl group by itself.

Examples of such a polyfunctional carboxylic acid group-containing monofunctional polymerizable monomer compound include the polyvalent carboxylic acid group-containing polymerizable monomer specifically exemplified in the section of the dental composition of the present invention. Of the bodies, those having one polymerizable unsaturated group can be used.

Among the polyfunctional carboxylic acid group-containing monofunctional polymerizable monomers, the malonic acid derivative represented by the general formula (7) is particularly preferably used from the viewpoint of tooth adhesion.

These polyfunctional carboxylic acid group-containing monofunctional polymerizable monomers may be used in admixture if necessary.

The content of the polyfunctional carboxylic acid group-containing monofunctional polymerizable monomer contained in the adhesive is preferably 5 parts by weight to 60 parts by weight, and more preferably 10 parts by weight or more, from the viewpoint of adhesiveness to teeth. 5
0 weight part is more preferable.

As will be described later, the adhesive may be composed of other than the above-mentioned polyfunctional carboxylic acid group-containing monofunctional polymerizable monomer, water-soluble hydroxyl group-containing polymerizable monomer and polyfunctional polymerizable monomer. Various polymerizable monomers can be contained as optional components. In that case, the content of the polyfunctional carboxylic acid group-containing monofunctional polymerizable monomer, the polyvalent carboxylic acid group-containing monofunctional polymerizable monomer, the water-soluble hydroxyl group-containing polymerizable monomer, polyfunctional 100 parts by weight of the total amount of the polymerizable polymerizable monomer and the polymerizable monomer contained as the other optional component (hereinafter,
The total content of all polymerizable monomers is 100 parts by weight).

The water-soluble hydroxyl group-containing polymerizable monomer contained in the adhesive is a water-soluble polymerizable monomer having at least one hydroxyl group and at least one polymerizable unsaturated group in one molecule. There is a known structure as long as it has such a structure. However, when 10 grams of the hydroxyl group-containing polymerizable monomer and 100 grams of water are mixed under a temperature condition of 25 ° C., when they are completely homogeneously mixed, the hydroxyl group-containing polymerizable monomer is water-soluble. And

Examples of such compounds include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate,
2,3-dihydroxypropyl methacrylate, 2,3
-Dihydroxybutyl methacrylate, 2,4-dihydroxybutyl methacrylate, 2-hydroxymethyl-
3-hydroxypropyl methacrylate, 2,3,4-
Trihydroxybutyl methacrylate, 2,2-bis (hydroxymethyl) -3-hydroxypropyl methacrylate, 2,3,4,5-tetrahydroxypentyl methacrylate, diethylene glycol monomethacrylate, triethylene glycol monomethacrylate, tetraethylene glycol monomethacrylate, Pentaethylene glycol monomethacrylate and polyhydric alcohols such as acrylates thereof, or (meth) acrylic acid esters of polyethylene glycols, (meth) acrylic acid amides of amino alcohols such as N-methylol methacrylamide and N-methylol acrylamide Kind of things.

Among the above water-soluble hydroxyl group-containing polymerizable monomers, 2-hydroxyethyl methacrylate and 2,3-dihydroxypropyl methacrylate are preferably used from the viewpoints of tooth adhesion and cost.

If desired, a plurality of these water-soluble hydroxyl group-containing polymerizable monomers may be mixed and used.

The content of the above-mentioned water-soluble hydroxyl group-containing monofunctional polymerizable monomer contained in the adhesive is 5 parts by weight from the viewpoint of the adhesive property of the teeth in 100 parts by weight of the total polymerizable monomers. ~ 50
Part by weight is preferable, and 10 to 40 parts by weight is more preferable.

The polyfunctional polymerizable monomer contained in the adhesive is not particularly limited as long as it is a polymerizable monomer having a plurality of polymerizable unsaturated groups in one molecule, and known compounds can be used. used.

Examples of such a compound include aromatic bifunctional monomers having a plurality of functional groups among the non-acidic polymerizable monomers specifically exemplified in the above dental composition section, Examples thereof include aliphatic bifunctional monomers, trifunctional monomers, tetrafunctional monomers and the like, and dicarboxylic acid group-containing polyfunctional monomers and the like. A plurality of these polyfunctional polymerizable monomers can be mixed and used as necessary.

The content of the polyfunctional polymerizable monomer contained in the adhesive is from 20 parts by weight to 90 parts by weight in the total 100 parts by weight of all the polymerizable monomers from the viewpoint of adhesiveness to the tooth. Is preferable, and 30 parts by weight to 80 parts by weight is more preferable.

The polyfunctional carboxylic acid group-containing polyfunctional polymerizable monomer or the polyvalent carboxylic acid group-containing monofunctional polymerizable monomer contained in the adhesive is usually a liquid or a solid having a high viscosity. From the viewpoint of operability, it is preferable to mix and use various other polymerizable monomers described below as optional components. Furthermore, since the polyvalent carboxylic acid group-containing polyfunctional polymerizable monomer or the polyvalent carboxylic acid group-containing monofunctional polymerizable monomer is usually expensive, any other inexpensive polymerizable monomer may be used. It is also preferable to use it after diluting it as a component.

Examples of the other polymerizable monomer include the same phosphoric acid group-containing polymerizable monomers as those specifically exemplified in the section of the dental composition of the present invention and monofunctional monofunctional monomers. Non-acidic polymerizable monomers classified into monomers, aromatic bifunctional monomers, aliphatic bifunctional monomers, trifunctional monomers, tetrafunctional monomers and the like, Carboxylic acid acidic polymerizable monomers such as a monocarboxylic acid group-containing polymerizable monomer and a polyvalent carboxylic acid group-containing polymerizable monomer can be used. A plurality of these polymerizable monomers can be mixed and used as necessary. When used by mixing with other polymerizable monomer, the compounding amount of the polyfunctional carboxylic acid group-containing polyfunctional polymerizable monomer or the polyvalent carboxylic acid group-containing monofunctional polymerizable monomer is From the viewpoint of adhesiveness, it is preferably 5 parts by weight or more and more preferably 10 parts by weight or more per 100 parts by weight of the total polymerizable monomers.

The adhesive contains a polymerization initiator for polymerization and curing. As such a polymerization initiator, the aryl borate compound used in the dental composition of the present invention or a known compound can be used without any limitation.

Specific examples of suitable polymerization initiators include:
Of the thermal polymerization initiators such as organic peroxides exemplified as optional components in the dental composition of the present invention, α-diketones, photosensitizers such as thioxanthones, and organometallic polymerization initiators. Other examples include photopolymerization initiators comprising azo compounds, α-aminoacetophenones, and dyes / trihalomethyl group-containing-s-triazine derivatives / aryl borate compounds. It is possible to mix and use a plurality of these polymerization initiators if necessary.

The addition amount of these polymerization initiators is not particularly limited as long as the effect is exhibited, but
0.01 to 100 parts by weight of all polymerizable monomers
Addition of 20 parts by weight is preferable, and addition of 0.05 to 10 parts by weight is more preferable.

The above thermal polymerization initiator and photosensitizer are preferably used in combination with a suitable polymerization accelerator.

Examples of such a polymerization accelerator include secondary and tertiary amines, amino acids, sulfinic acid salts, barbituric acids and the like which are exemplified as optional components in the dental composition of the present invention. To be It is possible to mix and use a plurality of these polymerization accelerators if necessary. The addition amount of these polymerization accelerators is not particularly limited as long as the effect is exhibited, but 0.01 to 20 parts by weight is added to 100 parts by weight of all polymerizable monomers in total. Is preferred, and addition of 0.05 to 10 parts by weight is more preferred.

It is preferable to add a small amount of a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether or butylhydroxytoluene to the adhesive, if necessary. It is also suitable to add a filler. By adding filler, improvement of mechanical strength, viscosity,
It is possible to control the liquidity.

Specific examples of such fillers are as follows:
Inorganic fillers such as glass, silicon oxide, titanium oxide, zirconium oxide, aluminum oxide, metal oxides such as silicon-zirconium composite oxide, silicon-titanium composite oxide, silicon nitride, aluminum nitride, titanium nitride. , Nitrides such as boron nitride, carbides such as silicon carbide and boron carbide, inorganic salts such as barium sulfate, calcium carbonate, calcium phosphate, etc., and organic fillers such as polymethylmethacrylate, polyethylmethacrylate, and polychlorination. Vinyl, polystyrene, polyesters, polyamides, polyurethanes,
Polymers or oligomers such as nylon, polysiloxanes and polysilanes can be mentioned. Furthermore, inorganic-organic composite fillers are also suitable. As the inorganic filler, it is usually preferable to use one treated with a silane coupling agent such as γ-methacryloyloxypropyltrimethoxysilane or vinyltriethoxysilane. The addition amount of these fillers is not particularly limited as long as the effect is not impaired, but is preferably 300 parts by weight or less based on 100 parts by weight of all polymerizable monomers, The addition of less than or equal to parts by weight is more preferred.

The method for preparing the adhesive is not particularly limited, and the polyfunctional carboxylic acid group-containing polyfunctional polymerizable monomer or the polyvalent carboxylic acid group-containing monofunctional polymerizable monomer, and the like may be used. The optional components to be blended may be weighed in the desired ratio and mixed by stirring to make them uniform.

[0102]

By using the composition of the present invention as a pretreatment agent for the tooth surface prior to the adhesive when the tooth and the filling material are adhered by the adhesive, only one pretreatment operation is required. The complicated pretreatment operation of further applying a primer after the acid aqueous solution treatment which has been performed is simplified.
Further, high adhesive strength can be obtained for both enamel and dentin.

[0103]

EXAMPLES The composition of the present invention will be specifically shown by the following examples, but the present invention is not limited to these examples. The abbreviations used in the text and examples
The abbreviations, adhesive strength measurement methods, and adhesive preparation methods are as follows.

(1) Abbreviations and abbreviations Bis-GMA: 2,2-bis (4- (2-hydroxy-3-methacryloyloxypropoxy) phenyl) propane 3G: triethylene glycol dimethacrylate HEMA: 2-hydroxyethyl methacrylate MAC -10: 11-methacryloyloxy-1,1-
Undecanedicarboxylic acid 4-META: 4-methacryloyloxyethyl trimellitate unhydride MTS: 2-methacryloyloxyethyl-3'-methacryloyloxy-2 '-(3,4dicarboxybenzoyloxy) propyl succinate HOMS: 2- Methacryloyloxyethyl hydrogen succinate phenyl-P: 2-methacryloyloxyethyl phenyl hydrogen phosphate PM: 2-methacryloyloxyethyl dihydrogen phosphate PM2: bis (2-methacryloyloxyethyl) hydrogen phosphate CQ: camphorquinone DMBE: Ethyl N, N-dimethyl-p-aminobenzoate CDAC: 3,3′-carbonylbis (7-diethylamino) coumarin TCT: 2,4,6- Squirrel (trichloromethyl) -s
-Triazine IPA: isopropyl alcohol PBNa: sodium tetraphenylboron FPBNa: tetrakis (p-fluorophenyl) boron sodium ClPBK: tetrakis (p-chlorophenyl) boron potassium BFPBB: butyltri (p-fluorophenyl) boron tetrabutylammonium (2) enamel Quality, dentin adhesive strength Within 24 hours after slaughter, bovine anterior teeth are removed, and under water injection, # 80
The enamel or dentin plane was carved so as to be parallel to the labial surface with 0 emery paper. Next, compressed air is blown onto these surfaces for about 10 seconds to dry, and then a double-sided tape having a hole with a diameter of 4 mm is fixed on this surface, and then paraffin wax with a hole having a thickness of 1.5 mm and a diameter of 6 mm is opened. Were fixed so as to be in the same center on the circular hole to form a simulated cavity. The dental composition of the present invention was thinly applied to the simulated cavity, left standing for 20 seconds, and then compressed air at about 1
Sprayed for 0 seconds to dry. Next, the adhesive was applied and irradiated with a visible light irradiator (white light, manufactured by Takara Belmont Co., Ltd.) for 10 seconds to cure the adhesive. Further, a dental composite resin (Palfiq Lite Posteria, manufactured by Tokuyama Corp.) was filled on it, and irradiated with a visible light irradiator for 30 seconds to prepare an adhesive test piece. After immersing the above-mentioned adhesion test piece in water at 37 ° C for 24 hours, the tensile adhesion strength between the tooth and the composite resin was measured at a crosshead speed of 10 mm / min using a tensile tester (Autograph, manufactured by Shimadzu Corporation). did.

The tensile adhesion strength of four pieces per test was measured by the above method, and the average value was taken as the adhesive strength.

The adhesive strength needs to be about 19 MPa for enamel and about 17 MPa for dentin in order to prevent the formation of gaps between the filling material and the surface of the tooth and the dropping of the filling material.

(3) Preparation of Adhesives Adhesives A to E were obtained as viscous liquids by stirring and mixing under the shade of light with the compositions shown below.

[0108] Adhesive G: Tokuso Light Bond [Tokuyama Corp.] attached bonding agent Adhesive H: Clearfill liner bond 2 (Kuraray)
Adhesive Example 1 attached to the attached bonding agent adhesive I; Scotchbond Multipurpose (3M). Phenyl-P (1.0 g), distilled water (6.0 g) and ethanol (2.9 g) were mixed to obtain a uniform solution. FPBN to this
0.1 g of a was added, the tooth surface was treated with this as a pretreatment material, and the adhesive surface was adhered using the adhesive material B, and the enamel and dentin adhesive strength was measured. The results are shown in Table 1.

Examples 2 to 14 Pretreatment materials were prepared according to the method of Example 1 and evaluated using different adhesives. Table 1 shows the composition of the pretreatment material, the adhesive used, and the results.

[0110]

[Table 1]

In all the compositions of Examples 1 to 14, the pretreatment material containing the phosphoric acid group-containing polymerizable monomer, water and the aryl borate compound compound provided good adhesion to both enamel and dentin. It is clear that the objects of the invention can be achieved.

Example 15 FPBN was added to a uniform solution of 1.0 g of phenyl-P, 1.0 g of MAC-10, 5.5 g of distilled water and 2.4 g of ethanol.
A 0.1 g was mixed to obtain a uniform solution. The tooth surface was treated with this as a pretreatment material and bonded using the adhesive material A, and the enamel and dentin adhesive strength was measured. The results are shown in Table 2.

Examples 15 to 41 Pretreatment materials were prepared according to the method of Example 15 and evaluated using the adhesives shown in Table 2. Table 2 shows the composition and results of the pretreatment material.

[0114]

[Table 2]

In all the compositions of Examples 15 to 41, the enamel and the enamel were treated with the pretreatment material containing the phosphoric acid group-containing polymerizable monomer, the polycarboxylic acid group-containing polymerizable monomer, water and the aryl borate compound. It is clear that the good adhesiveness to both dentin is obtained and the standard deviation of each adhesive strength is small, and the object of the present invention can be achieved.

Comparative Examples 1 to 7 Pretreatment materials were prepared according to the methods of Examples and evaluated using the adhesives shown in Table 3. Table 3 shows the composition and results of the pretreatment material.

[0117]

[Table 3]

In contrast to the above Examples, Comparative Examples 1 to 3 lacked one component of the phosphoric acid group-containing polymerizable monomer, aryl borate compound and water which are essential components of the present invention. Also in this case, it can be seen that the adhesive strength to dentin or enamel is reduced. Furthermore, Comparative Examples 4 to 7
The composition ratio of each essential component is outside the scope of the invention, and in any case, the adhesive strength to dentin or enamel is reduced. In Comparative Example 7, phosphoric acid was used instead of the phosphoric acid group-containing polymerizable monomer, and especially the dentin adhesive strength was lowered.

─────────────────────────────────────────────────── --Continued from the front page (56) References JP-A-8-319209 (JP, A) JP-A-7-97306 (JP, A) JP-A-5-253284 (JP, A) JP-A-58- 136602 (JP, A) JP 4-8368 (JP, A) JP 2-182701 (JP, A) JP 9-3109 (JP, A) JP 6-192029 (JP, A) JP-A-58-147476 (JP, A) JP-A-63-162769 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) A61K 6/00

Claims (2)

(57) [Claims] 1. (A) a phosphoric acid group-containing polymerizable monomer,
(B) Aryl borate compound and (C) water as main components, 5 to 50 wt% of (A) component, and (B) aryl borate compound 0.0 to 100 wt% of all constituents.
A dental composition comprising 1 to 10% by weight and 5 to 90% by weight of the component (C). 2. A polymerizable group-containing monomer (A),
(B) Aryl borate compound, (C) water and (D)
Containing a polyvalent carboxylic acid group-containing polymerizable monomer as a main component, the component (A) is 5 to 50% by weight, and the component (B) is 0.01 to 10% by weight, based on 100% by weight of all the constituent components. A dental composition comprising 5 to 90% by weight of component C) and 1 to 50% by weight of component (D).