JPH0840819A - Primer solution composition for dentine adhering - Google Patents

Abstract

PURPOSE:To obtain a primer solution composition for dentine adhering capable of simultaneously treating the surface of the enamelum of a tooth and the surface of its dentine without subjecting the enamelum and the dentine to an acid treatment and a water washing treatment, and capable of giving a sure adhesion dental treatment to a patient in a simple operation without giving an ache to the patient. CONSTITUTION:The primer solution composition for coating the surface of the dentine of a tooth to form an adhesive layer thereon comprises (a) at least one kind of metal compound selected from the group consisting of an iron compound, a copper compound and a cobalt compound, (b) a polymerisable monomer having an acidic group, and (c) water, or water and a water-miscible organic solvent. And the method for forming an adhesive layer on the surface of the dentine comprises applying the primer solution composition on the surface of the dentine and subsequently applying a curable composition comprising a trialkylboron or its partial oxide and a polymerizable monomer.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention is capable of simultaneously surface-treating enamel and dentin by a simple operation on the dentin, and suppressing pulp stimulation without opening the dentinal tubule to the dentin largely. The present invention relates to a possible primer composition and a method for sequentially applying the primer composition and a curable composition to the surface of the tooth structure to form an adhesive layer on the surface of the tooth structure.

[0002]

2. Description of the Related Art In the field of dental treatment, it is necessary to strongly bond a tooth substance with a material for repairing the tooth substance (for example, a polymer substance, metal, porcelain, etc.). Various proposals have been made.

Such an adhesive is generally composed of three components: (1) polymerizable monomer, (2) polymerization catalyst or polymerization initiator, and (3) filler. Typical examples of such an adhesive include (1) (meth) acrylic acid ester as a polymerizable monomer, and (2)
Adhesive composition comprising a mixture of benzoyl peroxide and an aromatic tertiary amine as a polymerization catalyst, or a catalyst component obtained by adding a sulfinate to this mixture, and (3) a filler such as a polymer and silica. Or (1) a (meth) acrylic acid ester as a polymerizable monomer,
(2) An adhesive composition comprising a photopolymerization initiator comprising camphorquinone as a photosensitizer and N, N-dimethylaminoethyl methacrylate as a reducing agent, and (3) a filler such as a polymer and silica. And further (1) (meth) acrylic acid ester as a polymerizable monomer,
An adhesive composition comprising (2) tributylborane partial oxide (TBBO) as a polymerization catalyst and (3) a filler such as a polymer and silica has been proposed.

In order to improve the adhesion of such an adhesive to the tooth structure, it has been proposed to use an adhesion promoting monomer or a monomer having an affinity with the tooth structure. Examples of the adhesion-promoting monomer or the monomer having affinity with the tooth substance include 4-methacryloyloxyethoxycarbonylphthalic acid (4-MET) or its anhydride (4-META) and 10-methacryloyloxydecylmalonic acid (MAC-). Examples thereof include a monomer having a carboxyl group (or a group capable of being converted into a carboxyl group) such as 10) and a monomer having a phosphoric acid group such as 10-methacryloyloxydecyl dihydrogen phosphate.

Pretreatment of the tooth surface is required in order to obtain a strong adhesive performance of such an adhesive to the tooth structure. For example, an aqueous solution of phosphoric acid or citric acid is applied to the surfaces of enamel and dentin at the same time, and then a total etching method of washing and drying with water, or a primer is further applied to the dentin surface after performing the total etching method. A total etching primer method of drying and an enamel etching-dentin primer method of applying a primer to the remaining dentin without opening the dentinal tubule after etching only the enamel are recommended.

The use of primers is described in the Journal of
Dental Research 63 1087-1089 (1984) in Munksg.
ard and Asmussen, E. et al. treated the dentin surface with a primer composed of an aqueous solution of 2-hydroxyethyl methacrylate, which is a water-soluble polymerizable monomer, after etching with EDTA (pH 7.4), The method of applying the adhesive is reported. In addition, JP-A-62-1
Japanese Patent No. 223289 proposes a primer composition composed of an acid and a water-soluble polymerizable monomer. The acid has a pKa between −10 and +10 and is characterized in that the water-soluble polymerized monomer has water solubility of at least 5% by weight in water.

Further, a primer containing a metal compound is disclosed in JP-A-5-339118 and JP-A-6-24928.
Japanese Unexamined Patent Publication No. 5-310524 and Japanese Unexamined Patent Publication No.
It is disclosed in Japanese Patent Publication No. 89821.

The total etching method or the total etching / primer method is performed by applying an etching agent, washing with water,
In addition to requiring multi-step operations such as drying, the dentinal tubules may be greatly opened to stimulate the pulp, which may cause a great pain to the patient. With the enamel etching-dentin primer method, the purpose of reducing the pain given to the patient was almost achieved, but it is necessary to apply the etching agent only to the enamel portion of the small and complicated cavity that is difficult to apply, The problem could not be resolved due to the time and effort involved.

As described above, it is possible to develop a primer capable of treating enamel and dentin at the same time without causing a pain to a patient and requiring a complicated treatment operation and exhibiting excellent adhesive performance for an adhesive. Strongly desired.

[0010]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a primer composition capable of simultaneously surface treating enamel and dentin on tooth material in order to solve the above problems. Another object of the present invention is to reduce the pain to the patient with a simple operation by simultaneously treating the surface of the enamel and the dentin at the time of restoration of the dentin and not requiring operations such as acid treatment and washing with water. Another object of the present invention is to provide a primer composition, that is, a tooth surface treatment agent, which can realize an excellent restoration effect. Still another object of the present invention is to provide a method for forming an adhesive layer on the tooth surface by sequentially applying the primer composition and the curable composition of the present invention to the tooth surface.

[0011]

According to the present invention, the above objects and advantages of the present invention are as follows: a) at least one metal compound selected from the group consisting of a) iron compounds, copper compounds and cobalt compounds. , B) a polymerizable monomer having an acidic group and c) water, or a water and a water-miscible organic solvent, to achieve a primer composition for treating a tooth surface.

In the present invention, the above metal compound a)
Are selected from iron compounds, copper compounds and cobalt compounds. Specifically, chlorides and fluorides of the above metals; salts of inorganic acids such as nitrates and sulfates; salts of acetates, acrylates, methacrylates and other organic acids; complexes with acetylacetone. Organic complexes such as are preferred. These metal compounds may have any valence. Examples of iron compounds include salts of inorganic acids such as iron chloride, iron nitrate and iron sulfate, salts of organic acids such as iron acetate, iron acrylate and iron methacrylate, and complex salts such as iron acetylacetone. be able to. Examples of copper compounds include salts of inorganic acids such as copper chloride, copper fluoride, copper nitrate and copper sulfate, salts of organic acids such as copper acetate, copper acrylate and copper methacrylate, and copper acetylacetone. The complex salts can be mentioned. Examples of cobalt compounds include salts of inorganic acids such as cobalt chloride, cobalt nitrate and cobalt sulfate, salts of organic acids such as cobalt acetate, cobalt acrylate and cobalt methacrylate,
And complex salts such as acetylacetone cobalt.

These metal compounds can be used alone or in combination. The amount of the metal compound compounded in the primer composition is preferably 0.0001.
Is in the range of 1% by weight.

In the primer composition of the present invention, b) a polymerizable monomer having an acidic group is used. As the polymerizable monomer having an acidic group, for example, a monomer having a carboxylic acid group and a carboxylic acid anhydride group, a monomer having a phosphoric acid group and a monomer having a sulfonic acid group are preferably used. Examples of the monomer containing a carboxylic acid group and its anhydride group include (meth) acrylic acid and its anhydride, 1,4-di (meth) acryloxyethylpyromellitic acid, 6- (meth) acryloxyethylnaphthalene. 1,2,6-tricarboxylic acid, N- (meth) acryloyl-p-aminobenzoic acid, N- (meth) acryloyl-o-aminobenzoic acid, N- (meth) acryloyl-
m-aminobenzoic acid, N- (meth) acryloyl-5-
Aminosalicylic acid, N- (meth) acryloyl-4-aminosalicylic acid, 4- (meth) acryloxyethyltrimellitic acid and its anhydride, 4- (meth) acryloxybutyltrimellitic acid and its anhydride, 4- ( (Meth) acryloxyhexyl trimellitic acid and its anhydride, 4- (meth) acryloxydecyl trimellitic acid and its anhydride, 2- (meth) acryloyloxybenzoic acid, 3- (meth) acryloyloxybenzoic acid, 4
-(Meth) acryloyloxybenzoic acid, β- (meth)
Acryloyloxyethyl hydrogen succinate, β- (meth) acryloyloxyethyl hydrogen maleate, β- (meth) acryloyloxyethyl hydrogen phthalate, 11- (meth) acryloyloxy-1,1-undecanedicarboxylic acid, p Examples thereof include vinylbenzoic acid.

As the monomer containing a phosphoric acid group, (2- (meth) acryloxyethyl) phosphoric acid, (2- (meth) acryloxyethylphenyl) phosphoric acid, 10- (meth) acryloxydecylphosphine Examples thereof include folic acid.

Examples of the sulfonic acid group-containing monomer include p-styrenesulfonic acid and 2-acrylamido-2-methylpropanesulfonic acid.

These polymerizable monomers having an acidic group can be used alone or in combination of two or more kinds.

Of these, N- (meth) acryloyl-5-aminosalicylic acid and N- (meth) acryloyl-
4-Aminosalicylic acid, 4- (meth) acryloxyethyltrimellitic acid and their anhydrides are particularly preferably used.

These polymerizable monomers having an acidic group can be used alone or in combination. The compounding amount of the polymerizable monomer having an acidic group in the primer composition is usually in the range of 0.1 to 30% by weight.

The primer composition of the present invention includes c) water,
Alternatively, water and a water-miscible organic solvent are used. The a) specific metal compound and the b) polymerizable monomer having an acidic group as described above are used by being dissolved or dispersed in water or water and a water-miscible organic solvent. As such a solvent, any solvent can be optionally used as long as it is not highly toxic to the human body, and preferred examples thereof include ethanol, isopropanol, butanol, acetone and tetrahydrofuran. These can be used alone or in combination. Further, in order to achieve an effective enamel surface treatment that can realize strong adhesion, the water of component c) or water in a water-miscible organic solvent is a),
When the total amount of the components b) and c) is 100 parts by weight, it is preferable to contain at least 40 parts by weight, more preferably 45 parts by weight or more, and particularly preferably 50 parts by weight or more. When the water content is 40 parts by weight or more, deashing necessary for adhesion can be easily obtained from the enamel surface, and the deashed apatite component does not reprecipitate, and effective adhesive strength can be obtained. It is preferable in terms.

In the tooth surface treating primer composition of the present invention, the above-mentioned a) a specific metal compound, b) a polymerizable monomer having an acidic group and c) water, or water and a water-miscible organic solvent are used. If necessary, it can be divided and stored at any ratio, and can be mixed again before use and applied to the tooth structure.

The above-mentioned primer composition of the present invention is applied to the surface of the tooth. After drying, the curable composition may be applied thereon to form an adhesive layer to adhere various materials to the tooth structure. At this time, after applying the curable composition, if necessary, before the composition is cured, a filler or repair material is laminated and the adhesive force of the curing agent is used to fill the filler or repair material. Can be adhered to the dental substance.

As the curable composition, various curable compositions known per se in the art can be used, but among others, those containing a trialkylboron or a partial oxide thereof are preferably used.

According to the present invention, therefore, a tooth characterized in that the tooth surface is further coated with the primer composition of the present invention and then with a curable composition containing a polymerization initiator and a polymerizable monomer. A method of forming an adhesive layer on a textured surface is also provided.

As described above, the curable composition applied on the primer composition contains a polymerization initiator and a polymerizable monomer or a polymerizable monomer and a filler. That is, this adhesive may be used as it is as an adhesive for a filler such as a metal, or may be an adhesive as a liner of a composite resin.

Examples of the polymerization initiator include organic peroxides, inorganic peroxides, alkylboranes, partial oxides of alkylboranes, α-diketone compounds, organic amine compounds,
Mention may be made of organic sulfinic acids, organic sulfinates, inorganic sulfur compounds and barbituric acids. These may be used alone or in combination of two or more. Examples of these polymerization initiators include a normal temperature chemical polymerization type, a photopolymerization type, and a dual type in which these are combined, for convenience. Examples of peroxides (polymerization initiators) used in the room temperature chemical polymerization type include diacetyl peroxide, dipropyl peroxide, dibutyl peroxide, dicapryl peroxide, dilauryl peroxide, benzoyl peroxide (BPO), p, p'-dioxide. Organic peroxides such as chlorobenzoyl peroxide, p, p'-dimethoxybenzoyl peroxide, p, p'-dimethylbenzoyl peroxide, p, p'-dinitrodibenzoyl peroxide and ammonium persulfate, potassium persulfate, potassium chlorate, bromine Mention may be made of inorganic peroxides such as potassium phosphate and potassium perphosphate. Of these, BPO is preferred.

The polymerization initiator used in the photopolymerization type is a polymerization initiator which can be photopolymerized by irradiation with ultraviolet rays or visible rays. There is no particular limitation on the polymerization initiator that can be used in such photopolymerization,
Α-diketone compounds such as benzyl, 4,4′-dichlorobenzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzophenone, 9,10-anthraquinone, diacetyl, d, l-camphaquinone (CQ) UV or visible light sensitizers such as

A reducing compound may be used in combination when the polymerization is carried out by a room temperature chemical polymerization or a photopolymerization type. Here, as the organic reducing compound, for example, N,
N-dimethylaniline, N, N-dimethyl p-toluidine (DMPT), N, N-diethyl p-toluidine, N,
N-diethanol p-toluidine (DEPT), N, N
-Dimethyl p-tert-butylaniline, N, N-dimethylanisidine, N, N-dimethyl p-chloroaniline, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminobenzoic acid and its alkyl ester, N, N-diethylaminobenzoic acid (DEA
BA) and its alkyl esters, aromatic amines such as N, N-dimethylaminobenzaldehyde (DMABAd); N-phenylglycine (NPG), N-tolylglycine (NTG), N, N- (3-methacryloyloxy) 2-hydroxypropyl) phenylglycine (NPG-GMA) and the like can be used in combination. Among these, DMPT, DEPT, DEABA, DMA
BAd, NPG and NTG can be preferably used.

In particular, in order to surely cure the curable composition and further improve the adhesiveness to the tooth structure, the following general formula (I)

[0030]

Embedded image

Here, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group which may contain a functional group or a substituent, and R ³ is a hydrogen atom or a metal.

Alternatively, the following general formula (II)

[0033]

Embedded image

Here, R ⁴ and R ⁵ each independently represent a hydrogen atom or an alkyl group, and R ⁶ is a hydrogen atom, an alkyl group which may contain a functional group or a substituent, or a functional group or a substituted group. Is an alkoxyl group which may contain a group,

At least one of the amine compounds represented by
It is preferable to include a seed.

Examples of the amine compound contained in the general formula (I) include NPG, NTG and NPG- which have already been described.
GMA etc. can be mentioned. Of these, NPG is particularly preferably used. Examples of the amine compound contained in the general formula (II) include N, N-dimethylaminobenzoic acid and its alkyl ester, N, N-diethylaminobenzoic acid (DEABA) and its alkyl ester, which are already described, and N, N- -Aliphatic alkylaminobenzoic acid and its alkyl represented by dipropylaminobenzoic acid and its alkyl ester, N-isopropylaminobenzoic acid and its alkyl ester, N-isopropyl-N-methylaminobenzoic acid and its alkyl ester, etc. Aliphatic alkylaminobenzaldehydes represented by esters, DMABAd, N, N-diethylaminobenzaldehyde, N, N-dipropylaminobenzaldehyde, N-isopropyl-N-methylaminobenzaldehyde and the like; N, N- Dimethyl Mino acetyl benzene, N, N-diethylamino-acetyl benzene, N, N-dipropylamino-acetyl benzene,
Examples thereof include aliphatic alkylaminoacetylbenzene and aliphatic alkylaminoacylbenzenes represented by N-isopropylaminoacetylbenzene, N-isopropyl-N-methylaminoacetylbenzene and the like. These amine compounds can be used alone or in combination.

Other examples of the reducing compound include benzenesulfinic acid, o-toluenesulfinic acid, p-toluenesulfinic acid, ethylbenzenesulfinic acid, decylbenzenesulfinic acid, dodecylbenzenesulfinic acid, chlorobenzenesulfinic acid, and naphthalene. Aromatic sulfinic acid such as sulfinic acid or salts thereof can also be used in combination.

As the inorganic reducing compound, a reducing inorganic compound containing sulfur can be preferably used. As such a compound, a reducing inorganic compound used as a redox polymerization initiator that can be used when polymerizing a radically polymerizable monomer in a medium such as water or an aqueous solvent is preferable, for example, sulfurous acid, bisulfite, and metasulfite. , Metabisulfite, pyrosulfite, thiosulfate, dithionous acid, 1,2thionic acid, hyposulfite, hydrosulfite and salts thereof. Of these, sulfite is preferably used, and sodium sulfite, potassium sulfite, sodium hydrogen sulfite, and potassium hydrogen sulfite are particularly preferable. These inorganic reducing compounds can be used alone or in combination.

Preferred examples of the polymerizable monomer used in the curable composition include (meth) acryloyl-based monomers. Examples of the (meth) acryloyl-based monomer include methyl (meth) acrylate,
Monofunctional (meth) acrylates such as ethyl (meth) acrylate, hexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene glycol di ( Bifunctional (meth) acrylates such as (meth) acrylate, hexamethylene glycol di (meth) acrylate, 2,2-bis [4-methacryloxyethoxy) phenyl] propane, and 2,2-bis (4-methacryloyloxypolyethoxyphenyl) propane. ) Tri- or higher-functional (meth) acrylates such as acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 4-methacryloyloxyethoxycarbonylphthalic acid and the like Anhydride, 5-methacryloyl aminosalicylic acid, 10 methacrylate may be mentioned acryloyl acid group-containing, such as oxy dihydrogen phosphate (meth) acryloyl compound. These polymerizable monomers can be used alone or in combination.

Examples of the filler used in the curable composition include polymer powder such as polymethylmethacrylate, glass powder, and metal oxide powder such as zirconium oxide. Alternatively, they can be used in combination.

[0041]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

[Examples 1 to 14] The labial side of bovine anterior teeth was cut to expose the enamel or dentin surface, which was then ground with No. 600 emery paper to form an adhesive surface.

This adhesive surface was washed with water and dried, then coated with primer solutions of various metal salts and acidic monomers shown in Table 1, and after 30 seconds, air blown with an air gun to dry. Then, a cellophane tape with a hole having a diameter of 5 mm was attached to the adhesive surface to define the adhesive area.

Next, on this primer, 50 parts by weight of methyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd., Wako special grade), 2,2-bis [4-methacryloxyethoxy) phenyl] propane (Shin Nakamura Chemical ( KK ester D-
2.6E) 30 parts by weight, 2-hydroxyethyl methacrylate (Wako Pure Chemical Industries, Ltd., Wako special grade) 15 parts by weight, 4
-Methacryloxyethyl trimellitic anhydride (manufactured by Sun Medical Co., Ltd.) in a mixture of 5 parts by weight and 30 parts by weight of tributyl boron partial oxide (TBBO: Sun Medical
(Manufactured by K.K.) was added as a polymerization initiator (curable composition) and lightly air-blown to spread the curable composition on a uniform coating film.

After being left for 30 seconds, a Teflon mold having a diameter of 5 mm and a thickness of 1 mm was attached to the adhesive surface, and a composite resin for dental treatment (manufactured by 3M Corporation,
Silax plus) was filled, and the composite resin was cured by irradiating visible light from a distance of 5 mm for 60 seconds using a visible light irradiator for dental treatment (Translux, manufactured by Kurzer Co., Ltd.).

On the cured composite resin, a polymethylmethacrylate (P) was prepared by using a rapid-hardening instant polymerization resin for dental treatment (manufactured by Sun Medical Co., Ltd., Metafast).
MMA) rods were adhered to obtain a sample for adhesion test.

The adhesion test sample was left at room temperature for 30 minutes, further immersed in distilled water at 37 ° C. for 24 hours, and then subjected to a tensile test to measure the adhesion strength between the PMMA rod and the tooth structure. The adhesive strength is an average value of the values measured on five test pieces.

The adhesive strength measured as described above is shown in Table 1.
Shown in

[0049]

[Table 1]

The compounds represented by the symbols in the table are shown below. 4-META: 4-methacryloxyethyl trimellitic anhydride (manufactured by Sun Medical Co.) β-MEHS: β-methacryloyloxyethyl hydrogen succinate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester SA)

[Comparative Examples 1 to 7] The bovine tooth bonding surface and the PMMA rod were bonded in the same manner as in Example 1 except that the primer solution having the composition shown in Table 2 was applied.

Table 2 shows the adhesive strength in these cases.

[0053]

[Table 2]

[0054]

According to the present invention, tooth enamel and dentin can be simultaneously surface-treated without acid treatment and washing with water. The operation provides a reliable adhesive dental treatment.

Claims (6)

[Claims] 1. A) at least one metal compound selected from the group consisting of iron compounds, copper compounds and cobalt compounds, b) a polymerizable monomer having an acidic group, and c).
A primer composition for treating a dentin surface, comprising water or water and a water-miscible organic solvent. 2. The primer composition according to claim 1, wherein the concentration of the metal compound is in the range of 0.0001 to 1% by weight. 3. The primer composition according to claim 1, wherein the concentration of the acidic monomer is in the range of 0.1 to 30% by weight. 4. At least 40 parts by weight of water of the component c) or water in a water-miscible organic solvent is contained for 100 parts by weight of the components a), b) and c) in total. 1. The primer composition of 1. 5. The primer composition according to claim 1, wherein the components a), b), and c) are divided into two and stored at an arbitrary ratio. 6. A tooth, characterized in that the primer solution composition of claim 1 is applied to the surface of the tooth structure and then a curable composition containing a trialkylboron or its partial oxide and a polymerizable monomer is applied. A method of forming an adhesive layer on a textured surface.