JP2925833B2 - Adhesive surface treatment agent for tooth - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a tooth surface treatment agent having adhesive properties. More particularly, the present invention relates to a surface treatment agent for teeth having excellent adhesion to dentin of a tooth by using a primer containing a specific metal salt.

[0002]

BACKGROUND OF THE INVENTION In the field of dental treatment, it is necessary to strongly bond dentin, particularly dentin, with a material for restoring the dentin (for example, polymer, metal, porcelain, etc.). Various adhesives have been proposed for this purpose.

[0003] Such a dental adhesive generally employs a three-component constitution of (1) a polymerizable monomer, (2) a polymerization catalyst or polymerization initiator, and (3) a filler. Typical examples of such a dental adhesive include (1) a polymerizable monomer, (2) a mixture of benzoyl peroxide as a polymerization catalyst and an aromatic tertiary amine, or a mixture of the mixture with sulfinic acid. (3) a catalyst component to which an acid salt is added;
An adhesive composition comprising a filler, or photopolymerization initiation comprising (1) a polymerizable monomer, (2) camphorquinone as a photosensitizer, and N, N-dimethylaminoethyl methacrylate as a reducing agent. An adhesive composition comprising an agent and (3) a filler; and (1) a polymerizable monomer;
(1 ′) 4-methacryloyloxyethoxycarbonylphthalic anhydride (4-META) as an adhesion-promoting monomer
An adhesive composition comprising (2) tributylborane partial oxide (TBBO) as a polymerization catalyst and (3) a filler (for example, polymethyl methacrylate, PMMA) has been proposed.

As described above, in the conventional adhesive composition, various compounds are used as a polymerization initiator of a polymerizable monomer, but a sufficient adhesive strength is not obtained except when TBBO is used. .

[0005] Therefore, it has been proposed to use an adhesion-promoting monomer or a monomer having an affinity for the tooth substance in order to improve the adhesiveness of such a tooth adhesive.
Examples of the adhesion-promoting monomer or the monomer having an affinity for the tooth substance include, for example, 4-methacryloyloxyethoxycarbonylphthalic acid (4-MET) or its anhydride (4-META) and 10-methacryloyloxydecylmalonic acid (MAC). Monomers having a carboxyl group (or a group that can be converted to a carboxyl group) such as -10) and monomers having a phosphate group such as 10-methacryloyloxydecyl dihydrogen phosphate.

[0006] There are two types of dentin, enamel and dentin.
In terms of adherence, the two are not equal. In general, adherence is good for enamel but poor for dentin.

[0007] Of the above-mentioned adhesives, when bonding to dentin treated with a citric acid solution containing ferric chloride using an adhesive using TBBO as a polymerization initiator, a considerable degree of adhesive strength is obtained. However, even when an adhesion promoting monomer is used, good adhesion to dentin is often not exhibited when other adhesives are used.

As described above, among the prior arts, the adhesive using TBBO is the most excellent. In order to develop better adhesive strength using this adhesive, it is desirable to perform pretreatment on the tooth material, and a stable adhesive strength can be obtained by this pretreatment method. Conventional methods using TBBO include, for example, treating dentin with a 10% aqueous citric acid solution containing 3% ferric chloride for 30 seconds (such a treatment is generally referred to as "10-3 treatment"). ) Is recommended, and this 10-3 treatment is highly useful as a treatment method for increasing the adhesive strength in dentin.

Further, when only enamel is treated, it is recommended to use a 65% aqueous solution of phosphoric acid. However, in this treatment, the adhesive strength of dentin is insufficient, and the enamel and dentin are separated. In the mixed region, enamel is treated with a phosphoric acid aqueous solution, and dentin is subjected to 10-3 treatment.

[0010]

[0011]

SUMMARY OF THE INVENTION An object of the present invention is to provide an adhesive surface treatment agent for tooth material capable of exhibiting high adhesive strength regardless of the method of pretreatment of the tooth material.

[0012]

SUMMARY OF THE INVENTION An adhesive surface treatment agent for a tooth of the present invention comprises a primer applied to the surface of a tooth and a curable composition applied on the primer. The primer comprises a solution containing at least one metal compound selected from the group consisting of a copper compound, an iron compound and a cobalt compound and a water-miscible monomer, and the curable composition comprises a trialkyl It is characterized by containing boron or its partial oxide and a (meth) acrylate monomer.

By using the adhesive surface treating agent for tooth material of the present invention, there is little change in adhesive strength due to the pretreatment method for tooth material. Therefore, there is no need to select a pretreatment method according to the type of the adhesive used as in the conventional case, and various methods can be adopted as the pretreatment method. Even if various pretreatment methods are employed, good adhesive strength is exhibited, and the adhesive force has little change with time.

[0014]

DETAILED DESCRIPTION OF THE INVENTION The adhesive surface treating agent for teeth according to the present invention will be specifically described below. As a pretreatment agent (etching agent) for the tooth substance, phosphoric acid, which is a component of the tooth, is more physiologically preferable than 10-3 solution or citric acid. It is preferable that the concentration of phosphoric acid used is low in consideration of the degree of damage to the tooth material.

The present inventor has studied the concentration of phosphoric acid in the treatment solution from such a viewpoint. As a result, instead of the phosphoric acid aqueous solution having a high concentration of 40 to 65% which is currently widely used, a lower concentration of 5 to 5% is used. It has been found that a 40% phosphoric acid aqueous solution can be used. In order to express good adhesive strength to the tooth treated using such a low-concentration phosphoric acid aqueous solution, a conventional adhesive for tooth cannot exhibit sufficient adhesive strength.

The dental adhesive of the present invention exhibits good adhesive strength especially to the tooth treated with the above-mentioned low-concentration phosphoric acid aqueous solution. The adhesive surface treatment agent for tooth material of the present invention comprises a primer applied on tooth material and a curable composition applied on the primer.

This primer is a solution containing a specific metal compound and a water-miscible monomer. In the present invention, the metal compound is selected from a copper compound, an iron compound and a cobalt compound. And as the metal compound used in the present invention, specifically, chlorides of the above metals,
Halides such as fluoride; salts of inorganic acids such as nitrates and sulfates; salts of acetates, acrylates, methacrylates and other organic acids; and organic complexes such as complexes with acetylacetone. These metal compounds may be of any valence. Examples of copper compounds that can be used in the present invention include salts of inorganic acids such as copper chloride, copper fluoride, copper nitrate and copper sulfate; copper acetate,
Mention may be made of salts of organic acids such as copper acrylate and copper methacrylate, and complex salts such as copper acetylacetone. Examples of iron compounds that can be used in the present invention 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 can be mentioned. Examples of cobalt compounds that can be used in the present invention 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; Complex salts such as acetylacetonate cobalt can be mentioned.

These metal compounds can be used alone or in combination. The amount of the metal compound in the primer is usually in the range of 0.0005 to 0.5% by weight. In particular, when the metal compound is a copper compound, the concentration of the copper compound in the primer component can be in the range of 0.0005 to 0.05% by weight. When the metal compound is an iron compound or a cobalt compound, the concentration of these compounds in the primer can be in the range of 0.005 to 0.5% by weight.

A water-miscible monomer is used as a primer component of the dental adhesive of the present invention. Water-miscible monomers include 2-hydroxyethyl methacrylate (HEM
A), 2-hydroxyethyl acrylate, hydroxypropyl methacrylate, 2,3-dihydroxypropyl methacrylate and N-vinylpyrrolidone. Particularly, in the present invention, 2-hydroxyethyl methacrylate is preferred as the water-miscible monomer. The concentration of the water-affinity monomer in the primer is usually 1 to
It is in the range of 50% by weight, preferably 5-40% by weight.

HE used as a primer of the present invention
It is already known that MA is used for bonding of dentin (see JP-A-63-221181). However, according to the method described in this publication, enamel is treated with a 65% phosphoric acid aqueous solution treatment, and dentin is treated with EDT.
It is necessary to treat with A.2Na-EDTA.Fe.Na for 60 seconds. According to the study of the present inventors, after uniformly treating enamel and dentin with phosphoric acid, HEMA is applied alone. Even when cured, not so good adhesive strength was developed. In particular, the adhesive strength to dentin tends to decrease. That is, in the conventional adhesive using HEMA, there is a problem that a good adhesive strength cannot be obtained unless the enamel and dentin are treated using different treatment agents. However, it is necessary to use a high-concentration aqueous solution of phosphoric acid, and it takes a long time to treat dentin. H as such a primer
As a result of examining an adhesive using a water-miscible monomer such as EMA, it was found that by adding a specific metal compound to the water-miscible monomer, extremely good adhesion was exhibited.

The specific metal compound and the water-miscible monomer as described above are used after being dissolved or dispersed in a solvent. Here, as the solvent for dissolving or dispersing the specific metal compound and the water-miscible monomer as described above,
Water and water-miscible organic solvents of water and ethanol, isopropanol, acetone, tetrahydrofuran and the like can be used.

The primer having such a composition may further contain another radical polymerizable monomer having a carboxyl group or a phosphate group. The mixing ratio of such other monomers can be appropriately set, but is usually used in an amount within the range of dissolving in the above-mentioned solvent.

The above-mentioned primer is a solution containing the above-mentioned specific metal compound and a water-miscible monomer. In order to secure storage stability, two kinds of these components are individually dissolved. It is also possible to prepare a solution and mix the two immediately before use.

In the present invention, the curable composition applied on the primer as described above comprises a trialkylboron (TBB or the like) or a partial oxide thereof (TBBO or the like) and a (meth) acrylate monomer. Examples of the (meth) acrylate monomer include methyl methacrylate and 4-methacryloyloxyethoxycarbonylphthalic acid. The curable composition may contain other components such as polymethyl methacrylate powder within a range that does not impair the properties of the treatment agent of the present invention. That is, the curable composition can act as an adhesive as it is, or may be an adhesive as a liner of a composite resin. A typical example of the composite resin used here is a TBBO-based resin, and among the commercially available TBBO-based resins, Super Bond C & B or D Liner (manufactured by Sun Medical Co., Ltd.) is preferably used. be able to.

The dental adhesive surface treating agent of the present invention is obtained by applying the above-mentioned primer to the surface of the pretreated tooth material, drying the primer, and then applying the above-mentioned curable composition to the surface of the primer. To treat the tooth surface. As described above, the phosphoric acid treatment is suitable for the pretreatment of the tooth material. In particular, a 5 to 40% phosphoric acid aqueous solution can be used for the pretreatment. In the pretreatment of dentin using such a low concentration of phosphoric acid, it is not necessary to treat dentin and enamel separately, and both can be treated uniformly. However, when using the adhesive of the present invention, the pretreatment of the tooth material is not limited to the above-mentioned treatment method using a low concentration of phosphoric acid, and the citric acid conventionally used is used. For example, a 10-3 treatment method, a treatment method using 65% phosphoric acid, or the like can be adopted.

After the application of the primer, the primer layer is formed on the tooth surface by removing the solvent. The curable composition is applied on the primer layer thus formed and cured. Further, if necessary, a curable composition can be applied, and a filler or a repair agent can be laminated before the composition is cured, and the composition can be adhered to tooth using the adhesive force of the curing agent. .

[0027]

The metal salt contained in the primer of the surface treating agent of the present invention is taken into the acid-treated tooth material and forms an oxidation / reduction system with TBBO to generate radicals. The polymerization reaction of the monomer in the HEMA and the curable composition is initiated, and the reaction proceeds rapidly. Therefore, the polymerization reaction proceeds from the tooth surface, and the curable composition is cured, so that a high adhesive strength is exhibited. Therefore, by using the adhesive surface treating agent of the present invention, it has become possible to simultaneously treat both enamel and dentin with a mild acid.

[0028]

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

[0029]

Example 1 The dentin surface was cut out by cutting the lip side surface of the cow's front teeth and polished with No. 600 emery paper to form an adhesive surface. This bonding surface is treated with a 40% phosphoric acid aqueous solution for 30 seconds,
After washing with water and drying, a plastic pressure-sensitive adhesive tape having a hole having a diameter of 5 mm was attached to the adhesive surface to define an adhesive area.

On the adhesive surface, 0.003 g of cupric chloride,
35 g of 2-hydroxyethyl methacrylate and 65
g of water was applied and dried. Then, 5% by weight of 4-methacryloyloxyethoxycarbonylphthalic anhydride (4-MET
10% by weight of tributyl boron partial oxide (TBBO: Sun Medical Co., Ltd.) in methyl methacrylate containing A)
Was mixed as a polymerization initiator and a polymethyl methacrylate powder (curable composition) was applied by a brushing method, and an acrylic rod was adhered.

After leaving it to stand at room temperature for 30 minutes and further immersing it in distilled water at 37 ° C. for 24 hours, a tensile test was carried out to measure the adhesive strength between the acrylic rod and the dentin (dentin). The adhesive strength is an average value measured on five test pieces.

The adhesive strength measured as described above is 1
It was 3.7 MPa.

[0033]

Examples 2 to 4 An acrylic rod was adhered in the same manner as in Example 1 except that the bovine front teeth pretreated with a phosphoric acid aqueous solution having the concentration shown in Table 1 were used instead of 40% phosphoric acid.
This adhesive strength was measured.

Table 1 shows the adhesive strength.

[0035]

[Table 1]

[0036]

Comparative Example 1 An acrylic rod was adhered in the same manner as in Example 1 except that after treating with a 40% phosphoric acid aqueous solution, the curable composition was directly applied without applying a primer.

The adhesive strength of this acrylic rod is 1.4 MPa.
Met.

[0038]

Comparative Example 2 The procedure of Example 1 was repeated, except that a primer containing no cupric chloride was applied after treatment with a 10% phosphoric acid aqueous solution, and a curable composition was applied on the primer. An acrylic stick was glued.

The adhesive strength of this acrylic rod was 6.3 MPa.

[0040]

Example 5 The procedure of Example 1 was repeated except that a primer consisting of 0.07 g of ferric chloride, 35 g of 2-hydroxyethyl methacrylate and 65 g of water was applied instead of the primer used in Example 1. Acrylic stick was glued.

The adhesive strength of this acrylic rod was 10.6 M
Pa.

[0042]

Example 6 The same procedure as in Example 1 was carried out except that a 40% aqueous phosphoric acid solution was used instead of a 40% aqueous phosphoric acid solution. As a primer, 0.01 g of cobalt chloride, 35 g of 2-hydroxyethyl methacrylate and 65 g of water were used. An acrylic bar was bonded in the same manner except that a primer was used.

The adhesive strength of this acrylic rod was 11.0 M
Pa.

[0044]

Examples 7 to 10 In Example 1, a 10% phosphoric acid aqueous solution was used in place of the 40% phosphoric acid aqueous solution.
Acrylic bars were adhered in the same manner except that a primer containing a copper salt shown in Table 2 was prepared in place of cupric chloride in the primer used in Example 2, and this was used.

Table 2 shows the bonding strength of the acrylic rod thus bonded.

[0046]

[Table 2]

[0047]

Example 11 An acrylic rod was adhered in the same manner as in Example 1, except that dentin was treated with a 10% aqueous citric acid solution for 60 seconds instead of the 40% aqueous phosphoric acid solution.

The adhesive strength of this acrylic rod is 12.0M
Pa.

[0049]

Comparative Example 3 In Example 1, dentin was treated with a 10% aqueous citric acid solution for 60 seconds instead of the 40% aqueous phosphoric acid solution, and then the curable composition was directly applied without using a primer. Except for the above, an acrylic bar was adhered in the same manner.

The adhesive strength of this acrylic rod is 2.0MP
a.

[0051]

Example 12 An acrylic rod was adhered in the same manner as in Example 1, except that dentin was treated with a 15% aqueous EDTA solution for 60 seconds instead of the 40% aqueous phosphoric acid solution.

The adhesive strength of this acrylic rod was 11.3 M
Pa.

[0053]

Comparative Example 3 In Example 1, dentin was treated with a 10% aqueous EDTA solution for 60 seconds instead of the 40% aqueous phosphoric acid solution, and then the curable composition was directly applied without using a primer. Bonded an acrylic bar in the same manner.

The adhesive strength of this acrylic rod was 2.0MP.
a.

[0055]

Example 13 An acrylic rod was adhered in the same manner as in Example 1 except that enamel surface was used instead of dentin and treated with a 10% phosphoric acid aqueous solution for 30 seconds.

The adhesive strength between this acrylic rod and enamel was 19.2 MPa.

[0057]

Comparative Example 5 An acrylic rod was adhered in the same manner as in Example 13 except that no primer was applied.

The adhesive strength between the acrylic bar and the enamel was 16.8 MPa.

[0059]

Example 14 In Example 1, dentin was treated with a 10% aqueous phosphoric acid solution instead of a 40% aqueous phosphoric acid solution, and as a primer, 0.003 g of cupric chloride and 35 g of 2-chloroacetic acid were used.
An acrylic rod was adhered in the same manner except that a primer consisting of hydroxyethyl methacrylate, 30 g of ethanol and 35 g of water was used.

The adhesive strength of this acrylic rod was 13.0 M
Pa.

[0061]

Example 15 In Example 1, dentin was treated with a 10% aqueous phosphoric acid solution instead of a 40% aqueous phosphoric acid solution, and 0.003 g of cupric chloride and 1 g of 4-methacryloyloxyethoxycarbonyl were used as primers. Phthalic acid (4-M
ET), 34 g of 2-hydroxyethyl methacrylate,
An acrylic rod was adhered in the same manner except that a primer consisting of 30 g of ethanol and 35 g of water was used.

The adhesive strength of this acrylic rod is 12.5M
Pa.

[0063]

Example 16 In Example 1, dentin was treated with a 10% phosphoric acid aqueous solution instead of a 40% phosphoric acid aqueous solution, and as a primer, 0.003 g of cupric chloride and 10 g of N—
An acrylic stick was adhered in the same manner except that a primer consisting of vinylpyrrolidone, 25 g of 2-hydroxyethyl methacrylate, and 65 g of water was used.

The adhesive strength of this acrylic rod was 11.3 M
Pa.

[0065]

Example 17 In Example 1, dentin was treated with a 10% phosphoric acid aqueous solution instead of a 40% phosphoric acid aqueous solution, and as a primer, 0.003 g of copper methacrylate and 30 g were used.
An acrylic rod was bonded in the same manner except that a primer consisting of 2,3-dihydroxypropyl methacrylate and 70 g of water was used.

The adhesive strength of this acrylic rod was 12.4 M
Pa.

Claims (5)

(57) [Claims] 1. A surface treatment agent for an adhesive tooth material comprising a primer applied to the surface of a tooth material and a curable composition applied on the primer, wherein the primer is a copper compound or an iron compound And a solution containing a water-miscible monomer and at least one metal compound selected from the group consisting of: a trialkylboron or a partial oxide thereof and a (meth) acrylate-based monomer. An adhesive surface treatment agent for dentin, comprising: 2. The adhesive surface treatment agent for teeth according to claim 1, wherein the concentration of the copper compound in the primer is in the range of 0.0005 to 0.05% by weight. 3. The dental adhesive surface treatment according to claim 1, wherein the concentration of the iron compound or the cobalt compound in the primer is in the range of 0.005 to 0.5% by weight. Agent. 4. The adhesive surface treating agent for teeth according to claim 1, wherein the solvent forming the primer is water or a mixture of water and a water-miscible organic solvent. 5. The water-miscible monomer is 2-hydroxyethyl methacrylate, and the concentration of 2-hydroxyethyl methacrylate in the primer component is 1 to 50.
The adhesive surface treatment agent for dentin according to claim 1, wherein the amount is within the range of% by weight.