JPH0789821A - Adhesive surface-treating agent for dental purposes - Google Patents

Abstract

PURPOSE:To obtain a surface-treating agent which can treat the tooth enamel and the dentin simultaneously to simplify the operations and prolongs the period of increased adhesion strength stably with improved reliance on the adhesion. CONSTITUTION:In the adhesive surface-treating agent for dental purposes comprising the primer to be coated on the tooth surface and a hardening composition to be coated on the primer, the primer is a solution containing a metal compound, at least one from copper, iron and cobalt compounds, a water- miscible monomers, and fluoride ion, while the curing composition contains trialkylboron, or its partially oxidized product and (meth)acrylate monomers.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a surface treating agent for dentin having adhesiveness. More specifically, the present invention relates to a surface treating agent for dentin, which has excellent adhesiveness to tooth dentin by using a primer containing fluoride ion and 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 example, polymer substance, metal, porcelain, etc.) for repairing the dentin, Various adhesives for that purpose have already been proposed.

Such a dental adhesive generally has a three-component constitution of (1) polymerizable monomer, (2) polymerization catalyst or polymerization initiator, and (3) filler. As a typical example of such a dental adhesive, (1) a polymerizable monomer, (2) a mixture of benzoyl peroxide as a polymerization catalyst and an aromatic tertiary amine-based compound, or a mixture thereof with sulfin A catalyst component to which an acid salt is added, and (3)
Photopolymerization initiation comprising an adhesive composition comprising a filler or (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 further (1) a polymerizable monomer,
(1 ') 4-methacryloyloxyethoxycarbonylphthalic anhydride (4-META) as adhesion promoting monomer
An adhesive composition comprising (2) tributylborane partial oxide (TBBO) as a polymerization catalyst and (3) a filler (eg polymethylmethacrylate, PMMA) has been proposed.

As described above, in the conventionally known adhesive composition, various compounds are used as the polymerization initiator of the polymerizable monomer. Among them, particularly excellent adhesiveness is obtained when TBBO is used. Is obtained.

On the other hand, it has been proposed to use an adhesion-promoting monomer or a monomer having an affinity with the tooth substance in order to improve the adhesiveness of the tooth substance adhesive. Examples of such a monomer include: Carboxyl groups (or groups that can be converted to carboxyl groups) such as 4-methacryloyloxyethoxycarbonylphthalic acid (4-MET) or its anhydride (4-META) and 10-methacryloyloxydecylmalonic acid (MAC-10) And a monomer having a phosphoric acid group such as 10-methacryloyloxydecyl dihydrogen phosphate.

Tooth substances include enamel and dentin,
In terms of adherence, the two are not equivalent, and generally the adherence is good for enamel, but dentin is often poor.

Among the adhesives, when the dentin treated with a citric acid solution containing ferric chloride is bonded with an adhesive using TBBO as a polymerization initiator, a considerable degree of adhesive force is exhibited.

[0008] As described above, the adhesive using TBBO is the best among the conventional techniques, and the tooth substance is treated with a 10% citric acid aqueous solution containing 3% ferric chloride for 30 seconds (such treatment). Is generally referred to as "10-3 processing") is recommended. This 10-3 process is
It is highly useful as a treatment method for increasing the adhesive strength in dentin. In this way, the presence of metal ions such as iron and copper provides stronger adhesion. This is because the metal ions absorbed in the dentin collagen act as a polymerization initiator together with TBBO, and the MMA polymerization starts from the collagen part, that is, the adhesive interface, so that the dentin and resin are avoided while avoiding the influence of polymerization shrinkage. It is often explained as being integrated. In order to exert such an effect of the metal ion, (1) a method of adding the metal ion to the pretreatment agent and (2) a method of causing the metal ion to act after the usual pretreatment are considered. Usually for MMA-TBBO resin (1)
However, the present inventors have already reported that it is also effective to use (2) as a primer.

[0009]

The object of the present invention is to further improve and stabilize the improvement of the adhesive strength by these metal ions.

[0010]

SUMMARY OF THE INVENTION The adhesive surface treating agent for tooth structure of the present invention comprises a primer applied on the surface of the tooth structure and an adhesive surface treating agent for the tooth structure comprising a curable composition applied on the primer. Wherein the primer comprises a solution containing at least one metal compound selected from the group consisting of copper compounds, iron compounds and cobalt compounds, a water-miscible monomer and a fluorine ion in an amount of 0.04% by weight or less. Becomes
The curable composition is characterized by containing a trialkylboron or a partial oxide thereof and a (meth) acrylate-based monomer.

By using the adhesive surface treatment agent for tooth structure of the present invention, the fluctuation of the adhesive strength due to the pretreatment method of the tooth structure is reduced. Therefore, it is not necessary to select a specific pretreatment method of 10-3 treatment as in the conventional case, and various pretreatment methods can be adopted. Even when various pretreatment methods are adopted as described above, good adhesive strength is exhibited and the change in adhesive force over time is small.

The adhesive surface treating agent for tooth structure of the present invention exhibits good adhesive strength even to a tooth structure treated with an aqueous phosphoric acid solution having a concentration of 5 to 40%.

[0013]

DETAILED DESCRIPTION OF THE INVENTION The adhesive surface treating agent for tooth structure according to the present invention will be specifically described below. The adhesive surface treating agent for teeth of the present invention comprises a primer applied on the teeth 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 copper compounds, iron compounds and cobalt compounds. Specific examples of the metal compound used here include chlorides and fluorides of the above metals, salts of inorganic acids such as nitrates and sulfates; acetates, acrylates, methacrylates and others. Salts of organic acids; organic complexes such as complexes with acetylacetone. These metal compounds may have any valence. Specific examples of copper compounds used herein include salts of inorganic acids such as copper chloride, copper fluoride, copper nitrate and copper sulfate; organic acids such as copper acetate, copper acrylate and copper methacrylate. Can be mentioned, as well as complex salts such as copper acetylacetone. Further, 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 acetylacetone iron. Can be mentioned. Further 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. Can be mentioned.

Further, by containing a specific copper compound in the primer, excellent adhesive strength can be obtained without necessarily obtaining the assistance of fluorine ions. That is, an adhesive surface treating agent for tooth structure comprising a primer applied to the surface of the tooth and a curable composition applied onto the primer, wherein the primer has the following formula (A) or (B): By using a tooth surface treating agent characterized by containing at least one compound selected from the copper salt compound shown in, good adhesive strength is expressed even in the absence of fluorine ions .

[0016]

[Chemical 3]

(A)

[0018]

[Chemical 4]

(B) However, in the above formulas (A) and (B), R ¹ and R ² each independently represent a methyl group or a hydrogen atom, and R ³ is —O—CO— or —. Represents any group of CO-O-.

Of course, the specific copper compound (A) or (B)
Also in the case of using, by using the above-mentioned fluorine ions in combination, it is possible to exhibit more excellent adhesive strength. The concentrations of these copper compounds (A) or (B) in the primer are the same as in the case of the above copper compounds.

These metal compounds can be used alone or in combination. The compounding amount of the metal compound in the primer is usually 0.0005 to 0.5 mol /
It is in the range of wt%. Particularly when the metal compound is a copper compound, the concentration of the copper compound in the primer component is 1 × 10 ⁻³ to 1 × 10 ⁻⁵ mol / wt%, and particularly when the metal compound is a copper compound, the primer is used. The concentration of the copper compound therein can be in the range of 5 × 10 ^{−4 to} 5 × 10 ⁻⁵ mol / wt%. Optimal concentration is 3 × 10 ^-4 mol
/ Wt% to 5x10 ^-4 mol / wt%. Here, "mol / wt%" is the percentage of the number of moles of the metal compound per weight.

The tooth adhesive primer of the present invention contains a predetermined amount of fluorine ions. Fluoride ion is
Part or all of them may be blended in the primer in the form of a salt with the above metal, or may be blended in the primer in the form of a salt with another metal. . Here, as the metal other than the above-mentioned metals, alkali metals such as lithium, potassium and sodium,
Mention may be made of alkaline earth metals such as magnesium and calcium. Such metal fluorides are
It is preferable that fluoride ions can be efficiently formed in the primer solution. Further, sodium fluoride and potassium fluoride can be preferably used as the fluoride that can be used in the present invention to form the fluoride ion in the primer. By using sodium fluoride or the like as the fluorine ion supply source, the fluorine ions can be supplied more stably than when the above metal fluoride is used.

The fluorine ion concentration in the primer of the present invention is 0.04% by weight or less, and the lower limit thereof is usually 0.001% by weight. Fluorine ion concentration is 0.00
If the amount is less than 1% by weight, there is a tendency that no significant difference is observed in the effect of fluoride ion. Further, even if it exceeds 0.04% by weight, the effect of improving the adhesive strength by the fluorine ion becomes small and becomes lower than that in the case of using the primer which does not contain the fluorine ion. Therefore, in the present invention, by setting the fluorine ion concentration in the primer within the above range, the adhesive strength is improved as compared with the case where the primer containing no fluorine ion is used. Further, by using a primer having a fluorine ion concentration in the range of 0.002 to 0.04% by weight, the effect of improving the adhesive strength and the temporal stability of the adhesive strength become more clear.

A water-miscible monomer is used as a primer component of the adhesive surface treating agent for teeth of the present invention. Examples of the water-miscible monomer include 2-hydroxyethyl methacrylate (HEMA), 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 in the range of 1 to 50% by weight, preferably 5 to 40% by weight.

Further, by mixing an aldehyde compound with this primer, the adhesive strength can be further increased. Glutaraldehyde can be mentioned as a suitable example of an aldehyde compound.

The concentration of such an aldehyde compound in the primer is usually 0.5 to 50% by weight.
The above-mentioned specific metal compound and water-miscible monomer are used after being dissolved or dispersed in a solvent. Here, as a solvent for dissolving or dispersing the specific metal compound and the water-miscible monomer as described above, water, and
A water-miscible organic solvent of water and ethanol, isopropanol, acetone, tetrahydrofuran or the like can be used.

Further, in the primer having such a composition, another radically polymerizable monomer having a carboxyl group or a phosphoric acid group may be further added. The blending ratio of such other monomer can be appropriately set, but it is usually used in an amount within the range in which the monomer is soluble.

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

In the present invention, the curable composition coated 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-based monomer. Examples of this (meth) acrylate-based monomer include methyl methacrylate (MMA) and 4-methacryloyloxyethoxycarbonylphthalic acid.
The curable composition may contain other components such as polymethylmethacrylate (PMMA) powder within a range that does not impair the properties of the treatment agent of the present invention. That is, as a typical example of this curable composition, MMA / PMMA-TBBO resin, Superbond C & B or D liner (Sun Medical Co., Ltd.)
Manufactured) can be preferably used.

The adhesive surface treatment agent for tooth structure of the present invention is prepared by applying the above-mentioned primer on the surface of pre-treated tooth structure and drying it, and then applying the above curable composition on the primer application surface. The tooth surface is treated by coating. Then, the phosphoric acid treatment is suitable for the pretreatment of the tooth substance as described above, and in particular, a 5-40% phosphoric acid aqueous solution can be used for the pretreatment. In the pretreatment of the tooth substance using such a low concentration of phosphoric acid, it is not necessary to treat the dentin and the enamel separately, and both can be treated uniformly, and there are many practical advantages. However, when using the adhesive of the present invention, the pretreatment of the tooth structure is not limited to the treatment method using the low concentration phosphoric acid as described above, and the conventionally used citric acid is used. Treatment method,
A 10-3 treatment method, a treatment method using 65% phosphoric acid, or the like can also be adopted.

After applying the primer in this manner, the solvent is removed to form a primer layer on the surface of the tooth structure. The curable composition is applied on the primer layer thus formed and cured. Further, if necessary, a curable composition may be applied, a filler or a repair material may be laminated before the composition is cured, and the adhesive force of the curing agent may be used to adhere to the tooth structure. .

[0032]

The metal salt contained in the primer of the surface treatment agent of the present invention is taken into the acid-treated tooth structure and forms an oxidation / reduction system with TBBO to generate a radical, thereby generating HEMA and The polymerization reaction of the monomers in the curable composition is initiated and the reaction is allowed to proceed rapidly. Therefore, the polymerization reaction proceeds from the aspect of the tooth structure and the curable composition is cured, so that high adhesive force is exhibited. Then, the presence of a specific amount of fluorine ions in this primer increases the adhesive strength. Furthermore, by using the adhesive surface treating agent of the present invention, it is possible to simultaneously treat both enamel and dentin with a mild acid. Furthermore, by using the adhesive surface treatment agent for teeth of the present invention, the temporal stability of the adhesive strength is improved.

[0033]

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

[0034]

Example 1 The labial surface of bovine anterior teeth was cut to expose the dentin surface, which was ground with No. 600 emery paper to form an adhesive surface. This adhesive surface is treated with a 10% phosphoric acid aqueous solution for 30 seconds,
After being washed with water for 30 seconds and dried for 30 seconds, a plastic adhesive tape having a hole with a diameter of 5 mm was attached to the adhesive surface to define the adhesive area.

0.003 g of cupric chloride,
35 g of 2-hydroxyethyl methacrylate and 65
A primer (fluoride ion concentration: 1.4 × 10 ⁻³ wt%) to which 0.003 wt% NaF was added was applied to a solution consisting of g of water and dried.

Then, 5% by weight on this primer
Methyl methacrylate containing 4-methacryloyloxyethoxycarbonylphthalic anhydride (4-META)
A liquid obtained by mixing 0% by weight of tributylboron partial oxide (TBBO: manufactured by Sun Medical Co., Ltd.) as a polymerization initiator and polymethylmethacrylate powder (curable composition) were applied by a writing method to prepare an acrylic stick. Glued.

After being left at room temperature for 30 minutes and further immersed in distilled water at 37 ° C. for 24 hours, a tensile test was conducted to measure the adhesive strength between the acrylic rod and the dentin (dentin). The adhesive strength is an average value of the values measured on five test pieces.

The adhesive strength at this time is shown in Table 1.

[0039]

Example 2 In Example 1, the amount of NaF added to the primer was 0.01% by weight (fluoride ion concentration: 4.5).
× was prepared a primer in the same manner except that the 10 ^-3 wt%), was adhered to the tooth and acrylic rods in the same manner except for using this primer. The adhesive strength at this time is shown in Table 1.

[0040]

[Example 3] In Example 1, the amount of NaF added to the primer was 0.03% by weight (fluoride ion concentration: 1.3).
(5 × 10 ⁻² wt%) except that the primer was prepared in the same manner, and the tooth substance and the acrylic rod were bonded in the same manner except that this primer was used. The adhesive strength at this time is shown in Table 1.
Shown in.

[0041]

[Comparative Example 1] In Example 1, a primer was prepared without adding NaF to the primer (fluoride ion concentration: 0% by weight), and the tooth substance and the acrylic rod were bonded in the same manner except that this primer was used. did. The adhesive strength at this time is shown in Table 1.

[0042]

Comparative Example 2 In Example 1, the amount of NaF added to the primer was 0.1% by weight (fluoride ion concentration: 4.52).
× was prepared a primer in the same manner except that the 10 ^-2 wt%), was adhered to the tooth and acrylic rods in the same manner except for using this primer. The adhesive strength at this time is shown in Table 1.

[0043]

Comparative Example 3 In Example 1, the amount of NaF added to the primer was 0.3% by weight (fluoride ion concentration: 1.36).
× was prepared a primer in the same manner except that the 10 ^-1 wt%), was adhered to the tooth and acrylic rods in the same manner except for using this primer. The adhesive strength at this time is shown in Table 1.

[0044]

[Table 1]

[0045]

[Example 4] As in Example 2, the bovine anterior teeth were treated with a 10% phosphoric acid aqueous solution for 30 seconds, washed with water for 30 seconds, and dried for 30 seconds, and then a plastic adhesive tape having a hole with a diameter of 5 mm was attached to the adhesive surface. A solution of 0.003 g of cupric chloride, 35 g of 2-hydroxyethyl methacrylate and 65 g of water, and 0.001% by weight of N.
Primer with aF added (fluoride ion concentration: 0.4
5 × 10 ⁻² % by weight) was applied and dried.

Then, on this primer, Example 2
The curable composition used in 1. was applied and an acrylic rod was adhered. With respect to the adhesive material of the tooth substance and the acrylic rod thus prepared, the change with time of the adhesive strength was examined. The results are shown in Table 2.

[0047]

[Comparative Example 4] In Example 4, an adhesive material of a tooth substance and an acrylic rod was prepared in the same manner as in Example 4 except that the primer to which NaF was not added was used, and the results of examining the change with time of the adhesive strength are shown. 2 shows.

[0048]

[Comparative Example 5] In Example 4, 10-3 treatment (treatment with 10 wt% citric acid-3 wt% ferric chloride aqueous solution) was carried out in place of the treatment with 10% phosphoric acid aqueous solution. Table 2 shows the results obtained by preparing an adhesive material between a tooth substance and an acrylic rod in the same manner as described above, except that the primer was not used, and examining the change with time of the adhesive strength.

[0049]

[Table 2]

Note) In the above table, the values in parentheses are standard deviations.

[0051]

Example 5 The same operation as in Example 1 was carried out except that NaF was not used and the copper compound CMP or CMS shown in Table 3 was used as the copper compound at the concentration shown in Table 3.

The results are shown in Table 3.

[0053]

[Table 3]

In the above table, "CMP" and "CM"
"S" represents the compound shown below.

[0055]

[Chemical 5]

[0056]

[Chemical 6]

Claims (5)

[Claims] 1. A dental adhesive surface treatment agent comprising a primer applied to the surface of a tooth and a curable composition applied on the primer, the primer comprising a copper compound, an iron compound and A curable composition comprising a solution containing at least one metal compound selected from the group consisting of cobalt compounds, a water-miscible monomer and a fluorine ion in an amount of 0.04% by weight or less, wherein the curable composition is trialkylboron or a compound thereof. An adhesive surface treatment agent for tooth structure, comprising a partial oxide and a (meth) acrylate-based monomer. 2. The concentration of the metal compound in the primer is in the range of 5 × 10 ^{−2 to} 5 × 10 ⁻⁴ mol / wt%, and the metal compound is a copper compound. The adhesive surface treatment agent for teeth according to claim 1. 3. The adhesive surface treatment agent for teeth according to claim 1, wherein the solvent forming the primer is water or a mixed solution of water and a water-miscible organic solvent. 4. 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 teeth according to claim 1, wherein the adhesive surface treatment agent is in the range of% by weight. 5. An adhesive surface treating agent for teeth comprising a primer applied to the surface of a tooth and a curable composition applied onto the primer, wherein the primer has the following formula (A) or A tooth surface treatment agent containing at least one compound selected from the copper salt compounds represented by (B); (A) [Chemical formula 2] (B) [In the above formulas (A) and (B), R ¹ and R ² each independently represent a methyl group or a hydrogen atom, and R ³ is —O—CO— or — Represents any group of CO-O-].