JPH02261442A - Method for treating dentine surface - Google Patents

Abstract

PURPOSE:To exhibit an excellent adhesive property by treating a dentine surface with a solution or dispersion containing a polymer having sulfonic acid group and then treating it with a solution or dispersion containing a polyvalent ion. CONSTITUTION:As a polymer containing sulfonic acid group, a homopolymer of a monomer to be polymerized having sulfonic acid group, its copolymer with another monomer, etc., are mentioned. In the first treatment, a solution or a dispersion containing the aforementioned polymer having sulfonic acid group is applied to a dentine, and this solution or dispersion preferably contains monovalent cation more preferably polyvalent cation. The dentine treated with the polymer solution is next treated with a solution containing a polyvalent ion. A solution containing divalent or higher ion is used as the treating solution, and such a cation is selected from a group consisting of calcium ion, iron ion, aluminum ion, copper ion, etc. It is possible, as a result, to bond with an excellent adhesive strength.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method of treating a tooth surface. More specifically, the present invention relates to a method for treating the surface of a tooth so that good adhesion of a dental material to the tooth is achieved.

Adhesive resins are used on enamel and dentin for the correction or restoration of teeth in the mouth.

When using such an adhesive resin, it is common to use the adhesive resin after etching the surface of the tooth in order to improve the adhesion between the adhesive resin and the tooth structure. Conventionally, phosphoric acid aqueous solution, a mixed solution of ferric chloride and citric acid, etc. have been used for etching.

However, since these treatment agents contain low-molecular acids, they penetrate deeply when applied to the tooth structure.

It can also damage healthy tooth structure, and if it penetrates into the pulp, it can cause severe pain and even destroy the living body, l11m.

Therefore, instead of the above-mentioned processing agents made of inorganic substances, pyrimers containing sulfonic acid groups have come to be used as processing agents (for example, as disclosed in Japanese Patent Application No. 60-1).
(See Publication No. 71024).

By using a treatment agent made of a polymer such as the one mentioned above, it works in the same way as a treatment agent made of an inorganic substance mentioned above in terms of treating the tooth surface, but such a polymer does not penetrate into the dentinal tubules. Furthermore, by using this polymer, damage to healthy tooth structure is reduced and the tooth surface is coated.

Adhesion that has the effect of suppressing the irritation that conventional adhesive resins give to living organisms is realized.

Currently, compositions consisting of monomers such as methacrylic acid esters and polymerization initiators are generally used as dentin-adhesive resins used for tooth correction or restoration. Examples include combinations of BPO) and N,N-dimethyltoluidine, or camphorquinones and N,N-dimethyltoluidine.

It is expected that during tooth straightening or restoration performed as described above, by treating the surface of the tooth with a polymer containing sulfonic acid groups, the bond between the tooth and the dental resin can be achieved safely. Ru.

However, when adhesive resins containing various polymerization initiators are used to bond the tooth surface treated with the above-mentioned sulfonic acid group-containing polymer, there are significant differences in adhesive strength depending on the type of initiator. Sometimes. In particular, compounds which are generally known as good initiators, such as N,N-dimethyltoluidine and benzoyl peroxide (BPO
), and when the tooth surface is treated with a polymer containing a sulfonic acid group as described above, the adhesive strength is significantly lower than the expected adhesive strength. The problem is that sometimes it doesn't work.

1. The present invention is an attempt to solve the above-mentioned problems associated with the prior art, and it is possible to achieve excellent adhesiveness regardless of the monomer components used, the polymerization initiator, etc. The purpose of the present invention is to provide a method for surface treatment of m-quality.

1 and 11 In the tooth surface treatment method according to the present invention, the tooth surface is treated with a solution or dispersion containing a polymer having a sulfonic acid group, and then the treated tooth surface is treated with multivalent ions. It is characterized in that it is treated with a solution or dispersion containing it.

According to the present invention, the tooth surface is treated with a polymer having sulfonic acid groups and polyvalent ions.

Regardless of the type of polymerization initiator used, the tooth substance and the polymer hardened by polymerization can be bonded with excellent adhesive strength.

Next, the tooth surface treatment method according to the present invention will be specifically explained.

In the tooth surface treatment method according to the present invention, the surface of one image is treated with a polymer solution or dispersion having sulfonic acid groups (hereinafter simply "
After treatment with a polymer solution (sometimes referred to as “polymer solution”),
The treatment is performed with a solution containing multivalent ions (hereinafter sometimes simply referred to as a "multivalent ion solution") or a dispersion.

First, a polymer containing a sulfonic acid group will be explained.

Polymers containing sulfonic acid groups used in the present invention include homopolymers of polymerizable monomers containing sulfonic acid groups, polymerizable monomers (or polymers) containing sulfonic acid groups and other monomers ( or a polymerizable polymer), and a pirimer grafted with a sulfonic acid group or a sulfonic acid group-containing monomer.

As the sulfonic acid group-containing monomer used in preparing the sulfonic acid group-containing pirimer used in the present invention, a compound having a monopolymerizable double bond and a sulfonic acid group can be used.

Note that the sulfonic acid group here may be in the form of a monovalent metal salt such as sodium salt, potassium salt, lithium salt, or ammonium salt.

Specific examples of such sulfonic acid group-containing monomers include allylsulfonic acid, methallylsulfonic acid, vinylsulfonic acid, P-styrenesulfonic acid, sulfoethyl methacrylate, tert,-butylacrylamide sulfonic acid, and compounds thereof. salt.

Among these, P-styrenesulfonic acid is particularly preferably used.

Furthermore, when the polymer containing a sulfonic acid group used in the present invention is a copolymer, examples of monomers that can be copolymerized with the above monomer containing a sulfonic acid group include ethylene, propylene, and butene-1. Olefins such as; Vinyl halides such as warm vinyl and vinyl bromide: #
Vinyl esters such as vinyl acid and vinyl propionate; Vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, and isobutyl vinyl ether; Alkenylbenzenes such as styrene, vinyltoluene, α-methylstyrene, chloromethylstyrene, and stilbene; Methyl acrylate, methyl methacrylate.

Ethyl methacrylate, butyl methacrylate.

Alkyl esters or glycidyl esters of acrylic acid or methacrylic acid such as glycidyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, nialic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride, P-methacryloxybenzoic acid, Examples include acids or acid anhydrides such as 2-hydroxy-3-methacryloxypropyl-N-phenylglycine, 4-methacryloxyethyl trimellitic acid, and 4-methacryloxyethyl trimellitic anhydride. Among these, methyl methacrylate is particularly preferably used.

Furthermore, when the polymer having a sulfonic acid group used in the present invention is a graft polymer, examples of the base polymer used to introduce the gelafute group include polyolefins such as polyethylene, polypropylene, and polybutene-1; Examples include polyvinyl halides such as polyvinyl chloride; polyalkenylbenzenes such as polystyrene and poly-α-methylstyrene; and poly(meth)acrylic esters such as polymethyl methacrylate and polyethyl methacrylate. Among these, polystyrene and polymethyl methacrylate are particularly preferred.

Compounds used to graft sulfonic acid groups onto base polymers such as those mentioned above include, for example, sulfuric acid 1, fuming sulfuric acid, liquid sulfite, ferrous sulfate, triethyl phosphate-sulfur trioxide complex, long chain acyl sulfates, etc. Mention may be made of the usual sulfonating agents. Such a graft! The conjugation can be performed using known methods to produce vR.

The weight average molecular weight in terms of polystyrene determined by GPC of the polymer having a sulfonic acid group used in the present invention is usually 500 to 10'', preferably 10' to 107''.
is within the range of In the present invention, when the polymer is a copolymer, what are repeating units that do not have a sulfonic acid group and repeating units that have a sulfonic acid group in the polymer?

In molar ratio, usually 0:100 to 99:1, preferably 30
The ratio is within the range of 0 to 80:20, and the above-mentioned repeating units are contained in such a ratio that the polymer exhibits water solubility.

Among the polymers having sulfonic acid groups shown above, preferred examples are shown below.

H3 However, in the above formula, the weight average molecular weight measured by the same method as above is usually 103 to 107, and m
/n is 9 molar ratio and is usually 0.11 to 0.67.

The polymers having sulfonic acid groups as described above are used in the form of solutions or dispersions. As the solvent or dispersion medium used in this case, a liquid capable of dissolving at least a portion of the polymer having a sulfonic acid group can be used. Especially considering the solubility and toxicity of the polymer, it is preferable to use water or a mixed solvent of water and ethanol as the solvent.

The concentration of the polymer at this time can be set appropriately, but it is usually preferable to use the above-mentioned polymer as a solution, and in this case, the concentration of the polymer is as follows.

Usually 0.01 to 30% by weight, preferably 1 to 1% by weight.
It is 0% by weight.

In the present invention, in the first treatment, a solution or dispersion containing a polymer having a sulfonic acid group as described above is applied to the tooth. Preferably, it contains valence ions.

Here, the polyvalent ions contained in the polymer solution include alkaline earth metal ions such as M section 29 and Ca'' Ba2°, aluminum ions, and iron ions.

Copper ions! ! ! Examples include lead ions and cobalt ions. Among these, metal polyvalent ions such as calcium ions, aluminum ions, and iron ions are particularly preferred.

In addition, the multivalent ion [M”
] There is no particular restriction on the concentration of [M'''] and the sulfonic acid group [SO3-], but preferably the molar ratio is [M'']/
It is desirable that multivalent ions are blended so as to have a relationship of [S O3-] < 1/n.

However, in the above formula, n represents the valence of the multivalent ion.

In the present invention, the treatment of tooth substance using the above-mentioned polymer solution involves applying the above-mentioned polymer solution to the cut tooth substance as desired, and reacting the tooth substance with the above-mentioned polymer having a sulfonic acid group. . When the polymer reacts with the tooth substance in this way, the polymer becomes poorly soluble or insoluble in water. Then, a polymer film in which sulfonic acid groups are bonded to the tooth substance is formed on the surface of the tooth substance.

Since the reaction between the polymer and the tooth substance as described above proceeds in a relatively short time, one reaction time is usually 1 to 300 seconds, preferably 10 to 120 seconds.

Although the effect of the multivalent ions that are optionally blended into the polymer solution as described above is not clear, there is a tendency for adhesive strength to improve by blending at least a predetermined amount of multivalent ions. Based on this, the present inventor speculates that the sulfonic acid group may bond with a portion of the sulfonic acid groups that are not bonded to the tooth substance to form a crosslinked structure.

Note that multivalent ions become difficult to penetrate into dentinal tubules when used in combination with the above-mentioned polymers.

After the tooth substance is treated using the polymer solution as described above, the tooth substance treated with the polymer solution is treated (post-treated) with a solution containing multivalent ions.

In this post-treatment, a treatment liquid containing cations of divalent or higher valence is used, and such cations include:

Although cations consisting of organic compounds such as ammonium ions derived from monoalkylamines such as methylamine, ethylamine, etc. can also be used, solutions containing cations derived from divalent or higher valent metals should be used. is preferred.

Specific examples of such multivalent metal ions include calcilaf ion, iron ion, strontium ion, aluminum ion, and chromium ion.

In addition to silver ions, transition metals, and lanthanum series.

Element ions in the actinium series can be mentioned.

Such multivalent metal ions are used by dissolving or dispersing corresponding metal salts such as chloride salts, nitrates, and acetates in a solvent such as water.

Furthermore, in the present invention, in addition to the above-mentioned metals, it is possible to use substances that can react with polymers containing sulfonic acid groups to form insoluble polymers. Examples of such materials include silica and alumina. Such substances are usually insoluble in solvents such as water.

Such substances are therefore usually used in the form of dispersions.

Particularly in the present invention, it is preferable to use a solution or dispersion containing calcium ions, aluminum ions, copper ions, and iron ions.

Furthermore, considering its affinity with tooth structure, it is preferable to use a solution or dispersion containing calcium ions.
Note that the multivalent metal ions and the like described above can be used alone or in combination of two types. Further, there are no particular limitations on the solvent used when preparing a solution containing multivalent metal ions as described above, and any liquid capable of dissolving or dispersing the metal salt as described above can be used. As such a liquid, water is usually used, and this water may further contain a small amount of alcohol (for example, ethanol).

The ion concentration of this treatment liquid is 0-6 to 9% by weight, preferably 10-3 to 10% by weight.

Further, the time for the treatment in which the solution or dispersion containing multivalent ions as described above is soaked is usually 1 to 300 seconds, preferably 10 to 120 seconds. By treating with a solution or dispersion containing multivalent ions as described above, the sulfonic acid groups remaining in the pirimer layer formed on the tooth surface react with the multivalent ions, forming a crosslinked structure. It is thought that the formation of such a crosslinked structure can prevent the photoinitiator from decreasing in activity due to reaction with the sulfonic acid group. Furthermore, since the polymerizable monomer penetrates into the details of the crosslinked structure formed as described above, it is thought that a stronger adhesive state is formed.

After applying the multivalent ion solution as described above, the tooth surface is usually dried by an appropriate means such as air blowing. Next, a curable adhesive composition is applied or filled onto the treated tooth surface and cured to develop adhesive strength with the dental resin.

By adopting the tooth surface method of the present invention carried out as described above, the polymerization of BPO and amine-based polymers, which have been difficult to develop when using conventional polymers having sulfonic acid groups, can be initiated. It also shows very high adhesion when using adhesives.

Conventionally known monomers can be used as the monomer components used in the polymerization using the above-mentioned polymerization initiators. That is, specific examples of adhesives that can be used by employing the treatment method of the present invention include adhesives using camphorquinones and amines as photoinitiators, and adhesives derived from tributylborane or tributylborane oxide. Examples include adhesives based on adhesives and adhesives containing benzoyl peroxides and amines.

Furthermore, specific examples of resins that can be used in these adhesives include phosphoric acid ester resins and methacrylic acid ester resins such as 4-M ETA resins.

Such an adhesive is applied to the tooth surface treated with a multivalent ion treatment liquid using a method such as the brush-laying method, and then hardened by leaving it at room temperature or by irradiating it with light. Ru. In addition, by employing the treatment method of the present invention, good adhesiveness can be expressed regardless of whether the tooth substance is enamel or dentin.

152 Emperor 1 According to the present invention, since the tooth surface is treated with a polymer solution having a sulfonic acid group and a solution containing polyvalent ions, the tooth surface can be treated with a polymer solution containing a sulfonic acid group and a solution containing polyvalent ions. It is possible to bond the material and the polymer polymerized by photopolymerization with excellent adhesive strength.

Moreover, when conventional polymer solutions containing sulfonic acid groups are used, it is difficult to develop sufficient adhesive strength, but even when a BPO-amine reaction initiator is used, excellent adhesive strength is developed. .

Next, the present invention will be explained in more detail by showing examples.
The present invention should not be construed as being limited by these Examples.

[Example] 21.0 g of methyl methacrylate of Volmer'- and 18.6 g of sodium p-styrenesulfonate were mixed in ethanol/water (weight ratio 1
: 1. 3) Reaction was carried out at 70° C. for 17 hours in the presence of 0.4 g of azobisisobutyronitrile in a solvent. 15 ml of 6N hydrochloric acid was added to this reaction solution and stirred for 2 hours.
Ethanol was distilled off under reduced pressure.

Next, this reaction mixture was filled into a dialysis tube and dialyzed in water for 2 to 3 days to remove azobisisobutyronitrile and unreacted monomers. Vacuum drying was performed using sodium to obtain a pale yellow transparent polymer.

The resulting polymer is 1 ms polystyrene with a known molecular weight.
Results of analysis using GPC as a sample.

The weight average molecular weight of this polymer is 108 or more.

The copolymerization molar ratio of methyl methacrylate component units and styrene sulfonic acid component units was 0.67:0.33.

The above polymer was dissolved in water to a polymer concentration of 10% by weight.

This polymer solution will be referred to as treatment liquid A.

Bomber-B's 0.1. A homogeneous solution was prepared by dissolving the above polymer of c and 0.012 g of ferric chloride in water to make a total amount of 100 g.

This polymer solution is referred to as treatment liquid B.

Ferric chloride, aluminum chloride, and copper chloride 5 Calcium chloride were each dissolved to a concentration of 0.05M, and 0.05Mm ferric chloride aqueous solution, 0.05M aluminum chloride aqueous solution, and 0.05M chloride were prepared. copper aqueous solution and 0.05
An aqueous solution of M calcium chloride was prepared.

0.0% ferric chloride. Dissolve LM so that it becomes 0.
6-order "L ball" made from a 1M ferric aqueous solution 2 The surface of the dentin of a raw tooth was ground with No. 600 water emery paper. After applying the treatment solution A to the ground dentin of a raw tooth and treating it for 1 minute, the tooth surface was washed with water and then dried using compressed air.

Thereafter, the tooth surface was further treated with a 0.1M ferric chloride aqueous solution for 30 seconds, washed with water, and then dried using compressed air.

5I on the surface-treated dentin as described above.
A perforated screen adhesive tape of φ was attached, and an acrylic ring with an inner diameter of 6 Iφ, an outer diameter of 8 mφ, and a thickness of 1 m was adhered with the adhesion surface defined.

Next, dental quick-hardening resin (
Filled with pressed resin) Metafast (manufactured by Sun Medical ■).

The sample prepared as described above was left at room temperature for 30 minutes, and then immersed in water at 37° C. for 24 hours to be cured.

The adhesive strength of the adhesive obtained as described above was measured as follows.

Using Autograph DSS-500 (manufactured by Shimadzu Corporation), the vR-produced adhesive as described above was
The tension between the dentin and Metafast was measured. In addition,
In the present invention, the tensile test was conducted by the method described above.

The results are listed in Table 1.

In addition, in the above-mentioned adhesion test, the adhesion test was conducted without using the treatment liquid A and the multivalent ion solution, but no adhesive strength was developed. M fruit is listed in Table 1 as a reference.

Ratio] Doctor L' 2 The same treatment as in Example 1 was performed except that the ferric chloride solution was not applied, and the dentin of a raw tooth and Metafast were adhered, and the adhesive force was measured.

The results are also listed in Table 1.

The same treatment as in Example 1 was performed except that treatment liquid A was not applied, and the dentin of a raw tooth and Metafast were bonded together, and the adhesive force was measured.

The results are also listed in Table 1.

In Example 1, instead of treatment solution A, treatment solution B containing multivalent ions was used, and instead of the 0.1M iron chloride solution, the solutions listed in Table 2 were used. The same process was performed except that the polyvalent ion solution used was used and the treatment time was changed as shown in Table 2, and the dentin of the natural tooth Φ and Metafast were bonded, and the adhesive force was measured.

The M fruits are listed in Table 2.

Comparative Example 51 The same treatment as in Example 2 was performed except that the polyvalent ion solution was not applied, and the dentin of a raw tooth and Metafast were bonded together, and the adhesive force was measured.

The results are also listed in Table 2.

11-14 The same treatment as in Example 2 was performed except that natural tooth enamel was used instead of bovine dentin, and the type of polyvalent ion solution used and the treatment time were as listed in Table 3. Then, the enamel of a natural tooth was bonded to Metafast, and the adhesive force was measured.

The results are listed in Table 3.

In addition, in the above-mentioned adhesion test, the adhesion test was conducted without using the treatment liquid A and the multivalent ion solution, but no adhesive strength was developed. The results are listed in Table 3 as a reference.

凰和dan 1 The same treatment as in Example 11 was performed except that the multivalent ion solution was not applied, and the enamel of a natural tooth and Metafast were bonded together, and the adhesive force was measured.

The results are also listed in Table 3.

In Example 11, treatment liquid A was used instead of treatment liquid B, and the same treatment was carried out except that the polyvalent ion solution was not used, and the material was bonded to Tafirst.

Teeth enamel and teeth Determine this adhesive strength Ta.

The results are also listed in Table 3.

Claims (3)

[Claims] (1) The tooth surface is treated with a solution or dispersion containing a polymer having a sulfonic acid group, and then the treated tooth surface is treated with a solution or dispersion containing polyvalent ions. A method of treating tooth surface. (2) The method for treating a tooth surface according to claim 1, wherein the solution or dispersion containing a polymer having a sulfonic acid group contains a polymer having a sulfonic acid group and a polyvalent ion. (3) The tooth surface according to claim 1 or 2, wherein the multivalent ion is at least one type of ion selected from the group consisting of calcium ions, aluminum ions, copper ions, and iron ions. processing method.