JPH02201A - Microfiller for dental use and filling method - Google Patents

Abstract

PURPOSE:To provide a safe dental microfiller easily applicable in a short time and consisting of tetrabasic calcium phosphate or tricalcium alpha-phosphate or a mixture of these phosphates and an adjuvant or further a coating agent. CONSTITUTION:The objective filler is composed of tetrabasic calcium phosphate (produced by calcining tricalcium phosphate and calcium oxide) or tricalcium alpha-phosphate (produced by mixing calcium carbonate with calcium pyrophosphate obtained by heating calcium hydrogen phosphate dihydrate, calcining the mixture and heating the calcination product) or a mixture of the above phosphates and an adjuvant (especially preferably a fluoride or a calcification promoting protein) or further a coating agent. Powder, granule, solution or paste containing tetrabasic calcium phosphate or tricalcium alpha-phosphate and optionally an adjuvant is rubbed to the surface of tooth and the tooth is coated with a polymer or a fluoride.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention provides a method for filling the pits and fissures of tooth enamel or the minute surface demineralization side using quaternary calcium phosphate or α-3-phosphate. Calcium or a filling material containing calcium or an auxiliary agent, or a coating agent mixed therewith, and rubbing these filling materials into the pits and fissures of the tooth surface or the minute surface demineralization side, or The present invention relates to a dental microfilling method for protecting and restoring the pits and fissures or minute surface demineralized side of tooth enamel by coating the core with a polymer or fluoride after rubbing.

(Prior art) Dental plaque settles on the surface of tooth enamel, and the acid produced by microorganisms gradually dissolves the enamel, causing minute scratches on the enamel (hereinafter referred to as demineralization). It is recognized that the ash side is remineralized and repaired by saliva),
- Once the enamel is demineralized, even if plaque is subsequently removed by tooth brushing, the plaque will immediately re-adhere to the demineralized side, and demineralization with acid will be repeated again. In this way, demineralization progresses by repeating decalcification, plaque removal, plaque re-attachment, and decalcification, and eventually progresses to cavities that can be detected with the naked eye. Conventional dental treatment involves scraping away the hard tissue of cavities that can be detected with the naked eye, including the surrounding healthy parts, and then filling the missing parts with various plastics and metals to replace the missing parts. . This method requires a high level of skill, and if the filling is not complete, tooth decay will begin to progress from the edges of the filling. By filling the pits and fissures of teeth, where cavities are likely to occur in recent years, or the demineralized side due to early demineralization, with sealants made of cyanoacrylate, polyurethane, and other polymers, and isolating them from the oral environment, cavities can be prevented. Sealant methods have been developed to prevent the occurrence of

The sealant method involves treating the pits and fissures or the demineralized side with an acid, depending on the sealant, and then applying the sealant.
It suppresses the occurrence of cavities by inhibiting the formation of dental plaque in that area and its effects. However, with this method, insufficient or excessive acid treatment, adhesion of saliva to the acid-treated surface, etc., reduce the adhesion of the sealant to the pits and fissures or the demineralized side, and too much sealant The filling of the agent is a mastication,
Occlusion causes damage. In this way, with the sealant method, there is a possibility that the sealant may fall off depending on the material of the sealant and the quality of the treatment technique, and the effectiveness greatly depends on the technique. Also, since the coated demineralized side does not come into contact with saliva, remineralization by saliva is difficult to occur. In addition, as a method of increasing resistance to caries by strengthening or protecting the tooth structure, applying fluoride ions to the tooth surface, drinking water,
It is also added to food. However, this method also requires special techniques for handling fluorine compounds. JP-A-47-1567 discloses a method for precipitating tooth enamel composition on the tooth surface using a gelatin-like substance as a medium prepared to have toxicity and a final pH that does not cause damage to the oral cavity. We have proposed a method in which placids are formed on the surface and transferred to hydroxyapatite. However, this method requires a long time for the transfer of brushed to hydroxyapatite, and also requires the combined use of a gelatin-like medium to help bond the brushed to the tooth surface.

[Problem to be solved by the invention]

Fluorine application as a method for strengthening the tooth surface, sealant method as a method for protecting pits and fissures and restoring the demineralized side, or JP-A-47-
Although there are methods disclosed in Japanese Patent No. 1567, all of them require special techniques and have the above-mentioned difficulties. The present invention provides a safe dental microfilling method for protecting pits and fissures and restoring the demineralized side that does not require special techniques and can be easily and quickly implemented, and a dental microfilling agent used therein. There is a particular thing.

[Means to solve the problem]

Tricalcium phosphate and calcium oxide were mixed in equimolar amounts and calcined at 1500°C for 2 hours to form Ca 3 (PO4
) z + Ca0− -muCa4(PO4) zO Quaternary calcium phosphate (Ca4(P
O4)20), and calcium hydrogen phosphate dihydrate (Ca
Calcium pyrophosphate (CagPzOJ, which is obtained by heating HPO4.2HzO) at 400 to 8oO℃ for several hours, is mixed with calcium carbonate (CaCOi) dried at 100℃ in an accurate equivalence ratio, and the mixture is heated to 1000 to 1100℃.
Bake for 5 days (mixing operation 2 to 3 times in the middle (without changing))
Then, by further heating at 1200 to 1300'C for 1 to 5 hours and then cooling, α-tricalcium phosphate produced by the reaction of aCa3CPO easily combined with the combined fourth
It has been found that calcium phosphate or α-tricalcium phosphate rapidly transforms into hydroxyapatite when it comes into contact with saliva. For example, a powder suspension of radioactive quaternary calcium phosphate obtained by firing calcium oxide containing radioactive calcium and tribasic calcium phosphate at 1500°C is prepared, and the suspension is applied to an artificial tooth prepared by sintering hydroxyapatite. The artificial tooth is immersed in the mixture, and the upper surface of the artificial tooth is polished by rotation through the rubber membrane. After a certain period of time, the artificial tooth is removed, immediately washed with a large amount of distilled water, and then PCS
A cocktail was added, and the amount of quaternary calcium phosphate bound to the artificial tooth was measured using a liquid scintillation colorator.

Similar tests were performed using radioactive Brasirad as a control and the results were compared. The amount of quaternary calcium phosphate bound was significantly larger than that of Brasilado. Both of the artificial teeth obtained in this way were added with omega saliva37
After being left for 2 hours at 0.degree. C., the surface was observed using a surface polarizing microscope, and it was found that the quaternary calcium phosphate had been rearranged into hydroxyapatite. Also α-phosphoric acid 3
Similar results were obtained for calcium. These results indicate that quaternary calcium phosphate or α-tricalcium phosphate binds efficiently to the tooth surface, covers demineralization scars or pits and fissures, and translocates to hydroxyapatite in the presence of saliva, remineralizing the tooth. It has been shown that it promotes

The present invention utilizes the property of quaternary calcium phosphate or α-tricalcium phosphate to selectively bind to the tooth surface, and uses quaternary calcium phosphate or α-phosphoric lucium to protect tooth pits and fissures. Alternatively, the present invention provides a microfiller for repairing the demineralized side and a method for using the same.

It is desirable that the quaternary calcium phosphate or α-tricalcium phosphate to be used be as fine particles as possible, and those finely pulverized to about 0.02 to 10 μm are generally used. Finely pulverized quaternary calcium phosphate or α-tricalcium phosphate is mixed with water or a coating agent, and the content is 5 to 95%.
% paste. The powder or paste is rubbed into the tooth after the plaque has been removed using fingertips, a brush, stick, cloth, or the like for at least 1 minute, preferably for at least 3 minutes.

Through this operation, the quaternary calcium phosphate or α-tricalcium phosphate is further refined and bonded to the pits and fissures or the microdemineralized side of the tooth surface. Since quaternary calcium phosphate and α-tricalcium phosphate are good calcium agents, any excess calcium agent remaining in the oral cavity may be swallowed as is.

It is preferable to rinse your mouth with water only once. Quaternary calcium phosphate or α-tricalcium phosphate bonded to tooth surfaces translocates to hydroxyapatite when in contact with saliva, promoting remineralization of teeth.

Quaternary calcium phosphate or α-tricalcium phosphate with fluorides such as sodium fluoride, sodium monofluorophosphate, stannous fluoride, and fluoroapatite, and hydroxyapatite such as phosvitin, casein, and hissidine-rich protein. Powders, granules, and solutions containing an appropriate amount of proteins that act as calcification catalysts and accelerators (hereinafter referred to as calcification-promoting proteins) or mixtures thereof as adjuvants;
Alternatively, it is preferable to use a paste as it promotes remineralization of the tooth and strengthens the covering layer. The amount of these adjuvants added is about 11,000 pp or less of fluoride and about 1% or less of calcification-promoting protein relative to quaternary calcium phosphate or α-tricalcium phosphate. Coating agents used in pastes include vinyl acetate, lacquer, polyacrylic acid, and gum arabic.

In this way, by simply rubbing powder, granules, solution or paste containing quaternary calcium phosphate or α-tricalcium phosphate onto the tooth surface, the composition of quaternary calcium phosphate can be changed to α-tricalcium phosphate.
Tricalcium phosphate binds to the tooth surface and remineralizes with saliva, and the presence of adjuvants increases remineralization and surface strength 6
Unlike conventional sealant treatments, the present method does not require treatments such as acid treatment, moisture proofing, and polymerization, and in addition, quaternary calcium phosphate, α-tricalcium phosphate, adjuvants, and coating agents do not have any adverse effects on living organisms. It can be easily performed without special techniques. Also, quaternary calcium phosphate, α-phosphate 3
Calcium is translocated to hydroxyapatite by the action of saliva, and hydroxyapatite is the same component as teeth.
Unlike conventional sealants, it is not a foreign substance to the tooth, so it binds strongly to the pits, fissures, and demineralized sides, so there is no fear of it coming off, and a completely restored tooth can be recreated. Furthermore, the paste consisting of quaternary calcium phosphate, α-tricalcium phosphate mineralization-promoting protein, and coating agent has an appropriate viscosity that makes it easy to apply to the tooth surface, and a plasticizer is added to make the film thickness uniform.
Applying a suitable amount of a solvent, diluent, etc. to the tooth surface has the advantage of strengthening the tooth surface and contributing to the aesthetic appearance of the tooth.

Furthermore, it is also possible to strengthen teeth by rubbing a powder, granule, solution, or paste containing quaternary calcium phosphate or α-tricalcium phosphate onto the tooth surface and then applying fluoride.

It is particularly preferred to rub quaternary calcium phosphate or α-tricalcium phosphate and mineralization-promoting protein-containing powder, granules, solution, or paste onto the tooth surface and then apply fluoride using a conventional method.

It is also possible to rub them into the tooth surface and then cover and protect the area with a polymer. The polymers used are those conventionally used as sealants, such as Epoxylite 9070, Nuvaseal, Epoxylite 9075, Enamelite, Delton, White Sealant, B&F Sealant, FizA Seal, Tees Matter N, Prisma Shield, and PerioSeal. Or shellac, polyvinyl acetate, polyvinyl butyral, ethyl cellulose, cellulose acetate phthalate, polyvinyl alcohol phthalate, styrene.
Acrylic acid copolymers, methyl acrylate/methacrylic acid copolymers, copolymers with vinyl pyridine or alkyl pyridine and other vinyl monomers, cellulose acetate diethylamino acetate, polyvinyl acetate diethylamino acetate, polyvinylamino acetal, polyvinyl alcohol derivatives, aminocellulose Derivatives, dimethylaminoethyl methacrylate/methyl methacrylate copolymer, vinyl pyridine or a copolymer of alkyl vinyl pyridine and acrylic acid, etc. are arbitrarily selected from polymers used in sustained release preparations for pharmaceuticals, and coated by a conventional method. .

Quaternary calcium phosphate α- rubbed into this coating
Since tricalcium phosphate and the adjuvant do not desorb, they are retained on the tooth surface for a long time and remineralized efficiently. A paste containing quaternary calcium phosphate or α-tricalcium phosphate and calcification-promoting protein, for example, hydrated alumina, anhydrous silicic acid, other abrasives; moisturizing agents such as glycerin, sorbitol, propylene glycol; sodium lauryl sulfate , foaming materials such as soap powder; caking materials such as carboxymethyl cellulose and carrageenan; fragrances; sweeteners; preservatives;
Adding medicinal ingredients such as breath odor remover and tooth stain remover, and using it like a toothpaste removes plaque and rubs quaternary calcium phosphate α-tricalcium phosphate and mineralization promoting protein into the tooth surface. This is an easy-to-use method that can be carried out simultaneously.

[Effect]

Utilizing the property that quaternary calcium phosphate, α-tricalcium phosphate, or a mixture of this and an adjuvant, binds selectively and strongly to the tooth pit and fissure or the demineralized side, quaternary calcium phosphate, α-tricalcium phosphate, By rubbing tricalcium phosphate or an adjuvant into the tooth surface, the tooth surface is protected, or the demineralized side is covered, and the natural healing power of remineralization by saliva is used to treat the early stages of tooth decay. The filling material and filling method of the present invention for treating demineralization, which is a stage, is a tooth strengthening method, a cavity prevention method, and a filling material that did not exist before, and is more complete than the conventional fluoride application method and sealant method. It has the significant advantage of not requiring any special techniques.

The present invention will be specifically described below with reference to Examples.

Example 1 50g of finely powdered quaternary calcium phosphate with a size of 10μ or less and 5 parts water
0mj! was added and treated with a crusher to obtain a paste.

After brushing your teeth, gargle thoroughly, apply the above paste on your fingertips, rub it into the tooth surface for 3 minutes, and then gargle lightly to wash away the excess paste from the day. The operation was performed every time after brushing teeth.

Example 2 50g of quaternary calcium phosphate crushed to less than ゜lOμ
Add 50ml of 00ppn+ sodium fluoride aqueous solution and make it into a paste using a crusher.After brushing, apply this paste to the toothbrush and brush the surface of the tooth for 3 minutes, and then lightly gargle. I always did this brushing after brushing my teeth.

Example 3 50g of quaternary calcium phosphate crushed to 10μ or less,
50 ml of water containing 0.01 ml of casein was added and made into a paste using a crusher. After brushing the teeth, the paste was applied to the fingertips and rubbed liberally into the tooth surface for 3 minutes. This operation was performed every time after brushing teeth.

Example 4゜Similarly to Example 3, rub the paste into the tooth surface, gargle to wash away the excess paste during the day, dry the tooth, apply NuvaSeal liquid on the tooth surface, harden with an ultraviolet lamp, and seal. did.

Example 5 To 100 ml of vinyl acetate were added 4 g of quaternary calcium phosphate and 0.04 ml of casein crushed to less than 10 μm and thoroughly mixed to form a uniform dispersion. After brushing the teeth, the teeth were dried with warm air, and the dispersion was evenly applied to the tooth surface with a brush and dried to obtain a glossy white and beautifully coated tooth surface.

Example 6゜50 g of finely powdered α-tricalcium phosphate of less than 1 Oμ and 50 mj of water! were added, mixed and kneaded in a mortar to obtain a paste. After brushing their teeth, they gargled thoroughly, applied the paste to their fingertips immediately, rubbed it into the tooth surface for 3 minutes, and then gargled lightly to wash away the excess paste during the day. Perform this operation every time after brushing your teeth.

Example 7 500 ppm of sodium fluoride was added to 50 g of α-tricalcium phosphate pulverized to less than 10 μm and processed in a mortar to obtain a wet mixed powder. After brushing your teeth, apply this powder on your toothbrush and brush the tooth surface for 3 minutes.
Excess powder was removed by gargling. Always do this brushing after brushing your teeth.

Example 8 After carrying out the same procedure as in Example 7, the tooth was dried, and NubaSeal liquid was applied on the tooth surface, and the tooth was cured with ultraviolet rays and sealed.

Reference Example 4 In order to measure the amount of calcium phosphate bound to the tooth surface, the following in vitro test was conducted.

(A) Synthesis of calcium tetraphosphate and Blatz 31 g of tricalcium phosphate and 5-6 g of calcium oxide (
(containing CaO) was uniformly mixed L and calcined at 1500°C for 2 hours to obtain quaternary calcium phosphate.

On the other hand, 0.1M Na1l*PO4100~200 ts
In the same manner as above, a 0.1 M CaCl solution was added dropwise to prepare a brat.The prepared calcium tetraphosphate and a brat were 0.1 M NaJPOn and 0.1 M NaJPOn, respectively.
Stored in NaH2POa solution and adjusted to 0.1 of each pH before use.
It was used after being resuspended in M phosphate buffer.

(B) Preparation of artificial tooth Hydroxyapatite was molded into a disk shape with a diameter of 1a11 and a thickness of 3 fins and sintered to prepare a hydroxyapatite tablet. The surface was polished to a uniform surface with 600 grit sandpaper, and then the powder was carefully removed by brushing while running distilled water, and the tooth was used as an artificial tooth.

<C> Five blind holes for fixing hydroxyapatite tablets with a diameter of lee and a depth of 2 m are provided in the lower part of the acrylic tank with a length of 12 ell, a width of 4 aa, and a depth of 10 days. Secure the tablet and
Calcium phosphate or Brat Suspension 5II11 was added to soak the tablet, and the top surface of the tablet was rotatably polished at a rate of once per second through the rubber membrane.

After a certain period of time, the tablet was taken out and immediately washed with a large amount of distilled water dropwise, PCS cocktail 21111 was added, and the radioactivity bound to the tablet was measured using a liquid scintillation counter.

(D>Results 4 Calcium phosphate and Brat were conducted at pH 9.0 and pH 5.0, respectively. The specific radioactivity of the hydroxyapatite used was 5.4 x 10'cPM/mg, and the brasside was 8.9 X l O'. Calculating from CPM/nwr, the amount of lucium tetraphosphate bound to the tablet was 5 μg after 5 minutes, and gradually increased to 1 after 40 minutes.
It reached 64 μg. This amount of binding was much higher than in the case of brushed (20 times after 5 minutes and 109 times after 40 minutes).

In addition, the pH at the time of rubbing should be the same, pH 5, 5, 6, 8,
Results conducted under conditions of 7, 4 and 8.5 also showed that the binding strength of the calcium tetraphosphate tablets was significantly greater. The results are shown in the table below.

A: Calcium 4 phosphate, B: Brushed number is the weight ratio of the amount bound to the surface of the hydroxyapatite tablet These results indicate that calcium 4 phosphate is selectively bound to the tooth surface.

〔Effect of the invention〕

A micro filler containing 4-calcium phosphate, α-3-calcium phosphate, or an adjuvant that binds strongly to the pits and fissures or minute demineralized sides of the tooth surface is rubbed into the tooth surface, or after rubbing it with a polymer. The final method of covering the pits and fissures or the demineralized side with the filler, and the natural healing power is enhanced by the action of saliva or an adjuvant to cause the repair of the demineralized side, is simply a microscopic treatment. Simply rubbing the filler into the tooth surface will have sufficient effect, and since tetracalcium phosphate and α-tricalcium phosphate are the best calcium agents, there is no harm in swallowing it, and there is no need to consider the chemical toxicity of the filler used.

Moreover, no special techniques are required for implementation. Therefore, it has the advantage that it can be easily carried out by the person himself/herself.

A terminal method that utilizes the natural healing power of remineralization by saliva and enhances it to stop cavities at the initial stage, and the microfilling agent used therein is the most effective method for preventing cavities that has not existed before. It can be said to be a means. The present invention can also be used to treat hypersensitivity or pyorrhea.

(voluntary) procedure April 25, 1986 Mr. Kunio Kogawa, Commissioner of the Patent Office ■Display of incident Patent Application No. 4826 of 1988 2. Name of the invention Dental microfillers and filling methods 3. Person who makes corrections Relationship to the incident: Patent applicant

Claims (6)

[Claims] (1) A dental microfiller characterized by blending quaternary calcium phosphate, α-tricalcium phosphate, or these with an adjuvant. (2) The filler according to claim 1, wherein the adjuvant is a fluoride or a mineralization-promoting protein. (3) The filler according to claim 1 or 2, further comprising a coating agent. (4) A dental microfilling method characterized by rubbing quaternary calcium phosphate, or α-tricalcium phosphate, or a powder, granule, solution, or paste containing them and an adjuvant into the tooth surface. (5) The filling method according to claim 4, wherein the adjuvant is a fluoride or a calcification-promoting protein. (6) After rubbing quaternary calcium phosphate or α-tricalcium phosphate, or a powder, granule, solution or paste containing them and an adjuvant into the tooth surface, coating the area with a polymer or fluoride. A dental microfilling method characterized by: