JPS5910641B2 - Dental caries prevention filling material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is a dental material based on α-cyanoacrylate, which can be directly applied to teeth as a caries prevention filling material, a caries progression inhibiting filling material, and other orthodontic adhesive materials. The present invention relates to a filler for a caries-preventing filling material that can also be used to bond adherends, and to a caries-preventing filling material using the filler.

Generally, α
- Cyanoacrylate systems, methyl methacrylate systems, and reaction product systems of bisphenol A and glycidyl methacrylate are known, but each has various drawbacks in use.

For example, among the aforementioned methyl methacrylate-based and reaction product-based caries-preventing filling materials of bisphenol A and glycidyl methacrylate, those that mix catalysts and monomers harden within 2 to 5 minutes after mixing. ,
Disadvantages include the need to quickly apply it to the teeth and the need to keep your mouth open after application until it hardens. On the other hand, those that are cured by ultraviolet light are
It has a long pot life, so it is easy to apply it to the teeth, but it will not harden unless it is exposed to ultraviolet light for at least one minute after that, so the patient must keep their mouth open during that time, and the patient The burden was extremely heavy. On the other hand, α-cyanoacrylate-based caries prevention filling materials harden quickly, but because of their high anionic polymerizability, they also harden due to moisture in the atmosphere or attached water, making it difficult to control. It was often unusable. To improve this drawback, Japanese Patent Application Laid-Open No. 49-119984
A method was attempted in which a thixotropic composition was prepared by adding dimethylformamide to a system consisting of α-cyanoacrylate and a filler, and after application, a setter was added dropwise to cure the composition. This method had many advantages, including a long pot life, suppression of polymerization shrinkage due to prepolymerization, ease of application, and rapid curing by adding one drop of setter after application. However, this system in which filler is mixed with α-cyanoacrylate is very unstable and tends to thicken and solidify in the distribution route, and the filler may precipitate.
Not only was it difficult to guarantee the quality of the product, but it was also extremely difficult to manage. That is, if a catalyst and a filler are individually mixed with α-cyanoacrylate, a suitable thixotropic composition cannot be obtained, and if an active catalyst such as dimethylformamide is added dropwise as a pre-curing agent at the time of use. , most of it hardens into so-called 6 lumps, and the thixotropic composition suitable for use is less than 1/4 of the initial amount, resulting in a large loss, and it is extremely difficult to drop a certain amount of the catalyst, dimethylformamide. It was difficult and even difficult. For example, when used as a preventive sealant, the amount of mixing at one time is usually around 100η, and the appropriate amount of dimethylformamide for this is 27!9. or about 10η,
The amount is 1 to 3 drops using a microsyringe. Therefore, in many cases, if the adhesive is not dropped carefully, an excessive amount may be used, resulting in a decrease in mechanical adhesive strength, which is extremely complicated to handle. Furthermore, when commercializing products, as a means of suppressing thickening and solidification phenomena during storage, SO2, which is a stabilizer for α-cyanoacrylate, and certain acids can be added to improve stability, but on the other hand, polymer There is a risk that the material as a material becomes weak and easily peels, cracks, and leaks, and loses its practical value as a filler. In order to remove adhering water that can act as a catalyst, the filler must be dehydrated by heating it at 600 to 700°C for about 2 hours in advance, and even if the filler that has been subjected to such heat treatment is dispersed, There is a disadvantage that after about 3 to 6 months, polymerization progresses and the viscosity increases. Furthermore, when adding a catalyst to a system consisting of α-cyanoacrylate and a filler to obtain a thixotropic composition, solid catalysts are difficult to disperse in α-cyanoacrylate, making it difficult to quickly obtain a thixotropic composition; In reality, only dimethylformamide can provide adequate thixotropy, and there are almost no other products that have similar effects, and there are many problems in various aspects, such as lack of versatility, making it difficult to put it into practical use. In addition, as in Japanese Patent Publication No. 47-47290, in which a mixture of an organic solid powder and an alkaline polymerization accelerator is used for α-cyanoacrylate, the dispersibility is poor, as is clear from Table 1 below. The disadvantage is that it is difficult to obtain a thixotropic composition.

That is, because the particle size of the solid powder used is coarse, it is easy to form lumps, and it is difficult to obtain a thixotropic composition. The pot life is determined mostly by the type and amount of the alkaline polymerization accelerator used, and the pot life is short, and if it has instant curing properties, it is extremely complicated and inconvenient to handle. Furthermore, JP-A-50-121
In adhesive cement made of powder components of α-cyanoacrylate and a basic amine activator, such as No. 25, the amine catalyst used is highly active, and when coated on ultrafine silica, the reaction progresses locally and instantaneously. It is difficult to obtain a thixotropic composition because it cures while generating heat and slumps easily occur.Also, it is not only complicated to pre-treat with a silane coupling agent to prevent deterioration of catalytic performance, but also has poor curing properties. Since this is mostly determined by the type and amount of the coated amine catalyst, there is no characteristic of pot life or instant curing.

Furthermore, in the case of the cyanoacrylate monomer disclosed in JP-A No. 50-128790, the porous particles containing an amine catalyst have a coarse particle size, and because the amine catalyst with strong activity is used, it is difficult to cure the monomer. The time is determined by the type and amount of the catalyst and the surface condition of the carrier particles.
A uniform thixotropic composition cannot be obtained due to the formation of lumps, and it cannot be applied in response to the specificity of dental use.
No. 4 had the drawback of causing similar problems.

A first object of the present invention is to provide a filler for a caries preventive filling material using α-cyanoacrylate, in which a thixotropic composition that can be instantly cured is made of α-cyanoacrylate by polymerizing a setter. It is also an object of the present invention to provide a filler which can be formed very well.

A second object of the present invention is to provide an improved caries-preventing filling material for dental use, which is a mixture of α-cyanoacrylate and a filler.

Furthermore, the third object of the present invention is to form a good thixotropic composition very easily, have a long pot life, and have an instant curing property that can be cured at any time in a short time of several seconds to several tens of seconds. An object of the present invention is to provide a caries-preventing filling material that has the following properties. The fourth object of the present invention is to provide a caries-preventing filling material that ensures quality assurance in the distribution channel, is easy to handle, is highly versatile, and has significantly improved performance as a filling material or adhesive. The goal is to provide the following. One aspect of the present invention is a filler for a caries preventive filling material using α-cyanoacrylate, in which a thixotropic composition that can be instantly cured by polymerizing a setter is applied to the α-cyanoacrylate. The filler is made of silica powder, and the filler is made of at least one of the group consisting of amino acids and acid amide compounds that have weak activity against α-cyanoacrylate. A filler for a caries-preventing filling material characterized by being recoated with a solid catalyst.

Another aspect of the present invention is that (1) α-cyanoacrylate and (2) silica powder are used as raw materials to be added sequentially during use, and the materials have weak activity against the α-cyanoacrylate. and (3) a filler coated with at least one solid catalyst from the group consisting of amino acids and acid amide compounds, and (3) having a strong activity against the α-cyanoacrylate and having a PKb in water of 1 to 12. This is an anti-caries filling material made of a basic amine compound.

The α-cyanoacrylate used in the present invention is represented by the general formula (wherein R is an alkyl group having 1 to 16 carbon atoms, a cyclohexyl group, a phenyl group, etc.), such as α-cyanoethyl acrylate and α-cyanomethyl acrylate. , α-cyanobutyl acrylate, α-cyanoisobutyl acrylate, α-cyanoamyl acrylate and α-cyanolauryl acrylate, in particular α-cyanoethyl acrylate may be selected as one of the preferred ones.

Next, the filler of the present invention, which forms a good thixotropic composition together with the above α-cyanoacrylate, is made of silica powder, and the filler contains amino acids and acids that have weak activity against the α-cyanoacrylate. It is coated with at least one solid catalyst of the group consisting of amide compounds. That is, the silica powder used as the material is an inorganic powder mainly composed of silica, such as silica containing almost no impurities, silica containing a small amount of alumina as an impurity, and silica containing a small amount of titanium oxide.
In any case, the particle size is 100 mμ or less, preferably 1~
It is used as ultrafine particles of 100 mμ. in this case,
Particles with a diameter of 100 mμ or more should be avoided because they tend to precipitate and separate, making it difficult to obtain good thixotropic properties. As mentioned above, in the present invention, the reason why a powder mainly composed of silica is used as the filler material is because the filler material has an influence on dispersibility and thixotropic property as shown in Table 1. Based on.

Next, at least one of an amino acid and an acid amide-based compound is used as a solid catalyst having weak catalytic activity against α-cyanoacrylate to coat this material. As the amino acid, monoamino monocarboxylic acid and monoamino dicarboxylic acid are effective, and preferably glycine, valine, methionine, glutamic acid, and tyrosine are used alone or in combination as the coating material. In addition, as acid amide compounds,
Acetamide, butyramide, α-chloroacetamide and benzamide are used alone or in combination as the coating material. Of course, it goes without saying that the above amino acids and acid amide compounds may be used in combination. When the material mainly composed of silica is coated with the solid catalyst, the amount of the solid catalyst is 1 to 50 parts by weight, preferably 5 parts by weight, based on 100 parts by weight of the material.
It is effective to use it in a range of 30 parts by weight.

To explain one example of the coating method, when the solid catalyst is an amino acid, a to c is weighed and placed in a conical beaker, stirred with a magnetic stirrer for about 1 hour, and then water is evaporated on a water bath. Then dry under reduced pressure (
The filler of the present invention, in which the material is coated with a solid catalyst, can be obtained by drying the material for 5 hours), thoroughly drying it, and grinding it into a fine powder using a pulverizer.

In addition, to explain an example in which the solid catalyst is an acid amide compound, after stirring for about 1 hour with a net stirrer, methanol is removed on a water bath, then drying under reduced pressure, and finally the flocculated filler is passed through a pulverizer. The filler of the present invention coated with a solid catalyst can be efficiently produced by the method of forming a fine powder.

Therefore, in the present invention, it is important to coat the material of the filler with the solid catalyst having a particularly weak activity because it makes it difficult for the filler to coagulate and at the same time prevents the cyanoacrylate from forming locally on the surface of the filler. To prevent the formation of hardened 6 clumps and to extend the pot life,
This is to ensure effective functionality in terms of quality assurance.

For example, when a catalyst with strong activity is coated, a lump of locally solidified cyanoacrylate is formed on the surface of the filler, making it impossible to obtain a thixotropic state. Fillers coated with a liquid catalyst tend to aggregate together, and the wet surface makes it difficult to disperse, and the initial amount of catalyst changes due to catalyst volatilization during storage. The solid catalyst is significant.

The type, blending range, and catalytic activity of the amino acid solid catalyst are shown in Table 2.

Further, the type, blending range, and catalytic activity of the solid catalyst of the acid amide compound are shown in Table 3.

Next, as a setter having strong activity against α-cyanoacrylate used in the present invention, a basic amine compound having a PKb in water of 1 to 12, preferably N-N-dimethylpara-toluidine, A curing accelerator such as N-N-diethyl para-toluidine, N-N-dimethylaniline, and N-N diethylaniline is usually added to a solvent such as ethanol or n-hexane, preferably at a concentration of 0.1 to 5 weight/volume. It is used by dissolving it in the range of %,
A material having a characteristic that it can be cured instantaneously, that is, within a very short period of time, from several seconds to several tens of seconds, preferably within 5 seconds, is used.

The PKb value refers to the ionization constant of a base, and is the ionization constant of a base. F. Hall and M. R. It can be measured by the method of Sprinkle (American Chemical Society, Vol. 54, 3469 (1932)).

However, in the present invention, since the filler mixed with α-cyanoacrylate is an ultrafine powder of 100 mμ or less, it is sufficiently penetrated into the minute pores of the enamel created by the acid treatment and hardened. The mechanical adhesion based on this is extremely strong.

Additionally, the thixotropic compositions formed according to the present invention typically have the characteristic that they can be used continuously for about 1 to 2 hours immediately after mixing, while curing them requires
As mentioned above, it also has the feature that it can be instantly cured by dropping a setter of a catalyst solution that has strong activity against α-cyanoacrylate. In this way, compositions that have a long pot life and can be cured instantly at any time can be used as intraoral materials, especially caries prevention filling materials, caries progression inhibiting filling materials, and orthodontic adhesives, with less burden on patients. It has extremely high practical utility. In addition, α- in the present invention
The mixing ratio of cyanoacrylate and filler mixed therein varies slightly depending on the type of catalyst coated on the filler material, but as shown in Table 4, it is generally α-cyanoacrylate. For 100 parts by weight,
In the case of a filler mainly composed of a particle size material of around 10 mμ, the amount is 5 to 13 parts by weight, preferably 7 to 10 parts by weight,
In the case of a filler mainly composed of a material with a broad distribution of 1 to 100 mμ, a good thixotropic composition can be obtained by using 5 to 25 parts by weight, preferably 8 to 18 parts by weight. be.

However, if the filler content is smaller than the above range, a good thixotropic composition cannot be obtained;
On the other hand, if it exceeds the limit, the thixotropy is too strong and it is inappropriate, and it is not only difficult to apply, but also the pot life will be shortened and the mechanical adhesive strength will be reduced, so it is important to maintain it within the above range. It is. In addition, α-cyanoacrylate 1
Table 4 shows the difference in thixotropy due to the blending amount of the filler based on 00 parts by weight and the grade of the powder material mainly composed of silica, which is the material of the filler.

Therefore, to explain how to use the composition of the present invention as an anti-caries filling material, a certain amount of filler coated with a solid catalyst and a corresponding α-
Mix the cyanoacrylate in a blender such as an amalgam mixer. Next, the occlusal surface of the molars is treated with an acid solution such as phosphoric acid for a certain period of time, washed with water, and dried by blowing compressed air. A thin layer of paint is applied, and a setter of N-N-dimethyl-paratoluidine solution is dropped onto the coated surface to instantly cure it. The above is a method for using it as a caries prevention filling material, but it can also be used as a filling material for inhibiting the progression of early caries in 1st or 2nd degree caries.
A similar procedure can be used without the need for cavity preparation. When used as an orthodontic adhesive, it is applied not to the occlusal surfaces of molars but to the smooth surfaces of front teeth and molars, and the catalyst solution is dripped after placing a bracket on the application surface. Of course, it is convenient and useful not only for intraoral use but also as a general adhesive. Next, examples of the present invention will be shown.

Example 1 First agent: α-cyanoethyl acrylate.

(Aron Alpha D Sankyo (trademark)) 2nd agent: Filler 1.

(Silica powder (distributed broadly with particle diameters of 1 to 100 mμ)
(coated with 10 parts by weight of acetamide per 100 parts by weight) Third agent: Setter of 2% ethanol solution of N-N-dimethyl-para-toluidine.

10 parts by weight of the second agent is mixed with 100 parts by weight of the first agent to obtain a thixotropic composition.

During this period, treat the occlusal surfaces of the patient's molars with 3 molar phosphoric acid for 1 minute, then rinse and dry. A thin layer of the previously prepared thixotropic composition is applied to the tooth surface and allowed to penetrate into the pits and fissures. Next, one drop of the third agent setter is added and cured to complete the operation. 3 Example 2 1st agent:
α-cyanoethyl acrylate.

Second agent: filler.

(Silica powder containing 1% alumina (particle size 1-30
mμ) 10 parts by weight of glycine per 100 parts by weight.
3) Part 3: Set of 2% hexane solution of N-N-dimethyl-para-toluidine.

100 parts by weight of the first agent and 10 parts by weight of the second agent are mixed to obtain a thixotropic composition.

The composition is applied with a thin brush to the occlusal surface of a patient's molars, which has been treated with 5 molar 4. phosphoric acid for 30 seconds, to penetrate into the pits and fissures.

Next, 1 to 2 drops of the third agent setter is added and cured, and the operation is completed. Example 3 First agent: α-cyanoisobutyl acrylate.

Second agent: filler. (Silica powder (particle size 1 to 30 mμ)
100 parts by weight, coated with 30 parts by weight of butylamide) 3rd agent: 0.5 parts of N-N-diethyl paratoluidine
% ethanol solution.

10 parts by weight of the second agent is mixed with 100 parts by weight of the first agent to obtain a thixotropic composition.

In the meantime, polysynch the occlusal surface of the patient's molars, and then
Treat with 0% citric acid aqueous solution for 1 minute, wash with water, and dry.
The previously prepared thixotropic composition is applied thinly to the entire crown of the tooth, allowing it to penetrate into the pits and fissures. Then, the third agent, setter, is added dropwise to complete the operation. Example 4 First agent: α-cyanomethyl acrylate.

Second agent: filler.

(100 parts by weight of silica powder (particle size 1 to 30 mμ) coated with 20 parts by weight of α-chloroacetamide) Third agent: A setter of a 5% ethanol solution of N-N-dimethyl-para-toluidine. .

A thixotropic composition is obtained by mixing 100 parts by weight of the first agent with 12 parts by weight of the second agent.

This composition is applied thinly to the entire occlusal surface of a molar tooth that has been treated with 3 molar phosphoric acid for 30 seconds, and is allowed to penetrate well into the pits and fissures. Next, 1 to 2 drops of the third agent setter is dropped onto the coated surface to harden it, and the operation is completed. Note that in each example, the second
A more uniform thixotropic composition can be obtained in a short time by placing a certain amount of the agent in a capsule, adding a corresponding amount of the first agent at the time of use, and mixing with a mixer such as an amalgam mixer.

In the present invention, when a certain amount of a filler coated with a solid catalyst of an amino acid or an acid amide compound that has weak activity against α-cyanoacrylate is mixed with the α-cyanoacrylate, a thixotropic coating that can be easily applied with a brush can be obtained. It was confirmed in the following experiment 1 that it is possible to form an adhesive composition characterized by the state of the adhesive, and that the composition exhibits extremely high stability and extremely strong mechanical adhesive strength.

Experiment 1 Regarding thixotropy, as described in JP-A-49-119984, a composition in which dimethylformamide is added as a second agent to a first agent consisting of α-cyanoacrylate and silica causes lumps. However, the composition of the present invention in which the alpha-cyanoacrylate and catalyst-coated silica are mixed at the time of use provides a uniform thixotropic composition without the formation of lumps.

That is, the composition of the present invention helps prevent the formation of lumps and has a thixotropic composition in its entirety. Experiment Regarding the stability of the composition (a) Sample: Sample A: α-cyanoethyl acrylate (Aron Alpha D Sankyo (trademark)).

Sample B: Agent consisting of α-cyanoacrylate and silica according to JP-A-49-119984.

Sample C: Sample B with a high concentration of stabilizer added.

(2.5 times the amount of stabilizer as sample B) Sample D: Sample B storage container packed in aluminum.

Sample E: The storage container of Sample C packed in aluminum.

(b) Storage conditions: Filled into a polyethylene container with a capacity equivalent to 2y and stored at 50°C and 100% relative humidity for 10 days.

(c) Results: Experiment Regarding adhesive strength (a) Sample: Sample A: Filler according to the invention.

Sample B: A filling material prepared from an agent consisting of α-cyanoacrylate and silica according to JP-A-49-119984.

Sample C: A filling material prepared from sample B with a 2.5 times the amount of stabilizer added.

Sample D: A commercially available product from a certain company.

(b) Test method: The labial surface of an extracted bovine front tooth is polished flat, etched with acid, washed with water and dried.

Next, a polymethyl methacrylate round rod (φ6
mm) and harden. After standing in water at 37° C. overnight, the tensile strength was measured using a strograph to determine the adhesive strength per unit area. (c) Results: In the present invention, α-cyanoacrylate is taken for the amount of a filler coated with a certain amount of a solid catalyst that has weak activity against α-cyanoacrylate.
A thixotropic composition with no clumps is formed and the total amount is uniform, and since α-cyanoacrylate and filler are separated and mixed at the time of use, quality assurance is accurate and stability is improved. , heat treatment of the filler is not required, catalyst measurement is not required at the time of use, making it easy to handle, and a variety of catalysts can be used, making it highly versatile; The composition has a long pot life of 1 to 2 hours, and if a strong catalyst solution (setter) is dropped after applying the thixotropic composition, it can be cured instantly, so it can be closed immediately and is easy to use for patients. It is easy to apply to the tooth surface, and because it is a thixotropic composition, it can be applied to a uniform thickness without flowing out even in the pits and fissures.The polymerization is carried out in two stages, so there is little volumetric shrinkage. Therefore, there are advantages in that the influence of internal stress is reduced, the filling material is less likely to peel off or leak later, and the adhesive strength is extremely high.

A composition that has a long pot life and can be instantly cured at any time is ideal as an intraoral material, especially as a caries prevention filling material, an initial caries progression inhibiting filling material, orthodontic adhesive. It also has the advantage of being an instant adhesive, with no risk of turning into a gel (*) even if stored for a long period of time, and exhibits excellent storage stability without changing over time.

Claims (1)

[Scope of Claims] 1. A thixotropic composition which is a filler for a caries preventive filling material using α-cyanoacrylate and which can be instantly cured by polymerizing a setter,
In the filler that can be formed together with the α-cyanoacrylate; the filler substantially has a particle size of 1 to 100
The material is made of silica powder consisting of particles in the range of mμ, and the material is coated with at least one solid catalyst from the group consisting of amino acids and acid amide compounds that have weak activity against the α-cyanoacrylate. A filler for caries prevention filling material. 2. The filler for caries prevention filling material according to claim 1, wherein the amino acid is at least one of the group consisting of monoaminomonocarboxylic acid and monoaminodicarboxylic acid. 3. The filler for caries prevention filling material according to claim 1, wherein the acid amide compound is at least one member of the group consisting of acetamide, butyramide, α-chloroacetamide, and benzamide. 4 The amino acid is glycine, valine, methionine,
at least one of the group consisting of glutamic acid and tyrosine
The filler for a caries-preventing filling material according to claim 2. 5 The solid catalyst is 1 part by weight for 100 parts by weight of the material.
The filler for a caries-preventing filling material according to any one of claims 1, 2, 3, or 4, which is coated in a proportion of ~50 parts by weight. 6. Should be added sequentially during use: (1) α-cyanoacrylate; (2) Substantially made of silica powder consisting of particles with a particle size in the range of 1 to 100 mμ, and the material is a filler coated with at least one solid catalyst from the group consisting of amino acids and acid amide compounds having weak activity towards acrylates; and (
3) A caries preventive filling material comprising a basic amine compound having a pKb in water of 1 to 12 and having a strong activity against the α-cyanoacrylate. 7 The α-cyanoacrylate is at least one of the group consisting of α-cyanoethyl acrylate, α-cyanomethyl acrylate, α-cyanobutyl acrylate, α-cyanoisobutyl acrylate, α-cyanoamyl acrylate, and α-cyanolauryl acrylate. A caries-preventing filling material according to claim 6. 8. The caries preventive filling material according to claim 6, wherein the amino acid is at least one member of the group consisting of monoamino monocarboxylic acid and monoamino dicarboxylic acid. 9. The caries preventive filling material according to claim 6, wherein the acid amide compound is at least one member of the group consisting of acetamide, butyramide, α-chloroacetamide, and benzamide. 10 The amino acid is glycine, valine, methionine,
at least one of the group consisting of glutamic acid and tyrosine
The caries-preventing filling material according to claim 8, which is: 11 The solid catalyst is 1 part by weight for 100 parts by weight of the material.
The caries-preventing filling material according to claim 6, 7, 8, 9, or 10, which is coated in a proportion of ~50 parts by weight. 12 The basic amine compound is N·N-dimethyl para-toluidine, N·N-diethyl para-toluidine, N·N
Claim 6 is at least one of the group consisting of -dimethylaniline and N·N-diethylaniline.
The caries prevention filling material described in Section 1. 13. Claim 6 or 7, wherein the ratio of the α-cyanoacrylate to the filler is 5 to 25 parts by weight of the filler to 100 parts by weight of the α-cyanoacrylate.
The caries prevention filling material described in Section 1. 14. The caries preventive filling material according to claim 6 or 12, wherein the basic amine compound is in a solvent.