JPS6310129B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention is capable of polymerization and polymerization at room temperature or by light irradiation.
The present invention relates to a caries-preventing filling material that hardens and gradually loses its coloring due to an organic pigment in an oral cavity atmosphere. [Prior art] Normally, the occlusal surface of human molars has a Y-shape or an
There are letter-shaped fissures and pits that are their gathering points.
These pits and fissures play an important role in the occlusal mechanism, but are also areas with an extremely high risk of caries development. That is, food and the like easily get stuck in the pits and fissures, and cleaning with a toothbrush does not reach the pits and fissures sufficiently, so microorganisms tend to live there. The fermentation action generates organic acids, which erodes the enamel in that area, leading to the development of caries. By the way, in the past, the general idea was that baby teeth were disposable, that permanent teeth would eventually erupt, and the oral cavities of children and young people were often left unused and overworked. However, in recent years,
Nationwide, the prevalence of cavities in baby teeth is decreasing, and cavities in baby teeth and permanent teeth of young children are becoming less severe. Possible reasons for this include a decrease in annual sugar consumption per person, an increase in the number of people receiving fluoride paint, and an increase in the number of people brushing their teeth twice a day. As interest in caries prevention increases, one of the measures to prevent caries is to seal the pits and fissures, which are the source of caries, with some kind of substance to prevent food residue from entering. This was considered to be an extremely effective method. Measures to prevent caries include first shaving the pits and fissures thin and filling them with amalgam; reacting an ammoniacal silver nitrate solution to the tooth surface to form a metal film to protect the tooth from external stimuli; Attempts have been made to fill the pits and fissures with zinc chloride, potassium ferrocyanide, or Katsupar cement, but these methods all have some drawbacks and have not been widely applied clinically. I couldn't reach it. Later, acrylic resins came into use, but this type of material also had drawbacks such as poor abrasion resistance, and was not clinically satisfactory. At present, a bisphenol A diglycidyl methacrylate resin has been developed to improve the drawbacks of this acrylic resin, and is widely used in clinical practice. Although many years have passed since the use of such filling materials for caries prevention, long-term progress reports have shown that the effectiveness of pit and fissure filling materials as a preventive measure is It is highly rated. On the other hand, from the perspective of occlusal theory, the pits and fissures play an important role, and filling the pits and fissures with a filling material artificially changes the occlusal surface morphology, and in some cases may cause occlusal changes. There are concerns that this will gradually have a negative impact on functionality. Therefore, it is preferable that the filling material for caries prevention is thin and narrow enough not to interfere with occlusion. However, the materials that are currently commonly used as filling materials for caries prevention are often in liquid form with low viscosity because they need to be filled into extremely narrow fissures of 50 to 100 microns. There is a high risk that the material will flow into the lower areas, resulting in a flat occlusal morphology after hardening. In addition, general sealants are often colorless and transparent, which makes it extremely difficult to identify the filled area and confirm the amount of filling, which causes the filling to be thick and wide over the occlusal surface. In addition, recently, red-colored materials have been commercially available for the purpose of making it easier to identify the material at the time of filling, but this material remains colored even after curing, so it is not aesthetically pleasing. It has a major drawback. [Object of the invention] The present invention makes it easy to identify the plugged area and confirm the amount of filling during filling by coloring, and after the filling, polymerizes and hardens at room temperature or by light irradiation.
Another object of the present invention is to provide a caries-preventing filling material whose coloring caused by organic pigments gradually disappears in an oral cavity atmosphere. [Structure of the Invention] The present invention provides a radically polymerizable aromatic dimethacrylate or diacrylate, a radically polymerizable aliphatic monomethacrylate or monoacrylate having one epoxy group in the hydrocarbon chain, a radical polymerization initiator, This filling material for caries prevention is composed of an organic pigment, polymerizes and hardens at room temperature or when exposed to light, and is characterized in that the coloring caused by the organic pigment gradually disappears in the oral atmosphere. [Effects of the Invention] Therefore, according to the present invention, since the material is strongly colored by the action of the organic pigment before curing, it is extremely easy to identify the filled area and confirm the filling amount at the time of filling. It is possible to fill the necessary amount correctly in the area, and it is possible to prevent changes in the occlusal surface morphology due to too thick filling. Furthermore, it gradually decolorizes in the oral cavity atmosphere and takes on a color tone that closely resembles that of a tooth, resulting in extremely excellent esthetics after the filling. In addition, it has extremely good adhesion to acid-etched enamel and is stable for long periods of time even under water, so it has excellent sealing properties, which is the most important property for a filling material for caries prevention. In good condition. [Example] Next, an example of the caries-preventing filling material of the present invention will be described. The radically polymerizable aromatic dimethacrylate or diacrylate (hereinafter referred to as agent A) used in the composition of the present invention is one that exhibits a liquid or starch syrup-like state at room temperature, is less harmful to the human body, and has the following properties: Examples include those that correspond to general formulas such as Here, R ₁ and R ₂ are hydrogen or methyl groups, R ₃ and R ₄
represents a hydrocarbon chain, which hydrocarbon may be substituted with one or more hydroxyl groups, and A represents an aromatic group such as phenylene, diphenylene or

In the crosslinked phenylene represented by the general formula [Formula], B represents lower alkylene, such as methylene, ethylene, ethylidene, isopropylene, butylene, etc. Next, another component, aliphatic monomethacrylate or monoacrylate (hereinafter referred to as agent B) which is capable of radical polymerization and has one epoxy group in the hydrocarbon chain, corresponds to the following general formula. Here, R ₅ represents hydrogen or a methyl group, R ₆ represents a hydrocarbon chain, and this hydrocarbon chain has one epoxy group. These components can be used alone or in combination of two or more. The mixing ratio of agent A and agent B can be set over a wide range, but agent A/agent B = 3/1 to 1/2.
Particularly preferred is a range of 2/1 to 2/3. Here A
If the ratio of the agent is too large, the viscosity of the monomer component becomes too high, which not only makes it extremely difficult to fill the pits and fissures, but also makes it extremely difficult for the decolorization reaction to occur after curing. On the other hand, if the proportion of agent B becomes too high, the properties such as abrasion resistance, mechanical strength, and water resistance of the material will be greatly reduced. By adding a radical polymerization initiator and an organic dye, which will be described later, to the monomer component that is a blend of these two components in an appropriate ratio, it will polymerize and harden at room temperature or by light irradiation, and will be able to be used as an organic material in the oral atmosphere. It becomes possible for the coloring caused by the pigment to gradually disappear. Next, when the material of the present invention is applied as a room temperature curing type, a redox initiator is used as a radical polymerization initiator in order to cause the room temperature polymerization reaction to occur effectively and rapidly. The oxidizing agents constituting the redox initiator used for this purpose include acetyl peroxide, propionyl peroxide,
Octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3.5.5−
Diacyl peroxides such as trimethylhexanoyl peroxide, succinic acid peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, m-trioyl peroxide, t-butyl peroxyacetate, t-butyl peroxyisobutylene rate,
t-butyl peroxy pivalate, t-butyl peroxy neodecanate, t-butyl peroxy
Included are peroxy esters such as 3.5.7-trimethylhexanate, t-butyl peroxylaurate, and t-butyl peroxybenzoate. These may be used alone or in combination of two or more. The amount of these oxidizing agents added is preferably set within the range of 0.5 to 10% by weight, particularly preferably 1.0 to 5% by weight, based on the total amount of monomers used. Here, the amount of oxidizing agent is 0.5% by weight
If the amount is less, the amount of the reducing agent described below must be considerably increased in order to cure within a predetermined time at room temperature, and in that case, the decolorization reaction will not occur efficiently. Furthermore, if the amount of the oxidizing agent is more than 10% by weight, the molecular weight of the polymer will be small and the mechanical strength will be poor. Further, examples of the reducing agent constituting the redox initiator used in the present invention include tertiary amines, naphthenates, mercaptans, organometallic compounds, and the like. Representative examples include NN′-dimethylaniline, NN′-diethylaniline, NN′-
Dimethyl-P-toluidine, NN'-diethyl-
P-toluidine, NN'-diethyl-m-toluidine, N-methyl-N'-β-hydroxyethylaniline, NN'-di(β-hydroxyethyl)
Examples include P-toluidine, zinc naphthenate (or nickel, cobalt, iron, tin, lead), methyl mercaptan, triethyl aluminum, triethyl boron, diethyl zinc, and the like. The amount of these additives must be set appropriately depending on the type and amount of the oxidizing agent used.
As mentioned above, if too much reducing agent is added, the decolorization reaction will be significantly inhibited, so the amount added should be 0.01 to 0.5% by weight, especially 0.05 to 0.2% by weight based on the total amount of monomers.
It is preferable to set it within the range of weight %. In addition, in order to polymerize and cure the material of the present invention by UV irradiation, as a radical polymerization initiator,
In addition to the above-mentioned oxidizing agent, a known ultraviolet sensitizer excited by ultraviolet rays may be used in combination. Sensitizers that can be used for this purpose include benzoin alkyl ethers and various substituted benzophenone derivatives, such as benzoin methyl ether, benzoin ethyl ether, benzoin butyl ether, 4,4'-dimethylbenzophenone, - methacryloxybenzophenone and similar known UV sensitizers. These may be used alone or in combination of two or more. The amount of these ultraviolet sensitizers added is preferably set within the range of 0.2 to 5% by weight, particularly 0.5 to 3% by weight based on the total amount of monomers. If the amount added is less than 0.2% by weight, disadvantages such as an unnecessarily long time required for the necessary polymerization will occur. Furthermore, if the amount added is more than 5% by weight, the resulting polymer will have a small molecular weight and poor mechanical strength. Note that a general mercury lamp can be used as the ultraviolet irradiation device necessary for curing the material of the present invention. Furthermore, in order to polymerize and cure the material of the present invention by irradiation with visible light, a photosensitizer excited by visible light may be used in combination with the above-mentioned oxidizing agent as a radical polymerization initiator. Examples of photosensitizers that can be used for this purpose include camphorquinone. Note that a halogen lamp can be used as the visible light irradiation device necessary for curing the material of the present invention. Furthermore, one or more organic pigments are added to the material of the present invention in order to make the color tone of the material at the time of filling significantly different from that of the tooth and to facilitate identification of the filled area. Any type of organic dye can be used as long as it has little harmful effect on the human body, but azo dyes are particularly preferred. In addition, since it is decolored after curing, any color can be used, but from the viewpoint of making it easier to distinguish it from tooth structure, red or blue colors are suitable. Examples of these are Pigment Red 57-1 (Resol Rubin) and Pigment Red 53.
(Lake Red CBA), Pigment Red 49 (Resol Red CA), Pigment Red 64 (Brilliant Lake Red R), Pigment Red 3 (Toluidine Red), Solven Red 23 (Sudan),
Pigment Red 4 (Permanent Red), Pigment Red 24 (Brilliant Fast Scarlet), Pigment Red 48 (Permanent Red)
F5R), Solvent Red 24 (Medicated Scarlet),
Includes Solvent Orange 7 (Oil Red XO), Pigment Orange (Hansa Orange), Solvent Orange 2 (Orange SS), etc. These organic dyes may be used alone or in combination of two or more. The amount added is preferably in the range of 0.001 to 0.02% by weight, particularly 0.005 to 0.01% by weight, based on the total amount of monomers.
If the amount added is small, the coloring property will be poor, making it difficult to identify when the material is filled into a tooth.
If the amount added is large, the decolorizing property will decrease and the color will not disappear completely. This decolorization occurs when the epoxy group contained in the B agent molecule contained in the material of the present invention attacks the chromophore and auxochrome in the organic dye molecule, and this reaction is caused by the redox initiator It is promoted by the oxidizing agent in the oxidizing agent, but is not affected by the reducing agent at all. Therefore, in a system where the amount of oxidizing agent is reduced and the amount of reducing agent is increased,
Gelation reaction occurs preferentially, and decolorization reaction becomes extremely difficult to occur. Conversely, when the amount of the oxidizing agent is increased and the amount of the reducing agent is decreased, the gelation reaction and the decoloring reaction occur efficiently, making it possible to gradually decolorize the product in the oral cavity atmosphere. However, even in this case, if the amount of organic dye added is increased more than necessary, it becomes difficult to attack all the chromophores and auxochromes, resulting in incomplete decolorization. In addition to the above-mentioned monomer components, the material of the present invention also contains trifunctional or tetrafunctional methacrylate or acrylate in order to increase the crosslinking density and improve the hardness and mechanical properties of the material. May be used together. Further, in order to reduce the viscosity of the monomer components described above, it is also possible to contain a radically polymerizable dilutable monomer (hereinafter referred to as a diluent). Such diluents may be selected from a wide variety of well-known low viscosity, radically reactive methacrylates or dimethacrylates suitable for use in the oral cavity. namely, alkyl methacrylates such as lower alkyl methacrylates, alkylene dimethacrylates such as lower alkylene dimethacrylates, alkylene and polyalkylene glycol monomers, and aliphatic mono- and dimethacrylates such as dimethacrylates, and methacrylates having a hydroxyl group within the lower alkyl methacrylates. etc. are included. Typical diluents included in the above group include the following: That is, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, secondary butyl methacrylate, ethylene dimethacrylate,
These include butylene dimethacrylate, ethylene glycol monomethacrylate, triethylene glycol dimethacrylate, 2-hydroxyethyl methacrylate, and the like. These diluents may be used alone or in combination of two or more, but if they are added in too large a quantity, the above-mentioned decolorization reactivity will be significantly reduced, so the amount added should be 30% by weight of the total amount of monomers.
It is preferable to do the following. In the material of the present invention, it is preferable to use a polymerization inhibitor in order to prevent premature polymerization of the monomer components and diluent described above and improve storage stability. In this case, a polymerization inhibitor may be selected from known hydroquinone derivatives. can. Examples of polymerization inhibitors that can be used for this purpose include hydroquinone, hydroquinone monomethyl ether, butylated hydroquinone, catechol, catechol methyl ether t-butylcatechol, pyrogallol, pyrogallol monomethyl ether, and pyrogallol dimethyl ether. Furthermore, the material of the present invention may contain an inorganic filler for the purpose of improving wear resistance, compressive strength, and water resistance, and imparting appropriate viscosity and thixotropic properties, and it is preferable to do so. As this inorganic filler, commonly used inorganic fillers such as silicon dioxide, aluminum oxide,
Titanium dioxide, α-quartz, zirconium dioxide,
Fine glass powder, hydroxyapatite, etc. can be used. These inorganic fillers may be used alone or in combination of two or more. The filling amount can be arbitrarily selected depending on the desired properties, but a range of 30 to 70% by weight is appropriate. If the filling amount is less than 30% by weight, the effect of adding the inorganic filler will not be sufficiently obtained, and the wear resistance and
Significant improvement in compressive strength etc. cannot be expected. Furthermore, if the filling amount is greater than 70% by weight, the viscosity of the material becomes very high and the penetration of the material into the pits and fissures is significantly reduced. In addition, when using the above-mentioned inorganic filler, the surface of the filler is treated with a coupling agent in order to improve the bond between the filler and the monomer component that is the binder, and to improve the physical properties of the cured product. It is preferable. Coupling agents that can be used for this purpose include both silane-based and titanium-based coupling agents. Silane coupling agents are effective in improving the mechanical strength and rigidity of cured products, while titanium coupling agents are effective in improving the flexibility of cured products. These may be used alone or in combination of two or more. Silane coupling agents that can be used for this purpose include vinyltrichlorosilane, vinyltris(βmethoxyethoxy)silane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyl-trimethoxysilane, β
(3.4-epoxycyclohexylethyltrimethoxy)silane, γ-glycidoxypropyltrimethoxysilane, N-β(aminoethylγ-aminopropyltrimethoxy)silane, N-β(aminoethyl)γ-aminopropylmethyldimethoxysilane , γ-aminopropyltriethoxysilane, N
-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, etc., but especially γ-methacryloxypropyl-
Preference is given to using trimethoxysilane. In addition, examples of titanium-based coupling agents include isopropyl triisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris(dioctylpyrophosphate) titanate, and tetra(2.2-diallyloxymethyl-1-butyl)bis(di-tridecyl). phosphite) titanate, bis(dioctylpyrophosphate)oxyacetate titanate, isopropyl isostearoyl diacryl titanate, isopropyl tri(dioctyl phosphate) titanate, and isopropyl dimethacryl isostearoyl titanate is particularly preferred. All of these can be surface treated according to conventional methods, and the amount used is 1/1 of the filler.
Approximately % by weight is appropriate. Furthermore, various fluorides can be added to the material of the present invention for the purpose of enhancing the acid resistance of tooth substance. Agents that can be used for this purpose include sodium monofluorophosphate, stannous fluoride, and sodium fluoride. If these drugs are added in too large a quantity, there is a risk of acute toxicity due to ingestion of large amounts of fluoride, so the amount added should be limited.
Must be below 1000ppm. Furthermore, a fungicide such as chlorhexidine may be added for the purpose of preventing caries. In order to efficiently mix the above-mentioned components and obtain a specified material composition, there are two methods: (1) liquid-liquid method, (2) powder-
Various methods can be employed, such as a liquid method, (3) a paste-paste method, and (4) a liquid-paste method. The liquid-liquid method is a method to be adopted when no inorganic filler is included, and when this method is applied to room temperature curing materials, it is necessary to use agent A, agent B, oxidizing agent, dilutable monomer, and radical polymerization inhibitor. A liquid component () consisting of agents, agent A, agent B, reducing agent, organic dye,
The liquid component (2) consists of a dilutable monomer and a radical polymerization inhibitor, and both components are mixed at the time of use. In this case, the organic dye is the liquid component ()
may be included. In addition, in order to apply this method to photocurable materials, a liquid component () consisting of agent A, agent B, dilutable monomer, and radical polymerization inhibitor is required.
and a liquid component () consisting of agent A, agent B, oxidizing agent, ultraviolet rays or photosensitizer, organic dye, and radical polymerization inhibitor, and both components are mixed at the time of use. The powder-liquid method is a method that can be used when incorporating an inorganic filler. The method is particularly suitable for cold-curing materials, in which case it is preferred to add the oxidizing agent to the powder component and the reducing agent to the liquid component. That is, it is made up of two components: the liquid component (2) described above and a powder component (2) consisting of an inorganic filler and an oxidizing agent, and both components are kneaded at the time of use. In this case, it is also possible to contain the organic dye on the powder component () side. This method can separate the radically polymerizable monomer and the oxidizing agent into different phases, improving the storage stability of the material, and by changing the powder/liquid ratio appropriately, the viscosity can be adjusted to suit the purpose. You can also get the advantage of Further, in this powder-liquid method, the powder component can be further divided into two components, and one can contain an oxidizing agent and the other can contain a reducing agent. In this case, since there is no need to include a reducing agent in the liquid component, the stability of the material is further improved. In addition, when applying this method to photocurable materials, the liquid component () described above
and a powder component consisting of an inorganic filler, an ultraviolet ray or photosensitizer, and an organic dye. The paste-paste method can also be adopted when containing an inorganic filler, and when this method is applied to a room temperature curing type, A agent, B agent, oxidizing agent, dilutable monomer,
A paste component () consisting of a radical polymerization inhibitor and an inorganic filler, and a paste component () consisting of an A agent, a B agent, a reducing agent, an organic dye, a dilutable monomer, a radical polymerization inhibitor, and an inorganic filler. It has two components, and both components are kneaded before use. This method has the advantage of improving the homogeneity of the components because the liquid and powder components can be thoroughly mixed in advance, but the radically polymerizable monomer and the oxidizing agent must be present in the same system. Therefore, there is also the disadvantage that the storage stability of the material is poor. In addition, in this method, an organic dye may be included in the paste component (). Further, when this method is applied to a photocurable material, ultraviolet rays or a photosensitizer may be contained instead of the reducing agent. In this case, ultraviolet rays or a photosensitizer can also be included in the paste component (). Furthermore, when applying the liquid-paste method to room-temperature curing materials, the paste components () described above
and a liquid component (2) in which the oxidizing agent is dissolved in a suitable plasticizer, and the two components are kneaded at the time of use. In addition, when applying this method to photocurable materials, it is sufficient to include ultraviolet rays or a photosensitizer in the liquid component (), and in that case, there is no need to add a reducing agent to the paste component (). . Plasticizers that can be used in this method include the well-known phthalate esters and derivatives of abietic acid. Examples of these include phthalate esters such as butyl phthalate, octyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, ethyl benzyl phthalate, butyl benzyl phthalate, and hydrogenated esters such as methyl abietate, butyl abietate, octyl abietate, etc. Esther can be given. This method improves the storage stability of the material because the radical polymerizable monomer and the radical polymerization initiator are separated into different phases, but has the disadvantage that the mechanical properties of the cured product decrease due to the plasticity used. Furthermore, it is also possible to use a one-component type for photocurable materials. That is, agent A,
One component consists of a B agent, an oxidizing agent, an ultraviolet ray or photosensitizer, an organic dye, a dilutable monomer, and a radical polymerization inhibitor. Moreover, it is also possible to make a composite type by incorporating an inorganic filler into the above components. Since these one-component materials do not need to be kneaded during use, the problem of bubble entrainment due to kneading can be avoided. The details of the present invention will be explained below with reference to Examples. However, needless to say, the present invention is not limited to the following examples. Example 1 [Liquid-liquid method] A monomer component consisting of 50 parts of 2.2-bis(P-2'hydroxy-3'methacryloxypropoxyphenyl)propane and 50 parts of glycidyl methacrylate,
Add 2.0 parts of benzoyl peroxide and 0.001 part of hydroquinone monomethyl ether to make liquid component (A).
was prepared. 2.0.3 part of NN'-dimethyl P-toluidine and 0.001 part of hydroquinone monomethyl ether were added to a monomer mixture consisting of 50 parts of 2-bis(P-2'-hydroxy-3'methacryloxypropoxyphenyl)propane and 50 parts of glycidyl methacrylate. A liquid component (B) was prepared. 0.3 g of liquid component (A) and 0.3 g of powder component (B) were kneaded for 30 seconds at room temperature of 25° C. and then allowed to stand, and the time until gelation started was measured. In addition, the materials mixed in the same manner as above were filled into a polyethylene mold with an inner diameter of 4 mm and a height of 8 mm, and after being left in the air at 25°C for 10 minutes and then in water at 37°C for 24 hours, the mold was removed and tested. A piece was prepared, and its compressive strength and compressive modulus were measured using an Instron universal testing machine at a loading rate of 0.5 mm/min. In addition, after polishing the surface of bovine tooth enamel with 1000-grit sandpaper until it became smooth and etching it with a 40% phosphoric acid aqueous solution for 60 seconds, the mixture was applied to the washed and dried surface. The acrylic rods were glued vertically, allowed to harden at room temperature for 10 minutes, and then immersed in water at 37°C for 24 hours. After dipping, an adhesion test was conducted using an Instron universal testing machine at a tensile speed of 0.2 mm/min. These results are shown in Tables 1 and 2. Example 2 [Powder-liquid method] A mixed monomer consisting of 50 parts of 2.2-bis(P-2'hydroxy-3'methacryloxypropoxyphenyl)propane and 50 parts of glycidyl methacrylate,
A liquid component () was prepared by adding 0.001 part of hydroquinone monomethyl ether. 40 parts of α-quartz powder with an average particle size of 10μ and 10 parts of silica with an average particle size of 40μ are added to 90 parts of an aqueous solution containing 0.5 parts of γ-methacryloxypropyltrimethoxysilane and 0.9 parts of acetic acid and stirred for 1 hour at room temperature. , further reacted at 60-80°C for 4-5 hours with stirring,
Filter and dry. A powder component (2) was prepared by adding 1.0 part of benzoyl peroxide to the mixed inorganic filler thus obtained. A powder component (2) was prepared by adding 0.15 parts of NN'-dimethyl P-toluidine and 0.005 parts of Pigment Red 48 (Permanent Red F5R) to 50 parts of the mixed inorganic filler. 0.30g of liquid component (), 0.15g of powder component ()
As in Example 1, using 0.15 g of powder component (2), kneaded at room temperature of 25° C. for 30 seconds and left to stand, and the time until gelation started was measured. In addition, the gelled material was immersed in water at 37°C, and the time required for complete decolorization was measured. Compressive strength and adhesive strength were also measured in the same manner as in Example 1. These results are shown in Tables 1 and 2. Example 3 [Paste-paste method] A monomer component consisting of 25 parts of 2.2-bis(P-2'hydroxy-3'methacryloxypropoxyphenyl)propane and 25 parts of glycidyl methacrylate,
50 parts of the mixed inorganic filler used in Example 1, NN'-
A paste component () was prepared by adding 0.15 part of dimethyl P-toluidine and 0.005 part of Pigment Red 48 (Permanent Red F5R). 2.2-bis(P-2'hydroxy-3'methacryloxypropoxyphenyl)propane 25 parts and triethylene glycol dimethacrylate 25 parts, to which were added 50 parts of the above mixed inorganic filler and 1.0 part of benzoyl peroxide. A paste component () was prepared by adding: Using 0.3 g of paste component () and 0.3 g of paste component (), the time until complete decolorization was measured in the same manner as in Example 1. In addition, compressive strength and adhesive strength were measured in the same manner as in Example 1. The results are shown in Tables 1 and 2. Example 4 [Liquid-paste method] A monomer component consisting of 25 parts of 2.2-bis(P-2'hydroxy-3'methacryloxypropoxyphenyl)propane and 25 parts of glycidyl methacrylate,
0.08 part of NN'-dimethyl P-toluidine, 0.003 part of Pigment Red 48 (Permanent Red F5R),
A paste component () was prepared by adding 50 parts of the mixed inorganic filler described above. A catalyst component (2) was prepared by adding 1 part of benzoyl peroxide to 10 parts of diethyl phthalate. 0.6g of paste component () and catalyst component ()
The gelation time, decolorization time, compressive strength, and adhesive strength were measured in the same manner as in Example 1 using 0.06 g of the sample. The results are shown in Tables 1 and 2. Example 5 [Ultraviolet curing method] 20 parts of 2.2-bis(P-2'hydroxy-3'methacryloxypropoxyphenyl)propane, 20 parts of glycidyl methacrylate, 10 parts of triethylene glycol dimethacrylate, Pigment Red 48 (permanent red) A paste component () was prepared by adding 0.005 parts of hydroquinone monomethyl ether (F5R), 0.001 parts of hydroquinone monomethyl ether, and 50 parts of the above-mentioned mixed inorganic filler. A catalyst component (2) was prepared by adding 2 parts of benzoyl peroxide and 1 part of benzoyl methyl ether to 20 parts of diethyl phthalate. 0.6g of paste component () and catalyst component ()
Mix 0.06g of
The sample was applied onto a ceramic plate and cured by irradiating it with ultraviolet light for 40 seconds. Next, the cured product was immersed in water at 37°C, and the time required for complete decolorization was measured. The results are shown in Table 1. Comparative Example 1 0.5 part of benzoyl peroxide was added to 50 parts of the mixed inorganic filler used in Example 1 to prepare a powder component (). A powder component (2) was prepared by adding 0.5 part of NN'-dimethyl-P toluidine and 0.005 part of Pigment Red 48 (Permanent Red F5R) to 50 parts of the mixed inorganic filler. Using 0.3g of the liquid component (), 0.15g of the powder component (), and 0.15g of the powder component () used in Example 1, the gelation time and decolorization were determined in the same manner as in Example 1. Measurements of time, compressive strength, and adhesive strength were made. The results are shown in Tables 1 and 2. Comparative Example 2 Hydroquinone monomethyl ether was added to a monomer mixture consisting of 50 parts of 2.2-bis(P-2'hydroxy-3'methacryloxypropoxyphenyl)propane and 50 parts of triethylene glycol dimethacrylate.
A liquid component () was prepared by adding 0.001 part. 0.3g of liquid component (), 0.15g of powder component () used in Example 1, 0.15g of powder component ()
The mixture was kneaded for 30 seconds at room temperature (°C), and the gelation time, decolorization time, compressive strength, and adhesive strength were measured in the same manner as in Example 1. The results are shown in Tables 1 and 2. Comparative Example 3 20 parts of 2.2-bis(P-2'hydroxy-3'methacryloxypropoxyphenyl)propane, 30 parts of triethylene glycol dimethacrylate, 0.005 parts of Pigment Red 48 (Permanent Red F5R),
Paste component () by adding 0.001 part of hydroquinone monomethyl ether and 50 parts of mixed inorganic filler
was prepared. 0.6 g of the paste component () and 0.06 g of the catalyst component () used in Example 4 were kneaded for 30 seconds at room temperature of 25°C, a portion of which was applied on a ceramic plate, and exposed to ultraviolet rays at 40°C. It was cured by irradiation for seconds. Next, the cured product was immersed in water at 37°C, and the time required for complete decolorization was measured. The results are shown in Table 1.

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Claims (1)

[Scope of Claims] 1 Radically polymerizable aromatic dimethacrylate or diacrylate, radically polymerizable aliphatic monomethacrylate or monoacrylate having one epoxy group in the hydrocarbon chain, radical polymerization initiator, organic type A filling material for caries prevention, which is composed of a pigment, polymerizes and hardens at room temperature or by light irradiation, and whose coloring due to the organic pigment gradually disappears in an oral atmosphere. 2. The caries prevention filling material according to claim 1, which contains an inorganic filler and is configured as a composite type.