JP2002114620A - Glass for dental filler and dental composition containing particle of the glass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a glass for dental filler, capable of being used as a filler in dental compositions, and capable of imparting the dental composition with X-ray contrasting characteristics, clarity, sustained-release properties of fluorine, durability, polishing suitability, and abrasion resistance which are required for the dental compositions, and to provide the dental composition containing particles of the glass. SOLUTION: This glass for dental filler comprises a fluorine-containing boroaluminosilicate glass which contains Si, B, and Al as elements for forming a glass skeletal structure, wherein the glass has a glass composition containing SiO2, B2O3, Al2O3, P2O5, BeO, MgO, CaO, an oxide of an X-ray contrasting element, an alkali metal oxide, and F, and further has such a mol ratio (on oxide basis) of Si and B to Al for forming the glass skeletal structure as follows: Al2O3:SiO2:B2O3=1.00:(1.50-2.50):(0.50-1.50). The dental composition contains the particles of the glass.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a dental filling glass and a glass particle thereof which can be used as a filler in a dental composition such as a crown material, a filling material, a prosthetic material and an adhesive material in the dental field. And a dental composition comprising:

[0002]

2. Description of the Related Art The following properties are required of composite restorations which are frequently used in the dental field in recent years. Mechanical strength that can withstand high occlusal pressure during mastication, durability under severe conditions, coefficient of thermal expansion similar to tooth, low polymerization shrinkage to prevent peeling from tooth during polymerization hardening, etc. Mechanical properties, color and transparency compatible with natural teeth, optical properties such as surface lubrication and glossiness observed during polishing, and non-toxic,
Biocompatibility such as insolubility and low water absorption is exemplified. In recent years, in particular, there has been a demand for a fluorine sustained-release property for strengthening and preventing dental caries and an X-ray contrast property for confirming the status of caries recurrence after treatment and discriminating it from enamel of the dental substance. .

Conventionally, it is composed of a polymerizable monomer, a polymerization initiator, and a filler such as an inorganic substance, an organic substance, or an organic-inorganic composite, which are polymerizable for restoration, prosthesis, artificial dental root, and other uses of a tooth defect. Composite restorations are used.
Among these components, there have been many reports on fillers. This is because it is considered that the characteristics of the filler affect the characteristics of the composite restoration material since the proportion of the filler in the composite restoration material is large.

In dental practice, X-ray photography is generally performed as a means for confirming the state of filling of a restoration immediately after treatment, the occurrence of secondary caries, and the like. At this time, in order to accurately judge the filling state of the restoration immediately after treatment and the occurrence of secondary caries, the filled composite restoration material and the surrounding dentin should be clearly distinguishable on an X-ray photograph is necessary. For that purpose, it is essential that the composite restoration material has X-ray contrast properties, and a high level is required. It is a minimum condition that it has higher X-ray opacity than the enamel and dentin constituting the dentin, and more preferably sufficient X-ray opacity that is not affected by the depth of the cavity That the composite restoration material has. In order to impart the X-ray contrast property to the composite restoration material, either the organic component such as a polymerizable monomer or the filler constituting the composite restoration material must have the X-ray contrast property. . JP-A-8-208417 and Japanese Patent Publication No. 28076 for the purpose of imparting X-ray contrast to an organic component
No. 41 describes that iodination or bromination of a polymerizable monomer as a component of the composite restoration material imparts X-ray contrast. However, in order to maintain other properties required for the composite restoration material, for example, low polymerization shrinkage and high mechanical strength, the ratio of the organic component in the composite restoration material is reduced. Contrast cannot be expected.

[0005] Therefore, in order to impart X-ray contrast to the composite restoration material, it is generally possible to easily impart X-ray contrast by using a filler having X-ray contrast. However, although the use of an X-ray opaque filler makes it possible to impart X-ray opacity to the composite restoration material, the transparency of the composite restoration material tends to decrease. This is because, by imparting X-ray contrast to the filler, the refractive index increases, and the difference in the refractive index from the organic component used in the composite restoration material increases. Composite restorations are designed to mimic the appearance of translucent natural teeth and must be compatible with color as well as transparency. In order to obtain transparency suitable for the tooth structure, the refractive indices of both the filler and the organic component must be similar. Tokuhei 3-
EP 17803 discloses a dental material containing a fluoride of a rare earth metal, and EP 0011735 A2 discloses a dental material containing a heavy metal compound which is solid and has low solubility. By compounding a large amount of these compounds in the composite restoration material, it is possible to impart high X-ray contrast, but it is difficult to maintain the transparency required for the composite restoration material, resulting in an opaque material. Problems arise in aesthetics. For this reason, glass-based fillers that can provide a certain degree of transparency while imparting X-ray contrast are generally used in a wide variety of dental materials.

In the field of dentistry, it is known that a cement material called glass ionomer cement or glass polyalkeneot cement has an effect of preventing or suppressing dental caries and strengthening teeth by releasing fluorine gradually. . These cement materials are hardened by mixing an acid-reactive fluorine-containing glass and an aqueous solution of a polycarboxylic acid, and exhibit material properties required for cement. There have been many reports on acid-reactive fluorine-containing glass used for this material, for example, Japanese Patent Publication No. 50-24328.
JP-A-62-11349 discloses a fluoroaluminosilicate glass containing silica, alumina and fluorine as main components and containing elements such as phosphorus and sodium, and JP-A-62-113749 discloses calcium, alumina, silica, fluorine and phosphorus. And sodium fluoroaluminosilicate glasses, respectively. However, this glass has a great problem in X-ray contrast, mechanical strength, water resistance, and the like, although fluorine is gradually released, as compared with the filling glass contained in the composite restoration material. These problems are due to the types and amounts of the elements constituting the glass. For this reason, attempts have been made to impart various characteristics to the acid-reactive fluorine-containing glass for the purpose of satisfying the required properties of the cement material also in this material. Glasses for dental glass ionomer cements for the purpose of imparting X-ray contrast have been reported. For example, JP-A-63-201038 does not contain Be, Mg and Ba among alkali metals and alkaline earth metals. Fluoroaluminosilicate glass, JP-A-63-
182238 discloses strontium-containing aluminofluorosilicate alkaline earth metal salt glasses. Japanese Patent Application Laid-Open No. Sho 61-215234 discloses a glass composition for a glass ionomer cement that surpasses the performance of a conventional glass ionomer cement and has X-ray contrast properties. These glasses impart X-ray contrast by containing strontium and other heavy metals in the glass composition. These glasses for glass ionomer cements are primarily used for cement compositions which react with aqueous polycarboxylic acids. A high level of X-ray contrast in these glasses increases the refractive index of the glass and causes a large difference in the refractive index from the aqueous solution of polycarboxylic acid, so that the cured cement composition becomes opaque. Occurs. Therefore, the degree of imparting the X-ray contrast to the glass was low, and was not clinically satisfactory. Also, glass for glass ionomer cement is inherently poor in water resistance,
Although the glass composition contains only a small or no element that lowers the water resistance, such as boron or an alkali metal element, the water resistance is still insufficient.

On the other hand, although the method of use is different from that of glass ionomer cement, many attempts have been made to impart various properties to dental filling glass contained in composite restorations. For example JP-in 8-225423 discloses SiO _2: 50 to 75 wt% ZrO _2: 5 to 30 wt% Li ₂ O: 0~5 wt% Na ₂ O: 0~25 wt% K ₂ O: 0~ 25 total weight percent alkali oxides: 0-25 wt% dental glass having good X-ray absorption free of barium consisting, Japanese German Patent No. 4443173C2 SiO _2: 50~75 wt% ZrO _2: > 12 to 30 wt% Li ₂ O: 0 to 5 wt% Na ₂ O: 0 to 25 wt% K ₂ O: 0 to 25 total weight percent alkali oxides: dental glasses consisting 0-25% by weight, SiO ₂ in JP-A-7-33476: 45-60 wt% B ₂ O _3: 5~20 wt% Al ₂ O _3: 5~20 wt% CaO: 0 wt% SrO: 15 to 35 weight % F ₂ : Flash composed of 0 to 2% by weight The patent discloses a dental glass which does not contain chromium and exhibits good X-ray absorption. These glasses are S
Since the iO ₂ content is as high as 45% by weight or more, the melting temperature at the time of glass production becomes high, and there is a problem in workability such as requiring special equipment. In addition, as the content of SiO ₂ increases, the glass hardness also increases, and it has characteristics that the opposing teeth are easily worn. When the content of ZrO ₂ or SrO is increased for imparting high X-ray contrast in these glass compositions, the refractive index increases, and there is no organic component having a corresponding refractive index, and a composite restoration material excellent in aesthetics Can not get. Furthermore, since it contains no or only a small amount of fluorine, the effect of fluorine by sustained release of fluorine cannot be expected. The SiO in JP 2000-143430 _2: 20 to 45 wt% Al ₂ O _3: 5 to 35 wt% B ₂ O _3: 0 wt% Na ₂ O: 1 to 10 wt% K ₂ O : 0-8 wt% Cs ₂ O: 0-8 _{wt% Na 2 O + K 2 O} + Cs 2 O: 1~15 wt% CaO: 0-8 wt% SrO: from 0 to 27 wt% ZnO: 2 to 20 wt% ZrO _2: 2-10 wt% P ₂ O _5: 0 wt% La ₂ O _3: 0 wt% F: 2 to 20 _{wt% B 2 O 3 + ZnO +} ZrO 2 + La 2 O 3> consisting of 20 wt% A barium-free radiopaque dental glass is disclosed. It has been known for a long time that zinc has antibacterial properties, and its use is not preferred since zinc content in the glass composition may elute and adversely affect the human body. In particular, use in dental compositions should be avoided. The X-ray imaging property can be imparted to the glass not by a single element but by a plurality of elements. However, the addition of a plurality of elements to the glass composition increases the refractive index of the glass. Cannot give a proper translucency to the surface, which adversely affects the aesthetics. In this glass composition, ZrO, which is an essential component for imparting X-ray contrast, is used.
_{Even if 2} and ZnO are contained, the effect is still insufficient.

[0008] US Patent No. 4215033 discloses S
iO ₂ , Al ₂ O ₃ , B ₂ O ₃ as main components, SrO, Ca
A boroaluminosilicate glass consisting of two phases containing at least one of O, ZnO and ZrO ₂ is disclosed. Since this glass does not contain fluorine, it does not have a fluorine sustained release property. Further, when a high level of X-ray opacity is imparted to this glass composition, a low refractive index cannot be maintained due to the absence of fluorine, resulting in a problem that the composite restoration material becomes opaque. U.S. Patent No. 5304586 discloses SiO _2: 40 to 56 wt% Al ₂ O _3: 4~12 wt% B ₂ O _3: 5~12 wt% BaO: 15 to 35 wt% F: 2 to 20 wt% ZrO ₂ : 0-7 wt% SrO: 0 to 18 wt% and US patents to the 4,920,082 discloses SiO _2: from 41.1 to 55.9 wt% Al ₂ O _3: 5.6~11 wt% B ₂ O ₃ : 6.5 to 10.3% by weight BaO: 24.7 to 33.6% by weight F: 3 to 6% by weight BaO as an essential element imparting X-ray contrast
A fluorine-containing boroaluminosilicate glass containing is disclosed. Since BaO is generally known to be toxic and its safety to living organisms has not been established, its use should be avoided because it may cause harm to the human body. Further, the content of SiO ₂ is 40% by weight.
On the other hand, the content is large, but the content of Al ₂ O ₃ and B ₂ O ₃ is as very small as 12% by weight or less. As a result, the glass skeletal structure has brittleness, and when this glass is used as a filler in a composite restoration material, it cannot withstand various stresses such as occlusal pressure and the like, and marginal fracture and body fracture occur. There are problems such as.

Japanese Patent Publication No. 58-21887 discloses a dental filling composition comprising a polyester resin and a glass filler, which oxidizes lanthanum, hafnium, strontium and tantalum at the time of melting. Na ₃ AlF ₆ as a substance and a carbonate or a fluxing agent,
The use of CaF ₂ , SrF ₂ and TaF ₃ is described. The use of a fluxing agent for producing glass or imparting sustained release of fluorine and the use of the above compound for imparting X-ray contrast are certainly effective. However, in order to impart glass properties such as high fluorine sustained release, a flexible glass skeleton structure that does not break, durability that does not dissolve in water or acid, and transparency that is compatible with tooth material, the use of the above compounds alone is not sufficient. It is completely inadequate and merely a part of the properties of the glass. In order to impart various properties required in dental practice to glass, the glass composition consisting of the elements forming the glass and their amounts is important, but this glass composition alone has high fluorine sustained release properties and does not break Glass properties such as a flexible glass skeleton structure, durability that does not dissolve in water, acid, and the like, and transparency suitable for tooth material cannot be provided. Although it is possible to have these properties by controlling the elements forming the glass skeleton and their amounts, there has been no glass and composite restoration material containing the glass particles that have achieved such properties.

[0010]

An object of the present invention is to provide a dental filling which can be used as a filler in dental compositions used in the dental field, such as crown materials, filling materials, prosthetic materials and adhesive materials. Glass for X-ray imaging, transparency, sustained release of fluorine,
An object of the present invention is to provide a dental filling glass capable of imparting durability, abrasiveness, and abrasion resistance. Another object of the present invention is to provide a dental composition containing the dental filling glass particles.

[0011]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, by providing glass particles having a specific glass composition and a dental composition containing the glass particles, This led to solving this problem. That is, the present inventors provide the following inventions in the present application. Si as the element to form a glass skeleton, a fluorine-containing boroalumino SiO in glass ₂ including B and Al: 15.0 to 35.0 wt% B ₂ O _3: 5.0-20.0 wt% Al ₂ O _3: 15.0 to 30.0 wt% P ₂ O _5: 0 to 10.0 wt% BeO: 0 to 10.0% by weight MgO: 0 to 10.0 wt% CaO: 0 to 10.0 wt% X-ray opaque element oxide: 25.0 to 50.0% by weight Alkali metal oxide: 1.0 to 10.0% by weight F: 5.0 to 15.0% by weight ), And the molar ratio (based on oxide) of Si, B and Al elements forming the glass skeleton is Al ₂ O ₃ : SiO ₂ : B ₂ O ₃ = 1.00: 1.50
2.50: A dental filling glass characterized in the range of 0.50 to 1.50. More preferably, the X-ray imaging element oxide is Sr
O, the alkali metal oxide is Na ₂ O, and the molar ratio (based on oxide) of Si, B and Al elements forming the glass skeleton is Al ₂ O ₃ : SiO ₂ : B ₂ O ₃ = 1 0.00: 1.60-
2.10: A dental filling glass characterized by the range of 0.75-1.25. A glass for dental filling, wherein the refractive index of the glass is in the range of 1.45 to 1.70. The present invention also provides dental filling glass particles, wherein the glass has an average particle diameter in a range of 0.01 to 30 μm. Further, (a) the dental filling glass particles described above,
Provided is a dental composition comprising (b) a polymerizable monomer and (c) a polymerization catalyst.

The following effects are provided by the above-mentioned present invention. The dental filling glass of the present invention has a high glass sustained release performance by having a specific glass composition. In addition, barium is generally known to be toxic, and zinc is known to have antibacterial properties.However, it is suspected that such a toxic or harmful effect on the human body is contained in the dental filling glass composition of the present invention. It is a glass that is very safe for the human body without containing elements. When a glass contains a high concentration of an X-ray opaque element for the purpose of imparting X-ray opacity, the refractive index becomes high and it becomes difficult to use it in a dental composition. However, the dental filling glass of the present invention can impart high X-ray contrast while maintaining a low refractive index even when a high concentration of X-ray contrast elements is contained by the effect of the specific glass composition. . In particular, excellent characteristics were observed when a single component of an X-ray opaque element was contained at a high concentration. The dental filling glass of the present invention contains S in the glass skeleton structure.
By containing the three elements i, Al and B, and setting these three elements within a specific molar ratio (on an oxide basis), a hardness close to that of enamel can be obtained. Further, by including the glass particles in the dental composition, excellent wear resistance can be imparted. Further, excellent optical characteristics such as transparency and light transmittance can be imparted. Judging from the glass composition of the present invention, the durability of the glass is generally inferior, but it was found that the glass of the present invention was also excellent in durability, contrary to expectation.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The dental filling glass (hereinafter referred to as glass) of the present invention is a fluorinated boroaluminosilicate glass containing Si, B and Al as elements forming a glass skeleton. _2: 15.0 to 35.0 wt% B ₂ O _3: 5.0-20.0 wt% Al ₂ O _3: 15.0 to 30.0 wt% P ₂ O _5: 0 to 10.0 wt % BeO: 0 to 10.0% by weight MgO: 0 to 10.0% by weight CaO: 0 to 10.0% by weight X-ray imaging element oxide: 25.0 to 50.0% by weight Alkali metal oxide: It is characterized by having a glass composition containing 1.0 to 10.0% by weight F: 5.0 to 15.0% by weight.

The glass of the present invention contains SiO ₂ as a glass-forming oxide in a range of 15.0 to 35.0% by weight. The presence of SiO ₂ in the glass contributes to the formation of the glass skeleton and affects the glass melting temperature and the glass strength. When the content of SiO ₂ is small, crystallization easily occurs, and it is difficult to produce a transparent glass. Also S
When the content of iO ₂ is large, the melting point of the glass unfortunately increases and the content of other elements must be adjusted, which affects the glass properties of the present invention. In addition, Si
When the O ₂ content increases, the glass skeleton structure becomes strong and the glass hardness increases, which is different from the glass characteristics of the present invention.

The glass of the present invention contains Al ₂ O ₃ of 15.0 to ₃
It is contained in the range of 0.0% by weight and contributes to both the formation of the glass skeleton and the modification of the glass skeleton. Al ₂ O ₃ improves the durability and hardness of the glass and also contributes to the incorporation of fluorine into the glass. When the content of Al ₂ O ₃ is reduced, the durability of the glass is reduced, and a required amount of fluorine cannot be taken into the glass. On the other hand, when the content of Al ₂ O ₃ is increased, the melting temperature is increased, which causes problems in workability and the like. It also increases the tendency of the glass to devitrify.

B_TwoO_ThreeGenerally reduces the melting temperature
Used as a flux. But B _TwoO_ThreeIs heat and water resistant
Tends to deteriorate durability such as resistance and chemical resistance
Therefore, its use as a flux is limited to a small amount. Of the present invention
Glass is B_TwoO_ThreeIn the range of 5.0 to 20.0% by weight
To form and modify the glass skeleton
Contribute. B_TwoO_ThreeGlass skeleton bone with lower content
The case structure becomes stronger and the mechanical strength of the glass becomes stronger.
However, the softness that does not wear the opposing teeth which is the object of the present invention
Is difficult to maintain. Also, B_TwoO_ThreeContent
As the number increases, durability such as heat resistance, water resistance and chemical resistance will increase.
Tends to be worse.

Al ₂ O ₃ and B ₂ O ₃ , when compared to SiO ₂ , act as glass amphoteric oxides and contribute to both formation of the glass skeleton and modification of the glass skeleton. Since these contribute at different rates depending on the overall glass composition,
As a result, of course, the properties of the glass are greatly affected. The glass of the present invention contains Al, Si and B as elements forming a glass skeleton, and the molar ratio (based on oxide) of these three elements is Al ₂ O ₃ : SiO ₂ : B ₂ O ₃ = 1.00: 1.50-2.
50: 0.50 to 1.50. More preferably _{Al 2 O 3: SiO 2:} B 2 O 3 = 1.00: 1.60~2.
10: 0.75 to 1.25. SiO ₂ and B ₂ O ₃ with respect al ₂ O ₃
If the molar ratio is less than or greater than the above range, the various properties aimed at by the present invention cannot be imparted to the glass.
In particular, it has an effect on the hardness of the glass, and it is difficult to impart softness to the glass, which is an object of the present invention, so as not to wear the opposing teeth. One of the features of the glass of the present invention is that it has a hardness closer to the hardness of enamel in the dentin than the conventionally used silica-based filler.

The X-ray opaque element oxide is contained in the glass of the present invention in the range of 25.0 to 50.0% by weight. When the content of the X-ray opaque element oxide is small, sufficient X-ray opacity cannot be imparted to the glass. In addition, when the content of the X-ray opaque element oxide is large, there is a tendency to crystallize, the refractive index increases, or a problem occurs in durability. The imparting of X-ray contrast to the glass of the present invention can be achieved by including SrO, BaO, ZnO, ZrO ₂ , La ₂ O ₃ and other heavy metal element oxides. La ₂ O ₃ is not preferable because its effect is not so much recognized because its X-ray absorption ability is remarkably inferior to other X-ray contrast element oxides. In addition, BaO is generally known to be toxic to living organisms when eluted, and ZnO has an antibacterial effect, so there is a suspicion of adverse effects on the human body. The use of is also not preferred. More preferably, SrO having a high level of X-ray contrast is used as a single component.

The glass of the present invention contains F in the range of 5.0 to 15.0% by weight. It is generally known that F acts as a strong flux when melting glass. However, in the present invention, the presence of fluorine is effective in lowering the refractive index of glass. Furthermore, when the glass of the present invention is used as a filler for a dental composition and the composition is filled into a cavity of a tooth, fluorine is continuously released to the tooth around the filler for a long period of time. It has the effect of strengthening the tooth structure or suppressing secondary caries. To achieve these effects, a fluorine content of at least 5.0% by weight is required. In addition, when the fluorine content is increased, the rate at which the fluorine evaporates from the melt at the time of melting and scatters to the outside increases, which is not effective because it is not taken into the glass and has poor durability. In addition, the tendency of glass separation and crystallization during melting is remarkable and should be avoided.

The alkali metal oxide is contained in the glass of the present invention in the range of 1.0 to 10.0% by weight. Alkali metal oxides have the effect of lowering the refractive index and improving the transparency in addition to the effect of lowering the melting temperature. In the present invention, a new effect of promoting the sustained release of fluorine from glass was recognized by the presence of the alkali metal oxide. K ₂ O, Na ₂
O, Cs ₂ O, Li ₂ O and the like can be mentioned, and Na ₂ O is more preferable. When the content of the alkali metal oxide is less than 1.0% by weight, the above-described effects inherent in the alkali metal oxide cannot be obtained. In addition, when the content of the alkali metal oxide is large, the durability of the glass decreases.

As an optional component, BeO is added to the glass of the present invention.
, MgO, CaO and P ₂ O ₅ . Their contents are each in the range of 0 to 10% by weight. If their content is large, the tendency of the glass to separate increases, and the durability deteriorates. Therefore, the content should be minimized. Further, in the present invention, the above-mentioned element oxides are contained in respective contents, but element oxides other than the above-mentioned element oxides can be contained within a range not impairing the glass function or effect of the present invention. For example, elemental oxides having coloring properties and the like can be given.

The refractive index of the glass of the present invention is 1.45 to 1.45.
70, more preferably 1.50 to 1.60.
Range. When the composite restoration is filled into the cavity after the dental caries treatment formed on the tooth, the transparency of the composite restoration and the dentin surrounding the filled composite restoration must be close to each other. If the transparency of the two is different, the aesthetic requirement is not satisfied, and the repaired portion looks like a foreign substance, which causes a problem in terms of aesthetics. In order for the composite restorative material to have a transparency close to that of the tooth material, it is necessary to adjust the refractive index of the filler and the organic component such as a polymerizable monomer constituting the composite restoration material. However, when a filler having high X-ray contrast is used, since the refractive index of the filler is high,
The difference in refractive index from the later-described organic components such as polymerizable monomers generally used in the dental field becomes large, and it is difficult to maintain appropriate transparency. Therefore, in order to ensure appropriate transparency, the degree of X-ray contrast must be suppressed. The glass of the present invention has a relatively low refractive index while having high X-ray contrast, and is close to the refractive index of a known organic component such as a polymerizable monomer. When the glass of the present invention is used as a filler, it is possible to impart appropriate transparency to the composite material to the composite material. The glass of the present invention is in principle amorphous.
When a crystal structure is present in the glass, light transmittance is deteriorated, and the composite restoration material tends to be opaque. However, as long as the glass function or effect of the present invention is not impaired, there is no problem even if it has a crystal structure.

There is no particular limitation on the production of glass having the above-described glass composition, and any method such as a melting method or a sol-gel method can be used. There is no particular limitation on the type of mixed raw material used for producing glass, and any raw material such as an oxide, a carbonate, a nitrate, a fluoride, and an organometallic compound can be used. Generally, a method of manufacturing by a melting method using a melting furnace is preferable from the viewpoint of ease of glass design and workability. When manufacturing in a melting furnace, it is necessary to melt the mixed raw materials at a high temperature and flow it out of the melting furnace at the stage of forming the glass melt, so the melting temperature is low and the viscosity of the glass melt is low. A lower one is preferred. In order to obtain such a situation, raw materials can be appropriately selected. The glass composition of the present invention can be confirmed by using instrumental analysis such as elemental analysis, Raman spectrum, and X-ray fluorescence analysis. Further, the theoretical value can be easily calculated from the raw material mixing amount at the time of raw material mixing. The glass composition of the present invention only needs to match either the theoretical value or the measured value.

After production, the glass of the present invention can be formed into particles by a known method. As a method for forming particles, any method such as wet or dry pulverization, classification and sieving can be used without any limitation, and it can be appropriately selected according to the average particle diameter of the desired particles. For example, the particles may be formed using a container driving medium mill such as a ball mill or a vibration mill, a pulverizing medium stirring mill such as an attritor, a sand grinder, an aniler mill, or a tower mill, or a jet mill. Further, there is no limitation even if drying steps such as vacuum, heating and freezing are used together. The average particle diameter of the glass particles of the present invention is in the range of 0.01 to 30 μm, and preferably in the range of 0.01 to 10.0 μm. More preferably, it is in the range of 0.01 to 5.0 μm. The average particle size of the glass particles can impart properties necessary for the dental composition, such as abrasiveness, surface smoothness after polishing, and gloss. It is known that these properties are generally excellent when the average particle diameter is small. However, the glass of the present invention is also a feature of the present invention in that, due to the effect of the specific glass composition, even if the average particle diameter of the glass is large, excellent polishing properties, surface smoothness after polishing and glossiness are imparted. . Further, the shape of the glass particles may be any shape such as a sphere, a plate, a crushed shape, and a scale, and is not particularly limited, but is more preferably a sphere.

Further, recently, it has been known that, when a dental composition containing hard inorganic particles, for example, silica-based particles, is filled in a cavity formed in the tooth material after caries treatment, the opposing tooth is worn. However, when the dental composition containing the glass particles of the present invention is filled, it is also an excellent feature that the opposing teeth are not worn due to the glass properties of the present invention. The glass particles of the present invention can be used for a dental composition by treating the surface of the particles by a known method. Examples include surfactants, fatty acids, organic acids, inorganic acids, silane coupling agents, titanate coupling agents, polysiloxanes, and the like. These surface treatment methods are preferable in that they improve the wettability between the organic component and the glass particle surface and impart excellent properties to the dental composition, and the surface treatment can be appropriately selected according to the required properties. . Further, there is no limitation even if a special surface treatment agent and / or a special surface treatment method is used on the surface of the glass particles for the purpose of making the glass particles multifunctional. Further, organic-inorganic composite particles can be prepared by a known method using the glass particles of the present invention and used for a dental composition. For example, a method of microencapsulating or grafting the surface of glass particles with an organic substance, a method of radically polymerizing after introducing a polymerizable functional group or a polymerizable initiation group on the surface of the glass particles, a method of preparing a polymer bulk containing glass particles generated in advance. There are a pulverizing method and a method of producing particles by emulsion polymerization, suspension polymerization and dispersion polymerization in a state where a polymerizable monomer and glass particles coexist. These methods can be appropriately selected as needed.

Another embodiment of the present invention is a dental composition containing the above-mentioned glass particles of the present invention. In particular, it is a dental composition containing (a) the glass particles of the present invention, (b) a polymerizable monomer, and (c) a polymerization initiator. By including the glass particles of the present invention, the dental composition can be imparted with excellent properties of glass, such as X-ray contrast, transparency, sustained release of fluorine, durability, polishing, and abrasion resistance. .

The polymerizable monomers that can be used in the dental composition together with the glass particles of the present invention include known monofunctional and polyfunctional polymerizable monomers generally used as dental compositions. It can be used from monomers. A typical example that is generally preferably used is a polymerizable monomer having an acryloyl group and / or a methacryloyl group. In the present invention, both the acryloyl group-containing polymerizable monomer and the methacryloyl group-containing polymerizable monomer are represented by (meth) acrylate or (meth) acryloyl. A specific example is as follows. Monofunctional monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate,
Hexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate,
Lauryl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, allyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, glycerol (meth) acrylate, isobonyl (meth) ) Acrylate compounds such as acrylates, silane compounds such as γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane, 2- (N, N-dimethylamino) ) Ethyl (meth) acrylate, N-methylol (meth) acrylamide,
Nitrogen-containing compounds such as diacetone (meth) acrylamide, aromatic bifunctional monomer: 2,2-bis (4- (meth)
Acryloyloxyphenyl) propane, 2,2-bis (4- (3- (meth) acryloyloxy-2-hydroxypropoxy) phenyl) propane, 2,2-bis (4- (meth) acryloyloxyethoxyphenyl)
Propane, 2,2-bis (4- (meth) acryloyloxydiethoxyphenyl) propane, 2,2-bis (4
-(Meth) acryloyloxytetraethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxypentaethoxyphenyl) propane, 2,2-
Bis (4- (meth) acryloyloxydipropoxyphenyl) propane, 2 (4- (meth) acryloyloxyethoxyphenyl) -2 (4- (meth) acryloyloxydiethoxyphenyl) propane, 2 (4- (meth) Acryloyloxydiethoxyphenyl) -2 (4
-(Meth) acryloyloxytriethoxyphenyl)
Propane, 2 (4- (meth) acryloyloxydipropoxyphenyl) -2 (4- (meth) acryloyloxytriethoxyphenyl) propane, 2,2-bis (4
-(Meth) acryloyloxydipropoxyphenyl)
Propane, 2,2-bis (4- (meth) acryloyloxyisopropoxyphenyl) propane, etc.

Aliphatic difunctional monomers: 2-hydroxy-3-acryloyloxypropyl methacrylate, neopentyl glycol di (meth) hydroxypivalate
Acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate,
Triethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,3-butanediol di ( Trifunctional monomers such as (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and glycerin di (meth) acrylate: trimethylolpropane tri (meth)
Acrylate, trimethylolethane tri (meth) acrylate, trimethylol methane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, etc. Tetrafunctional monomer: pentaerythritol tetra (meth)
Specific examples of acrylates, ditrimethylolpropanetetra (meth) acrylate, and the like, and urethane-based polymerizable monomers; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate; 3-chloro-2 A polymerizable monomer having a hydroxyl group such as hydroxypropyl (meth) acrylate, methylcyclohexane diisocyanate, methylene bis (4-cyclohexyl isocyanate), hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, diisocyanate methyl methylbenzene, 4, Having a difunctional or trifunctional or higher urethane bond derived from an adduct with a diisocyanate compound such as 4-diphenylmethane diisocyanate Distearate (meth) acrylate. In addition to the (meth) acrylate-based polymerizable monomer, other polymerizable monomers depending on the purpose of the dental composition, for example, a monomer, oligomer or oligomer having at least one polymerizable group in the molecule. There is no limitation even if a polymer is used. In addition, there is no problem even if a substituent such as an acidic group or a fluoro group is present in the same molecule.

In the present invention, the polymerizable monomer includes not only a single component but also a mixture of a plurality of polymerizable monomers. When the viscosity of the polymerizable monomer is extremely high at room temperature or when it is solid, it is preferable to use the polymerizable monomer in combination with a polymerizable monomer having a low viscosity as a mixture of the polymerizable monomers. This combination is not limited to two types, and may be three or more types. Further, since a polymer composed of only a monofunctional polymerizable monomer does not have a crosslinked structure, the mechanical strength of the polymer generally tends to be inferior. for that reason,
When a polymerizable monomer is used, it is preferably used together with a polyfunctional polymerizable monomer. The most preferred combination of polymerizable monomers is a method in which an aromatic compound of a bifunctional polymerizable monomer is used as a main component and an aliphatic compound of a bifunctional polymerizable monomer is used. Specifically, 2,2-bis (4- (3-methacryloyloxy-2-hydroxypropoxy) phenyl) propane (Bis-GMA) and / or dimethacryloyloxyethyl-2,2,4
-A combination of trimethylhexamethylene-1,6-dicarbamate (UDMA) and triethylene glycol dimethacrylate (TEGDMA).

When the dental composition containing the glass particles of the present invention is provided with tooth or base metal adhesiveness, a part or all of the polymerizable monomer may be a phosphoric acid group, a carboxylic acid group, a sulfonic acid group or the like. It is effective to use a polymerizable monomer containing an acid group in the molecule. In order to improve the noble metal adhesion, it is also effective for the present invention to use a polymerizable monomer containing a sulfur atom in the molecule. Specific examples of these polymerizable monomers having an adhesive ability are as follows. Carboxylic acid group-containing polymerizable monomer: (meth) acrylic acid,
1,4-di (meth) acryloyloxyethyl pyromellitic acid, 6- (meth) acryloyloxynaphthalene-
1,2,6-tricarboxylic acid, N- (meth) acryloyl-p-aminobenzoic acid, N- (meth) acryloyl-5
-Aminosalicylic acid, 4- (meth) acryloyloxyethyl trimellitic acid and its anhydride, 4- (meth)
Acryloyloxybutyl trimellitic acid and its anhydride, 2- (meth) acryloyloxybenzoic acid, β-
(Meth) acryloyloxyethyl hydrogen succinate, β- (meth) acryloyloxyethyl hydrogen maleate, 11- (meth) acryloyloxy-1,1-undecanedicarboxylic acid, p-vinylbenzoic acid and the like.

Phosphoric acid group-containing monomer: 2- (meth) acryloyloxyethyl dihydrogen phosphate,
3- (meth) acryloyloxypropyl dihydrogen phosphate, 10- (meth) acryloyloxydecyl dihydrogen phosphate, bis (2-
(Meth) acryloyloxyethyl) hydrogen phosphate, 2- (meth) acryloyloxyethyl phenyl hydrogen phosphate and the like. Sulfonic acid group-containing monomer: 2- (meth) acrylamide-2-methylpropanesulfonic acid, 4- (meth) acryloyloxybenzenesulfonic acid, 3- (meth) acryloyloxypropanesulfonic acid and the like. Polymerizable monomer containing a sulfur atom: (meth) acrylate having a triazine thiol group, (meth) acrylate having a mercapto group, (meth) acrylate having a polysulfide group, (meth) having a thiophosphate group
Examples include acrylate, (meth) acrylate having a disulfide cyclic group, (meth) acrylate having a mercaptodithiazole group, (meth) acrylate having a thiouracil group, and (meth) acrylate having a thiirane group. There is no problem even if these polymerizable monomers are used alone or in combination of two or more.

The polymerization initiator that can be used in the dental composition together with the glass particles of the present invention is not particularly limited, and a known radical generator can be used without any limitation.
The polymerization initiator is generally one that initiates polymerization by mixing immediately before use (chemical polymerization initiator), one that initiates polymerization by heating or heating (thermal polymerization initiator), and one that initiates polymerization by light irradiation. (Photopolymerization initiator). Examples of the chemical polymerization initiator include a redox-type polymerization initiation system composed of an organic peroxide / amine compound or an organic peroxide / amine compound / sulfinate, an organic peroxide / amine compound / borate compound, and oxygen and water. Organometallic type polymerization initiator system that initiates polymerization by reacting,
Further, the sulfinic acid salts and the borate compounds can also initiate polymerization by reacting with a polymerizable monomer having an acidic group. Specific examples of the organic peroxide include benzoyl peroxide, parachlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, acetyl peroxide, lauroyl peroxide, tertiary butyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane,
2,5-dihydroperoxide, methyl ethyl ketone peroxide, tertiary butyl peroxybenzoate, and the like. As the amine compound,
A secondary or tertiary amine in which an amine group is bonded to an aryl group is preferred, and specific examples include p-N, N'-dimethyl-toluidine, N, N'-dimethylaniline,
N′-β-hydroxyethyl-aniline, N, N′-di (β-hydroxyethyl) -aniline, pN, N′-
Di (β-hydroxyethyl) -toluidine, N-methyl-aniline, pN-methyl-toluidine and the like.

Specific examples of the sulfinates include sodium benzenesulfinate, lithium benzenesulfinate, sodium p-toluenesulfinate and the like. As the borate compound,
Trialkylphenylboron, trialkyl (p-fluorophenyl) boron (alkyl group is n-butyl group, n-
Octyl group, n-dodecyl group, etc.), lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt and the like. In addition, as the organometallic polymerization initiator,
Organic boron compounds such as triphenylborane, tributylborane, and tributylborane partial oxide are exemplified. As the thermal polymerization initiator by heating or heating, azo compounds such as azobisisobutyronitrile, methyl azobisisobutyrate and azobiscyanovaleric acid are preferably used in addition to the above-mentioned organic peroxides. On the other hand, examples of the photopolymerization initiator include those composed of a photosensitizer, and a photosensitizer / photopolymerization accelerator.

Specific examples of the photosensitizer include:
Benzyl, camphorquinone, α-naphthyl, acetonaphthene, p, p′-dimethoxybenzyl, p, p′-dichlorobenzylacetyl, pentanedione, 1,2-phenanthrenequinone, 1,4-phenanthrenequinone,
Α-diketones such as 3,4-phenanthrenequinone, 9,10-phenanthrenequinone and naphthoquinone; benzoin alkyl ethers such as benzoin, benzoin methyl ether and benzoin ethyl ether; thioxanthone, 2-chlorothioxanthone and 2-methylthioxanthone; 2-isopropylthioxanthone, 2-methoxythioxanthone, 2-hydroxythioxanthone, 2,
Thioxanthones such as 4-diethylthioxanthone and 2,4-diisopropylthioxanthone, benzophenones such as benzophenone, p-chlorobenzophenone and p-methoxybenzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6 Acylphosphine oxides such as -dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, 2-benzyl-dimethylamino-1- (4-morpholinophenyl) -butanone-1,
Α-aminoacetophenones such as 2-benzyl-diethylamino-1- (4-morpholinophenyl) -propanone-1, benzyldimethylketal, benzyldiethylketal, benzyl (2-methoxyethylketal)
Bis (cyclopentadienyl) -bis
[2,6-difluoro-3- (1-pyrrolyl) phenyl]
-Titanium, bis (cyclopentadienyl) -bis (pentanefluorophenyl) -titanium, bis (cyclopentadienyl) -bis (2,3,5,6-tetrafluoro-
And titanocenes such as 4-disiloxyphenyl) -titanium.

Specific examples of the photopolymerization accelerator include N, N-dimethylaniline, N, N-diethylaniline, N, N-di-n-butylaniline, N, N-dibenzylaniline, p- N, N-dimethyl-toluidine, m-
N, N-dimethyl-toluidine, p-N, N-diethyl-
Toluidine, p-bromo-N, N-dimethylaniline,
m-chloro-N, N-dimethylaniline, p-dimethylaminobenzaldehyde, p-dimethylaminoacetophenone, p-dimethylaminobenzoic acid, p
-Dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid amino ester, N, N-dimethylanthranilic acid methyl ester, N, N-dihydroxyethylaniline,
p-N, N-dihydroxyethyl-toluidine, p-dimethylaminophenyl alcohol, p-dimethylaminostyrene, N, N-dimethyl-3,5-xylidine, 4-
Dimethylaminopyridine, N, N-dimethyl-α-naphthylamine, N, N-dimethyl-β-naphthylamine,
Tributylamine, tripropylamine, triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, N, N-dimethylhexylamine, N,
N-dimethyldodecylamine, N, N-dimethylstearylamine, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate,
Tertiary amines such as 2,2 '-(n-butylimino) diethanol; secondary amines such as N-phenylglycine; 5-butylbarbituric acid; 1-benzyl-5-phenylbarbituric acid; Tin compounds such as barbituric acids, dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, dioctyltin diversate, dioctyltin bis (isooctyl mercaptoacetate) salt, and tetramethyl-1,3-diacetoxydistannoxane , Lauryl aldehyde,
Aldehyde compounds such as terephthalaldehyde, dodecyl mercaptan, 2-mercaptobenzoxazole,
Examples thereof include sulfur-containing compounds such as 1-decanethiol and thiosalicylic acid. Further, in order to improve the photopolymerization accelerating ability, in addition to the photopolymerization accelerator, citric acid, malic acid,
Addition of oxycarboxylic acids such as tartaric acid, glycolic acid, gluconic acid, α-oxyisobutyric acid, 2-hydroxypropanoic acid, 3-hydroxypropanoic acid, 3-hydroxybutanoic acid, 4-hydroxybutanoic acid, dimethylolpropionic acid is effective It is a target.

These polymerization initiators can be used alone or in combination of two or more. Further, they can be used in combination regardless of the polymerization form or the type of polymerization initiator. The amount of the polymerization initiator to be added may be appropriately selected according to the intended use. Generally, 0.1 to polymerizable monomer.
It may be selected from the range of 1 to 10 parts by weight. Among the polymerization initiators described above, it is a preferred embodiment to use a photopolymerization initiator that generates a radical by light irradiation, and is most preferable in that the dental composition can be polymerized in a state where air is little mixed. It is preferably used. Further, among the photopolymerization initiators, a combination of α-diketone and tertiary amine is more preferable, and an aromatic amine in which an amino group such as camphorquinone and ethyl pN, N-dimethylaminobenzoate is directly bonded to a benzene ring is preferable. Alternatively, a combination of an aliphatic amine having a double bond in a molecule such as N, N-dimethylaminoethyl methacrylate is most preferable. In addition, depending on the intended use, coumarin-based, cyanine-based, thiazine-based sensitizing dyes, halomethyl group-substituted -s-triazine derivative, diphenyliodonium salt compound or the like by irradiation of Brönsted acid or Lewis acid. The resulting photoacid generator, quaternary ammonium halides, transition metal compounds and the like can also be used as appropriate. A second filler other than the glass particles of the present invention can be blended as a dental composition. As the second filler, those known as dental fillers, for example, quartz, amorphous silica, clay, aluminum oxide, talc, mica, kaolin, glass, barium sulfate, zirconium oxide, titanium oxide, silicon nitride, aluminum nitride , Titanium nitride, silicon carbide, boron carbide, calcium carbide, hydroxyapatite, inorganic substances such as calcium phosphate; polymethyl methacrylate, polyethyl methacrylate, polyvinyl chloride,
Organic substances such as polymers or oligomers such as polystyrene, polyester, and nylon; and organic-inorganic composites can be suitably used. There is no problem even if the second filler is used alone or in combination of two or more. In addition, it is more preferable that the second filler is generally surface-treated with a titanate coupling agent, an aluminate coupling agent, or a silane coupling agent which is commonly used. The mixing ratio of the second filler can be appropriately selected as needed, and may be selected, for example, from a range of 1 to 90 parts by weight.

Further, in the dental composition, an ultraviolet absorber such as 2-hydroxy-4-methylbenzophenone, and polymerization of hydroquinone, hydroquinone monomethyl ether, 2,5-ditert-butyl-4-methylphenol and the like are included. Inhibitors, anti-tarnish agents, antibacterial agents, coloring pigments,
Other conventionally known components such as additives can be optionally added as needed. Packaging form of the dental composition of the present invention,
There is no particular limitation, and any one of a one-pack packaging form and a two-pack packaging form or any other form is possible depending on the type of polymerization initiator or purpose of use, and can be appropriately selected according to the application.

[0038]

EXAMPLES Hereinafter, the present invention will be described in more detail and specifically with reference to Examples, but the present invention is not limited thereto. The performance evaluation methods of the glass particles and the dental composition employed in the following examples are as follows. Refractive index measurement Evaluation purpose: To evaluate the refractive index of glass particles. Evaluation method: Several kinds of immersion liquids for refractive index measurement having an arbitrary refractive index were prepared using tricresyl phosphate and dioctyl adipate (both manufactured by Daihachi Chemical Industry Co., Ltd.).
Examples 1 to 8 and Comparative Examples 2, 4,
After collecting a small amount of the glass particles generated in Steps 7 to 10, several drops of the prepared immersion liquid were added dropwise, mixed uniformly, and covered with a cover glass to obtain a test specimen for measurement. The test specimen for measurement was placed on a stage of a polarizing microscope (manufactured by Nikon Corporation: 400 times), and the refractive index (23 ° C.) of the glass particles was measured by the Becke line method. In addition, the measurement was performed about ten different glass particles in the same measurement test body, and the average value was calculated | required.

(2) Bending test evaluation purpose: The bending strength of the dental composition test specimen is evaluated. Evaluation method: After filling the prepared dental composition into a stainless steel mold, placing a cover glass on both sides and pressing it with a glass plate, and using a photopolymerization irradiator (Griplight II: manufactured by Shofu Co., Ltd.) Light irradiation was carried out for 30 seconds each time to cure. After curing, the cured product was taken out of the mold, and the back surface was irradiated with light again in the same manner.
mm: rectangular parallelepiped). The test piece was immersed in water at 37 ° C. for 24 hours and then subjected to a bending test. The bending test was performed using an Instron universal tester (Instron 5567, manufactured by Instron) at a distance between fulcrums of 20 mm and a crosshead speed of 1 mm / min. In addition, the test was performed with 10 test pieces, and the average value was evaluated.

(3) Durability test (bending test after long-term immersion in water) Evaluation purpose: To evaluate the bending strength of a dental composition specimen after long-term immersion in water. Evaluation method: After filling the prepared dental composition into a stainless steel mold, placing a cover glass on both sides and pressing it with a glass plate, and using a photopolymerization irradiator (Griplight II: manufactured by Shofu Co., Ltd.) Light irradiation was carried out for 30 seconds each time to cure. After curing, the cured product was taken out of the mold, and the back surface was irradiated with light again in the same manner.
mm: rectangular parallelepiped). The test piece was immersed in water at 37 ° C. for 3 weeks and then subjected to a bending test. The bending test was performed using an Instron universal tester (Instron 5567, manufactured by Instron) at a distance between fulcrums of 20 mm and a crosshead speed of 1 mm / min. In addition, the test was performed with 10 test pieces, and the average value was evaluated.

(4) Fluorine sustained release test evaluation purpose: To evaluate the amount of fluorine sustained release from the dental composition test specimen. Evaluation method: After filling the prepared dental composition into a stainless steel mold, placing a cover glass on both sides and pressing it with a glass plate, and using a photopolymerization irradiator (Griplight II: manufactured by Matsukaze Co., Ltd.) The paste was cured by irradiating light at 30 places for 30 seconds. After curing, remove the cured product from the mold,
It was a test body (15φ × 1 mm: disk-shaped). Put the specimen in a plastic container containing 5 ml of distilled water,
After sealing, it was left in a 37 ° C. thermostat for 1 week. After standing for one week, the container was taken out of the thermostat, and the amount of fluorine eluted from the disc-shaped test piece into the distilled water was measured using a fluorine ion composite electrode (Mo).
Del 96-09: Orion Research) and an ion meter (Model 720A: Orion Research). At the time of measurement, 0.5% of TISABIII (manufactured by Orion Research) was used as an ionic strength modifier.
ml was added. In addition, the calibration curve was created in 0.02, 0.1,
The test was performed using 1, 10, and 50 ppm standard solutions. In addition,
The test was performed with five test pieces, and the average value was evaluated.

(5) X-ray contrast test evaluation purpose: To evaluate the X-ray contrast performance of a dental composition test specimen. Evaluation method: After filling the prepared dental composition into a stainless steel mold, placing a cover glass on both sides and pressing it with a glass plate, and using a photopolymerization irradiator (Griplight II: manufactured by Matsukaze Co., Ltd.) The paste was cured by irradiating light at 30 places for 30 seconds. After curing, remove the cured product from the mold,
A test body (15 φ × 2 mm: disk-shaped) was used. An aluminum plate having a thickness different from that of the test piece is placed on an X-ray film (DIF100, manufactured by Hanshin R & D Laboratories) installed in an X-ray inspection apparatus (DCX-100N, manufactured by Asahi Xentogen Co., Ltd.). X-ray irradiation was performed under the condition of time: 0.4 seconds. After the irradiation, the X-ray film was developed and fixed using a fixing solution and a fixing solution (manufactured by Hanshin Institute of Technology: DQD), and dried. After drying, a densitometer (Konica:
Using PDA-100), the thickness of an aluminum plate having the same X-ray contrast as the test specimen was determined. Note that aluminum plates having different thicknesses at 0.5 mm intervals were used.
In addition, the test was performed with three test pieces, and the average value was evaluated.

(6) Evaluation of Impact Rotation Abrasion Test Purpose: To evaluate the amount of self-wear and the amount of wear against enamel of a dental composition specimen. Evaluation method: An evaluation method will be described below with reference to FIGS. In the drawings, 1 is an upper specimen (cured dental composition), 2 is a lower specimen, 3 is bovine enamel, 4 is a brass ring, and 5 is an epoxy resin. After filling the prepared dental composition into a stainless steel mold, a cover glass was placed on the mold and pressed against a glass plate, and then pressed using a photopolymerization irradiator (Grip Light II: manufactured by Matsukaze Co., Ltd.). From 3
Light irradiation was performed for 0 seconds to cure the paste. After curing,
After taking out the cured product from the mold, light irradiation was similarly performed for 30 seconds from both directions on the side surface of the cured product, and this was used as an upper test body (bombshell type: dimensions, FIG. 1) for the impact rotation wear test. The length of the specimen was measured using a micrometer.
Moreover, after removing the root part of the extracted cow front tooth, a test piece (5 × 5 × 3 mm: rectangular parallelepiped) was formed using a cutting tool, and then placed in a brass ring 4 (12φ × 15 mm), and epoxy resin was used. Embedded. After the epoxy resin was cured, the bovine tooth enamel 3 embedded in the epoxy resin 5 whose test surface was polished with Sandpaper # 600 and # 1200 was used as the lower test body (FIG. 2) for the impact rotation wear test. The upper and lower specimens were mounted on a collision rotation wear tester, respectively, and a collision rotation wear test was performed. FIG. 3A and FIG.
b. As shown in FIGS. 3a and 3b, the test was performed with one cycle of collision (FIG. 3a) and rotation (FIG. 3b). After the test, the length of the upper specimen was measured using a micrometer, and the wear depth of the lower specimen was measured using a profilometer (SE-30H, manufactured by Kosaka). The amount of change in the length changed by the abrasion of the upper specimen was defined as the amount of self-wear, and the depth of the lower specimen generated by the abrasion was defined as the amount of paired enamel abrasion. The impact rotation wear test was performed under the conditions of impact load: 7.5 kgF, rotation angle: ± 15 ° (reciprocation), cycle: 10,000 times, immersion in water at 37 ° C. The test was performed using six test pieces, and the average value was used for evaluation. The rotation angle refers to an angle at which the upper specimen is rotated around the vertical axis in one direction and then in the opposite direction after the collision (see FIG. 3B).

(7) Transparency test evaluation purpose: To evaluate the light transmittance of the dental composition test specimen. Evaluation method: After filling the prepared dental composition into a stainless steel mold, placing a cover glass on both sides and pressing it with a glass plate, and using a photopolymerization irradiator (Griplight II: manufactured by Matsukaze Co., Ltd.) The paste was cured by irradiating light at 30 places for 30 seconds. After curing, the cured product (25φ × 1
mm: disk-shaped) and polished in order using sandpaper # 600 and # 1200 to obtain a thickness of 0.8.
mm, which was used as a test specimen (25 φ × 0.8 mm: disk shape). Next, the surface of the test piece was mirror-finished by buffing, and then the test piece was attached to a haze meter (HM-150, manufactured by Murakami Color Research Laboratory), and the total light transmittance was measured. In addition, the test was performed with three test pieces, and the average value was evaluated. The total light transmittance of the air layer was set to 100%.

Examples 1-8 and Comparative Examples 1-10 Oxides such as silica sand, kaolin, aluminum hydroxide, aluminum oxide, cryolite, sodium carbonate, strontium carbonate, aluminum fluoride, sodium fluoride, carbonates and the like Example 1 in Table 1 using raw materials such as fluoride
The theoretical values were calculated so that the respective glass compositions of Comparative Examples 1 to 8 and Comparative Examples 1 to 10 were obtained, and the respective raw materials were weighed. After weighed various raw materials are uniformly mixed using a ball mill to prepare a raw material mixture, the raw material mixture is placed in a melting furnace at 1250.
Melted at １1400 ° C. Thereafter, the melt was taken out of the melting furnace and cooled on a cold steel plate, in a roll or in water to produce glass. Table 1 shows the melting state and the appearance of the produced glass in each of the examples and comparative examples. Next, the produced glass was pulverized for 10 hours using a vibration mill to obtain glass particles having an average particle diameter of 3.0 μm. Using the glass particles, the refractive index (23 ° C.) of the glass was measured according to a conventional method. Then, 9 parts by weight of γ-methacryloyloxypropyltrimethoxysilane (hereinafter referred to as γ)
-MPS) to obtain a silane-treated glass filler.

Preparation of resin composition 2,2-bis (4- (3-methacryloyloxy-60 parts by weight 2-hydroxypropoxy) phenyl) propane (Bis-GMA) Triethylene glycol dimethacrylate (TEGDMA) 40 parts by weight Camphor Resin composition comprising 0.3 parts by weight of quinone 2 parts by weight of ethyl pN, N-dimethylaminobenzoate 18 parts by weight of ultrafine silica (thickener) was prepared.

Preparation of Dental Composition After kneading at a ratio of 300 parts by weight of the silane-treated glass filler produced in Examples 1 to 8 and Comparative Examples 2, 4 and 7 to 10 parts by weight of the resin composition. By defoaming, paste-like dental compositions A to N were prepared. (Table 1)

Test 1 Using the prepared dental compositions A, C, I, J and N, a bending test, a durability test and an impact rotational wear test were conducted in accordance with the evaluation methods described above. Table 2 shows the test results.
It was shown to. Test 2 Using the prepared dental compositions C, D, K, and L, a fluorine sustained release test was performed according to the evaluation method described above. Table 3 shows the test results. Test 3 Using the prepared dental compositions C, E, F, G, H and M, an X-ray contrast test and a transparency test were performed in accordance with the evaluation methods described above. Table 4 shows the test results.

[0049]

[Table 1]

[0050]

[Table 2]

[0051]

[Table 3]

[0052]

[Table 4]

[0053]

The present invention is a dental filling glass having a specific glass composition which can be used for a dental composition. By including the glass particles as a filler in the dental composition, excellent X-ray contrast properties, It can impart transparency, sustained release of fluorine, durability, abrasiveness and abrasion resistance.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view showing an upper specimen (cured dental composition) used in a collision rotational wear test.

FIG. 2 is a cross-sectional view showing a lower test body (cow enamel embedded) used in the impact rotational wear test.

FIGS. 3A and 3B are schematic diagrams showing a procedure of a collision rotational wear test, wherein FIG. 3A is a schematic diagram showing a collision, and FIG. 3B is a schematic diagram showing rotation.

[Explanation of symbols]

 1: Upper specimen (cured dental composition) 2: Lower specimen 3: Bovine enamel 4: Brass ring 5: Epoxy resin

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Mitsuharu Mizuno 11th Fukuinakami Takamatsucho, Higashiyama-ku, Kyoto-shi, Kyoto Prefecture Shofunai Co., Ltd. F-term (reference)

Claims (5)

[Claims] 1. A glass skeleton comprising Si,
SiO ₂ with fluorine-containing boro aluminosilicate glass containing B and Al: from 15.0 to 35.0 wt% B ₂ O _3: 5.0~20.0 wt% Al ₂ O _3: 15.0~30.0 wt% P ₂ O _5: 0~10.0 wt% BeO: 0 to 10.0 wt% MgO: 0 to 10.0 wt% CaO: 0 to 10.0 wt% X-ray contrast property element oxides: 25 0.0 to 50.0% by weight Alkali metal oxide: 1.0 to 10.0% by weight F: 5.0 to 15.0% by weight The molar ratio (based on the oxide) of Si, B and Al elements is as follows: Al ₂ O ₃ : SiO ₂ : B ₂ O ₃ = 1.00: 1.50
2.50: The glass for dental filling, which is in the range of 0.50 to 1.50. 2. The X-ray imaging element oxide is SrO,
The alkali metal oxide is Na ₂ O, and the molar ratio (based on the oxide) of Si, B and Al elements forming the glass skeleton is Al ₂ O ₃ : SiO ₂ : B ₂ O ₃ = 1.00: 1. .60-
2.10: The dental filling glass according to claim 1, wherein the ratio is in the range of 0.75 to 1.25. 3. The glass has a refractive index of 1.45 to 1.70.
The dental filling glass according to claim 1 or 2, wherein 4. The glass particles for dental filling according to claim 1, wherein the average particle diameter is in a range of 0.01 to 30 μm. 5. A dental composition comprising (a) the glass particles for dental filling according to any one of claims 1 to 4, (b) a polymerizable monomer, and (c) a polymerization catalyst.