JP2000336011A - Composition for dentistry - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a dental composition which gives a cured product having excellent surface gloss, excellent transparency and excellent mechanical characteristics, has excellent operability and curability, and has an excellent X-ray contrast image property, by compounding a specific (meth)acrylate monomer, a filler comprising specific particulate silica and specific X-ray imaging glass powder, and a polymerization initiator. SOLUTION: This dental composition comprises (A) a (meth)acrylate monomer [for example, methyl (meth)acrylate], (B) a filler comprising (i) particulate silica having an average particle diameter of <0.01 μm and (ii) X-ray imaging glass powder, wherein the content of particles having particle diameters of >=0.01 μm in the component (i) is <=40 wt.%, and (C) a polymerization initiator (for example, acetyl peroxide). The difference between the refractive index of the component (ii) and the refractive index of the cured product of the component (A) is <=0.05. In the composition, the components (i), the component (ii) and the component C are preferably contained in amounts of 1 to 100 pts.wt., 50 to 1,000 pts.wt., and 0.001 to 10 pts.wt., respectively, per 100 pts.wt. of the component A.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to dental compositions. More specifically, the present invention can form a cured product having excellent surface lubricity, transparency, and mechanical properties, and furthermore, has excellent operability and curability (particularly, photocurability) of the composition itself. To a composition for use. The invention further relates to a dental composition, preferably having excellent X-ray contrast properties.

[0002]

2. Description of the Related Art Conventionally, as a filler used for a dental composition such as a composite resin, a hard resin or an artificial tooth, for example, as disclosed in Japanese Patent Application Laid-Open No. 5-194135, an average particle size of 0 is disclosed. Pulverized glass powder of 0.1 to 5 μm and / or silica fine particles having an average particle diameter of 0.01 to 0.04 μm are used. In such a dental composition, the treatment state is often confirmed by X-ray photography at the time of dental treatment. Therefore, the crushed glass powder contained in the dental composition includes an X-ray at the time of dental treatment. A powder obtained by pulverizing glass containing barium, strontium, or the like having X-ray contrast so as to enable imaging is used. The crushed glass powder is generally manufactured, for example, by crushing the above-mentioned glass. However, it is difficult to crush glass into small pieces using the conventional glass crushing technology.
Glass powder of about 10 μm to about 10 μm is used.

However, it is very difficult to form a glossy finished surface clinically similar to natural teeth using a dental composition containing such a glass powder having a large particle diameter. Was. In order to solve such a problem containing such a glass powder, recently, the average particle size is 2
Composite resins and the like using finely ground glass having a size of μm or less have been developed. As described above, in the composite resin using the finely ground glass, although the surface gloss, which has been regarded as a disadvantage of the composite resin using the conventional ground glass powder, is improved, the dental composition containing such ground glass powder includes: There are many points to be improved with respect to operability, transparency, photocurability, X-ray contrast, and the like.

[0004] In particular, with regard to operability, in a dental composition to which only ground glass powder is added, there is a problem that the paste often becomes sticky, and the paste becomes sticky and adheres to a device during treatment. there were. In order to prevent such stickiness of the dental composition, it is effective to increase the viscosity of the matrix resin by adding an appropriate amount of fine particle silica as described later.

However, such fine particle silica has a refractive index of about 1.45, and the refractive index of a matrix resin (cured resin) or glass powder (usually 1.50 to 1.55).
(Approximately 1.55), there is a new problem that the transparency of the cured product decreases as the amount of the fine powder glass increases. That is, with respect to the transparency of the teeth, a dental resin or a hard resin used for the incisal end portion of the front teeth or the like often requires extremely high transparency in appearance. In many cases, such a part is required to have a light transmittance of 480 nm, which is the irradiation wavelength of the dental light irradiator, of 10% or more. On the other hand, in areas such as dentin, there are no such appearance problems,
Dental resin or hard resin may have relatively low transparency, and can be used even if the transparency is 1% or less. However, even with such dentin, since a pigment such as titanium oxide or red iron oxide is blended in order to adjust the color tone of the tooth, it is preferable that the transparency be high in order to increase the degree of freedom of coloring. Also, when the transparency is high, in the case of a photopolymerization type dental material, there is an advantage that the curing depth is deep and the polymerization rate is high, so that the mechanical properties are improved.

From such a viewpoint, in the dental composition containing no pigment, the above constituent transmittance is preferably at least 0.05%, more preferably at least 1%, and practically. Is desirably 5% or more. On the other hand, the filler has an average particle size of 0.01 to 0.04 μm.
Although the dental composition using only the finely divided silica of m as the inorganic filler exhibits extremely high surface lubrication, such finely divided silica cannot be provided with X-ray contrast properties. Dental compositions containing only silica do not have X-ray contrast.

[0007] Such a fine particle silica has a very large specific surface area as compared with the crushed glass powder, and the filling amount of the crushed glass powder that can be blended with the dental composition when the crushed glass powder is used as a filler is increased. While the maximum is 80 to 85% by weight, the filling amount of the particulate silica is 3 at the maximum.
It is about 0 to 50% by weight. As a result, a dental composition having only fine-particle silica as a filler has A) increased polymerization shrinkage, B) increased water absorption, C) increased thermal expansion coefficient, D) poor mechanical properties, etc. Problem.

As a method of reducing polymerization shrinkage using fine-particle silica, a dental filler using a composite filler obtained by pulverizing a cured product obtained by previously mixing and curing fine-particle silica with a monomer as a filler is used. Compositions are known. However, although polymerization shrinkage is reduced in such a dental composition, even with such a composite filler,
Other problems remain.

[0009]

SUMMARY OF THE INVENTION The present invention is to solve the above-mentioned problems in the dental composition. That is, an object of the present invention is to provide a dental composition excellent in surface lubricity, transparency and mechanical properties of a cured product containing no pigment or the like.

Another object of the present invention is to provide a dental composition having excellent operability and curability (particularly, photocurability). Another object of the present invention is to provide a dental composition having excellent X-ray contrast properties.

[0011]

The dental composition of the present invention comprises at least a (meth) acrylate monomer, a filler and a polymerization initiator, wherein the dental composition comprises It contains fine-particle silica having an average particle size of less than 0.01 μm and X-ray contrast glass powder, and the content of particles having a particle size of 0.01 μm or more in the fine-particle silica having an average particle size of less than 0.01 μm is 40% by weight. % Or less, and the difference between the refractive index of the X-ray opaque glass powder and the refractive index of the cured product of the (meth) acrylate monomer is 0.05 or less.

Further, the dental composition of the present invention further contains glass powder as a filler, and the difference between the refractive index of the glass powder and the refractive index of the cured product of the above (meth) acrylate monomer is 0. .05 or less, and the glass powder preferably has X-ray opacity. The dental composition of the present invention contains, as a filler, fine-particle silica having an average particle diameter of less than 0.01 μm as described above, and a cured product of this dental composition has excellent surface smoothness and transparency. Shows properties and mechanical properties. Further, the dental composition of the present invention contains fine silica particles having an average particle diameter of less than 0.01 μm as a filler, and thus has excellent operability and curability, particularly excellent photocurability. Then, by further mixing a glass powder containing an atom having X-ray contrast as a filler, the dental composition of the present invention has X-ray contrast.

[0013]

DETAILED DESCRIPTION OF THE INVENTION Next, the dental composition of the present invention will be specifically described. The dental composition of the present invention contains at least a (meth) acrylate monomer as a polymerizable component, and further contains a filler and a polymerization initiator. The polymerizable component used in the present invention is a (meth) acrylate monomer.

In the present invention, the polymerizable component includes
(Meth) acrylate monomers are used. The (meth) acrylate monomer includes a monofunctional monomer and a polyfunctional monomer. Examples of the monofunctional monomer used in the present invention include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) Alkyl esters of (meth) acrylic acid such as acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, and adamantyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate , 2- or 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 1,2- or 1,3-dihydroxy Step Hydroxyalkyl esters of (meth) acrylic acid such as propyl mono (meth) acrylate and erythritol mono (meth) acrylate; diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol Polyethylene glycol mono (meth) acrylate such as mono (meth) acrylate; ethylene glycol monomethyl ether (meth) acrylate, ethylene glycol monoethyl ether (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) Acrylate, polyethylene glycol monomethyl ether (meth) acrylate, Propylene glycol monoalkyl ether (meth) acrylate of (poly) glycol monoalkyl ether (meth) acrylate;
Fluoroalkyl esters of (meth) acrylic acid such as perfluorooctyl (meth) acrylate and hexafluorobutyl (meth) acrylate; γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltri (trimethyl) Silane compounds having a (meth) acryloxyalkyl group such as (siloxy) silane; carboxylic acid-containing (meth) such as β-methacryloyloxyethyl hydrogen phthalate, β-methacryloyloxyethyl hydrogen succinate, β-methacryloyloxyethyl maleate; ) Acrylate, 3-
Examples thereof include halogen-containing (meth) acrylates such as chloro-2-hydroxypropyl methacrylate, and (meth) acrylates having a heterocyclic ring such as tetrafurfuryl (meth) acrylate.

Examples of polyfunctional monomers include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and hexylene glycol di (meth) acrylate. (Meth) acrylate, trimethylopropane tri (meth)
Acrylates, poly (meth) acrylates of alkane polyols such as pentaerythritol tetra (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate,
Polyoxyalkane polyol poly (such as polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, dibutylene glycol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate) (Meth) acrylate; an aliphatic, alicyclic or aromatic (meth) acrylate represented by the following formula;

[0016]

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(In the above formula, R represents a hydrogen atom or a methyl group, m and n each represent 0 or a positive number, and R ¹ represents the following aromatic group or alicyclic group.) );

[0018]

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An alicyclic or aromatic epoxy di (meth) acrylate represented by the following formula:

[0020]

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(In the above formula, R represents a hydrogen atom or a methyl group, n represents 0 or a positive number, and R ¹ represents-
_{(CH 2) 2 -, -} (CH 2) 4 -,

[0022]

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Represents ). Further, polyfunctional (meth) acrylates having a urethane bond in a molecule represented by the following formula can be exemplified.

[0024]

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In the above formula, R represents a hydrogen atom or a methyl group, and R ¹ represents — (CH ₂ ) ₂ —, — (CH ₂ )
_{4 -, - (CH 2)} 6 -,

[0026]

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Represents the following. In the above examples, monofunctional polymerizable (meth) acrylates include alkyl methacrylates such as methyl methacrylate (refractive index 1.42), ethyl methacrylate (refractive index 1.42), and 2-hydroxyethyl methacrylate ( Hydroxyl-containing (meth) acrylates such as 1.45), diethylene glycol monomethyl ether methacrylate (refractive index 1.44),
(Meth) acrylate having an ethylene glycol chain in a molecule such as tetraethylene glycol monomethyl ether methacrylate (refractive index: 1.45) is preferably used.

As the polyfunctional polymerizable (meth) acrylate, an ethylene glycol chain is included in a molecule such as ethylene glycol dimethacrylate (refractive index 1.45) or triethylene glycol dimethacrylate (refractive index 1.46). Having di (meth) acrylate,

[0029]

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(However, in the above formula, R represents a methyl group, m + n is 2.6 on average; refractive index is 1.54)

[0031]

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(However, in the above formula, R represents a methyl group; refractive index 1.54)

[0033]

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(Wherein, in the above formula, R represents a methyl group; refractive index 1.48) and a compound represented by 1,3-
Bismethacryloxyethoxybenzene (refractive index: 1.5
2) and the like are particularly preferably used. And the (meth) acrylate monomer preferably used in the present invention has a refractive index in the range of 1.40 to 1.65, preferably
Monomers in the range of 1.45 to 1.65. These can be used alone or as a mixture of two or more kinds to adjust the mechanical properties and refractive index of the cured product.
When using multiple acrylate monomers, typically
A monomer having a higher refractive index and a monomer having a lower refractive index than the target refractive index are mixed to adjust the refractive index.

In the dental composition of the present invention, as the (meth) acrylate monomer, the refractive index of a filler described later, particularly the glass powder blended as the filler, and the refractive index of the cured product of the (meth) acrylate monomer It is preferable to select and use a monomer whose difference from the ratio is 0.05 or less, and furthermore, this difference is 0 to 0.0
It is particularly preferable to select and use a monomer so as to fall within the range of 2.

Usually, the (meth) acrylate monomer is polymerized so that the refractive index of the cured product becomes higher than that of the monomer by about 0.02 to 0.03. Furthermore, (meta)
The refractive index of the acrylate monomer is usually higher than the refractive index of a monomer having no such group or element by including a heavy element such as a polar group such as a hydroxyl group or a carboxylic acid group, an aromatic ring, or a halogen atom. It tends to be high, and the refractive index of a monomer having such a group or atom is usually in the range of 1.48 to 1.54. In contrast, the refractive index of a monomer having only an alkyl group as a skeleton or a (meth) acrylic monomer having a fluorinated alkyl group tends to be lower than that of a monomer having no such group. The refractive index of such a (meth) acrylic monomer is usually 1.40 to
It is within the range of 1.48.

The dental composition of the present invention contains a filler. The dental composition of the present invention, as a filler,
It contains finely divided silica having an average particle diameter of less than 0.01 μm. The fine silica used as a filler in the present invention has an average particle diameter of 0.001 to 0.00.
Particulate silica in the range of 9 μm is preferred. In addition,
In the present invention, the average particle diameter is an average particle diameter of primary particles. This fine particle silica has an average particle diameter as described above, but the particle diameter contained in the fine particle silica is 0.1.
The content of particles having a particle size of 0.01 μm or more is preferably small since the content of particles having a particle size of 0.01 μm or more in the above-mentioned fine particle silica is 40% by weight or less, and preferably 40% by weight or less. 20% by weight or less.

By blending the fine particle silica having such an average particle diameter as a filler, the operability of the dental composition of the present invention is improved. That is, the average particle diameter of the fine particle silica is much smaller than that of the glass powder or the composite filler, and the average particle diameter is usually 1/100 or less of the average particle diameter of the glass powder or the composite filler. is there. When the fine particle silica having such an average particle diameter is added to the (meth) acrylate monomer, the added fine particle silica serves as a viscosity modifier for the (meth) acrylate monomer, and the softness and tackiness of the dental composition. Can be balanced. And, the smaller the average particle size of the particulate silica, the easier it is to adjust the stickiness and the like with a small amount of addition.

This fine-particle silica is usually high-purity colloidal silica produced by a gas phase method. As the fine-particle silica, for example, high-purity colloidal silica produced by a gas phase method can be used as it is, or high-purity colloidal silica can be treated with a silane compound such as dimethyldichlorosilane to make it hydrophobic. In addition, it is preferable to use a methacryloxysilane treatment or an aminosilane treatment in which the affinity with the matrix resin is improved.

The refractive index of the fine particle silica is usually 1.4.
It is near 5. The average particle diameter of this fine particle silica is as large as that of silica conventionally used as a filler, and the wavelength of visible light (380 to 780 nm = 0.38 to 0.78).
When the average particle diameter is close to μm), light is scattered by the silica particles, so that the transparency of the obtained cured product is reduced. However, the fine particle silica used as a filler in the present invention has an average particle diameter of 0.0.
Since the average particle diameter is less than 1 μm and much smaller than the wavelength of visible light, the transparency of the cured product of the dental composition of the present invention is reduced even by adding such fine particle silica. Hard to do. That is, the transmittance of visible light is hardly hindered by such fine particle silica. Moreover, the use of such fine-particle silica reduces the viscosity of the dental composition of the present invention, and can prevent the dental composition from adhering to dental instruments.

Such a fine particle silica is generally used in an amount of 5 to 250 parts by weight, preferably 10 to 250 parts by weight, per 100 parts by weight of the (meth) acrylate monomer in the dental composition of the present invention.
It is used in an amount of up to 200 parts by weight, particularly preferably in the range of 20 to 150 parts by weight. By using the above-mentioned amount of the fine particle silica having the average particle diameter as described above, the transparency of the cured product is hardly reduced, and the surface property of the obtained cured product, that is, the smoothness of the surface is significantly improved. I do.

The dental composition of the present invention contains the above-mentioned fine particle silica as a filler, and preferably further contains glass powder as a filler. The glass powder used as a filler in the present invention generally has an average particle size of 2 μm or less, and preferably 0.1 μm or less.
Use ~ 1.5 μm powder. Further, the refractive index of the glass powder is preferably at least 1.50, and more preferably in the range of 1.52 to 1.65. Further, the difference between the refractive index of the glass powder used in the present invention and the refractive index of the cured product of the (meth) acrylate monomer in the dental composition into which the glass powder is blended is 0.05 or less. It is preferable to use a powder, and it is particularly preferable to use a glass powder having a difference in refractive index of 0.02 or less. That is, the glass powder used in the present invention has a refractive index very similar to that of a cured product of a (meth) acrylate monomer. By using such a glass powder, the light transmittance of the cured product of the dental composition of the present invention is improved.

The glass powder used in the present invention is X
It is preferable to have a line contrast property. In general, it is important in the clinic that the presence of the filler can be clearly identified on the radiograph. In order to impart X-ray contrast to glass powder,
Barium, strontium, zirconium, bismuth, tungsten, germanium,
X-ray opaque elements (heavy metal elements) such as molybdenum and lanthanide are added.

As described above, when a heavy metal element is added for imparting X-ray contrast to glass powder, the refractive index of the glass powder increases as the amount of addition increases. Therefore, the content of the heavy metal element in the glass powder in the dental composition of the present invention has a meaning of imparting X-ray contrast to the glass powder and a meaning of adjusting the refractive index of the glass powder. .

When the difference between the refractive index of the above-mentioned cured product of the (meth) acrylate monomer and the glass powder is more than 0.05, the transparency of the cured composition is reduced, and the photocurability is reduced. The physical properties of the cured product may be reduced due to a decrease in depth or insufficient progress of the curing reaction. When adjusting the refractive index of the glass powder, the transparency of the glass powder before curing (composition) is adjusted by adjusting the refractive index of the glass powder between the refractive index of the monomer before curing and the refractive index of the cured monomer. There is an advantage that there is no change between the transparency of the composition (cured body) before and after curing, and when the refractive index of the cured monomer is adjusted to the refractive index of the glass powder, the transparency of the composition after curing is reduced. It has the advantage of being the best.
These methods of adjusting the refractive index can be used at any time according to clinical requirements.

Usually, the dental composition of the present invention containing about 60% by weight or more of the X-ray opaque glass powder having an average particle diameter of about submicron to several μm has a refractive index of the glass powder of 1. If it is 50 or more, the cured product becomes transparent and its presence can be clearly confirmed by X-rays. The glass powder used at this time may be a single glass powder or a mixture of two or more glass powders having different compositions. When a plurality of glass powders having different compositions are used, the transparency of the cured product after curing the dental composition of the present invention is high by approximating the refractive indices of the glass powders used as closely as possible. Can be secured.

Such a glass powder is usually 5 to 10 parts by weight based on 100 parts by weight of the (meth) acrylate monomer.
It is used in an amount of 00 parts by weight, preferably 100 to 700 parts by weight. In the dental composition of the present invention, a composite filler can be used as a filler.

The composite filler used in the present invention comprises:
For example, a (meth) acrylate monomer, powdered glass and / or finely divided silica, and a polymerization initiator such as benzoyl peroxide are mixed, heated, and then polymerized.
It can be produced by pulverizing the obtained polymer. By using such a composite filler, the dental composition of the present invention reduces polymerization shrinkage during curing. In addition, since such a composite filler can be produced by polymerizing a (meth) acrylate monomer under conditions (for example, heat polymerization) capable of increasing the polymerization rate more than photopolymerization, the mechanical properties of the cured product are reduced. It is higher than the cured product obtained by photopolymerization. Therefore, by blending such a composite filler, the mechanical properties and abrasion resistance of the cured product of the dental composition of the present invention are improved. Further, the refractive index (refractive index of the composite filler itself) between the glass powder and / or fine powder particles used for the composite filler and the cured (meth) acrylate monomer constituting the composite filler is as described in the above (meta). High transparency can be obtained by approximating the refractive index of the cured acrylate monomer to the fine powder of silica and / or glass powder. In particular, the difference in the refractive index between the composite filler used in the present invention and the above-mentioned cured (meth) acrylate monomer is preferably 0.1%.
Below, particularly preferably 0.05 or less,
It is possible to obtain higher transparency. Regarding the method of making the refractive index difference as described above, see Japanese Patent Application Laid-Open No. 9-7762.
Publication No. 6 can be referred to. If necessary, other fillers or pigments other than powdered glass and finely divided silica, such as silica powder and metal oxide, may be added to the composite filler. The average particle size of the composite filler is usually 1 to 100 μm, preferably 5 to 20 μm.
m.

Such a composite filler is usually used in an amount of 1 to 50 parts by weight based on 100 parts by weight of the (meth) acrylate monomer.
It is used in an amount of 0 parts by weight, preferably 5 to 200 parts by weight. In the present invention, as the filler, specific fine particle silica is used as described above, and if necessary, glass powder and / or a composite filler is used. When a glass powder and / or a composite filler is used, the total filler amount in the dental composition of the present invention is usually 50 to 1500 parts by weight based on 100 parts by weight of the (meth) acrylate monomer. Within the range, preferably 100 to
The amount of each filler is adjusted and blended so as to fall within the range of 700 parts by weight. When a glass powder and / or a composite filler is used as the filler, the total amount of these is usually set to 1 to 500 times (weight), preferably 5 to 100 times the fine particle silica. .

[0050] The dental composition of the present invention contains a polymerization initiator. As the polymerization initiator to be added to the dental composition of the present invention, known compounds can be used without limitation. For example, a photopolymerization initiator, an organic peroxide, a diazo compound, a redox compound and the like can be used. Specifically, when a photopolymerization initiator is used, a photosensitizer alone or a combination of a photosensitizer and a photopolymerization accelerator can be used.

Examples of the photosensitizer include benzyl and camphor.
Quinone, α-naphthyl, p, p'-dimethoxybenzyl, pentadione, 1,4-phenanthrenequinone, naphthoquinone,
Known α-diketone compounds, such as trimethylbenzoyldiphenylphosphine oxide, which are excited by irradiation with visible light or ultraviolet light to initiate polymerization, and can be used alone or as a mixture of two or more. Among them, camphorquinone and trimethylbenzoyldiphenylphosphine oxide are preferably used.

Examples of the photopolymerization accelerator include N, N-dimethylaniline, N, N-diethylaniline, N, N-dibenzylaniline, N, N, -dimethyl-p-toluidine, N, N-diethyl-p -Toluidine, N, N-dihydroxyethyl-p-toluidine, p-
N, N-dimethylaminobenzoic acid, pN, N-diethylaminobenzoic acid, pN, N-dimethylaminobenzoic acid ethyl, pN, N-
Ethyl diethylaminobenzoate, pN, N-Dimethylaminobenzoate, pN, N-Diethylaminobenzoate, pN, N-Dimethylaminobenzaldehyde, pN, N-Dimethylaminobenzoate 2-n-butoxyethyl, pN, N 2-n-butoxyethyl diethylaminobenzoate, pN, N-dimethylaminobenzonitrile, pN, N-diethylaminobenzonitrile, pN, N-dihydroxyethylaniline, p-dimethylaminophenethyl alcohol, N, N-dimethyl Tertiary amines such as aminoethyl methacrylate, triethylamine, tributylamine, tripropylamine and N-ethylethanolamine; a combination of the tertiary amine with citric acid, malic acid and 2-hydroxypropanoic acid; 5-butyl Babiruturic acids such as aminobavirturic acid and 1-benzyl-5-phenylbabirtolic acid; Peroxide, it may be mentioned organic peroxides such as di -tert- butyl peroxide, may be mixed one kind or two or more kinds. Above all, pN,
Ethyl N-dimethylaminobenzoate, pN, N-methylaminobenzoate, pN, N-dimethylaminobenzoic acid 2-n-
A tertiary aromatic amine having a nitrogen atom directly bonded to an aromatic or an aliphatic tertiary amine having a polymerizable group, such as butoxyethyl and N, N-dimethylaminoethyl methacrylate, can be suitably used.

In order to terminate the curing promptly, a combination of a photosensitizer and a photopolymerization accelerator is preferable, and camphorquinone or trimethylbenzoyldiphenylphosphine oxide and pN, N-dimethylaminobenzoate or Combinations of tertiary aromatic amine ester compounds in which a nitrogen atom is directly bonded to an aromatic, such as 2-n-butoxyethyl pN, N-dimethylaminobenzoate, can be suitably used.

When using an organic peroxide or a diazo compound as the polymerization initiator, the type thereof is not limited. However, when the polymerization is to be completed in a short time, the decomposition half-life at 80 ° C. is 10%. Compounds that are less than or equal to the time are preferred. Specifically, examples of organic peroxides include diacyl peroxides such as acetyl peroxide, isobutyl peroxide, decanoyl peroxide, benzoyl peroxide, and succinic acid peroxide; diisopropyl peroxydicarbonate, and di-2-peroxide. Peroxydicarbonates such as ethylhexylperoxydicarbonate and diallylperoxydicarbonate; tert
Peroxyesters such as -butylperoxyisobutyrate, tert-butylneodecanate, and cumeneperoxyneodecanate; and peroxide sulfonates such as acetylcyclohexylsulfonyl peroxide.

The diazo compounds include 2,2'-azobisisobutyronitrile, 4,4'-azobis (4-cyanovaleric acid), and 2,2'-azobis (4-methoxy-2, 4-dimethoxyvaleronitrile), 2,2'-azobis (2-cyclopropylpropionitrile) and the like. Among them, benzoyl peroxide and 2,2′-azobisbutyronitrile can be suitably used.

The use of a redox initiator system as a polymerization initiator is not limited, but a combination of the above organic peroxide and a tertiary amine; organic peroxide / sulfinic acid or an alkali metal salt thereof / Combinations of tertiary amines; combinations of inorganic peroxides such as potassium persulfate and sodium sulfite, and combinations of inorganic peroxides such as inorganic peroxide and sodium hydrogen sulfite and inorganic reducing agents. Among them, benzoyl peroxide and N, N-dimethyl-p-toluidine, and benzoyl peroxide and N, N-dihydroxyethyl-p-toluidine are preferably used.

These polymerization initiators are preferably used in an amount of 0.0 based on 100 parts by weight of the (meth) acrylate monomer.
It is used in an amount ranging from 01 to 10% by weight. In the dental composition of the present invention, the content of the (meth) acrylate monomer is preferably in the range of 5 to 50% by weight, and more preferably in the range of 10 to 30% by weight.

The dental composition of the present invention contains at least a (meth) acrylate monomer, a filler and a polymerization initiator, and further contains a pigment, a dye, a stabilizer, a polymer powder, an ultraviolet absorber and the like. May be.
The dental composition of the present invention can be used by filling it into a drilled hole, and can be used for bonding or bonding of dentin such as anterior teeth, production of temporary teeth, pontic of bridge, forehead crown, etc. Can be used.

[0059]

The dental composition of the present invention comprises at least
A (meth) acrylate monomer, a filler and a polymerization initiator are contained, and the dental composition of the present invention comprises:
The dental composition contains, as a filler, fine-particle silica having an average particle size of less than 0.01 μm, and further preferably contains glass powder. The dental composition has surface lubricity, transparency and mechanical properties. It is possible to form a cured product having excellent heat resistance. Moreover, by containing such a filler,
The dental composition of the present invention has good operability and curability (particularly, photocurability). Further, by using glass powder having X-ray contrast as glass particles, the dental composition of the present invention has excellent X-ray contrast. By using such a dental composition having X-ray contrast, treatment can be performed while confirming the site of use.

[0060]

EXAMPLES The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples. A list and abbreviations of the materials used in the following examples are described below. Monomer Bis-GMA: 2,2-bis [4- (2-hydroxy-3-methacryloxypropoxy) phenyl] propane (refractive index: 1.54) TEGDMA: triethylene glycol dimethacrylate (refractive index: 1.46) UDMA: 1 2,6-bis (methacryloxyethyloxycarbonylamino) -2,2,4- (or -2,4,4-) trimethylhexane (refractive index: 1.48) Bis-MPEPP: 2,2-bis (4-methacrylic Roxypolyethoxyphenyl) propane (refractive index 1.54) TMPT: trimethylolpropane trimethacrylate (refractive index: 1.47) BMEB: 1,3-bismethacryloxyethoxy benzene (refractive index: 1.52) Glass powder : 30 barium oxide by a conventional method borosilicate glass (refractive index 1.55) containing by weight%, 3 wt% of [3- (methacryloyloxy) propyl] trimethoxysilane treated with those Ultrafine silica R-812: average particle diameter 0.007μm Colloidal silica with dimethyldichlorosilane treated those hydrophobic (particle size 0.01μ
About 10% of particles with a particle size of m or more: Nippon Aerosil Co., Ltd.
R-972: Colloidal silica having an average particle size of 0.014 μm and treated with dimethyldichlorosilane to make it hydrophobic (particle size: 0.01 μm)
About 85% of particles with a particle size of m or more: Nippon Aerosil Co., Ltd.
Preparation of Sample, Measurement of Physical Properties and Measurement of Refractive Index Measurement was carried out at 20 ° C. according to a standard method using an Abbe refractometer (manufactured by Atago Co., Ltd .: Model 1T).

The curing method of the composition The trial-produced composite resin was charged into a mold having a predetermined shape, and then irradiated with a visible light irradiator (Translux manufactured by Kulzer).
CL) and cured by irradiating visible light for 60 seconds. Bending strength and X-ray contrast The test was performed according to ISO-4049 (1988) 7.8 (bending strength) and 7.11 (X-ray contrast).

The bending strength was measured at a crosshead speed of 1 mm / min using an Autograph AGS-2000G manufactured by Shimadzu Corporation.
Was measured. The X-ray contrast was measured using an X-ray controller DCX-100 manufactured by Asahi Roentgen Kogyo Co., Ltd. ・ Light transmittance: Fill a composite resin into a 1mm thick Teflon mold with a rectangular hole 10mm wide x 25mm long, sandwich both sides with a polyester film and a glass plate, and use a visible light irradiator (Translux CL made by Kulzer). It was cured by irradiating it with visible light for 60 seconds. Regarding the method of irradiating the visible light, it was made possible to irradiate all the samples uniformly and sufficiently with reference to the description of 7.8.2.2 of ISO4049 (1988). The light transmittance of this sample was measured using an ultraviolet-visible spectrophotometer (UV-160A, manufactured by Shimadzu Corporation).

A 1 mm thick Teflon mold with a circular hole having a surface gloss of 20 mm is filled with a composite resin, and both sides are sandwiched between a polyester film and a glass plate. Then, a visible light irradiator (Translux CL manufactured by Kulzer) is used. ) To cure the sample by irradiating visible light for 60 seconds per location. Regarding the method of irradiating the visible light, it was made possible to irradiate all the samples uniformly and sufficiently with reference to the description of 7.8.2.2 of ISO4049 (1988). The surface of this sample was first polished with a water-resistant abrasive paper of No. 600, followed by No. 2000, and then finish-polished using a finishing disc (1982SF) of a polishing disc Sof-Lex manufactured by 3M. The gloss of this surface was measured using a gloss meter (VGS type) manufactured by Nippon Denshoku Industries Co., Ltd. at a reflection angle of 60 degrees.

[0064]

Example 1 (Comparison of light transmittance) As shown below,
A model experiment was conducted on how the light transmittance of a cured product of a monomer mixture to which fine-particle silica having an average particle size of about 0.01 μm was added was changed.

In a monomer mixture (refractive index: 1.52) obtained by mixing 70 parts by weight of Bis-MPEPP and 30 parts by weight of TEGDMA, 0.5 part by weight of camphorquinone and 0.5 part by weight of ethyl N, N-dimethylaminobenzoate were dissolved. R-812 to this monomer
40 parts by weight were mixed to obtain a uniform paste. This paste was placed in a stainless steel mold having a hole of 1 mm in thickness and 20 mm in diameter, covered with slide glass on both sides, and then using a visible light irradiator (α-light: manufactured by Morita Tokyo Seisakusho). The paste was cured by irradiating visible light for 180 seconds on each side. The cured paste is removed from the mold and both sides are 2,000
No. water-resistant abrasive paper, followed by mirror polishing with 0.05 μm alumina fine particles. Table 1 shows the light transmittance of this sample at each wavelength.

[0066]

Comparative Example 1 0.5 part by weight of camphorquinone and 0.5 part by weight of ethyl N, N-dimethylaminobenzoate were dissolved in a monomer mixture (refractive index: 1.52) obtained by mixing 70 parts by weight of Bis-MPEPP and 30 parts by weight of TEGDMA. . R-972 to this monomer
40 parts by weight were mixed to obtain a uniform paste. This paste was placed in a stainless steel mold having a hole of 1 mm in thickness and 20 mm in diameter, covered with slide glass on both sides, and then using a visible light irradiator (α-light: manufactured by Morita Tokyo Seisakusho). The paste was cured by irradiating visible light for 180 seconds on each side. The cured paste is removed from the mold and both sides are 2,000
No. water-resistant abrasive paper, followed by mirror polishing with 0.05 μm alumina fine particles. Table 1 shows the light transmittance of this sample at each wavelength.

[0067]

[Table 1]

As can be seen from Table 1, the light transmittance of Example 1 is higher than that of Comparative Example 1 over all wavelengths of visible light. This tendency becomes more remarkable as the wavelength becomes shorter. In particular, the light transmittance becomes twice or more at around 480 nm, which is the peak wavelength of the visible light irradiator for dental use.

[0069]

Example 2 (Preparation of composite filler) 70 parts by weight of Bis-GMA and T
EGDMA 30 parts by weight and a monomer mixture (refractive index 1.5
In 2), 0.5 parts by weight of benzoyl peroxide was dissolved.
This is mixed with Ba glass having an average particle size of 1 μm (barium oxide
A borosilicate glass (refractive index: 1.55) containing 3% by weight of [3- (methacryloyloxy) propyl] trimethoxysilane is mixed with 400 parts by weight of a borosilicate glass containing 3% by weight, and uniformly mixed. And This paste was heated at 120 ° C. for 15 minutes while applying pressure using a compression molding machine to cure the paste. This paste is pulverized using a ball mill and sieved to obtain an average particle size of about 10 μm.
Was prepared.

[0070]

Example 3 (Preparation of Composite Filler) Monomer mixture (refractive index: 70 parts by weight of Bis-MPEPP and 30 parts by weight of TMPT)
0.52 parts by weight of benzoyl peroxide was dissolved in 1.52). This was well mixed with 400 parts by weight of Ba glass having an average particle size of 1 μm (the same as the Ba glass used in the composite filler A) to obtain a uniform paste. This paste was heated at 120 ° C. for 15 minutes while applying pressure using a compression molding machine to cure the paste. This paste was ground using a ball mill and sieved to prepare a composite filler B having an average particle size of about 10 μm.

[0071]

Example 4 (Preparation of composite resin) Bis-GMA 70
0.5 part by weight of camphorquinone and 0.5 part by weight of N, N-dimethylaminobenzoic acid ethyl ester were dissolved in a monomer mixture (refractive index: 1.52) obtained by mixing 30 parts by weight of TEGDMA with 30 parts by weight of TEGDMA. Ba glass 400 with an average particle size of 1 μm is added to this monomer.
Parts by weight and 50 parts by weight of R-812 were mixed to obtain a dental composition as a uniform paste.

Table 2 shows the composition of the dental composition, the physical properties of the cured product of the dental composition, and the operability of the dental composition.

[0073]

Example 5 Bis-MPEPP 65 parts by weight, UDMA 20 parts by weight and TEGD
0.5 parts by weight of camphorquinone and 0.5 parts by weight of N, N-dimethylaminobenzoic acid ethyl ester were dissolved in a monomer mixture (refractive index: 1.52) mixed with 15 parts by weight of MA. To this monomer, 450 parts by weight of the composite filler B and R-81250 parts by weight were mixed to obtain a dental composition as a uniform paste.

Table 2 shows the composition of the dental composition, the physical properties of the cured product of the dental composition, and the operability of the dental composition.

[0075]

Example 6 0.5 part by weight of camphorquinone and 0.5 part by weight of ethyl N, N-dimethylaminobenzoate were dissolved in a monomer mixture (refractive index: 1.52) obtained by mixing 70 parts by weight of Bis-GMA and 30 parts by weight of TEGDMA. . 200 parts by weight of Ba glass having an average particle size of 1 μm, 150 parts by weight of a composite filler A,
50 parts by weight of R-812 were mixed to obtain a dental composition as a uniform paste.

Table 2 shows the composition of the dental composition, the physical properties of the cured product of the dental composition, and the operability of the dental composition.

[0077]

Example 7 0.5 part by weight of camphorquinone and 0.5 part by weight of ethyl N, N-dimethylaminobenzoate were dissolved in a monomer mixture (refractive index: 1.52) obtained by mixing 70 parts by weight of Bis-MPEPP and 30 parts by weight of TEGDMA. 250 parts by weight of Ba glass having an average particle size of 1 μm, 150 parts by weight of a composite filler B,
50 parts by weight of R-812 were mixed to obtain a dental composition as a uniform paste.

Table 2 shows the composition of the dental composition, the physical properties of the cured product of the dental composition, and the operability of the dental composition.

[0079]

Example 8 65 parts by weight of Bis-MPEPP, 20 parts by weight of UDMA and TEGD
0.5 parts by weight of camphorquinone and 0.5 parts by weight of N, N-dimethylaminobenzoic acid ethyl ester were dissolved in a monomer mixture (refractive index: 1.52) mixed with 15 parts by weight of MA. This monomer was mixed with 240 parts by weight of Ba glass having an average particle diameter of 1 μm, 100 parts by weight of a composite filler B, and 50 parts by weight of R-812 to obtain a dental composition as a uniform paste.

Table 2 shows the composition of the dental composition, the physical properties of the cured product of the dental composition, and the operability of the dental composition.

[0081]

Example 9 0.5 part by weight of camphorquinone and 0.5 part by weight of ethyl N, N-dimethylaminobenzoate were dissolved in a monomer mixture (refractive index: 1.52) obtained by mixing 70 parts by weight of Bis-GMA and 30 parts by weight of TEGDMA. . 230 parts by weight of Ba glass having an average particle size of 5 μm, 150 parts by weight of a composite filler A,
50 parts by weight of R-812 were mixed to obtain a dental composition as a uniform paste.

Table 2 shows the composition of the dental composition, the physical properties of the cured product of the dental composition, and the operability of the dental composition.

[0083]

Comparative Example 3 0.5 part by weight of camphorquinone and 0.5 part by weight of ethyl N, N-dimethylaminobenzoate were dissolved in a monomer mixture (refractive index: 1.52) obtained by mixing 70 parts by weight of Bis-MPEPP and 30 parts by weight of TEGDMA. To this monomer, 320 parts by weight of Ba glass having an average particle diameter of 1 μm and 150 parts by weight of a composite filler B were mixed to obtain a dental composition as a uniform paste.

Table 2 shows the composition of the dental composition, the physical properties of the cured product of the dental composition, and the operability of the dental composition.

[0085]

Comparative Example 4 Camphorquinone was added to a monomer mixture (refractive index: 1.47) obtained by mixing 20 parts by weight of UDMA and 80 parts by weight of TEGDMA.
5 parts by weight and N, N-dimethylaminobenzoic acid ethyl ester
0.5 parts by weight were dissolved. This monomer has an average particle size of 1μ
240 parts by weight of Ba glass, 150 parts by weight of composite filler A, R-81
The dental composition was obtained as a uniform paste by mixing 250 parts by weight.

Table 2 shows the composition of the dental composition, the physical properties of the cured product of the dental composition, and the operability of the dental composition. And

[0087]

Example 10 0.5 part by weight of camphorquinone and 0.5 part by weight of ethyl N, N-dimethylaminobenzoate were dissolved in a monomer mixture (refractive index: 1.52) obtained by mixing 55 parts by weight of Bis-MPEPP and 45 parts by weight of BMEB. . To this monomer mixture, 240 parts by weight of Ba glass having an average particle size of 1 μm, and a composite filler B100
Parts by weight and 50 parts by weight of R-812 were mixed to obtain a dental composition as a uniform paste. Table 2 shows the composition of the dental composition, the physical properties of the cured product of the dental composition, and the operability of the dental composition.

[0088]

[Table 2]

Claims (9)

[Claims] 1. A dental composition containing at least a (meth) acrylate monomer, a filler and a polymerization initiator, wherein the dental composition comprises, as a filler, finely divided silica having an average particle size of less than 0.01 μm and X. X-ray-contrast glass powder containing a line-contrast glass powder, wherein the content of particles having a particle diameter of 0.01 μm or more in fine-particle silica having an average particle diameter of less than 0.01 μm is 40% by weight or less, And a difference between the refractive index of the cured product of the (meth) acrylate monomer and the refractive index of the cured product of the above (meth) acrylate monomer is 0.05 or less. 2. A particle diameter of 0.0 in fine-particle silica having an average particle diameter of less than 0.01 μm contained in the dental composition.
The dental composition according to claim 1, wherein the content of particles having a particle size of 1 µm or more is 20% by weight or less. 3. The X-ray opaque glass powder has a refractive index of 1.
The dental composition according to claim 1, wherein the composition is 50 or more. 4. The dental composition according to claim 1, wherein the X-ray contrast-enhancing glass powder has an average particle size of 2 μm or less. 5. The method according to claim 1, wherein the X-ray opaque glass powder is (meth)
The dental composition according to any one of claims 1 to 4, wherein the dental composition is contained as a composite filler formed by an acrylate monomer and an X-ray opaque glass powder. 6. The transmittance of light having a wavelength of 480 nm measured on a cured product having a thickness of 1 mm of the dental composition of 0.05%.
The dental composition according to claim 1, wherein the composition is the above. 7. The dental composition according to claim 1, wherein the amount of the (meth) acrylate monomer in the dental composition is 100 parts by weight.
Fine silica particles having an average particle diameter of less than 0.01 μm
The amount in the range of 0 parts by weight, the X-ray-contrast
The dental composition according to claim 1, wherein the amount of the polymerization initiator is in the range of 1,000 parts by weight, and the amount of the polymerization initiator is in the range of 0.001 to 10 parts by weight. 8. The dental composition according to claim 1, wherein the amount of the (meth) acrylate monomer in the dental composition is 100 parts by weight.
The dental composition according to claim 5, wherein the composite filler is contained in an amount within a range of 1 to 500 parts by weight. 9. The dental composition according to claim 1, wherein the polymerization initiator is a photopolymerization type initiator.