WO2023182241A1

WO2023182241A1 - Composition for dental material and dental material

Info

Publication number: WO2023182241A1
Application number: PCT/JP2023/010757
Authority: WO
Inventors: 直志柿沼; 絵梨安保; 洋子小杉
Original assignee: 三井化学株式会社
Priority date: 2022-03-24
Filing date: 2023-03-17
Publication date: 2023-09-28

Abstract

A composition for a dental material containing inorganic particles supporting at least one metal component selected from the group consisting of silver and zinc, a (meth)acrylate compound, and a polymerization initiator.

Description

Compositions for dental materials and dental materials

The present disclosure relates to compositions for dental materials and dental materials.

A dental material composition such as a composite resin generally contains a dental material composition containing a monomer, a filler, a polymerization initiator, a polymerization inhibitor, a pigment, and the like.
As the composition for dental materials, a radically polymerizable polyfunctional methacrylate composition is sometimes used from the viewpoints of in-vivo safety of the monomer and mechanical strength and abrasion resistance of the cured product.

For example, Patent Document 1 describes an amine compound (A) having two or more amino groups, an iso(thio)cyanate compound (B) having two or more iso(thio)cyanate groups, and one polymerizable group. A (meth)acrylate (D) which is a reaction product of the above-mentioned hydroxy (meth)acrylate compound (C) is described.
[Patent Document 1] International Publication No. 2019/107322

A wide variety of bacteria reside in the oral cavity, and these bacteria form dental plaque starting from sugar, leftover food, etc., and eventually form a biofilm. Biofilm formation can be suppressed by antibacterial agents, antifouling coats, etc.

However, methods of suppressing biofilm formation using antibacterial agents, antifouling coats, etc. have many drawbacks. For example, antibacterial agents have problems such as biological safety and initial digestion, and antifouling coats have problems such as complicated processing and easy peeling.

From the viewpoint of obtaining antibacterial properties while ensuring biosafety, ease of processing, etc., it is envisaged to use a composition for dental materials containing a monomer and simple silver as an antibacterial component. However, there is room for improvement in antibacterial properties of dental material compositions containing silver alone. Furthermore, sulfur components that cause bad breath exist in the oral cavity, and when a dental material composition containing silver ions is used in the oral cavity, this composition, a dental material containing a cured product of the composition, There is a problem in that the material tends to turn black over time.

The present disclosure has been made in view of the above, and provides a dental material composition that has excellent antibacterial properties and suppresses discoloration due to sulfur components, and a dental material containing a cured product of this dental material composition. With the goal.

Means for solving the above problems include the following aspects.
<1> A composition for dental materials, comprising inorganic particles carrying at least one metal component selected from the group consisting of silver and zinc, a (meth)acrylate compound, and a polymerization initiator.
<2> The composition for dental materials according to <1>, wherein the inorganic particles contain one or more compounds selected from the group consisting of aluminosilicate and phosphate glass.
<3> The composition for dental materials according to <1> or <2>, wherein the content of the inorganic particles is 0.01% by mass to 15% by mass with respect to the total amount of the composition for dental materials. .
<4> The content of the inorganic particles according to any one of <1> to <3> is 0.01 parts by mass to 40 parts by mass based on 100 parts by mass of the (meth)acrylate compound. Composition for dental materials.
<5> The dental material composition according to any one of <1> to <4>, further comprising a filler other than the inorganic particles.
<6> The composition further contains a filler other than the inorganic particles, and the content of the filler other than the inorganic particles is 50% by mass or less based on the total content of fillers contained in the dental material composition. Alternatively, the dental material composition according to any one of <1> to <4>, which does not contain fillers other than the inorganic particles.
<7> The composition for dental materials according to any one of <1> to <6>, wherein the (meth)acrylate compound includes a (meth)acrylate compound containing two or more (meth)acryloyl groups.
<8> A dental material comprising a cured product of the dental material composition according to any one of <1> to <7>.

According to the present disclosure, it is possible to provide a dental material composition that has excellent antibacterial properties and suppresses discoloration due to sulfur components, and a dental material containing a cured product of this dental material composition.

In the present disclosure, numerical ranges indicated using "~" include the numerical values written before and after "~" as minimum and maximum values, respectively.
In the numerical ranges described step by step in this disclosure, the upper limit or lower limit described in one numerical range may be replaced with the upper limit or lower limit of another numerical range described step by step. . Furthermore, in the numerical ranges described in this disclosure, the upper limit or lower limit of the numerical range may be replaced with the values shown in the Examples.
In the present disclosure, "(meth)acryloyl" means acryloyl or methacryloyl, and "(meth)acrylate" means acrylate or methacrylate.
In the present disclosure, the dental material composition refers to a composition in which the dental material composition itself, a cured product of the dental material composition, or a product obtained by further processing the cured product can be used as a dental material. means.
In this disclosure, when referring to the amount of each component in a composition, if there are multiple substances corresponding to each component in the composition, unless otherwise specified, the amount of each component in the composition is means the total amount.
In the present disclosure, the specific inorganic particles may be read as silver-supported zeolite, zinc-supported zeolite, silver-zinc-supported zeolite, silver-supported zirconium compound, zinc-supported zirconium compound, or silver-zinc-supported zirconium compound.

<Composition for dental materials>
The dental material composition of the present disclosure comprises inorganic particles (hereinafter also referred to as "specific inorganic particles") on which at least one metal component selected from the group consisting of silver and zinc is supported, and (meth)acrylate It contains a compound and a polymerization initiator.

The dental material composition of the present disclosure includes at least one of silver-supported inorganic particles, zinc-supported inorganic particles, and silver and zinc-supported inorganic particles as specific inorganic particles. include. This provides excellent antibacterial properties and suppresses discoloration due to sulfur components. More preferably, by using specific inorganic particles, the antibacterial effect can be easily maintained for a long period of time and discoloration such as blackening can be suppressed compared to the case where silver alone is used.

Metals such as silver alone and zinc exhibit excellent antibacterial properties, but when used in dental materials such as dental composite resins, adhesives, and cement materials, they may cause color changes during product storage or after product use. is remarkable. In addition, when ionic antibacterial compounds containing metal ions are used in dental materials, the antibacterial compounds tend to react with acidic group-containing monomers such as acidic (meth)acrylate compounds, reducing their hardenability. There is a possibility that the polymerization initiator contained in the material and the antibacterial compound interact to reduce the polymerizability, antibacterial properties, etc.

In the dental material composition of the present disclosure, specific inorganic particles are used in place of the above metal species and ionic antibacterial compound. Therefore, it is possible to suppress changes in color tone during product storage or after product use, and it is also possible to suitably suppress reactions with acidic group-containing monomers, interactions with polymerization initiators, and the like.

(Specific inorganic particles)
The dental material composition of the present disclosure includes inorganic particles (specific inorganic particles) on which at least one metal component selected from the group consisting of silver and zinc is supported. The specific inorganic particles are not particularly limited as long as they support at least one of silver and zinc. The specific inorganic particles may be inorganic particles on which only silver is supported, may be inorganic particles on which only zinc is supported, or may be inorganic particles on which only silver and zinc are supported, The inorganic particles may support at least one of silver and zinc and a component other than silver and zinc.
One type of specific inorganic particles may be used alone, or two or more types may be used in combination.

The inorganic particles on which at least one of silver and zinc is supported preferably have a porous structure from the viewpoint of supporting ability of metal components.

The inorganic particles supporting at least one of silver and zinc are not particularly limited, and include, for example, aluminosilicate (zeolite, etc.), silica gel, silicate glass, phosphate glass (calcium phosphate, zirconium phosphate, etc.), Examples include magnesium aluminate metasilicate, clay minerals, and ceramics.
Examples of clay minerals include kaolin, montmorillonite, and talc.
The inorganic particles supporting at least one of silver and zinc may be used alone or in combination of two or more.

Specific inorganic particles can be obtained by supporting silver ions, zinc ions, etc. on inorganic particles supporting at least one of silver and zinc through an ion exchange reaction.

It is preferable that the specific inorganic particles contain one or more compounds selected from the group consisting of silicon-containing compounds and zirconium-containing compounds from the viewpoint of antibacterial properties, ability to support metal components, and the like.

The silicon-containing compound is not particularly limited as long as it contains silicon element, and examples thereof include aluminosilicate (such as zeolite), silica gel, silicate glass, and magnesium aluminate metasilicate.
Among these, the silicon-containing compound preferably contains zeolite, and the specific inorganic particles are preferably silver-supported zeolite, zinc-supported zeolite, silver/zinc-supported zeolite, or the like.
Examples of silicon-containing compounds contained in zeolite include silicon dioxide and aluminosilicate.

The zeolite (aluminosilicate) may be a natural zeolite or a synthetic zeolite. Specific examples of the zeolite include A-type zeolite, .

The zeolite may be, for example, a compound represented by the following formula (1).
XM _2/n O・Al ₂ O ₃・YSiO ₂・ZH ₂ O... (1)
In formula (1), M is an element such as silver or sodium, X, Y and Z are the molar ratios of each component, and n is the valence of M.

The zirconium-containing compound is not particularly limited as long as it contains the zirconium element, and examples thereof include zirconium phosphate, zirconium dioxide, and the like.

The inorganic particles supporting at least one of silver and zinc may contain phosphorus compounds such as zirconium phosphate, phosphorus oxide, and calcium phosphate. In particular, the phosphorus compound is preferably phosphate glass. Furthermore, it is preferable that the inorganic particles contain a zirconium-containing compound (particularly, contain zirconium phosphate).

When the specific inorganic particles include a zirconium-containing compound, the specific inorganic particles may include a silver-supported zirconium compound, a zinc-supported zirconium compound, or a silver/zinc-supported zirconium compound.

It is preferable that the specific inorganic particles contain one or more compounds selected from the group consisting of aluminosilicate and phosphate glass from the viewpoint of antibacterial properties, ability to support metal components, etc.

Certain inorganic particles have excellent antibacterial properties and suppress discoloration caused by sulfur components. In the dental material composition of the present disclosure, if the content of specific inorganic particles increases, physical property values such as bending strength may decrease, and if the content of specific inorganic particles decreases, discoloration may be suppressed. It can be more effective. From these viewpoints, it is preferable that the content of specific inorganic particles is small, while on the other hand, in order to exhibit antibacterial properties, it is preferable that the content of specific inorganic particles is large. That is, if specific inorganic particles can exhibit antibacterial properties with a smaller amount, it is possible to enhance the effect of suppressing discoloration and suppress a decrease in physical property values such as bending strength. From this point of view, the specific inorganic particles in the present disclosure are preferably aluminosilicates (such as zeolites).

The amount of silver, the amount of zinc, or the total amount of silver and zinc in a specific inorganic particle may be independently, for example, from 0.1% by mass to 5.0% by mass, and from 0.5% by mass to 2% by mass. It may be .5% by mass.

The volume average particle diameter (D50) of the specific inorganic particles may be, for example, 0.1 μm to 20 μm, 0.5 μm to 15 μm, 1.0 μm to 12 μm, 3 It may be .0 μm to 12 μm.
The volume average particle diameter (D50) of a specific inorganic particle can be measured using a laser diffraction/scattering particle size distribution analyzer.

The content of the specific inorganic particles is preferably 0.01% by mass to 15% by mass based on the total amount of the dental material composition, from the viewpoint of antibacterial properties and the prevention of excessive use of the specific inorganic particles. It is preferably 0.1% by mass to 15% by mass, even more preferably 0.5% by mass to 10% by mass, and particularly preferably 1% by mass to 8% by mass.

The content of the specific inorganic particles should be 0.01 parts by mass to 40 parts by mass based on 100 parts by mass of the (meth)acrylate compound, from the viewpoint of antibacterial properties and the prevention of excessive use of the specific inorganic particles. is preferably 0.01 parts by mass to 30 parts by mass, more preferably 0.1 parts by mass to 20 parts by mass, and particularly preferably 0.5 parts by mass to 15 parts by mass. .

((meth)acrylate compound)
The dental material composition of the present disclosure includes a (meth)acrylate compound. A (meth)acrylate compound is a compound that contains at least one (meth)acryloyl group and undergoes a radical polymerization reaction with a polymerization initiator to form a polymer.
The (meth)acrylate compounds may be used alone or in combination of two or more.

The number of (meth)acryloyl groups contained in the (meth)acrylate compound may be one or two or more.
The number of (meth)acryloyl groups is preferably 2 or more and 10 or less, more preferably 2 or more and 6 or less, and even more preferably 2 or more and 4 or less.

Examples of (meth)acrylate compounds include monofunctional (meth)acrylate compounds containing only one (meth)acryloyl group and polyfunctional (meth)acrylate compounds containing two or more (meth)acryloyl groups.

Examples of monofunctional (meth)acrylate compounds include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 1,3-dihydroxypropyl (meth)acrylate, Examples include 2,3-dihydroxypropyl (meth)acrylate.

Among polyfunctional (meth)acrylate compounds, bifunctional (meth)acrylate compounds containing two (meth)acryloyl groups include:
2,2-bis((meth)acryloyloxyphenyl)propane, 2,2-bis[4-(3-(meth)acryloyloxy)-2-hydroxypropoxyphenyl]propane, 2,2-bis(4-( Aromatic aromas such as meth)acryloyloxyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypolypropoxyphenyl)propane, etc. Difunctional (meth)acrylate compounds based on group compounds;
Erythritol di(meth)acrylate, sorbitol di(meth)acrylate, mannitol di(meth)acrylate, pentaerythritol di(meth)acrylate, dipentaerythritol di(meth)acrylate, glycerol di(meth)acrylate, ethylene glycol di(meth)acrylate ) acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate Acrylate, 1,3-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate 1 , 2-bis(3-methacryloyloxy-2-hydroxypropyloxy)ethane, 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate (UDMA), etc. meth)acrylate compounds;

Among polyfunctional (meth)acrylate compounds, tri- or higher-functional (meth)acrylate compounds containing three or more (meth)acryloyl groups include trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, Trimethylolmethane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate Acrylate, N,N-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)propane-1,3-diol]tetramethacrylate, 1,7-diacryloyloxy-2,2,6, Examples include 6-tetraacryloyloxymethyl-4-oxyheptane.

The (meth)acrylate compound preferably contains a (meth)acrylate compound containing two or more (meth)acryloyl groups, an aromatic hydrocarbon group (for example, a phenylene group) or a urethane bond, and two or more (meth)acryloyl groups. ) It is more preferable to include a (meth)acrylate compound containing an acryloyl group (hereinafter also referred to as an "aromatic ring or urethane bond-containing compound"), and two or more aromatic hydrocarbon groups or two or more urethane bonds and It is more preferable to include a (meth)acrylate compound containing two or more (meth)acryloyl groups.

The (meth)acrylate compound may or may not contain an acidic (meth)acrylate compound. In the dental material composition of the present disclosure, since specific inorganic particles are used as the antibacterial component, the reaction between the acidic group-containing monomer and the antibacterial component is suitably suppressed.

Examples of acidic (meth)acrylate compounds include compounds containing an acidic group such as a phosphoric acid group, a pyrophosphoric acid group, a thiophosphoric acid group, a phosphonic acid group, a sulfonic acid group, a carboxylic acid group, and a (meth)acryloyl group. It will be done.

From the viewpoint of adhesive strength to the adherend, the acidic group-containing monomers include 10-(meth)acryloyloxydecyl dihydrogen phosphate (MDP), 1,3-di(meth)acryloyloxypropyl dihydrogen phosphate, and 2- (meth)acryloyloxyethyl dihydrogen phosphate, 4-(meth)acryloyloxyethyl trimellitate anhydride, 4-(meth)acryloyloxyethyl trimellitate, 2-(meth)acrylamido-2-methylpropanesulfonic acid , 11-(meth)acryloyloxyundecane-1,1-dicarboxylic acid, and dihydroxyethyl methacrylate trimethylhexyl dicarbamate are preferred.

The content of the (meth)acrylate compound may be 10% by mass to 90% by mass, 30% by mass to 80% by mass, or 50% by mass, based on the total amount of the dental material composition. It may be up to 70% by mass.

The content of the aromatic ring or urethane bond-containing compound may be 30 parts by mass to 100 parts by mass, or 50 parts by mass to 95 parts by mass, based on 100 parts by mass of the (meth)acrylate compound. The amount may be 70 parts by mass to 90 parts by mass.

The (meth)acrylate compound of the present disclosure is preferably liquid at room temperature (for example, 25°C).

(Polymerization initiator)
The dental material composition of the present disclosure includes a polymerization initiator.
The polymerization initiator can be a general polymerization initiator used in the dental field, and is usually selected in consideration of the polymerizability and polymerization conditions of the (meth)acrylate compound contained in the composition for dental materials. Ru.

As the polymerization initiator, for example, a redox-based polymerization initiator that is a combination of an oxidizing agent and a reducing agent is preferable. When using a redox-based polymerization initiator, the oxidizing agent and reducing agent may be packaged separately, and the two may be mixed immediately before use.

Examples of polymerization initiators include organic peroxides such as diacyl peroxides such as benzoyl peroxide and decanoyl peroxide/aromatic amines, cumene hydroperoxide/thiourea, ascorbic acid/copper salts, and organic A redox polymerization initiator such as a peroxide/amine compound/sulfinic acid (or salt thereof) type can be used. In addition, trialkylboranes such as tributylborane and its partial oxides, 5-butylbarbituric acid, 5-butyl-2-thiobarbituric acid-based catalysts, etc. are also suitably used as polymerization initiators. .

When performing thermal polymerization by heating, polymerization initiators such as peroxides and azo compounds are preferred.
The peroxide is not particularly limited, and examples thereof include benzoyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, and the like. The azo compound is not particularly limited and includes, for example, azobisisobutyronitrile.

In the case of photopolymerization by irradiation with visible light, α-diketones such as camphorquinone and acetylbenzoyl; benzoyl alkyl ethers such as benzoylethyl ether; thioxanthone derivatives such as 2-chlorothioxanthone and methylthioxanthone; benzophenone, p, p' Examples include photopolymerization catalysts such as benzophenone derivatives such as -methoxybenzophenone; acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 2,6-dimethoxybenzoyldiphenylphosphine oxide.
In addition to these polymerization initiators, amine compounds such as dimethylaminoethyl methacrylate, N,N-dimethyl-p-toluidine, ethyl p-dimethylaminobenzoate, 2-butoxyethyl 4-(dimethylamino)benzoate, It is preferable to use co-catalyst components such as aldehyde compounds such as citronellal and dimethylaminobenzaldehyde, and compounds having a thiol group such as 2-mercaptobenzoxazole and decanethiol.
The above polymerization initiators may be used alone or in combination of two or more.

The content of the polymerization initiator may be 0.01% by mass to 5% by mass, 0.03% by mass to 1% by mass, or 0.01% by mass to 5% by mass, based on the total amount of the dental material composition. It may be from .05% by weight to 0.5% by weight.

(filler)
The dental material composition of the present disclosure may or may not contain fillers other than the specific inorganic particles described above. As the filler other than the specific inorganic particles, general fillers used in the dental field can be used.
Fillers other than specific inorganic particles are generally classified into organic fillers and inorganic fillers.
Fillers other than the specific inorganic particles used in the present disclosure are preferably inorganic fillers.

Examples of the organic filler include polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, crosslinked polymethyl methacrylate, crosslinked polyethyl methacrylate, ethylene-vinyl acetate copolymer, and Examples include fine powder such as styrene-butadiene copolymer.

Inorganic fillers include, for example, various glasses (mainly containing silicon dioxide, containing heavy metals, oxides such as boron and aluminum as necessary), various ceramics, diatomaceous earth, kaolin, clay minerals (montmorillonite, etc.) , activated clay, synthetic zeolite, mica, calcium fluoride, ytterbium fluoride, calcium phosphate, barium sulfate, zirconium dioxide, titanium dioxide, hydroxyapatite, and other fine powders. Specific examples of such inorganic fillers include barium borosilicate glass such as barium boroaluminosilicate glass (Kimbleraysorb T3000, Schott 8235, Schott GM27884 and Schott GM39923, IS 50 1103 Dental Glass (manufactured by FERRO), etc. ), strontium boroaluminosilicate glasses (such as Raysorb T4000, Schott G018-093 and Schott GM32087), lanthanum glasses (such as Schott GM31684), fluoroaluminosilicate glasses (such as Schott G018-091 and Schott G018-117), zirconium and/or Examples include boroaluminosilicate glasses containing cesium (such as Schott G018-307, G018-308 and G018-310).
Among these, barium borosilicate glass and strontium boroaluminosilicate glass are preferred as the inorganic filler.

Further, it is also possible to use an organic-inorganic composite filler obtained by adding a polymerizable compound to these inorganic fillers in advance, making it into a paste, polymerizing and curing it, and pulverizing it.
Further, in the dental material composition, a composition containing microfiller having a particle size of 0.1 μm or less is one of the preferred embodiments for dental composite resin. Preferable materials for the filler having such a small particle size include silica (eg, Aerosil (trade name)), alumina, zirconia, titania, and the like. Blending such an inorganic filler with a small particle size is advantageous in obtaining polishing smoothness of the cured composite resin.

When the dental material composition of the present disclosure contains fillers other than specific inorganic particles, the content of the filler may be 50% by mass or less, and 5% by mass or less based on the total amount of the dental material composition. % to 50% by weight, 10% to 45% by weight, and 20% to 40% by weight.

When the composition for dental materials of the present disclosure contains fillers other than specific inorganic particles, the content of the filler is 50% by mass or less based on the total content of fillers contained in the composition for dental materials. It may be 5% by mass to 50% by mass, 10% by mass to 45% by mass, or 20% by mass to 40% by mass.
The total content of fillers means the total content of specific inorganic particles and fillers other than specific inorganic particles.

The dental material composition of the present disclosure may contain components other than the above-mentioned components as appropriate depending on the purpose. For example, it may contain a polymerization inhibitor to improve storage stability. Further, in order to adjust the color tone, known pigments such as pigments and dyes may be included. Furthermore, in order to improve the hardness of the cured product, a known reinforcing material such as fiber may be included.

The dental material composition of the present disclosure may or may not contain antibacterial components other than the specific inorganic particles.
The content of antibacterial components other than specific inorganic particles may be 5% by mass or less, 3% by mass or less, 1% by mass or less based on the total amount of the dental material composition. It may be 0% by mass.

The dental material composition of the present disclosure is preferably liquid at room temperature (for example, 25° C.).
The dental material composition of the present disclosure preferably has a viscosity (hereinafter also simply referred to as "viscosity") of 10 mPa·s to 1,000,000 mPa·s as measured by an E-type viscometer at 25° C. and 50 rpm. .
Here, rpm means revolutions per minute.
In particular, when the composition for dental materials of the present disclosure is used in a method for manufacturing a stereolithographic object by stereolithography, when the viscosity is 10 mPa·s to 6000 mPa·s, Excellent handling properties for dental material compositions.
When used in a method for manufacturing a stereolithographic object by stereolithography, the viscosity of the dental material composition of the present disclosure is more preferably from 10 mPa·s to 6000 mPa·s, and more preferably from 20 mPa·s to 5000 mPa·s. is more preferable, and particularly preferably 100 mPa·s to 3000 mPa·s.
Further, when the composition for dental materials of the present disclosure is used as a dental restorative material, the viscosity of the composition for dental materials of the present disclosure is 1000 mPa·s to 1000000 mPa·s from the viewpoint of improving the handling properties as a dental restorative material. It is more preferably 2000 mPa·s to 500000 mPa·s, and particularly preferably 5000 mPa·s to 300000 mPa·s.

The dental material composition of the present disclosure is preferably used for stereolithography or dental restorative materials.
Among optical modeling, the dental material composition of the present disclosure can be suitably used in a modeling method using a 3D printer.
In the present disclosure, "stereolithography" is one type of three-dimensional modeling method using a 3D printer.

The stereolithography may be inkjet stereolithography or liquid bath stereolithography (that is, stereolithography using a liquid bath).
The stereolithography may be a liquid bath type stereolithography.
Examples of liquid bath type stereolithography include DLP (Digital Light Processing) type stereolithography, LCD (Liquid Crystal Display) type stereolithography, and SLA (Stereolithography) type stereolithography.
In the DLP method and the LCD method, planar light is irradiated onto the dental material composition in the liquid tank.
In the SLA method, a dental material composition in a liquid tank is scanned with a laser beam.

The dental material composition of the present disclosure may be used for dental treatment.
For example, the dental treatment method of the present disclosure may include a step of polymerizing the dental material composition of the present disclosure in the oral cavity to obtain a cured product. As described above, the method including the step of polymerizing in the oral cavity to obtain a cured product is suitable, for example, when the composition for dental materials is used for dental adhesive resin cement, composite resin for filling and restoration, and the like.

The dental treatment method of the present disclosure may include a step of polymerizing the dental material composition of the present disclosure outside the oral cavity to obtain a cured product, and a step of applying the cured product into the oral cavity. In this way, the step of polymerizing outside the oral cavity to obtain a cured product may be a step of polymerizing the dental material composition in a cast mold to obtain a cured product, or polymerizing by stereolithography to obtain a cured product. It may be a process. The cured product obtained outside the oral cavity may be processed as necessary, and the cured product after processing may be applied inside the oral cavity. The method of obtaining a cured product by polymerizing outside the oral cavity is suitable, for example, when the cured product is used for CAD/CAM resin blocks, temporary crowns, artificial teeth, etc.

<Dental materials>
The dental material of the present disclosure includes a cured product of the dental material composition of the present disclosure. The dental material of the present disclosure preferably includes a cured product obtained by stereolithography (i.e., a stereolithography product). The dental material of the present disclosure has excellent antibacterial properties, and discoloration due to sulfur components is suppressed.

The composition for dental materials of the present disclosure and the dental materials of the present disclosure include dental restorative materials, denture base resins, denture base lining materials, impression materials, bonding materials (resin cement, resin-added glass ionomer cement, etc.). ), dental adhesives (orthodontic adhesives, cavity coating adhesives, etc.), tooth fissure sealants, resin blocks for CAD/CAM, temporary crowns, artificial tooth materials, prosthetics, used in the oral cavity Examples include medical instruments and models (Zingiba mask, etc.).
Examples of dental restorative materials include composite resins for dental crowns, composite resins for filling carious cavities, composite resins for building abutments, and composite resins for filling restorations.
Examples of prosthetics include complete dentures, partial dentures, and the like.
Appliances used in the oral cavity include sports mouthpieces, mouthguards, orthodontic mouthpieces, splints such as occlusal adjustment splints or temporomandibular joint disorder treatment splints, and splints used to treat sleep apnea syndrome. Examples include mouthpieces.

Examples of the present disclosure will be shown below, but the present disclosure is not limited to the following examples. The abbreviations of compounds used in the examples of the present disclosure are shown below.
UDMA: 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl) dimethacrylate 3G: Triethylene glycol dimethacrylate CQ: Camphorquinone DMBE: 2-Butoxyethyl 4-(dimethylamino)benzoate Luperox: Luperox 531M80 (Arkema Yoshitomi Co., Ltd.)
Ag: Silver powder Silver-supported zeolite: Aluminosilicate, manufactured by Sinanen Zeomic Co., Ltd., D50: 5.5 μm to 10 μm
Silver-supported phosphate glass: manufactured by Sinanen Zeomic Co., Ltd., D50: 8.0 μm to 12 μm

[Preparation of test pieces for antibacterial evaluation: Examples 1 to 4, and Comparative Examples 1 to 3]
3.2 parts by mass of UDMA, 0.8 parts by mass of 3G, 0.05 parts by mass of CQ, and 0.05 parts by mass of DMBE were placed in a container and stirred at 50°C until uniform. Next, silica glass: GM8235 (1 μm, surface silane treatment amount: 3%) and various inorganic materials (the above-mentioned Ag, silver-supported phosphate glass, or silver-supported zeolite) were blended at the mass ratio shown in Table 1, and defoaming was performed. went. In this way, a photopolymerizable composition was prepared.
A 25 μm thick PET film was placed on the glass, and a 1 mm thick silicone mold was placed on top of it. The prepared composition was placed in the mold, another PET film was placed on the composition, and then another glass was covered from above.
After that, the two pieces of glass were pressed together, and using Alphalight V LCR11 (manufactured by Morita Co., Ltd.), light was irradiated on the front and back sides for 3 minutes each to completely cure them, and Examples 1 to 4 and Test pieces for antibacterial evaluation of Comparative Examples 1 and 2 were prepared.
A test piece for antibacterial evaluation (a test piece serving as a standard for antibacterial evaluation) of Comparative Example 3 was prepared in the same manner as in Example 1, except that no inorganic material was used.

[Antibacterial evaluation 1 (thermal cycle not performed)]
A test piece for antibacterial evaluation (3.5 cm long, 3.5 cm wide, and 1 mm thick) was ultrasonically cleaned in ethanol for 10 minutes, and then the ethanol was replaced with ultrapure water and the ultrasonic cleaning was performed again for 10 minutes. The remaining (meth)acrylate compound was removed.
Next, the antibacterial evaluation test piece was subjected to an antibacterial test against Streptococcus mutans NBRC13955 (distributed by the Biotechnology Center of the National Institute of Technology and Evaluation) according to the method described in JIS Z 2801:2012. was carried out as follows, and the antibacterial activity value was calculated.

First, three test pieces were disinfected with an 80% by mass ethanol aqueous solution and thoroughly dried. Next, Streptococcus mutans was cultured overnight in Brain Heart Infusion Medium (Nippon Becton Dickinson Model No. 237500), and the number of bacteria was adjusted to 2.5 x 10 ⁵ cells/mL to 10 x 10 ⁵ cells/mL in the same medium. After diluting and placing 225 μL per test piece, a sterilized PET film (3 cm long, 3 cm wide, and 25 μm thick) was placed and brought into close contact.
This test piece was cultured at 37°C for 24 hours under microaerobic conditions (specifically, oxygen concentration 6% by volume) using an anaerobic/microaerobic culture jar system Anoxomat Mark II (Central Kagaku Boeki Co., Ltd.). went. Thereafter, the culture solution was collected and diluted using phosphate buffered saline, seeded on a brain heart infusion agar medium, and cultured at 37° C. for 48 hours under microaerobic conditions, and the number of viable bacteria was measured. The formula for calculating the antibacterial activity value R is as follows.
In addition, in this test, Comparative Example 3 in Table 1 was treated as an unprocessed test piece.
R=(Ut-U0)-(At-U0)=Ut-At
R: Antibacterial activity value U0: Average value of the logarithm of the number of viable bacteria immediately after inoculation of the untreated test piece Ut: Average value of the logarithm of the number of viable bacteria 24 hours after inoculation of the untreated test piece At: Antibacterial treated test piece The average value of the logarithm of the number of viable bacteria after 24 hours

The antibacterial activity value R is an index of antibacterial properties; the larger the value, the higher the antibacterial activity, and a value of 2.0 or more is judged to have antibacterial activity.
The results are shown in Table 1.

[Antibacterial evaluation 2 (thermal cycle implementation)]
For each Example and Comparative Example, the antibacterial properties were evaluated after being subjected to 10,000 thermal cycles (immersion at 55° C. for 30 seconds and immersion at 5° C. for 30 seconds alternately).
The results are shown in Table 1.

[Evaluation of hue change]
A hue change test was conducted as follows.
First, 10 mg of sulfur powder was added to 1 kg of distilled water and stirred at 50° C. to prepare a sulfur aqueous solution. After that, the antibacterial evaluation test piece prepared in the same manner as in [Antibacterial evaluation 1] above was immersed in the sulfur preparation solution, left to stand at 37°C for 24 hours, and then the presence or absence of a hue change was confirmed using a loupe and a microscope. did.
The results are shown in Table 1.

As shown in Table 1, in Examples 1 to 4, high antibacterial properties were confirmed in antibacterial evaluation 1 and antibacterial evaluation 2, and no change in hue of the antibacterial evaluation test pieces was observed.
On the other hand, in Comparative Example 1, it was confirmed that antibacterial properties were low in antibacterial evaluation 1 and antibacterial evaluation 2, and the antibacterial evaluation test piece turned black. In Comparative Example 2, high antibacterial properties were obtained in antibacterial evaluation 1, but it was confirmed that antibacterial properties were low in antibacterial evaluation 2, and the antibacterial evaluation test piece turned black.

[Preparation of test pieces for antibacterial evaluation: Examples 5 to 8, and Comparative Examples 4 to 5]
3.2 parts by mass of UDMA, 0.8 parts by mass of 3G, and 0.032 parts by mass of Luperox were placed in a container and stirred at 50°C until uniform. Next, silica glass: GM8235 (1 μm, surface silane treatment amount: 3%) and various inorganic materials (the above-mentioned Ag, silver-supported phosphate glass, or silver-supported zeolite) were blended in the mass ratio shown in Table 2, and then desorbed. Made bubbles. In this way, a thermally polymerizable composition was prepared.
A silicone mold with a thickness of 1 mm was placed on top of the glass. The prepared composition was placed in the mold, and another sheet of glass was placed over the composition.
Thereafter, the two pieces of glass were pressed together and heated in an oven at 100° C. for one hour to completely cure the glass to prepare test pieces for antibacterial evaluation of Examples 5 to 8 and Comparative Example 4.
A test piece for antibacterial evaluation of Comparative Example 4 was prepared in the same manner as in Example 5, except that no inorganic material was used.
Antibacterial evaluation 1 (thermal cycle not performed) and hue change test were conducted in the same manner as in Example 1. The results are shown in Table 2.

As shown in Table 2, in Examples 5 to 9, high antibacterial properties were confirmed in antibacterial evaluation 1, and no change in the hue of the antibacterial evaluation test pieces to black was observed.
On the other hand, in Comparative Example 5, it was confirmed that the antibacterial evaluation test piece turned black.

The disclosures of Japanese Patent Application No. 2022-048776 filed on March 24, 2022 and Japanese Patent Application No. 2022-204889 filed on December 21, 2022 are incorporated herein by reference in their entirety. .
All documents, patent applications, and technical standards mentioned herein are incorporated by reference to the same extent as if each individual document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference. Incorporated herein by reference.

Claims

A composition for dental materials, comprising inorganic particles carrying at least one metal component selected from the group consisting of silver and zinc, a (meth)acrylate compound, and a polymerization initiator.
The dental material composition according to claim 1, wherein the inorganic particles include one or more compounds selected from the group consisting of aluminosilicate and phosphate glass.
The composition for dental materials according to claim 1, wherein the content of the inorganic particles is 0.01% by mass to 15% by mass based on the total amount of the composition for dental materials.
The composition for dental materials according to claim 1, wherein the content of the inorganic particles is 0.01 parts by mass to 40 parts by mass based on 100 parts by mass of the (meth)acrylate compound.
The dental material composition according to claim 1, further comprising a filler other than the inorganic particles.
further comprising a filler other than the inorganic particles, and the content of the filler other than the inorganic particles is 50% by mass or less with respect to the total content of fillers contained in the dental material composition;
Or, the dental material composition according to claim 1, which does not contain any filler other than the inorganic particles.
The composition for dental materials according to claim 1, wherein the (meth)acrylate compound includes a (meth)acrylate compound containing two or more (meth)acryloyl groups.
A dental material comprising a cured product of the dental material composition according to any one of claims 1 to 7.