JP6779068B2 - Method for manufacturing dental curable composition - Google Patents

Description

The present invention relates to a method for producing a dental curable composition preferably used as a dental material, particularly a dental composite resin or a dental cement, which can replace a part or the whole of a natural tooth in the field of dentistry.

The dental curable composition is a mixture of an inorganic filler, a polymerizable monomer, and a polymerizable initiator, and is the most suitable material for filling and repairing a tooth defect including tooth decay today. It is a frequently used material. The composition can exert a preferable effect as a dental material by using a specific compounding component or adjusting the compounding component ratio or the like, and is used, for example, in applications such as composite resin and cement. .. Composite resins have become a widely used dental material today as a material for repairing tooth defects, including tooth decay. Cement is used to bond dental prostheses such as zirconia and ceramics, and demand is increasing. In any of the dental curable compositions, in the paste before polymerization curing or in a highly viscous liquid state, it is necessary to have appropriate operability, and the consistency is an index thereof. The user often has a desired consistency, and if the consistency changes over time, the workability of the user is impaired, which may cause clinical troubles.

Examples of the method for producing a dental curable composition for the purpose of preventing such a change in consistency with time and improving operability include the methods described in Patent Documents 1 and 2. Specifically, Patent Document 1 describes a method of kneading a composite material containing a fine particle filler, a silane-treated filler, a polymerizable monomer, and a polymerization initiator using a mixing blade such as a kneader or a planetary mixer. Has been done.

Patent Document 2 describes a method for producing a curable dental restoration material, such as stirring with a mechanical stirrer and a kneading method such as a mortar and a planetary kneader.

Patent No. 5716118 International Publication 2010/067790

However, in the dental curable composition produced by the above method, although the inorganic filler and the polymerizable monomer are kneaded, they are not completely kneaded, so that the consistency changes with time. I was not fully satisfied with the long-term physical stability.

An object of the present invention is to provide a method for producing a dental curable composition having excellent long-term stability in terms of consistency. Another object of the present invention is to provide a method for producing a dental curable composition having excellent long-term stability in terms of mechanical strength.

As a result of diligent studies to solve the above problems, the present inventors have obtained a method for producing a dental curable composition having a step of applying acoustic energy, whereby dental curing having stable consistency over a long period of time is used. They have found that a sex composition can be obtained, and have completed the present invention.

That is, the present invention relates to a method for producing a dental curable composition, which comprises a step of applying acoustic energy to a pretreatment composition containing an inorganic filler, a polymerizable monomer and a polymerization initiator.

The dental curable composition obtained by the production method of the present invention has long-term stability in terms of consistency. In addition, the dental curable composition obtained by the production method of the present invention has long-term stability in terms of mechanical strength.

In the present invention, acoustic energy produced by an acoustic mixer is used for a pretreatment composition containing an inorganic filler, a polymerizable monomer and a polymerization initiator (hereinafter, simply referred to as “pretreatment composition”). In particular, the acoustic energy preferably has a frequency of 10 to 100 Hz, and more preferably a frequency of 20 to 90 Hz. If it is less than 10 Hz, it may not be possible to provide sufficient energy required to mix the pretreatment composition.

The acoustic energy described above is supplied to the pre-treatment composition using some known origin, but generally supplies energy to a container filled with the pre-treatment composition by periodic linear displacement. Is preferable. In the present invention, the gravitational energy supplied by the linear displacement is about 10 times the gravitational acceleration (10G = 10 × 9.80665m / s ² ) to about 100 times the gravitational acceleration (100G =) with respect to the untreated composition. It is more preferable to generate 100 × 9.80665 m / s ² ). Of course, a number of mechanical or electronic converter arrangements can be utilized to provide the periodic linear displacements required to generate the desired gravitational acceleration in the desired frequency domain, although An example of commercially available equipment suitable for supplying the required acoustic energy is the Resodyn® Acoustic Mixers (Inc.), which can handle from a few grams of lab scale to a few kilograms of production scale. is there.

The dental curable composition produced in the present invention relates to dental materials (particularly dental composite resins, dental cements) that can replace part or all of natural teeth in the field of dentistry. The composition comprises an inorganic filler, a polymerizable monomer, and a polymerization initiator. As the inorganic filler, one surface-treated with a silane coupling agent may be used.

The inorganic filler used in the present invention will be described below. The inorganic filler is not particularly limited, and known inorganic particles can be used. Specifically, various types of glass (silicon dioxide (quartz, quartz glass, silica gel, etc.) or silicon dioxide as a main component and containing boron and / or aluminum together with various heavy metals), alumina, various ceramics, diatomaceous earth, Conventionally known kaolin, clay minerals (montmorillonite, etc.), activated clay, synthetic zeolite, mica, silica, calcium fluoride, itterbium fluoride, calcium phosphate, barium sulfate, zirconium dioxide (zirconia), titanium dioxide (titania), hydroxyapatite, etc. You can use the thing of. Further, the inorganic filler contains organic-inorganic composite particles (organic-inorganic composite filler) obtained by preliminarily adding a polymerizable monomer to the inorganic particles to form a paste, then polymerizing and curing the inorganic particles, and pulverizing the mixture. May be good. As the material of the inorganic filler, the inorganic particles or the organic-inorganic composite particles may be used alone or in combination of two or more.

Further, important physical properties desired for dental composite resins and dental cements include transparency and X-ray contrast properties similar to those of natural teeth. Transparency is achieved by matching the refractive indexes of the inorganic filler and the cured polymerizable monomer as much as possible. Further, in order to impart X-ray contrast, an inorganic oxide containing a heavy metal element such as zirconium, barium, titanium, lantern, and strontium is used as a material for the inorganic filler. The refractive index of the inorganic filler containing the heavy metal element is usually high and is in the range of 1.5 to 1.6. Further, the refractive index of the cured product of the (meth) acrylate-based monomer can usually be adjusted within the range of 1.5 to 1.6. In the present invention, for example, the curable composition containing the inorganic filler containing the heavy metal element and the (meth) acrylate-based monomer as the polymerizable monomer is composed of the inorganic filler and the polymerizable monomer. Since the difference in refractive index can be adjusted to be small, the obtained dental composite resin and dental cement are useful because they can easily obtain not only X-ray contrast property but also high transparency.

The form of the inorganic particles is not particularly limited, and various shapes such as crushed, plate-shaped, scaly, fibrous (short fibers, long fibers), needle-shaped, whiskers, and spherical shapes are used. The inorganic particles may be in the form of aggregated primary particles having the above-mentioned shape, or may be a combination of primary particles having different shapes. In the present invention, the inorganic particles may be subjected to some kind of treatment (for example, pulverization) so as to have the above-mentioned shape.

The particle size of the inorganic particles may have a size that is usually used as an inorganic filler for dental composite resins or dental cements. For example, the average particle size is 1.0 nm to 10 μm (particle size range:: Those having a diameter of 0.50 nm to 50 μm) can be mentioned. The average particle size is preferably 2.0 nm to 5.0 μm (particle size range: 0.50 nm to 20 μm), and preferably 5.0 nm to 3.0 μm (particle size range: 1.0 nm to 10 μm). Is more preferable. In the present specification, the particle size of the inorganic particles means the particle size (average primary particle size) of the primary particles of the inorganic particles, and the particle size range includes 95% of the primary particles of the inorganic particles. It is the range of particle size. Even if inorganic particles not included in the specified particle size range are unintentionally contained in the inorganic filler, there is no particular limitation as long as the effect of the present invention is not impaired.

In this specification, the average particle size of the inorganic particles can be determined by a laser diffraction / scattering method or an electron microscope observation. Specifically, the laser diffraction / scattering method is used to measure the particle size of inorganic particles having a particle size of 0.10 μm or more, and the electron is used to measure the particle size of inorganic particles (ultrafine particles) having a particle size of less than 0.10 μm. Microscopic observation is convenient.

The laser diffraction / scattering method can be measured by using, for example, a laser diffraction type particle size distribution measuring device (SALD-2100, manufactured by Shimadzu Corporation) using a 0.2% sodium hexametaphosphate aqueous solution as a dispersion medium.

The average particle size can be measured by observing with an electron microscope, for example, by taking a picture of inorganic particles with a transmission electron microscope (H-800NA type manufactured by Hitachi, Ltd.) and observing 200 particles in the unit field of view of the picture. The particle size of the above) can be measured by using an image analysis type particle size distribution measurement software (Macview (Mount Tech Co., Ltd.)). At this time, the particle diameter of the particles is obtained as the diameter of a perfect circle having the same area as the particles, and the average primary particle diameter is calculated from the number of particles and each particle diameter.

In the production method of the present invention, an inorganic filler in which two or more kinds of inorganic particles having different materials, particle size distributions, and morphologies are mixed or combined may be used, and within a range that does not impair the effects of the present invention. , Unintentionally, particles other than inorganic particles may be contained as impurities.

The blending amount of the inorganic filler is not particularly limited, but is preferably 30 to 95% by mass, more preferably 35 to 90% by mass, still more preferably 40 to 85% by mass, based on the total amount of the pre-treatment composition.

Further, as the inorganic filler, inorganic particles that have been surface-treated in advance with a surface treatment agent can be used. By applying the surface treatment to the inorganic particles, the compatibility with the polymerizable monomer is improved, and the inorganic filler and the polymerizable monomer tend to become a paste.

As the surface treatment agent, a known surface treatment agent can be used, and for example, an organic metal compound such as an organic silicon compound, an organic titanium compound, an organic zirconium compound, and an organic aluminum compound; a phosphoric acid group, a pyrophosphate group, and a thiophosphate. An acidic group-containing organic compound having at least one acidic group such as a group, a phosphonic acid group, a sulfonic acid group, and a carboxylic acid group can be used. When two or more kinds of surface treatment agents are used, a mixture of two or more kinds of surface treatment agents may be applied to the inorganic filler. As a method for surface-treating the inorganic particles, a known method can be used without particular limitation.

Examples of the organic silicon compound include compounds represented by R ¹ _n SiX _4-n (in the formula, R ¹ is a substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms, and X is a carbon number of carbon atoms. It represents an alkoxy group, an acetoxy group, a hydroxy group, a halogen atom or a hydrogen atom of 1 to 4, and n is an integer of O to 3. However, a plurality of R ¹ and X are different even if they are the same as each other. May be.).

The organic silicon compound is, for example, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, isobutyltrimethoxysilane. , Vinyltrimethoxysilane, Vinyltriethoxysilane, Vinyltris (β-methoxyethoxy) silane, 3,3,3-trifluoropropyltrimethoxysilane, Methyl-3,3,3-trifluoropropyldimethoxysilane, β-( 3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, γ- (meth) acryloxy Propylmethyldimethoxysilane, γ- (meth) acryloxipropylmethyldiethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxy Silane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercapto Propyltrimethoxysilane, trimethylsilanol, methyltrichlorosilane, methyldichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, vinyltrichlorosilane, trimethylbromosilane, diethylsilane, vinyltriacetoxysilane, ω-( Meta) acryloxyalkyltrimethoxysilane [carbon number between (meth) acryloxi group and silicon atom: 3 to 12, for example, γ-methacryloxypropyltrimethoxysilane], ω- (meth) acryloxialkyltri Examples thereof include ethoxysilane [the number of carbon atoms between the (meth) acryloxy group and the silicon atom: 3 to 12, for example, γ-methacryloxypropyltriethoxysilane, etc.]. In the present invention, the notation "(meth) acryloxy" is used to include both a methacryloxy group and an acryloxy group.

The organosilicon compound is preferably a coupling agent having a functional group capable of copolymerizing with a polymerizable monomer. For example, ω- (meth) acryloxyalkyltrimethoxysilane [(meth) acryloxy group and silicon Carbon number between atoms: 3-12], ω- (meth) acryloxyalkyltriethoxysilane [carbon number between (meth) acryloxy group and silicon atom: 3-12], vinyltrimethoxysilane, Vinyl triethoxysilane, vinyl triacetoxysilane, γ-glycidoxypropyltrimethoxysilane and the like are preferable.

Examples of the organic titanium compound include tetramethyl titanate, tetraethyl titanate, tetraisopropyl titanate, tetra n-butyl titanate, butyl titanate dimer, tetra (2-ethylhexyl) titanate and the like.

Examples of the organic zirconium compound include zirconium isopropoxide, zirconium n-butoxide, zirconium acetylacetonate, and zirconium acetate.

Examples of the organoaluminum compound include aluminum acetylacetonate and aluminum organolate chelate compounds.

Examples of the acidic group-containing organic compound containing a phosphoric acid group include 2-ethylhexyl acid phosphate, stearyl acid phosphate, 2- (meth) acryloyloxyethyl dihydrogen phosphate, and 3- (meth) acryloyloxypropyl dihydro. Genphosphate, 4- (meth) acryloyloxybutyl dihydrogenphosphate, 5- (meth) acryloyloxypentyl dihydrogenphosphate, 6- (meth) acryloyloxyhexyl dihydrogenphosphate, 7- (meth) acryloyloxyheptyl Dihydrogenphosphate, 8- (meth) acryloyloxyoctyl dihydrogenphosphate, 9- (meth) acryloyloxynonyl dihydrogenphosphate, 10- (meth) acryloyloxydecyldihydrogenphosphate, 11- (meth) acryloyl Oxyundecyldihydrogen phosphate, 12- (meth) acryloyl oxide decyldihydrogenphosphate, 16- (meth) acryloyloxyhexadecyldihydrogenphosphate, 20- (meth) acryloyloxyeicosildihydrogenphosphate, bis [2- (Meta) acryloyloxyethyl] hydrogen phosphate, bis [4- (meth) acryloyloxybutyl] hydrogen phosphate, bis [6- (meth) acryloyloxyhexyl] hydrogen phosphate, bis [8- (meth) ) Acryloyloxyoctyl] hydrogen phosphate, bis [9- (meth) acryloyloxynonyl] hydrogen phosphate, bis [10- (meth) acryloyloxydecyl] hydrogen phosphate, 1,3-di (meth) acryloyloxypropyl Dihydrogenphosphate, 2- (meth) acryloyloxyethylphenylhydrogenphosphate, 2- (meth) acryloyloxyethyl-2-bromoethylhydrogenphosphate, bis [2- (meth) acryloyloxy- (1-hydroxymethyl) ) Ethyl] Hydrogen phosphate, and acid groups thereof, alkali metal salts, ammonium salts and the like can be mentioned.

Further, as the acidic group-containing organic compound having an acidic group such as a pyrophosphate group, a thiophosphate group, a phosphonic acid group, a sulfonic acid group, and a carboxylic acid group, for example, those described in WO2012 / 042911 are preferably used. Can be done.

The surface treatment agent may be used alone or in combination of two or more. Further, in order to enhance the chemical bond between the inorganic filler and the polymerizable monomer and improve the mechanical strength of the cured product of the dental curable composition, the surface treatment agent may be used with the polymerizable monomer. An acidic group-containing organic compound having a functional group that can be copolymerized is more preferable.

The amount of the surface treatment agent used is not particularly limited, and for example, 0.1 to 50 parts by mass is preferable with respect to 100 parts by mass of the inorganic filler.

The polymerizable monomer will be described below. As the polymerizable monomer, a known polymerizable monomer used for dental composite resin, dental cement and the like can be used without any limitation, but in general, a radical polymerizable monomer is preferable. The radically polymerizable monomer includes, for example, esters such as α-cyanoacrylic acid, (meth) acrylic acid, α-halogenated acrylic acid, crotonic acid, cinnamic acid, sorbic acid, maleic acid, and itaconic acid. Examples thereof include meta) acrylamide, (meth) acrylamide derivative, vinyl ester, vinyl ether, mono-N-vinyl derivative, styrene derivative and the like. Among these, (meth) acrylic acid ester and (meth) acrylamide derivative are preferable, and (meth) acrylic acid ester is more preferable. In the present invention, the notation "(meth) acrylic" is used to include both methacrylic and acrylic. Examples of (meth) acrylic acid ester-based and (meth) acrylamide derivative-based polymerizable monomers are shown below.

(I) Monofunctional (meth) acrylate and (meth) acrylamide derivative Methyl (meth) acrylate, isobutyl (meth) acrylate, benzyl (meth) acrylate, lauryl (meth) acrylate, 2- (N, N-dimethylamino) Ethyl (meth) acrylate, 2,3-dibromopropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, propylene glycol mono (meth) Acrylate, glycerin mono (meth) acrylate, erythritol mono (meth) acrylate, N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N- (dihydroxyethyl) (meth) acrylamide, (meth) acryloyl oxide decyl Examples thereof include pyridinium bromide, (meth) acryloyl oxide decyl pyridinium chloride, (meth) acryloyloxyhexadecyl pyridinium chloride, (meth) acryloyl oxydecyl ammonium chloride, and 10-mercaptodecyl (meth) acrylate.

(Ii) Bifunctional (meth) acrylate Ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol Di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 2,2-bis [4- [3-acryloyloxy-2-hydroxypropoxy] phenyl] propane, 2,2-bis [4- ( 3-Metaacryloyloxy-2-hydroxypropoxy) phenyl] propane (commonly known as Bis-GMA)), 2,2-bis [4- (meth) acryloyloxyethoxyphenyl] propane, 2,2-bis [4- (meth) ) Acryloyloxypolyethoxyphenyl] Propane, 1,2-bis [3- (meth) acryloyloxy2-hydroxypropoxy] ethane, pentaerythritol di (meth) acrylate, [2,2,4-trimethylhexamethylenebis (2) -Power Lubamoyloxyethyl)] Dimethacrylate (commonly known as UDMA), 2,2,3,3,4,4-hexafluoro-1,5-pentyldi (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate And so on.

(Iii) Trifunctional or higher (meth) acrylate Trimethylolpropane tri (meth) acrylate, trimethylolethanetri (meth) acrylate, tetramethylolmethanetri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol Hexa (meth) acrylate, N, N'-(2,2,4-trimethylhexamethylene) bis [2- (aminocarboxy) propan-1,3-diol] tetra (meth) acrylate, 1,7-diacryloyl Oxy-2,2,6,6-tetraacryloyloxymethyl-4-oxaheptane and the like can be mentioned.

Further, in order to have adhesiveness to the tooth substance and the prosthesis, a polymerizable monomer having an acidic group in the polymerizable monomer can also be used. These can be used individually by 1 type or in combination of 2 or more types as appropriate. As the polymerizable monomer, a polymerizable monomer having at least one acidic group selected from the group consisting of a phosphoric acid group, a thiophosphate group, a phosphonic acid group, a sulfonic acid group, and a carboxylic acid group is preferable. Is.

As the polymerizable monomer having a phosphoric acid group, the above-mentioned acidic group-containing organic compound containing a phosphoric acid group can be used.

Examples of the acidic group-containing polymerizable monomer having an acidic group such as a pyrophosphate group, a thiophosphate group, a phosphonic acid group, a sulfonic acid group, and a carboxylic acid group include the above-mentioned pyrophosphate group and thiophosphate group. An acidic group-containing organic compound having an acidic group such as a phosphonic acid group, a sulfonic acid group, and a carboxylic acid group can be used.

Further, in addition to these (meth) acrylic acid ester-based and (meth) acrylamide derivative-based polymerizable monomers, a cationically polymerizable oxylan compound or oxetane compound is also preferably used.

The blending amount of the polymerizable monomer is not particularly limited, but is preferably 3 to 60% by mass, more preferably 7 to 55% by mass, and further 13 to 50% by mass with respect to the total amount of the composition before treatment. preferable. Each of the above-mentioned polymerizable monomers may be used alone or in combination of two or more. Further, the polymerizable monomer used in the present invention is preferably in a liquid state, but it does not necessarily have to be in a liquid state at room temperature, and the environment of the step of bringing the polymerizable monomer into contact with the powder press-molded body. It doesn't matter if it is liquid underneath. Further, even a solid polymerizable monomer can be mixed and dissolved with other liquid polymerizable monomers before use.

Next, the polymerization initiator will be described. Examples of the polymerization initiator include a heat polymerization initiator, a photopolymerization initiator, and a chemical polymerization initiator. These may be used alone or in combination of two or more.

Examples of the heat polymerization initiator include organic peroxides and azo compounds.

Examples of the organic peroxide used as the heat polymerization initiator include ketone peroxides, hydroperoxides, diacyl peroxides, dialkyl peroxides, peroxyketals, peroxyesters, peroxydicarbonates and the like.

Examples of the ketone peroxide include methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, methylcyclohexanone peroxide, cyclohexanone peroxide and the like.

Examples of the hydroperoxide include 2,5-dimethylhexane-2,5-dihydroperoxide, diisopropylbenzenehydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, 1,1,3,3-. Examples thereof include tetramethylbutylhydroperoxide. Examples of the diacyl peroxide include acetyl peroxide, isobutyryl peroxide, benzoyl peroxide, decanoyyl peroxide, 3,5,5-trimethylhexanoyl peroxide, 2,4-dichlorobenzoyl peroxide, and lauroyl peroxide. And so on. Examples of the dialkyl peroxide include di-t-butyl peroxide, dicumyl peroxide, t-butyl cumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, and 1, Examples thereof include 3-bis (t-butylperoxyisopropyl) benzene and 2,5-dimethyl-2,5-di (t-butylperoxy) -3-hexine. Examples of the peroxyketal include 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, and 2,2-bis (). Examples thereof include t-butylperoxy) butane, 2,21-bis (t-butylperoxy) octane, and 4,4-bis (t-butylperoxy) valeric acid-n-butyl. Examples of the peroxy ester include α-cumylperoxyneodecanoate, t-butylperoxyneodecanoate, t-butylperoxypivalate, and 2,2,4-trimethylpentylperoxy-2-ethyl. Hexanoate, t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, di-t-butylperoxyisophthalate, di-t-butylperoxyhexahydroterephthalate , T-Butylperoxy-3,3,5-trimethylhexanoate, t-butylperoxyacetate, t-butylperoxybenzoate, t-butylperoxymaleic acid and the like. Examples of the peroxydicarbonate include di-3-methoxyperoxydicarbonate, di-2-ethylhexyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, diisopropylperoxydicarbonate, and diisopropyldicarbonate. Examples thereof include -n-propylperoxydicarbonate, di-2-ethoxyethylperoxydicarbonate and diallylperoxydicarbonate.

Among these organic peroxides, diacyl peroxide is preferably used from the viewpoint of overall balance of safety, storage stability and radical generation ability, and among them, benzoyl peroxide is more preferably used.

Examples of the azo compound include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 4,4'-azobis (4-cyanovaleric acid), and the like. Examples thereof include 1,1'-azobis (cyclohexane-1-carbonitrile), dimethyl-2,2'-azobis (isobutyrate), and 2,2'-azobis (2-aminopropane) dihydrochloride.

Examples of the photopolymerization initiator include (bis) acylphosphine oxides, α-diketones, coumarins and the like.

Among the (bis) acylphosphine oxides, the acylphosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2 , 4,6-trimethylbenzoylmethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, benzoyldi- (2,6-dimethylphenyl) Examples thereof include phosphonates and salts thereof. Examples of bisacylphosphine oxides include bis (2,6-dichlorobenzoyl) phenylphosphine oxide, bis (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, and bis (2,6-dichlorobenzoyl)-. 4-propylphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4 4-trimethylpentylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,5,6-trimethyl) Benzoyl) -2,4,4-trimethylpentylphosphine oxide, salts thereof and the like can be mentioned. Among these (bis) acylphosphine oxides, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide And 2,4,6-trimethylbenzoylphenylphosphine oxide sodium salt are preferred.

Examples of α-diketones include diacetyl, dibenzyl, camphorquinone, 2,3-pentadione, 2,3-octadione, 9,10-phenanthrene quinone, 4,4'-oxybenzyl, and acenaphthenquinone. Can be mentioned. Of these, camphorquinone is preferred.

Examples of coumarins include 3,3'-carbonylbis (7-diethylamino kumarin), 3- (4-methoxybenzoyl) coumarin, 3-thienoyl coumarin, 3-benzoyl-5,7-dimethoxy kumarin, 3-benzoyl- 7-methoxykumarin, 3-benzoyl-6-methoxykumarin, 3-benzoyl-8-methoxykumarin, 3-benzoyl kumarin, 7-methoxy-3- (p-nitrobenzoyl) coumarin, 3- (p-nitrobenzoyl) Kumarin, 3,5-carbonylbis (7-methoxykumarin), 3-benzoyl-6-bromokumarin, 3,3'-carbonylbiskumarin, 3-benzoyl-7-dimethylaminocoumarin, 3-benzoylbenzo [f] Kumarin, 3-carboxykumarin, 3-carboxy-7-methoxykumarin, 3-ethoxycarbonyl-6-methoxykumarin, 3-ethoxycarbonyl-8-methoxykumarin, 3-acetylbenzo [f] kumarin, 3-benzoyl-6 -Nitro kumarin, 3-benzoyl-7-diethylamino kumarin, 7-dimethylamino-3- (4-methoxybenzoyl) coumarin, 7-diethylamino-3- (4-methoxybenzoyl) coumarin, 7-diethylamino-3- (4) -Diethylamino) coumarin, 7-methoxy-3 (4-methoxybenzoyl) coumarin, 3- (4-nitrobenzoyl) benzo [f] coumarin, 3- (4-ethoxycinnamoyl) -7-methoxycumin, 3- ( 4-Dimethylaminocinnamoyle) coumarin, 3- (4-diphenylaminocinnamoyle) coumarin, 3-[(3-dimethylbenzothiazole-2-ylidene) acetyl] coumarin, 3-[(1-methylnaphtho [1,2] -D] Thiazol-2-ylidene) Acetyl] coumarin, 3,3'-carbonylbis (6-methoxycumarin), 3,3'-carbonylbis (7-acetoxycmarin), 3,3'-carbonylbis (7) -Dimethylaminocoumarin), 3- (2-benzothiazoyl) -7- (diethylamino) coumarin, 3- (2-benzothiazoyl) -7- (dibutylamino) coumarin, 3- (2-benzoimidazole) -7- (diethylamino) coumarin, 3- (2-benzothiazoyl) -7- (dioctylamino) coumarin, 3-acetyl-7- (dimethylamino) coumarin, 3,3'-carbonylbis (7-dibutylamino) Kumarin), 3,3'-carbonyl- 7-Diethylaminocoumarin-7'-bis (butoxyethyl) aminocoumarin, 10- [3- [4- (dimethylamino) phenyl] -1-oxo-2-propenyl] -2,3,6,7-tetrahydro- 1,1,7,7-Tetramethyl 1H, 5H, 11H- [1] benzopyrano [6,7,8-ij] quinolizidine-11 on, 10- (2-benzothiazoyl) -2,3,6, 7-Tetrahydro-1,1,7,7-Tetramethyl 1H, 5H, 11H- [1] Phenylpyrano [6,7,8-ij] Quinolizidine-11-one, etc. JP-A-9-3109, JP-A-P. Examples include the compounds described in JP No. 10-245525.

Among the above-mentioned coumarin compounds, 3,3'-carbonylbis (7-diethylaminocoumarin) and 3,3'-carbonylbis (7-dibutylaminocoumarin) are preferable.

Among these photopolymerization initiators, at least one selected from the group consisting of (bis) acylphosphine oxides, α-diketones, and coumarins widely used in dental curable compositions should be used. Is preferable. Further, such a photopolymerization initiator may be capable of efficiently performing photopolymerization in a shorter time by further adding a polymerization accelerator, if necessary.

Examples of the polymerization accelerator suitable for the photopolymerization initiator include mainly tertiary amines, aldehydes, compounds having a thiol group, sulfinic acid and salts thereof.

Examples of the tertiary amine include N, N-dimethylaniline, N, N-dimethyl-p-toluidine, N, N-dimethyl-m-toluidine, N, N-diethyl-p-toluidine, N, N-. Dimethyl-3,5-dimethylaniline, N, N-dimethyl-3,4-dimethylaniline, N, N-dimethyl-4-ethylaniline, N, N-dimethyl-4-isopropylaniline, N, N-dimethyl- 4-t-butylaniline, N, N-dimethyl-3,5-di-t-butylaniline, N, N-bis (2-hydroxyethyl) -3,5-dimethylaniline, N, N-bis (2) -Hydroxyethyl) -p-toluidine, N, N-bis (2-hydroxyethyl) -3,4-dimethylaniline, N, N-bis (2-hydroxyethyl) -4-ethylaniline, N, N-bis (2-Hydroxyethyl) -4-isopropylaniline, N, N-bis (2-hydroxyethyl) -4-t-butylaniline, N, N-bis (2-hydroxyethyl) -3,5-diisopropylaniline, N, N-bis (2-hydroxyethyl) -3,5-di-t-butylaniline, 4- (N, N-dimethylamino) benzophenone, 4- (N, N-dimethylamino) ethyl benzoate, 4 -(N, N-dimethylamino) butyl benzoate, 4- (N, N-dimethylamino) n-butoxyethyl benzoate, 4- (N, N-dimethylamino) benzoate (2-methacryloyloxy) ethyl, etc. Tertiary aromatic amines; trimethylamine, triethylamine, tributylamine, N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-lauryldiethanolamine, triethanolamine, 2- (dimethylamino) ethyl (meth) ) Acrylic, N-methyldiethanolamine di (meth) acrylate, N-ethyldiethanolamine di (meth) acrylate, triethanolamine mono (meth) acrylate, triethanolamine di (meth) acrylate, triethanolamine tri (meth) acrylate, etc. Tertiary aliphatic amines can be mentioned.

Examples of aldehydes include dimethylaminobenzaldehyde, terephthalaldehyde and the like. Examples of the compound having a thiol group include 2-mercaptobenzoxazole, decanethiol, 3-mercaptopropyltrimethoxysilane, thiobenzoic acid and the like.

Examples of sulfinic acid and salts thereof include p-toluenesulfinic acid, sodium p-toluenesulfinate, potassium p-toluenesulfinate, lithium p-toluenesulfinate, calcium p-toluenesulfinate, benzenesulfinic acid, and benzenesulfin. Sodium acid, potassium benzenesulfinate, lithium benzenesulfinate, calcium benzenesulfinate, 2,4,6-trimethylbenzenesulfinic acid, sodium 2,4,6-trimethylbenzenesulfinate, 2,4,6-trimethylbenzenesulfin Potassium acid, lithium 2,4,6-trimethylbenzenesulfinate, calcium 2,4,6-trimethylbenzenesulfinate, 2,4,6-triethylbenzenesulfinic acid, sodium 2,4,6-triethylbenzenesulfinate, Potassium 2,4,6-triethylbenzenesulfinate, lithium 2,4,6-triethylbenzenesulfinate, calcium 2,4,6-triethylbenzenesulfinate, 2,4,6-triisopropylbenzenesulfinate, 2, Sodium 4,6-triisopropylbenzenesulfinate, potassium 2,4,6-triisopropylbenzenesulfinate, lithium 2,4,6-triisopropylbenzenesulfinate, calcium 2,4,6-triisopropylbenzenesulfinate, etc. Can be mentioned.

When performing normal temperature polymerization, for example, a redox-based polymerization initiator (chemical polymerization initiator) such as an organic peroxide / amine-based or an organic peroxide / amine / sulfinic acid (or a salt thereof) -based is preferably used. Be done. When a redox-based polymerization initiator is used, it is necessary to take a packaging form in which the oxidizing agent and the reducing agent are separately packaged, and mix the two immediately before use. Examples of the oxidizing agent of the redox-based polymerization initiator include organic peroxides such as diacyl peroxide, peroxy ester, dialkyl peroxide, peroxyketal, ketone peroxide, and hydroperoxide. Specifically, examples of the diacyl peroxide include benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, m-toroil peroxide and the like. Examples of the peroxy ester include t-butyl peroxybenzoate, bis-t-butyl peroxyisophthalate, 2,5-dimethyl-2,5-bis (benzoyl peroxide) hexane, and t-butyl peroxy-2. -Ethyl hexanoate, t-butylperoxyisopropyl carbonate can be mentioned. Examples of the dialkyl peroxide include dicumyl peroxide, di-t-butyl peroxide, and lauroyl peroxide. Examples of the peroxyketal include 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane. Examples of the ketone peroxide include methyl ethyl ketone peroxide. Examples of the hydroperoxide include t-butyl hydroperoxide. As the reducing agent of the redox-based polymerization initiator, a tertiary aromatic amine having no electron-withdrawing group in the aromatic ring is usually used, and for example, N, N-dimethylaniline, N, N-dimethyl-p-toluidine. , N, N-dimethyl-m-toluidine, N, N-diethyl-p-toluidine, N, N-dimethyl-3,5-dimethylaniline, N, N-dimethyl-3,4-dimethylaniline, N, N -Dimethyl-4-ethylaniline, N, N-dimethyl-4-isopropylaniline, N, N-dimethyl-4-t-butylaniline, N, N-dimethyl-3,5-di-t-butylaniline, N , N-bis (2-hydroxyethyl) -3,5-dimethylaniline, N, N-bis (2-hydroxyethyl) -p-toluidine, N, N-bis (2-hydroxyethyl) -3,4- Dimethylaniline, N, N-bis (2-hydroxyethyl) -4-ethylaniline, N, N-bis (2-hydroxyethyl) -4-isopropylaniline, N, N-bis (2-hydroxyethyl) -4 Examples thereof include -t-butylaniline, N, N-bis (2-hydroxyethyl) -3,5-diisopropylaniline and N, N-bis (2-hydroxyethyl) -3,5-di-t-butylaniline. .. In addition to the above, in addition to oxidation-reduction initiators such as cumenehydroperoxide / thiourea, ascorbic acid / Cu ²⁺ salt, organic sulfinic acid (or its salt) / amine / peroxide, tributylborane , Organic sulfinic acid and the like are also preferably used.

The polymerization accelerator used as the chemical polymerization initiator can be selected from the polymerization accelerators used in the general industry, and among them, the polymerization accelerator used for dental applications is preferably used. In addition, the polymerization accelerator is used alone or in combination of two or more. Specific examples thereof include amines, sulfinic acid and salts thereof, copper compounds, tin compounds and the like.

As the amines used as the polymerization accelerator of the chemical polymerization initiator, an aliphatic amine and a tertiary aromatic amine having an electron-withdrawing group in the aromatic ring can be used. Examples of the aliphatic amine include primary aliphatic amines such as n-butylamine, n-hexylamine and n-octylamine; and secondary aliphatic amines such as diisopropylamine, dibutylamine and N-methylethanolamine; Examples of the polymerization accelerator of the photopolymerization initiator include tertiary aliphatic amines and the like. Among these, from the viewpoint of curability and storage stability of the composition, a tertiary aliphatic amine is preferable, and among them, N-methyldiethanolamine and triethanolamine are more preferable.

Examples of the tertiary aromatic amine having an electron-withdrawing group in the aromatic ring used as the polymerization accelerator of the chemical polymerization initiator include ethyl 4- (N, N-dimethylamino) benzoate and 4- ( Butyl N, N-dimethylamino) benzoate, n-butoxyethyl 4- (N, N-dimethylamino) benzoate, 4- (N, N-dimethylamino) ethyl benzoate (2-methacryloyloxy) ethyl, 4- Examples thereof include (N, N-dimethylamino) benzophenone. Among these, ethyl 4- (N, N-dimethylamino) benzoate, n-butoxyethyl 4- (N, N-dimethylamino) benzoate and 4- (N, N-dimethylamino) benzoate can be imparted to the composition with excellent curability. At least one selected from the group consisting of (N, N-dimethylamino) benzophenone is preferably used.

Examples of sulfinic acid and a salt thereof used as a polymerization accelerator of the chemical polymerization initiator include those exemplified as the polymerization accelerator of the photopolymerization initiator described above, and sodium benzenesulfinate, sodium p-toluenesulfinate, 2 , 4,6-Triisopropylbenzene Sodium sulfinate is preferred.

As the copper compound used as the polymerization accelerator, for example, acetylacetone copper, cupric acetate, copper oleate, cupric chloride, cupric bromide and the like are preferably used.

Examples of the tin compound used as the polymerization accelerator include di-n-butyl tin dilaurate, di-n-octyl tin dimalate, di-n-octyl tin dilaurate, di-n-butyl tin dilaurate and the like. Particularly suitable tin compounds are di-n-octyl tin dilaurate and di-n-butyl tin dilaurate.

Among these, it is preferable to use a photopolymerization initiator and a heat polymerization initiator in combination, and a combination of (bis) acylphosphine oxides and diacyl peroxide is more preferable.

The amount of the polymerization initiator to be blended is not particularly limited, but from the viewpoint of curability and the like of the obtained composition, 0.001 to 30 parts by mass of the polymerization initiator is contained with respect to 100 parts by mass of the polymerizable monomer. Is preferable. When the blending amount of the polymerization initiator is 0.001 part by mass or more, there is no possibility that the polymerization will proceed sufficiently and the mechanical strength will be lowered, and more preferably 0.05 part by mass or more, still more preferably 0. . 1 part by mass or more. On the other hand, when the blending amount of the polymerization initiator is 30 parts by mass or less, sufficient mechanical strength can be obtained even when the polymerization performance of the polymerization initiator itself is low, and there is no possibility of causing precipitation from the composition. , More preferably 20 parts by mass or less.

In addition to the above components, the pretreatment composition using acoustic energy of the present invention has a pH adjuster, an ultraviolet absorber, an antioxidant, a polymerization inhibitor, a colorant, a pigment, an antibacterial agent, and an X-ray contrast agent, depending on the purpose. , Additives such as thickeners and fluorescent agents may be further contained.

The pre-treatment composition can be prepared without particular limitation as long as it contains a polymerizable monomer. For example, it can be prepared by mixing a polymerizable monomer with a polymerization initiator, if necessary.

As the pigment, a known pigment used in a dental composite resin or a dental cement can be used without any limitation. The pigment may be any of an inorganic pigment and / or an organic pigment, and examples of the inorganic pigment include chromium acid salts such as yellow lead, zinc yellow and barium yellow; ferrocyanides such as navy blue; silver vermilion and cadmium yellow. Sulfides such as zinc sulfide and cadmium red; sulfates such as barium sulfate, zinc sulfate and strontium sulfate; oxides such as antimony white, zinc white, titanium white, red iron oxide and chromium oxide; water such as aluminum hydroxide Oxides: silicates such as calcium silicate and ultramarine blue; carbons such as carbon black and graphite. Examples of organic pigments include ditron pigments such as naphthol green B and naphthol green Y; nitro pigments such as naphthol S and resolefast yellow 2G; insoluble pigments such as permanent red 4R, brilliant fast scarlet, hanza yellow and benzidine yellow. Azo pigments; sparingly soluble azo pigments such as resole red, lake red C, lake red D; soluble azo pigments such as brilliant carmine 6B, permanent red F5R, pigment scarlet 3B, Bordeaux 10B; phthalocyanine blue, phthalocyanine green, sky Phthalocyanine pigments such as blue; basic dye pigments such as Rhodamine lake, malakite green lake and methyl violet lake; acidic dye pigments such as peacock blue lake, eosin lake and quinoline yellow lake can be mentioned. The pigment can be used in one kind or a combination of two or more kinds, and is appropriately selected according to a desired color tone.

The blending amount of the pigment in the pre-treatment composition is appropriately adjusted according to a desired color tone and is not particularly limited, but is preferably 0.000001 parts by mass or more, more preferably 0, with respect to 100 parts by mass of the curable composition. It is .00001 parts by mass or more, preferably 5 parts by mass or less, and more preferably 1 part by mass or less. Further, it is preferably 0.000001 to 5 parts by mass, and more preferably 0.00001 to 1 part by mass.

The pretreatment composition used in the present invention is not particularly limited as long as it contains an inorganic filler, a polymerizable monomer and a polymerization initiator, and is in a state according to the application (1 paste) by a method known to those skilled in the art. It can be easily manufactured in a state (state, 2 paste state, powder-liquid state, molded state). When using a chemical polymerization initiator or a polymerization initiator having both chemical polymerizable properties and photopolymerizable properties, a packaging form in which a composition containing an organic peroxide and a composition containing a reducing agent are separately packaged is used. It is necessary to mix the two immediately before use.

The curable composition of the present invention is obtained by supplying acoustic energy to a pretreatment composition containing an inorganic filler, a polymerizable monomer, and a polymerization initiator and mixing them. The container used for the mixing method is not particularly limited, but a plastic container or a glass container is preferable from the viewpoint of handleability. The order in which each component is added may be arbitrary. For example, the polymerizable monomer and the polymerization initiator may be separately mixed with the inorganic filler, and the obtained mixtures may be further mixed with each other. Further, it is also possible to separately prepare a polymerizable monomer-containing composition in which a polymerization initiator is dissolved in a polymerizable monomer in advance. In this case, an inorganic filler and a polymerizable monomer composition are prepared. (For example, a solution of the polymerizable monomer composition) can be mixed to obtain the pretreatment composition. In addition, another aspect of the present invention includes a method for treating a dental curable composition, which has the same steps as the above-mentioned method for producing a dental curable composition.

The curable composition obtained in the present invention needs to have an appropriate consistency for proper use by the user, for example, a consistency showing a paste-like morphology, a consistency showing a paste-like morphology, and a slightly viscous composition. It is preferably highly liquid. The consistency is preferably 5 mm to 100 mm, more preferably 7 mm to 80 mm, further preferably 10 mm to 70 mm, and particularly preferably 10 mm to 40 mm. If the consistency is less than 5 mm, the paste is hard and the usability is deteriorated, and air bubbles are likely to be involved, which causes troubles. On the other hand, if the consistency is larger than 100 mm, the paste drips too much and the operability is poor. In the present specification, the consistency means that 0.5 mL of a sample in which the curable composition is allowed to stand at 25 ° C. for 2 hours is raised in the center of a glass plate (5 cm × 5 cm) in a constant temperature room (humidity 40%) at 25 ° C. A 40 g glass plate (5 cm x 5 cm) was placed on the glass plate (5 cm x 5 cm), and the arithmetic mean of the major axis and minor axis of the sample measured through the glass plate after 120 seconds was calculated (unit: mm). ). The major axis refers to the longest diameter passing through the center of the sample in the plane of the glass plate, and the minor axis is orthogonal to the major axis of the sample among the diameters passing through the center of the sample in the plane of the glass plate. Refers to what you do. Further, the curable composition obtained in the present invention was measured under the above conditions after being allowed to stand at 25 ° C. for 2 hours after preparation under the above conditions and after being stored (standing) at 25 ° C. for 360 days after preparation. The rate of change from the consistency is preferably within ± 5.0%, more preferably within ± 3.0%. The curable composition obtained in the present invention was measured under the above conditions after being allowed to stand at 25 ° C. for 2 hours and then stored under the above conditions, and after being stored at 25 ° C. for 720 days (standing). The rate of change from the consistency is preferably within ± 5.0%, more preferably within ± 3.0%. Further, in the curable composition obtained in the present invention, the rate of change between the consistency after standing at 50 ° C. for 2 hours after preparation and the consistency measured after storing (standing) at 50 ° C. for 360 days after preparation is different. It is preferably within ± 5.0%, and more preferably within ± 3.0%. Further, in the curable composition obtained in the present invention, the rate of change between the consistency after standing at 50 ° C. for 2 hours and the consistency measured after storing (standing) at 50 ° C. for 720 days from the preparation is ± 5. It is preferably within 0.0%, more preferably within ± 3.0%.

Moreover, since the obtained dental curable composition needs to have a strength that can withstand actual clinical use, the bending strength was measured as an index thereof. The method was in accordance with ISO4049: 2009.

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples, and many modifications are made in the art within the technical idea of the present invention. It is possible by a person with ordinary knowledge.

Production Example 1 of Polymerizable Monomer Composition
In 70 parts by mass of 2,2-bis (methacryloyloxypolyethoxyphenyl) propane (with an average addition molar number of ethoxy groups of 2.6, commonly known as D2.6E) and 30 parts by mass of triethylene glycol dimethacrylate (TEGDMA), 0.2 parts by mass of phenylquinone as a photopolymerization initiator, 0.3 parts by mass of ethyl 4- (N, N-dimethylamino) benzoate as a polymerization accelerator, 0.25 parts by mass of 2,4,6-trimethylbenzoyldiphenylphosphine oxide A polymerizable monomer-containing composition (A-1) was prepared by dissolving 0.3 parts by mass of tynubin 326, which is an ultraviolet absorber, by mass, and a trace amount of pigment.

Hereinafter, the surface treatment of the inorganic particles was carried out by the following method. 100 g of inorganic particles were dispersed in 2000 g of ethanol with a mechanical stirrer, and 1 g of acetic acid and γ-methacryloxypropyltrimethoxysilane were added in an amount of a predetermined percentage. After stirring at 25 ° C. for 2 hours, ethanol was distilled off under reduced pressure with an evaporator to obtain a target product (inorganic particles treated with γ-methacryloxypropyltrimethoxysilane).

Example 1 [Preparation of dental composite resin]
In a 300 mL plastic container, 33 g of the polymerizable monomer composition (A-1) and 7% γ-methacryloxypropyltrimethoxy of barium glass “GM27884 NF180” (average particle size: 0.18 μm, manufactured by Schott). 67 g of silane treated product was put in and a plastic lid was put on. This container was placed in a Resodyn® acoustic mixer (manufactured by Resodyn Acoustic Mixers, Inc.), and acoustic energy was applied for 30 minutes under the condition of generating 50 times the gravitational acceleration to obtain a paste-like dental composite resin. Prepared. Table 1 shows the data of changes over time regarding the evaluated consistency and bending strength.

Example 2 [Preparation of dental composite resin]
In a 300 mL plastic container, 60 g of the polymerizable monomer composition (A-1) and 7% γ-methacryloxypropyltrimethoxy of barium glass “GM27884 NF180” (average particle size: 0.18 μm, manufactured by Schott). A plastic lid containing 127 g of a silane-treated product and 9 g of a 2% silane-treated product (manufactured by Nikki Catalyst Kasei Co., Ltd.) of silica microbead P500 (aggregates of ultrafine particles having an average particle diameter of 12 nm and an average particle diameter of 2 μm). Did. This container was placed in a Resodyn® acoustic mixer (manufactured by Resodyn Acoustic Mixers, Inc.), and acoustic energy was applied for 120 minutes under the condition of generating 10 times the gravitational acceleration to obtain a paste-like dental composite resin. Prepared. Table 1 shows the data of changes over time regarding the evaluated consistency and bending strength.

Example 3 [Preparation of dental composite resin (flowable composite resin)]
In a 300 mL plastic container, 38 g of the polymerizable monomer composition (A-1) and 5% γ-methacryloxypropyl of barium glass “GM27884 UF0.4” (average particle size: 0.4 μm, manufactured by Schott). A plastic containing 58 g of a trimethoxysilane treated product and 4 g of a 2% silane treated product (manufactured by Nikki Catalyst Kasei Co., Ltd.) of silica microbead P1000 (aggregates of ultrafine particles having an average particle diameter of about 16 nm, aggregate average particle diameter of 5 μm). I put a lid made of plastic. This container is placed in a Resin® acoustic mixer (manufactured by Resin Acoustic Mixers, Inc.), and acoustic energy is applied for 60 minutes under the condition of generating 100 times the gravitational acceleration, and the dentistry has a relatively high fluidity. Composite resin (generally called flowable composite resin) was prepared. Table 1 shows the data of changes over time regarding the evaluated consistency and bending strength.

Production Example 2 of Polymerizable Monomer Composition
D2.6E 40 parts by mass, TEGDMA 18 parts by mass, 2,2-bis [4- (3-methacryloyloxy-2-hydroxypropoxy) phenyl] propane 30 parts by mass, and 10-methacryloyloxydecyldihydrogen phosphate 10. A polymerizable monomer-containing composition (A-2) was prepared by dissolving 0.2 parts by mass of camphorquinone, 1.8 parts by mass of benzoyl peroxide, and a trace amount of pigment as a polymerization initiator in parts by mass.

Production Example 3 of Polymerizable Monomer Composition
D2.6E 70 parts by mass, TEGDMA 26 parts by mass, 2,2-bis [4- (3-methacryloyloxy-2-hydroxypropoxy) phenyl] propane 2 parts by mass, N, N-bis (2-hydroxyethyl) Polymerization by dissolving a small amount of pigment in 0.5 parts by mass of -p-toluidine, 0.05 parts by mass of n-butoxyethyl 4- (N, N-dimethylamino) benzoate, and 2 parts by mass of triethanolamine. A sex monomer-containing composition (A-3) was prepared.

Example 4 [Preparation of A1 paste constituting dental cement]
In a 300 mL plastic container, 35 g of the polymerizable monomer composition (A-2) and 2% γ-methacryloxypropyltrimethoxysilane treatment of barium glass “GM8235 K4” (average particle size: 1 μm, manufactured by Schott). 50g of product, 15g of 3% γ-methacryloxypropyltrimethoxysilane treated product of light anhydrous silicic acid "Aerosil (registered trademark) OX 50" (average particle size: about 40 nm, manufactured by Nippon Aerodil Co., Ltd.), made of plastic I put the lid on. This container is placed in a Resodyn® acoustic mixer (manufactured by Resodyn Acoustic Mixers, Inc.), and acoustic energy is applied for 40 minutes under the condition of generating 80 times the gravity acceleration, and the A1 paste constituting the dental cement is applied. Was prepared. The data of the change with time regarding the consistency of the evaluated A1 paste is shown in Table 1. The data on the change over time regarding the bending strength of the dental cement was measured by kneading 1 g of A1 paste of Example 4 and 1 g of B1 paste of Example 5 below, and the results were measured in the column of Example 4 in Table 1. It was shown to.

Example 5 [Preparation of B1 paste constituting dental cement]
In a 300 mL plastic container, 35 g of the polymerizable monomer composition (A-3) and 3% γ-methacryloxypropyl of barium glass "GM27884 UF2.0" (average particle size: 2.0 μm, manufactured by Schott). 50 g of trimethoxysilane treated product, 14 g of 3% γ-methacryloxypropyltrimethoxysilane treated product of light anhydrous silicic acid "Aerosil (registered trademark) OX 50" (average particle size about 40 nm, manufactured by Nippon Aerosil Co., Ltd.), polymerization accelerator 1 g of sodium 2,4,6-triisopropylbenzenesulfinate was added and covered with a plastic lid. This container is placed in a Resodyn® acoustic mixer (manufactured by Resodyn Acoustic Mixers, Inc.), and acoustic energy is applied for 90 minutes under the condition of generating 20 times the gravitational acceleration, and the B1 paste constituting the dental cement is applied. Was prepared. The data of the change with time regarding the consistency of the evaluated B1 paste is shown in Table 1.

Comparative Example 1 [Preparation of Dental Composite Resin]
In Example 1, instead of using a Resodyn® acoustic mixer, a twin mix device (Dalton, universal mixing stirrer STX-03) was used for 20 minutes under the condition of revolution 52 rotation 172, followed by revolution 83. A paste-like dental composite resin was prepared by mixing for 10 minutes under the condition of rotation 260. Table 1 shows the data of changes over time regarding the evaluated consistency and bending strength.

Comparative Example 2 [Preparation of Dental Composite Resin]
In Example 1, instead of using a Resin® acoustic mixer, a planetary mixer (Mazelstar KK-400W, manufactured by Kurabo) was used to mix for 30 minutes under the conditions of revolution 600 rotation 500 and paste-like dentistry. Composite resin for preparation was prepared. Table 1 shows the data of changes over time regarding the evaluated consistency and bending strength.

Comparative Example 3 [Preparation of A2 paste constituting dental cement]
In Example 4, instead of using a Pasteyn (registered trademark) acoustic mixer, a planetary mixer (Mazelstar KK-400W manufactured by Kurabou Co., Ltd.) was used to mix for 30 minutes under the conditions of revolution 600 rotation 500 to form dental cement. A2 paste was prepared. The data of the change with time regarding the consistency of the evaluated A2 paste is shown in Table 1. The data on the change over time regarding the bending strength of the dental cement was measured by kneading 1 g of A2 paste of Comparative Example 3 and 1 g of B2 paste of Comparative Example 4 below, and the results were measured in the column of Comparative Example 3 in Table 1. It was shown to.

Comparative Example 4 [Preparation of B2 paste constituting dental cement]
In Example 5, instead of using a Pasteyn (registered trademark) acoustic mixer, a planetary mixer (Mazelstar KK-400W manufactured by Kurabo) is used to mix for 30 minutes under the conditions of revolution 600 rotation 500 to form dental cement. B2 paste was prepared. The data of the change with time regarding the consistency of the evaluated B2 paste is shown in Table 1.

Test Example 1 (Consistency)
The paste-like curable composition obtained in each Example and Comparative Example was stored (standing) at a temperature of 25 ° C. or 50 ° C. for a predetermined period (2 hours, 360 days, 720 days). 5 mL was weighed and allowed to stand in a constant temperature room at 25 ° C. (humidity 40%) so as to be raised in the center of a glass plate (5 cm × 5 cm). A 40 g glass plate (5 cm × 5 cm) was placed on the glass plate, and the major axis and the minor axis of the sample after 120 seconds were measured through the glass plate, and the arithmetic mean of both was calculated and used as the consistency (mm).

Test Example 2 (Bending strength)
The international standard for bending test ISO 4049: 2009 was followed. The samples (paste and composition) obtained in each Example and Comparative Example were stored (standing) at 25 ° C. or 50 ° C. for a predetermined period (2 hours, 360 days, 720 days) in the same manner as in Test Example 1. After filling these samples in a stainless steel mold (dimensions 2 mm x 2 mm x 25 mm), the top and bottom are pressure-welded with a slide glass, and 2 each from both sides with a dental technician light irradiator (Morita, Alphalite II). The sample was irradiated with light for each minute and cured to obtain a cured product. For each Example and Comparative Example, five cured products were prepared, and the cured products were taken out from the mold and then stored in distilled water at 37 ° C. for 24 hours. The bending strength was measured under the conditions of span: 20 mm and crosshead speed: 1 mm / min using an Instron universal testing machine, and the average value of the measured values of each test piece was calculated and used as the bending strength. The results are shown in Table 1. The A1 paste and B1 paste obtained in Examples 4 and 5 are used as dental cement by mixing them with a kneading stick, a mixing tip (dental kneading instrument), or the like. In the book, 1 g each of A1 paste and B1 paste was taken out on kneaded paper, mixed with a kneading stick for 1 minute to make a dental cement paste, and then the bending strength was measured. Similarly, with respect to the A2 paste and B2 paste obtained in Comparative Examples 3 and 4, 1 g each of A2 paste and B2 paste was taken out on kneaded paper and mixed with a kneading stick for 1 minute to make a dental cement paste. Then, the bending strength was measured.

From the above results, the dental curable compositions prepared in Examples 1 to 5 have extremely small changes in consistency and viscosity over the long term, whereas the dental curable compositions prepared in Comparative Examples 1 and 2 have been prepared. The viscosity changed by 2.0 mm or more immediately after the preparation after 360 days, and it can be seen that the feel of the composition changed significantly. Similarly, the dental curable compositions prepared in Comparative Examples 3 and 4 also changed in consistency by 1.0 mm or more immediately after preparation after 360 days, and the mechanical strength was also greatly impaired. In addition, the dental curable compositions prepared in Examples 1 to 5 are also excellent in long-term mechanical strength of the cured product.

The production method of the present invention is useful for producing a dental curable composition having stable consistency for a long period of time and having excellent handleability.

Claims (4)

Inorganic filler, a polymerizable monomer and a polymerization initiator, the composition of the pretreatment acoustic energy, have a step of applying acoustic energy, the frequency of the acoustic energy is 10-100 Hz, A method for producing a dental curable composition. The manufacturing method according to claim 1, wherein the acoustic energy generates a gravity acceleration of 10 times to 100 times. The production method according to claim 1 or 2, wherein the dental curable composition is a dental composite resin. The production method according to claim 1 or 2, wherein the dental curable composition is a dental cement.