JP2019098073A - Method for manufacturing dental mill blank - Google Patents

Abstract

To provide a method for manufacturing a dental mill blank capable of improving the yield of dental mill blanks by suppressing occurrences of damage and minute cracks in an inorganic filler molded body, and capable of providing dental mill blanks excellent in mechanical strength.SOLUTION: A method for manufacturing a dental mill blank includes a process (process 1) for holding an inorganic filler molded body formed by press molding an inorganic filler at 50-160°C, and a process (process 2) for bringing the inorganic filler molded body acquired in process 1 into contact with a polymerizable monomer-containing composition, and polymerizing and curing the polymerizable monomer. The holding time in process 1 is preferably 0.5 hours or more. The inorganic filler is preferably a material subjected to surface treatment.SELECTED DRAWING: None

Description

  The present invention relates to a method of manufacturing a dental mill blank.

  In recent years, CAD / CAM systems in which dental prostheses such as inlays and crowns are designed by a computer and cut and manufactured by a milling apparatus have become widespread. Heretofore, ceramic materials have generally been used as materials for mill blanks, which are materials to be cut used in the present system, because of emphasis on aesthetics. However, dental prostheses manufactured from ceramic mill blanks are brittle materials with high hardness, so problems such as damage to the mating teeth, chipping due to impact such as cutting or occlusion, etc. was there.

  In order to solve such a subject, examination of the mill blank which used the composite material containing a polymer resin and an inorganic filler is performed recently. Mill blanks using such a composite material have moderate hardness that does not damage opposing teeth, and are excellent in impact resistance and are being processed into dental prostheses and are beginning to be used clinically.

  Inorganic filling as a method of manufacturing a dental mill blank using a composite material capable of providing a dental prosthesis excellent in mechanical strength, abrasion resistance, surface lubricity, and abrasion resistance of mating teeth. There is known a method in which an inorganic filler molded body obtained by press-molding a material is brought into contact with a polymerizable monomer-containing composition to polymerize and cure the polymerizable monomer (see Patent Document 1).

International Publication No. 2014/021343

  In the method of Patent Document 1, the inorganic filler molded body may be damaged or damaged during handling before the inorganic filler molded body formed by pressing the inorganic filler is brought into contact with the polymerizable monomer-containing composition. When contacting with the monomer-containing composition to impregnate it, micro cracks may occur due to expansion of the inorganic filler molded body, etc., and such breakage or cracks occur. In such a case, the yield of the dental mill blank may be reduced because it is necessary to remove the portion. There is also room for further improvement in mechanical strength.

  Therefore, the present invention can improve the yield of dental mill blanks by suppressing the occurrence of breakage and micro cracks in the inorganic filler molded body, and can provide dental mill blanks having excellent mechanical strength. It is an object of the present invention to provide a method of manufacturing a dental mill blank.

  As a result of intensive investigations to achieve the above object, the present inventors heated the inorganic filler molded body before contacting the polymerizable monomer-containing composition with the inorganic filler molded body after press molding. By treating, it is possible to suppress the occurrence of breakage and minute cracks in the inorganic filler molded body, improve the yield of the dental mill blank, and become a dental mill blank excellent in mechanical strength. Based on the findings, the inventors have further studied and completed the present invention.

That is, the present invention includes the following [1] to [8].
[1] A step (Step 1) of holding at 50 to 160 ° C. an inorganic filler compact obtained by press-molding an inorganic filler, and the inorganic filler compact and the polymerizable monomer obtained in Step 1 The manufacturing method of a dental mill blank including the process (step 2) of making a containing composition contact, and polymerizing-hardening a polymerizable monomer (process 2).
[2] The production method according to [1], wherein the retention time in the step 1 is 0.5 hours or more.
[3] The production method according to [1] or [2], wherein the inorganic filler is subjected to surface treatment.
[4] The manufacturing method according to [3], wherein the surface-treated inorganic filler is obtained by mixing an inorganic filler and a surface treatment agent.
[5] The production method according to [4], wherein the temperature from the mixing of the inorganic filler and the surface treatment agent to the time immediately before the pressing is maintained at 50 ° C. or less.
[6] The method according to [4] or [5], which comprises the steps of mixing the inorganic filler and the surface treatment agent in the presence of a solvent and removing the solvent after the mixing.
[7] The production method according to [6], wherein the solvent contains water.
[8] The process according to [6] or [7], wherein the temperature at which the solvent is removed is 0 to 50 ° C.

  According to the present invention, it is possible to improve the yield of dental mill blanks by suppressing the occurrence of breakage and micro cracks in the inorganic filler compact, and to provide a dental mill blank which is excellent in mechanical strength. Provided is a method of manufacturing a dental mill blank.

Hereinafter, the present invention will be described in detail.
The method for producing a dental mill blank according to the present invention comprises the steps of: holding an inorganic filler compact at 50 to 160 ° C. by pressing an inorganic filler (step 1); and the inorganic filling obtained in step 1 The process (step 2) of making a material molded object and a polymerizable monomer containing composition contact, and polymerizing-hardening a polymerizable monomer is included. As a result, the occurrence of breakage or minute cracks in the inorganic filler compact can be suppressed, the yield of the dental mill blank can be improved, and the dental mill blank is excellent in mechanical strength.

[Inorganic filler]
As the inorganic filler, known inorganic particles used as a filler for a dental composite resin can be used. Examples of the inorganic particles include various glasses (for example, silicon dioxide (quartz, quartz glass, silica gel, etc.), particles containing silicon as a main component and containing various heavy metals such as boron and / or aluminum), alumina, various ceramics , Diatomaceous earth, kaolin, clay minerals (montmorillonite etc), activated clay, synthetic zeolite, mica, silica, calcium fluoride, ytterbium fluoride, calcium phosphate, barium sulfate, zirconium dioxide (zirconia), titanium dioxide (titania), hydroxyapatite Etc. In addition, the inorganic filler may be an organic-inorganic composite particle (organic-inorganic composite filler) obtained by adding a polymerizable monomer to the above-mentioned inorganic particle, polymerizing and curing it, and then grinding it. In addition, an inorganic filler may be used individually by 1 type, and may use 2 or more types together.

  Important physical properties desired for a dental restoration material include the same transparency and radiography as natural teeth. Among these, the transparency can be achieved by matching the refractive index of the inorganic filler and the polymerizable monomer after curing as much as possible. On the other hand, X-ray contrast can be imparted by using, as the inorganic filler, an inorganic filler (oxide or the like) containing a heavy metal element such as zirconium, barium, titanium, lanthanum or strontium. The refractive index of such inorganic fillers containing heavy metal elements is usually high and in the range of 1.5 to 1.6. In the present invention, for example, when a (meth) acrylate monomer is used as the polymerizable monomer, the refractive index of the (meth) acrylate monomer is usually in the range of 1.5 to 1.6. Therefore, even when combined with such a high refractive index inorganic filler having X-ray contrast properties, the refractive index difference can be adjusted to be small, and the transparency of the resulting dental mill blank can be improved.

  Examples of the inorganic filler having a high refractive index capable of imparting the above-mentioned X-ray contrast property include, for example, barium boroaluminosilicate glass (for example, “E3000” manufactured by Esstech, “8235” manufactured by Schott, GM27884 "," GM39923 ", etc.) Strontium boroaluminosilicate glass (eg," E4000 "manufactured by Esstech," G018-093 "," GM32087 "manufactured by Schott, etc.), lanthanum glass (eg, Schott) Of “GM31684” and the like, fluoroaluminosilicate glass (eg, “G018-091”, “G018-117” and the like manufactured by Schott, etc.), glass containing zirconia (eg, “G018-310” manufactured by Schott, etc.) "G018-159" etc.), strontium Glass (for example, “G018-163”, “G018-093”, “GM32087”, etc. manufactured by Schott, etc.), glass containing zinc oxide (eg, “G018-161”, manufactured by Schott, etc.), calcium Glass (For example, "G018-309" by Shot Corporation etc. etc.) etc. are mentioned.

  There are no particular limitations on the shape of the inorganic filler, and various shapes such as crushed, plate, scaly, fibrous (short fibers, long fibers, etc.), needles, whiskers, and spheres can be used. . The inorganic filler may be in the form of aggregation of primary particles in the above shape, or may be in combination of different shapes. In addition, the inorganic filler may have been subjected to some treatment (for example, grinding treatment) so as to have the above-mentioned shape.

  There is no restriction | limiting in particular in the particle diameter of an inorganic filler, The inorganic filler which has a particle diameter which can be used for press molding can be used. The particle size of the inorganic filler can be approximately the same as the particle size of the filler that is usually used as a filler for dental composite resins. The specific particle size of the inorganic filler is preferably 0.001 μm or more, more preferably 0.002 μm or more, and still more preferably 0.005 μm or more as an average particle size. And 10 μm or less is preferable, 5 μm or less is more preferable, 3 μm or less is more preferable, and 1 μm or less is particularly preferable. The particle size range is preferably 0.0005 μm or more, more preferably 0.001 μm or more, and preferably 50 μm or less, more preferably 20 μm or less, and 10 μm or less Is more preferable, and 3 μm or less is particularly preferable. In the present specification, the particle size of the inorganic filler means the particle size of primary particles of the inorganic filler, the above average particle size means the average primary particle size of the inorganic filler, and the above particle size The range is a range of particle sizes that satisfy the number of particles of 95% or more of the inorganic filler, and particles which do not satisfy the defined particle size range may be unintentionally contained in a small amount.

  The average particle size of the inorganic particles can be determined by a laser diffraction scattering method or electron microscopic observation of the particles. Specifically, the particle size of particles of 0.1 μm or more is easily determined by laser diffraction scattering method, and the particle size of ultrafine particles of less than 0.1 μm is easily determined by electron microscope observation It is.

  In the laser diffraction scattering method, for example, measurement is performed using a 0.2% aqueous sodium hexametaphosphate solution as a dispersion medium with a laser diffraction type particle size distribution measuring apparatus (for example, “SALD-2100” manufactured by Shimadzu Corporation). The average particle size can be determined.

  In electron microscopic observation, for example, a transmission electron microscope (for example, “H-800NA type” manufactured by Hitachi, Ltd., etc.) of a particle is taken, and the particle diameter of particles (200 or more) observed in unit field of the photograph The average particle diameter can be determined by measuring the particle diameter using an image analysis type particle size distribution measurement software ("Macview" manufactured by Mountech Co., Ltd.). At this time, the particle diameter of the particles is determined as a circle equivalent diameter which is the diameter of a circle having the same area as the particles, and the average particle diameter is calculated from the number of particles and the particle diameter.

  In the present invention, the inorganic filler may be press-molded to form a molded body (inorganic filler molded body) made of the inorganic filler. Therefore, two or more types of inorganic fillers having different materials, particle diameters, particle size distributions, and shapes may be used in combination or in combination, as long as the molded body can be prepared. In the range which does not impair the effect of the present invention, components other than an inorganic filler may be contained as impurities.

Below, the preferable aspect of the inorganic filler in this invention is mentioned.
Sub-Micron Filler As one of the preferred embodiments of the present invention, an inorganic filler having an average particle diameter of 0.1 μm to 1 μm and an average particle diameter of 0.05 μm to 5 μm (Filler) can be mentioned. The particle size of such a submicron filler is preferably 0.5 μm or less as an average particle size, and more preferably 0.3 μm or less. By using a submicron filler, it is possible to obtain a dental mill blank that provides a dental prosthesis having a suitable combination of mechanical strength and aesthetics (abrasion resistance and lubricity). When a submicron filler is used, the content of the submicron filler in the inorganic filler is preferably 90% by mass or more, more preferably 95% by mass or more, and substantially 100% by mass. Is more preferred.

  It is preferable that the above-mentioned submicron filler has a spherical shape because it can obtain a dental mill blank that provides a dental prosthesis having a suitable combination of mechanical strength and aesthetics (abrasion resistance and lubricity). . Here, the term "spherical" includes up to approximately spherical and does not necessarily have to be a perfect sphere. Generally, a photograph of particles is taken using a scanning electron microscope, and 30 particles observed in the unit field of view of the photograph are arbitrarily selected, and the particle diameter in the direction orthogonal to the maximum diameter of each particle is the maximum. The average value (average uniformity) is preferably 0.6 or more, more preferably 0.8 or more, and 0.9 or more, when the uniformity obtained by dividing by the diameter is determined. Is more preferred.

  As a spherical submicron filler, for example, silica particles; oxide particles of at least one metal selected from the group consisting of Groups 2, 4 and 12 and 13 of the periodic table; Periodic Table Preferred examples include composite oxide particles containing at least one metal atom selected from the group consisting of Group 2, Group 4, Group 12, and Group 13, silicon atom, and oxygen atom. . Specific examples thereof include, for example, amorphous silica, quartz, cristobalite, tridymite, alumina, titanium dioxide, strontium oxide, barium oxide, zinc oxide, zirconium oxide, hafnium oxide, silica zirconia, silica zirconia, silica titania, silica titania barium oxide And particles of silica alumina, silica titania sodium oxide, silica titania potassium oxide, silica zirconia sodium oxide, silica zirconia potassium oxide, silica barium oxide, silica strontium oxide and the like. As spherical submicron fillers, particles of a composite oxide containing silica particles, oxide particles of metal of Group 4 of the periodic table, metal atoms of Group 4 of the periodic table, silicon atoms, and oxygen atoms Preferably, particles of silica-zirconia are more preferable because they have an X-ray contrast property and wear resistance makes it possible to obtain a dental mill blank. As a manufacturing method of a spherical submicron filler, the method described, for example, in JP-A-58-110414 or WO 2009/133913 can be adopted. Hydroxyapatite can also be used as a spherical submicron filler.

The specific surface area of the submicron filler is preferably 5 to 25 m ² / g. In the present specification, the specific surface area can be measured by a specific surface area BET method according to a conventional method.

  When using a submicron filler, it is substantially difficult to make the content of the inorganic filler 80% by mass or more in the dental composite resin manufactured by the usual method, but according to the manufacturing method of the present invention For example, a dental mill blank having a content of the inorganic filler of 80% by mass or more can be easily obtained. In the case of using such a submicron filler, the content of the inorganic filler in the dental mill blank is preferably 80% by mass or more, more preferably 81% by mass or more, still more preferably 82% by mass or more, particularly preferably It is 84% by mass or more, preferably 95% by mass or less, more preferably 92% by mass or less. In addition, in this specification, content of the inorganic filler in dental mill blank means the content rate of inorganic filler per unit mass of dental mill blank.

Ultrafine particle filler In another preferable embodiment of the present invention, the inorganic filler contains an inorganic filler (ultrafine particle filler; nanoparticles) having an average particle diameter of 0.001 μm or more and less than 0.1 μm. The following embodiments are included. The particle diameter of such an ultrafine particle filler is preferably 0.005 μm or more, more preferably 0.01 μm or more, and preferably 0.05 μm or less as an average particle diameter. More preferably, it is not more than .04 μm. The use of the ultrafine particle filler makes it possible to obtain a dental mill blank excellent in transparency and polishing lubricity. When an ultrafine particle filler is used, the content of the ultrafine particle filler in the inorganic filler is preferably 90% by mass or more, more preferably 95% by mass or more, and substantially 100% by mass. Is more preferred.

As said ultrafine particle filler, the well-known ultrafine particle filler used for dental composite resin etc. can be used. As the ultrafine particle filler, for example, inorganic oxide particles such as silica, alumina, titania, zirconia or the like, or composite oxide particles composed thereof, calcium phosphate, hydroxyapatite, yttrium fluoride, ytterbium fluoride, barium titanate, titanium Acidic potassium particles and the like can be preferably exemplified. The ultrafine particle filler may be used alone or in combination of two or more. Among these, particles of silica, alumina, titania, silica / alumina composite oxide, silica / zirconia composite oxide prepared by flame thermal decomposition method are preferable, and specifically, “Aerosil (registered trademark) manufactured by Nippon Aerosil Co., Ltd. Trademarks OX 50 "," Aerosil (registered trademark) 50 "," Aerosil (registered trademark) 130 "," Aerosil (registered trademark) 200 "," Aerosil (registered trademark) 380 "," Aerosil (registered trademark) MOX 80 ", "Aerosil (R) R972", "Aerosil (R) RY50", "Aeroxide (R) AluC", "Aeroxide (R) TiO ₂ P 25", "VP Zirconium Oxide 3-YSZ", "VP Zirconium" Oxide 3-YSZ PH "etc. is mentioned. The shape of the ultrafine particle filler is not particularly limited, and can be appropriately selected.

The specific surface area of the ultrafine particle filler is preferably 30 m ² / g or more, more preferably 40 m ² / g or more, further preferably 50 m ² / g or more, and 500 m ² / g or less. It is preferable that there be some, more preferably 400 m ² / g or less, and even more preferably 200 m ² / g or less.

  Generally, in the dental composite resin, it becomes more difficult to increase the content as the particle size of the inorganic filler to be blended becomes smaller, but especially in the case of the ultrafine particle filler as described above, the tendency becomes remarkable . When a polymerizable monomer and an ultrafine particle filler are mixed to obtain a paste-like composite resin, the content of the ultrafine particle filler is at most about 60% by mass, and practically, the content is 65% by mass or more It is difficult to blend in However, according to the manufacturing method of the present invention, a dental mill blank having an inorganic filler content of 65% by mass or more can be easily obtained. The content of the inorganic filler in the dental mill blank in the case of using such an ultrafine particle filler is preferably 65% by mass or more, more preferably 70% by mass or more, and further preferably 75% by mass or more. Preferably it is 95 mass% or less, More preferably, it is 90 mass% or less, More preferably, it is 88 mass% or less.

  The ultrafine particle filler may be aggregated particles in which individual particles are aggregated. Among them, when the particle diameter of the aggregated particles is 1 to 20 μm, preferably 2 to 10 μm, a dental mill blank which is more excellent in mechanical strength can be obtained. When using agglomerated particles, the content of the agglomerated particles in the inorganic filler is preferably 90% by mass or more, more preferably 95% by mass or more, and substantially 100% by mass. preferable. The average particle size of the aggregated particles is measured using a 0.2% aqueous sodium hexametaphosphate solution as a dispersion medium with a laser diffraction type particle size distribution measuring apparatus (for example, "SALD-2100" manufactured by Shimadzu Corporation). be able to.

  Usually, commercially available ultrafine particle fillers are present as aggregates, but 10 mg of ultrafine particle fillers are added to 300 mL of water (dispersion medium) to which water or a surfactant such as 5% by mass or less of sodium hexametaphosphate is added, When dispersion treatment is performed for 30 minutes with ultrasonic power of 40 W output and 39 KHz frequency, it has only a weak cohesion such as dispersion to the particle size indicated by the manufacturer. However, the above-described aggregated particles are typically those in which particles which are hardly dispersed even under such conditions are strongly aggregated.

  There is no particular limitation on the method of producing the above-mentioned agglomerated particles from commercially available ultrafine particle fillers, but in order to further enhance the cohesion, the particles contacted by heating to near the temperature just before the ultrafine particle filler melts It is preferable to use a method of heating to such an extent as to cause slight fusion. In this case, in order to control the shape of the aggregated particles, it may be prepared in advance a form of aggregation before heating, for example, after the ultrafine particle filler is put in a suitable container and pressurized or once dispersed in a solvent A method of removing the solvent by a method such as spray drying may be adopted.

  Further, as another method for producing the above-mentioned aggregated particles, a sol such as silica sol, alumina sol, titania sol, zirconia sol or the like produced by a wet method is used and dried by a method such as freeze drying or spray drying, The method of heat-processing as needed is also preferable. According to this method, it is possible to obtain aggregated particles in which the particles are strongly aggregated. Specific examples of the sol include “Sea Hoster” (trade name) manufactured by Nippon Shokuhin Co., Ltd., “OSCAL” (trade name) manufactured by JGC Catalysts & Chemicals Co., Ltd., “QUEEN TITANIC” (trade name), and “Snow” manufactured by Nissan Chemical. Tex "(trade name)," alumina sol "(trade name)," CELNAX "(trade name)," Nano Use "(trade name) and the like.

  As the above-described aggregated particles, the surface of silica-based fine particles as described in JP-A-2008-115136, WO 2009/133913, etc. is a composite oxide comprising at least zirconium, silicon and oxygen. It is an amorphous inorganic oxide fine particle group formed by covering, and amorphous powder etc. whose average particle diameter is 1-20 micrometers can also be used conveniently.

  The content of the inorganic filler in the dental mill blank in the case of using agglomerated particles is preferably 65% by mass or more, more preferably 70% by mass or more, still more preferably 75% by mass or more, and preferably 95 It is in the range of not more than mass%, more preferably not more than 90 mass%, still more preferably not more than 88 mass%.

-Hybrid type filler Furthermore, as another preferable embodiment in the present invention, the inorganic filler is the above-mentioned ultrafine particle filler, and the average particle diameter is 0.2 μm or more and 2 μm or less, and the particle diameter range is 0.1 μm. The aspect which contains the inorganic filler which is 10 micrometers or less and is included is mentioned. In the present specification, such an ultrafine particle filler and an inorganic filler having an average particle diameter of 0.2 μm to 2 μm and a particle diameter range of 0.1 μm to 10 μm are mixed (mixed). The inorganic filler is referred to as a hybrid filler. By using a hybrid filler, it is possible to obtain a dental mill blank which is more excellent in mechanical strength. When a hybrid filler is used, the content of the hybrid filler in the inorganic filler is preferably 90% by mass or more, more preferably 95% by mass or more, and substantially 100% by mass. Is more preferred. Hereinafter, the above “inorganic filler having an average particle diameter of 0.2 μm to 2 μm and a particle size range of 0.1 μm to 10 μm” is simply referred to as “inorganic filler of 0.2 μm or more for hybrid” It may be described as

  The particle diameter of the hybrid inorganic filler of 0.2 μm or more is preferably 0.4 μm or more, and preferably 1.5 μm or less as an average particle diameter. The particle size range is preferably 5 μm or less. As a 0.2 micrometer or more inorganic filler for hybrids, the inorganic filler which has a composition as described in the description of the said submicron filler can be used.

  The mass ratio of the ultrafine particle filler in the hybrid type filler to the inorganic filler of 0.2 μm or more for the hybrid ([ultrafine particle filler] / [inorganic filler of 0.2 μm or more for the hybrid]) is 1/1 to It is preferably in the range of 1/20, and more preferably in the range of 1/3 to 1/10.

  The following combinations may be mentioned as specific examples of such a hybrid filler. For example, as a specific example of the ultrafine particle filler, inorganic oxide particles such as silica, alumina, zirconia, and titania, or composite oxide particles made of these are preferable, and among these, it is represented by "Aerosil" (trade name) Such highly dispersible silica, highly dispersible alumina as typified by "Aeroxide" (trade name), titania, and zirconia are more preferable. Further, specific examples of the inorganic filler of 0.2 μm or more for hybrid include barium boroaluminosilicate glass, lanthanum glass, strontium boroaluminosilicate glass, feldspar, mullite, quartz, “Pyrex” (registered trademark) as described above. (Trademark) glass, silica glass and the like are preferable.

  The content of the inorganic filler in the dental mill blank in the case of using the hybrid filler is preferably 80% by mass or more, more preferably 85% by mass or more, still more preferably 88% by mass or more, and preferably It is 96 mass% or less, more preferably 95 mass% or less.

-Surface treatment It is preferable that an inorganic filler is what was surface-treated beforehand. The use of the surface-treated inorganic filler can more effectively suppress the occurrence of breakage and micro cracks in the inorganic filler molded body, and the mechanical strength of the obtained dental mill blank Can be further improved. Furthermore, an inorganic filler molded body formed by press-molding an inorganic filler is brought into contact with the later-described polymerizable monomer-containing composition, and the polymerizable monomer-containing composition intrudes into the gaps of the inorganic filler. At the time of mixing, the compatibility between the surface of the inorganic filler and the polymerizable monomer-containing composition is improved, and there is also an advantage that the polymerizable monomer-containing composition is easily infiltrated.
When surface treatment is applied to the hybrid type filler, the surface treatment is applied to each of the ultrafine particle filler constituting the hybrid type filler and the inorganic filler of 0.2 μm or more for the hybrid, and then mixed. A hybrid type filler may be used, or a mixture of an ultrafine particle filler and an inorganic filler of 0.2 μm or more for hybrid may be subjected to surface treatment.

  As a surface treatment agent used for surface treatment, a known surface treatment agent can be used. For example, an organic metal compound such as an organosilicon compound, an organotitanium compound, an organozirconium compound, an organoaluminum compound, and a phosphate group An organic compound having at least one acidic group such as a pyrophosphoric acid group, a thiophosphoric acid group, a phosphonic acid group, a sulfonic acid group or a carboxylic acid group (an organic compound having an acidic group) can be used. The surface treatment agent may be used alone or in combination of two or more. When two or more surface treatment agents are used, the surface treatment layer may be a surface treatment layer of a mixture of two or more surface treatment agents, or a multilayer structure in which a plurality of surface treatment layers are laminated. It may be a surface treatment layer.

Examples of the organosilicon compound include compounds represented by R ¹ _n SiX _4-n (wherein, R ¹ is a substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms, and X is An alkoxy group having 1 to 4 carbon atoms, an acetoxy group, a hydroxyl group, a halogen atom or a hydrogen atom is shown, n is an integer of 0 to 3, provided that when there are a plurality of R ¹ and X, they are respectively identical May be different or different).

  Specific examples of the organosilicon compound include, for example, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, isobutyl Trimethoxysilane, 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-glycidoxypro Pirtriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-methacryloyloxypropylmethyldiethoxysilane, N- (β-aminoethyl) γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) γ- Aminopropyltrimethoxysilane, N- (β-aminoethyl) γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-Mercaptopropyltrimethoxysilane, trimethylsilanol, methyltrichlorosilane, methyldichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, vinyltrichloride Lolosilane, trimethylbromosilane, diethylsilane, vinyltriacetoxysilane, ω- (meth) acryloyloxyalkyltrimethoxysilane [carbon number between (meth) acryloyloxy group and silicon atom: 3 to 12, for example, γ- Methacryloyloxypropyl trimethoxysilane etc.], ω- (meth) acryloyloxyalkyltriethoxysilane [carbon number between (meth) acryloyloxy group and silicon atom: 3 to 12, eg, γ-methacryloyloxypropyltriethoxy Silane etc.] and the like. In the present invention, the expression "(meth) acryloyl" is used to mean that both methacryloyl and acryloyl are included.

  Among these, since the mechanical strength of the dental mill blank obtained by enhancing the chemical bondability between the inorganic filler and the polymerizable monomer can be improved, etc., it can be copolymerized with the polymerizable monomer. A coupling agent having a functional group is preferred, and ω- (meth) acryloyloxyalkyltrimethoxysilane [carbon number between (meth) acryloyloxy group and silicon atom: 3 to 12], ω- (meth) acryloyloxy Alkyltriethoxysilane [carbon number between (meth) acryloyloxy group and silicon atom: 3 to 12], vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, γ-glycidoxypropyltrimethoxysilane Is more preferred.

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

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

  As an organic aluminum compound, aluminum acetylacetonate, an aluminum organic acid salt chelate compound, etc. are mentioned, for example.

  Examples of the organic compound having a phosphate group include 2-ethylhexyl acid phosphate, stearyl acid phosphate, 2- (meth) acryloyloxyethyl dihydrogen phosphate, 3- (meth) acryloyloxypropyl dihydrogen phosphate, 4- (Meth) acryloyloxybutyl dihydrogen phosphate, 5- (meth) acryloyloxypentyl dihydrogen phosphate, 6- (meth) acryloyl oxyhexyl dihydrogen phosphate, 7- (meth) acryloyl oxyheptyl dihydrogen phosphate 8- (Meth) acryloyloxyoctyl dihydrogen phosphate, 9- (Meth) acryloyl oxynonyl dihydrogen phosphate, 10- (meth) Acryloyl oxydecyl dihydrogen phosphate, 11- (meth) acryloyl oxyundecyl dihydrogen phosphate, 12- (meth) acryloyl oxydodecyl dihydrogen phosphate, 16- (meth) acryloyl oxyhexadecyl dihydrogen phosphate, 20 -(Meth) acryloyloxy icosyl dihydrogen phosphate, bis [2- (meth) acryloyl oxyethyl] hydrogen phosphate, bis [4- (meth) acryloyl oxy butyl] hydrogen phosphate, bis [6 (meth) Acryloyl oxyhexyl] hydrogen phosphate, bis [8- (meth) acryloyloxyoctyl] hydrogen phosphate, bis [9- (meth) acryloyl ester Sininyl] hydrogen phosphate, bis [10- (meth) acryloyloxydecyl] hydrogen phosphate, 1,3-di (meth) acryloyloxypropyl dihydrogen phosphate, 2- (meth) acryloyloxyethyl phenyl hydrogen phosphate, 2- (meth) acryloyloxyethyl-2-bromoethyl hydrogen phosphate, bis [2- (meth) acryloyloxy- (1-hydroxymethyl) ethyl] hydrogen phosphate, and their acid chlorides, alkali metal salts, Ammonium salts and the like can be mentioned.

  Moreover, as an organic compound which has acidic groups other than the above, such as a pyrophosphoric acid group, a thio phosphoric acid group, a phosphonic acid group, a carboxylic acid group, the thing as described in international publication 2012/042911 etc. is mentioned, for example. Can be used.

  The use amount of the surface treatment agent is not particularly limited, and is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and 3 parts by mass or more with respect to 100 parts by mass of the inorganic filler. The content is more preferably 50 parts by mass or less, more preferably 20 parts by mass or less, and still more preferably 10 parts by mass or less.

The surface treatment method is not particularly limited, and any known method may be employed. For example, as described in Patent Document 1, the inorganic filler and the surface treatment agent may be used as a solvent (including water if necessary). Method of removing the solvent followed by heating after mixing in the presence of the organic filler), and a method of removing the solvent after heating (refluxing etc.) the inorganic filler and the surface treating agent in the presence of the solvent, etc. Can be adopted. Here, the heating temperature can be, for example, more than 50 ° C. and 160 ° C. or less.
On the other hand, even when the inorganic filler is press-formed to form an inorganic filler molded body, even if the inorganic filler molded body is press-formed at a high pressure, the occurrence of breakage or micro cracks in the inorganic filler molded body can be effectively suppressed. In addition, since the mechanical strength of the dental mill blank obtained can be further improved, the surface treatment obtained by mixing the inorganic filler and the surface treatment agent in the presence of a solvent as needed is applied. When press molding an inorganic filler (surface-treated inorganic filler) to form an inorganic filler molded body, a period from mixing of the inorganic filler and the surface treatment agent to immediately before performing press molding is not heated condition It is preferable to adopt the following method.

  The temperature under the above non-heating conditions can be, for example, 50 ° C. or less, preferably 40 ° C. or less, more preferably 30 ° C. or less, and still more preferably 25 ° C. or less. The temperature of the above may be maintained within the above range. The temperature under the above non-heating conditions can be, for example, -20 ° C or higher, preferably 0 ° C or higher.

  The surface treatment agent used in the surface treatment inorganic filler to be subjected to press molding in the above method in which the period from mixing of the inorganic filler and the surface treating agent to immediately before performing press molding is non heating condition May remain as it is without reacting (typically existing on the surface of the inorganic filler), or even if a part of the surface treatment agent used has reacted. Good. By setting the time from mixing of the inorganic filler and the surface treatment agent to immediately before performing press molding under non-heating conditions, the ratio of unreacted surface treatment agent in the surface treated inorganic filler is increased, and It is considered that the occurrence of breakage and micro cracks in the inorganic filler compact can be more effectively suppressed, and the mechanical strength of the resulting dental mill blank can be further improved.

  The type of the solvent is not particularly limited. For example, water; methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol, isobutanol, 1-pentanol, isopentanol, cyclohexanol, methylcyclohexanol Alcohols such as acetone; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ethers such as diethyl ether, tetrahydrofuran and 1,4-dioxane; esters such as ethyl acetate and methyl acetate; N, N-dimethylformamide, N, N-dimethyl Amides such as acetamide; Hydrocarbons such as n-hexane, methylcyclohexane, toluene, xylene and styrene; Halogenated hydrocarbons such as chloroform, carbon tetrachloride, 1,2-dichloroethane and 1,2-dichloroethylene; Such as carbon, and the like. These solvents may be used alone or in combination of two or more. Among these, water, alcohol and hydrocarbon are preferable, and water, methanol, ethanol, isopropanol and toluene are more preferable. Further, the solvent preferably contains water at least partially. Thus, for example, when an organosilicon compound is used as the surface treatment agent, the silyl group it contains can be converted to a silanol group by hydrolysis or the like. The conversion may be carried out by acid catalysis. When mixing an inorganic filler and a surface treating agent in the presence of a solvent, it is preferable to remove the solvent by distillation or the like after the mixing.

  In the case of mixing the inorganic filler and the surface treatment agent in the presence of a solvent and removing the solvent after the mixing, the temperature at which the solvent is removed is a failure or a minute crack in the inorganic filler compact. It is preferable that the temperature is 50 ° C. or less, and preferably 40 ° C. or less, because the occurrence of the above can be suppressed more effectively, and the mechanical strength of the dental mill blank obtained can be further improved. Is more preferable, 30 ° C. or less is more preferable, 0 ° C. or more is preferable, 10 ° C. or more is more preferable, and 20 ° C. or more is more preferable.

  When the inorganic filler and the surface treatment agent are mixed in the presence of a solvent and the solvent is removed after the mixing, the time between the removal of the solvent and the time immediately before the press molding described later is performed. Although there is no particular limitation, it is possible to more effectively suppress the occurrence of breakage and micro cracks in the inorganic filler molded body, and to further improve the mechanical strength of the obtained dental mill blank, etc. Therefore, it is preferably 1 hour or more, more preferably 6 hours or more, and still more preferably 12 hours or more. The upper limit of the time is not particularly limited, and the time may be, for example, 3 years or less, 1 year or less, 7 days or less, 2 days or less, or 24 hours or less.

  When the inorganic filler and the surface treatment agent are mixed in the presence of a solvent and the solvent is removed after the mixing, the temperature between the removal of the solvent and the time immediately before the press forming described later is And 50 ° C. or less, because it is possible to more effectively suppress the occurrence of breakage and minute cracks in the inorganic filler molded body and to further improve the mechanical strength of the dental mill blank obtained. The temperature is preferably maintained at 40 ° C. or less, more preferably 30 ° C. or less. There is no restriction | limiting in particular in the lower limit of the said temperature, For example, what is necessary is just to hold | maintain at 0 degreeC or more, holding | maintenance at 10 degreeC or more is preferable, and holding | maintenance at 20 degreeC or more is more preferable.

-Inorganic filler for multilayer structure The inorganic filler molded body obtained by press-molding the inorganic filler may have a single layer structure or a multilayer structure. As a multilayer structure, for example, one obtained by separately pressing two or more different inorganic fillers in layers, one obtained by separately pressing one inorganic filler in layers, and the like can be mentioned. In any case, a dental mill blank having layers different in color tone, transparency, physical properties and the like can be obtained. A dental mill blank having such a multilayer structure can provide a clinically useful dental prosthesis. For example, an inorganic filler, which is adjusted to increase transparency after polymerization curing of the polymerizable monomer, is disposed in the first layer, and an inorganic filler adjusted to have an ivory color tone after polymerization curing of the polymerizable monomer When the filler is disposed in the second layer, the resulting dental mill blank is cut to produce a crown, and the cosmetically superior crown having the enamel layer on the upper layer and the dentin layer on the lower layer Can be made.

  There is no restriction | limiting in particular in the preparation method of the said inorganic filler which can make the color tone after superposition | polymerization hardening desired, For example, the method of mixing and dispersing a pigment (colored particle etc.) in an inorganic filler, etc. are mentioned.

As said pigment, the well-known pigment used for a dental composition can be used. The pigment may be any of an inorganic pigment and an organic pigment.
Examples of inorganic pigments include chromate salts such as yellow lead, zinc yellow and barium yellow; ferrocyanides such as bitumen; sulfides such as silver tin, cadmium yellow, zinc sulfide, antimony white and cadmium red; barium sulfate, sulfate Sulfates such as zinc and strontium sulfate; oxides such as zinc white, titanium white, red iron oxide, iron black, yellow iron oxide and chromium oxide; hydroxides such as aluminum hydroxide; silicates such as calcium silicate and ultramarine blue Carbon such as carbon black and graphite.
Examples of organic pigments include nitroso pigments such as naphthol green B and naphthol green Y; nitro pigments such as naphthol S and lisol fast yellow 2G; insoluble azo such as permanent red 4R, brilliant fast scarlet, Hansa yellow and benzidine yellow Based pigments; sparingly soluble azo pigments such as lisole 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 blue Phthalocyanine-based pigments such as rhodamine lake; basic dye-based pigments such as malachite green lake and methyl violet lake; peacock blue lake; eosin lake; And acid dye-based pigments such as yellow lake and the like.
One of these pigments may be used alone, or two or more thereof may be used in combination, which can be appropriately selected according to the intended color tone. Among these pigments, titanium white (local titanium oxide etc.), which is an inorganic pigment excellent in heat resistance, light resistance and the like, bengara, iron black and yellow iron oxide are preferable.

  The content of the pigment is not particularly limited and can be appropriately adjusted according to the target color tone, but is preferably 0.01 mass ppm or more as a ratio in the layer in which the pigment is blended, and 0. It is more preferably 1 mass ppm or more, and preferably 5 mass% or less, more preferably 1 mass% or less.

  As a method of uniformly mixing and dispersing the pigment in the inorganic filler, a known powder mixing and dispersing method can be adopted. Either a dry method or a wet method may be used, but it is possible to more uniformly mix and disperse, etc. From the above, a method is preferable in which the inorganic filler and the pigment are mixed in the presence of a solvent and then the solvent is removed (e.g., evaporated). The above mixing can be carried out using a known method, for example, using a dispersing machine such as a sand mill, bead mill, attritor, colloid mill, ball mill, ultrasonic crusher, homomixer, dissolver, homogenizer, etc. it can. The mixing conditions can be appropriately selected according to the particle size and amount of the inorganic filler or pigment used; the type and amount of the solvent; the type of the dispersing machine, etc .; and the dispersion according to the dispersion state of each component, etc. Dispersion conditions such as time, stirring tool, and rotational speed can be appropriately selected. As the above solvent, water and / or a solvent compatible with water is preferable, and as the solvent, alcohol (for example, ethanol, methanol, isopropanol etc.), ether, ketone (eg acetone, methyl ethyl ketone etc) etc. Can.

  Moreover, as a method for setting the color tone after polymerization and curing as desired, the inorganic filler itself is specified as in the case of colored glass other than the method of mixing and dispersing the pigment as described above in the inorganic filler. It is also possible to adopt a method of using one having a color. As such an inorganic filler itself having a specific color, for example, commercially available porcelain powder, for example, "VM" (trade name) or "VM 7" (trade name) manufactured by VITA, Inc., Kurare Noritake Dental Co., Ltd. Examples thereof include “Noritake super porcelain AAA” (trade name) and “Cerabian ZR” (trade name) manufactured by a company, and these may be pulverized to adjust the particle size as needed.

  As a method for making transparency after polymerization hardening desired, the method of adjusting the refractive index and particle diameter of an inorganic filler, etc. are mentioned, for example. In general, the transparency of the resin in which the inorganic filler is dispersed is higher as the difference in refractive index between the inorganic filler and the resin is smaller, and as the particle diameter is separated from the wavelength (0.4 to 0.7 μm) of visible light. It has been known. Therefore, for example, a method using an inorganic filler having the same refractive index as possible after polymerization curing of a polymerizable monomer-containing composition to be impregnated as an inorganic filler used in a highly transparent layer is preferably adopted. can do. In addition, you may employ | adopt the method of adjusting the refractive index of a polymerizable monomer so that it may correspond with the refractive index of an inorganic filler.

  As a method for making the physical properties after polymerization curing desired, for example, an inorganic filler excellent in lubricity is disposed in the layer corresponding to the enamel layer, and a layer corresponding to the dentin layer in the inner layer is disposed. A method of arranging an inorganic filler excellent in mechanical strength can be adopted. The combination of such inorganic fillers can provide an extremely useful crown prosthesis which is excellent in clinical and intraoral durability.

  As an inorganic filler used for the layer applicable to an enamel layer, the thing similar to the above-mentioned ultrafine particle filler and a submicron filler etc. is mentioned, for example. On the other hand, as an inorganic filler used for the layer applicable to a dentin layer, the thing similar to the above-mentioned submicron filler, the aggregation particle of an ultrafine particle filler, a hybrid type filler, etc. are mentioned, for example. As a specific combination, for example, an ultrafine particle filler is used for the layer corresponding to the enamel layer, and a submicron filler is used for the layer corresponding to the dentin layer, or a submicron filler is used for the layer corresponding to the enamel layer The aspect etc. which use a hybrid type filler for the layer applicable to a dentin layer can be mentioned.

  The content of the inorganic filler in the dental mill blank in the case of forming an inorganic filler compact having a multilayer structure is preferably 60% by mass or more, more preferably 65% by mass or more, and still more preferably 70% by mass or more Also, it is preferably 96% by mass or less, more preferably 94% by mass or less, still more preferably 92% by mass or less.

〔Press molding〕
The inorganic filler molded body used in step 1 is formed by pressing an inorganic filler. There is no restriction | limiting in particular in the method of press-molding an inorganic filler, A well-known method is employable. A specific method of press molding is, for example, a method of filling an inorganic filler into a press die of a desired size and pressing using an upper punch and a lower punch by a uniaxial press. .

  The pressing pressure at the time of uniaxial pressing can be appropriately set to an optimal value depending on the size of the target inorganic filler compact, the type of inorganic filler and the particle diameter, etc., and can usually be 10 MPa or more. . By increasing the pressing pressure, the inorganic filler is densely packed, and the gap between the inorganic fillers is sufficiently narrowed, and the content of the inorganic filler per unit volume is obtained in the dental mill blank obtained. You can raise it. As a result, the mechanical strength, the abrasion resistance and the surface lubricity of the dental prosthesis obtained from the dental mill blank are further improved. From this point of view, the higher the pressing pressure, the better. However, in view of productivity such as the size of the inorganic filler molded body and equipment factors, the pressing pressure may be usually 200 MPa or less. From the above viewpoints, the pressing pressure is preferably 20 MPa or more, more preferably 25 MPa or more, and preferably 180 MPa or less, more preferably 150 MPa or less, and 100 MPa The following is more preferable, and 80 MPa or less is particularly preferable. Although the press time in a uniaxial press can be suitably set according to press pressure, it may be usually 1 to 120 minutes.

  The press forming may be performed by a cold isostatic pressing (CIP) process. In this case, only the CIP step may be adopted, or both the method other than the method by the CIP step such as the above-mentioned uniaxial press and the method by the CIP step may be adopted. More specifically, press forming may be performed by the CIP process without performing the uniaxial press, or after the press forming by the uniaxial press, the press forming may be performed by the CIP process. In the press forming by the CIP process, generally, a press pressure higher than that of the uniaxial press can be applied, and since the pressure can be uniformly applied to the inorganic filler from the three-dimensional direction, the press forming by the CIP process By doing this, it is possible to eliminate undesirable microvoids inside the inorganic filler molded body and unevenness in the state of aggregation of the inorganic filler, and the compressive density of the inorganic filler is further improved, and the inorganic filler is contained. It is possible to obtain a dental mill blank which is very high in quantity. When press molding is performed by the CIP process without uniaxial pressing, the inorganic filler is filled in a container rich in elasticity such as silicone rubber or polyisoprene rubber, and this is used as it is or under reduced pressure (including vacuum). Can then be subjected to the CIP process. In addition, when press forming is further performed in the CIP step after press forming in the uniaxial press, the formed body obtained by the uniaxial press may be subjected to the CIP step as it is or under reduced pressure (including vacuum). it can.

  It is preferable that the pressure at the time of press molding by the CIP process is also high. The CIP process can use, for example, a CIP apparatus that can be pressurized to about 1000 MPa manufactured by Kobe Steel. The pressure in the CIP step is preferably higher regardless of the presence or absence of a uniaxial press, but in consideration of productivity, when performing a uniaxial press, it is preferably 30 MPa or more, more preferably 50 MPa or more, still more preferably 100 MPa or more Also, it is preferably 500 MPa or less, more preferably 400 MPa or less, and still more preferably 300 MPa or less. Moreover, when performing press molding by a CIP process without performing uniaxial pressing, it is preferably 30 MPa or more, more preferably 50 MPa or more, further preferably 100 MPa or more, and preferably 1000 MPa or less, more preferably 800 MPa or less More preferably, it is 700 MPa or less. The pressurizing time in the CIP process can be appropriately set in accordance with the press pressure, but usually, it may be 1 to 60 minutes.

  In addition, as a method of the press molding in the case of obtaining the inorganic filler molded object of the above multilayer structures, the following methods are employable, for example. That is, a first inorganic filler is filled in a die for uniaxial press fitted with a lower punch, the upper punch is set in the die, and the first inorganic filler is pressed. Next, the upper punch is removed, and a second inorganic filler is filled on the pressed aggregate of the first inorganic filler, and the upper punch is set again to obtain the second inorganic filler. Press. Such an operation is repeated according to the desired number of layers, and then taken out from the mold to obtain an inorganic filler molded article having a multilayer structure. In addition, the press pressure at the time of a press can be suitably set according to the kind, quantity, etc. of the inorganic filler to be used, and the press pressure in each layer may mutually be same or different. In addition, after the mold is filled with the first inorganic filler, the surface is smoothed and the second inorganic filler is filled thereon without pressing, and the first inorganic filler and the A method of pressing the two inorganic fillers together may be employed.

  In order to obtain an inorganic filler molded body having a multilayer structure, as described above, the molded body may be obtained by press-molding the inorganic filler at one time, or may be newly obtained on a separately molded molded body. Although the said molded object may be obtained by press-molding an inorganic filler, after laminating | stacking the molded object shape | molded separately, you may obtain the said molded object by press-molding.

  There is no restriction | limiting in particular in the shape or size of the inorganic filler molded object formed by press molding, According to the shape and size of the dental mill blank mentioned later, it can adjust suitably.

[Step 1]
In step 1, the inorganic filler compact is maintained at 50 to 160 ° C. By performing such heat treatment, it is possible to suppress the occurrence of breakage and minute cracks in the inorganic filler molded body, improve the yield of dental mill blanks, and have excellent mechanical strength. It becomes.

  When the temperature of the heat treatment is less than 50 ° C., it is difficult to obtain the above effects. Moreover, when the temperature of heat processing exceeds 160 degreeC, it will become easy to produce a crack in the dental mill blank obtained. From such a viewpoint, the temperature of the heat treatment is preferably 60 ° C. or more, more preferably 70 ° C. or more, still more preferably 80 ° C. or more, and particularly preferably 90 ° C. or more. The temperature is preferably 150 ° C. or less, more preferably 140 ° C. or less, still more preferably 130 ° C. or less, and particularly preferably 120 ° C. or less.

  The heat treatment time (holding time) is not particularly limited, but is preferably 0.5 hours or more, more preferably 2 hours or more, because the effects of the present invention are more significantly exhibited. 3 hours or more is more preferable, 6 hours or more is particularly preferable, and 100 hours or less is preferable, 50 hours or less is more preferable, and 30 hours or less is more preferable. It is particularly preferable that it is 15 hours or less.

  There is no restriction | limiting in particular in the apparatus used for heat processing, For example, a hot air dryer, an electric furnace, etc. are mentioned.

[Step 2]
In step 2, the inorganic filler molded body obtained in step 1 is brought into contact with the polymerizable monomer-containing composition to polymerize and cure the polymerizable monomer. By bringing the inorganic filler molding into contact with the polymerizable monomer-containing composition, the polymerizable monomer-containing composition intrudes into the gaps of the inorganic filler, and as a result, the polymerizable monomer-containing composition A composition having a structure in which the inorganic filler is very closely dispersed is obtained. From such a point of view, in the present invention, it is preferable to use an inorganic filler molded body which is not in the form of a sintered porous body.

  Generally, in the particle-dispersed composite material, the smaller the particle diameter of the inorganic filler dispersed in the resin, the better the polishing lubricity, and the crown restoration capable of maintaining the gloss in the oral cavity for a long time It becomes material. On the other hand, as the particle diameter of the inorganic filler becomes smaller, it becomes more difficult to pack the inorganic filler in the composite material at a high density, and the mechanical strength and the abrasion resistance of the cured product tend to be lowered. On the other hand, in the present invention, a step of contacting an inorganic filler molded body formed by press-molding an inorganic filler and a polymerizable monomer-containing composition to polymerize and cure the polymerizable monomer (step Since the dental mill blank is manufactured through 2), high density filling is possible even if the particle size of the inorganic filler is small, and the dental prosthesis obtained from the dental mill blank is excellent in gloss, And, the strength and the abrasion resistance are also improved.

  The content of the inorganic filler in the dental mill blank obtained by the present invention varies depending on the particle diameter, shape, etc. of the inorganic filler to be used, but is preferably 60% by mass or more, more preferably 70% by mass or more More preferably, it is 80% by mass or more, particularly preferably 82% by mass or more, and most preferably 85% by mass or more, and preferably 96% by mass or less, more preferably 95% by mass or less.

  The content of the inorganic filler in the dental mill blank can be determined by measuring the mass of the ignition residue of the dental mill blank. As a method of measuring the mass, a dental mill blank is put in a crucible and heated in an electric furnace at a temperature of 575 ° C. for a predetermined time (for example, 2 hours) to incinerate the organic resin component. A measuring method can be adopted. In addition, in this method, in the case of the dental mill blank obtained using the inorganic particle to which surface treatment was given, the surface treating agent is usually incinerated as an organic resin component.

[Polymerizable monomer-containing composition]
Polymerizable Monomer As the polymerizable monomer contained in the polymerizable monomer-containing composition, known polymerizable monomers used for dental composite resins etc. can be used. Radically polymerizable monomers are preferably used. Specific examples of the radically polymerizable monomer include, for example, α-cyanoacrylic acid, (meth) acrylic acid, α-halogenated acrylic acid, crotonic acid, cinnamic acid, sorbic acid, sorbic acid, maleic acid, itaconic acid and the like carboxylic acids (Meth) acrylamide; (meth) acrylamide derivatives; vinyl esters; vinyl ethers; mono-N-vinyl derivatives; styrene derivatives and the like. Among these, esters of carboxylic acids and (meth) acrylamide derivatives are preferable, (meth) acrylic esters and (meth) acrylamide derivatives are more preferable, and (meth) acrylic esters are more preferable. In addition, in this specification, the expression "(meth) acryl" is used by the meaning which includes both methacryl and an acryl. Examples of (meth) acrylic acid esters and (meth) acrylamide derivatives are shown below.

(I) Monofunctional (meth) acrylic acid ester and (meth) acrylamide derivative For example, 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 ( Meta) acrylamide, (meth) acryloyloxydodecyl pyridinium bromide, (meth) acryloyloxy dodecyl pyridinium chloride, (meth) acryloyloxy hexadecyl pyridinium chloride, (meth) acryloyl oxydecyl ammonium chloride, 10-mercaptodecyl (meth) acrylate, etc. Can be mentioned.

(Ii) Difunctional (meth) acrylic acid ester For example, 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-methacryloyloxy-2-hydroxypropoxy] phenyl] propane (generally called Bis-GMA), 2,2-bis [4- (meth) acryloyloxyethoxyphenyl] propane, 2,2-bis [4 -(Meth) acryloyloxypolyethoxyphenyl] Lopane, 1,2-bis [3- (meth) acryloyloxy-2-hydroxypropoxy] ethane, pentaerythritol di (meth) acrylate, [2,2,4-trimethylhexamethylene bis (2-carbamoyloxyethyl)] Examples include dimethacrylate (commonly called UDMA), 2,2,3,3,4,4-hexafluoro-1,5-pentyldi (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate and the like.

(Iii) Trifunctional or higher (meth) acrylic acid esters For example, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate , Dipentaerythritol hexa (meth) acrylate, N, N '-(2,2,4-trimethylhexamethylene) bis [2- (aminocarboxy) propane-1,3-diol] tetra (meth) acrylate, 1, 7-diacryloyloxy-2,2,6,6-tetra (meth) acryloyloxymethyl-4-oxyheptane and the like.

  In addition to the above-mentioned radical polymerizable monomers, cationic polymerizable monomers such as oxirane compounds and oxetane compounds can also be used as the polymerizable monomers.

  As the polymerizable monomer, one type may be used alone, or two or more types may be used in combination. The polymerizable monomer is preferably in the form of liquid, but is not necessarily in the form of liquid at normal temperature, and the environment at the time of bringing the inorganic filler molded body into contact with the polymerizable monomer-containing composition In liquid form can be used. Furthermore, even if it is a solid polymerizable monomer, it can be used by mixing and dissolving with other liquid polymerizable monomers.

  The viscosity (25 ° C.) of the polymerizable monomer is preferably 10 Pa · s or less, more preferably 5 Pa · s or less, and still more preferably 2 Pa · s or less. On the other hand, when two or more kinds of polymerizable monomers are mixed and used, or when diluted and used in a solvent, the viscosity of each polymerizable monomer does not have to be in the above range, and it is used In the state (mixed / diluted state), the viscosity is preferably in the above range.

  The content of the polymerizable monomer in the polymerizable monomer-containing composition can be, for example, 50% by mass or more, preferably 80% by mass or more, and more preferably 90% by mass or more. Preferably, the content is 95% by mass or more, and more preferably 98% by mass or more.

-Polymerization initiator In Step 2, as described later, the polymerizable monomer is polymerized and cured. Therefore, the polymerizable monomer composition may contain a polymerization initiator in order to facilitate polymerization and curing. As a polymerization initiator, a polymerization initiator used in general industry can be used, and in particular, a polymerization initiator used for dental use can be preferably used. As the polymerization initiator, for example, at least one selected from the group consisting of a thermal polymerization initiator, a photopolymerization initiator, and a chemical polymerization initiator can be used.

(I) Heat polymerization initiator As a heat polymerization initiator, organic peroxides, azo compounds, etc. are mentioned, for example.

  Examples of organic peroxides include, for example, ketone peroxides, hydroperoxides, diacyl peroxides, dialkyl peroxides, peroxyketals, peroxyesters, peroxydicarbonates and the like.

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

  As the hydroperoxide, for example, 2,5-dimethylhexane-2,5-dihydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, etc. Can be mentioned.

  Examples of the diacyl peroxide include acetyl peroxide, isobutyryl peroxide, benzoyl peroxide, decanoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide and the like.

  As the dialkyl peroxide, for example, di-t-butyl peroxide, dicumyl peroxide, t-butyl cumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 1,3-bis ( Examples include t-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) -3-hexyne and the like.

  As peroxyketal, for example, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (t-butyl) Examples include peroxy) butane, 2,2-bis (t-butylperoxy) octane, 4,4-bis (t-butylperoxy) valeric acid n-butyl ester and the like.

  As peroxy esters, for example, α-cumylperoxyneodecanoate, t-butylperoxyneodecanoate, t-butylperoxypivalate, 2,2,4-trimethylpentylperoxy-2-ethylhexanoate, 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-butylperoxymaleate and the like.

  Examples of peroxydicarbonates include di-3-methoxyperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, diisopropylperoxydicarbonate, di-n-propylperoxy Dicarbonate, di-2-ethoxyethylperoxydicarbonate, diallylperoxydicarbonate and the like can be mentioned.

  Among these organic peroxides, diacyl peroxides are preferable, and benzoyl peroxide is more preferable among them, from the comprehensive balance of safety, storage stability and radical formation ability.

  As the azo compounds, for example, 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 4,4′-azobis (4-cyanovaleric acid), 1,1′-azobis (1-cyclohexanecarbonitrile), dimethyl-2,2′-azobis (isobutyrate), 2,2′-azobis (2-amidinopropane) dihydrochloride and the like.

(Ii) Photopolymerization initiator As the photopolymerization initiator, those widely used in dental curable compositions can be preferably used, for example, (bis) acyl phosphine oxides, α-diketones, Coumarins etc. are mentioned.

  Among the (bis) acyl phosphine oxides, as the acyl phosphine oxide, for example, 2,4,6-trimethyl benzoyl diphenyl phosphine oxide, 2,6-dimethoxy benzoyl diphenyl phosphine oxide, 2,6-dichloro benzoyl diphenyl phosphine Oxide, 2,4,6-trimethyl benzoyl methoxyphenyl phosphine oxide, 2,4,6-trimethyl benzoyl ethoxy phenyl phosphine oxide, 2,3,5,6- tetramethyl benzoyl diphenyl phosphine oxide, benzoyl di- (2,6- Dimethylphenyl) phosphonates, salts thereof and the like can be mentioned.

  Among the (bis) acyl phosphine oxides, as the bisacyl phosphine oxide, for example, bis (2,6-dichlorobenzoyl) phenyl phosphine oxide, bis (2,6-dichlorobenzoyl) -2,5-dimethylphenyl Phosphine oxide, bis (2,6-dichlorobenzoyl) -4-propylphenyl phosphine oxide, bis (2,6-dichlorobenzoyl) -1-naphthyl phosphine oxide, bis (2,6-dimethoxybenzoyl) phenyl phosphine oxide, bis (2,6-Dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) Phenylphos In'okishido, bis (2,3,6-trimethylbenzoyl) -2,4,4-trimethylpentyl phosphine oxide, and salts thereof, and the like.

  Among these (bis) acyl phosphine oxides, 2,4,6-trimethyl benzoyl diphenyl phosphine oxide, 2,4,6- trimethyl benzoyl methoxy phenyl phosphine oxide, bis (2,4,6- trimethyl benzoyl) phenyl phosphine The sodium salt of the oxide, 2,4,6-trimethyl benzoyl phenyl phosphine oxide is preferred.

  Examples of α-diketones include diacetyl, benzyl, camphorquinone, 2,3-pentadione, 2,3-octadione, 9,10-phenanthrenequinone, 4,4′-oxybenzyl, acenaphthenequinone and the like. . Among these, camphor quinone is preferable.

  As coumarins, for example, 3,3'-carbonylbis (7-diethylamino coumarin), 3- (4-methoxybenzoyl) coumarin, 3-thienyl coumarin, 3-benzoyl-5,7-dimethoxycoumarin, 3-benzoyl -7-methoxycoumarin, 3-benzoyl-6-methoxycoumarin, 3-benzoyl-8-methoxycoumarin, 3-benzoylcoumarin, 7-methoxy-3- (p-nitrobenzoyl) coumarin, 3- (p-nitrobenzoyl) ) Coumarin, 3,5-carbonylbis (7-methoxycoumarin), 3-benzoyl-6-bromocoumarin, 3,3'-carbonylbiscoumarin, 3-benzoyl-7-dimethylaminocoumarin, 3-benzoylbenzo [f ] Coumarin, 3-carboxy coumarin, 3-carboxy-7-methoxy Coumarin, 3-ethoxycarbonyl-6-methoxycoumarin, 3-ethoxycarbonyl-8-methoxycoumarin, 3-acetylbenzo [f] coumarin, 3-benzoyl-6-nitrocoumarin, 3-benzoyl-7-diethylaminocoumarin, 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-methoxycoumarin, 3- (4-dimethylaminocinnamoyl) coumarin, 3- (4 -Diphenylaminocinnamoyl) coumarin, 3-[(3-di Thilbenzothiazol-2-ylidene) acetyl] coumarin, 3-[(1-methylnaphtho [1,2-d] thiazol-2-ylidene) acetyl] coumarin, 3,3'-carbonylbis (6-methoxycoumarin), 3,3'-Carbonylbis (7-acetoxycoumarin), 3,3'-carbonylbis (7-dimethylaminocoumarin), 3- (2-benzothiazoyl) -7- (diethylamino) coumarin, 3- (2) -Benzothiazoyl) -7- (dibutylamino) coumarin, 3- (2-benzoimidazoyl) -7- (diethylamino) coumarin, 3- (2-benzothiazoyl) -7- (dioctylamino) coumarin, 3 -Acetyl-7- (dimethylamino) coumarin, 3,3'-carbonylbis (7-dibutylaminocoumarin), 3,3'-car Bonyl-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] quinolizine-11-one, 10- (2-benzothiazoyl) -2, 3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H, 5H, 11H- [1] benzopyrano [6,7,8-ij] quinolizine-11-one and the like.

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

(Iii) Chemical polymerization initiator As a chemical polymerization initiator, a redox type polymerization initiator etc. are mentioned, for example. As the said redox type polymerization initiator, an organic peroxide-amine type | system | group, an organic peroxide-amine-sulfinic acid (or its salt) type | system | group, etc. can be used preferably. When using a redox type polymerization initiator, it is preferable to pack the oxidizing agent and the reducing agent separately and to mix them immediately before use.

  As an oxidizing agent of a redox type polymerization initiator, organic peroxides etc. are mentioned, for example. As the organic peroxides, known ones can be used, and specifically, the organic peroxides exemplified in the heat polymerization initiator can be used. As the organic peroxides, diacyl peroxides are preferable in view of the comprehensive balance of safety, storage stability and radical forming ability, and among them, benzoyl peroxide is more preferable.

  As a reducing agent for the redox polymerization initiator, usually, a tertiary aromatic amine having no electron withdrawing group on the aromatic ring is used. Examples of tertiary aromatic amines having no electron withdrawing group in the aromatic ring 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-tert-butylaniline, N, N-dimethyl-3,5-di-tert-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-hydroxy) (Tyl) -4-ethylaniline, N, N-bis (2-hydroxyethyl) -4-isopropylaniline, N, N-bis (2-hydroxyethyl) -4-tert-butylaniline, N, N-bis ( 2-hydroxyethyl) -3,5-diisopropylaniline, N, N-bis (2-hydroxyethyl) -3,5-di-t-butylaniline and the like.

  The polymerization initiator may be used alone or in combination of two or more. For example, as a polymerization initiator, a heat polymerization initiator and a photopolymerization initiator may be used in combination, and in this case, it is preferable to use a diacyl peroxide and (bis) acyl phosphine oxides in combination.

  The content of the polymerization initiator in the polymerizable monomer-containing composition is not particularly limited, but from the viewpoint of polymerization curability and the like, it is 0.001 parts by mass or more with respect to 100 parts by mass of the polymerizable monomer. Is more preferably 0.05 parts by mass or more, further preferably 0.1 parts by mass or more. Even when the polymerization performance of the polymerization initiator itself is low when the amount of the polymerization initiator used is at least the above lower limit, a dental mill blank obtained by sufficiently advancing the polymerization and thus a dental prosthesis obtained therefrom The strength of the object is improved. On the other hand, the content of the polymerization initiator is preferably 30 parts by mass or less, and more preferably 20 parts by mass or less, with respect to 100 parts by mass of the polymerizable monomer. Precipitation of a polymerization initiator can be suppressed because content of a polymerization initiator is below the said upper limit.

-Polymerization accelerator When using a polymerization initiator, you may use a polymerization accelerator together. By using a polymerization accelerator in combination, there are cases where polymerization and curing can be efficiently performed in a short time. As the said polymerization accelerator, the polymerization accelerator used by the general industrial field can be used, Especially the polymerization accelerator used for dental use can be used preferably. A polymerization accelerator may be used individually by 1 type, and may use 2 or more types together.

  Examples of polymerization accelerators suitable for the photopolymerization initiator include tertiary amines, aldehydes, thiols, sulfinic acid and salts thereof.

  Examples of tertiary amines 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-tert-butylaniline, N, N-dimethyl-3,5-di-tert-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-tert-butylaniline, N, N-bis (2-hydroxyethyl) -3,5-diisopropyl Aniline, N, N-bis (2-hydroxyethyl) -3,5-dibutylaniline, n-butoxyethyl 4- (N, N-dimethylamino) benzoate, 4- (N, N-dimethylamino) benzoate (2-methacryloyloxy) ethyl, ethyl 4- (N, N-dimethylamino) benzoate, butyl 4- (N, N-dimethylamino) benzoate, N-methyldiethanolamine, 4-dimethylaminobenzophenone, trimethylamine, triethylamine N-Methyldiethanolamine N-ethyldiethanolamine N-n-butyldiethanol Min, N-lauryldiethanolamine, triethanolamine, 2- (dimethylamino) ethyl methacrylate, N-methyldiethanolamine dimethacrylate, N-ethyldiethanolamine dimethacrylate, triethanolamine monomethacrylate, triethanolamine dimethacrylate, triethanolamine trimethacrylate Methacrylate etc. are mentioned.

  Examples of aldehydes include dimethylamino benzaldehyde and terephthalaldehyde.

  Examples of the thiols include 2-mercaptobenzoxazole, decanethiol, 3-mercaptopropyltrimethoxysilane, thiobenzoic acid and the like.

  Examples of sulfinic acid and salts thereof include benzenesulfinic acid, sodium benzenesulfinate, potassium benzenesulfinate, calcium benzenesulfinate, lithium benzenesulfinate, p-toluenesulfinic acid, sodium p-toluenesulfinate, p-toluene Potassium sulfinate, calcium p-toluenesulfinate, lithium p-toluenesulfinate, 2,4,6-trimethylbenzenesulfinic acid, sodium 2,4,6-trimethylbenzenesulfinate, 2,4,6-trimethylbenzenesulfin Acid potassium, calcium 2,4,6-trimethylbenzenesulfinate, lithium 2,4,6-trimethylbenzenesulfinate, 2,4,6-triethylbenzenesulfinic acid, 2,4,6- Sodium lyethylbenzenesulfinate, potassium 2,4,6-triethylbenzenesulfinate, calcium 2,4,6-triethylbenzenesulfinate, lithium 2,4,6-triethylbenzenesulfinate, 2,4,6-triisopropyl Benzenesulfinic acid, sodium 2,4,6-triisopropylbenzenesulfinate, potassium 2,4,6-triisopropylbenzenesulfinate, calcium 2,4,6-triisopropylbenzenesulfinate, 2,4,6-trithio And lithium isopropylbenzenesulfinate.

  Moreover, as a polymerization accelerator suitable for a chemical polymerization initiator, amines, sulfinic acid and its salt, a copper compound, a tin compound etc. are mentioned, for example.

Amines used as a polymerization accelerator for chemical polymerization initiators are divided into aliphatic amines and aromatic amines.
Examples of the aliphatic amines include primary aliphatic amines such as n-butylamine, n-hexylamine and n-octylamine; and secondary aliphatic amines such as diisopropylamine, dibutylamine and N-methylethanolamine N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-lauryldiethanolamine, 2- (dimethylamino) ethyl methacrylate, N-methyldiethanolamine dimethacrylate, N-ethyldiethanolamine dimethacrylate, triethanolamine mono Tertiary such as methacrylate, triethanolamine dimethacrylate, triethanolamine trimethacrylate, triethanolamine, trimethylamine, triethylamine, tributylamine Such as aliphatic amines. Among these, from the viewpoint of polymerization curing property and storage stability, tertiary aliphatic amines are preferable, and N-methyldiethanolamine and triethanolamine are more preferable.

  Examples of the aromatic amine include 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-tert-butylaniline, N, N-bis (2-hydroxyethyl) -3,5-di-isopropylaniline, N, N-bis (2-hydroxyethyl) -3 5-di-tert-butylaniline, 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-tert-butylaniline, N, N-dimethyl-3,5-di-tert-butylaniline, ethyl 4- (N, N-dimethylamino) benzoate, 4- (N, N- Methyl dimethylamino) benzoate, n-butoxyethyl 4- (N, N-dimethylamino) benzoate, 2- (methacryloyloxy) ethyl 4- (N, N-dimethylamino) benzoate, 4- (N, N -Dimethylamino) benzophenone, butyl 4- (N, N-dimethylamino) benzoate and the like. Among these, N, N-bis (2-hydroxyethyl) -p-toluidine, ethyl 4- (N, N-dimethylamino) benzoate, 4- (N, from the viewpoint of being able to impart excellent polymerization curing properties. At least one selected from the group consisting of n-dimethylaminoethyl benzoate, and 4- (N, N-dimethylamino) benzophenone is preferred.

  As a sulfinic acid and its salt used as a polymerization accelerator of a chemical polymerization initiator, what was illustrated as a polymerization accelerator of the above-mentioned photoinitiator etc. is mentioned, for example, A sodium benzene sulfinate, p-toluene sulfinic acid Sodium, sodium 2,4,6-triisopropylbenzenesulfinate is preferred.

  As a copper compound used as a polymerization promoter of a chemical polymerization initiator, for example, acetylacetone copper, cupric acetate, copper oleate, cupric chloride, cupric bromide and the like can be mentioned.

  Examples of tin compounds used as a polymerization accelerator for chemical polymerization initiators include di-n-butyltin dimaleate, di-n-octyltin dimaleate, di-n-octyltin dilaurate, di-n-butyltin dilaurate, etc. Can be mentioned. Among these, di-n-octyltin dilaurate and di-n-butyltin dilaurate are preferable.

  The content of the polymerization accelerator in the polymerizable monomer-containing composition is not particularly limited, but is 0.01 parts by mass or more with respect to 100 parts by mass of the polymerizable monomer from the viewpoint of polymerization curability and the like. Is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, and preferably 10 parts by mass or less, more preferably 3 parts by mass or less.

-Other components In addition to the above components, the polymerizable monomer-containing composition may, depending on the purpose, be a pH adjuster, an ultraviolet absorber, an antioxidant, a polymerization inhibitor, a colorant, a pigment, an antibacterial agent, an X-ray It may further contain other components such as contrast agents, thickeners, fluorescent agents, solvents and the like.

  There is no restriction | limiting in particular in the preparation method of a polymerizable monomer containing composition, For example, it is prepared by mix | blending and mixing arbitrary components, such as a polymerization initiator, a polymerization accelerator, and another component, with a polymerizable monomer. can do.

  In general, the lower the viscosity of the polymerizable monomer-containing composition, the faster the penetration speed into the inorganic filler molded body. The viscosity (25 ° C.) of the polymerizable monomer-containing composition is preferably 10 Pa · s or less, more preferably 5 Pa · s or less, and still more preferably 2 Pa · s or less. Although the said viscosity can be adjusted by selecting the kind of polymerizable monomer suitably etc., a polymerizable monomer also except the viewpoint which adjusts the viscosity of the polymerizable monomer containing composition containing it. It is preferable to carry out in consideration of the mechanical strength and refractive index of the dental mill blank to be obtained. The viscosity of the polymerizable monomer-containing composition can also be reduced, for example, by including a solvent. In this case, the solvent can be distilled off by the subsequent pressure reduction operation.

[Contact of Inorganic Filler Molded Body and Polymerizable Monomer-Containing Composition]
There is no particular limitation on the method for bringing the inorganic filler molded body into contact with the polymerizable monomer-containing composition in step 2, and a method capable of causing the polymerizable monomer-containing composition to penetrate into the gaps of the inorganic filler A method of immersing the inorganic filler molded body in the polymerizable monomer-containing composition can be preferably adopted because it can be adopted and it is simpler. By the immersion, the polymerizable monomer-containing composition can gradually infiltrate into the inorganic filler molded body by capillary action. It is preferable that the surrounding environment at this time is under a reduced pressure atmosphere, since permeation of the liquid polymerizable monomer-containing composition is promoted. In addition, the permeation of the polymerizable monomer-containing composition can be further promoted by repeating the operation of returning to normal pressure after being reduced in pressure (operation of reduced pressure / normal pressure) a plurality of times, and the polymerizable monomer can be further enhanced. The time until the contained composition completely penetrates the inside of the inorganic filler molded body can be shortened. The degree of pressure reduction under the above pressure-reduced atmosphere can be appropriately adjusted according to the viscosity of the polymerizable monomer-containing composition, the particle diameter of the inorganic filler, etc., but is preferably 10 kPa or less, and 5 kPa or less The pressure is more preferably 2 kPa or less, further preferably 0.1 Pa or more, more preferably 1 Pa or more, and still more preferably 10 Pa or more. The reduced pressure atmosphere may be vacuum (for example, about 1 × 10 ⁻⁸ to 1 × 10 ⁻¹ Pa).

  Further, as a method other than the method of immersing the inorganic filler compact in the polymerizable monomer-containing composition as described above, pressure is applied to the inorganic filler compact obtained in Step 1 to polymerize it. You may employ | adopt the method of sending a monomer containing composition into an inorganic filler molded object. Here, when the heat treatment in step 1 is performed in a mold used for press molding, a method of feeding the polymerizable monomer-containing composition into the inorganic filler molded body in the mold can be employed. . According to this method, it is possible to carry out step 2 continuously in the mold as it is. The pressure at the time of feeding the polymerizable monomer-containing composition into the inorganic filler molded body under pressure is preferably 2 MPa or more, more preferably 10 MPa or more, and still more preferably 20 MPa or more.

  In addition, penetration of the polymerizable monomer-containing composition into the inorganic filler molded body can be performed more efficiently, and the polymerizable monomer-containing composition is allowed to permeate into the inorganic filler molded body without gaps. Since it can be carried out, the inorganic filler material apparently impregnated with the polymerizable monomer-containing composition obtained by immersing the inorganic filler molded body in the polymerizable monomer-containing composition as described above You may employ | adopt the method of putting a molded object on pressurization conditions for a fixed time. As the method of the said pressurization, a CIP apparatus etc. can be used, for example. The pressure at the time of pressurization is preferably 20 MPa or more, more preferably 50 MPa or more, and further preferably 100 MPa or more. Further, the operation of returning to normal pressure after pressurization (operation of pressurization / normal pressure) may be repeated multiple times.

  The temperature at the time of bringing the inorganic filler molding and the polymerizable monomer-containing composition into contact with each other can more efficiently penetrate the polymerizable monomer-containing composition into the interior of the inorganic filler molding. In view of the above, the temperature is preferably 0 ° C. or more, more preferably 10 ° C. or more, still more preferably 20 ° C. or more, and may be 30 ° C. or more, 40 ° C. or more, further 50 ° C. Moreover, it is preferable that it is 70 degrees C or less, and it is more preferable that it is 60 degrees C or less.

  The contact time at the time of contacting the inorganic filler molded product with the polymerizable monomer-containing composition is the type of inorganic filler, the size of the inorganic filler molded product, the penetration degree of the polymerizable monomer, the contact method, etc. It can also be adjusted as appropriate. For example, in the case of adopting a method of immersing the inorganic filler molded body in the polymerizable monomer-containing composition, the contact time can be 0.1 to 240 hours, and in particular, it is immersed under a reduced pressure atmosphere In the case where the contact time can be 0.5 to 120 hours, on the other hand, the method of feeding the polymerizable monomer-containing composition into the inorganic filler compact by applying pressure to the inorganic filler compact When employed, the contact time can be 0.2 to 48 hours.

[Polymerization and Curing of Polymerizable Monomer]
A state in which the polymerizable monomer-containing composition intrudes the inside of the inorganic filler molded body by bringing the inorganic filler molded body obtained in step 1 into contact with the polymerizable monomer-containing composition (polymerizable monomer By carrying out the polymerization hardening of the polymerizable monomer contained in the said polymerizable monomer containing composition in the state into which the containing composition was impregnated, the dental mill blank made into the objective can be obtained.

  There is no restriction | limiting in particular in the method of polymerization hardening, According to the kind etc. of a polymerization initiator used, polymerization methods, such as heat polymerization, photopolymerization, chemical polymerization, can be employ | adopted suitably. When heat-polymerizing, there is no restriction | limiting in particular in heating temperature, For example, it can be in the range of 40-150 degreeC. Moreover, there is no restriction | limiting in particular also in heating time, For example, it can be in the range of 1 to 70 hours. The heat polymerization may be performed in one step or in multiple steps, and in the case of the latter, the heating temperature can be appropriately changed. On the other hand, in the case of photopolymerization, the light used is not particularly limited, and may be visible light, ultraviolet light, or other light. The time of photopolymerization is also not particularly limited, and may be, for example, in the range of 1 to 20 minutes. Further, from the viewpoint of obtaining a dental mill blank having a higher mechanical strength by increasing the polymerization rate, a method of performing heat polymerization after photopolymerization may be adopted.

  In the case of polymerization curing, when the inorganic filler molded body in the state impregnated with the polymerizable monomer-containing composition is polymerized and cured in an inert gas atmosphere such as nitrogen gas or under reduced pressure (including vacuum), the polymerization rate is The mechanical strength of the dental mill blank that can be enhanced can be further improved. When polymerizing and curing under reduced pressure (including vacuum), polymerization is carried out in a state where the inorganic filler compact in a state impregnated with the polymerizable monomer-containing composition is packed in a vacuum pack or the like from the viewpoint of productivity and the like. It is preferred to carry out the curing. In this case, polymerization curing can also be carried out by pressure heating polymerization using an autoclave or the like.

  Moreover, since polymerization hardening can further improve the mechanical strength of the dental mill blank obtained, etc., the inorganic filler molded body in the state impregnated with the polymerizable monomer-containing composition remains pressurized. You may go. By placing the inorganic filler molded body in a state of being impregnated with the polymerizable monomer-containing composition under pressure, the polymerizable monomer-containing composition is more effective to the minute gaps of the inorganic filler molded body. It is also possible to suppress the remaining of minute air bubbles.

  The pressure in the case of carrying out polymerization curing in the pressurized state is preferably 20 MPa or more, more preferably 50 MPa or more, still more preferably 100 MPa or more, and particularly preferably 200 MPa or more. The pressure is preferably as high as possible, and can be appropriately set in consideration of the capacity of the pressure device to be actually used. As the said pressurizing apparatus, an autoclave, a CIP apparatus, a HIP (hot isostatic pressure) apparatus etc. are mentioned, for example. For example, a CIP apparatus which can be pressurized to about 1000 MPa manufactured by Kobe Steel, Ltd. can be used. When the polymerization and curing are performed in a pressurized state, heat polymerization in which polymerization and curing are performed by heating may be employed, or photopolymerization or chemical polymerization may be employed.

  As a preferable specific pressure polymerization method, for example, the inorganic filler molded body in a state in which the polymerizable monomer-containing composition is impregnated is put in a plastic bag, a rubber tube or the like in a vacuum pack and sealed, and a CIP device The method etc. which superpose | polymerize, pressurizing, etc. are mentioned. By doing so, the mechanical strength of the dental mill blank obtained can be further improved. In the case of performing polymerization while applying pressure using a CIP device, the processing chamber of the CIP device may be warmed after applying a predetermined pressure. More specifically, for example, 30 minutes to 24 hours after applying a predetermined pressure to the inorganic filler molded body in a state of being impregnated with the polymerizable monomer-impregnated composition at room temperature in the processing chamber of the CIP apparatus The method of raising temperature to predetermined | prescribed ultimate temperature over about time may be mentioned. As the said reach | attainment temperature, it can be in the range of 80-180 degreeC, for example. The polymerization time and the ultimate temperature can be set in consideration of the decomposition temperature of the polymerization initiator to be used, and the like.

  The cured product obtained in step 2 may be used as it is as a dental mill blank, but if heat treatment is performed after polymerization curing, the stress strain generated inside the cured product can be alleviated, and the resulting dental product is obtained. It is possible to suppress breakage during cutting when obtaining a dental prosthesis from a mill blank or during clinical use of the dental prosthesis. The temperature of the heat treatment can be, for example, in the range of 80 to 150 ° C. Moreover, as time of the said heat processing, it can be 10 to 120 minutes, for example.

  The hardened material obtained in step 2 may be cut to a desired size, cut, surface-polished, etc., as necessary, to form a dental mill blank.

[Dental mill blank]
The dental mill blank obtained by the production method of the present invention is used for dental applications, and can be used for applications such as cutting, carving, cutting and the like to produce dental prostheses. By using the dental mill blank, an esthetic dental prosthesis having high mechanical properties and excellent abrasion resistance and lubricity can be obtained. The dental prosthesis includes, for example, dental restorations such as inlays, onlays, veneers, crowns, bridges, etc .; abutment teeth, dental posts, dentures, dentures, implant members (fixtures, abutments, etc.), etc. Can be mentioned. The above processing on dental mill blanks is preferably performed using a dental CAD / CAM system. Examples of the dental CAD / CAM system include, for example, a "CEREC" system manufactured by Shirona Dental Systems, and a "Katana" system manufactured by Kuraray Noritake Dental Co., Ltd.

  There is no restriction | limiting in particular in the shape of the dental mill blank obtained by the manufacturing method of this invention, According to the intended application etc., it can set suitably, For example, prismatic columns, such as triangular prism, square prism, hexagonal prism; It can be in the shape of a cylinder (disc-like) or the like.

  There is no particular limitation on the size of the dental mill blank obtained by the manufacturing method of the present invention, and for example, the size can be set to a commercially available dental CAD / CAM system. Specific examples of the size include a 40 mm × 20 mm × 15 mm prism, suitable for producing a single-tooth defect bridge, a 17 mm × 10 mm × 10 mm prism, suitable for producing an inlay, an onlay, etc. Etc., 14 mm × 18 mm × 20 mm prism, long span bridge, disk shape with a diameter of 100 mm and a thickness of 10 to 28 mm, and the like.

  EXAMPLES The present invention will be specifically described below by way of Examples, but the present invention is not limited by these Examples.

Production Example 1
. Preparation of polymerizable monomer-containing composition (1) 70 parts by mass of [2,2,4-trimethylhexamethylene bis (2-carbamoyloxyethyl)] dimethacrylate (UDMA) and triethylene glycol dimethacrylate (TEGDMA) In 30 parts by mass, 1 part by mass of benzoyl peroxide (BPO) was dissolved as a thermal polymerization initiator to prepare a polymerizable monomer-containing composition (1).

Production Example 2
Preparation of Polymerizable Monomer-Containing Composition (2) Benzoyl peroxide as a heat polymerization initiator in 100 parts by mass of [2,2,4-trimethylhexamethylene bis (2-carbamoyloxyethyl)] dimethacrylate (UDMA) A polymerizable monomer-containing composition (2) was prepared by dissolving 1 part by mass of (BPO).

Production Example 3
· Preparation of polymerizable monomer-containing composition (3) 70 parts by mass of [2,2,4-trimethylhexamethylene bis (2-carbamoyloxyethyl)] dimethacrylate (UDMA) and 2,2-bis [4- 1 part by mass of benzoyl peroxide (BPO) as a thermal polymerization initiator is dissolved in 30 parts by mass of acryloyloxypolyethoxyphenyl] propane (average of 2.6 ethoxy groups in the molecule; commonly called D 2.6 E), and then it is polymerizable. A monomer-containing composition (3) was prepared.

Production Example 4
Production of surface-treated inorganic filler (1) 100 g of commercially available ultrafine particle silica ("Aerosil (registered trademark) OX 50", average primary particle diameter: 0.04 μm, BET specific surface area: 50 m ² / g) manufactured by Nippon Aerosil Co., Ltd. It disperse | distributed to 500 mL, 7 g of (gamma)-methacryloyl oxypropyl trimethoxysilane and 5 g of water were added, and it stirred at room temperature (25 degreeC) for 2 hours. The solvent is distilled off under reduced pressure (distillation temperature 25 ° C. and distillation time 1 hour), heated at 90 ° C. for 3 hours, and further kept at room temperature (25 ° C.) for 24 hours to obtain surface treated inorganic filler (1) Obtained.

Production Example 5
-Production of surface-treated inorganic filler (2) In Production Example 5, the same procedure as in Production Example 4 was followed, except that the solvent was distilled off under reduced pressure and then the heat treatment was not performed and kept at room temperature (25 ° C) for 24 hours. A surface-treated inorganic filler (2) was obtained.

Example 1
(1) 4.25 g of the surface-treated inorganic filler (1) (immediately after holding at room temperature (25 ° C.) for 24 hours) obtained in the above-mentioned Production Example 4 was divided into 15.0 mm × 18.5 mm rectangular holes Placed on the lower punch rod of the press mold with. The powder was leveled by tapping, the upper punch bar was set on the top, and uniaxial pressing (press pressure: 10 kN (36 MPa), pressing time: 3 minutes) was performed using a table press. The upper punch bar and the lower punch bar were removed from the mold, and the inorganic filler compact formed by aggregation of the surface-treated inorganic filler was taken out. The size of the inorganic filler compact was 15.0 mm × 18.5 mm × 15.3 mm.
(2) The obtained inorganic filler molded body was placed in a hot air drier and heat treated by holding it at 90 ° C. for 12 hours.
(3) The obtained inorganic filler molded body was immersed in the polymerizable monomer composition (1) at room temperature (25 ° C.) and degassed under reduced pressure (20 Pa, 90 seconds). The reduced pressure was released to obtain an inorganic filler molded article (polymerizable monomer-impregnated molded article) impregnated with the polymerizable monomer-containing composition. As a result of visual observation of the polymerizable monomer-impregnated molded product, no breakage or micro cracks were found. Primary polymerization is carried out by heating the obtained polymerizable monomer-impregnated molded body at 55 ° C. for 18 hours using a hot air drier, and then addition heating is carried out by further heating at 110 ° C. for 3 hours Thus, the desired dental mill blank was obtained.

[Examples 2 to 7 and Comparative Examples 1 to 3]
In Example 1, except that the type of the surface-treated inorganic filler, the temperature and time of the heat treatment in (2), and the type of the polymerizable monomer-containing composition were changed as described in Table 1 A dental mill blank was obtained in the same manner as in Example 1.

(Test Example 1)
-Measurement of bending strength The bending strength of the obtained dental mill blank was measured by the following method. That is, a test piece (1.2 mm × 4.0 mm × 14.0 mm) was produced from the manufactured dental mill blank using a diamond cutter. This is set in a universal testing machine (manufactured by Shimadzu Corporation), and the bending strength is measured according to the three-point bending test method (JDMAS 245: 2017 according to the provisions of 2017) under the conditions of cross head speed 1 mm / min and distance between supporting points 12 mm. It was measured. The results are shown in Table 1.

(Test Example 2)
Evaluation of Yield Forty similar dental mill blanks were produced in each Example or Comparative Example, and these were visually observed. The yield (%) was determined by dividing the number of dental mill blanks free of breakage or cracks by the total number (40). The results are shown in Table 1.

(Test Example 3)
In each example or comparative example Measurement of moldings expansion size heat treatment of an inorganic filler molded bodies made in (2) was measured to its volume and V1mm ^3. Further, the size of the polymerizable monomer-impregnated molded product obtained in (3) was measured, and the volume was set to V2 mm ³ . From these values, the expansion coefficient of the molded product was determined by the following equation. The results are shown in Table 1.
Expansion rate of molded body (%) = 100 × (V2-V1) / (V1)

Claims (8)

  A step (Step 1) of holding at 50 to 160 ° C. an inorganic filler molded body obtained by press-molding an inorganic filler, and the inorganic filler molded body obtained in Step 1 and a polymerizable monomer-containing composition And a step of polymerizing and curing the polymerizable monomer by bringing them into contact with each other (Step 2).   The manufacturing method of Claim 1 whose holding time in the said process 1 is 0.5 hours or more.   The method according to claim 1, wherein the inorganic filler is subjected to surface treatment.   The method according to claim 3, wherein the inorganic filler subjected to the surface treatment is obtained by mixing an inorganic filler and a surface treating agent.   The method according to claim 4, wherein the temperature between the mixing of the inorganic filler and the surface treatment agent and the time immediately before the pressing is maintained at 50 ° C or less.   The method according to claim 4 or 5, comprising the steps of: mixing the inorganic filler and the surface treatment agent in the presence of a solvent; and removing the solvent after the mixing.   7. The method of claim 6, wherein the solvent comprises water.   The process according to claim 6 or 7, wherein the temperature at which the solvent is removed is 0 to 50 ° C.