JP2019099539A - Inorganic filler composite for producing dental mill blank - Google Patents

Abstract

To provide an inorganic filler composite capable of producing with good yield, a dental mill blank in which there is less crack or wane, excellent in mechanical strength, a production method of the dental mill blank using the composite, and the dental mill blank excellent in mechanical strength with less crack or wane.SOLUTION: There are provided: an inorganic filler composite used for producing a dental mill blank including an inorganic filler and polymer, comprising the inorganic filler and a binder on a surface of the inorganic filler; a production method of the dental mill blank including the inorganic filler and polymer, including a step for bringing an inorganic filler molded body formed by press molding the inorganic filler composite including the inorganic filler and the binder on the surface thereof, into contact with a polymerizable monomer containing composition, for polymerizing and curing the polymerizable monomer; and the dental mill blank including the inorganic filler composite including the inorganic filler and the binder on the surface thereof, and the polymer.SELECTED DRAWING: None

Description

  The present invention relates to an inorganic filler composite used for producing a dental mill blank, a method for producing a dental mill blank using the same, and a dental mill blank. More specifically, inlays, onlays, veneers, crowns, bridges, abutments, dental posts, dentures, dentures, implant members (fixtures, abutments), for example, by cutting with a dental CAD / CAM system. And a method of manufacturing a dental mill blank using the same, and a dental mill blank using the same.

  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. In such a system, a block body in the shape of a rectangular parallelepiped, a cylinder, a disk, etc. having an appropriate size is supplied, and this is set in a cutting machine and cut out to restore a crown shape or a dentition shape. Get As materials for blocks, various materials such as glass ceramics, zirconia, titanium, acrylic resin, and composite materials containing a polymer resin and an inorganic filler have been proposed.

  For example, Patent Document 1 discloses a dental mill using a composite material capable of providing a dental prosthesis which is excellent in mechanical strength, abrasion resistance, surface lubricity, and abrasion resistance of mating teeth. As a method for producing a blank, a method is described in which an inorganic filler molded body obtained by press-molding an inorganic filler is brought into contact with a polymerizable monomer-containing composition to polymerize and cure the polymerizable monomer. There is.

International Publication No. 2014/021343

  As a result of investigations by the present inventors, in the manufacturing method described in Patent Document 1, a crack is generated on the surface or the inside of the inorganic filler molded body or a chip is generated on the surface of the inorganic filler molded body during press molding. In some cases, the yield of the inorganic filler molded product and thus the yield of the dental mill blank may deteriorate, and the dental mill blank obtained from the inorganic filler molded product having a crack generated therein is It turned out that mechanical strength tends to fall. That is, the production method described in Patent Document 1 has room for further improvement in terms of yield and mechanical strength.

  The present invention has been made to solve the above-mentioned problems of the prior art, and is an inorganic filler composite which can produce a dental mill blank excellent in mechanical strength with few cracks and chips with high yield. It is an object of the present invention to provide a method of manufacturing a dental mill blank using the inorganic filler composite and a dental mill blank excellent in mechanical strength with less cracks and chips.

  As a result of intensive studies to achieve the above object, the present inventors produced an inorganic filler and an inorganic filler containing a binder present on the surface thereof in producing a dental mill blank containing an inorganic filler and a polymer. When the composite is used as a raw material, the occurrence of cracks and chips in the inorganic filler compact obtained by press molding can be effectively suppressed, and a dental mill blank excellent in mechanical strength is produced with high yield. It has been found that the present invention can be achieved, and the present invention has been completed based on the findings.

The present invention is as follows.
[1] An inorganic filler composite used for producing a dental mill blank containing an inorganic filler and a polymer, the inorganic filler composite comprising an inorganic filler and a binder present on the surface thereof.
[2] The inorganic filler according to [1], wherein the binder is at least one selected from the group consisting of a polymerizable monomer, a polymer obtained by polymerizing the polymerizable monomer, a wax and a plasticizer. Complex.
[3] The inorganic filler composite according to [1], wherein the binder is at least one of polymerizable monomers forming a polymer contained in a dental mill blank.
[4] The inorganic filler composite according to any one of [1] to [3], including one in which the inorganic filler is surface-treated with a surface treatment agent.
[5] The inorganic filler composite according to any one of [1] to [4], wherein the content of the binder is 0.1 to 10% by mass.
[6] A method for producing a dental mill blank containing an inorganic filler and a polymer, which is formed by pressing an inorganic filler and an inorganic filler composite containing a binder present on the surface thereof. And a step of bringing a polymerizable monomer into contact with the polymerizable monomer-containing composition to polymerize and cure the polymerizable monomer.
[7] The production method according to [6], wherein the binder is at least one selected from the group consisting of a polymerizable monomer, a polymer obtained by polymerizing the polymerizable monomer, a wax, and a plasticizer.
[8] The production method according to [6], wherein the binder is at least one of polymerizable monomers contained in the polymerizable monomer-containing composition.
[9] The production method according to any one of [6] to [8], wherein the inorganic filler is surface-treated with a surface treatment agent.
[10] The method according to any one of [6] to [9], wherein the content of the binder in the inorganic filler composite is 0.1 to 10% by mass.
[11] An inorganic filler composite comprising an inorganic filler and a binder present on the surface thereof, and a dental mill blank comprising a polymer.
[12] The dental mill according to [11], wherein the binder is at least one selected from the group consisting of a polymerizable monomer, a polymer obtained by polymerizing the polymerizable monomer, a wax and a plasticizer. blank.
[13] The dental mill blank according to [11], wherein the binder is a polymer formed by polymerizing at least one of polymerizable monomers for forming a polymer contained in a dental mill blank.
[14] The dental mill blank according to any one of [11] to [13], wherein the inorganic filler is surface-treated with a surface treatment agent.
[15] The dental mill blank according to any one of [11] to [14], wherein the binder content in the inorganic filler composite is 0.1 to 10% by mass.

  According to the present invention, an inorganic filler composite capable of producing a dental mill blank excellent in mechanical strength with less cracks and chips with good yield, and producing a dental mill blank using the inorganic filler composite A dental mill blank excellent in method and mechanical strength with less cracks and chips is provided.

Hereinafter, the present invention will be described in detail.
[Inorganic filler composite]
The mineral filler composites of the present invention are used in the manufacture of dental mill blanks comprising mineral fillers and polymers. And the said inorganic filler composite contains an inorganic filler and the binder which exists on the surface.

  When the inorganic filler composite has the above-mentioned configuration, a dental mill blank excellent in mechanical strength with few cracks and chips can be manufactured with a good yield.

  Although the present invention is not limited at all, the following can be considered as the reason for achieving the above effect. That is, cracks and chips in the inorganic filler molded body obtained by press molding may cause friction between the mold and the inorganic filler such as a mold and a pack bag, and the inorganic filler molded body may expand when pressure is released. It is believed that this phenomenon is caused by a phenomenon called “springback,” but by using an inorganic filler composite having a binder on the surface, the fluidity of the inorganic filler is improved and the friction with the mold is reduced. Is less likely to occur, and the frequency of occurrence of cracks and chips in the resulting inorganic filler compact is believed to be reduced. Further, by using an inorganic filler composite having a binder on the surface, in addition to the reduction of cracks in the inorganic filler molded body as described above, for example, the obtainable inorganic filler molded body and the polymerizable unit amount to be a polymer When the polymerizable monomer-containing composition is caused to enter the interstices of the inorganic filler composite by bringing the polymerizable monomer-containing composition into contact with the body, the surface of the inorganic filler and the polymerizable monomer-containing composition are brought into contact It is believed that the mechanical strength of the resulting dental mill blank is improved due to, for example, better compatibility with the composition.

-Inorganic filler As an inorganic filler which constitutes an inorganic filler composite, publicly known inorganic particles used as a filler of 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 indices of the inorganic filler and the polymer 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 (meth) acrylic acid ester is used as a polymerizable monomer for forming a polymer, the refractive index of (meth) acrylic acid ester is usually in the range of 1.5 to 1.6. Because of this, even when combined with such a high refractive index inorganic filler having X-ray contrast properties, the difference in refractive index 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 borosilicate 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,“ Scheme ” GM31684 "and the like), fluoroaluminosilicate glass (for example," G018-091 "and" G018-117 "and the like manufactured by Schott, etc.), glass containing zirconia (for example," G018-310 "and" G018 manufactured by Schott, etc.) -159 "etc.), strontium containing (Eg, “G018-163”, “G018-093,” “GM32087, etc.” manufactured by Schott, etc.), glasses containing zinc oxide (eg, “G018-161”, manufactured by Schott, etc.), calcium-containing Glass (for example, "G018-309" manufactured by Schott, etc.) and the like.

  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.

The inorganic filler contains an inorganic filler (A) and an inorganic filler (B) from the viewpoint of obtaining a dental mill blank more effectively with less occurrence of cracks and excellent mechanical strength and aesthetics. Here, when the average primary particle diameter of the inorganic filler (A) is a μm and the average primary particle diameter of the inorganic filler (B) is b μm, the following formulas (I) and (II) are satisfied: preferable.
0.12 ≦ a ≦ 0.70 (I)
3 ≦ b / a (II)

  The said average primary particle diameter (a) of an inorganic filler (A) exists in the range of 0.12-0.70 micrometer. By using the inorganic filler (A) having the average primary particle diameter, it is possible to more efficiently obtain a dental mill blank that is less likely to be cracked and is more excellent in mechanical strength and aesthetics. From such a viewpoint, the average primary particle size (a) of the inorganic filler (A) is preferably 0.15 μm or more, and preferably 0.50 μm or less.

It is preferable that the said average primary particle diameter (b) of an inorganic filler (B) satisfy | fills the following formula (III).
0.8 ≦ b ≦ 10 (III)
That is, it is preferable that the average primary particle diameter (b) of an inorganic filler (B) exists in the range of 0.8-10 micrometers. By using the inorganic filler (B) having the average primary particle diameter, it is possible to more efficiently obtain a dental mill blank which is less likely to be cracked and is more excellent in mechanical strength and aesthetics. From such a viewpoint, the average primary particle size (b) of the inorganic filler (B) is more preferably 1.0 μm or more, and more preferably 5.0 μm or less.

  The average primary particle diameter of the inorganic filler can be determined by a laser diffraction scattering method, and specifically, for example, 0, using a laser diffraction type particle size distribution measuring apparatus (“SALD-2100” manufactured by Shimadzu Corporation) An aqueous solution of 2% sodium hexametaphosphate can be measured as a dispersion medium.

  The average primary particle size (b) of the inorganic filler (B) is three or more times the average primary particle size (a) of the inorganic filler (A). When b / a is in the range of the above-mentioned formula (II), a dental mill blank with less generation of cracks and more excellent in mechanical strength and aesthetics can be obtained more efficiently. From such a viewpoint, b / a is preferably 5 or more, and more preferably 7 or more. There is no restriction | limiting in particular in the upper limit of b / a, For example, it can be 70 or less, 40 or less, 25 or less, or 15 or less.

  In the inorganic filler, the content of the inorganic filler (A) / the content (volume / volume) of the inorganic filler (B) is preferably 5/95 to 50/50. From the fact that the effects of the present invention are more remarkably exhibited, the content of the inorganic filler (A) / the content (volume / volume) of the inorganic filler (B) is more than 10/90. It is more preferably 15/85 or more, particularly preferably 20/80 or more, more preferably 40/60 or less, still more preferably 35/65 or less, 30 / It is particularly preferred that it is 70 or less. Each content of the inorganic filler (A) and the inorganic filler (B) on a volume basis can be determined based on a value obtained by dividing each mass by the density of the material constituting the respective inorganic filler. . In addition, when an inorganic filler is surface-treated as mentioned later, the said ratio is each content of the inorganic filler (A) and inorganic filler (B) before the said surface treatment is given. It may be calculated based on The contents of the inorganic filler (A) and the inorganic filler (B) on a volume basis can be determined, for example, by imaging a cross section of a dental mill blank with an electron microscope.

  The inorganic filler may contain an inorganic filler other than the above-mentioned inorganic filler (A) and inorganic filler (B). The ratio of the total of the inorganic filler (A) and the inorganic filler (B) in all the inorganic fillers used in the production of dental mill blanks is that the effects of the present invention are more remarkably exhibited, etc. The content is preferably 50% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, and 95% by mass or more, 98% by mass or more, and further 100% by mass. It is also good.

-Surface treatment It is preferable that an inorganic filler is what was surface-treated beforehand. By using the surface-treated inorganic filler, the mechanical strength of the resulting dental mill blank can be further improved. In addition, an inorganic filler molded body obtained by press-molding an inorganic filler is brought into contact with the later-described polymerizable monomer-containing composition, and the polymerizable monomer-containing composition is formed in the gaps of the inorganic filler composite. There is also an advantage that the surface of the inorganic filler conforms well to the polymerizable monomer-containing composition, and the polymerizable monomer-containing composition can easily infiltrate.
In the case where the inorganic filler is previously surface-treated as described above, it is sufficient that the inorganic filler includes the surface-treated one with a surface treatment agent, and only a part of the inorganic filler (preferably, 50% by mass or more of the inorganic filler, more preferably 80% by mass or more of the inorganic filler, and even more preferably 95% by mass or more of the inorganic filler) may be surface-treated with a surface treatment agent, or the inorganic filler All may be surface-treated with a surface treatment agent. In particular, in the case of using two or more types of inorganic fillers, only one of them may be subjected to surface treatment, or all may be subjected to surface treatment. In the latter case, each surface-treated inorganic filler may be prepared separately, or may be prepared by subjecting a mixture of a plurality of inorganic fillers to a 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 in combination, 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. As the surface treatment method, known methods can be used without particular limitation.

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 bonding between the inorganic filler and the polymerizable monomer or binder can be further improved, etc. Organosilicon compounds having a functional group that can be polymerized are preferable, and ω- (meth) acryloyloxyalkyltrimethoxysilane [carbon number between (meth) acryloyloxy group and silicon atom: 3 to 12], ω- (meth) ) Acryloyloxyalkyltriethoxysilane [carbon number between (meth) acryloyloxy group and silicon atom: 3 to 12], vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, γ-glycidoxypropyl Trimethoxysilane 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 amount of the surface treatment agent to be used is not particularly limited, and is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the inorganic filler before the surface treatment.

-Binder The inorganic filler composite of the present invention contains a binder, and the binder is present on the surface of the above-mentioned inorganic filler.

  The type of binder is not particularly limited, and, for example, polymerizable monomers (radically polymerizable monomers, cationically polymerizable monomers, etc.), polymers formed by polymerizing polymerizable monomers, waxes, plasticizers Etc. A binder may be used individually by 1 type, and may use 2 or more types together. Among these, heating is performed in the case of producing a dental mill blank by a method including the step of polymerizing and curing the polymerizable monomer by bringing the inorganic filler compact into contact with the polymerizable monomer-containing composition. Since the mechanical strength of the dental mill blank obtained when polymerizing and curing the polymerizable monomer is further improved, etc., the inorganic filler before polymerization and curing (for example, when it is subjected to press molding) The binder contained in the composite is preferably at least one selected from the group consisting of a polymerizable monomer, a wax and a plasticizer, and at least one selected from the group consisting of a polymerizable monomer and a plasticizer. Is more preferably, the polymerizable monomer is further preferable, and the inorganic filler after polymerization curing (for example, in the dental mill blank to be obtained) The binder contained in the combination is preferably at least one selected from the group consisting of a polymer formed by polymerizing a polymerizable monomer, a wax, and a plasticizer, and a weight formed by polymerizing the polymerizable monomer. It is more preferable that it is at least one selected from the group consisting of a combination and a plasticizer, and it is more preferable that it is a polymer obtained by polymerizing a polymerizable monomer.

  Specific examples of the polymerizable monomer used as a binder include a polymerizable monomer described later as a polymerizable monomer for forming a polymer contained in a dental mill blank, and in particular, radical polymerization Monomers are preferred. Moreover, the said polymerizable monomer used as a binder is a polymerizable monomer which forms the polymer contained in the dental mill blank finally obtained (Typically the below-mentioned polymerizable monomer containing composition) It is preferable that it is at least 1 sort (s) of the polymerizable monomers contained in things. Similarly, as a specific example of the polymer used as a binder, a polymer obtained by polymerizing a polymerizable monomer described later as a polymerizable monomer for forming a polymer contained in a dental mill blank, etc. Particularly preferred are polymers formed by polymerization of radically polymerizable monomers. Moreover, the said polymer used as a binder is contained in the polymerizable monomer (it is typically included in the below-mentioned polymerizable monomer containing composition) which forms the polymer contained in the dental mill blank finally obtained. It is preferable that it is a polymer formed by polymerizing at least one of the polymerizable monomers).

  The polymerizable monomer is preferably a difunctional (meth) acrylic acid ester, although it depends on the type of the polymerizable monomer that forms the polymer contained in the dental mill blank, etc. -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] propane, [2,2,4-trimethylhexamethylene bis (2- Carbamoyloxyethyl)] dimethacrylate (commonly called UDMA) is more preferred.

  Examples of the wax include paraffin wax, polyethylene wax, polyolefin wax, liquid paraffin wax and the like.

  Examples of the plasticizer include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, di (2-ethylhexyl) phthalate, dinormal octyl phthalate, diisononyl phthalate, dinonyl phthalate, diisodecyl phthalate, butyl phthalate Phthalates such as benzyl; dioctyl adipate; diisononyl adipate; dinormhexyl adipate; adipic esters such as dinormodecyl adipate; polyethylene glycol (PEG).

  The content of the binder in the inorganic filler composite is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and further preferably 0.5% by mass or more Is more preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less. When the content of the binder is the above lower limit or more, the effect as the binder is more effectively expressed, and when the content of the binder is the above or lower limit, the flowability is improved, and the machine with few cracks and chips Dental mill blanks having excellent mechanical strength can be manufactured with higher yield.

-Preparation of inorganic filler composite There is no restriction | limiting in particular in the preparation method of the inorganic filler composite of this invention, For example, it can obtain by mixing an inorganic filler and a binder. The mixing may be carried out in the presence of a solvent, in which case the solvent is preferably removed by distillation or the like after mixing.

[Polymer]
The mineral filler composites of the present invention are used in the manufacture of dental mill blanks comprising mineral fillers and polymers. There is no restriction | limiting in particular in the polymer which comprises a dental mill blank, What a polymerizing monomer polymerizes can be used, The superposition | polymerization in the polymerizable monomer containing composition containing a polymerizable monomer can be used It is preferable that the functional monomer be polymerized and cured.

Polymerizable Monomer As a polymerizable monomer for forming a polymer (a polymerizable monomer for forming a structural unit contained in a polymer), known polymerizable monomers used for dental composite resins etc. may be used. A monomer can be used, and in general, a radically polymerizable monomer is suitably 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)] Dimethacrylate (commonly called UDMA), 2,2,3,3,4,4-hexafluoro-1,5-pentyl 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 even if it is a solid polymerizable monomer, the polymerizability of other liquids is also possible. It is also possible to mix and dissolve the monomer.

  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.

Polymerization initiator In order to obtain a polymer by polymerizing the polymerizable monomer, a polymerization initiator can be used to facilitate the polymerization, and in particular, the polymerizable monomer in the polymerizable monomer-containing composition can be used. When the polymer is obtained by polymerizing and curing the monomer, the polymerizable monomer-containing composition preferably further includes a polymerization initiator. 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 the organic peroxides include ketone peroxides, hydroperoxides, diacyl peroxides, dialkyl peroxides, peroxyketals, peroxy esters, peroxy dicarbonates and the like.

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

  Examples of the hydroperoxide include 2,5-dimethylhexane-2,5-dihydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide Etc.

  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.

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

  Examples of the peroxyketal include 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, and 2,2-bis (t-). Butylperoxy) butane, 2,2-bis (t-butylperoxy) octane, 4,4-bis (t-butylperoxy) valeric acid n-butyl ester and the like can be mentioned.

  Examples of the peroxy esters include α-cumylperoxyneodecanoate, t-butylperoxyneodecanoate, t-butylperoxypivalate, and 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 the peroxydicarbonate include di-3-methoxyperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, diisopropylperoxydicarbonate, di-n-propyl Peroxydicarbonate, 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.

  Examples of the azo compounds include, for example, 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), and 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- dimethyl And phenyl) phosphonates and salts thereof.

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

  Examples of the coumarins include 3,3′-carbonylbis (7-diethylaminocoumarin), 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-nitro) Benzoyl) coumarin, 3,5-carbonylbis (7-methoxycoumarin), 3-benzoyl-6-bromocoumarin, 3,3′-carbonylbiscoumarin, 3-benzoyl-7-dimethylaminocoumarin, 3-benzoylbenzo [3 f] coumarin, 3-carboxy coumarin, 3-carboxy-7-me Xycoumarin, 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 Dimethylbenzothiazol-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'- Carbonyl-7-diethylaminocoumarin-7'-bis (butoxyethyl) aminocoumarin, 10- [3- [4- (dimethylamino) phenyl] -1-oxo-2-propenyl] -2,3,6,7- Tetrahydro-1,1,7,7-tetramethyl-1H, 5H, 11H- [1] benzopyrano [6,7,8-ij] 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; 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 peroxide, known ones can be used, and specifically, the organic peroxides exemplified in the description of 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 use amount of the polymerization initiator is not particularly limited, but is preferably 0.001 parts by mass or more, and more preferably 0.05 parts by mass or more with respect to 100 parts by mass of the polymerizable monomer from the viewpoint of polymerizability and the like. The content is more 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 use amount 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 the usage-amount of a polymerization initiator is below the said upper limit.

Polymerization accelerator When using the polymerization initiator, a polymerization accelerator may be used in combination, in particular, in the case of obtaining a polymer by polymerizing and curing the polymerizable monomer in the polymerizable monomer-containing composition In addition, the polymerizable monomer-containing composition may further contain a polymerization accelerator together with a polymerization initiator. By using the polymerization accelerator in combination, the polymerization may 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-di-t-butylaniline, n-butoxyethyl 4- (N, N-dimethylamino) benzoate, 4- (N, N-dimethyl) (Amino) benzoic acid (2-methacryloyloxy) ethyl, ethyl 4- (N, N-dimethylamino) benzoate, butyl 4- (N, N-dimethylamino) benzoate, N-methyldiethanolamine, 4- (N, N-Dimethylamino) benzophenone, trimethylamine, triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, Nn- Tyldiethanolamine, N-lauryldiethanolamine, triethanolamine, 2- (dimethylamino) ethyl methacrylate, N-methyldiethanolamine dimethacrylate, N-ethyldiethanolamine dimethacrylate, triethanolamine monomethacrylate, triethanolamine dimethacrylate, triethanolamine Trimethacrylate 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 can be divided into aliphatic amines and aromatic amines having an electron withdrawing group in the aromatic ring.
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, tertiary aliphatic amines are preferable, and N-methyldiethanolamine and triethanolamine are more preferable, from the viewpoint of polymerizability and storage stability.

  Examples of the aromatic amine having an electron withdrawing group in the aromatic ring include N, N-bis (2-hydroxyethyl) -p-toluidine, ethyl 4- (N, N-dimethylamino) benzoate, 4- Methyl (N, N-dimethylamino) benzoate, n-butoxyethyl 4- (N, N-dimethylamino) benzoate, 2- (methacryloyloxy) ethyl 4- (N, N-dimethylamino) benzoate, 4 Tertiary aromatic amines such as-(N, N-dimethylamino) benzophenone, butyl 4- (N, N-dimethylamino) benzoate and the like can be mentioned. Among these, N, N-bis (2-hydroxyethyl) -p-toluidine, ethyl 4- (N, N-dimethylamino) benzoate, 4- (N, N) from the viewpoint of being able to impart excellent curability. -Dimethylaminobenzoic acid) At least one selected from the group consisting of n-butoxyethyl 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 use amount of the polymerization accelerator is not particularly limited, but is preferably 0.01 parts by mass or more with respect to 100 parts by mass of the polymerizable monomer from the viewpoint of polymerizability etc. Some are more preferable, 1 part by mass or more is further preferable, 10 parts by mass or less is preferable, and 3 parts by mass or less is more preferable.

  Since the content of the polymer in the dental mill blank to be produced shows that the effects of the present invention are more significantly exhibited, etc., an ash obtained by ashing the dental mill blank at 600 ° C. for 2 hours Preferably 50% by volume or more, more preferably 80% by volume or more, still more preferably 90% by volume or more, and 95% by volume or more, or substantially 100% by volume. May be

[Other ingredients]
In addition to inorganic fillers and polymers, dental mill blanks have pH adjusters, ultraviolet absorbers, antioxidants, colorants, pigments, antibacterial agents, X-ray contrast agents, thickeners, and fluorescence depending on the purpose. It may further contain other ingredients such as an agent.

[Method of producing dental mill blank]
The method for producing a dental mill blank containing an inorganic filler and a polymer using the inorganic filler composite of the present invention is not particularly limited, but a dental mill blank having desired physical properties can be made more efficiently. From the fact that it can be obtained, etc., the step of polymerizing and curing the polymerizable monomer by bringing the inorganic filler molded body obtained by press molding the above-mentioned inorganic filler composite into contact with the polymerizable monomer-containing composition It is preferable to manufacture by the method of including.

-Press molding The above-mentioned inorganic filler molded body is formed by press molding an inorganic filler composite. There is no restriction | limiting in particular in the method of press-molding an inorganic filler composite, A well-known method is employable. As a specific method of press molding, for example, a method of filling an inorganic filler composite in a press die having a desired size, and pressing by a uniaxial press using an upper punch and a lower punch is mentioned. Be

  The pressing pressure at the time of uniaxial pressing can be appropriately set to an optimum value depending on the size of the target inorganic filler compact, the type of inorganic filler or inorganic filler composite, particle diameter, etc. It can be more than. The higher the pressing pressure, the easier it is to obtain a desired dental mill blank, and the stability of the inorganic filler compact when contacting the obtained inorganic filler compact with the polymerizable monomer-containing composition is improved. For this reason, it is preferable, but it is preferable to suppress the occurrence of cracks and chips in the inorganic filler molded body based on the size of the inorganic filler molded body, the productivity such as equipment factors, and the friction with the mold due to excessive load. In consideration of the surface, the pressing pressure is usually 200 MPa or less. From the above viewpoint, 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. The pressing time can be appropriately set in accordance with the pressing pressure, but may usually be 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 molded body from the three-dimensional direction, the press by the CIP process By performing the molding, it is possible to eliminate the undesirable minute voids inside the inorganic filler molded body and the unevenness of the aggregation state of the inorganic filler or the inorganic filler composite, and the compressive density of the inorganic filler is further improved. Thus, a dental mill blank having a high content of inorganic filler can be obtained. In addition, when performing press molding by a CIP process without performing uniaxial pressing, the inorganic filler complex 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 (vacuum condition) Can 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 makes it easy to obtain a dental mill blank desired with a higher pressure regardless of the presence or absence of a uniaxial press and bring the obtained inorganic filler compact into contact with the polymerizable monomer-containing composition. It is preferable because the stability of the inorganic filler molding is improved. The pressure in the CIP step is preferably 30 MPa or more in consideration of productivity, suppression of generation of cracks and chips in the inorganic filler molded body based on friction with the mold due to excessive load, etc. More preferably, it is 50 MPa or more, more preferably 100 MPa or more, and preferably 300 MPa or less, more preferably 250 MPa or less, further preferably 200 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.

  The inorganic filler molded body obtained by press-molding the inorganic filler composite may have a single layer structure or a multilayer structure. As a multilayer structure, for example, mutually different inorganic filler composites (for example, both inorganic fillers (A) and inorganic fillers (B) as inorganic fillers, inorganic filler composites having different compositions, etc.) And the like, or the same kind of inorganic filler composite (for example, the same kind including both inorganic filler (A) and inorganic filler (B) as an inorganic filler) The inorganic filler composite and the like) may be separately press-formed into layers, and in any case, dental mill blanks 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 composite, which is adjusted to increase transparency after polymerization curing of the polymerizable monomer, is disposed in the first layer, and dentine color tone can be obtained after polymerization curing of the polymerizable monomer. When the prepared inorganic filler composite is disposed in the second layer, when the resulting dental mill blank is cut to produce a crown, the upper layer has an enamel color tone in the upper layer and has a dentin color tone in the lower layer. It is possible to make a crown which is superior by the nature.

  There is no particular limitation on the method of preparing the above inorganic filler composite which can make the desired color tone after polymerization and curing, for example, a method of mixing and dispersing a pigment (colored particles etc.) in the inorganic filler composite, etc. It can be 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 composite, a well-known powder mixing and dispersing method can be adopted, and either a dry method or a wet method may be used, but it is possible to mix and disperse more uniformly. It is preferable to use a method of removing the solvent (eg, distilling off) after mixing the inorganic filler composite and the pigment in the presence of a solvent, since this can be done. 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 inorganic filler composite or pigment used, type and amount of solvent, type of dispersing machine, etc. Dispersion of each component Dispersion conditions such as the dispersion time, the stirring tool, and the number of rotations can be appropriately selected according to the situation and the like. The solvent is preferably water and / or a solvent compatible with water, and the solvent includes alcohols (eg, ethanol, methanol, isopropanol etc.), ethers, ketones (eg acetone, methyl ethyl ketone etc.), etc. Can be used.

  Moreover, as a method for making the color tone after polymerization curing desired, other than the method of mixing and dispersing the pigment as described above in the inorganic filler composite, the inorganic filler itself is like the colored glass. It is also possible to adopt a method using one having a specific 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, an inorganic filler having the same refractive index as possible after the polymerization and curing of the polymerizable monomer-containing composition to be impregnated as the inorganic filler contained in the inorganic filler composite used in the highly transparent layer A method of using a material can be preferably adopted. In addition, you may employ | adopt the method of selecting a polymerizable monomer suitably so that it may correspond to the refractive index of an inorganic filler.

  As a method for setting the physical properties after polymerization curing as desired, for example, an inorganic filler composite excellent in lubricity is disposed in the layer corresponding to the enamel layer, and corresponds to the dentin layer of the inner layer. As the layer, a method of arranging an inorganic filler composite excellent in mechanical strength can be adopted. The combination of such inorganic filler composites can provide an extremely useful crown prosthesis which has excellent clinical durability in the oral cavity.

  As a method of press molding in the case of obtaining an inorganic filler molded body having a multilayer structure, for example, the following method can be adopted. That is, a first inorganic filler composite is filled in a mold (die) for a uniaxial press fitted with a lower punch, and the upper punch is set in the mold to obtain the first inorganic filler composite. Press. Next, the upper punch is removed, and a second inorganic filler composite is filled on the pressed aggregate of the first inorganic filler composite, and the upper punch is set again, The inorganic filler composite is pressed. 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 composite 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 composite, the surface is smoothed and the second inorganic filler composite is filled thereon without pressing, and the first inorganic filler composite is filled. A method of pressing the filler composite and the second inorganic filler composite together may be employed.

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

  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.

· Contact of inorganic filler molding with polymerizable monomer-containing composition By bringing the above-mentioned inorganic filler molding into contact with the polymerizable monomer-containing composition, polymerization is caused in the gaps of the inorganic filler composite. As a result, a composition having a structure in which the inorganic filler is very closely dispersed in the polymerizable monomer-containing composition is obtained. From such a point of view, in the above manufacturing method, it is preferable to use an inorganic filler molded body which is not in the form of a porous body which has been sintered and communicated.

  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 above manufacturing method, the inorganic filler molded body formed by press-molding the inorganic filler composite is brought into contact with the polymerizable monomer-containing composition to polymerize the polymerizable monomer. Since the dental mill blank is manufactured through the hardening process, high density filling is possible, and the dental prosthesis obtained from the dental mill blank is excellent in gloss and has improved strength and wear resistance. It becomes a thing.

There is no restriction | limiting in particular in the method to which an inorganic filler molded object and a polymerizable monomer containing composition are made to contact, The method which can make a polymerizable monomer containing composition penetrate the clearance gap of an inorganic filler composite is employ | adopted The method of immersing the inorganic filler molded body in the polymerizable monomer-containing composition can be preferably adopted because it can be carried out 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 depending on the viscosity of the polymerizable monomer-containing composition and the particle diameter of the inorganic filler or the inorganic filler composite, but it is 10 kPa or less The pressure is preferably 5 kPa or less, more preferably 2 kPa or less, 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).

  In addition, as a method other than the method of immersing the inorganic filler compact in the polymerizable monomer-containing composition as described above, the pressure is applied as it is in a state where the inorganic filler composite is press-formed in a mold. A method may be employed in which the polymerizable monomer-containing composition is fed to the inorganic filler molded body in the mold. According to this method, it is possible to carry out polymerization and curing of the polymerizable monomer 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 bringing the inorganic filler molding and the polymerizable monomer-containing composition into contact with each other depends on the type of the inorganic filler or the inorganic filler composite, the size of the inorganic filler molding, and the polymerizable monomer. It may differ depending on the degree of penetration, the method of contact, etc., and can be appropriately adjusted. 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 generally 0.1 to 240 hours. In particular, in the case of immersion under a reduced pressure atmosphere, the contact time can be 0.5 to 120 hours. On the other hand, when adopting a method of feeding a polymerizable monomer-containing composition to an inorganic filler molded body by applying pressure to the inorganic filler molded body, the contact time may be 0.2 to 48 hours. it can.

Polymerizable monomer-containing composition The content of the polymerizable monomer in the polymerizable monomer-containing composition used in the above-mentioned production method can be, for example, 50% by mass or more, and 80% % Or more is preferable, 90% by mass or more is more preferable, 95% by mass or more is more preferable, and 98% by mass or more is particularly preferable.

  The polymerizable monomer-containing composition preferably further includes the above-described polymerization initiator, and preferably further includes the above-described polymerization accelerator. The contents of the polymerization initiator and the polymerization accelerator in the polymerizable monomer-containing composition may be the same as the amounts of the polymerization initiator and the polymerization accelerator used. In addition, when the dental mill blank contains the above-mentioned other components, the polymerizable monomer-containing composition may contain these other components.

  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. Moreover, the viscosity of the polymerizable monomer-containing composition can be lowered by raising the temperature to accelerate permeation. The temperature may be a temperature in the above-described range as a temperature at which the inorganic filler molded body and the polymerizable monomer-containing composition are brought into contact with each other.

· Polymerization and curing of polymerizable monomer A state in which the polymerizable monomer-containing composition enters the inside of the inorganic filler molded body by bringing the inorganic filler molded body into contact with the polymerizable monomer-containing composition (polymerizability The target dental mill blank can be obtained by performing polymerization curing of the polymerizable monomer contained in the polymerizable monomer-containing composition) in a state in which the monomer-containing composition is impregnated). .

  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 impregnated with the polymerizable monomer-containing composition is put in a vacuum pack and sealed, and polymerization is performed while pressing using a CIP device or the like. And the like. 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, after applying a predetermined pressure to the inorganic filler molded body in a state in which the polymerizable monomer-containing composition is impregnated at room temperature in a processing chamber of a CIP device, 30 minutes to 24 hours 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 by polymerization curing as described above may be used as it is as a dental mill blank, but if heat treatment is carried out after polymerization curing, the stress strain generated inside the cured product may be alleviated. It is possible to suppress breakage during cutting processing when obtaining a dental prosthesis from the obtained dental mill blank and 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.

  In addition, the cured product obtained by the polymerization curing as described above may be cut into a desired size, cut, or surface-polished as necessary to obtain a dental mill blank.

[Dental mill blank]
The dental mill blank of the present invention comprises an inorganic filler composite and a polymer comprising an inorganic filler and a binder present on the surface thereof. The description of each component such as the inorganic filler composite, the polymer and the like contained in the dental mill blank is the same as that described above, and the redundant description will be omitted here. The binder contained in the inorganic filler composite contained in the dental mill blank of the present invention is, as described above, at least one of the polymerizable monomers forming the polymer contained in the dental mill blank. Is preferably a polymer formed by polymerization. The dental mill blank of the present invention can be produced by the method of producing a dental mill blank described above.

  The dental mill blank in the present invention is used in dental applications, and can be used in applications for producing dental prostheses by processing such as cutting, carving, cutting and the like. By using the dental mill blank, a dental prosthesis excellent in mechanical strength and aesthetics 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.

  The shape of the dental mill blank in the present invention is not particularly limited, and can be appropriately set according to the intended application etc. For example, prismatic columns such as triangular prisms, quadrangular prisms, hexagonal prisms, etc .; And so on.

  There is no particular limitation on the size of the dental mill blank in 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 Hereinafter, the present invention will be specifically described by showing Examples and Comparative Examples, but the present invention is not limited at all by the following Examples. The contents of each component used are described below.

Inorganic filler UF 2.0: barium glass (average primary particle diameter 2.0 μm, manufactured by Schott)
UF 1.0: barium glass (average primary particle diameter 1.0 μm, manufactured by Schott)
NF 180: barium glass (average primary particle diameter 0.18 μm, manufactured by Schott)
· Surface treatment agent γ-MPS: γ-methacryloyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)
· Binder UDMA: [2, 2, 4- trimethylhexamethylene bis (2-carbamoyloxyethyl)] dimethacrylate Bis-GMA: 2, 2- bis [4-[3-methacryloyloxy 2-hydroxypropoxy] phenyl] Propane PEG: Polyethylene glycol, "PEG 600" (Evermore Japan)
Polyolefin wax: "High wax 100 PHP 10A" (made by Mitsui Chemicals)
Polymerizable monomer UDMA: [2,2,4-trimethylhexamethylene bis (2-carbamoyloxyethyl)] dimethacrylate polymerization initiator THP: 1,1,3,3-tetramethylbutyl hydroperoxide (day Oil company)

Production Example 1
Preparation of Inorganic Filler Composite (F1) 100 parts by mass of a mixture of 75 parts by volume of UF 2.0 and 25 parts by volume of NF 180 are dispersed in 300 parts by mass of ethanol, 2.5 parts by mass of γ-MPS, 0.15 acetic acid A mass part and 5 mass parts of water were added, and it stirred at room temperature for 2 hours. Then, 1 mass part of UDMA was added as a binder, and it stirred at room temperature for 10 minutes. The solvent was distilled off under reduced pressure, and the resultant was further dried at 90 ° C. for 3 hours to obtain an inorganic filler composite (F1) having an inorganic filler surface-treated with a surface treatment agent and a binder present on the surface.

Production Example 2
Preparation of Inorganic Filler Composite (F2) 100 parts by mass of a mixture of 75 parts by volume of UF 1.0 and 25 parts by volume of NF 180 is dispersed in 300 parts by mass of ethanol, 5 parts by mass of γ-MPS, 0.15 parts by mass of acetic acid And 5 parts by mass of water were added and stirred at room temperature for 2 hours. Then, 1 mass part of UDMA was added as a binder, and it stirred at room temperature for 10 minutes. The solvent was distilled off under reduced pressure, and drying was further carried out at 90 ° C. for 3 hours to obtain an inorganic filler composite (F2) having an inorganic filler surface-treated with a surface treatment agent and a binder present on the surface.

Production Example 3
Preparation of Inorganic Filler Composite (F3) 100 parts by mass of a mixture of 75 parts by volume of UF 2.0 and 25 parts by volume of NF 180 are dispersed in 300 parts by mass of ethanol, 2.5 parts by mass of γ-MPS, 0.15 acetic acid A mass part and 5 mass parts of water were added, and it stirred at room temperature for 2 hours. Then, 1 mass part of Bis-GMA was added as a binder, and it stirred at room temperature for 10 minutes. The solvent was distilled off under reduced pressure, and the resultant was further dried at 90 ° C. for 3 hours to obtain an inorganic filler composite (F3) having an inorganic filler surface-treated with a surface treatment agent and a binder present on the surface.

Production Example 4
Preparation of Inorganic Filler Composite (F4) 100 parts by mass of a mixture of 75 parts by volume of UF 2.0 and 25 parts by volume of NF 180 are dispersed in 300 parts by mass of ethanol, 2.5 parts by mass of γ-MPS, 0.15 acetic acid A mass part and 5 mass parts of water were added, and it stirred at room temperature for 2 hours. Then, 1 mass part of PEG was added as a binder, and it stirred at room temperature for 10 minutes. The solvent was distilled off under reduced pressure, and the resultant was further dried at 90 ° C. for 3 hours to obtain an inorganic filler composite (F4) having an inorganic filler surface-treated with a surface treatment agent and a binder present on the surface.

Production Example 5
Preparation of Inorganic Filler Composite (F5) 100 parts by mass of a mixture of 75 parts by volume of UF 2.0 and 25 parts by volume of NF 180 are dispersed in 300 parts by mass of ethanol, 2.5 parts by mass of γ-MPS, 0.15 acetic acid A mass part and 5 mass parts of water were added, and it stirred at room temperature for 2 hours. Thereafter, 1 part by mass of a polyolefin wax as a binder was added and stirred at room temperature for 10 minutes. The solvent was distilled off under reduced pressure, and the resultant was further dried at 90 ° C. for 3 hours to obtain an inorganic filler composite (F5) having an inorganic filler surface-treated with a surface treatment agent and a binder present on the surface.

Production Example 6
Preparation of Inorganic Filler Composite (F6) 100 parts by mass of UF 2.0 is dispersed in 300 parts by mass of ethanol, 2 parts by mass of γ-MPS, 0.15 parts by mass of acetic acid and 5 parts by mass of water are added Stir for hours. Then, 1 mass part of UDMA was added as a binder, and it stirred at room temperature for 10 minutes. The solvent was distilled off under reduced pressure, and the resultant was further dried at 90 ° C. for 3 hours to obtain an inorganic filler composite (F6) having an inorganic filler surface-treated with a surface treatment agent and a binder present on the surface.

Production Example 7
Preparation of Inorganic Filler Composite (F7) 100 parts by mass of a mixture of 75 parts by volume of UF 2.0 and 25 parts by volume of NF 180 are dispersed in 300 parts by mass of ethanol, 2.5 parts by mass of γ-MPS, 0.15 acetic acid A mass part and 5 mass parts of water were added, and it stirred at room temperature for 2 hours. Then, 0.2 mass parts of UDMA was added as a binder, and it stirred at room temperature for 10 minutes. The solvent was distilled off under reduced pressure, and the resultant was further dried at 90 ° C. for 3 hours to obtain an inorganic filler composite (F7) having an inorganic filler surface-treated with a surface treatment agent and a binder present on the surface.

Production Example 8
Preparation of Inorganic Filler Composite (F8) 100 parts by mass of a mixture of 75 parts by volume of UF 2.0 and 25 parts by volume of NF 180 are dispersed in 300 parts by mass of ethanol, 2.5 parts by mass of γ-MPS, 0.15 acetic acid A mass part and 5 mass parts of water were added, and it stirred at room temperature for 2 hours. Thereafter, 2 parts by mass of UDMA as a binder was added and stirred at room temperature for 10 minutes. The solvent was distilled off under reduced pressure, and the resultant was further dried at 90 ° C. for 3 hours to obtain an inorganic filler composite (F8) having an inorganic filler surface-treated with a surface treatment agent and a binder present on the surface.

Production Example 9
Preparation of Inorganic Filler (F9) 100 parts by mass of UF 2.0 is dispersed in 300 parts by mass of ethanol, 2 parts by mass of γ-MPS, 0.15 parts by mass of acetic acid and 5 parts by mass of water are added and stirred at room temperature for 2 hours did. The solvent was distilled off under reduced pressure, and the residue was further dried at 90 ° C. for 3 hours to obtain an inorganic filler (F9) surface-treated with a surface treatment agent.

Production Example 10
-Preparation of polymerizable monomer-containing composition (P1) In 99 parts by mass of UDMA, 1 part by mass of THP as a polymerization initiator was dissolved to prepare a polymerizable monomer-containing composition (P1).

Example 1
(1) 7.0 g of the inorganic filler composite (F1) obtained in the above production example was placed on a lower punch rod of a press die having a rectangular hole of 14.5 mm × 18 mm. The powder was leveled by tapping, the upper punch bar was set on top, and uniaxial pressing (press pressure: 10 kN (38.3 MPa), pressing time: 2 minutes) was performed using a table press. The upper punch rod and the lower punch rod were removed from the mold, and the compact in which the inorganic filler composite (F1) was aggregated was taken out. The compact was subjected to press molding (pressure: 170 MPa, pressing time: 5 minutes) in the CIP step to obtain a mineral filler compact.
(2) The obtained inorganic filler molded body is immersed in the polymerizable monomer-containing composition (P1), decompressed (10 hPa) for degassing, and allowed to stand at 70 ° C. for 48 hours. There was obtained an inorganic filler molded article (polymerizable monomer-impregnated molded article) impregnated with the monomer-containing composition. The polymerizable monomer-impregnated molded product was heated at 110 ° C. for 7 hours using a hot air drier, and then heated at 150 ° C. for 7 hours to obtain a desired rectangular parallelepiped dental mill blank.

[Examples 2 to 8 and Comparative Example 1]
A rectangular parallelepiped dental mill blank was obtained in the same manner as in Example 1 except that the type of the inorganic filler composite was changed as described in Table 1 in Example 1. In Comparative Example 1, an inorganic filler (F9) was used instead of the inorganic filler composite (F1).

(Test Example 1)
Evaluation of Yield of Moldings 100 moldings were produced for each example or comparative example, and the presence or absence of cracks and chips in these moldings was evaluated by the following method. That is, first, the presence or absence of cracks and chips on the surface of the molded body was visually evaluated. Moreover, the presence or absence of the crack inside a molded object was evaluated using the X-ray imaging apparatus. And the number of the molded object which did not have a crack and chipping on the surface and inside either was calculated | required, and the yield was computed by the following formula. The results are shown in Table 1.
Yield (%) = 100 × [number of moldings without cracks and chips] / [number of all moldings (100)]

(Test Example 2)
· Measurement of bending strength (without immersion and after immersion in water at 37 ° C (1 month))
The bending strength of the obtained dental mill blank was measured by the following method. That is, a test piece (1.2 mm × 4 mm × 14 mm) was produced from the manufactured dental mill blank using a diamond cutter, and was polished with # 2000 abrasive paper. This is as it is (without immersion) and after it is immersed in water at 37 ° C. for 1 month (after immersion in water at 37 ° C. (1 month)), it is set in a universal tester (made by Shimadzu Corporation) The bending strength was measured by a three-point bending test method (according to the definition of JDMAS 245: 2017) under the conditions of 1 mm / min and a distance between supporting points of 12 mm. The results are shown in Table 1. The bending strength is preferably 250 MPa or more, more preferably 270 MPa or more, still more preferably 300 MPa or more, and particularly preferably 320 MPa or more without immersion. The bending strength is preferably 200 MPa or more, more preferably 220 MPa or more, still more preferably 240 MPa or more, and preferably 270 MPa or more after immersion in water at 37 ° C. (1 month). Is particularly preferred.

  In Examples 1 to 8, most of the molded articles produced in the process of producing the dental mill blank were free of cracks and chips, and the production yield of the molded articles was very high. In addition, the obtained dental mill blank had high flexural strength both before and after immersion in water at 37 ° C for 1 month, and was excellent in mechanical strength.

  On the other hand, Comparative Example 1 was inferior to the example in the production yield of the molded product and the mechanical strength of the dental mill blank.

Claims (15)

  An inorganic filler composite for use in the manufacture of a dental mill blank comprising an inorganic filler and a polymer, the inorganic filler composite comprising an inorganic filler and a binder present on the surface thereof.   The inorganic filler composite according to claim 1, wherein the binder is at least one selected from the group consisting of a polymerizable monomer, a polymer obtained by polymerizing the polymerizable monomer, a wax and a plasticizer.   The inorganic filler composite according to claim 1, wherein the binder is at least one of polymerizable monomers forming a polymer contained in a dental mill blank.   The inorganic filler composite according to any one of claims 1 to 3, wherein the inorganic filler comprises one that has been surface-treated with a surface treatment agent.   The inorganic filler composite according to any one of claims 1 to 4, wherein the content of the binder is 0.1 to 10% by mass.   A method for producing a dental mill blank containing an inorganic filler and a polymer, which is formed by pressing an inorganic filler and an inorganic filler composite containing a binder present on the surface thereof, and an inorganic filler compact and polymerizability A production method comprising the step of contacting a monomer-containing composition and polymerizing and curing a polymerizable monomer.   The production method according to claim 6, wherein the binder is at least one selected from the group consisting of a polymerizable monomer, a polymer obtained by polymerizing the polymerizable monomer, a wax and a plasticizer.   The manufacturing method according to claim 6, wherein the binder is at least one of polymerizable monomers contained in the polymerizable monomer-containing composition.   The production method according to any one of claims 6 to 8, wherein the inorganic filler comprises one having been surface-treated with a surface treatment agent.   The manufacturing method in any one of Claims 6-9 whose content of the binder in an inorganic filler composite is 0.1-10 mass%.   An inorganic filler composite comprising an inorganic filler and a binder present on the surface thereof and a dental mill blank comprising a polymer.   The dental mill blank according to claim 11, wherein the binder is at least one selected from the group consisting of a polymerizable monomer, a polymer obtained by polymerizing the polymerizable monomer, a wax and a plasticizer.   The dental mill blank according to claim 11, wherein the binder is a polymer obtained by polymerizing at least one kind of polymerizable monomers forming the polymer contained in the dental mill blank.   The dental mill blank according to any one of claims 11 to 13, wherein the inorganic filler comprises one having been surface-treated with a surface treatment agent.   The dental mill blank according to any one of claims 11 to 14, wherein the content of the binder in the inorganic filler composite is 0.1 to 10% by mass.